Coordination Compounds with Benzoguanamine Ligand - American

ARTICLE pubs.acs.org/crystal

Effect of Different Carboxylates on a Series of Ag(I) Coordination Compounds with Benzoguanamine Ligand Hong-Jun Hao,† Di Sun,† Yun-Hua Li, Fu-Jing Liu, Rong-Bin Huang,* and Lan-Sun Zheng State Key Laboratory of Physical Chemistry of Solid Surface, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

bS Supporting Information ABSTRACT: The ultrasonic reactions of Ag 2 O with benzoguanamine and ancillary carboxylate ligands under the ammoniacal condition gave eight new coordination compounds (CCs), namely, [Ag 4 (bga)6 (mal)2 ] (1), [Ag4(bga)6(mlc)2] (2), [Ag(bga)2(tpa)0.5]n (3), {[Ag(bga)(suc)0.5] 3 C2H5OH}n (4), {[Ag(bga)(pta)0.5] 3 CH3OH}n (5), {[Ag(bga)(ox)0.5] 3 C2H5OH 3 H2O}n (6), {[Ag2(bga)2(dnb)2] 3 DMF}n (7), and [Ag2(bga)2(pma)0.5(H2O)]n (8) (bga = benzoguanamine, H2mal = malonic acid, H2mlc = maleic acid, H2tpa = terephthalic acid, H2suc = succinic acid, H2pta = phthalic acid, H2ox = oxalic acid, Hdnb = 3,5dinitrobenzoic acid, H4pma = pyromellitic acid, and DMF = N,N0 -dimethylformamide). All CCs have been characterized by elemental analyses, IR spectra, and single-crystal X-ray diffraction. Compounds 1 and 2 are 0D discrete molecules and contain centrosymmetric [Ag2(mal)]2 and [Ag2(mlc)]2 units, respectively, which are extended to 1D supramolecular chains through intermolecule N
H 3 3 3 N complementary hydrogen bonds. Compounds 3 and 4 contain similar 1D [Ag2(tpa)]n and [Ag2(suc)]n infinite chains incorporating monodentate bga ligand as an ornament. It is noteworthy that the Ag 3 3 3 Ag interaction was exclusively observed in the 1D chain of compound 4, which may be caused by different coordination environments of the Ag(I) center between 3 and 4. The Ag 3 3 3 π interactions further extend the 1D chains into 2D sheet in 4. In 5 and 6, the μ2-bga ligands link Ag(I) ions to form 1D helical chains, which are further extended by μ2-dicarboxylate to 2D 63-hcb net incorporating different dimensions of hexagonal grids. Compound 7 is a 1D chain containing [Ag2(dnb)2] subunits, to which the monodentate and bidentate bga ligands as well as DMF coordinate. Compound 8 is a 2D sheet structure incorporating μ6-η1:η1:η1:η1:η1:η0:η1:η0 pma, monodentate and bidentate bga ligands. The results show that the structural diversity (0D
2D) of the CCs is mainly attributed to the usage of diverse ancillary carboxylate ligands as well as diverse coordination modes of bga ligand. Moreover, the photoluminescence properties of the CCs 1
6 were also investigated in the solid state at room temperature.

’ INTRODUCTION Research into coordination compounds (CCs) has been extensively pursued due to not only their structural novelty but also promising applications in the fields of catalysis, storage, luminescence, conductivity, nonlinear optics (NLO), ferroelectricity, and magnetism.1 The CCs formed by Ag(I) and multitopic N-donor ligands have attracted interest for a number of reasons. The Ag(I) center has a close-shell electronic configuration and can adopt diverse coordination numbers from 2 to 8, with no strong energetic preference for any particular geometry.2 Because the formation of the CCs is very sensitive to various factors such as solvent system,3 counteranion,4 pH value of the solution,5 reaction temperature, ratio of ligand to metal ion, and coordination geometry of central metals and organic ligands,6 prediction and control of the supramolecular assembly remain huge challenges, and much more elaborate and systematic work is required in the crystal engineering field. The bga is a versatile amino-containing N-heterocyclic ligand, which can coordinate up to five metal centers and may exhibit diverse metal binding patterns such as the endocyclic nitrogen r 2011 American Chemical Society

atom7 or the exocyclic nitrogen atom of amino group,8 occasionally in equilibrium,9 and simultaneously both positions, either in a chelating or in a bridging fashion,10 inferring from our and other group's work. Moreover, the presence of the amino groups of bga could form hydrogen bonds with either endocyclic nitrogen atom or solvent molecules as well as anions. Additionally, the bga ligand has a rigid aromatic phenyl ring, which also has a potential contribution to generate π 3 3 3 π stacking, C
H 3 3 3 π, and Ag 3 3 3 π interactions. It is also noteworthy that the triazine is a good candidate of the π-acidic system to form an anion 3 3 3 π interaction based on some experimental and extensive theoretical studies, when endocyclic nitrogen atoms coordinate with metal centers.11 On the other hand, the multidentate carboxylates are important auxiliary organic ligands and have been widely used as good candidates for building CCs because of their diverse coordination modes and orientations.12 Although Received: April 27, 2011 Revised: June 7, 2011 Published: June 09, 2011 3564

dx.doi.org/10.1021/cg200534x | Cryst. Growth Des. 2011, 11, 3564–3578

Crystal Growth & Design fascinating structures and properties of silver(I) CCs have been widely investigated, only a few silver(I)
bga CCs have been studied,13 and the silver(I)
bga with an auxiliary ligand system has not been reported by now. On the basis of our previous studies,14 herein, we focus on the self-assembly of silver(I) and bga incorporating carboxylate as an auxiliary ligand and obtained eight new CCs, namely, [Ag4(bga)6(mal)2] (1), [Ag4(bga)6(mlc)2 ] (2), [Ag(bga)2 (tpa)0.5 ]n (3), {[Ag(bga)(suc)0 .5 ] 3 C2H5OH}n (4), {[Ag(bga)(pta)0.5] 3 CH3OH}n (5), {[Ag(bga)(ox)0.5] 3 C2H5OH 3 H2O}n (6), {[Ag2(bga)2(dnb)2] 3 DMF}n (7), and {[Ag2(bga)2(pma)0.5] 3 H2O}n (8) (bga = benzoguanamine, H2mal = malonic acid, H2mlc = maleic acid, H2tpa = terephthalic acid, H2suc = succinic acid, H2pta = phthalic acid, H2ox = oxalic acid, Hdnb = 3,5-dinitrobenzoic acid, H4pma = pyromellitic acid, and DMF = N,N0 -dimethylformamide), ranging from 0D to 2D structures.

’ EXPERIMENTAL SECTION Materials and General Methods. All chemicals and solvents used in the syntheses were of analytical grade and used without further purification. IR spectra were measured on a Nicolet 740 FTIR Spectrometer at the range of 4000
400 cm
1. Elemental analyses were carried out on a CE instruments EA 1110 elemental analyzer. Photoluminescence spectra were measured on a Hitachi F-4500 Fluorescence Spectrophotometer (slit width, 5 nm; sensitivity, high). TG curves were measured from 25 to 800 °C on a SDT Q600 instrument at a heating rate 5 °C/min under the N2 atmosphere (100 mL/min). X-ray powder diffractions were measured on a Panalytical X-Pert pro diffractometer with Cu KR radiation. Preparation of Compounds 1
8. [Ag4(bga)6(mal)2] (1). Ag2O (23.1 mg, 0.1 mmol), H2mal (20.8 mg, 0.2 mmol), and bga (37.4 mg, 0.2 mmol) were dissolved in water
ethanol
methanol
DMF mixed solvent (10 mL, v/v/v/v: 2/4/3/1) under stirring. Then, aqueous NH3 solution (25%, 8 drops) was dropped into the mixture to give a clear solution under ultrasonic treatment (160 W, 40 kHz, 50 °C). The resultant solution was allowed to evaporate slowly in darkness at room temperature for several days to afford the product as needlelike colorless crystals of 1 (yield, 35%, based on silver). Anal. calcd (found) for Ag4C60H58N30O8: C, 40.97 (40.95); H, 3.32 (3.62); N, 23.89 (24.52) %. IR (KBr): ν (cm
1) = 3310 (m), 3190 (s), 1622 (m), 1590 (m), 1541 (s), 1492 (m), 1452 (m), 1428 (w), 1398 (m), 1256 (w), 824 (w), 780 (w), 698 (w), 621 (w). [Ag4(bga)6(mlc)2] (2). The synthesis of 2 was similar to that of 1 but with H2mlc (23.2 mg, 0.2 mmol) in place of H2mal. The resultant solution was allowed to evaporate slowly in darkness at room temperature for several days to afford the product as lamellar colorless crystals of 2 (yield, 14%, based on silver). Anal. calcd (found) for Ag4C62H58N30O8: C, 41.77 (42.01); H, 3.28 (3.16); N, 23.57 (24.11) %. IR (KBr): ν (cm
1) = 3310 (m), 3190 (m), 1622 (m), 1590 (m), 1541 (s), 1492 (m), 1542 (m), 1452 (m), 1428 (m), 1398 (m), 1256 (w), 824 (w), 780 (w), 698 (w). [Ag(bga)2(tpa)0.5]n (3). The synthesis of 3 was similar to that of 1 but with H2tpa (33.2 mg, 0.2 mmol) in place of H2mal. The resultant solution was allowed to evaporate slowly in darkness at room temperature for several days to afford the product as block-shaped colorless crystals of 3 (yield, 24%, based on silver). Anal. calcd (found) for AgC22H20N10O2: C, 46.82 (46.74); H, 3.57 (3.63); N, 24.82 (24.59) %. IR (KBr): ν (cm
1) = 3309 (s), 3183 (s), 1625 (s), 1590 (m), 1542 (s), 1452 (m), 1400(s), 1357 (m), 1071 (w), 1004 (w), 993 (w), 823 (m), 779 (w), 745 (m), 696 (w), 614 (w), 580(w). {[Ag(bga)(suc)0.5] 3 C2H5OH}n (4). The synthesis of 4 was similar to that of 1 but with H2suc (23.6 mg, 0.2 mmol) in place of H2mal. The

ARTICLE

resultant solution was allowed to evaporate slowly in darkness at room temperature for several days to afford the product as block-shaped colorless crystals of 4 (yield, 68.9%, based on silver). Anal. calcd (found) for AgC13H17N5O3: C, 39.12 (38.80); H, 4.29 (4.31); N, 17.54 (18.09) %. IR (KBr): ν (cm
1) = 3310 (m), 3190 (m), 1622 (m), 1590 (m), 1541 (s), 1452 (m), 1428(m), 1398 (m), 1257 (w), 825 (w), 780 (w), 698 (w). {[Ag(bga)(pta)0.5] 3 CH3OH}n (5). The synthesis of 5 was similar to that of 1 but with H2pta (33.2 mg, 0.2 mmol) in place of H2mal. Blockshaped colorless crystals of 5 were obtained (yield, 56%, based on silver). Anal. calcd (found) for AgC14H15N5O3: C, 41.10 (40.86); H, 3.70 (3.44); N, 17.12 (17.17)%. IR (KBr): ν (cm
1) = 3309 (s), 3183 (s), 1625 (m), 1590 (s), 1542 (m), 1452 (m), 1400 (s), 1357 (m), 1071 (w), 993 (w), 823 (m), 779 (w), 745 (m), 696 (w), 614 (w), 580 (w). {[Ag(bga)(ox)0.5] 3 C2H5OH 3 H2O}n (6). The synthesis of 6 was similar to that of 1 but with H2ox (25.2 mg, 0.2 mmol) in place of H2mal. Block-shaped colorless crystals of 6 were obtained (yield, 50%, based on silver). Anal. calcd (found) for AgC12H11N5O4: C, 36.29 (36.51); H, 2.79 (2.34); N, 17.64 (18.02)%. IR (KBr): ν (cm
1) = 3310 (m), 3190 (m), 1623 (m), 1590 (m), 1541 (s), 1493 (m), 1453 (m), 1428 (m), 1398 (m), 1256 (w), 1173 (w), 825 (w), 780 (w), 698 (w), 621 (w). {[Ag2(bga)2(dnb)2] 3 DMF}n (7). The synthesis of 7 was similar to that of 1 but with Hdnb (42.4 mg, 0.2 mmol) in place of H2mal. Blockshaped colorless crystals of 7 were obtained (yield, 35%, based on silver). Anal. calcd (found) for Ag2C35H31N15O13: C, 38.73 (38.51); H, 2.88 (3.01); N, 19.36 (19.56)%. IR (KBr): ν (cm
1) = 3410 (m), 3190 (m), 3107 (m), 1508 (w), 1492 (w), 1452 (w), 1398 (m), 1345 (m), 1259 (w), 1084 (w), 899 (w), 824 (w), 799 (w), 732 (w), 719 (w), 624 (s), 544 (s). [Ag2(bga)2(pma)0.5(H2O)]n (8). The synthesis of 8 was similar to that of 1 but with H4pma (50.8 mg, 0.2 mmol) in place of H2mal. Colorless lamellar crystals of 8 were obtained (yield, 60%, based on silver). Anal. calcd (found) for Ag2C23H21N10O5: C, 37.68 (37.22); H, 2.89 (3.12); N, 19.10 (19.55)%. IR (KBr): ν (cm
1) = 3391 (m), 3311 (m), 3137 (m), 1618 (m), 1589 (m), 1453 (m), 1389 (m), 1321 (w), 1264 (w), 1137 (w), 1075 (w), 823 (w), 778 (w), 707 (w), 617 (w), 589 (m), 582 (w), 551 (s). X-ray Crystallography. Single crystals of the compound 1
8 with appropriate dimensions were chosen under an optical microscope and quickly coated with high vacuum grease (Dow Corning Corporation) before being mounted on a glass fiber for data collection. Data for 1
6 and 8 were collected on a Rigaku R-AXIS RAPID Image Plate singlecrystal diffractometer with graphite-monochromated Mo KR radiation source (λ = 0.71073 Å) operating at 50 kV and 90 mA in ω scan mode. A total of 44  5.00° oscillation images were collected, each being exposed for 100 s. The cell refinement and data reduction for 1
6 and 8 were accomplished with the PROCESS-AUTO processing program.15 Absorption correction was applied by correction of symmetry-equivalent reflections using the ABSCOR program.16 Data for 7 were collected on a Bruker-AXS CCD single-crystal diffractometer with graphite-monochromated Mo KR radiation source (λ = 0.71073 Å). A preliminary orientation matrix and unit cell parameters were determined from 3 runs of 20 frames each, and each frame corresponds to a 0.3° scan in 5 s, followed by spot integration and least-squares refinement. For 7, data were measured using ω scans of 0.3° per frame for 10 s until a complete hemisphere had been collected. Cell parameters were retrieved using SMART software and refined with SAINT on all observed reflections.17 Data reduction was performed with the SAINT software and corrected for Lorentz and polarization effects. Absorption corrections were applied with the program SADABS.17 In all cases, the highest possible space group was chosen. All structures were solved by direct methods using SHELXS-9718 and refined on F2 by full-matrix least-squares procedures with SHELXL-97.19 Atoms were located from iterative examination of difference F maps following least-squares refinements 3565

dx.doi.org/10.1021/cg200534x |Cryst. Growth Des. 2011, 11, 3564–3578

3566

a

0.0305

460

R1 = 0.0288,

Rint

parameters

final R indices

wR2 = 0.2595 1.274 and
1.798

wR2= 0.0918 0.867 and
0.750

wR2 = 0.0982 0.905 and
0.841

max/ min, ΔF (e Å
3)

R1 = Σ||Fo|
|Fc||/Σ|Fo|, wR2 = [Σw(Fo2
Fc2)2]/Σw(Fo2)2]1/2.

R1 = 0.1057,

R1 =, 0.0403,

wR2 = 0.2323

R1 = 0.0841,

174

0.0765

1648

0.961 2255

1140

4, 1.704

173

2200.4(8)

90.00

90.00

11.752(2) 90.00

14.555(3)

12.864(3)

R1 = 0.0329,

wR2= 0.0680

R1 = 0.0288,

469

0.0328

5350

1.255 6429

892

1, 1.801

173

1643.9(6)

110.89(3)

104.36(3)

14.104(3) 107.60(3)

13.529(3)

10.553(2)

R indices (all data)

wR2 = 0.0834

5738

obsd reflns [I > 2σ(I)]

[I > 2σ(I)]

1.263 6350

μ (mm
1) unique reflns

1, 1.790

Z, Dcalcd (Mg/m3)

880

173

T (K)

F(000)

1631.8(5)

V (Å3)

13.693(4) 65.698(18)

c (Å) R (°)

78.834(18)

13.3282(19)

b (Å)

71.073(13)

10.3963(16)

a (Å)

β (°)

Pnnm

P1

P1

space group

γ (°)

orthorhombic

triclinic

triclinic

564.35

AgC22H20N10O2

crystal system

Ag4C62H58N30O8 1782.86

Ag4C60H58N30O8

3

1758.84

2

formula weight

1

empirical formula

compound

Table 1. Crystal Data for 1
8a

wR2 = 0.1091 0.751 and
0.757

R1 = 0.0399,

wR2 = 0.0771

R1 = 0.0299,

199

0.0386

2414

1.392 2866

402

2, 1.803

173

735.2(3)

74.74(3)

68.88(3)

10.029(2) 71.54(3)

9.3917(19)

8.9500(18)

P1

triclinic

399.19

AgC13H17N5O3

4

wR2 = 0.0820 0.792 and
0.730

R1 = 0.0337,

wR2 = 0.0782

R1 = 0.0293,

209

0.0354

2672

1.334 3006

1640

8, 1.768

173

1610.9(6)

90.00

96.5610(10)

19.6558(7) 90.00

7.5329(3)

20.9002(9)

C2/c

monoclinic

409.18

AgC14H15N5O3

5

wR2 = 0.1415 1.439 and
0.907

R1 = 0.0411,

wR2 = 0.1203

R1 = 0.0378,

196

0.0258

2478

1.339 2612

1576

8, 1.721

173

3066.2(11)

90.00

101.59(3)

19.443(4) 90.00

7.4193(15)

21.698(4)

C2/c

monoclinic

397.13

AgC12H11N5O4

6

wR2 = 0.0703 0.703 and
0.427

R1 = 0.0277,

wR2 = 0.0701

R1 = 0.0275,

588

0.0217

6868

1.080 6929

2176

4, 1.826

173

3948.0(10)

90.00

118.940(2)

10.381(2) 90.00

32.4616(16)

13.3870(14)

Cc

monoclinic

1085.49

Ag2C35H31N15O13

7

wR2 = 0.1736 1.443 and
1.692

R1 = 0.0789,

wR2 = 0.1295

R1 = 0.0502,

362

0.0507

3350

1.619 4910

726

2, 1.941

173

1254.58(17)

77.0190(19)

81.997(2)

12.0882(10) 81.934(2)

11.2106(9)

9.6559(7)

P1

triclinic

733.24

Ag2C23H21N10O5

8

Crystal Growth & Design ARTICLE

dx.doi.org/10.1021/cg200534x |Cryst. Growth Des. 2011, 11, 3564–3578

Crystal Growth & Design

ARTICLE

Table 2. Selected Bond Lengths (Å) and Angles (°) for 1
8 N3
Ag1 N10
Ag2

2.302(3)

O4
Ag2

2.151(3)

i

Ag1
O4

compound 1a 2.187(2) N11
Ag1

2.295(3)

Ag2
O4i

2.385(2)

2.457(2)

Ag2
O1i

O2
Ag1

N11
Ag1
N3

113.85(9)

N3
Ag1
O4i

127.53(8)

N3
Ag1
O2

N11
Ag1
O4i

109.05(8)

N11
Ag1
O2

121.66(8)

O4i
Ag1
O2

i

O4
Ag2
O4

79.46(8)

i

O4
Ag2
O1

88.76(7)

N10
Ag2
O1

compound 2

i

N10
Ag2
O4

162.97(9)

86.68(7)

N10
Ag2
O4i

110.93(8)

106.67(8)

O4i
Ag2
O1i

75.40(7)

b

2.333(3)

Ag1
O2

2.490(3)

Ag1
O4i

2.346(3)

Ag2
O1i

Ag1
N1

2.378(3)

Ag1
O1

2.664(3)

Ag2
N6

2.153(3)

Ag2
O1

120.25(11)

O4i
Ag1
O1

N21
Ag1
N1

108.99(10)

N1
Ag1
O1

O4
Ag1
O2

135.25(10)

O1
Ag2
O1

N21
Ag1
O1

118.44(9)

i

i

86.44(10) 124.13(9) 77.37(10)

2.695(2)

95.19(8)

Ag1
N21 N21
Ag1
O4i

2.624(2)

2.186(3) 2.544(3)

O4i
Ag1
N1

94.33(10)

O2
Ag1
O1

50.51(8)

N21
Ag1
O2

94.42(10)

N6
Ag2
O1i

165.17(10)

N1
Ag1
O2

100.36(10)

N6
Ag2
O1

111.05(10)

2.268(8) 100.14(12)

Ag1
O1i N3
Ag1
O1

2.537(5) 99.58(12)

2.274(3)

O1
Ag1
O2i

156.69(10)

2.343(2)

N2i
Ag1
O1

151.33(8)

2.320(4) 111.11(13)

Ag1
O2 O1i
Ag1
O2

compound 3c N3
Ag1 N3
Ag1
O1i N6
Ag1
N3

2.271(7) 99.58(12) 126.1(2)

O1
Ag1 O1i
Ag1
O1

2.537(5) 135.6(2)

N6
Ag1
O1

100.14(12)

N6
Ag1 N6
Ag1
O1i

compound 4d Ag1
O1

2.266(3)

O2i
Ag1
N3

100.75(11)

Ag1
N3 O1
Ag1
N3

2.386(3)

Ag1
O2i

101.64(11) compound 5e

i

Ag1
N2

2.304(2)

O1
Ag1
N1

89.22(8)

Ag1
N1 N2
Ag1
N1 i

2.397(2)

Ag1
O1

112.15(9) compound 6f

ii

Ag1
N3 N3
Ag1
O1i

2.262(4) 142.61(15)

Ag1
N1 N3
Ag1
O2

2.372(4) 105.51(12)

O1i
Ag1
N1ii

94.85(13)

N1ii
Ag1
O2

133.42(13)

Ag1
O1i N3
Ag1
N1ii

2.408(3) 70.77(12)

compound 7g Ag1
O10

2.251(3)

Ag2
O9

2.267(3)

Ag1
O11

2.323(3)

Ag2
O12

2.282(3)

Ag1
N5

2.408(3)

Ag2
N13i

2.453(3)

Ag1
N12

2.469(3)

Ag2
O13

2.496(3)

O10
Ag1
O11

140.61(11)

O9
Ag2
O12

160.56(12)

O10
Ag1
N5

95.64(10)

O9
Ag2
N13i

87.28(10)

O11
Ag1
N12

83.64(10)

O12
Ag2
O13

96.43(11)

N5
Ag1
N12

116.71(10)

N13i
Ag2
O13

133.82(11)

O11
Ag1
N5

98.16(9)

O12
Ag2
N13i

103.77(10)

O10
Ag1
N12

121.86(12)

O9
Ag2
O13

compound 8

86.78(12)

h

Ag1
O3

2.208(5)

Ag1
O4i

2.209(5)

Ag1
N2

2.411(5)

Ag2
O1W

Ag2
N6

2.324(6)

Ag2
N1

2.321(6)

Ag2
O2ii

2.527(5)

O3
Ag1
O4i

116.17(19)

O4i
Ag1
N2

105.36(18)

N1
Ag2
O1W

102.1(2)

N6
Ag2
O1W N6
Ag2
O2

ii

112.2(2) 99.1(2)

O3
Ag1
N2 N1
Ag2
N6

95.71(18) 134.0(2)

N1
Ag2
O2ii ii

O1W
Ag2
O2

81.14(18)

2.489(7) 158.54(18)

a Symmetry code: (i)
x + 2,
y + 2,
z + 1. b Symmetry code: (i)
x + 1,
y,
z + 1. c Symmetry code: (i) x, y,
z. d Symmetry code: (i)
x + 2,
y,
z + 1. e Symmetry code: (i)
x + 1/2, y
1/2,
z + 1/2. f Symmetry codes: (i)
x + 2, y,
z + 3/2; (ii)
x + 3/2, y + 1/2,
z + 3/2. g Symmetry code: (i) x,
y + 2, z + 1/2. h Symmetry codes: (i)
x + 1,
y + 2,
z; (ii)
x,
y + 1,
z.

of the earlier models. Hydrogen atoms were placed in calculated positions and included as riding atoms with isotropic displacement parameters 1.2
1.5 times Ueq of the attached C or N atoms. The hydrogen atoms attached to oxygen were refined with O
H = 0.85 Å, and Uiso(H) = 1.2Ueq(O). The hydrogen atoms of the free ethanol molecule in 6 could not be found because of disorder. All structures were examined using the Addsym subroutine of PLATON20 to ensure that no additional symmetry could be applied to the models. Pertinent crystallographic data collection and refinement parameters are collated in Table 1. Selected bond lengths and angles for 1
8 are collated in Table 2. The hydrogen bond geometries for 1
8 are shown in Table S1 (Supporting Information).

’ RESULT AND DISCUSSION Synthesis. The syntheses of compounds 1
8 were carried out in the darkness to avoid photodecomposition and summarized in Scheme 1. As is well-known, the reactions of Ag(I) with carboxylates in aqueous solution often result in the formation of insoluble silver salts, presumably due to the fast coordination of the carboxylates to Ag(I) ions to form polymers.21 Hence, properly lowering the reaction speed, such as using ammoniacal conditions or layer-separation diffusion method, may favor to the formation of crystalline products.22 The ultrasonic method has found an important niche in the preparation of inorganic 3567

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Scheme 1. Preparation Route of Ag(I) Mixed-Ligand CCs from the N-Donor and O-Donor Ligands

materials.23 The high local temperatures and pressures, combined with extraordinarily rapid cooling, provide a unique means for driving chemical reactions under extreme conditions. In this system, ultrasound technique also realizes the rapid (10 min) and efficient (max 30 different experiments in one batch) preparation of CCs.24 Structure Descriptions. [Ag4(bga)6(mal)2] (1). The X-ray crystal structure analysis shows that compound 1 crystallizes in the triclinic P1 space group. The asymmetric unit of 1 consists of two Ag(I) ions, three bga ligands, and one mal anion. As shown in Figure 1a, Ag1 is coordinated by two Ntriazine atoms (N3) from two different bga ligands and two O atoms from two mal anions, and Ag2 is coordinated by one Ntriazine atom (N3) and three O atoms from three carboxyl groups. Both Ag1 and Ag2 adopt distorted tetrahedral coordination geometries with the bond angles spanning from 86.68(7) to 127.53(8) and 75.40(7) to 162.97(9)°, respectively. The distortion of the tetrahedron can be indicated by the calculated value of the τ4 parameter introduced by Houser25 to describe the geometry of a four-coordinated metal system, which is 0.79 for Ag1 and 0.61 for Ag2, respectively (for perfect tetrahedral geometry, τ4 = 1). The mal anion acts as a bridging ligand with a mode of μ4-η0:η1:η1:η3 to complete the centrosymmetric molecule of 1. The Ag
N and Ag
O bond lengths fall in the range 2.151(3)
2.302(3) and 2.187(2)
2.695(2) Å, respectively, which are comparable to the

related CCs.26 It can be clearly seen that the phenyl and triazinyl rings of two bga ligands are not located in the same plane, and the corresponding interplanar angles are 13.5 and 32.9°, respectively. Differently, the remaining bga has a nearly coplanar configuration with a small interplanar angle of 2.5°. Notably, Ag1 is not in the same plane as both two triazinyl rings giving distances between these planes and Ag1 being 0.91 and 0.76 Å, respectively, while Ag2 is almost coplanar with the triazinyl ring and only deviates 0.11 Å from it. The large deviations of Ag1 may be caused by the steric hindrance effect of two bga ligands simultaneously coordinated to one Ag(I) center. After carefully checking this structure, we also found that the bond lengths of Ag1
N [2.302(3) and 2.295(3) Å] are longer than that of Ag2
N [2.151(3) Å], which indicates that the Ag(I) ions have adaptive coordination behaviors under different environments. Furthermore, the intramolecular N
H 3 3 3 O hydrogen bonds [N1 3 3 3 O2 = 3.008(4), N6 3 3 3 O2 = 3.066(4), N2 3 3 3 O3 = 3.003(4), and N14 3 3 3 O3 = 2.931(4) Å] partially attribute to the stability of this discrete molecule (Figure 1b). As shown in Figure 1c, the adjacent molecules of 1 are connected through complementary N
H 3 3 3 N hydrogen bonds [R22(8) motif]27 to form a 1D ribbon [N6
H6B 3 3 3 N5ii = 2.975 (4), N1
H1A 3 3 3 N9ii = 3.237 (4) Å]. On the other hand, the amino groups (donors) from one 1D chain interact with carboxyl groups (acceptors) of another neighboring 1D chain through 3568

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Figure 1. (a) Coordination environment of the Ag(I) ions and the linkage modes of ligands in 1 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The molecular structure of 1 incorporating intramolecular hydrogen bonds (cyan dashed lines). (c) The 1D chain structure incorporating intermolecular hydrogen bonds (cyan dashed lines) [symmetry code: (i)
x + 2,
y + 2,
z + 1].

N
H 3 3 3 O hydrogen bonds [R42(8) motif], which extend the 1D chain into 2D supramolecular sheet [N15
H15B 3 3 3 O1iv = 3.058(4), N15
H15C 3 3 3 O1 = 3.027(3) Å, Figure S1 in the Supporting Information]. Meanwhile, the interchain C
H 3 3 3 π interactions with the mean C 3 3 3 Cg distance of 3.610(4) Å including hydrogen bonding consolidate the resulting 2D supramolecular sheet (Table S2 and Figure S2 in the Supporting Information). The intersheet π 3 3 3 π stacking involving triazine 3 3 3 triazine and triazine 3 3 3 phenyl rings further extend the 2D sheet into 3D supramolecular framework [Cg2 3 3 3 Cg3 = 3.724(2), Cg3 3 3 3 Cg6vi = 3.748(3), Cg4 3 3 3 Cg7v = 3.859(2) Å; Cg2, Cg3, Cg4, Cg6, and Cg7 are centroids of rings N3/C1/ N5/C3/N4/C2, N8/C11/N10/C10/N9/C12, N11/C19/ N12/C20/N13/C2, C13
C18, and C22
C27, respectively, Figure S3 in the Supporting Information]. [Symmetry codes: (ii)
x + 2,
y + 3,
z + 1; (iv)
x + 3,
y + 2,
z + 1; (v) 3
x,
y + 2, 2
z; (vi)
x + 1, 3
y, 1
z.] [Ag4(bga)6(mlc)2] (2). The structure of compound 2 is similar to 1, which is also a 0D structure. An inversion center is located in the middle of parallelogram comprising of Ag2, Ag2i, O1, and O1i. So, in the asymmetric unit, there are two Ag(I) ions, three bga ligands, and one mlc anion. As shown in Figure 2a, Ag1 displays a square-pyramidal coordination geometry, completed by two Ntriazine (N3) atoms from two different bga ligands and three O atoms belonging to two mlc anions. Addison28 has defined a geometric parameter τ5 (τ5 = [(θ
j)/60], where θ and j are the angles between the donor atoms forming the basal plane in square-pyramidal geometry) to five-coordinate metal system as an index of the degree of distortion. The τ5 parameter for Ag1 is 0.19 (for ideal square-pyramidal geometry, τ5 = 0). The coordination environment of Ag2 can be described as a nearly

T-shaped geometry, which is constructed by one Ntriazine (N3) and two O atoms from two carboxyl groups with the largest angle of 165.17(10)°. The Ag
N and Ag
O bond distances are within the expected ranges, whereas the Ag2
O3 separation of 2.782 Å can be taken as a weak coordination interaction. The interplanar angles corresponding to triazinyl and phenyl rings of two different bga coordinating with Ag1 are 40.4 and 9.1°, respectively, and Ag1 is not coplanar with triazinyl ring. In contrast, Ag2, trazinyl and phenyl rings are in the same plane. This dissimilarity indicates that a crowded coordination environment makes a torsion angle between two rings of the same bga ligand. The mlc anion adopts a μ4-η0:η3:η1:η1 bridging mode to complete the molecule of 2. The molecules of compound 2 are extended to a 3D supramolecular framework by different types of hydrogen bonds. In detail, as shown in Figure 2c, complementary N
H 3 3 3 N hydrogen bonds [N10
H10B 3 3 3 N3iii = 3.089(4), N4
H4B 3 3 3 N22ii = 3.181(4) Å] extend the discrete molecules to 1D chain, and then, the N
H 3 3 3 O hydrogen bonds incorporating a R42(8) motif extend the 1D chain into 2D net, which is very analogous to 1. However, another kind of N
H 3 3 3 N hydrogen bond [N24
H24B 3 3 3 N2ii = 3.067(5) Å] finally extends the 2D sheet to 3D supramolecular framework where the π 3 3 3 π stacking between neighboring triazinyl and phenyl rings [Cg3 3 3 3 Cg4 = 3.599(2), Cg4 3 3 3 Cg7iv = 3.852(2), Cg5 3 3 3 Cg8v = 3.878(2) Å; Cg3, Cg4, Cg5, Cg7, and Cg8 are centroids of rings: N1/C8/ N2/C7/N3/N9, N6/C16/N7/C17/N8/C18, N21/C26/N22/ C25/N23/C27, C10
C15, and C19
C24 respectively, Figure S4 in the Supporting Information] was observed. The C
H 3 3 3 π interactions with the average C 3 3 3 Cg distance of 3.583(6) Å and π 3 3 3 π stacking contribute to the stability of the resultant 3D 3569

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Figure 2. (a) Coordination environment of the Ag(I) ions and the linkage modes of ligands in 2 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The molecule structure of 2 incorporating intramolecular hydrogen bonds (cyan dashed lines). (c) The 1D chain structure [symmetry code: (i)
x + 1,
y,
z + 1].

supramolecular framework (as shown in Figures S4 and S5 in the Supporting Information). [Symmetry codes: (i)
x + 1,
y,
z + 1; (ii)
x + 1,
y,
z; (iii)
x + 2,
y + 1,
z + 1; (iv) 1
x, 1
y, 1
z; (v) 2
x,
y,
z.] [Ag(bga)2(tpa)0.5]n (3). When H2mlc is replaced by H2tpa, we obtain a 1D coordination polymer, which crystallizes in the orthorhombic Pnnm space group. Each asymmetric unit is composed of half Ag(I) ion, one bga ligand, and a quarter of tpa anion. Analysis of the local symmetry of the metal atoms and ligands shows that all of them locate in the special positions. In detail, a C2 axis passes through the tpa anion along C13 and C14 atoms, and at the same time, a mirror along the ab plane bisects the tpa anion and two different bga ligands. The Ag(I) ions are also located on the mirror [site occupancy factor (SOF) = 1/2]. As shown in Figure 3a, the Ag(I) ion is coordinated by two Ntriazine (N3) atoms from two different bga ligands and two O atoms from two carboxyl groups to form a distorted tetrahedral coordination geometry (τ4 = 0.70) in which the largest bond angle and the longest bond length are 135.6(2)° and 2.537(5) Å, respectively. It is notable that compound 3 has a bimetallic subunit in which the tpa anion clamps a pair of Ag(I) ions with a syn
syn mode to give a [Ag2C2O4] planar eight-membered ring lying on an inversion center. The Ag 3 3 3 Ag distance is 4.131 Å, which is obviously longer than the twice the van der Waals radius of Ag(I) and indicates no obvious Ag 3 3 3 Ag interaction.29 On the other hand, as shown in Figure 3b, the binuclear Ag(I) units are linked by tpa anions with a symmetrical μ4-η1:η1:η1:η1 bridging mode to form 1D infinite chains. Meanwhile, two pairs

of bga ligands monodentately coordinated to Ag(I) ions in a direction symmetry for the eight-membered ring plane. The phenyl and triazinyl rings of two bga ligands are almost located in the same plane, and the corresponding interplanar angles are 6.5 and 8.1°, respectively. Both distances between Ag(I) and triazinyl rings of the two bga are 0.22 Å. From the above analysis, although two bga ligands simultaneously coordinated to one Ag(I) center like in 1, the 1D chain structure gives enough space for bga coordinating with Ag(I). There are aromatic π 3 3 3 π stacking [centroid 3 3 3 centroid distances: 3.757(6), 3.532(5), 3.531(5), and 3.848(5) Å] and C
H 3 3 3 π interaction [C5
H5C 3 3 3 Cg = 3.304(12) Å] between different chains. The average centroid 3 3 3 centroid distance and dihedral angle are 3.667(6) Å and 6.34°, respectively (Figures S6 and S7 in the Supporting Information). Because of the steric effect of substituent phenyl groups, bga is just a monodentate ligand and does not extend the 1D chain to a higher dimensionality. {[Ag(bga)(suc)0.5] 3 C2H5OH}n (4). When we introduced H2suc acid into the silver/bga system, we also obtained a 1D chain similar to compound 3 but crystallized in the triclinic P1 space group. One Ag(I) ion, a half of suc anion, one bga ligand, and one noncoordinated ethanol molecule constitute the asymmetric unit of 4. The suc locates on the crystallographic inversion center (midpoint of bond C11
C11iv). As shown in Figure 4a, the Ag(I) ion lies in a Y-shaped geometry completed by two O atoms from two distinct suc anions and one N atom (N3) from bga ligand. There is a dihedral angle of 6.9° between traizinyl and phenyl rings of bga. The bond angles and lengths around Ag(I) 3570

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Figure 3. (a) Coordination environment of the Ag(I) ion and the linkage modes of ligands in 3 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The 1D chain structure incorporating [Ag2C2O4] subunits [symmetry codes: (i) x, y,
z; (iv)
x,
y, z; (v)
x,
y, 1
z; and (vi) x, y, 1
z].

ion range from 100.75(11) to 156.69(10)° and 2.274(3) to 2.386(3) Å, respectively. Without consideration of Ag 3 3 3 Ag interaction, there also exist a [Ag2C2O4] subunit similar to that in compound 3 but with the Ag(I) ion in a different coordination geometry. As shown in Figure 4b, suc anion adopts a μ4-η1:η1:η1:η1 bridging mode to link Ag(I) ions to form a nearly planar 1D fishbonelike chain. The torsion angle formed by four successive carbon atoms on suc is 180 °C, indicating an anti
anti conformation of suc. As compared to compound 3, two symmetry-related Ag(I) ions are closely coupled via a Ag 3 3 3 Ag interaction, and the distance between them in 4 is 3.0183(9) Å, suggesting so-called argentophilic interaction,30 which may be caused by a steric hindrance effect originating from the different coordination modes of the Ag(I) ions in 3 and 4. Two kinds of N
H 3 3 3 O hydrogen bonds (N
H 3 3 3 Osuc and N
H 3 3 3 Oethanol) coexist within the 1D chain. The amino group and suc ligand are hydrogen bonded through intrachain hydrogen bonds [N4
H4B 3 3 3 O1 = 2.922(4) Å and N5
H5C 3 3 3 O2i = 2.928(4) Å] to form two R11(6) hydrogen bond motifs. The solvent ethanol molecule as a double hydrogen acceptor is anchored in the chain through another kind of hydrogen bond [N4
H4C 3 3 3 O3 = 2.881(4) and N5
H5B 3 3 3 O3ii = 2.967(4) Å] giving a R43(13) motif. The 1D chain structure was strengthened by these two kinds of N
H 3 3 3 O hydrogen bonds. Moreover, there is no obvious π 3 3 3 π stacking and C
H 3 3 3 π interactions in 4. After carefully analyzing the crystal packing of the molecules, we surprisingly found the existence of the closest contacts between Ag and phenyl ring of bga, which is associated with the C2 and C3 atoms. To the best of my knowledge, many Ag(I)
PAH (polycyclic aromatic hydrocarbon) compounds have been reported and show that arenes usually function as neutral π donors to exhibit the η2 coordination mode.31 In 4, the

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closest Ag 3 3 3 C contact between the neighboring 1D chain is 3.006(5) Å (Ag1 3 3 3 C3v), which falls in the normal ranges reported for the related compounds.32 Although the second closest Ag 3 3 3 C contact [Ag1 3 3 3 C2v = 3.144(4) Å] is slightly longer as compared to those found for Ag(I)
PAH compound, it is still below the sum of van der Waals radii of Ag(I) ion and carbon atom (3.42 Å).29a According to the previously documented Ag(I)
PAH compounds, Ag(I) has high affinity to ligate at the shortest carbon
carbon bond due to the high π-electron density,33 and this tendency is not maintained in 4 [C2
C3 = 1.389(6) Å, the fourth shortest C
C bond in bga], indicative of the not highest π-electron density accumulated on this bond. Herein, the Ag 3 3 3 C interaction sites are not necessarily the shortest C
C-bonded carbon atoms, which may be dominated by various factors, such as steric hindrance, the size and geometry of the aromatic, molecular packing energy, and other structural details. Although Ag 3 3 3 C interactions have been widely observed, such interactions involving bga ligand in the solid state have rarely been documented in the literature. These Ag 3 3 3 C interactions have been successfully used to bring 1D chains close to each other to create a 2D supramolecular sheet (Figure 4c), which is further consolidated by hydrogen bond formed between ethanol and suc ligand [O3
H3A 3 3 3 O1iii = 2.780(4) Å]. [Symmetry codes: (i)
x + 2,
y,
z + 1; (ii) x, y
1, z; (iii)
x + 1,
y + 1,
z + 1; (iv)
x,
y + 1, z; (v)
x + 1,
y, z.] {[Ag(bga)(pta)0.5] 3 CH3OH}n (5). When using aromatic H2pta as auxiliary ligand, a 2D sheet of 5 was obtained. The X-ray crystal structure analysis suggests that compound 5 crystallizes in the monoclinic C2/c space group. The C2 axis passes through the midpoints of bond C11
C11v and C13
C13v; therefore, the crystallographic asymmetric unit of 5 is comprised of two Ag(I) ions, one bga ligand, a half of pta anion, and one uncoordinated methanol molecule. As shown in Figure 5a, each central Ag(I) ion adopts a Y-shaped coordination geometry with two N atoms (N1 and N5) of bga ligands and one O atom of pta anion [Ag1
N2i = 2.304(2), Ag1
N1 = 2.397(2), and Ag1
O1 = 2.343(2) Å]. We can easily find that there is a large interplanar angle between triazinyl and phenyl rings with a value of 41.8°, and the Ag(I) is not in the same plane to triazinyl ring giving a distance between triazinyl planes and Ag(I) being 0.8 Å. The bga ligands act as bidentate N1,N5-donor to link Ag(I) ions to form a 1D helical chain along the b-axis. The helix possesses a helical pitch of 7.53 Å and is concentric with crystallographic C2 axis. As shown in Figure 5b, μ2-η0:η1:η1:η0 pta anions fabricated the 1D helical chains to form an infinite 2D network in which an alternate arrangement of left- and right-handed helices was observed. To better understand the structure of 5, the topological analysis is employed.34 We can consider the Ag(I) ions as 3-connecting nodes, and each two neighboring Ag(I) ions were linked via bridging ligands (bga or pta ligand) to form Ag6 hexagonal rings. On the basis of above analysis, the 2D structure can be simplified to a hexagonal 63-hcb net with the grid dimensions of 5.630(4) Å  6.126(4) Å. Interestingly, two ligands (one bga and one tpa) not only coordinated with Ag1 but also interacted with it through Ag 3 3 3 π interactions (Figure S8 in the Supporting Information). The shortest and longest Ag 3 3 3 C contacts are 2.994(3) and 3.198(3) Å, respectively. Finally, the uncoordinated methanol molecules (both acceptor and donor) fill in the void of the 2D net through Omethanol
H 3 3 3 Opta [2.721(4) Å] and Nbga
H 3 3 3 Omethanol [2.932(4) Å] hydrogen bonds, which further extend the 2D sheet into 3D supramolecular framework (Figure 5d). Weak aromatic 3571

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Figure 4. (a) Coordination environment of the Ag(I) ion and the linkage modes of ligands in 4 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The 1D chain structure incorporating [Ag2C2O4] subunits. (c) Ag 3 3 3 C interaction in 4 [symmetry codes: (i)
x + 2,
y,
z + 1; (iv)
x + 2,
y + 1,
z + 1].

π 3 3 3 π stacking interactions also exist between the adjacent phenyl and triazinyl rings forming the columns of π 3 3 3 π stacking along the b-axis [Cg1 3 3 3 Cg2i = 3.9598(18), Cg2 3 3 3 Cg1i = 3.6059(18) Å; Cg1 and Cg2 are centroids of ring N1/C2/ N3/C1/N2/C3 and C4
C9, Figure S9 in the Supporting Information]. [symmetry codes: (i)
x + 1/2,
1/2 + y,
z + 1/2; (v)
x + 1, y, 1/2
z.] {[Ag(bga)(ox)0.5] 3 C2H5OH 3 H2O}n (6). It was found that compound 6 crystallizes in the monoclinic C2/c space group. In the asymmetric unit, one Ag(I) ion, one bga ligand, a half of ox anion, one lattice water molecule, and one noncoordinating ethanol molecule were identified. A C2 axis passes through the midpoint of C
C single bond of ox. As shown in Figure 6a, the Ag(I) is coordinated by two N atoms (N1 and N5) from two distinct bga ligands and two O atoms from two carboxyl groups in one ox anion to form a distorted tetrahedral coordination geometry with τ4 of 0.60. The bond angles and bond lengths around Ag(I) range from 70.77(12) to 142.61(15)° and 2.262(4) to 2.408(3) Å, respectively. There is also a 39.2° interplanar angle between triazinyl and phenyl rings, and the deviation distance between Ag(I) and triazinyl planes has a value of 0.6 Å. The deviations may be caused by the different bidentate N1,N5 coordination of bga. Similar to compound 5, bga acts as bidentate N1,N5-donor to ligate Ag(I) ions to form a 1D helical chain along the b-axis with the pitch of 7.42 Å. The ox anion takes a μ4-η1:η1:η1:η1 bridging mode to link the 1D helical chains to an infinite 2D sheet containing Ag6 hexagonal rings. Analogously, the 2D sheet can also be considered as a 63-hcb net by topological analysis approach. The dimension of the grid in 6 is

6.036(7) Å  6.078(2) Å, larger than that in 5, which is caused by the distance of opposite O atoms of different carboxyl groups. Because of the different sizes of the grid, one lattice water molecule and ethanol molecule were simultaneously accommodated in the grid of 6, while only methanol molecules can be kept in the smaller grid of 5. The amino groups of bga ligands are hydrogen bonded to a lattice water molecule with the N5
H5A 3 3 3 O1Wv distance of 2.981(7) Å and a lattice water molecular interaction with carboxyl groups through O1W
1WC 3 3 3 O2vi of 2.872(6) Å to extend the 2D sheet to 3D supramolecular framework. The columns of π 3 3 3 π stacking between the alternating triazine and phenyl rings are formed along b-axis, which make a significant contribution to consolidate the 2D sheet structure [Cg3 3 3 3 Cg4ii = 3.992(3), Cg3 3 3 3 Cg4vi = 3.540(3) Å; Cg3 and Cg4 are centroids of ring N1/C1/N2/C2/N3/C3 and C4
C9, Figure S10 in the Supporting Information]. [symmetry codes: (ii)
x + 3/2, y + 1/2,
z + 3/2; (v) x + 1/2,
y
1/2, z + 1/2; (vi)
x + 3/2, y
1/2,
z + 3/2.] {[Ag2(bga)2(dnb)2] 3 DMF}n (7). When we introduce Hdnb into the silver/bga system, we obtain a 1D chain structure. It was found that compound 7 crystallizes in the acentric Cc space group. Each asymmetric unit is comprised of two Ag(I) ions, two bga ligands, two dnb, and one coordinated DMF. As shown in Figure 7a, The Ag1 is surrounded by two N atoms (N1 and N3) from two distinct bga ligands and two O atoms from two dnb anions to form a distorted tetrahedral coordination geometry with a τ4 value of 0.69. The bond angles and bond lengths around Ag1 range from 83.68(9) to 140.65(10)° and 2.251(3) to 2.468(3) Å, respectively. The Ag2 also exhibits a distorted 3572

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Figure 5. (a) Coordination environment of the Ag(I) ion and the linkage modes of ligands in 5 with 50% thermal ellipsoid probability. Hydrogen atoms and solvents are omitted for clarity. (b) The 2D sheet structure incorporating left- and right-handed helices along the b-axis. (c) Representation of the hexagonal 63-hcb net grid (green stick, pta; yellow stick, bga). (d) The hydrogen bonds extend the 2D sheet into 3D supramolecular network [symmetry codes: (i)
x + 1/2, y
1/2,
z + 1/2; (v) 1
x, y,
z + 1/2].

tetrahedral coordination geometry (τ4 is 0.47) with one N atoms (N3) from bga and three O atoms (two Odnb and one ODMF). The largest bond angle and the longest bond length around Ag2 are 160.60(10)° and 2.495(3) Å, respectively. It is interesting to note that the two bga ligands take different coordination modes, N3 monodentate mode and N1,N3 bidentate mode. The phenyl and triazinyl rings of two bga ligands are not located in the same plane, and the corresponding interplanar angles are 30.7 and 26.9°, respectively. Notably, Ag1 is almost located in the same plane to the triazinyl rings of the monodentate bga with the deviation distance of 0.3 Å, but there is a large distance (1.75 Å) between Ag1 and triazinyl ring of the bidentate bga. There exist a bimetallic subunit in which two dnb anions clamp a pair of Ag(I) ions to form a subunit of [Ag2C2O4] planar eight-membered ring. In the intrasubunit, the closest Ag 3 3 3 Ag interaction is 3.1280(4) Å, slightly longer than that in 4. The μ2-N1,N3 bga links the bimetallic subunits to form a 1D chain. The presence of complementary N
H 3 3 3 N hydrogen bonds [N8
H8A 3 3 3 N6ii = 3.009(4), N9
H9B 3 3 3 N7iii = 3.270(4) Å] leads adjacent 1D chains of 7 to form a 2D sheet. Furthermore, weak π 3 3 3 π stacking interactions found between the neighboring triazinyl rings of bga and phenyl rings of dnb ligands combine with N
H 3 3 3 ODMF hydrogen bond to contribute to the stability of the resultant 3D supramolecular framework [Cg1 3 3 3 Cg4 = 3.464(3), Cg2 3 3 3 Cg5v = 3.899(2), Cg3 3 3 3 Cg5iii = 3.912(3), and Cg3 3 3 3 Cg6ii = 3.821(2) Å; Cg1
Cg6 are centroids of ring N5/C8/N6/ C7/N7/C9, N12/C16/N14/C17/N13/C18, C1
C6, C10
C15, C20
C25, and C27
C32, Figure S11 in the Supporting

Information)]. [symmetry codes: (ii) x + 1/2,
y + 1/2, z + 1/2; (iii)
x + 1/2,
y + 1/2, z
1/2; (v) x, y,
1 + z.] [Ag2(bga)2(pma)0.5(H2O)]n (8). When pyromellitic acid was employed in the reaction system as an auxiliary ligand, a 2D structure was obtained. X-ray diffraction analysis reveals that the compound 8 belongs to triclinic P1 space group. The asymmetry unit of 8 consists of two Ag(I) ions, two bga ligands, a coordinated water molecule, and a half of pma anion, which locates on an inversion center. The coordination environments of center metals are depicted in Figure 8a. The Ag1 exhibits a Y-shaped configuration involving two O atoms of two carboxyl groups from two different pma anions with Ag1
O bond distances of 2.208(5) and 2.209(5) Å, one N atom (N3) from bidentate bga ligand. The Ag2 adopts a distorted tetrahedral coordination geometry (τ4 is 0.78) completed by two O atoms (Owater and Opma) and two N atoms from one monodentate and one bidentate bga ligands, respectively. In the asymmetry unit, two bga serve as monodentate ligand using N1 site, which is an unusual monodentate coordination mode among eight CCs. The bidentate bga possesses a distinct coordination mode using N1 and N3, respectively. The auxiliary pma ligand is in a μ6-bridging fashion with each carboxyl group in μ2-η1:η1, μ2-η1:η1, μ1-η1:η0, and μ1-η1:η0 modes; hereby, the whole pma ligand adopts a μ6η1:η1:η1:η1:η1:η0:η1:η0 coordination fashion linking six Ag(I) ions. The pma anions employ two μ2-η1:η1-carboxyl group to form binuclear Ag(I) units similar to 4, which are further extended to 1D chain (Figure 8b). The closest Ag 3 3 3 Ag contact is 3.0382(11) Å. These chains are further connected by the bidentate bga with a μ2-N1,N3 coordination mode and μ1-η1:η0 3573

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Figure 6. (a) Coordination environment of the Ag(I) ion and the linkage modes of ligands in 6 with 50% thermal ellipsoid probability. Hydrogen atoms and solvents are omitted for clarity. (b) The 2D sheet structure incorporating left- and right-handed helices along the b-axis. (c) Representation of the hexagonal 63-hcb net (green stick, ox; yellow stick, bga). (d) The hydrogen bonds extend the 2D sheet into 3D supramolecular network [symmetry codes: (i)
x + 2, y,
z + 3/2; (ii)
x + 3/2, y + 1/2,
z + 3/2].

carboxyl groups to give 7 a 2D sheet structure (Figure 8c). There also exist interplanar angles in two kinds of bga between phenyl and triazinyl rings, and the corresponding value are 26.1 and 20.4°, respectively. Finally, the complementary N
H 3 3 3 N hydrogen [N10
H10A 3 3 3 N7v = 2.965(9) Å] and O1W
H1WB 3 3 3 N8iv with a distance of 2.853(9) Å make great contributions to give the 3D supramolecular framework. The π 3 3 3 π stacking between neighboring triazinyl and phenyl rings [Cg1 3 3 3 Cg1iii = 3.676(4) Å, Cg1 is centroids of ring: N1/C7/N3/C9N2/C8, Figure S12 in the Supporting Information] also can be found in compound 8. The C
H 3 3 3 π interactions [C 3 3 3 Cg = 3.513(9) Å] cooperating with π 3 3 3 π stacking interactions consolidate the resultant 3D supramolecular framework as shown in Figure S13 in the Supporting Information. [symmetry codes: (iii)
x,
y + 2,
z; (iv)
x,
y + 1,
z + 1; (v)
x
1,
y + 1,
z + 1.] Structural Comparison of CCs 1
8 and the Influencing Factors. As it is shown in the descriptions above, a novel family of silver(I) CCs 1
8 with the benzoguanamine and different carboxylate ligands were successfully synthesized and characterized. On the basis of the X-ray analysis results, the crystal structures of CCs 1
8 ranging from discrete tetranuclear molecules to polymeric 2D sheet indicate that not only the introduction of different auxiliary carboxylate ligands into the silver/bga system but also the different coordination modes of benzoguanamine play important roles in determining the structures of the silver(I) CCs (Scheme 2). In the eight CCs, both carboxylates and benzoguanamine exhibit the capability of diversifying the structures through

changing their coordination modes and configurations. For 1 and 2, both of them are 0D CCs, and carboxylates show similar μ4 chelating coordination modes. The carboxylates as well as the monodentate bga ligand do not contribute to any extension of the discrete molecules. For 3 and 4, both tpa and suc adopt a μ4 coordination mode, which extends the molecules into 1D infinite chain. The bga in 3 and 4 is also monodentate ligand contributing nothing to the extension of 1D chain to 2D sheet. In 5 and 6, bga changes to a bidentate μ2-N1,N5 bridging ligand, which links the Ag(I) ions into helical 1D chain. Either μ2-pta or μ2-ox ligand extends the 1D chain to 2D 63-hcb net. Because of the different coordination mode of the auxiliary ligand, bga alternatively acts as a bidentate μ2-N1,N5-donor to fine-tune themselves to satisfy the coordination preference. Meanwhile, the distance of opposite O atoms in different carboxyl groups makes a great contribution to the different size of grids in 63-hcb net of 3 and 4. For 7, dnb has only one carboxyl group and adopts a μ2 coordination mode, which cannot increase the dimensionality. However, bidentate μ2-N1,N3 bga ligand links the [Ag2(dnb)2] subunit to 1D chain. For 8, the secondary ligand pma first uses two para-μ2-carboxyl groups to form a 1D chain, which was extended to 2D sheet by another pair of para-μ1-carboxyl groups and bidentate μ2-N1,N3 bga ligand. In a word, not only the coordination modes and configurations of carboxylate but also the coordination modes of bga ligand significantly contributed to the diverse structures of 1
8. FT-IR Spectra, X-ray Power Diffraction Analyses, and Thermogravimetric Analyses. The IR spectra (Figure S14 in the Supporting Information) of compounds 1
8 show features 3574

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Figure 7. (a) Coordination environments of the Ag(I) ions and the linkage modes of ligands in 7 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The 1D chain structure incorporating [Ag2C2O4] subunits. DMF molecules and monodentate bga ligands are omitted for clarity.

attributable to the carboxylic and amino group stretching vibrations. No band in the region 1690
1730 cm
1 indicates complete deprotonation of the carboxyl groups. The characteristic bands of the carboxylic groups are shown in the range 1541
1625 cm
1 for asymmetric stretching and 1345
1492 cm
1 for symmetric stretching. The splitting of νas(COO) indicates the different coordination modes of carboxylate,35 in agreement with their crystal structures. The N
H asymmetric and symmetric stretching bands fall in the ranges of 3410
3309 and 3107
3190 cm
1 respectively. To check the phase purities of compounds 1
8, the X-ray powder diffraction patterns of them were recorded at room temperature. As shown in Figure S15 in the Supporting Information, the peak positions of simulated and experimental patterns are in good agreement with each other, demonstrating the phase purity of the product. The dissimilarities in intensity may be due to the preferred orientation of the crystalline powder samples. The thermogravimetric (TG) analysis was performed in N2 atmosphere on polycrystalline samples of compounds 1
8, and the TG curves are shown in Figure 9. The TGA curves of 1
3 display similar character. The decompositions of them start at ∼175 °C, accompanying the release of the bga and dicarboxylate ligands. For 4, a weight loss of 10.97% (calcd, 11.53%) at 80
165 °C corresponds to complete loss of lattice ethanol molecule. The higher observed temperature than the boiling point of ethanol is attributed to the presence of hydrogen bonds between the networks and the solvent molecules. Its framework is stable to 210 °C, and then, the framework begins to collapse. Compound 5 shows a first weight loss of 7.48% at 50
160 °C, corresponding to the loss of

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Figure 8. (a) Coordination environments of the Ag(I) ions and the linkage modes of ligands in 8 with 50% thermal ellipsoid probability. Hydrogen atoms are omitted for clarity. (b) The 1D chain structure incorporating [Ag2C2O4] subunits. Monodentate bga ligands are omitted for clarity. (c) The 2D sheet structure. The cyan lines represent bidentate coordinated bga, and monodentate bga ligands are omitted for clarity.

Scheme 2. Coordination Modes of bga and Carboxylate Ligands

methanol molecule (calcd, 8.31%). It remains stable to 230 °C, and then, the framework decomposes in two steps. Compound 6 contains two kinds of solvent molecules: water and ethanol. Its TGA curve shows two steps of loss of solvents at the temperature ranges of 30
68 °C for water (calcd, 4.47%; found, 4.69%) and 3575

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compounds 1 and 6 are similar to that found for the free bga ligand in terms of position and band shape. Nevertheless, the emission bands of compounds 1 and 6 mainly due to an intraligand emission state as reported for d10 metal compounds with N-donor ligands.37 To understand the nature of the emission bands, we analyzed the photoluminescence properties of the corresponding free ligand and found that free bga ligand does not emit any photoluminescence in the range 450
600 nm. The redshifted emissions and enhancement of luminescences of 2
5 were attributed to two factors. One is bga ligand coordination to the metal center, which effectively increases the rigidity of the ligand and reduces the loss of energy by radiationless decay, and another one is the emission of ligand-to-metal charge-transfer.38

Figure 9. TGA curves for complexes 1
8.

’ CONCLUSIONS Eight new CCs have been prepared by mixed benzoguanamine and carboxylate ligands under the ultrasonic treatment. They show diverse structures and dimensionalities from 0D discrete molecule (1 and 2), 1D chains (3, 4, and 7) to 2D sheets (5, 6, and 8). The diversity of structures results from the various carboxylates and diverse coordination modes of benzoguanamine. Interestingly, these eight CCs provide a way of understanding abundant weak interactions, such as hydrogen bonds, Ag 3 3 3 Ag argentophilicity, π 3 3 3 π stacking effects, and Ag 3 3 3 π and C
H 3 3 3 π interactions, and these interactions in 1
8 further assemble the structures into supramolecular frameworks. In addition, CCs 1
6 display solid-state fluorescent emission. ’ ASSOCIATED CONTENT

bS

Supporting Information. Crystallographic data in CIF format, additional figures of the structures, hydrogen-bonding geometries, X-ray power diffraction, and IR spectra for 1
8. This material is available free of charge via the Internet at http:// pubs.acs.org.

’ AUTHOR INFORMATION Figure 10. Photoluminescence spectra of compounds 1
6.

68
141 °C for ethanol (calcd, 11.41%; found, 11.98%). The decomposition of the solvent-free 6 starts at 170 °C. As for 7, the TGA curve displays a weight loss of 7.31% from 150 to 180 °C, cooresponding to loss of coordinated DMF molecule (calcd, 6.73%). Between 180 and 274 °C, no weight loss was observed. After that, the framework collapses in two steps. Compounds 8 shows the first weight loss of 2.58% and corresponds to the loss of coordinated water molecules (calcd, 2.46%). Then, the framework keeps stable to 270 °C, and then, the framework similarly collapses in two steps as presented in compounds 1, 5, and 7. Photoluminescence Properties. Emissive CCs are of great current interest because of their various applications in chemical sensors, photochemistry, and electroluminescent display.36 Thus, the photoluminescence properties of 1
6 as well as free ligands were examined in the solid state at room temperature as shown in Figure 10 and Figure S16 in the Supporting Information. The intense emission bands are observed at 344 nm (λex = 300 nm) for 1, 455 nm (λex = 300 nm) for 2, 486 nm (λex = 300 nm) for 3, 496 nm (λex = 300 nm) for 4, 514 nm (λex = 320 nm) for 5, and 338 nm (λex = 300 nm) for 6 at room temperature. Although the maximum emission wavelengths of compounds 1 and 6 undergo a blue shift, the emission bands for

Corresponding Author

*Fax: 86-592-2183074. E-mail: [email protected]. Author Contributions †

These authors contributed equally to this work.

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Crystal Growth & Design

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dx.doi.org/10.1021/cg200534x |Cryst. Growth Des. 2011, 11, 3564–3578