Supramolecular Silver(I), Copper(I), and Mercury(II) Complexes with

Article pubs.acs.org/crystal

Supramolecular Silver(I), Copper(I), and Mercury(II) Complexes with Thiamacrocycles Exhibiting Different Types of Endo- or Exocoordination Modes: From Monomer and Dimer to OneDimensional and Two-Dimensional Polymers Published as part of the Crystal Growth & Design virtual special issue IYCr 2014 - Celebrating the International Year of Crystallography Hyun Jee Kim,†,‡ In-Hyeok Park,† Ji-Eun Lee,† Ki-Min Park,† and Shim Sung Lee*,† †

Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, South Korea Forensic Chemistry Division, Busan Institute, National Forensic Service, Yangsan 626-724, South Korea

‡

S Supporting Information *

ABSTRACT: A range of supramolecular complexes of O3S2donor (L1-L3) and O2S3-donor (L4) macrocycles with different ring sizes (L1: 16-membered, L2: 17-membered, L3 and L4: 18membered) were synthesized and structurally characterized. For the 11 complexes (1−11), the structural topologies and the types of coordination modes including mono- to multinuclear and endo- to exocyclic ones via M−S bonds have been discussed in terms of the possible exocoordination modes proposed. The reactions of L1, L3, and L4 with the silver(I) salts (BF4− and CF3COO−) afforded four complexes 1−4 with different topologies: two endocyclic mononuclear complexes [Ag(L1)NO3] (1) and [Ag(L1)]BF4 (2), and two exocyclic complexes [Ag(L3)(CF3COO)]n (3) and [Ag2(L4)2(CF3COO)2] (4) with a two-dimensional (2D) coordination network and cyclic dimer structures, respectively. In the reactions with copper(I) iodide, L1−L4 afforded the Cu4I4-cubane linked 2D coordination polymer {[(Cu4I4)(L1)2]·CH2Cl2}n (5), one-dimensional (1D) tubular coordination polymer {[(Cu4I4)(L2)2]· 0.8CH2Cl2·0.2CH3CN}n (6), Cu2I2-rhomboid linked 2D coordination polymer [(Cu2I2)(L3)2]n (7), and 2D coordination polymer [(Cu2I2)(L4)2]n (8), respectively. The reactions of the above ligands with mercury(II) salts (I− and SCN−) gave a cyclic dimer complex [Hg2(L3)2I4] (9), mononuclear complex [Hg(L4)I2] (10), and 2D coordination polymer [Hg2(L3)(SCN)4]n (11). The structural comparison of the complexes reveals that even small structural variations in the macrocycles result in a dramatic impact on the topology of the supramolecular products mainly due to the different coordination modes.

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INTRODUCTION Sulfur-bearing macrocycles (thiamacrocycles) often show unusual coordinating behavior toward soft metal ions, giving rise to supramolecular complexes with diverse topologies.1 For example, thiaphilic metals such as Ag(I), Cu(I), Hg(II), and platinum group metals are forced to adopt an exocyclic coordination (metal coordinates outside the cavity) that tends to lead to the formation of coordination polymers, as well as to discrete metallo-suprastructures bearing less-common stoichiometries.2 Recently, we have reported the thiaphilic metal complexes of dithiamacrocycles via diverse types of coordination modes upon variations of the donor atoms, counterions, or sulfur-to-sulfur distances.3 In addition to the endocyclic complexation (Type I in Chart 1), the bischelating dithiamacrocycle rigidified with aromatic subunit(s) tends to show a convergent (Type II-a) or divergent (Type II-b) exocoordination, which leads the formation of a discrete or continuous coordination species, respectively. In this case (dithia system), the sulfur-to-sulfur separation is decisive.4 The trithia system seems to be more © 2014 American Chemical Society

complicated. Unlike the symmetrical coordination behaviors of the dithia system (Type II-a and II-b), two modes (Type II-d and II-e) of the trithia system are unsymmetrical because the three consecutive sulfur donors in the rigid or semirigid macrocyclic system hardly coordinate to one metal ion, simultaneously.4b,5 Thus, only two neighboring sulfurs coordinate to the metal ion with one sulfur remaining unbound (Type II-d). Otherwise, the third sulfur atom coordinates to the different metal ion in addition to the Type II-d mode (Type IIe). The formation of the endo-/exocyclic complexes also has been reported by us,4c,5b,6 but no such products were available to prepare in the present macrocyclic system. To investigate the coordination modes of the thiamacrocycles represented in Chart 1 systematically, our initial interest in the present work is that ring size changes of the dithiamacrocycle analogues influence the frameworks of their Received: July 1, 2014 Revised: November 3, 2014 Published: November 12, 2014 6269

dx.doi.org/10.1021/cg500966z | Cryst. Growth Des. 2014, 14, 6269−6281

Crystal Growth & Design

Article

manner. The bond distances for Ag-donors are comparable with those reported previously for such bonds.8 Unlike the anion coordination in 1, the anion in the tetrafluoroborate complex [Ag(L1)]BF4 (2) remains uncoordinated. Thus, the silver(I) center in 2 is five-coordinate, being bound to all donors of L1 (Figure 2a). Such a cationic complex part in 2 presumably promotes additional intermolecular interactions via Ag1···S2A (3.106 Å) and Ag···π interactions (Ag···C 3.109−3.611 Å, dashed lines in Figure 1b) between the silver atom and the neighboring ligand. A similar endocyclic dinuclear complex [Ag2(L3)2](PF6)2 derived from L3 with AgPF6 was reported by us previously.9 With respect to the cavity size of L1, the preferred endocyclic mode (Type I in Chart 1) of 1 and 2 is due to the metal-cavity size fitting, allowing all the O3S2-donors in the macrocycle to bind tightly toward the metal center. Regarding the anion coordination ability, the anion noncoordinated complex 1 is due to the weaker affinity of the BF4− ion, allowing the approach of the adjacent complex to form a pseudodimer. In contrast, the nitrate with the stronger affinity toward the silver(I) center forms the typical anion coordinated 1:1:1 complex as shown in 2. Preparation and Structures of Silver(I) Trifluoroacetate Complexes with L3 and L4 (3 and 4). By virtue of one donor variations of O2S2D-donor (L3: D = O, L4: D = S) macrocycles with an 18-membered ring size toward silver(I) trifluoroacetate, two complexes (3 and 4) with different topologies were isolated as shown in Scheme 2. In marked contrast to the endocoordination in 1 and 2, both of the complexes 3 and 4 show different types of exocoordination modes. The reaction of 18-membered O3S2-macrocycle L3 with silver(I) trifluoroacetate in methanol/dichloromethane afforded colorless two-dimensional (2D) polymeric complex [Ag(L3)(CF3COO)]n (3) (Figure 3). The asymmetric unit of 3 contains one L3, one Ag atom, and one trifluoroacetate ion. The selected geometric parameters are presented in Table 3. The 2D network of 3 basically contains a Ag-(μ-CF3COO)2-Ag rhomboid core bonded to four ligands via Ag−S bonds [2.445(2) and 2.544(1) Å] (Figure 3a). Accordingly, the Ag center is tetrahedrally coordinated by two S donors from two adjacent ligands via the divergent exocyclic coordination mode (Type II-b) to form a 1D wavy array of the macrocycles (Figure 3b,c). The silver(I) coordination is completed by two monodentate μ2-CF3COO ions which link two silver(I) ions to form a 2D double-deck structure (Figure 3b,d). The gross geometry of 3 can be described as a fishnet pattern (Figure 3c). The preference of the generation of the 2D structure in two directions is due to the one-dimensional (1D) wavy arrays of the dithiamacrocycles via the formation of the Ag−S bonds with the divergent exocoordination followed by the crosslinking of these 1D arrays with the anions via the formation of the Ag−O bonds.

Chart 1. Coordination Modes of Dithia- and Trithiamacrocycles toward Thiaphilic Metal Ion (M)

products in the reactions with the thiaphilic metal ions. And also, we were motivated to extend our synthetic work to the preparation of further supramolecular products incorporating the trithiamacrocycle analogue. In this regard, we employed three dithiamacrocycles (L1−L3 in Chart 2) with different sizes (16−18 membered rings) and one trithiamacrocycle (L4; 18membered ring). Given the possibility of the proposed diverse coordination modes in Chart 1, we have attempted the syntheses of the discrete and continuous coordination products. In particular, the trithiamacrocycle L4 with three consecutive sulfur donors in the ring cavity is expected to form unique products through the unsymmetrical exocyclic coordination modes.

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RESULTS AND DISCUSSION Macrocycles L1−L4 were synthesized as described by us previously.7 In this work, we expand this family of complexes and describe the synthesis and comparative structural properties of 11 complexes characterized by single-crystal X-ray diffraction (Table 1). Preparation and Structures of Silver(I) Complexes with L1 (1 and 2). Using a smaller (16-membered) O2S2macrocycle L1, two silver(I) complexes with different anions (nitrate and tetrafluoroborate) which show an endocyclic coordination were isolated as depicted in Scheme 1. In complexation of L1 with silver salts in methanol/ dichloromethane, we were able to isolate one nitrato complex 1 (Figure 1) and one anion-coordination free complex 2 (BF4− form, Figure 2). The selected geometric parameters of 1 and 2 are presented in Table 2 for comparison. The X-ray analysis reveals that 1 is a typical endocyclic 1:1:1 (metal-to-ligand-toanion, Type I in Chart 1) complex [Ag(L1)NO3]. In 1, the Ag atom in the center of the ring cavity is seven-coordinated by all donors from L1 in which the macrocycle slightly folds such that an unsymmetrical but apparently favorable cavity is formed. Two other sites are occupied by one nitrate ion in a bidentate Chart 2. Dithia- and Trithiamacrocycles Used in This Work

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Table 1. Crystal Data and Experimental Data for 1−11 1 formula formula weight temperature crystal system space group Z a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Dcalc (g/cm3) 2θmax (deg) final R indices [I > 2σ(I)] R indices (all data) no. of reflection used [>2σ(I)] refinement

2

3

4

5

6

C19H22Ag1B1F4O3S2 557.17 173(2) monoclinic C2/c 8 19.5642(14) 8.9547(6) 25.1758(18) 90 106.3930(10) 90 4231.3(5) 1.749 54.00 0.0915, 0.1978

C19H22Ag1N1O6S2 532.37 173(2) monoclinic Pn 2 8.8256(14) 12.510(2) 9.9956(16) 90 111.405(3) 90 1027.5(3) 1.721 54.00 0.0497, 0.1198

C46H52Ag2F6O8S6 1254.98 173(2) triclinic P1̅ 1 9.894(4) 10.357(5) 12.430(6) 89.095(7) 78.449(9) 78.738(12) 1223.6(10) 1.703 52.00 0.0592, 0.1085

C23H26Ag1F3O5S2 611.43 173(2) monoclinic P21/n 4 10.1524(6) 19.0883(12) 13.0188(8) 90 94.7100(10) 90 2514.4(3) 1.615 56.60 0.0577, 0.1137

C39H46Cl2Cu4I4O6S4 1571.66 173(2) monoclinic P21/c 4 12.6467(6) 16.1425(7) 24.7042(11) 90 95.8420(10) 90 5017.2(4) 2.081 52.00 0.0378, 0.0924

C41.8H50.8Cl0.4Cu4I4N0.8O6S4 1564.61 173(2) triclinic P1̅ 2 11.9075(5) 12.0382(5) 19.6302(7) 94.0100(10) 94.0810(10) 113.2690(10) 2563.65(18) 2.027 52.00 0.0416, 0.1095

0.1304, 0.2197

0.0512, 0.1225

0.1562, 0.1401

0.0890, 0.1248

0.0730, 0.1243

0.0562, 0.1278

4587 [R(int) = 0.0640]

3744 [R(int) = 0.0512]

4733 [R(int) = 0.1029]

5924 [R(int) = 0.0498]

9850 [R(int) = 0.0479]

9899 [R(int) = 0.0297]

full-matrix

full-matrix 7

full-matrix 8

full-matrix

full-matrix

full-matrix

formula formula weight temperature crystal system space group Z a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) Dcalc (g/cm3) 2θmax (deg) final R indices [I > 2σ(I)] R indices (all data) no. of reflection used [>2σ(I)] refinement

C21H26Cu1I1O3S2 580.98 173(2) orthorhombic Pbca 8 17.1748(10) 14.8738(9) 17.6476(10) 90 90 90 4508.2(5) 1.712 54.00 0.0602, 0.1391 0.0875, 0.1587 4897 [R(int) = 0.0519] full-matrix

C21H26Cu1I1O2S3 597.04 298(2) monoclinic P21/n 4 10.9164(8) 16.9206(12) 12.5108(9) 90 90.6320(10) 90 2310.8(3) 1.716 54.00 0.0382, 0.0748 0.0426, 0.0760 4997 [R(int) = 0.0189] full-matrix

To examine the effect of the donor type on the above reaction type, the synthetic procedure for 3 was repeated employing O2S3-macrocycle L4 instead of O3S2-macrocycle L3. Colorless crystalline product 4 was obtained, and the X-ray analysis reveals that 4 is a discrete cyclic dimer complex [Ag2(L4)2(CF3COO)2] (Figure 4). Because of the existence of an inversion center, the asymmetric unit of 4 contains one L4, one Ag atom, and one trifluoroacetate ion. The selected geometric parameters are presented in Table 4. Each Ag atom is bound to two neighboring sulfur donors from one macrocycle and one sulfur donor from another macrocycle to form a 10membered metallacycle incorporating two Ag atoms, with a convergent/divergent mixed exocyclic coordination mode (Type II-e in Chart 1). The tetrahedral coordination sphere of the Ag atom is completed by an additional bond to a monodentate trifluoroacetate ion. The S−Ag−S bite angles

9

10

11

C21H26Hg1I2O2S3 860.99 173(2) monoclinic P21/n 4 18.1835(8) 7.6700(3) 18.3764(8) 90 92.2010(10) 90 2561.02(19) 2.233 54.00 0.0391, 0.0867 0.0584, 0.0964 5517 [R(int) = 0.0374] full-matrix

C42H52Hg2I4O6S4 1689.86 173(2) triclinic P1̅ 1 8.7385(7) 11.8613(9) 13.8704(11) 108.6610(10) 91.5140(10) 109.8430(10) 1266.42(17) 2.216 52.00 0.0210, 0.0510 0.0234, 0.0520 4909 [R(int) = 0.0195] full-matrix

C25H26Hg2N4O3S6 1024.04 173(2) orthorhombic Pbcn 4 19.8176(13) 11.1889(7) 14.1296(13) 90 90 90 3133.1(4) 2.171 56.84 0.0427, 0.0922 0.0931, 0.1132 3921 [R(int) = 0.0776] full-matrix

around the Ag atom vary from 85.2(1) (S3−Ag1−S2) to 141.9(1) (S1A−Ag1-S3). These large deviations of the angles from the regular tetrahedron are due to the formation of the 5membered and 10-membered metallarings upon complexation. It is interesting to compare the structural patterns of the two complexes 3 and 4. In 3, the dithia ring system allows the divergent exocoordination mode to form a 1D, and further cross-linking by anion generates the resulting fishnet-like 2D structure. The trithia ring system 4 serves the chance to form more Ag−S bonds via the mixed exocoordination mode, and the anion remains as a terminal ligand. The observed donor type effect in the present thiamacrocycles on the resulting topological products is meaningful in terms of the coordination mode-directed approach. Preparation and Structure of the Copper(I) Iodide Complexes (5−8). Four copper(I) iodide complexes 5−8 6271



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Scheme 1. Silver(I) Complexes of L1 with Different Anions

Table 2. Selected Bond Distances (Å) and Bond Angles (deg) for 1 and 2

Figure 1. Mononuclear silver(I) nitrate complex [Ag(L1)NO3] (1) showing an endocyclic coordination mode (Type I).

1

2

Ag1−S1 Ag1−S2 Ag1−O1 Ag1−O2 Ag1−O3 Ag1−O4 Ag1−O5

2.504(2) 2.529(2) 2.853(5) 2.846(5) 2.828(6) 2.616(7) 2.646(6)

2.497(2) 2.520(2) 2.813(6) 2.882(6) 2.718(7)

S1−Ag1−S2 S1−Ag1−O1 S1−Ag1−O2 S1−Ag1−O3 S1−Ag1−O4 S1−Ag1−O5 S2−Ag1−O1 S2−Ag1−O2 S2−Ag1−O3 S2−Ag1−O4 S2−Ag1−O5 O1−Ag1−O2 O1−Ag1−O3 O1−Ag1−O4 O1−Ag1−O5 O2−Ag1−O3 O2−Ag1−O4 O2−Ag1−O5 O3−Ag1−O4 O3−Ag1−O5 O4−Ag1−O5

144.4(1) 77.7(1) 123.3(1) 74.0(1) 128.1(2) 91.8(1) 119.1(1) 76.1(1) 70.5(1) 86.0(2) 108.6(1) 46.3(1) 113.5(2) 87.0(2) 110.4(2) 115.9(1) 66.4(2) 112.8(1) 154.1(2) 129.1(2) 48.1(2)

147.4(1) 77.0(1) 121.6(1) 73.2(2)

122.8(1) 76.8(1) 74.8(2)

46.7(2) 114.0(2)

112.1(2)

macrocycle to form an extended layer structure. The gross framework of 5 can be considered as a wavy square-grid, and the Cu4I4 linkers locate at the nodes of the square-grid framework (Figure 5c,d). Accordingly, four Cu−S bonds between the cubane core and sulfur donors coming from four ligands occupy well separated positions via the divergent exocoordination mode (Type II-b in Chart 1). And the squaregrids formed are tilted and folded to minimize steric hindrance. The preferred 2D structure of 5 is associated with the coordination vectors of the S-donor in each macrocycle around the cubane center oriented almost orthogonally, and this is reflected in the observed layer structure. Next, the reaction of CuI with O 3 S 2 -macrocycle L 2 incorporating a medium cavity (17-membered) yielded emissive product 6 whose X-ray analysis reveals that 6 is 1D polymeric complex {[(Cu4I4)(L2)2]·0.8CH2Cl2·0.2CH3CN}n (Figure 6). Again, the asymmetric unit of the complex part of 6 contains two L2 and one Cu4I4 cubane cluster. The gross framework of 6 can be described as a tubular structure linked with the Cu4I4 cubane unit which locates at the node of the tubular channel (Scheme 3, Figure 6c,d). Similar to the case of 5, each copper atom in the Cu4I4 unit is tetrahedrally coordinated to three μ3-iodide atoms and one sulfur donor of L2. Then, the cubane cores are interconnected by the ligands through Cu−S bonds to produce the 2 + 2 type large metallacycles, which are further pillared by bridging two ligands, leading to the formation of a 1D cylindrical tube with an elliptical channel along the a-axis.

Figure 2. Mononuclear silver(I) tetrafluoroborate complex [Ag(L1)]BF4 (2) showing an endocyclic coordination mode (Type I): (a) cationic complex part and (b) pairwise intermolecular Ag-π and Ag···S interactions. Noncoordinating anion is omitted. Symmetry code: (A) −x + 0.5, −y + 0.5, −z.

with different types of network patterns but same coordination mode (divergent exocoordination mode, Type II-b in Chart 1) were prepared by reaction of each ligand as depicted in Scheme 3. In these reactions, a dichloromethane solution of L1-L4 was allowed to diffuse slowly to an acetonitrile solution of 1 equiv of CuI in a capillary tube. Slow evaporation of the solution afforded the pale yellow crystalline products 5−8 suitable for Xray analysis. First, the reaction of CuI with O 3 S 2 -macrocycle L 1 incorporating a relatively small cavity (16-membered) yielded an emissive product whose X-ray analysis confirms that 5 is a 2D network complex {[(Cu4I4)(L1)2]·CH2Cl2}n (Figure 5). The asymmetric unit of the complex part contains two L1 and one Cu4I4 cubane cluster (Figure 5a). Interestingly, the macrocycles are linked with the Cu4I4 cluster units, whose geometry resembles a distorted cube with alternating vertices of Cu and I atoms. The cubane Cu4I4 unit locates at the center of four macrocycles; the four Cu atoms in each cluster are each tetrahedrally coordinated by an S atom from an adjacent 6272



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Scheme 2. Silver(I) Trifluoroacetate Complexes of L3 and L4

Figure 3. 2D silver(I) trifluoroacetate coordination polymer [Ag(L3)(CF3COO)]n (3) showing a divergent exocyclic coordination mode (Type IIb): (a) core coordination unit, (b) 2D double-deck network, (c) simplified fishnet pattern, and (d) side view of the 2D double-deck network. Symmetry codes: (A) −x + 1, −y, −z + 1; (B) −x + 1.5, y − 0.5, −z + 1.5; (C) −x + 1.5, y + 0.5, −z + 1.5.

The preparation of corresponding CuI complexes with L3 and L4 incorporating a larger cavity (18-membered) were proceeded, and complexes 7 and 8 were obtained, respectively. Complex 7 adopts a 2D network with the formula [(Cu2I2)-

(L3)2]n (Figure 7). The asymmetric unit of the complex part of 7 contains two L3 and one rhomboidal Cu2I2 unit. Each copper atom in the Cu2I2 core is tetrahedrally coordinated to two μ2iodide atoms, and two sulfur donors of two different L3 via 6273



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Table 3. Selected Bond Distances (Å) and Bond Angles (deg) for 3a Ag1−O4A Ag1−O4

2.346(3) 2.494(3)

Ag1−S2 Ag1−S1B

2.445(1) 2.544(1)

O4A−Ag1−S2 S2−Ag1−O4 S2−Ag1−S1B

135.0(1) 112.8(1) 125.8(1)

O4A−Ag1−O4 O4A−Ag1−S1B O4−Ag1−S1B

74.6(1) 94.4(1) 98.9(1)

Table 5. Selected Bond Distances (Å) and Bond Angles (deg) for 5a

Symmetry operations: (A) −x + 1, −y, −z + 1; (B) −x + 3/2, y − 1/ 2, −z + 3/2.

Cu1−S1 Cu3−S2B Cu1−I1 Cu1−I4 Cu2−I2 Cu3−I2 Cu3−I4 Cu4−I2

2.326(2) 2.307(2) 2.715(1) 2.683(1) 2.653(1) 2.733(1) 2.651(1) 2.635(1)

Cu2−S5A Cu4−S3 Cu1−I3 Cu2−I1 Cu2−I3 Cu3−I3 Cu4−I1 Cu4−I4

2.317(2) 2.322(2) 2.659(1) 2.647(1) 2.693(1) 2.705(1) 2.693(1) 2.701(1)

Figure 4. Cyclic dimer structure of silver(I) trifluoroacetate complex [Ag2(L4)2(CF3COO)2] (4) showing a convergent/divergent mixed exocyclic coordination mode (Type II-e): (a) front view and (b) side view. Symmetry code: (A) −x + 1, −y, −z.

S1−Cu1−I1 S1−Cu1−I4 S2B−Cu3−I3 S3−Cu4−I1 S3−Cu4−I4 S5A−Cu2−I2 Cu1−I3−Cu2 Cu1−I4−Cu4 Cu2−I1−Cu4 Cu2−I3−Cu3 Cu3−I4−Cu4 Cu4−I2−Cu2 I1−Cu2−I2 I1−Cu4−I4 I2−Cu4−I1 I3−Cu1−I1 I3−Cu3−I2 I4−Cu3−I2

103.2(1) 107.5(1) 105.2(1) 102.1(1) 107.9(1) 109.1(1) 64.1(1) 63.3(1) 64.5(1) 59.4(1) 61.9(1) 65.3(1) 108.0(1) 112.9(1) 107.1(1) 108.3(1) 114.6(1) 110.9(1)

S1−Cu1−I3 S2B−Cu3−I2 S2B−Cu3−I4 S3−Cu4−I2 S5A−Cu2−I1 S5A−Cu2−I3 Cu1−I3−Cu3 Cu2−I1−Cu1 Cu2−I2−Cu3 Cu3−I4−Cu1 Cu4−I1−Cu1 Cu4−I2−Cu3 I1−Cu2−I3 I2−Cu2−I3 I2−Cu4−I4 I3−Cu1−I4 I4−Cu1−I1 I4−Cu3−I3

112.6(1) 100.7(1) 113.1(1) 114.0(1) 108.1(1) 104.1(1) 61.0(1) 64.0(1) 59.5(1) 61.3(1) 62.9(1) 61.7(1) 109.4(1) 117.8(1) 112.5(0) 112.1(1) 112.8(1) 111.7(1)

a

a Symmetry operations: (A) x, −y + 1/2, z + 1/2; (B) −x, y+1/2, −z + 1/2.


a

Ag1−O3 Ag1−S3

2.459(6) 2.558(2)

Ag1−S1A Ag1−S2

2.481(2) 2.681(2)

O3−Ag1−S1A S1A−Ag1−S3 S1A−Ag1−S2

108.6(2) 141.9(1) 127.1(1)

O3−Ag1−S3 O3−Ag1−S2 S3−Ag1−S2

92.7(2) 83.8(2) 85.2(1)

together with the steric effect (hindrance) between the ligands may, in part, induce the formation of the well-ordered 2D structure. Some other examples of the layered copper(I) halide complexes with thiamacrocycles have been reported by us10 and others.11 It is also interesting to compare the influence of ring size and donor type of the macrocycles L1−L4 on the respective structures of CuI complexes 5−8. Despite such variations, all four macrocycles behave as bidentate ligands toward two different copper atoms via Cu−S bonds with a divergent exocoordination mode (Type II-b in Chart 1). So, except L2, the assembly reactions gave 2D coordination polymers in which their connectivity patterns are similar due to the preference of the tetrahedral geometry of the CunIn (n = 2 or 4) clusters formed. The observed coordination modes and connectivity patterns appear to reflect both the formations of the CunIn clusters and their preferential coordination to the sulfur donors in the thiamacrocycle system. However, it is hard to explain the ring size effect on the dimensionalities of the resulting networks with the possible exocoordination modes proposed. Some of the copper(I) halide complexes are luminescent.12 So, the solid state photoluminescence studies were carried out for 5−8 at room temperature. Upon irradiation by UV light (λex = 365 nm), both of 5 and 6 exhibit bright green emission (λem = 533 nm) in the solid state due to the cluster-centered excited state with mixed halide-to-metal charge transfer character (Figure 9).13 Complexes 7 and 8 were found to be nonemissive. Preparation and Structures of Mercury(II) Complexes (9−11). On complexation with mercury(II) salts (iodide and

Symmetry operation: (A) −x + 1, −y, −z.

Cu−S bonds with a divergent exocoordination mode (Type IIb in Chart 1, Figure 7a). Since the Cu2I2 linker locates at the node of the grid framework (Figure 7b), the gross geometry of 7 has a square-grid connectivity and also can be described as a brick walk pattern (Figure 7c) with a double-deck structure (Figure 7b,d). The complexation of CuI with the trithia system L4 gave nonemissive product 8, and the X-ray analysis reveals that 8 is a 2D polymeric network with the formula [(Cu2I2)(L4)2]n (Figure 8). The asymmetric unit of 8 contains two L4 and one Cu2I2 cluster unit. The network of 8 also involves the rhomboidal Cu2I2 core bonded to four ligands in the doubledeck via Cu−S bonds with a divergent exocoordination mode (Type II-e in Chart 1) (Figure 8a,b). One sulfur atom in the middle of three sulfur segment remains unbound. So, the fishnet-like gross geometry of 8 (Figure 7c) is similar to that of 3 (Figure 3c). A single net unit of 8 contains four asymmetric units where each ligand is interconnected by the Cu2I2 linking units, alternately. The repulsive interaction among sulfur donors in the trithia ring L4 provides the torsion angles between two neighboring sulfur atoms being indicative of antiarrangement. Such conformation of trithiamacrocycle L4 6274



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a

Cu1−S4 Cu3−S3B Cu1−I2 Cu1−I4 Cu2−I2 Cu3−I1 Cu3−I4 Cu4−I2

2.312(2) 2.313(2) 2.630(1) 2.661(1) 2.692(1) 2.727(1) 2.642(1) 2.708(1)

Cu2−S2A Cu4−S1 Cu1−I3 Cu2−I1 Cu2−I4 Cu3−I3 Cu4−I1 Cu4−I3

2.317(2) 2.299(2) 2.787(1) 2.625(1) 2.689(1) 2.694(1) 2.817(1) 2.598(1)

S2A−Cu2−I1 S2A−Cu2−I4 S1−Cu4−I2 S4−Cu1−I2 S4−Cu1−I4 S3B−Cu3−I3 Cu1−I2−Cu2 Cu1−I4−Cu2 Cu2−I1−Cu4 Cu3−I1−Cu4 Cu3−I4−Cu1 Cu4−I3−Cu1 I1−Cu2−I2 I2−Cu1−I3 I2−Cu4−I1 I3−Cu4−I1 I4−Cu1−I3 I4−Cu3−I1

108.1(1) 100.8(1) 109.2(1) 120.3(1) 107.4(1) 99.3(1) 62.7(1) 62.3(1) 61.1(1) 58.2(1) 63.0(1) 59.9(1) 115.3(1) 111.3(1) 108.7(1) 114.2(1) 110.4(1) 108.4(1)

S2A−Cu2−I2 S1−Cu4−I1 S1−Cu4−I3 S4−Cu1−I3 S3B−Cu3−I1 S3B−Cu3−I4 Cu1−I2−Cu4 Cu2−I1−Cu3 Cu2−I2−Cu4 Cu3−I3−Cu1 Cu3−I4−Cu2 Cu4−I3−Cu3 I1−Cu2−I4 I2−Cu1−I4 I3−Cu3−I1 I3−Cu4−I2 I4−Cu2−I2 I4−Cu3−I3

111.3(1) 90.7(1) 116.6(1) 92.2(1) 101.2(1) 119.3(1) 60.6(1) 63.0(1) 61.8(1) 60.7(1) 63.3(1) 61.3(1) 110.1(1) 113.3(1) 114.0(1) 114.9(1) 110.4(1) 114.0(1)


a

Hg1−I1 Hg1−S2

2.657(1) 2.675(1)

Hg1−I2 Hg1−S1A

2.673(1) 2.824(1)

I1−Hg1−I2 I2−Hg1−S2 I2−Hg1−S1A

129.3(1) 99.8(1) 113.0(1)

I1−Hg1−S2 I1−Hg1−S1A S2−Hg1−S1A

123.9(1) 98.2(1) 82.8(1)

Symmetry operation: (A) −x, −y + 1, −z + 2.

Scheme 3. Copper(I) Iodide Complexes of L1−L4

Symmetry operations: (A) −x + 1, −y, −z; (B) x − 1, y, z.

Table 7. Selected Bond Distances (Å) and Bond Angles (deg) for 7a Cu1−S2 Cu1−I1B

2.296(2) 2.660(1)

Cu1−S1A Cu1−I1

2.310(2) 2.664(1)

S2−Cu1−S1A S1A−Cu1−I1B S1A−Cu1−I1

127.6(1) 106.4(1) 103.0(1)

S2−Cu1−I1B S2−Cu1−I1 I1B−Cu1−I1

104.9(1) 101.4(1) 113.7(1)

Symmetry operations: (A) −x + 3/2, y + 1/2, z; (B) −x + 1, −y + 1, −z + 1. a

Table 8. Selected Bond Distances (Å) and Bond Angles (deg) for 8a Cu1−S1A Cu1−I1B

2.294(1) 2.640(1)

Cu1−S3 Cu1−I1

2.349(1) 2.647(1)

S1A−Cu1−S3 S3−Cu1−I1B S3−Cu1−I1

108.4(1) 104.2(1) 100.0(1)

S1A−Cu1−I1B S1A−Cu1−I1 I1B−Cu1−I1

119.8(1) 109.9(1) 112.4(2)

Symmetry operations: (A) −x + 3/2, y + 1/2, −z + 3/2; (B) −x + 1, −y + 2, −z + 2. a

thiocyanate), three supramolecular complexes (9−11) were obtained for L3 and L4 as depicted in Scheme 4. Slow diffusion of a dichloromethane solution of L3 into an acetonitrile solution of mercury(II) iodide afforded a colorless crystalline product 9. The X-ray analysis reveals that 9 is a cyclic dimer complex [Hg2(L3)2I4] (Figure 10). Selected geometric parameters are presented in Table 10. The asymmetric unit of 9 contains one L3, one mercury atom, and one iodide ion. Similar

to 4, two exocyclic Hg atoms link the two macrocycles via Hg− S bonds with a divergent exocoordination mode (Type II-b in Chart 1) to form a cyclic dimer type M2L2 complex. The coordination geometry of each Hg atom is tetrahedral with two coordination sites being occupied by two S donors from two different macrocycles to form a 16-membered metallacycle. The mercury(II) coordination is completed by two iodide ions. 6275



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Figure 5. 2D coordination polymer {[(Cu4I4)(L1)2]·CH2Cl2}n (5) showing a divergent exocyclic coordination mode (Type II-b): (a) core coordination unit, (b) coordination environment of the Cu4I4 cubane linker, (c) 2D polymeric network, and (d) simplified 2D wavy square-grid pattern. Noncoordinating solvent molecule is omitted. Symmetry codes: (A) x, −y + 0.5, z + 0.5; (B) −x, y + 0.5, −z + 0.5; (C) −x, y − 0.5, −z + 0.5; (D) x, −y + 0.5, z − 0.5.

Figure 6. 1D coordination polymer {[(Cu4I4)(L2)2]·0.8CH2Cl2·0.2CH3CN}n (6) showing a divergent exocyclic coordination mode (Type II-b): (a) core coordination unit, (b) coordination environment of the Cu4I4 cubane linker, (c) 1D tubular structure, and (d) cross section of the tube. Noncoordinating solvent molecules are omitted. Symmetry codes: (A) −x + 1, −y, −z; (B) x − 1, y − 1, z; (C) x + 1, y + 1, z.

S distance 5.789(1) Å] toward two different Hg atoms than that of the O donor (O3) which remains uncoordinated. To examine the role of donor in the formation of mercury(II) iodide complexes, the reaction was repeated with L4, and the complex 10 was isolated. Unlike 9, complex 10 is a simple mononuclear species with the formula [Hg(L4)I2]

Bond angles around Hg atom vary from 82.8(1)° (S2−Hg1− S1A) to 129.3(1)° (I1−Hg1−I2) mainly due to the larger steric hindrance between two iodide ions in the coordination sphere. The unusual exocyclic dimer complex 9 seems to be obtained because of higher affinity of the far separated two S donors [S··· 6276



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Figure 7. 2D coordination polymer [(Cu2I2)(L3)2]n (7) showing a divergent exocyclic coordination mode (Type II-b): (a) core coordination unit, (a) top view of the 2D network with a double-deck structure, (c) simplified brick walk pattern, and (d) side view of the double-deck network. Symmetry codes: (A) −x + 1.5, y + 0.5, z; (B) −x + 1, −y + 1, −z + 1; (C) −x + 1.5, y − 0.5, z.

with the corresponding values [2.5−2.8 Å] for related systems;14 they are slightly shorter than those for Hg−SSCN (av. 2.470 Å). The Hg atom is five-coordinate, being bound to one sulfur atom of L3 and four thiocyanate ions via two Hg− SSCN and two Hg−NSCN bonds. The coordination geometry can best be described as a distorted trigonal bipyramid with one S donor of L3, two S atoms from two thiocyanate ions defining the trigonal plane and the axial positions occupied by two N atoms from additional two thiocyanate ions [∠N1B−Hg1− N2A 166.3(1)°], with the macrocycle adopting a highly folded configuration. Also, the oxygen atom (O2) between two sulfur donors remains uncoordinated. The 2D network in this case appears to be dominated by the presence of a linear Hg1-(μ1,3-SCN)2-Hg1 repeating unit with the flexible L3 acting as a bridging component via its exocoordinated sulfur donor sites which are bound orthogonally to the mercury-containing chain. Previously, we reported one structure incorporating infinite Hg(II) bridging thiocyanato chains that are linked in a similar manner by dithiamacrocycle with tribenzo-subunit.14

(Figure 11). The Hg atom which lies outside the cavity is fourcoordinate, being bound by two neighboring sulfur donors (S1 and S2) and another sulfur donor (S3) remains uncoordinated showing an unsymmetrical exocoordination mode (Type II-d in Chart 1). Instead two iodide ions occupy the remaining sites to form a distorted tetrahedral environment, with tetrahedral angles falling in the range 78.0(1)° (S1−Hg1−S2) to 134.7(1)° (I1−Hg1−I2). The large deviations are due to formation of the five-membered chelate ring via Hg−S bonds and also the larger repulsive interaction between two iodide ions in the coordination sphere. In 10, the preferred unsymmetrical exocyclic mononuclear structure is mainly due to the shorter sulfur-to-sulfur distance [S1···S2 distance, 3.456(3) Å] by the replacement of one oxygen donor (O3 in L3) in 9 with one sulfur (S2). Comparing the structures of 9 and 10 serves a good case for the control of resulting topologies depending on the sulfur-to-sulfur distance through the donor type effect in the analogous macrocycles. In addition, the treatment of L3 with mercury(II) thiocyanate in same condition afforded a 2D polymeric complex [Hg2(L3)(SCN)4]n (11) (Figure 12a). The asymmetric unit of 11 contains a half molecule of L3, one mercury atom, and two thiocyanate ions. The 2D network of 11 is made up the 1D “looped” backbones composed of Hg1-(μ1,3-SCN)2-Hg1 repeating units (Figure 12b). These linear “looped” chains are further cross-linked by L3 via Hg−S(thioether) bonds with a divergent exocoordination mode (Type II-b in Chart 1), yielding the 2D framework. Thus, the gross geometry of 11 can be described as a brick wall pattern (Figure 12c). The Hg− S(thioether) bond length [Hg1−S1 2.546(2) Å] agree well

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CONCLUSION This work present the synthesis and structural characteristics of a range of discrete and continuous metallosupramolecules of dithia- and trithiamacrocycles incorporating dibenzo-subunit mainly based on the exocyclic coordination. The observed exocoordination behaviors for the thiamacrocycle systems are discussed in terms of the exomodes approach proposed. Some structures of the isolated products based on the different 6277



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Figure 8. 2D coordination polymer [(Cu2I2)(L4)2]n (8) showing a divergent exocyclic coordination mode (Type II-b): (a) core coordination unit, (a) top view of the 2D network with a double-deck structure, (c) simplified fishnet pattern, and (d) side view of the double-deck network. Symmetry codes: (A) −x + 1.5, y + 0.5, −z + 1.5; (B) −x + 1, −y + 2, −z + 2; (C) −x + 1.5, y − 0.5, −z + 1.5.

Figure 9. Solid state photoluminescence spectra of (a) 5 and (b) 6 at room temperature (excitation at 365 nm).

the ligand conformations are too complicated to explain with the proposed exomode approach. The controllable endo- or exocoordination is still a challenging task in the area of crystal engineering to more fully understand the methodology of the construction of the new topological products and also to develop associated novel materials.

exocoordination types are readily influenced by several factors such as donor type effect, interdonor distance, and size/ flexibility of the ring cavities that could easily control. Thus, each or sum of the factor(s) shows a strong relationship with the exocoordination mode to give the specific resulting product. As an example for the donor type effect, O3S2- and O2S3macrocycles afforded a 2D network and a cyclic dimer via a divergent and a convergent/divergent mixed exomode, respectively. In the above example, the interdonor distance (S···S) also can be a controlling factor to give different products with the convergent or the divergent exomodes. The O3S2macrocycles with 16−18 membered ring sizes resulted in the formations of a 1D or a 2D networks via the divergent exomode; however, the different dimensionalities depending on

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EXPERIMENTAL SECTION

General Methods. All commercial reagents including solvents were of analytical reagent grade where available. NMR spectra were recorded on a Bruker Advance 300 spectrometer (300 MHz). The FTIR spectra were measured with a Nicolet iS 10 spectrometer. The mass spectra were obtained on a Thermo Scientific LCQ spectrometer. The elemental analysis was carried out on a LECO CHNS-932 elemental analyzer. Melting points are uncorrected. 6278



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Scheme 4. Mercury(II) Complexes of L3 and L4

Table 11. Selected Bond Distances (Å) and Bond Angles (deg) for 11a Hg1−S1 Hg1−S3 Hg1−N2B

2.546(2) 2.441(3) 2.709(1)

Hg1−S2 Hg1−N1A

2.498(2) 2.588(1)

S1−Hg1−S2 S1−Hg1−N1C S2−Hg1−S3 S2−Hg1−N2B S3−Hg1−N2B

106.1(1) 84.8(2) 123.9(1) 101.0(1) 80.3(1)

S1−Hg1−S3 S1−Hg1−N2B S2−Hg1−N1A S3−Hg1−N1A N1A−Hg1−N2B

129.9(1) 88.4(1) 92.3(2) 95.1(2) 166.3(1)

Symmetry operations: (A) −x + 3/2, y + 1/2, z; (B) −x + 3/2, y − 1/2, z.

a

Figure 11. Mononuclear mercury(II) iodide complex [Hg(L4)I2] (10) showing an unsymmetrical convergent exocyclic coordination mode (Type II-d): (a) front view and (b) side view. mg, 0.055 mmol) in dichloromethane (2 mL). Slow evaporation of the solution gave colorless crystalline product suitable for X-ray analysis. Yield: 87%. Mp 228−230 °C (decomp.). IR (KBr pellet) 2922, 2863, 1507, 1490, 1457, 1419, 1300, 1254, 1219, 1188, 1164, 1117, 1084 (BF4−), 998, 966, 753, 669, 533, 521 cm−1. Anal. Calcd for [C19H22AgBF4O3S2]: C, 40.96; H, 3.98; S, 11.51. Found: C, 40.46; H, 4.21; S, 11.65%. MS (ESI) m/z: 469.58 [Ag(L1)]+. Preparation of 3, [Ag(L3)(CF3COO)]n. Silver(I) tetrafluoroacatate (13.6 mg, 0.062 mmol) in methanol (2 mL) was added to a solution of L3 (20.0 mg, 0.051 mmol) in dichloromethane (2 mL). The colorless precipitate obtained was separated and dissolved in acetonitrile. Slow evaporation of the acetonitrile solution afforded colorless crystalline product that proved suitable for X-ray analysis. Yield: 50%. Mp 214− 216 °C (decomp.). IR (KBr pellet) 2951, 2930, 2867, 1667 (CF3COO−), 1599, 1496, 1472, 1455, 1418, 1291, 1243, 1196, 1131, 1108, 1056, 1048, 958, 834, 762, 753, 721, 668 cm−1. Anal. Calcd for [C23H26AgF3O5S2]: C, 45.18; H, 4.29; S, 10.49. Found: C, 44.14; H, 4.21; S, 10.32%. Preparation of 4, [Ag2(L4)2(CF3COO)2]. Silver tetrafluoroacatate (13.0 mg, 0.059 mmol) in methanol (2 mL) was added to a solution of L4 (20.0 mg, 0.049 mmol) in dichloromethane (2 mL). The colorless precipitate obtained was separated and dissolved in acetonitrile. Slow evaporation of the acetonitrile solution afforded colorless crystalline product that proved suitable for X-ray analysis. Yield: 75%. Mp 185− 187 °C. IR (KBr pellet) 2925, 2875, 1673 (CF3COO−), 1598, 1587, 1491, 1473, 1456, 1418, 1328, 1291, 1251, 1229, 1207, 1166, 1126, 1101, 1101, 1058, 1024, 963, 831, 798, 752, 719, 678, 571, 519 cm−1. Anal. Calcd for [C46H52Ag2F6O8S6]: C, 44.02; H, 4.18; S, 15.33. Found: C, 43.95; H, 4.11; S, 15.68%. MS (ESI) m/z: 513.75 [Ag(L4)]+. Preparation of 5, {[(Cu4I4)(L1)2]·CH2Cl2}n. A dichloromethane (2 mL) solution of L3 (20.0 mg, 0.053 mmol) was allowed to diffuse slowly into a acetonitrile (2 mL) solution of CuI (22.3 mg, 0.117 mmol) in a capillary tube (i.d. 5 mm). The pale yellow single crystals suitable for X-ray analysis were obtained in the tube. Yield: 80%. Mp 213-215 °C. IR (KBr pellet) 2969, 2923, 2866, 1653, 1598, 1587, 1559, 1491, 1449, 1419, 1291, 1243, 1187, 1162, 1107, 1063, 945, 748, 669 cm−1. Anal. Calcd for [C40H48Cu4I4O6S4]: C, 31.71; H, 3.19; S, 8.47. Found: C, 31.98; H, 3.26; S, 8.47%.

Figure 10. Cyclic dimer structure of mercury(II) iodide complex [Hg2(L3)2I4] (9) showing a divergent exocyclic coordination mode (Type II-b): (a) from view and (b) side view.

Table 10. Selected Bond Distances (Å) and Bond Angles (deg) for 10 Hg1−I2 Hg1−S1

2.654(1) 2.739(2)

Hg1−I1 Hg1−S2

2.672(1) 2.755(2)

I2−Hg1−I1 I1−Hg1−S1 I1−Hg1−S2

134.7(1) 101.7(1 101.2(1)

I2−Hg1−S1 I2−Hg1−S2 S1−Hg1−S2

114.7(1) 111.7(1) 78.0(1)

Preparation of 1, [Ag(L1)NO3]. Silver(I) nitrate (11.3 mg, 0.067 mmol) in methanol (2 mL) was added to L1 (20.0 mg, 0.055 mmol) in dichloromethane (2 mL). A fine powder, which precipitated from the solution, was filtered off. Slow evaporation of the solution afforded crystalline product suitable for X-ray analysis. Yield: 83%. Mp 216− 228 °C (decomp.). IR (KBr pellet) 2924, 2855, 1589, 1507, 1491, 1457, 1411, 1384 (NO3−), 1299, 1253, 1226, 1186, 1162, 1122, 1101, 1079, 1044, 1005, 769, 754, 689, 652 cm−1. Anal. Calcd for [C19H22AgNO6S2]: C, 42.86; H, 4.17; N, 2.63; S, 12.05. Found: C, 42.46; H, 4.15; N, 2.64; S, 12.68%. MS (ESI) m/z: 469.67 [Ag(L1)]+. Preparation of 2, [Ag(L1)]BF4. Silver(I) tetrafluoroborate (12.9 mg, 0.067 mmol) in methanol (2 mL) was added to a solution of L1 (20.0 6279



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Figure 12. 2D mercury(II) thiocyanate coordination polymer [Hg2(L3)(SCN)4]n (11) showing a divergent exocyclic coordination mode (Type IIb): (a) core coordination unit and (b) 2D brick wall network. Symmetry codes: (A) −x + 1.5, y + 0.5, z; (B) −x + 1.5, y − 0.5, z; (C) −x + 2, y, −z + 0.5. Preparation of 6, {[(Cu4I4)(L2)2]·0.8CH2Cl2·0.2CH3CN}n. A dichloromethane (2 mL) solution of L1 (20.0 mg, 0.055 mmol) was allowed to diffuse slowly into an acetonitrile (2 mL) solution of CuI (23.1 mg, 0.122 mmol) in a capillary tube (i.d. 5 mm). The pale yellow single crystals suitable for X-ray analysis were obtained in the tube. Yield: 85%. Mp 207−209 °C. IR (KBr pellet) 2922, 2856, 1601, 1587, 1489, 1456, 1419, 1219, 1163, 1184, 1100, 1047, 1013, 750, 669 cm−1. Anal. Calcd for [C39.2H46.2Cl0.8Cu4I4N0.2O6S4]: C, 30.68; H, 3.03; S, 8.36. Found: C, 30.10; H, 2.92; S, 8.52%. Preparation of 7, [(Cu2I2)(L3)2]n. A dichloromethane (2 mL) solution of L3 (20.0 mg, 0.051 mmol) was allowed to diffuse slowly into an acetonitrile (2 mL) solution of CuI (21.5 mg, 0.113 mmol) in a capillary tube (i.d. F5 mm). The pale yellow single crystals suitable for X-ray analysis were obtained in the tube. Yield: 87%. Mp 203−205 °C. IR (KBr pellet) 2919, 2877, 1653, 1598, 1559, 1492, 1473, 1455, 1419, 1395, 1290, 1246, 1235, 1186, 1158, 1104, 1042, 1012, 754, 668, 616 cm−1. Anal. Calcd for [C42H52Cu2I2O6S4]: C, 43.41; H, 4.51; S, 11.04. Found: C, 43.26; H, 4.28; S, 10.99%. Preparation of 8, [(Cu2I2)(L4)2]n. A dichloromethane (2 mL) solution of L4 (20.0 mg, 0.049 mmol) was allowed to diffuse slowly into an acetonitrile (2 mL) solution of CuI (20.6 mg, 0.109 mmol) in a capillary tube (i.d. 5 mm). The pale yellow single crystals suitable for X-ray analysis were obtained in the tube. Yield: 88%. Mp 211−213 °C. IR (KBr pellet) 2921, 1598, 1491, 1473, 1453, 1419, 1290, 1244, 1100, 1047, 991, 958, 751 cm−1. Anal. Calcd for [C42H52Cu2I2O4S6]: C, 42.24; H, 4.39; S, 16.11. Found: C, 41.80; H, 4.51; S, 16.37%. Preparation of 9, [Hg2(L3)2I4]. A dichloromethane (2 mL) solution of L3 (20.0 mg, 0.051 mmol) was allowed to diffuse slowly into a methanol (2 mL) solution of HgI2 (27.9 mg, 0.062 mmol) in a capillary tube (i.d. 5 mm). The colorless single crystals suitable for Xray analysis were obtained in the tube. Yield: 85%. Mp 155−157 °C. IR (KBr pellet) 2957, 2926, 2878, 1598, 1493, 1472, 1454, 1395, 1315, 1289, 1251, 1110, 1054, 1045, 1032, 958, 755, 683, 668 cm−1. Anal. Calcd for [C42H52Hg2I4O6S4]: C, 29.85; H, 3.10; S, 7.59. Found: C, 29.83; H, 3.09; S, 7.74%. MS (ESI) m/z: 718.67 [Hg(L)I]+. Preparation of 10, [Hg(L4)I2]. A dichloromethane (2 mL) solution of L4 (20.0 mg, 0.049 mmol) was allowed to diffuse slowly into a methanol (2 mL) solution of HgI2 (26.8 mg, 0.059 mmol) in a capillary tube (i.d. 5 mm). The colorless single crystals suitable for Xray analysis were obtained in the tube. Yield: 88%. Mp 188−190 °C. IR (KBr pellet) 2950, 2916, 2868, 1975, 1585, 1491, 1475, 1466, 1454, 1272, 1247, 1239, 1208, 1119, 1096, 1058, 1045, 1025, 958, 849, 748, 669 cm−1. Anal. Calcd for [C21H26HgI2O2S3]: C, 29.29; H, 3.04; S, 11.17. Found: C, 29.26; H, 3.01; S, 11.46%. MS (ESI) m/z: 734.98 [Hg(L)I]+. Preparation of 11, [Hg2(L3)(SCN)4]n. A dichloromethane (2 mL) solution of L3 (20.0 mg, 0.051 mmol) was allowed to diffuse slowly into a methanol (2 mL) solution of Hg(SCN)2 (35.7 mg, 0.112 mmol) in a capillary tube (i.d. 5 mm). The pale yellow single crystals suitable for X-ray analysis were obtained in the tube. Yield: 83%. Mp 179−181

°C. IR (KBr pellet) 2924, 2113 (SCN−), 1653, 1559, 1491, 1456, 1291, 1247, 1107, 1057, 751, 668 cm −1 . Anal. Calcd for [C25H26Hg2N4O3S6]: C, 29.32; H, 2.56; N, 5.47; S, 18.79. Found: C, 29.39; H, 2.52; N, 5.55; S, 19.28%. X-ray Crystallographic Analysis. All diffraction data, except that for 11, were measured on a Bruker SMART CCD diffractometer equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å). The cell parameters for the compounds were obtained from a least-squares refinement of the spot (from 45 collected frames) using the SMART program. The intensity data were processed using the Saint Plus program. All of the calculations for the structure determination were carried out using the SHELXTL package (version 6.22).15 Absorption corrections were applied using XPREP and SADABS.16 The diffraction data for 11 were collected on a Bruker SMART APEX II ULTRA diffractometer equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å) generated by a rotating anode. The cell parameters for the compounds were obtained from a leastsquares refinement of the spot (from 36 collected frames). Data collection, data reduction, and semiempirical absorption correction were carried out using the software package of APEX2.17 All of the calculations for the structure determination were carried out using the SHELXTL package.18 In all cases, all non-hydrogen atoms were refined anisotropically, and all hydrogen atoms except coordinated water molecules were placed in idealized positions and refined isotropically in a riding manner along with the their respective parent atoms. Relevant crystal data collection and refinement data for the crystal structures of 1−11 are summarized in Table 1.

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ASSOCIATED CONTENT

S Supporting Information *

PXRD patterns. Crystallographic data in CIF format and additional crystal structures. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by NRF (2012R1A4A1027750 and 2013R1A2A2A01067771), South Korea. REFERENCES

(1) (a) Lindoy, L. F.; Meehan, G. V.; Vasilescu, I. M.; Kim, H. J.; Lee, J.-E.; Lee, S. S. Coord. Chem. Rev. 2010, 254, 1713. (b) Lindoy, L. F.

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