Reactions of (E)-5-(Pyridin-4-yl-methyleneamino) isophthalic Acid

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Reactions of (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2) with Triorganotin Oxides and –Chloride. Formation of 1D- and 2D-Coordination Polymers Vadapalli Chandrasekhar, Chandrajeet Mohapatra, and Ramesh Metre Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg401201w • Publication Date (Web): 29 Aug 2013 Downloaded from http://pubs.acs.org on September 2, 2013

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Crystal Growth & Design

Reactions of (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2) with Triorganotin Oxides and –Chloride. Formation of 1D- and 2D-Coordination Polymers Vadapalli Chandrasekhar,*a,b Chandrajeet Mohapatraa and Ramesh K. Metrea a

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India

b

Tata Institute of Fundamental Research, Centre for Interdisciplinary Sciences, 21, Brundavan

Colony, Narsingi, Hyderabad- 500075,India

*E-mail: [email protected];[email protected]; Phone: (+91) 512-259-7259. Fax: (+91) 521-259-0007/7436.

ACS Paragon Plus Environment


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Abstract: The reaction of (n-Bu3Sn)2O with (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2) in a stoichiometric ratio of 1:1 resulted in the formation of a 2D coordination polymer [(n-Bu3Sn)2(µ-L)]n (1). The structure of 1 contains a 36-membered macrocycle as its repeating building block. The reactions of Me3SnCl or (Ph3Sn)2O with LH2, on the other hand, result in the generation of [(Me3Sn)2(µ-L)(H2O)]n (a neutral 1D coordination polymer) (2) and [(Ph3Sn)(µL)(Et3NH)]n (an anionic 1D coordination polymer) (3) respectively. Compounds 1-3 show a rich supramolecular architecture in their solid-state as a result of multiple secondary interactions.

Introduction Apart from their utility in various areas including catalysis, organotin compounds, in general, and organooxotin compounds in particular are of considerable interest because they display a rich structural diversity.1 Many interesting types of organoxotin compounds, possessing novel structural features, have been discovered in the reactions of organotin oxides, -hydroxides and oxide-hydroxides with protic acids (carboxylic acids, phosphinic acids, phosphonic acids and sulfonic acids).2-4 Another reason of interest among this family of compounds is the realization that the organostannoxane core can be used as an inert scaffold to support a functional periphery.5 In light of the recent surge of research activity in metal-organic frameworks6 there have also been attempts to delineate the reaction products involving appropriate organotin substrates and dicarboxylic acids.7 However, this field is still sparsely investigated. Recent work from some research groups7(a)-(f) and ours7(g)-(n) have thrown open the exciting possibilities that exist in these systems. Thus, for example, Höpfl and co-workers have reported the isolation of novel macrocycles and coordination polymers in the reactions of diorganotin compounds with aromatic dicarboxylic acids.7(c) From our research group we have explored the reactions of organotin compounds with pyrazole dicarboxylic acids as well as pyridine dicarboxylic acids and


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have shown the formation of novel macrocycles and coordination polymers (Chart 1). More recently we have also reported selective gas adsorption (H2 and CO2 over N2) property of a 4connected 3-fold interpenetrated triorganotin coordination polymer with a sqc-topology. This coordination polymer involved the use of an imidazole-4,5-dicarboxylic acid as the reactant.7(m) Many of the above studies involved diorganotin precursors and dicarboxylic acids. We have felt that a better understanding can be achieved if the reactions involving triorganotin compounds with dicarboxylic acids are studied, since the complexities would be much less in this system. Accordingly, we have investigated the reactions of (n-Bu3Sn)2O, Me3SnCl and (Ph3Sn)2O with (E)-5-(pyridin-4-yl-methyleneamino)isophthalic acid (LH2) and the products obtained viz., [(nBu3Sn)2(µ-L)]n (1),

[(Me3Sn)2(µ-L)(H2O)]n (2) and

[(Ph3Sn)(µ-L)(Et3NH)]n (3) were

characterized as coordination polymers.

Chart 1. (a) The repeating unit of [(Bz2Sn)6(L)4(µ-OH)2(Bz2SnCl)2]n 7(k) (b) Schematic figure of [{n-Bu2Sn(2,5-pdc)(H2O)}3]

7(c)

(c) Macrocyclic repeating unit of [(n-Bu3Sn)2(n-Bu2Sn)2(µ-

L1)2(µ-OH)2]n 7(l) (d), (e) and (f) Macrocyclic repeating units of [(n-Bu3Sn)4(µ-L3)2]n7(l).



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Results and Discussion The reaction of LH2 with various triorganotin precursors (n-Bu3Sn)2O, Me3SnCl and (Ph3Sn)2O afforded compounds 1-3 (Scheme 1; see also experimental section). 1 is a 2D-coordination polymer built by the fusion of 36-membered macrocycle repeat units. 2 and 3 are 1Dcoordination polymers. While 2 is a neutral coordination polymer, 3 is anionic and contains triethylammonium counter cations. Compounds 1−3 do not retain their structural integrity in solution as evidenced by electrospray ionization mass spectrometry (ESI-MS) (see experimental Section).

Scheme 1 O

O

HO

OH N

N

LH2

N

nBu Sn nBu O nBu O nBu O Sn O nBunBuO

(Ph3 Sn)2O

Me3 SnCl Et3N

(n-Bu3 Sn)2 O

Me

OH 2

O

Sn Me O Me

O Sn

Et3 N

Sn

O

O

N

1

Sn n

N

Ph O Sn Sn Ph Ph

N

Me O Sn Me

N

O

N

N

Me

N

H

N

n Sn

2


3

n

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X-ray Crystal Structure of 1 The X-ray crystal structure of 1 is depicted in Figure 1a. Selected metric parameters of 1 are summarized in Table 2. Compound 1 is a 2D coordination polymer owing to the 4.11101 coordination mode of the ligand (Chart 2a). Each ligand binds to four tin atoms which includes a bidentate coordination of one carboxylate group and a monodentate coordination of another carboxylate group along with coordination from the

pyridine nitrogen (Figure 1b).

Two

different types of tin centers are present in 1. Both of these (Sn1 and Sn2) are 5-coordinated in a distorted trigonal bipyramidal geometry. In Sn1 both the axial positions are occupied by oxygen atoms [O1 and O3; Sn1-O1, 2.099(5)Å; Sn1-O3, 2.474(4)Å] (see Supporting Information). On the other hand the axial positions around Sn2 are occupied by an oxygen and a nitrogen atom [O4 and N2; Sn2-O4, 2.181(4); Sn2-N2, 2.509(5) Å] (see Supporting Information). The 2D coordination polymer of 1 contains inter-connected 36-membered tetranuclear macrocyclic rings (Figure 1c). In spite of its large size, the 36-membered macrocylic ring is nearly planar. The mean plane information for the macrocylic ring is summarized in Supporting Information. The packing organization reveals that the 2D sheets are arranged parallel to each other with a slight offset in an AB type arrangement (Figure 1d). Intermolecular C-H--π interactions serve as the glue between the stacked sheets. The inter layer distance is approximately ~15 Å [A--A distance]. It is interesting to compare the structure of 1 with some literature precedents. Thus, we have reported previously a 2D-coordination polymer consisting of a tetranuclear macrocycle (Sn4O6C2) (Chart 1a).7(k) A coordination polymer containing a trinuclear macrocycle (Sn3O3N3C9) was reported by Höpfl and co-workers in the reactions of diorganotin compounds with pyridine-2,5-dicarboxylic acid (Chart 1b).7(c) The orientation of the coordination sites of the ligand LH2, used in the present study, are comparable with pyridine-3,5-dicarboxylic acid (Chart



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2b). We have also reported, recently an organotin-based 2D coordination polymer, by using pyridine-3,5-dicarboxylic acid. This compound was shown to contain three types of organotin macrocycles [28-membered (Sn4O6C16N2)], [20-membered (Sn4O6C8N2)] and [24-membered (Sn4O6N2C12)] (Charts 1d-1f).

7(l)

However, in spite of the fact that in the latter as well in the

present instance the ligand is involved in a 4.11101 coordination (Chart 2a) compound 1 contains only one type of organotin macrocycle (Sn4O6N4C22) as discussed above.

M

M O

M M

O

M O

O O

O

O M

O

O

O

O

O

O

HO O

N

O

M OH

O

N

N

HO

N

OH

N

N

N

M

M

4.11101 1

3.10101 2

N

2.01010 3

(a)

N

(b)

Chart 2. (a) Coordination modes of ligand LH2 in compounds 1-3 (Harris notation used as per reference 8) (b) Schematic representation showing the similarity between pyridine-3,5dicarboxylic acid and LH2.


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(a)

(b)

(c)

(d)



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Figure 1. (a) 2D polymeric structure of compound 1 (b) Coordination mode of ligand (c) An isolated 36-membered macrocycle (d) AB packing of 2D parallel sheets (butyl groups have been omiited from Figures 1c and 1d)

X-ray Crystal structure of 2 The X-ray crystal structure of 2 is shown in Figure 2a. Selected metric parameters of this compound are summarized in Table 2. Compound 2 is a 1D coordination polymer formed as a result of the 3.10101 coordination mode of the ligand LH2 (Chart 2a). In 2, the ligand binds to three tin centers; both the carboxylate groups are monodentate along with the pyridine nitrogen atom (Figure 2b). The growth of the coordination polymer is arrested at the Sn2 centre as a result of coordination by a terminal water molecule. Consequently, 2 forms a 1D coordination polymer. Similar to 1, in this instance also the two tin centers (Sn1 and Sn2) are five-coordinate in a distorted tbp coordination geometry (Supporting Information). While the Sn1 centre contains an oxygen (O1) and a nitrogen (N1) in its axial sites [Sn1-O1, 2.165(4)Å; Sn1-N1, 2.532 (4)Å; O1Sn1-N1 175.22(15)°]

the Sn2 centre contains two oxygen atoms (O3 and O5) in its axial sites

[Sn2-O3, 2.175(4) Å; Sn2-O5, 2.434(5) Å; O3-Sn2-O5, 171.7 (2)°]. The terminal H2O (O5) is involved in O-H--O hydrogen bonding with a carboxylate oxygen atom [O5-H1W--O4, 2.020 (5) Å; D-H-A angle, 172.2 (6)°; O5-H2W--O2, 2.005 (7); D-H-A angle, 165.2 (8)°] (Figure 2c). In addition a C-H---N interaction between a methyl proton of the trimethyl tin motifs of one 1D chain with the nitrogen atom N2 of another 1D chain [C18-H18---N2, 3.362(5)Å; D-H-A angle, 155.75(38)°] is also seen (Supporting Information). These two kinds of secondary interactions collectively afford a 3D supramolecular architecture (Figure 2c).


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(a)

(b)

(c)

Figure 2. (a) 1D polymeric structure of 2 (b) Coordination mode of the ligand (c) 3D supramolecular architecture of 2. (Methyl groups are omitted from Figure 2c)

X-ray Crystal structure of 3 In contrast to the structures of 1 and 2 where all the coordinating atoms take part in binding with the tin centers, in 3, only the two carboxylate groups participate, both in a monodentate manner; the pyridine nitrogen atom is not involved in coordination (Chart 2a). Such a 2.01010 mode of coordination leads to the formation a 1D coordination polymer (Figure 3a). Another point of



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difference is that 3 is an anionic coordination polymer; the asymmetric unit contains two triphenyl tin units bound to two different, fully deprotonated ligands. The charge is balanced by the presence of triethylammonium cations (Figure 3b). Selected metric parameters of 3 are summarized in Table 2. The crystal packing reveals that two 1D chains of 3 are stacked together by means of three different π-π interactions (Figure 3c). (a)

(b)

(c)

Figure 3. (a) 1D polymeric structure of 3 (b) asymmetric unit of 3 (c) π-π stacking between 1D anionic chains of 3 [A (pink), 3.771(7)Å; B (blue), 3.730(7)Å and C (green), 3.934(6)Å] .


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Conclusion The reactions of triorganotin compounds with (E)-5-(pyridin-4-ylmethyleneamino)isophthalic acid (LH2) afforded 2D and 1D coordination polymers. Reaction of (n-Bu3Sn)2O with LH2 produces a 2D coordination polymer 1 containing 36-membered macrocycles as repeating blocks. In contrast, the reaction of Me3SnCl with the ligand LH2 afforded a 1D coordination polymer 2 which shows extended supramolecular assembly in the solid-state. Unlike 1 and 2 which are neutral coordination polymers, the reaction of (Ph3Sn)2O with LH2 results in the generation of an anionic 1D coordination polymer 3.

Experimental Section Solvents were distilled and dried prior to use according to standard procedures. (n-Bu3Sn)2O, Me3SnCl, (Ph3Sn)2O, isonicotinaldehyde and 5-aminoisophthalic acid (all from Aldrich) were used as received. Melting points were measured using a JSGW melting point apparatus and are uncorrected. Elemental analyses were carried out using a Thermoquest CE instruments model EA/110 CHNS-O elemental analyzer. Infrared spectra were recorded as KBr pellets on a FT-IR Bruker-Vector Model. 1H and 119Sn NMR spectra were obtained on a JEOL-DELTA2 500 model spectrometer using CDCl3 as the solvent. Chemical shifts were referenced with respect to tetramethylsilane (for 1H NMR) and tetramethyltin (for

119

Sn NMR) respectively.

119

Sn NMR

spectra were recorded under broad-band decoupled conditions. Thermogravimetric Analysis was carried out on a Perkin Elmer Pyris 6 Thermogravimetric analyzer. UV−Vis spectra were recorded on a Perkin-Elmer Lambda 20 UV−Vis spectrometer in a 1 × 10−5 M methanol solution. The steady-state emission spectra were measured using a Perkin-Elmer LS-55 model spectrophotometer in a 1 × 10−5 M methanol solution.



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Synthesis (E)-5-(Pyridin-4-ylmethyleneamino)isophthalic acid (LH2) The synthesis of LH2 is depicted in Scheme 2. To a solution of isonicotinaldehyde (0.107 g, 1 mmol) in 20 mL EtOH, 5-aminoisophthalic acid (0.181g, 1 mmol) was added. The mixture was stirred for 2 h at room temperature to afford a pale-yellow precipitate of LH2 (Scheme 2). This was washed with methanol several times and dried. Yield: 0.26 g (96 %). Mp: >230 °C. Anal. Calcd for C14H10N2O4 (270.06 g) (%): C, 62.22, H, 3.73, N, 10.37; Found: C 62.17, H 3.71, N, 10.42. IR(KBr, cm-1): 3387.33 (b), 3070.46 (m), 2448 (w), 1717.42 (s), 1614.93 (s), 1414.36 (m), 1228.50 (s), 1193.99 (s), 823.11 (s), 760.68 (s), 677.94 (s), 505.17 (m), 473.33 (w). 1H NMR (500 MHz, ppm): δ = 8.75-8.76 (d, 1H); 8.71-8.72 (d, 1H); 8.55 (s, 1H); 8.06 (s, 2H); 7.82-7.83 (d, 1H); 7.74-7.75 (d, 1H). ESI-MS: m/z (%) 269.0537 [M-H]- (100) . O

O

HO O

OH

O CHO

HO

OH

EtOH

+ N

NH2

N

RT

N

LH2 Scheme 2. Synthesis of ligand (LH2).

[(n-Bu3Sn)2(µ-L)]n (1) (n-Bu3Sn)2O (0.23 mL, 0.5 mmol) was added to a mixture of LH2 (0.135g, 0.5 mmol) in 40 mL of toluene. The mixture of was heated under reflux for 9 h. The reaction mixture was cooled to room temperature and evaporated to yield 1 as a powder. This was dissolved in n-hexane and left


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for crystallization to afford crystals of 1. Yield: 0.34 g (80 %). Mp: >230 °C. Anal. Calcd for C38H62N2O4Sn2 (848.33 g) (%): C 53.80; H 7.37; N 3.30; Found: C 53.67, H 7.42, N, 3.46. IR (KBr, cm-1): 3419.87 (b), 2954 (s), 2922.55 (s), 2854 (m), 2869.78 (m), 1647.26 (s), 1605.25 (s), 1569.06 (s), 1385.23 (s), 1320.13 (s), 773.39 (m), 724.31 (m), 672.84 (m). 1H NMR (500 MHz, ppm): δ = 8.75-8.76 (d, 1H, LH2); 8.71-8.72 (d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2); 7.82-7.83 (d, 1H, LH2); 7.74-7.75 (d, 1H, LH2); 0.89-0.92 (t, 15H, butyl CH3); 1.30-1.41 (m, 10H, butyl -CH2-); 1.63-1.72 (b, 20H, butyl Sn-CH2-CH2-).119Sn NMR (500 MHz, ppm): δ = 121.81;

130.66.

ESI-MS:

m/z

(%) 291.1146

[n-Bu3Sn]+

(52);

364.1635

[(n-

Bu3SnH)(Na)(H2O)MeOH]+ (42); 625.2206 [(Bu3Sn)2(CHOO)]+ (100).

[(Me3Sn)2(µ-L)(H2O)]n (2) A mixture of Me3SnCl (0.099g, 0.5 mmol), LH2 (0.135g, 0.5 mmol) and triethyl amine (0.21 mL, 1.5 mmol) in 30 mL EtOH was stirred for 1 day to afford a clear yellow solution. The mixture was filtered and kept for slow evaporation to get single crystals of 2. Yield: 0.21 g (68 %). Mp: >230 °C. Anal. Calcd for C20H28N2O5Sn2 (613.87 g) (%): C 39.13; H 4.60; N 4.56; Found: C 39.09, H 4.69, N, 4.67. IR (KBr, cm-1): 3417.16 (b), 2990.39 (m), 2921.41 (m), 1673.94 (s), 1608.84 (s), 1562.96 (s), 1413.99 (s), 1375.19 (s), 1249.92 (s), 1232.50 (s), 772.48 (s), 685.78 (m), 596.68 (m), 549.89 (m). 1H NMR (500 MHz, ppm): δ = 8.75-8.76 (d, 1H, LH2); 8.71-8.72 (d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2); 7.82-7.83 (d, 1H, LH2); 7.74-7.75 (d, 1H, LH2); 0.51 (s, 9H, Sn-CH3).119Sn NMR (500 MHz, ppm): δ = 24.46 . ESI-MS: m/z (%) 197.0046 [(Me3Sn)(MeOH)]+ (38); 206.0056 [[(Me3Sn)(Na)(H2O)]+ (27); 372.9478 [(Me3Sn)2(HCOO]+ (12).



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[(Ph3Sn)(µ-L)(Et3NH)]n (3) A mixture of (Ph3Sn)2O (0.179g, 0.25 mmol), LH2 (0.135g, 0.5 mmol) and triethyl amine (0.21 mL, 1.5 mmol) in 30 mL EtOH was stirred for 1 day to afford a clear yellow solution. The mixture was filtered and kept for slow evaporation to get single crystals of 3. Yield: 0.27 g (75 %). Mp: charred at 210 °C. Anal. Calcd for C38H39N3O4Sn (720.44 g) (%): C 63.35; H 5.46; N 5.83; Found: C 63.29, H 5.53, N, 5.92. IR (KBr, cm-1): 3343.72 (b), 3043.35 (m), 2989.14 (m), 2698.52 (b), 1718.30 (m), 1625.16 (s), 1601.07 (s), 1573.82 (s), 1480.48 (m), 1429.47 (s), 777.05 (m), 732.83 (m), 699.33 (s), 553.98 (s), 456.10 (s). 1H NMR (500 MHz, ppm): δ = 8.758.76 (d, 1H, LH2); 8.71-8.72 (d, 1H, LH2); 8.55 (s, 1H, LH2); 8.06 (s, 2H, LH2); 7.82-7.83 (d, 1H, LH2); 7.74-7.75 (d, 1H, LH2); 7.35-7.44 (m, 15H, Sn-Ph); 3.07-3.11 (q, 6H, -CH2- Et3NH); 1.21-1.23 (t, 9H, -CH3 Et3NH). ESI-MS: m/z (%) 351.0209 [Ph3Sn]+ (30); 745.0406 [(Ph3Sn)2(HCOO)]+ (10).

X-ray Crystallography The crystal data for 1-3 were collected on a Bruker SMART APEX CCD Diffractrometer. SMART software package (version 5.628) was used for collecting data frames, SAINT software package (version 6.45) for integration of the intensity and scaling and SADABS was used for absorption correction. The structures were solved and refined by full-matrix least squares on F2 using SHELXTL software package.9 Non-hydrogen atoms were refined with anisotropic displacement parameters. Figures (1-3) and their bonding parameters were obtained from DIAMOND 3.1f software package.10 CCDC reference numbers for 1, 2 and 3 are 935287, 935288 and 935289 respectively.


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Acknowledgments We thank the Department of Science and Technology (DST), India, and Council of Scientific and Industrial Research (CSIR), India, for financial support. V.C. is thankful to the Department of Science and Technology for a J. C. Bose fellowship. C.M. and R. K.M. thanks UGC, India, for a Senior Research Fellowship.

Supporting Information Crystallographic information files (CIFs) for 1-3, Details of photophysical studies, TGA, Additional DIAMOND figures for 1-3. This information is available free of charge via the Internet at http://pubs.acs.org/.

Table 1. Crystal data and structure refinement parameters of 1-3 Parameters

1

2

3

Empirical formula

C38 H62 N2 O4 Sn2

C20 H28 N2 O5 Sn2

C38 H39 N3 O4 Sn

Formula weight

848.28

613.82

720.43

Temperature

293(2) K

293(2)K

293(2)K

Wavelength

0.71069Å

0.71069 Å

0.71069Å

Crystal system, space group

Monoclinic, P21/n

Monoclinic, P21/n

Monoclinic, P21/n

Unit cell dimensions

a = 10.335(5)Å

a = 6.915(5)Å

a = 18.736(5)Å

b = 27.054(5)Å

b = 12.362(5)Å

b = 11.368(5)Å

c = 15.012(5)Å

c = 27.938(5)Å

c = 31.720(5)Å

α = 90°

α = 90 °

α = 90°

β = 99.885(5)°

β = 96.110(5)°

β = 97.254(5)°

γ = 90°

γ = 90 °

γ = 90°

3

3

Volume

4135(3)Å

2375(2)Å

6702(4)Å3

Z, Calculated density

4,1.363 Mg/m3

4,1.717 Mg/m3

8, 1.428 Mg/m3

Absorption coefficient

1.244mm-1

2.134mm-1

0.807mm-1

F(000)

1744

1208 3

2960 3

Crystal size

0.21x 0.15x 0.11mm

0.19 x 0.13 x 0.09 mm

0.23 x 0.16 x 0.12mm3

θ range for data collection

2.04 to 25.50°.

2.21 to 26.00 °.

1.20 to 25.50°.



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Limiting indices

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Reactions of (E)-5-(Pyridin-4-yl-methyleneamino) isophthalic Acid

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