A Co-Crystal Strategy to Tune the Supramolecular Patterns and

Article pubs.acs.org/crystal

A Co-Crystal Strategy to Tune the Supramolecular Patterns and Luminescent Properties: Ten Well-Designed Salts Assembled by Arenedisulfonic Acid with Diverse Diamines Zhao-Peng Deng, Li-Hua Huo,* Hui Zhao, and Shan Gao* Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People’s Republic of China S Supporting Information *

ABSTRACT: Ten salts assembled by arenedisulfonic acid with hydrazine, flexible aliphatic diamines, rigid and semirigid aromatic diamines, namely, (H2HA)2+·(NDS)2− (1), (H2EDA)2+·(NDS)2− (2), (H2PDA)2+·(NDS)2− (3), (H2BTDA)2+·(NDS)2− (4), (H2BDMA)2+·(NDS)2−·2H2O (5), 2(o-HBDA)+· (NDS)2− (6), (m-H2BDA)2+·(NDS)2− (7), (H2MBDA)2+·(NDS)2−·3H2O (8), (H2SDA)2+·(NDS)2−·H2O (9), and 2(HSDA)+·(NDS)2−·H2O (10) (H2NDS = 1,5naphthalenedisulfonic acid, HA = hydrazine, EDA = 1,2-ethanediamine, PDA = 1,3propanediamine, BTDA = 1,4-butanediamine, BDMA = 1,3-benzenedimethanamine, o-BDA = 1,2-benzenediamine, m-BDA = 1,3-benzenediamine, MBDA = 4methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline), have been constructed and characterized by elemental analysis, infrared, thermogravimetric analysis, phospholuminescence, and powder and single-crystal X-ray diffraction. Structural analyses indicate that the nature of the diamines can effectively influence the final structures of the salts through diverse noncovalent bonding interactions, such as hydrogen bonds, π···π stacking, N−H···π, C−H···π, and lone pair···π interactions, which result in six types of architectures. Crystals 1− 3 exhibit a three-dimensional (3-D) pillared layered supramolecular network with the diammonium cations being sandwiched among the sulfonate groups, while crystal 4 exhibits a 3-D “honeycomb” network with the −(CH2)4− groups being encapsulated among the NDS2− anions. In comparison with crystal 4, crystals 5, 7, and 8 exhibit a different 3-D supramolecular network, in which the phenylene, phenyl, and methylphenyl groups interpenetrate with the naphthyl rings of NDS2− anions through continuous π···π interactions. Crystal 6 is two-dimensional pillared layered network with the o-HBDA+ cations arranging along the two sides of the layer. Crystal 9 possesses an organic 3-D supramolecular network formed by the C−H···π and sulfonyl involved lone pair···π interactions which encapsulates a one-dimensional (1-D) infinite [−SO3···H3N−]n nanotube in the large voids. By contrast, crystal 10 possesses an organic 3-D supramolecular network formed by intricate C−H···π, π···π, and sulfonyl involved C/N−H···O interactions which encapsulates 1-D “centipede-shaped” [−SO3···H3N−]n chains in the large voids. Luminescent investigations demonstrate that the salts containing aliphatic diamines exhibit stronger emission intensity than those containing aromatic diamines. This result indicates that the H2NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the luminescent signal.

■

INTRODUCTION Rational design and assembly of supramolecules by the cocrystal strategy has become a subject of growing interest in recent years owing to their intriguing supramolecular patterns and potential applications in the field of photochemistry, biomedicine, and pharmaceutics.1,2 Generally, a co-crystal is a multicomponent assembly held together by noncovalent interactions.2a It can be viewed as an addition to the existing class of crystalline solids (polymorphs, hydrates/solvates, and salts).3 From the principles of crystal engineering and supramolecular chemistry,4 formation of supramolecular patterns relies on intermolecular noncovalent bonding interactions and molecular packing patterns, in which these intermolecular interactions include hydrogen bonds,5 π···π stacking,6 C−H···π,7 cation···π,8 as well as the anion···π interaction (and more generally the lone pair-π interaction).9 © 2012 American Chemical Society

Therefore, the choice of supramolecular formers is a crucial issue for constructing supramolecular architectures and modifying the properties of organic molecules in the solid state. The sulfonate group (−SO3), with a symmetry of C3v, is not only an excellent binding group for constructing metal complexes10 but also an outstanding synthon for assembling salts with proper organic amine molecules, such as the primary ammonium cations (R−NH3+).11 As the case for −SO3, the −NH3+ cation also has the “AB3” form and exhibits a similar C3v symmetry. The three acceptor oxygen atoms on the −SO3 themselves have a closely related tetrahedral geometry to the three donor H atoms on the −NH3+ cations. Thus, the equal Received: April 9, 2012 Revised: May 6, 2012 Published: May 8, 2012 3342

dx.doi.org/10.1021/cg3004855 | Cryst. Growth Des. 2012, 12, 3342−3355

Crystal Growth & Design

Article

Structural analyses indicate that the nature of the diamines can effectively influence the final structures of the salts through different noncovalent bonding interactions. Crystals 1−3 exhibit a three-dimensional (3-D) pillared layered supramolecular network, while crystals 4 and 5 present a 3-D supramolecular network with the H2BTDA2+and H2BDMA2+ cations interpenetrated with the NDS2− anions. Crystal 6 is two-dimensional (2-D) pillared layered network with the o-HBDA+ cations, whereas crystals 7 and 8 exhibit a 3-D supramolecular network with the m-H2BDA2+ and H2MBDA2+ cations interpenetrated with the NDS2− anions. The two protonated amine groups of semirigid H2SDA2+ cations in crystal 9 form hydrogen bonds with −SO3 groups, thus generating a 3-D supramolecular network with the sulfonyl group involved in lone pair···π interactions. By contrast, in crystal 10, only one amine group of semirigid HSDA+ cations is protonated, which involves in the formation of hydrogen bonding interactions with −SO3 groups, resulting in a 3-D supramolecular network together with the sulfonyl involved C/N−H···O interactions. Moreover, thermal stabilities and luminescent properties of the 10 salts are also investigated.

number of separated hydrogen bond donor and acceptor sites with matched geometry and stereoavailability allows the formation of diverse supramolecular patterns. To date, some salts of arenesulfonates and primary ammonium cations have been reported based on the Cambridge Structural Database CSD search,12 in which most of the primary amines involved are monoamines and some interesting and synthetic work is reported. In 2006 and 2009, Tohnai and co-workers reported salts of anthracene-2,6-disulfonic acid (2,6-ADS) with a wide variety of primary monoamines, and their studies revealed that the salts presented seven types of crystal forms and corresponding molecular arrangements of anthracene moieties depended on the nature of the monoamine, which then influenced the fluorescent properties of salts.13 In 2007, the same work group readily prepared a series of salts from simple molecules: triphenylmethylamine (TPMA) and a variety of monosulfonic acids, which exhibited [4 + 4] ion-pair clusters consisting of four TPMA and four monosulfonic acid components. Because of their nanoscale sizes, these clusters might also have potential as quantum dots.14 Five years later, in 2012, they constructed a family of salts with the host comprising of TPMA and 1,8-ADS which encapsulated different guest solvent molecules. Interestingly, these salts displayed a wide range of emission colors from blue to orange-yellow depending on the included guests under UV irradiation.15 Moreover, the salts of guanidinium sulfonates (GS) have also been best investigated in the past few years owing to the matched geometry and stereoavailability between the guanidinium cations and the sulfonate anions.16 By contrast, systematic research on the supramolecular patterns and properties of salts constructed from arenedisulfonates and diamines is less common despite crystal structures of some scattered salts being reported.17 Hence, to this contribution, we reported here the supramolecular patterns and luminescent properties of 10 salts assembled by 1,5naphthalenedisulfonic acid (H2NDS) with hydrazine, four flexible aliphatic diamines, three rigid and one semirigid aromatic diamines (Scheme 1), namely, (H2HA)2+·(NDS)2‑ (1), (H2EDA)2+·(NDS)2‑

■

EXPERIMENTAL SECTION

General Procedures. All chemicals and solvents were of A. R. grade and used without further purification in the syntheses. Elemental analyses were carried out with a Vario MICRO from Elementar Analysensysteme GmbH, and the infrared spectra (IR) were recorded from KBr pellets in the range of 4000−400 cm−1 on a Bruker Equinox 55 FT-IR spectrometer. Powder X-ray diffraction (PXRD) patterns for the three complexes were measured at 293 K on a Bruker D8 diffractometer (Cu Kα, λ = 1.54059 Å). The TG analyses were carried out on a Perkin-Elmer TG/DTA 6300 thermal analyzer under flowing N2 atmosphere, with a heating rate of 10 °C min−1. UV−vis spectra were measured on a Perkin-Elmer Lambda 900 ultraviolet−visible spectrometer. Luminescence spectra were measured on a Perkin-Elmer LS 55 luminescence spectrometer. Synthesis of (H2HA)2+·(NDS)2− (1). A 5 mL methanol solution of hydrazine monohydrate (99% pure, 1 mmol, 0.05 mL) was added to an aqueous solution (5 mL) of 1,5-naphthalenedisulfonic acid tetrahydrate (1 mmol, 360 mg). The mixture was stirred for 10 min at 343 K in a water bath, and then filtered after cooling to room temperature. Colorless crystals of 1 suitable for X-ray diffraction were isolated from the filtrate after four days. Yield: 81%. Elemental analysis calcd (%) for C10H12N2O6S2: C 37.50, H 3.78, N 8.75; found: C 37.44, H 3.83, N 8.78. IR (ν/cm−1): 3446m, 3050−2557br,s, 1571m, 1527m, 1506m, 1241m, 1220s, 1201s, 1157s, 1114m, 1033s, 789s, 765s, 601s. Synthesis of (H2EDA)2+·(NDS)2− (2). A similar procedure as for crystal 1 was employed to prepare crystal 2 by changing the hydrazine hydrate into 1,2-ethanediamine (99% pure, 1 mmol, 0.07 mL). Colorless crystals of 2 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 61%. Elemental analysis calcd (%) for C12H16N2O6S2: C 41.37, H 4.63, N 8.04; found: C 41.32, H 4.59, N 7.99. IR (ν/cm−1): 3448 m, 3168−2831br,s, 1614m, 1529m, 1502m, 1334m, 1243s, 1224s, 1195s, 1155s, 1112m, 1031s, 788s, 767s, 609s. Synthesis of (H2PDA)2+·(NDS)2− (3). A similar procedure as for crystal 1 was employed to prepare crystal 3 by changing the hydrazine hydrate into 1,3-propanediamine (98% pure, 1 mmol, 0.08 mL). Colorless crystals of 3 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 79%. Elemental analysis calcd (%) for C13H18N2O6S2: C 43.08, H 5.01, N 7.73; found: C 43.12, H 4.95, N 7.77. IR (ν/cm−1): 3448m, 3148−2897br,s, 1613m, 1527s, 1504m, 1336m, 1243s, 1226s, 1197s, 1155s, 1091m, 1031s, 786s, 765s, 611s. Synthesis of (H2BTDA)2+·(NDS)2− (4). A similar procedure as for crystal 1 was employed to prepare crystal 4 by changing the hydrazine hydrate into 1,4-butanediamine (98% pure, 1 mmol, 0.1 mL). Colorless crystals of 4 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 83%. Elemental analysis calcd

Scheme 1. Schematic Representation of Molecules Used in This Article

(2), (H2PDA)2+·(NDS)2− (3), (H2BTDA)2+·(NDS)2− (4), (H2BDMA)2+·(NDS)2−·2H2O (5), 2(o-HBDA)+·(NDS)2− (6), (m-H2BDA)2+·(NDS)2− (7), (H2MBDA)2+·(NDS)2−·3H2O (8), (H 2 SDA) 2+ ·(NDS) 2− ·H 2 O (9), and 2(HSDA) + · (NDS)2−·H2O (10) (HA = hydrazine, EDA = 1,2-ethanediamine, PDA = 1,3-propanediamine, BTDA = 1,4-butanediamine, BDMA = 1,3-benzenedimethanamine, o-BDA = 1,2benzenediamine, m-BDA = 1,3-benzenediamine, MBDA = 4-methyl-1,3-benzenediamine, SDA = 4,4′-sulfonyldiamiline). 3343



Article

U(H) = 1.5Ueq (N, O). The hydrogen atoms of water molecules in crystal 9 were fixed by WinGX with O−H = 0.85 Å and U (H) = 1.5Ueq (O). All calculations were carried out with the SHELXTL97 program.18 The CCDC reference numbers are 873407−873416 for crystals 1−10. Selected hydrogen bond parameters for crystals 1−10 are presented in Table 2.

(%) for C14H20N2O6S2: C 44.67, H 5.36, N 7.44; found: C 44.63, H 5.40, N 7.41. IR (ν/cm−1): 3444m, 3190−2908br,m, 1630m, 1595m, 1489s, 1334m, 1233m, 1214s, 1185s, 1153s, 1035s, 788m, 764s, 611s. Synthesis of (H2BDMA)2+·(NDS)2−·2H2O (5). A similar procedure as crystal 1 was employed to prepare crystal 5 by changing the hydrazine hydrate into 1,3-benzenedimethanamine (98% pure, 1 mmol, 0.13 mL). Colorless crystals of 5 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 78%. Elemental analysis calcd (%) for C18H24N2O8S2: C 46.95, H 5.25, N 6.08; found: C 46.93, H 5.20, N 6.05. IR (ν/cm−1): 3452m, 3145−2841br,s, 1631m, 1596m, 1525m, 1501m, 1455m, 1384m, 1338m, 1243s, 1213s, 1182s, 1149s, 1035s, 788s, 767s, 607s. Synthesis of 2(o-HBDA)+·(NDS)2− (6). A similar procedure as for crystal 1 was employed to prepare crystal 6 by changing the hydrazine hydrate into 1,2-benzenediamine (1 mmol, 108 mg). Colorless crystals of 6 suitable for X-ray diffraction were isolated from the filtrate after four days. Yield: 70%. Elemental analysis calcd (%) for C22H24N4O6S2: C 52.37, H 4.79, N 11.10; found: C 52.40, H 4.83, N 11.07. IR (ν/cm−1): 3455m, 3378m, 3104−2862br,s, 1633m, 1558m, 1502m, 1462m, 1323m, 1238s, 1216s, 1193s, 1153s, 1037s, 782m, 742m, 613s. Synthesis of (m-H2BDA)2+·(NDS)2− (7). A similar procedure as for crystal 1 was employed to prepare crystal 7 by changing the hydrazine hydrate into 1,3-benzenediamine (1 mmol, 108 mg). Colorless crystals of 7 suitable for X-ray diffraction were isolated from the filtrate after five days. Yield: 74%. Elemental analysis calcd (%) for C16H16N2O6S2: C 48.48, H 4.07, N 7.07; found: C 48.51, H 4.02, N 7.11. IR (ν/cm−1): 3413m, 3120−2895br,m, 1633m, 1589m, 1544s, 1496m, 1336m, 1251s, 1220s, 1187s, 1157s, 1031s, 798m, 765m, 612s. Synthesis of (H2MBDA)2+·(NDS)2−·3H2O (8). A similar procedure as for crystal 1 was employed to prepare crystal 8 by changing the hydrazine hydrate into 4-methyl-1,3-benzenediamine (1 mmol, 122 mg). Brown crystals of 8 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 78%. Elemental analysis calcd (%) for C17H24N2O9S2: C 43.96, H 5.21, N 6.03; found: C 43.93, H 5.17, N 6.06. IR (ν/cm−1): 3461m, 3058−2642br,s, 1638m, 1556m, 1508m, 1332m, 1238s, 1216s, 1197s, 1157s, 1035s, 788m, 767m, 619s. Synthesis of (H2SDA)2+·(NDS)2−·H2O (9). A similar procedure as for crystal 1 was employed to prepare crystal 9 by changing the hydrazine hydrate into 4,4′-sulfonyldiamiline (1 mmol, 136 mg). Colorless crystals of 9 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 78%. Elemental analysis calcd (%) for C22H22N2O9S3: C 47.65, H 4.00, N 5.05; found: C 47.62, H 3.95, N 5.01. IR (ν/cm−1): 3459m, 3071−2611br,m, 1630m, 1596m, 1521m, 1494m, 1423m, 1323m, 1240m, 1220s, 1191m, 1155s, 1105m, 1029s, 782m, 765m, 678s, 611s. Synthesis of 2(HSDA)+·(NDS)2−·H2O (10). A similar procedure as for crystal 9 was employed to prepare crystal 10 by increasing the amount of 4,4′-sulfonyldiamiline (2 mmol, 272 mg). Yellow crystals of 10 suitable for X-ray diffraction were isolated from the filtrate after three days. Yield: 83%. Elemental analysis calcd (%) for C34H34N4O11S4: C 50.86, H 4.27, N 6.98; found: C 50.83, H 4.32, N 7.02. IR (ν/cm−1): 3421s, 3344s, 3085−2888br,s, 1632m, 1595m, 1488m, 1455m, 1417m, 1325m, 1232m, 1211s, 1197m, 1155s, 1089s, 1049s, 788m, 765m, 682m, 609m. X-ray Crystallographic Measurements. Table 1 provides a summary of the crystal data, data collection, and refinement parameters for the crystals 1−10. All diffraction data were collected at 295 K on a RIGAKU RAXIS-RAPID diffractometer with graphite monochromatized Mo-Kα (λ = 0.71073 Å) radiation in ω scan mode. All structures were solved by direct method and difference Fourier syntheses. All non-hydrogen atoms were refined by full-matrix leastsquares techniques on F2 with anisotropic thermal parameters. The hydrogen atoms attached to carbons were placed in calculated positions with C−H = 0.93 Å (aromatic H atoms), C−H = 0.97 Å (methylene H atoms), C−H = 0.96 Å (methyl H atoms), and U (H) = 1.2Ueq (C) in the riding model approximation. The hydrogen atoms of nitrogen atoms in crystals 1−10 and the hydrogen atoms of water molecules in crystals 5, 8, and 10 were located in difference Fourier maps and were also refined in the riding model approximation, with N−H and O−H distance restraint (0.86(1) or 0.85(1) Å) and

■

RESULTS AND DISCUSSION Syntheses. As stated in the introduction, formation of supramolecules relies on intermolecular noncovalent bonding interactions and molecular packing patterns. Therefore, the choice of supramolecular formers is crucial to the final architectures of supramolecules. Herein, based on the consideration of the structural diversities and the potential ability of forming noncovalent bonding interactions, hydrazine, four flexible aliphatic diamines, three rigid, and one semirigid aromatic diamines were employed to react with 1,5-naphthalenedisulfonic acid in a mixed methanol−water solution, leading to the formation of crystals 1−10. It should be clarified that crystal 2 had been incidentally synthesized in our previous work for the prepared cobalt-sulfonate complex.19 As systematic research of the supramolecular patterns based on arenedisulfonate and diamines, we synthesized this crystal by using a simple method again and an additional single crystal X-ray diffraction experiment was also carried out. Crystals 1−5 and 7−9 can be easily obtained as 1:1 salts. By contrast, during the experiments, despite the ratio of the reactants being changed from 1:1 to 1:3 with an increasing amount of H2NDS, crystal 6 was only obtained as a 2:1 salt. The main reason may be attributed to the formation of the strong N−H···π interactions between adjacent o-HBDA+ cations and the steric effect originated from the short distance between the two amines groups in the rigid o-BDA molecule in comparison with the flexible EDA molecule. Moreover, for the long semirigid SDA molecule, a different ratio between the reactants was accomplished to investigate the influence of the bonding ability of the sulfonyl group on the final architectures. Thus, 1:1 (9) and 2:1 (9) salts were synthesized. As anticipated, various weak forces, that is, hydrogen bonding, π···π stacking, N−H···π, C−H···π, and lone pair···π interactions, play a key role in stabilizing the self-assembly process observed for all salts. Moreover, the final architectures partially depend on the hydrogen bonding modes of the −SO3 and −NH3 groups. Structure Description of Crystals 1−3. As illustrated in Figure 1a−c, the structures of crystals 1−3 all comprise one diammonium cation and one NDS2− anion, which form cation···anion pairs through the hydrogen bonding interactions (Table 2). The diammonium cation and the NDS2− anion are all located at special positions. The −SO3 groups and −NH3 groups in the three crystals all interact with each other through the N−H···O hydrogen bonding interactions to form a 2-D layer structure (Scheme 2). Subsequently, the naphthyl rings of the NDS2− anions direct alternately to both sides of the layer and also extend the layers into a 3-D pillared layered supramolecular network with the diammonium cations being sandwiched among the sulfonate groups (Figure 1d−f). The distances between the two sulfonate walls are 3.970(2), 4.321(2), and 5.917(2) Å (the shortest distances between the opposite S atoms), respectively. It should be noted that the naphthyl rings of the NDS2− anions in the three crystals are all involved in the C−H···π interactions20 between the π electron density of naphthyl ring and adjacent CH group, resulting in the formation of a 2-D layer structure as shown in Figure 2, in which four naphthyl rings form a “dumbbell” like ring. As the length of 3344



Article

Table 1. Crystal Data and Structure Refinement Parameters of Crystals 1−10 crystals

1

2a

3

4

5

empirical formula formula weight space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z Dc/g cm−3 μ (Mo Kα)/mm−1 F(000) reflections collected unique reflections parameters R (int) GOF on F2 final R indices [I ≥ 2σ(I)]

C10H12N2O6S2 320.34 P21/c 10.837(2) 7.6503(15) 7.2566(15) 90.00 95.41(3) 90.00 598.9(2) 2 1.776 0.474 332 5616 1358 100 0.0434 1.069 R1 = 0.0387 wR2 = 0.1041 6

C12H16N2O6S2 348.39 P21/c 11.187(2) 8.2310(16) 8.5011(17) 90.00 100.26(3) 90.00 770.2(3) 2 1.502 0.376 364 7301 1755 109 0.0593 1.080 R1 = 0.0508 wR2 = 0.1251 7

C13H18N2O6S2 362.41 C2/c 25.475(5) 7.4957(15) 7.9814(16) 90.00 91.11(3) 90.00 1523.8(5) 4 1.580 0.383 760 4943 1724 114 0.0994 1.043 R1 = 0.0632 wR2 = 0.1297 8

C14H20N2O6S2 376.44 C2/c 17.786(4) 10.674(2) 9.3039(19) 90.00 116.72(3) 90.00 1577.7(7) 4 1.585 0.373 792 7585 1809 118 0.0453 1.030 R1 = 0.0434 wR2 = 0.1118 9

C18H24N2O8S2 460.51 P1̅ 8.7396(17) 9.920(2) 13.624(3) 69.27(3) 72.65(3) 77.08(3) 1045.1(4) 2 1.463 0.303 484 10374 4754 301 0.0368 1.090 R1 = 0.0559 wR2 = 0.1588 10

C22H24N4O6S2 504.57 C2/c 39.141(8) 7.2708(15) 7.8823(16) 90.00 92.90(3) 90.00 2240.3(8) 4 1.496 0.287 1056 10585 2551 169 0.0387 1.084 R1 = 0.0403 wR2 = 0.1037

C16H16N2O6S2 396.43 P2/n 9.1443(18) 8.0163(16) 12.632(3) 90.00 109.40(3) 90.00 873.4(4) 2 1.507 0.342 412 8398 2007 128 0.0412 1.093 R1 = 0.0430 wR2 = 0.1083

C17H24N2O9S2 464.50 P21/c 13.383(3) 12.706(3) 13.944(3) 90.00 118.35(3) 90.00 2086.7(10) 4 1.478 0.308 976 20046 4761 308 0.0516 1.065 R1 = 0.0569 wR2 = 0.1721

C22H22N2O9S3 554.60 P1̅ 5.7543(12) 14.022(3) 14.952(3) 83.94(3) 81.13(3) 84.37(3) 1181.2(4) 2 1.559 0.372 576 18950 5352 343 0.0423 1.031 R1 = 0.0657 wR2 = 0.1828

C34H34N4O11S4 802.89 C2/c 28.300(6) 7.0286(14) 22.237(4) 90.00 126.43(3) 90.00 3558.8(18) 4 1.498 0.334 1672 16657 4045 258 0.0533 1.064 R1 = 0.0468 wR2 = 0.1224

complexes empirical formula formula weight space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z Dc/g m−3 μ (Mo Kα)/mm−1 F(000) reflections collected unique reflections parameters R (int) GOF on F2 final R indices [I ≥ 2σ(I)] a

This structure has been reported in our previous work.19

generates 2-D layers (Scheme 2), which are pillared by the naphthyl rings of the NDS2− anions to generate a 3-D “honeycomb” network with the H2BTDA2+ cations being encapsulated among the NDS2− anions (Figure 3b). Alternately, this 3-D “honeycomb” network can also be understood in the following manner. First, the −NH3 groups of the H2BTDA2+ cations interlink with the NDS2− anions through hydrogen bonding interactions between O2, O3, H1N2, and H1N3 (N1−H1N2···O2iv, 2.955(2) Å, N1−H1N3···O3, 2.961(2) Å), giving rise to a one-dimensional (1-D) nanotube along the c-axis (Figure S1, Supporting Information). The −(CH2)4− groups are encapsulated in the channels. Then, adjacent nanotubes are further joined by the hydrogen bonding interactions between O1, O3, H1N1, H1N2, and H1N3 (N1−H1N1···O1iii, 2.755(2) Å, N1−H1N2···O1v, 3.001(2) Å, N1−H1N3···O3v, 2.963(2) Å),

the three diamines increases, the distances of C···π in C−H···π interactions exhibit a regular change from 3.488(2) in 1 (∠C−H···π = 138.3°), 3.642(2) in 2 (∠C−H···π = 115.3°), to 3.806(4) Å in 3 (∠C−H···π = 136.8°). Structure Description of Crystals 4 and 5. Increasing the length of the aliphatic diamine leads to the formation of a 3-D supramolecular network in crystals 4 and 5. The structure of crystal 4 consists of one H2BTDA2+ cation and one NDS2− anion (Figure 3a), while the structure of crystal 5 consists of one H2BDMA2+ cation, two NDS2− anions, and two water molecules (Figure 4a). The H2BTDA2+ cation and the NDS2− anions in the two crystals are all located at special positions. All the components in the unit cell connect with each other through the hydrogen bonding interactions (Table 2). In crystal 4, the linkage of −SO3 groups and −NH3 groups 3345



Article

Table 2. Hydrogen Bond Parameters for Crystals 1−10a D−H···A 1 N(1)−H(1N1)···O(1)iii N(1)−H(1N2)···O(2)iv N(1)−H(1N2)···O(3)v N(1)−H(1N3)···O(3) 2 N(1)−H(1N1)···O(2) N(1)−H(1N1)···O(1) N(1)−H(1N2)···O(2)iii N(1)−H(1N3)···O(1)iv 3 N(1)−H(1N1)···O(3)iii N(1)−H(1N1)···O(1)iv N(1)−H(1N2)···O(3) N(1)−H(1N3)···O(2)v 4 N(1)−H(1N1)···O(1)iii N(1)−H(1N2)···O(2)iv N(1)−H(1N2)···O(1)v N(1)−H(1N3)···O(3) N(1)−H(1N3)···O(3)v 5 O(1W)−H(1W1)···O(2W) O(1W)−H(1W2)···O(6)iii O(2W)−H(2W1)···O(3) O(2W)−H(2W2)···O(1)iv N(1)−H(1N1)···O(1) N(1)−H(1N2)···O(1W)v N(1)−H(1N3)···O(4)vi N(2)−H(2N1)···O(6) N(2)−H(2N2)···O(5)vii N(2)−H(2N3)···O(2)viii 6 N(1)−H(1N1)···O(2)ii N(1)−H(1N2)···O(1)iii

d(D−H)

d(H···A)

d(D···A)

∠(DHA)

0.86 0.85 0.85 0.86

1.845 2.042 2.426 1.893

2.701 2.780 3.035 2.748

176.5 144.2 128.8 177.1

0.86 0.86 0.87 0.86

2.32 2.37 1.94 1.94

3.060 3.141 2.777 2.795

145 149 162 173

0.85 0.85 0.86 0.85

2.09 2.52 2.04 2.05

2.920 2.948 2.876 2.818

164 112 165 150

0.86 0.85 0.85 0.86 0.86

1.920 2.229 2.43 2.235 2.39

2.755 2.955 3.001 2.961 2.963

163 143.1 124.6 142 124.8

0.85 0.85 0.87 0.87 0.86 0.87 0.87 0.86 0.86 0.86

2.64 2.07 2.10 2.316 2.012 1.997 1.976 1.994 1.934 1.878

3.245 2.892 2.836 3.177 2.868 2.791 2.823 2.826 2.795 2.731

129 163 142 168 174 151 163 163 176 169

0.86 0.86

1.964 2.049

2.811 2.898

171.2 168.8

D−H···A

d(D−H)

d(H···A)

d(D···A)

∠(DHA)

N(1)−H(1N3)···O(1) N(2)−H(2N1)···O(3)ii 7 N(1)−H(1N1)···O(3) N(1)−H(1N2)···O(1)iii N(1)−H(1N3)···O(2)iv 8 O(1W)−H(1W1)···O(3W)iii O(1W)−H(1W2)···O(3W)iv O(2W)−H(2W1)···O(6)v O(2W)−H(2W2)···O(6)ii O(3W)−H(3W1)···O(2W) O(3W)−H(3W2)···O(1) N(1)−H(1N1)···O(1W) N(1)−H(1N2)···O(4)ii N(1)−H(1N3)···O(1) N(2)−H(2N1)···O(3)iv N(2)−H(2N2)···O(2)i N(2)−H(2N3)···O(5) 9 O(1W)−H(1W2)···O(6)iii N(1)−H(1N1)···O(2)iii N(1)−H(1N2)···O(1) N(1)−H(1N3)···O(4)iv N(2)−H(2N1)···O(5) N(2)−H(2N2)···O(1W) N(2)−H(2N3)···O(1)v 10 O(1W)−H(1W)···O(3)ii N(1)−H(1N1)···O(5)iii N(1)−H(1N2)···O(1W)iv N(1)−H(1N3)···O(1)iii N(2)−H(2N1)···O(3)v N(2)−H(2N2)···O(2)vi

0.86 0.86

1.997 2.53

2.854 3.222

176.5 139

0.86 0.86 0.86

1.88 1.94 1.92

2.734 2.785 2.756

176 164 162

0.86 0.86 0.85 0.85 0.85 0.85 0.87 0.87 0.87 0.86 0.86 0.86

2.00 2.04 2.175 2.31 1.938 1.994 1.849 1.903 1.909 1.909 1.900 1.904

2.826 2.846 3.014 3.058 2.764 2.837 2.722 2.769 2.770 2.758 2.749 2.729

162 157 169 146 165 170 175 177 169 169 168 159

0.85 0.86 0.86 0.86 0.86 0.86 0.86

2.55 2.070 2.124 1.91 1.898 1.953 1.944

3.063 2.868 2.915 2.773 2.754 2.792 2.806

119.7 155 153 165 171 166 177

0.85 0.86 0.86 0.86 0.85 0.85

1.940 2.118 2.098 1.933 2.20 2.172

2.763 2.922 2.941 2.775 2.991 2.981

162 155 165 163 156 158

a Symmetry operations: For 1, iii −x, y − 1/2, −z + 1/2; iv x, y, z − 1; v x, −y + 1/2, z − 1/2. For 2, iii −x + 1, y + 1/2, −z + 3/2; iv x, −y + 3/2, z + 1/2. For 3, iii x, −y, z + 1/2; iv x, y, z + 1; v x, −y + 1, z + 1/2. For 4, iii −x + 1/2, y + 1/2, −z + 1/2; iv x, −y + 1, z + 1/2; v −x + 1/2, −y + 1/2, −z + 1. For 5, iii −x, −y, −z + 1; iv −x, −y, −z; v x + 1, y, z; vi x, y − 1, z; vii −x + 1, −y + 1, −z + 1; viii x, y + 1, z. For 6, ii x, −y, z + 1/2; iii x, −y + 1, z + 1/2. For 7, iii −x + 1, −y, −z + 1; iv −x + 3/2, y, −z + 3/2. For 8, i −x + 1, −y + 1, −z + 1; ii −x, −y + 1, −z; iii x, −y + 3/2, z − 1/2; iv −x + 1, y − 1/2, −z + 1/2; v x, y + 1, z. For 9, iii x − 1, y, z; iv −x, −y + 1, −z + 1; v x, y + 1, z. For 10, ii −x, y, −z + 1/2; iii −x + 1/2, −y + 1/2, −z + 1; iv −x + 1/2, −y + 3/2, −z + 1; v x + 1/2, y − 1/2, z; vi x + 1/2, y + 1/2, z.

thus generating the 3-D “honeycomb” network (Figure 3b). Different from the above three crystals 1−3, the naphthyl rings in crystal 4 are parallel with each other in an interlaced mode with the shortest centroid-to-centroid distance being 4.257(6) Å. Thus, no π···π and C−H···π interactions are detected during the supramolecular assembly. Different from crystal 4, the −SO3 groups and −NH3 groups here interact with each other through the N−H···O hydrogen bonding interactions to form finite [(SO3)4(NH3)4] clusters, which are subsequently bridged by pairs of O2w molecules at the points of O1 atoms and the remaining O3 atoms to generate another R44(12) graph set which then connect the clusters into a 1-D tape (Figure S2, Supporting Information). The other water molecule, O1w, forms hydrogen bonding interactions with O6, O2w, and the remaining H1N2 atoms and extends the aforementioned 1-D tape into a 2-D layer motif (Figure 4b). Meanwhile, another two types of rings with the graph sets R68(16) and R810(24) are formed. Moreover, the

naphthyl rings of the NDS2− anions and the phenyl rings of the H2BDMA2+ cations direct alternately to both sides of the layer and extend the layers into a 3-D supramolecular network (Figure 4c). It should be noted that extensive π···π interactions among these aromatic rings are observed. The centroid-tocentroid distance between the S1-containing naphthyl ring and phenyl ring is 3.898(2) Å, while the centroid-to-centroid distance between the S2-containing naphthyl ring and phenyl ring is 3.675(2) Å (Figure 4c). Such continuous π···π interactions strengthen the stability of the 3-D network and lead to a different 3-D network from crystal 4. Structure Description of Crystal 6. As shown in Figure 5a, the structure of crystal 6 consists of two o-HBDA+ cations and one NDS2− anion which is located at a special position. The three parts connect to each other through the hydrogen bonding interactions (Table 2). Adjacent −SO3 groups and −N1H3 groups interact with each other through hydrogen bonding interactions to form a 2-D (6,3) layer 3346



Article

Figure 1. Structures of crystals 1 (a), 2 (b), and 3 (c), and the 3-D pillared layered supramolecular networks of crystals 1 (d), 2 (e), and 3 (f) showing the diammonium cations sandwiched by the sulfonate groups.

(Scheme 2). The naphthyl rings of the NDS2− anions direct to only one side of the layer, whereas the phenyl rings of the o-HBDA+ cations direct to the other side. Such arrangement extends the above single layer into a 2-D pillared layered network (Figure 5b). It is interesting to note that the H2N2 atoms of the unprotonated −N2H2 groups form strong N−H···π interactions (3.426(2) Å, ∠N−H···π = 154.7°) with the phenyl rings instead of participating in the formation of hydrogen bonding interactions, and thus generating a 1-D chain structure along the c-axis (Figure 5b). Owing to the existence of such interactions, the phenyl rings of the o-HBDA+ cations are not intercrossed with the naphthyl rings of the NDS2− anions as observed in crystal 5. Instead, the C−H···π interactions20 (C1−H1···π, 3.750(2) Å, ∠C−H···π = 135.3°) between the π

electron density of naphthyl ring and adjacent CH group are observed as the case in crystals 1−3, which also result in the formation of a 2-D layer structure as shown in Figure 2. Owing to such interactions, the phenyl rings of the adjacent layers arrange in head-to-head mode along the a-axis (Figure 5b). Structure Description of Crystals 7 and 8. Reaction of H2NDS with two similar aromatic diamines, m-BDA and MBDA, results in two different crystals 7 and 8. The structure of crystal 7 consists of one m-HBDA2+ cation and one NDS2− anion (Figure 6a), while the structure of crystal 8 consists of one H2MBDA2+ cation, two NDS2− anions, and three water molecules (Figure 7a). The m-HBDA2+ cation and the NDS2− anions in the two crystals are all located at special positions. All the components in the unit cell connect with each other 3347



Article

Scheme 2. Diverse Supramolecular Patterns Formed by Sulfonic and Ammonium Ions in Crystals 1−10

motif (Scheme 2). Adjacent layers are further linked into a 3-D supramolecular network through the hydrogen bonding interactions involving the remaining H1N1, O6, and (H2O)6 cluster formed by pairs of water molecules (Figure 7b). As the case in crystal 5, the phenyl and naphthyl rings in the two crystals 7 and 8 are all intercrossed with each other, which provides the chance for the formation of π···π interactions. The centroid-to-centroid distance in crystal 7 is 3.595(1) Å, while the centroid-to-centroid distances in crystal 8 are 3.621(2), 3.875(2) (S1-containing naphthyl ring) and 3.678(2), 3.864(2) Å (S2-containing naphthyl ring), respectively. Such π···π interactions strengthen the stability of the 3-D network and result in a similar 3-D network as observed in crystal 5 (Figures 6c and 7c). Structure Description of Crystals 9 and 10. In order to investigate the influence of the bonding ability of the sulfonyl group in the semirigid aromatic diamine on the final architectures, a different ratio between the reactants is accomplished, which leads to the formation of two monohydrate 1:1 and 2:1 salts. The structure of crystal 9 consists of one H2SDA2+ cation, two NDS2− anions, and one water molecule (Figure 8a), while the structure of crystal 10 consists of one HSDA+ cation, one NDS2− anion, and one water molecule (Figure 9a). The NDS2− anions in the two crystals and water molecule in crystal 10 are all located at special positions. All the components in the unit cell connect with each other through the hydrogen bonding interactions (Table 2). The bent angles occurring at the point of the sulfonyl group are 105.5° and 104.5°, respectively. In crystal 9, adjacent −SO3 groups and −NH3 groups interact with each other through the N−H···O hydrogen bonding interactions to form a 1-D nanotube along the a-axis with the water molecules filled in the channels and connected to the inner wall through O1w−H1w2···O6iii and N2−H2N2···O1w

Figure 2. 2-D layer structure formed by C−H···π interactions with the red shadow showing the differences of bonds and angles among crystals 1−3 and 6.

through the hydrogen bonding interactions (Table 2). In crystal 7, the −SO3 groups and −NH3 groups interact with each other through the N−H···O hydrogen bonding interactions to form 1-D ribbons (Scheme 2), which are further linked into a 2-D layer through the phenyl rings of the protonated m-HBDA2+ cations, leading to larger rings described by the graph set R44(20) (Figure 6b). Moreover, the naphthyl rings of the NDS2− anions insert into the space formed by the phenyl rings and extend adjacent layers into 3-D supramolecular network (Figure 6c). By contrast, the −SO3 groups and −NH3 groups in crystal 8 interact with each other through the N−H···O hydrogen bonding interactions to form a 2-D layer 3348



Article

Figure 3. (a) Structure of crystal 4. (b) 3-D “honeycomb” network of crystal 4.

interactions (Figure 8b). Meanwhile, the organic parts also interact with each other through the noncovalent bonding interactions to generate a 3-D network with huge 1-D channels (Figure 8c). On the one hand, the sulfonyl group points to the phenyl ring of adjacent cation, which indicates the possible existence of lone pair···π interactions. A careful inspection following this speculation finds that the distances of 3.760(3) and 3.529(3) Å between the O7, O8 and the centroid of the phenyl ring (plane-centroid-anion angle α = 75.3 and 75.8 o) are below the maximum bonding interaction distance of 3.82 Å as calculated from Pythagoras’ theorem,21 suggesting the existence of lone pair···π interactions. On the other hand, the C−H···π interactions20 (C19−H19···π, 3.649(4) Å, ∠C−H···π = 129.3°, C6−H6···π, 3.760(5) Å, ∠C−H···π = 129.2°) between the π electron density of aryl ring and adjacent CH group are observed. The combination of these lone pair···π and C−H···π interactions, not involving any hydrogen bonding interactions, results in the formation of the 3-D supramolecular network with large channels. Moreover, the aforementioned 1-D nanotubes fill in the channels, thus giving rise to the final 3-D network (Figure S3, Supporting Information).

Figure 4. (a) Structure of crystal 5. (b) 2-D layer formed by O1w molecules linking 1-D tapes. (c) 3-D supramolecular framework strengthened by π···π interactions between the naphthyl rings and the phenyl rings.

Adjacent sulfonate groups and unprotonated −N2H2 groups in crystal 10 interact with each other through the N−H···O hydrogen bonding interactions to form a 1-D chain motif along the b-axis, which is decorated by the “arms” formed by sulfonyl group and protonated −N1H3 group (Figure S4, Supporting Information). Subsequently, the water molecules, as tetrapod synthons, join adjacent two 1-D chains at the points of H1N2 and O3 to generate a 1-D “centipede-shaped” chain 3349



Article

Figure 5. (a) Structure of crystal 6. (b) Packing diagram of crystal 6 showing the N−H···π interactions denoted as white dashed lines.

(Figure 9b). In comparison with crystal 9, the O atoms of the sulfonyl groups here form C/N−H···O interactions with adjacent HSDA+ cations (C7−H7···O4, 3.191(6) Å, N1− H1N1···O5, 2.922(3) Å), leading to 2-D layer motifs together with the π···π interactions between two HSDA+ cations (centroid-to-centroid distance being 3.928(2) Å), which are further extended into 3-D supramolecular network with huge 1-D channels (Figure 9c) through C−H···π interactions20 among phenyl rings and naphthyl rings (C14−H14···π, 3.747(4) Å, ∠C−H···π = 148.3°; C17−H17···π, 3.649(2) Å, ∠C−H···π = 147.0°). As observed in crystal 9, the aforementioned 1-D “centipede-shaped” chains fill in the channels, thus giving rise to the 3-D supramolecular network (Figure S5, Supporting Information). Hydrogen Bonding Modes of the −SO3 and −NH3 Groups. Both −SO3 and −NH3 groups have three sites to form hydrogen bonding interactions; hence, multiple hydrogen bonding modes could be generated according to the different environments. For clarity, the hydrogen bonding modes of the two −SO3 and −NH3 groups are denoted as AnAnAn (A = O or H, n = 0, 1, 2). As shown in Scheme 2, the −SO3 and −NH3 groups in the 10 salts exhibit different hydrogen bonding modes, which then leads to the formation of diverse [−SO3···H3N−]n motifs. In crystal 10, the −SO3 and −NH3 groups exhibit a simple A1A0A0 hydrogen bonding mode and interconnect with each other to form the smallest [−SO3···H3N−] units, which are interlinked through the unprotonated −N2H2 groups to form a 1-D chain. Two −SO3 and two −NH3 groups in crystal 5 exhibit A1A1A0 (S1, N1) and A1A1A1 (S2, N2) hydrogen bonding modes. The interconnection among the four groups generates a finite [−SO3···H3N−]4 cluster which contains three identical R44(12) graph sets consisting of two −SO3 and two −NH3 groups, that is, [2 + 2] ring. While the −SO3 and −NH3 groups

Figure 6. (a) Structure of crystal 7. (b) 2-D layer extended by the phenyl rings of the m-HBDA2+ cations bridging 1-D [−SO3···H3N−]n ribbons. (c) 3-D supramolecular network strengthened by π···π interactions between the naphthyl rings and the phenyl rings.

in crystal 7 both present A1A1A1 hydrogen bonding mode, and they connect each other to form a 1-D chain, which contains 3350



Article

Figure 7. (a) Structure of crystal 8. (b) 3-D supramolecular network formed by (H2O)6 clusters (red shadow) bridging 2-D [−SO3···H3N−]n layer. (c) 3-D supramolecular network strengthened by π···π interactions between the naphthyl rings and the phenyl rings.

modes as observed in crystal 9. However, adjacent donors and acceptors link each other to form a 2-D planar layer containing identical [3 + 3] rings described by the graph set R56(16). Similarly, the two −SO3 and two −NH3 groups in crystal 8 also exhibit A1A1A0 (S2, N1) and A1A1A1 (S1, N2) modes as obseved in crystal 5. Owing to the different connection direction, a 2-D planar layer consisting of [5 + 5] rings described by the graph set R10 10(30) is formed instead of the finite [−SO3···H3N−]4 cluster. In crystals 1−3, the −NH3 groups all exhibit the A2A1A1 mode, while the −SO3 groups exhibit the

continuous 12-membered rings described by the graph set R44(12) ([2 + 2] ring). In crystal 9, two pairs of −SO3 and −NH3 groups show different A2A1A0 (S1) and A1A1A1 (S2, N1, N2) hydrogen bonding modes. Such intricate modes join adjacent donors and acceptors to generate a 1-D nanotube. The wall of the nanotube is composed of identical [5 + 5] rings described by the graph set R910(28). It should be noted that the same hydrogen bonding modes can also result in different motifs due to the different connection direction. For example, the −SO3 and −NH3 groups in crystal 6 present the same 3351



Article

Figure 9. (a) Structure of crystal 10. (b) Side view and upward view of the 1-D “centipede-shaped” chain bridging by the tetrapod water molecules. (c) 3-D supramolecular network formed by the naphthyl and phenyl rings through C−H···π, π···π, and sulfonyl involved C/N− H···O interactions with huge 1-D channels.

Figure 8. (a) Structure of crystal 9. (b) 1-D [−SO3···H3N−]n nanotube with the water molecules encapsulated. (c) 3-D supramolecular network formed by the naphthyl and phenyl rings through C−H···π and sulfonyl involved lone pair···π interactions with huge 1-D channels.

crystals, the interactions between the −SO3 and −NH3 groups generate 2-D layer motifs, in which the −NH3 groups in crystals 1 and 2 are sandwiched between the −SO3 groups. The −NH3 groups in crystal 3 are only involved in a single planar layer due

A2A1A1 mode in crystals 1 and 3 and A2A2A0 mode in crystal 2. Because of the similar hydrogen bonding modes in the three 3352



Article

to the long aliphatic spacer between the two −NH3 groups. However, despite the similar modes, they exhibit different hydrogen bonding rings. For 1, the layers contain [2 + 4] and [2 + 2] rings described by the graph set R44(14) and R33(8). For 2, the layers contain [2 + 4] and [4 + 4] rings described by the graph set R46(12) and R48(16). For 3, the layers contain two types of [2 + 2] rings described by the graph set R33(8) and R44(12). In contrast to the above nine crystals, −SO3 and −NH3 groups in crystal 4 present more intricate modes of A2A2A1 and connect with each other to give rise to a 2-D planar layer motif which contains [1 + 1] and three types of [3 + 3] rings described by the graph set R22(4), R22(6), R33(8), and R44(12) (Scheme 2). From these discussions, we can conclude that the diverse hydrogen bonding modes of the sulfonate and −NH3 groups are prone to form high dimensional hydrogen bonding motifs, which then influence the final supramolecular networks. Structural Diversities Tuned by Various Diamines. From the standpoint of crystal engineering, the construction of salts mainly depends on the intermolecular noncovalent bonding interactions. Therefore, the properties of the organic molecules involved will influence the structural diversities of the final salts. In this article, hydrazine, four flexible aliphatic diamines, three rigid and one semirigid aromatic diamines are employed to construct salts with H2NDS. Structural analyses indicate that six types of architectures are formed with the above diamines. For crystals 1−5, three types of architectures are formed owing to the different length of the aliphatic spacers, −(CH2)n− (n = 0, 2−4) and −CH2−Ph−CH2−. In crystals 1−3, the protonated HA, EDA, and PDA molecules are all sandwiched between the −SO3 groups through hydrogen bonding interactions owing to the short and flexible or no spacer, which further link by the naphthyl rings of the NDS2− anions into a 3-D pillared layered supramolecular network. Meanwhile, the C−H···π interactions among the naphthyl rings of the NDS2− anions are detected in the three crystals. However, owing to the long and flexible −(CH2)4− and −CH2−Ph− CH2− spacers, the distances of 6.253 and 6.742 Å in crystals 4 and 5 between the two terminal −NH3 groups are close to that of the two terminal −SO3 groups of NDS2− anions (6.854 and 6.873 Å), which lead to the formation of another two types of 3D supramolecular network instead of the 3-D pillared layered network. Because of the shorter distances of 6.253 Å between the two terminal −NH3 groups than that of 6.854 Å between the two terminal −SO3 groups, crystal 4 exhibits a “honeycomb” network. However, crystal 5 shows a different supramolecular network from crystal 4 due to the existence of π···π interactions among the intercrossed naphthyl rings and phenyl rings. In comparison, crystals 6−10 containing aromatic diamines exhibit another three types of architectures. In crystal 6, only one of the two amines is protonated and interacts with the sulfonate group through hydrogen bonding interactions to form a 2-D (6,3) layer. Then, the naphthyl rings extend adjacent two layers into 2-D pillared layered network with the o-HBDA+ cations arranging along the two sides of the layer. The other unprotonated amine group forms strong N−H···π interactions with the phenyl ring instead of participating in the formation of hydrogen bonding interactions. The C−H···π interactions between the naphthyl groups of the NDS2− anions are also detected as observed in crystals 1−3. Different from crystal 6, both the m-HBDA2+ and the H2MBDA2+ cations in crystals 7 and 8 interpenetrate with the NDS2− anions, thus leading to the formation of a similar 3-D supramolecular network as observed in crystal 5 through the hydrogen bonding and π···π stacking

interactions. The semirigid SDA molecule can provide additional supramolecular interaction site of the sulfonyl group and result in different structures from the flexible aliphatic diamines and rigid aromatic diamines. In crystal 9, the two protonated amine groups are involved in the hydrogen bonding interactions with sulfonate groups, which leads to the formation of a 1-D nanotube. Adjacent nanotubes link to each other through eight H2SDA2+ cations and NDS2− anions, thus generating a 3-D supramolecular network with four H2SDA2+ cations captured S1-containing NDS2− anions and two H2SDA2+ cations captured S2-containing NDS2− anions through the C−H···π and lone pair···π interactions. By contrast, in crystal 10, the hydrogen bonding interactions among sulfonates, water molecules, protonated and unprotonated amine groups link them into a 1-D “centipede-shaped” chain. Adjacent chains link to each other through six HSDA+ cations and NDS2− anions, generating a 3-D supramolecular network with two HSDA+ cations capturing one NDS2− anion through the C−H···π and π···π interactions. In a word, as a result of the existence of the sulfonyl group, crystal 9 possesses an organic 3-D supramolecular network formed by the C−H···π and lone pair···π interactions which encapsulates a 1-D infinite [−SO3···H3N−]n nanotube as guests, while crystal 10 possesses an organic 3-D supramolecular network formed by intricate C−H···π, π···π, and C/N−H···O interactions which encapsulates a 1-D “centipede-shaped” [−SO3···H3N−]n chain as guests. Accordingly, the nature of the diamines can effectively influence the final architectures of the salts through different noncovalent bonding interactions. IR Spectroscopy. The stretching bands around 3400 cm−1 in the IR spectra of crystals 1−10, as well as the broad and strong stretching bands appearing in the range of 3190− 2557 cm−1, can be attributed to the existence of the primary ammonium cations, water molecules, as well as the formation of extensive hydrogen bonding interactions. The bands appearing in the range of 1638−1455 cm−1 in crystals 1−10 are ascribed to the νCC and νC−N stretching vibrations of the NDS2− anions and aromatic diamines. The IR spectra of the 10 crystals show that the characteristic vibrations of νas(SO3−) in crystals 1−10 are in the range of 1251−1149 cm−1, whereas the νs(SO3−) absorptions are in the range of 1049−1029 cm−1.10b,c Moreover, the separated sharp and strong bands of 3378 cm−1 in crystal 6 and 3344 cm−1 in crystal 10 are attributed to the νN−H stretching vibrations, because the diamines in the two crystal are only monoprotonated. Thermogravimetric Analysis. To examine the thermal stability of the 10 crystals, powder X-ray diffraction (PXRD) patterns for solid samples of crystals 1−10 are first measured at room temperature as illustrated in Figure S6, Supporting Information. The patterns are highly similar to their simulated ones (based on the single-crystal X-ray diffraction data), indicating that the single-crystal structures are really representative of the bulk of the corresponding samples. Their stabilities were analyzed on crystalline samples by thermogravimetric analyses (TGA) from room temperature to 500 °C at a rate of 10 °C min−1, under N2 atmosphere. As shown in Figure S7, Supporting Information, the sharp weight losses of crystals 1−4 occurred in the range of 310−350, 312−420, 315−380, and 360−430 °C, respectively. Crystal 5 lost the water molecules in the range of 50−172 °C with the observed weight loss of 7.68% (calcd 7.83%), and then the following sharp weight loss occurred between 310 and 390 °C. Meanwhile, Figure S8, Supporting Information shows the TG curves of crystals 6−10, in which crystals 6 and 7 exhibit a sharp weight loss in the range 3353



Article

of 256−320 and 300−360 °C, respectively. For the three hydrate crystals 8−10, gradually weight losses of water molecules were observed. The loss of water molecules in crystals 8−10 began at 65, 54, and 48 °C and finished at 120, 160, and 180 °C, respectively. The observed weight loss of 11.75% in 8, 3.51% in 9, and 2.39% in 10 is reasonably close to the calculated value (11.64% in 8, 3.25% in 9, and 2.24% in 10). Then, the sharp weight losses occurred in the range of 270−320, 300−325 and 280−330 °C for crystals 8−10. Luminescent Property. The luminescent properties of crystals 1−10 and the reactants at room temperature were investigated. The HA, EDA, PDA, BTDA, and BDMA molecules cannot exhibit obvious emission under UV irradiation, while the o-BDA, m-BDA, MBDA, and SDA molecules exhibit strong emissions at 354 (λex = 285 nm), 342 (λex = 313 nm), 341 (λex = 279 nm), and 377 nm (λex = 248 nm), respectively. For clarity, the 10 salts are divided into series I (crystals 1−5), II (crystals 6−8), and III (crystals 9, 10) to be discussed. For series I, as shown in Figure S9, Supporting Information, upon the different excitations, the emission spectra of crystals 1−5 exhibit a similar shape and maximum at 376 (λex = 345 nm), 388 (λex = 250 nm), 397 (λex = 340 nm), 359 (λex = 243 nm), and 348 nm (λex = 243 nm), respectively. The emission bands of these crystals are probably assigned to the intraligand (IL) π−π* transitions of H2NDS because the resemblance of the emission spectra in comparison with free H2NDS molecules (λex = 353 nm, λem = 407 nm). Meanwhile, the emission intensities of the five crystals are significantly larger than that of H2NDS molecules, especially for crystals 1, 4, and 5 (Figure 10). The increasing emission intensity of crystals is

transfer and the quantum efficiency, thus affording the strong emission intensity of the final crystal. On the other hand, for crystal 5, the π···π interactions among the naphthyl and phenyl rings increase the mobility of the electrons, thus enhancing the chance of intraligand charging transfer and the quantum efficiency. Therefore, crystal 5 exhibits the strongest emission intensity among the five crystals constructed from aliphatic diamines. For series II, as shown in Figure S10, Supporting Information, upon the different excitations, the emission spectra of crystals 6−8 exhibit a maximum at 345 (λex = 241 nm), 337 (λex = 241 nm), and 340 (λex = 287 nm), respectively. In contrast to the reactants, the emission bands of crystals 6−8 are probably assigned to the intraligand (IL) π−π* transitions of their corresponding aromatic diamine molecules. Different from series I, the emission intensities of the three crystals in series II are all obviously decreased in comparison with the corresponding aromatic diamine molecules, which could be explained as follows. For crystals 7 and 8, partial excited electrons of m-H2BDA2+ and H2MBDA2+ transfer to the excited state of NDS2− through the π···π interactions, which are then quenched through the nonradioactive transition. The quantum efficiency is subsequently reduced, thus resulting in the decrease of the emission intensity. The nearly quenching luminescent emission of the monoprotonated crystal 6 could be ascribed to the formation of the strong N−H···π interactions and the asymmetric amine group and ammonium cation attached to the phenyl ring, which result in the asymmetric charge distribution in the phenyl ring of the o-HBDA+, and subsequently effectively limit the charge transfer and decrease the quantum efficiency. For series III, as shown in Figure S10, Supporting Information, upon the different excitations, the emission spectra of crystals 9 and 10 exhibit maximum at 344 (λex = 288 nm) and 407 nm (λex = 330 nm). Although the mechanism for the emission is not clear at this moment, the adscription of the emission can be achieved according to those of series I and II. In contrast to the emission spectrum of SDA, the emission band of crystal 9 is probably assigned to the intraligand (IL) π−π* transitions of SDA molecule because the resemblance of their emission spectra. The decreasing of the emission intensity of this crystal is similar as the case in series II. By contrast, the emission band of crystal 10 is probably be assigned to the intraligand (IL) π−π* transitions of H2NDS because of the resemblance of the emission spectra in comparison with free H2NDS molecules. The increase of the emission intensity of this crystal is similar as the case in series I and can be probably attributed to the formation of the continuous C−H···π interactions among adjacent NDS2− and HSDA+, which effectively restrict the flexibility and increase the rigidity of the NDS2− anions, thus reducing the loss of energy.22 Owing to the visibly emission differences between the aliphatic diamines containing series and rigid aromatic diamines containing series, H2NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the luminescent signal.

Figure 10. Comparison of the emission intensities among the reactants and crystals 1−10.

probably attributed to the formation of extensive hydrogen bonds, which effectively restrict the flexibility and increase the rigidity of the NDS2− anions, such as the parallel naphthyl rings in crystal 4, thus reducing the loss of energy.22 Moreover, it is interesting to note that the emission intensities and the blue shift values of crystals 1−3 exhibit a regular decreasing with the sequence of 1−3. This change may be mainly ascribed to the diverse structures of the three crystals. As depicted above, all the three crystals exhibit a similar 3-D pillared layered supramolecular network extended by the hydrogen bonding interactions and the C−H···π interactions. However, the C···π distances in the three crystals are increased from 3.488(2) (in 1), to 3.642(2) (in 2), and 3.806(4) Å (in 3). The short C···π distance increases the chance of intraligand charging

■

CONCLUSIONS In summary, 10 well-designed supramolecular patterns of salts assembled by 1,5-naphthalenedisulfonic acid with hydrazine, four flexible aliphatic diamines, three rigid and one semirigid aromatic diamines have been synthesized and characterized. The nature of the diamines can effectively influence the final architectures of the salts through different hydrogen bonding 3354



Article

(8) (a) Ma, J. C.; Dougherty, D. A. Chem. Rev. 1997, 97, 1303. (b) Schneider, H. J. Angew. Chem., Int. Ed. 2009, 48, 3924. (9) (a) Egli, M.; Sarkhel, S. Acc. Chem. Res. 2007, 40, 197. (b) Schottel, B. L.; Chifotides, H. T.; Dunbar, K. R. Chem. Soc. Rev. 2008, 37, 68. (10) (a) Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem. Soc. Rev. 2009, 38, 1430. (b) Deng, Z.-P.; Huo, L.-H.; Li, M.-S.; Zhang, L.-W.; Zhu, Z.-B.; Zhao, H.; Gao, S. Cryst. Growth Des. 2011, 11, 3090. (c) Fang, X.-Q.; Deng, Z.-P.; Huo, L.-H.; Wan, W.; Zhu, Z.-B.; Zhao, H.; Gao, S. Inorg. Chem. 2011, 50, 12562. (11) (a) Reddy, D. S.; Duncan, S.; Shimizu, G. K. H. Angew. Chem., Int. Ed. 2003, 42, 1360. (b) Videnova-Adrabinska, V. Coord. Chem. Rev. 2007, 251, 1987. (c) Chandrasekhar, V.; Singh, P. Cryst. Growth Des. 2010, 10, 3077. (12) Cambridge Structure Database search, CSD Version 5.27 (November 2005) with 19 updates (January 2006-Nov 2011). (13) (a) Mizobe, Y.; Ito, H.; Hisaki, I.; Miyata, M.; Hasegawa, Y.; Tohnai, N. Chem. Commun. 2006, 2126. (b) Mizobe, Y.; Hinoue, T.; Yamamoto, A.; Hisaki, I.; Miyata, M.; Hasegawa, Y.; Tohnai, N. Chem.Eur. J. 2009, 15, 8175. (14) Tohnai, N.; Mizobe, Y.; Doi, M.; Sukata, S.; Hinoue, T.; Yuge, T.; Hisaki, I.; Matsukawa, Y.; Miyata, M. Angew. Chem., Int. Ed. 2007, 46, 2220. (15) Hinoue, T.; Miyata, M.; Hisaki, I.; Tohnai, N. Angew. Chem., Int. Ed. 2012, 51, 155. (16) (a) Russell, V. A.; Evans, C. C.; Li, W. J.; Ward, M. D. Science 1997, 276, 575. (b) Pivovar, A. M.; Holman, K. T.; Ward, M. D. Chem. Mater. 2001, 13, 3018. (c) Holman, K. T.; Pivovar, A. M.; M. Ward, D. Science 2001, 294, 1907. (d) Holman, K. T.; Pivovar, A. M.; Swift, J. A.; Ward, M. D. Acc. Chem. Res. 2001, 34, 107. (e) Custelcean, R.; Ward, M. D. Angew. Chem., Int. Ed. 2002, 41, 1724. (f) Burke, N. J.; Burrows, A. D.; Mahon, M. F.; Warren, J. E. CrystEngComm 2006, 8, 931. (17) (a) Leverd, P. C.; Berthault, P.; Lance, M.; Nierlich, M. Eur. J. Inorg. Chem. 2000, 133. (b) Perret, F.; Bonnard, V.; Danylyuk, O.; Suwinska, K.; Coleman, A. W. New J. Chem. 2006, 30, 987. (c) Su, X.; Guo, D.-S.; Liu, Y. CrystEngComm 2010, 12, 947. (d) Yin, W.-X.; Huang, X.-Y.; Xu, X.-M.; Meng, X.-G. Acta Crystallogr. 2010, C66, o508. (18) Sheldrick, G. M. SHELXTL-97, Program for Crystal Structure Solution and Refinement; University of Gottingen: Göttingen, Germany, 1997. (19) Zhu, Z.-B.; Gao, S.; Ng, S. W. Acta Crystallogr. 2009, E65, o2658. (20) (a) Shi, Y.-Y.; Sun, J.; Huang, Z.-T.; Zheng, Q.-Y. Cryst. Growth Des. 2010, 10, 314. (b) Hazra, S.; Sarkar, B.; Naiya, S.; Drew, M. G. B.; Frontera, A.; Escudero, D.; Ghosh, A. Cryst. Growth Des. 2010, 10, 1677. (21) Mooibroek, T. J.; Black, C. A.; Gamez, P.; Reedijk, J. Cryst. Growth Des. 2008, 8, 1082. (22) Rendell, D. Fluorescence and Phosphorescence; Wiley: New York, 1987.

interactions and other noncovalent bonding interactions, such as π···π stacking, N−H···π, C−H···π, as well as the lone pair···π interactions. Different hydrogen bonding modes formed by −SO3 and −NH3 groups result in diverse [1 + 1], [2 + 2], [2 + 4], [3 + 3], [4 + 4], and [5 + 5] hydrogen bonding rings, which then generate six types of architectures with the assistance of the above noncovalent bonding interactions. Luminescent investigations demonstrate that the salts containing aliphatic diamines exhibit stronger emission intensity than those containing aromatic diamines. This result indicates that the H2NDS might be used to distinguish the aliphatic diamine from aromatic diamine qualitatively through the luminescent signal. The present study provides a strategy to tune the supramolecular patterns and modify the luminescent properties of salts assembled by arenesulfonic acids and diamines. Further investigation on syntheses, structures, and properties of salts constructed from other arenesulfonic acids and amines are also underway in our laboratory.

■

ASSOCIATED CONTENT

S Supporting Information *

Additional figures, PXRD patterns, TG curves, UV spectra, emission spectra for all crystals, as well as the X-ray crystallographic files in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (S. G.); E-mail: lhhuo68@ yahoo.com (L-H. H.). Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work is financial supported by the Key Project of Natural Science Foundation of Heilongjiang Province (No. ZD200903), Key Project of Education Bureau of Heilongjiang Province (No. 12511z023, No. 2011CJHB006), the Innovation team of Education Bureau of Heilongjiang Province (No. 2010td03) and Program for New Century Excellent Talents in University (NCET-06-0349). We thank the University of Heilongjiang (Hdtd2010-04) for supporting this study.

■

REFERENCES

(1) (a) Yan, D.; Delori, A.; Lloyd, G. O.; Frišcǐ ć, T.; Day, G. M.; Jones, W.; Lu, J.; Wei, M.; Evans, D. G.; Duan, X. Angew. Chem., Int. Ed. 2011, 50, 12483. (b) Frišcǐ ć, T. Chem. Soc. Rev. 2012, 41, 3493. (2) (a) Schultheiss, N.; Newman, A. Cryst. Growth Des. 2009, 9, 2950. (b) Fábían, L.; Hamill, N.; Eccles, Moynihan, K. S. H. A.; Maguire, A. R.; McCausland, L.; Lawrence, S. E. Cryst. Growth Des. 2011, 11, 3522. (c) Arenas-García, J. I.; Herrera-Ruiz, D.; Mondragón-Vásquez, K.; Morales-Rojas, H.; Höpfl, H. Cryst. Growth Des. 2012, 12, 811. (3) Almarsson, Ö .; Zaworotko, M. Chem. Commun. 2004, 1889. (4) Desiraju, G. Angew. Chem., Int. Ed. 2003, 34, 2311. (5) (a) Parthasarathi, R.; Subramanian, V.; Sathyamurthy, N. J. Phys. Chem. A 2006, 110, 3349. (b) Jeffrey, G. A. An Introduction to Hydrogen Bonding; Oxford University Press: Oxford, 1997. (6) (a) Janiak, C. J. Chem. Soc., Dalton Trans. 2000, 3885. (b) Grimme, S.; Antony, J.; Schwabe, T.; Muck-Lichtenfeld, C. Org. Biomol. Chem. 2007, 5, 741. (7) (a) Takahashi, H.; Tsuboyama, S.; Umezawa, Y.; Honda, K.; Nishio, M. Tetrahedron 2000, 56, 6185. (b) Nishio, M. CrystEngComm 2004, 6, 130. 3355


A Co-Crystal Strategy to Tune the Supramolecular Patterns and

Recommend Documents