Synthesis and crystal structure of oktakis(dimethylsulphoxide-κ1O)gadolinium(III) [tetrabromido-μ2-bromido-μ2-sulfido-di-μ3-sulfido-μ4-sulfido-tetracopper(I)-tungsten(VI)], C16H48O8S12Br5Cu4GdW

Yunfeng Ye; Guodong Tang; Jun Qian

doi:10.1515/ncrs-2020-0591

Open Access Published by De Gruyter (O) January 8, 2021

Synthesis and crystal structure of oktakis(dimethylsulphoxide-κ¹O)gadolinium(III) [tetrabromido-μ₂-bromido-μ₂-sulfido-di-μ₃-sulfido-μ₄-sulfido-tetracopper(I)-tungsten(VI)], C₁₆H₄₈O₈S₁₂Br₅Cu₄GdW

Yunfeng Ye , Guodong Tang and Jun Qian

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2020-0591

Abstract

C₁₆H₄₈O₈S₁₂Br₅Cu₄GdW, monoclinic, P2₁ (no. 4), a = 11.576(2) Å, b = 12.407(3) Å, c = 17.582(3) Å, β = 100.76(3)°, V = 2480.8(9) Å³, Z = 2, R_gt(F) = 0.0446, wR_ref(F²) = 0.1169, T = 293 K.

CCDC no.: 2035932

The asymmetric unit of the title crystal structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Red block
Size:	0.22 × 0.20 × 0.18 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	9.87 mm⁻¹
Diffractometer, scan mode:	Rigaku Satum 724⁺, φ and ω
θ_max, completeness:	25.3°, 99%
N(hkl)_measured, N(hkl)_unique, R_int:	11490, 6878, 0.039
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 5277
N(param)_refined:	441
Programs:	Bruker [1], Olex2 [2], SHELX [3], [4], PLATON [5]

Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²).

Atom	x	y	z	U_iso*/U_eq
W1	0.13443 (8)	0.68772 (7)	0.22458 (5)	0.0190 (2)
Gd1	0.70752 (8)	0.11726 (8)	0.25551 (5)	0.0101 (2)
Br1	0.2800 (2)	0.40576 (19)	0.19271 (14)	0.0314 (6)
Br2	−0.0621 (2)	0.4782 (2)	−0.00076 (12)	0.0313 (6)
Br3	0.1677 (2)	0.3866 (2)	0.40569 (13)	0.0346 (6)
Br4	0.3093 (2)	0.9085 (2)	0.44834 (13)	0.0331 (6)
Br5	0.5191 (2)	0.6317 (2)	0.15024 (16)	0.0419 (7)
Cu1	0.0359 (3)	0.5647 (2)	0.10787 (16)	0.0277 (7)
Cu2	0.2326 (3)	0.8057 (2)	0.34381 (15)	0.0254 (7)
Cu3	0.1726 (3)	0.4957 (2)	0.29721 (16)	0.0301 (7)
Cu4	0.3324 (2)	0.6116 (3)	0.18259 (14)	0.0296 (7)
S1	−0.0014 (5)	0.5616 (5)	0.2278 (3)	0.0273 (14)
S2	0.1739 (5)	0.6942 (5)	0.1051 (3)	0.0230 (12)
S3	0.0713 (6)	0.8458 (5)	0.2569 (3)	0.0333 (16)
S4	0.3005 (5)	0.6438 (4)	0.3107 (3)	0.0239 (14)
S5	0.9700 (5)	0.2369 (5)	0.2094 (3)	0.0257 (13)
S6	0.5886 (7)	0.3314 (7)	0.1352 (4)	0.051 (2)
S7	0.7256 (5)	0.3572 (4)	0.3575 (3)	0.0219 (13)
S8	0.5144 (5)	0.0969 (5)	0.3867 (3)	0.0252 (13)
S9	0.4426 (5)	0.0275 (5)	0.1384 (3)	0.0273 (14)
S10	0.6509 (5)	−0.1509 (5)	0.2963 (4)	0.0290 (14)
S11	0.8701 (5)	0.0728 (5)	0.4390 (3)	0.0259 (14)
S12	0.8253 (5)	−0.0393 (5)	0.1190 (3)	0.0273 (14)
O1	0.5167 (12)	0.0431 (12)	0.2195 (8)	0.023 (3)
O2	0.6066 (14)	0.1624 (12)	0.3527 (8)	0.028 (4)
O3	0.7315 (14)	0.3021 (12)	0.2804 (8)	0.025 (4)
O4	0.8647 (12)	0.1598 (12)	0.1975 (8)	0.025 (4)
O5	0.6180 (13)	0.2084 (12)	0.1425 (8)	0.028 (4)
O6	0.8637 (12)	0.1245 (13)	0.3617 (8)	0.025 (3)
O7	0.7073 (12)	−0.0475 (11)	0.3282 (8)	0.022 (3)
O8	0.7409 (13)	−0.0267 (12)	0.1788 (8)	0.027 (4)
C1	1.018 (2)	0.227 (2)	0.1202 (12)	0.038 (7)
H1A	1.0177	0.1527	0.1048	0.057*
H1B	1.0958	0.2557	0.1255	0.057*
H1C	0.9655	0.2671	0.0815	0.057*
C2	0.5945 (18)	0.4310 (19)	0.3366 (12)	0.026 (5)
H2A	0.5890	0.4657	0.2873	0.039*
H2B	0.5939	0.4845	0.3760	0.039*
H2C	0.5289	0.3832	0.3352	0.039*
C3	0.717 (2)	0.392 (2)	0.1086 (16)	0.052 (8)
H3A	0.6966	0.4615	0.0858	0.078*
H3B	0.7456	0.3468	0.0720	0.078*
H3C	0.7770	0.4005	0.1540	0.078*
C4	0.496 (3)	0.340 (3)	0.0408 (18)	0.080 (11)
H4A	0.4987	0.4118	0.0211	0.120*
H4B	0.4166	0.3223	0.0448	0.120*
H4C	0.5234	0.2901	0.0064	0.120*
C5	0.367 (3)	−0.090 (3)	0.1463 (18)	0.069 (9)
H5A	0.2901	−0.0735	0.1558	0.103*
H5B	0.4089	−0.1323	0.1884	0.103*
H5C	0.3602	−0.1305	0.0990	0.103*
C6	0.324 (3)	0.115 (3)	0.1360 (19)	0.080 (10)
H6A	0.2979	0.1127	0.1848	0.120*
H6B	0.2603	0.0935	0.0955	0.120*
H6C	0.3473	0.1872	0.1263	0.120*
C7	0.804 (2)	−0.1801 (18)	0.0862 (13)	0.031 (6)
H7A	0.8474	−0.2270	0.1247	0.046*
H7B	0.8320	−0.1887	0.0385	0.046*
H7C	0.7221	−0.1979	0.0784	0.046*
C8	0.741 (2)	0.024 (2)	0.0360 (14)	0.045 (7)
H8A	0.6708	−0.0166	0.0181	0.067*
H8B	0.7866	0.0282	−0.0043	0.067*
H8C	0.7202	0.0959	0.0494	0.067*
C9	0.989 (2)	−0.020 (2)	0.4446 (13)	0.040 (7)
H9A	0.9594	−0.0896	0.4270	0.060*
H9B	1.0301	−0.0253	0.4973	0.060*
H9C	1.0425	0.0049	0.4126	0.060*
C10	0.593 (3)	−0.207 (2)	0.3762 (16)	0.053 (8)
H10A	0.6515	−0.2042	0.4225	0.080*
H10B	0.5705	−0.2811	0.3649	0.080*
H10C	0.5248	−0.1669	0.3835	0.080*
C11	0.945 (2)	0.1663 (19)	0.5045 (12)	0.037 (7)
H11A	1.0037	0.2018	0.4818	0.056*
H11B	0.9812	0.1299	0.5509	0.056*
H11C	0.8899	0.2187	0.5167	0.056*
C12	0.818 (2)	0.4654 (18)	0.3621 (14)	0.030 (6)
H12A	0.8965	0.4406	0.3605	0.044*
H12B	0.8189	0.5040	0.4095	0.044*
H12C	0.7920	0.5123	0.3190	0.044*
C13	1.099 (2)	0.160 (2)	0.2627 (13)	0.051 (8)
H13A	1.1091	0.1752	0.3170	0.077*
H13B	1.1685	0.1803	0.2439	0.077*
H13C	1.0854	0.0839	0.2545	0.077*
C14	0.400 (2)	0.197 (2)	0.3917 (15)	0.052 (7)
H14A	0.4166	0.2334	0.4407	0.078*
H14B	0.3248	0.1616	0.3863	0.078*
H14C	0.3973	0.2485	0.3507	0.078*
C15	0.5746 (19)	0.089 (2)	0.4881 (11)	0.029 (6)
H15A	0.6482	0.0509	0.4955	0.044*
H15B	0.5208	0.0507	0.5140	0.044*
H15C	0.5869	0.1600	0.5092	0.044*
C16	0.769 (2)	−0.238 (2)	0.2994 (18)	0.054 (8)
H16A	0.8319	−0.2016	0.2823	0.081*
H16B	0.7444	−0.2989	0.2661	0.081*
H16C	0.7943	−0.2634	0.3515	0.081*

Source of material

A mixture of 0.0570 g CuBr (0.4 mmol), 0.0474 g KBr (0.4 mmol) and 0.0350 g (NH₄)₂WS₄ (0.1 mmol) were added to 3 mL DMSO with strong stirring to obtain an orange solution. After that, 0.0343 g Gd(NO₃)₃ (0.1 mmol) was quickly added in this mixed solution and stirred for 30 min to get a deep red solution. After filtration, 1 mL DMSO was successively added on the top of the above filtrate as buffer solution. Subsequently, 5 mL of isopropyl alcohol was layered carefully on the buffer DMSO solution. Orange crystals were obtained after 10 days at room temperature in dark with a yield of 0.104 g (60% based W).

Experimental details

The structure was solved by direct methods and refined using the SHELX software [3]. All of the hydrogen atoms were placed in the calculated positions (see Table 2).

Comment

Heterothiometallic Mo(W)/S/Cu(Ag) clusters have attracted much attention because of their intriguing skeletal structures and topologies [6], [7], as well as the potential applications in non-linear optical (NLO) materials [8], [9] NLOs are of great interest due to their multifunctional applications in optical fibers, ultrafast optical communication, optical computing, logic devices, optical switching, and optical limiting [10], [11], [12]. As a result, considerable efforts in crystal engineering have been devoted to the design and syntheses of various kinds of Mo(W)/S/Cu(Ag) clusters with unique NLO properties [13], [14], [15], [16]. Until now, many Mo(W)/S/Cu(Ag) clusters have been synthesized to achieve a variety of structures, which origin from the assembly of (NH₄)₂MS₄ (M = Mo, W) or (NH₄)₂MOS₃ (M = Mo, W) precursors with different cuprous salts or silver salts [17]. To further study the structure-activity relationship of Mo(W)/S/Cu(Ag) clusters, here we introduced CuBr as the cuprous salt and prepared a semi-open cubic cluster with extra side.

As shown in the figure, the asymmetric unit of the title structure consists of the anion [WS₄Cu₄Br₅]³⁻ and the cation [Gd(DMSO)₈]³⁺. The Gd(III) cation is coordinated by O atoms from eight DMSO molecules. The anion is a cluster, which contains three differently coordinated sulfido ligands (μ₂–S, μ₃–S and μ₄–S), two differently bonded bromido ligands (μ₂–Br and terminal Br), and three different coordination environments for the Cu(I) centers. Cu1 is coordinated by two μ₃–S atoms and one terminal Br in a T-shaped mode and connected with two Cu atoms and W through two μ₃–S bridges. Cu2 is coordinated with one μ₂–S, one μ₄–S and a terminal Br in a planar triangular mode. Cu3 and Cu4 have the same coordination environment, in which the Cu center is coordinated with one μ₃–S, one μ₄–S, one μ₂–Br and one terminal Br atom to form a distorted tetrahedral coordination configuration. The W(VI) is 4-coordinated by four S atoms, displaying a distorted tetrahedron. The whole structure of title cluster exhibits a semi-open cubic cluster with an additional face, which is different to the common pentanuclear cluster [18].

Corresponding author: Jun Qian, School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang, Jiangsu, 212013, P. R. China, E-mail: junqian8203@ujs.edu.cn

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 51602130

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: National Natural Science Foundation of China (grant No. 51602130).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

1. BRUKER. SAINT, APEX2 and SADABS; Bruker AXS Inc.: Madison, Wisconsin, USA, 2009.Search in Google Scholar

2. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339–341; https://doi.org/10.1107/s0021889808042726.Search in Google Scholar

3. Sheldrick, G. M. SHELXT - integrated space-group and crystal-structure determination. Acta Crystallogr. 2015, A71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar

4. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar

5. Spek, A. L. Single-crystal structure validation with the program PLATON. J. Appl. Crystallogr. 2003, 36, 7–13; https://doi.org/10.1107/s0021889802022112.Search in Google Scholar

6. Zhang, C., Song, Y. L., Wang, X. Correlations between molecular structures and third-order nonlinear optical functions of heterothiometallic clusters: a comparative study. Coord. Chem. Rev. 2007, 251, 111–141; https://doi.org/10.1016/j.ccr.2006.06.007.Search in Google Scholar

7. Zhang, C., Cao, Y., Zhang, J. F., Meng, S. C., Matsumoto, T., Song, Y. L., Ma, J., Chen, Z. X., Tatsumi, K., Humphrey, M. G. Modulation of third-order nonlinear optical properties by backbone modification at polymeric pillared-layer heterometallic clusters. Adv. Mater. 2008, 20, 1870–1875; https://doi.org/10.1002/adma.200702645.Search in Google Scholar

8. Cariati, E., Macchi, R., Roberto, D., Ugo, R., Galli, S., Casati, N., Macchi, P., Sironi, A., Bogani, L., Caneschi, A., Gatteschi, D. Polyfunctional inorganic-organic hybrid materials: an unusual kind of NLO active layered mixed metal oxalates with tunable magnetic properties and very large second harmonic generation. J. Am. Chem. Soc. 2007, 129, 9410–9420; https://doi.org/10.1021/ja0710712.Search in Google Scholar

9. Cariati, E., Macchi, R., Roberto, D., Ugo, R., Galli, S., Masciocchi, N., Sironi, A. The surface of inorganic oxides or zeolites as a nonconventional reaction medium for the selective synthesis of metal carbonyl complexes and clusters. Chem. Mater. 2007, 19, 3704–3711; https://doi.org/10.1021/cm071003e.Search in Google Scholar

10. Beheshti, A., Clegg, W., Nobakht, V., Harrington, R. W. Metal-to-ligand ratio as a design factor in the one-pot synthesis of coordination polymers with [MS4Cun] (M = W or Mo, n = 3 or 5) cluster nodes and a flexible pyrazole-based bridging ligand. Cryst. Growth Des. 2013, 13, 1023–1032; https://doi.org/10.1021/cg301106g.Search in Google Scholar

11. Zhang, J. F., Liu, Y. H., Feng, J. Y., Gong, L. P., Humphrey, M. G., Zhang, C. Decanuclear cluster-based metal-organic framework with a (3,11)-connected topology and highly sensitive 2,4,6-trinitrophenol detection. Inorg. Chem. 2019, 58, 9749–9755; https://doi.org/10.1021/acs.inorgchem.9b00745.Search in Google Scholar

12. Dini, D., Calvete, M. J. F., Hanack, M. Nonlinear optical materials for the smart filtering of optical radiation. Chem. Rev. 2016, 116, 13043–13233; https://doi.org/10.1021/acs.chemrev.6b00033.Search in Google Scholar

13. Zhang, J. F., Jia, D., Humphrey, M. G., Meng, S. C., Zaworotko, M. J., Cifuentes, M. P., Zhang, C. Ammonium-crown ether supramolecular cation-templated assembly of an unprecedented heterobicluster-metal coordination polymer with enhanced NLO properties. Chem. Commun. 2016, 52, 3797–3800; https://doi.org/10.1039/c5cc10076c.Search in Google Scholar

14. Lu, Z. Z., Zhang, R., Pan, Z. R., Li, Y. Z., Guo, Z. J., Zheng, H. G. Metal-organic frameworks constructed from versatile WS4Cux(x-2) units: micropores in highly interpenetrated systems. Chem. Eur J. 2012, 18, 2812–2824; https://doi.org/10.1002/chem.201101963.Search in Google Scholar

15. Chen, X., Li, H. X., Zhang, Z. Y., Zhao, W., Lang, J. P., Abrahams, B. F. Activation and amplification of the thirdorder NLO and luminescent responses of a precursor cluster by a supramolecular approach. Chem. Commun. 2012, 48, 4480–4482; https://doi.org/10.1039/c2cc30581j.Search in Google Scholar

16. Lang, J. P., Xu, Q. T., Yuan, R. X., Abrahams, B. F. {[WS4Cu4(4,4′-bpy)]4[WS4Cu4I4(4,4′-bpy)2]}∞ — an unusual 3D porous coordination polymer formed from the preformed cluster [Et4N]4WS4Cu4I6. Angew. Chem. Int. Ed. 2004, 43, 4741–4745; https://doi.org/10.1002/anie.200460076.Search in Google Scholar

17. Zhang, J. F., Meng, S. C., Song, Y. L., Zhou, Y. M., Cao, Y., Li, J. H., Zhao, H. J., Hu, J. C., Wu, J. H., Humphrey, M. G., Zhang, C. Syntheses, structural, theoretical, and nonlinear optical studies of non-interpenetrating three-dimensional nest-shaped-cluster MoOS3Cu3-based coordination polymers. Cryst. Growth Des. 2011, 11, 100–109; https://doi.org/10.1021/cg1009779.Search in Google Scholar

18. Wang, H. M., Han, Y., Niu, Y. Y., Zhang, Z. H., Hou, H. W., Zhu, Y. External template-assisted self-assembly: design and synthesis of the [MoOS3Cu3]+ based supramolecular polymeric clusters. CrystEngComm 2012, 14, 3125–3130; https://doi.org/10.1039/c2ce06518e.Search in Google Scholar

Received: 2020-11-10

Accepted: 2020-12-15

Published Online: 2021-01-08

Published in Print: 2021-03-26

This work is licensed under the Creative Commons Attribution 4.0 International License.