Bis(dimethyl sulfoxide-κO)tetra­kis­(μ2-3,4,5-tri­meth­oxy­benzoato-κ2O:O′)dizinc

Deutsch, D.; Zevaco, T.; Walter, O.

doi:10.1107/S1600536813023118

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page m519

doi:10.1107/S1600536813023118

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Bis(dimethyl sulfoxide-κO)tetrakis(μ₂-3,4,5-trimethoxybenzoato-κ²O:O′)dizinc

Diana Deutsch,^a Thomas Zevaco ^a and Olaf Walter ^a ^*

^aIKFT, KIT-Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
^*Correspondence e-mail: olaf.walter@kit.edu

(Received 10 May 2013; accepted 17 August 2013; online 23 August 2013)

The colourless title complex, [Zn₂(C₁₀H₁₁O₅)₄(C₂H₆OS)₂], crystallizes with one half-molecule in the asymmetric unit, the other half of the molecule being generated by a crystallographic inversion center. The structure shows a μ₂-O:O′-bridging mode of the four 3,4,5-trimethoxybenzoate ligands finally stabilizing the two Zn^II atoms in the dinuclear complex in a distorted square-pyramidal environment. The fifth coordination site in the apical position of the pyramid is occupied by a coordinating dimethyl sulfoxide solvent molecule equally disordered over two positions.

Related literature

For the structures of (μ₂-benzoato-κO,O′)(dimethylsulfoxide-κO)dizinc complxes with no more additional ligands, see: Pham et al. (2008 ); Reger et al. (2011 ); Tao (2002 ); Yang et al. (2005 ); Zevaco et al. (2007 ).

Experimental

Crystal data

[Zn₂(C₁₀H₁₁O₅)₄(C₂H₆OS)₂]
M_r = 1131.75
Monoclinic, C 2/c
a = 18.854 (2) Å
b = 13.937 (2) Å
c = 19.249 (2) Å
β = 90.082 (3)°
V = 5058.0 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 200 K
0.6 × 0.4 × 0.4 mm

Data collection

Siemens SMART CCD 1000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.555, T_max = 1
29984 measured reflections
6234 independent reflections
4049 reflections with I > 2σ(I)
R_int = 0.121

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.164
S = 1.03
6234 reflections
378 parameters
19 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XPMA (Zsolnai, 1996 ) and ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813023118/kj2227sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023118/kj2227Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813023118/kj2227Isup3.mol

checkCIF report

Comment top

In bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc the two Zn(ii) ions are embedded in a distorted square pyramidale environment. Four 3,4,5-trimethoxybenzoato-ligands are forming four µ₂-O,O'-bridges between the two Zn-atoms. The coordination number is completed by a dmso solvent molecule in apical position. The Zn—O bond distances are determined in the range between 2.019 (3) Å and 2.042 (3) Å for the carboxylato-O atoms whereas the Zn—O bond distance to the coordinated solvent molecule is significantly shorter with 1.966 (3) Å. These findings are in accordance with the literature data for the so-called paddle-wheel structures formed by complexes of the type bis(dimethylsulfoxide-κO)tetrakis(µ₂-carboxylato-O,O')dizinc. In Pham et al. (2008) the Zn—O bond distances to carboxylato-O atoms are determined to in the mean 2.046 (3) Å whereas the Zn—O (dmso) bond distance is significantly shorter with 1.984 (3) Å. In Reger et al. (2011) Zn—O bond distances between 2.032 (2) and 2.051 (2) Å or of 197.2 (2) and 197.4 (2) Å are reported. In Tao et al. (2002) and Yang et al. (2005) these findings are confirmed furthermore: the corresponding Zn—O distances to the coordinated dmso are significantly shorter with 1.982 (3) Å or with 1.970 (2) and 1.981 (2) Å than those for the corresponding Zn—O bond lengths concerning the carboxylato groups (2.012 (2)–2.064 (3) Å). Changes in the coordination number of the central Zn(ii) ion like e.g. in Zevaco et al. (2007) influences significantly the Zn—O bond distances: for the Zn atom in a distorted tetrahedral environment Zn—O (carboxylato) bond lengths are found to be shorter with 1.933 (2) Å whereas they are determined to 2.073 (2) - 2.122 (2) Å for a Zn-atom in distorted octahedral coordination geometry. The structural features of bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc with the two Zn(ii) ions in a distorted square-pyramidal environment with their here reported bond lengths fit well within the in the literature reported related complexes.

Related literature top

For the structures of (µ₂-benzoato-κO,O')(dimethylsulfoxide-κO)dizinc(II) complexes with no more additional ligands, see: Pham et al. (2008); Reger et al. (2011); Tao (2002); Yang et al. (2005); Zevaco et al. (2007).

Experimental top

bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc is obtained from the reaction of 2.0 g (24.6 mmol) zinc oxide and 10.43 g (49.2 mmol) of 3,4,5-trimethoxybenzoic acid in water under refluxing for 4 h. The solvent is evaporated until formation of a white powder which was filtered off and dissolved in 150 ml DMSO at ca 120° C. The solution was filtered and allowed to cool down to RT. The solvent was evaporated slowly. Single crystals of bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc are isolated in 70% yield.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: XPMA (Zsolnai, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. View of the molecular structure of bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc; ellipsoids at 50% probability level (Symmetry codes: -x + 0.5, -y + 1.5,-z + 1).

Bis(dimethyl sulfoxide-κO)tetrakis(µ₂-3,4,5-trimethoxybenzoato-κ²O:O')dizinc top

Crystal data top

[Zn₂(C₁₀H₁₁O₅)₄(C₂H₆OS)₂]	F(000) = 2352
M_r = 1131.75	D_x = 1.486 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.854 (2) Å	Cell parameters from 6943 reflections
b = 13.937 (2) Å	θ = 2.4–26.0°
c = 19.249 (2) Å	µ = 1.11 mm⁻¹
β = 90.082 (3)°	T = 200 K
V = 5058.0 (11) Å³	Quader, colourless
Z = 4	0.6 × 0.4 × 0.4 mm

Data collection top

Siemens SMART CCD 1000 diffractometer	6234 independent reflections
Radiation source: fine-focus sealed tube	4049 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.121
Detector resolution: 8 pixels mm^-1	θ_max = 28.4°, θ_min = 1.8°
ω scan	h = −25→25
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −18→18
T_min = 0.555, T_max = 1	l = −25→24
29984 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0719P)² + 9.9666P] where P = (F_o² + 2F_c²)/3
6234 reflections	(Δ/σ)_max < 0.001
378 parameters	Δρ_max = 0.64 e Å⁻³
19 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Zn₂(C₁₀H₁₁O₅)₄(C₂H₆OS)₂]	V = 5058.0 (11) Å³
M_r = 1131.75	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.854 (2) Å	µ = 1.11 mm⁻¹
b = 13.937 (2) Å	T = 200 K
c = 19.249 (2) Å	0.6 × 0.4 × 0.4 mm
β = 90.082 (3)°

Data collection top

Siemens SMART CCD 1000 diffractometer	6234 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	4049 reflections with I > 2σ(I)
T_min = 0.555, T_max = 1	R_int = 0.121
29984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	19 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.64 e Å⁻³
6234 reflections	Δρ_min = −0.79 e Å⁻³
378 parameters

Special details top

Experimental. Spectroscopic data: ¹H{³¹P} NMR (dmso D₆): δ = 7.18, s, 1H, CH(arom); 3.72, s, 6H, OCH₃; 3.62, s, 3H, OCH₃; ¹³C{¹H} NMR (dmso D₃): δ = 172.0; 152.7; 140.4; 130.4; 107.1; 60.6; 56.2; IR [cm^-1]: 2995 (m); 2940 (m); 2837 (m); 1622 (m); 1577 (s); 1520 (s); 1464 (m); 1396 (versus); 1228 (s); 1127 (versus); 1000 (m); 786 (s); 759 (w); 733 (m)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. XRD measurements were performed on a Siemens SMART CCD 1000 diffractometer with monochromated Mo Kα-irradiation collecting a full sphere of data in the θ–range from 1.82 to 28.36°. 1674 frames were collected with an irradiation time of 10 s per frame and ω–scan technique with Δω = 0.45°. The data were integrated with SAINT and corrected to Lorentz and polarization effects and a numerical adsorption correction with SADABS was applied. The structure was solved by direct methods and refined to an optimum R₁ value with SHELXL. Visualization for evaluation was performed with XPMA and figures were created with ORTEP. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. [tetrakis(µ₂-3,4,5-trimethoxybenzoato-O,O')-bis(dimethylsulfoxide-O)-di-\ zinc(ii)] shows in its structure a 1:1 disorder at the following positions: C8, C18, C21, c22. The first two mentioned C atoms make part of two methoxy substituents whereas the last two mentioned C atoms represent a disorder in the coordinated dmso solvent molecule. Refinement of the disordered parts of the molecules has been performed using the 'same distance' restraint in order to resolve the disorders in a chemically correct manner. The data of the structure have been deposited at the CCDC with the reference number 865280.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.24683 (2)	0.64467 (3)	0.49759 (2)	0.02114 (14)
O1	0.28914 (16)	0.6564 (2)	0.59493 (14)	0.0376 (7)
O2	0.29608 (16)	0.8154 (2)	0.59516 (14)	0.0397 (7)
O3	0.4123 (3)	0.8959 (3)	0.82388 (19)	0.0800 (14)
O4	0.4061 (2)	0.7307 (3)	0.89858 (18)	0.0728 (13)
O5	0.35347 (18)	0.5704 (2)	0.84426 (15)	0.0482 (8)
O6	0.14999 (15)	0.6644 (2)	0.53982 (17)	0.0421 (8)
O7	0.15605 (15)	0.8236 (2)	0.54213 (16)	0.0390 (7)
O8	−0.0668 (3)	0.9179 (3)	0.6706 (3)	0.121 (2)
O9	−0.14597 (19)	0.7596 (3)	0.6733 (2)	0.0750 (13)
O10	−0.09936 (16)	0.5933 (2)	0.62088 (17)	0.0476 (8)
O11	0.24529 (16)	0.5055 (2)	0.48119 (17)	0.0442 (8)
C1	0.30386 (19)	0.7354 (3)	0.6224 (2)	0.0265 (8)
C2	0.3325 (2)	0.7336 (3)	0.6957 (2)	0.0298 (9)
C3	0.3596 (2)	0.8172 (3)	0.7236 (2)	0.0400 (11)
H3	0.3603	0.8734	0.6975	0.033 (8)*
C4	0.3856 (3)	0.8163 (4)	0.7910 (2)	0.0520 (13)
C5	0.3835 (3)	0.7325 (3)	0.8304 (2)	0.0468 (12)
C6	0.3549 (2)	0.6487 (3)	0.8021 (2)	0.0352 (9)
C7	0.3299 (2)	0.6497 (3)	0.73393 (19)	0.0290 (8)
H7	0.3115	0.5941	0.7142	0.033 (8)*
C8	0.416 (2)	0.9766 (12)	0.7778 (13)	0.18 (2)	0.5
H8A	0.4454	0.9605	0.7386	0.150*	0.5
H8B	0.4368	1.0302	0.8020	0.150*	0.5
H8C	0.3696	0.9932	0.7621	0.150*	0.5
C8X	0.3946 (18)	0.9896 (9)	0.7979 (12)	0.103 (9)	0.5
H8D	0.4173	1.0376	0.8259	0.150*	0.5
H8E	0.3441	0.9984	0.7996	0.150*	0.5
H8F	0.4104	0.9954	0.7507	0.150*	0.5
C9	0.4808 (4)	0.7422 (4)	0.9088 (3)	0.084 (2)
H9A	0.5057	0.7195	0.8686	0.18 (2)*
H9B	0.4955	0.7060	0.9488	0.18 (2)*
H9C	0.4914	0.8089	0.9160	0.18 (2)*
C10	0.3126 (3)	0.4904 (3)	0.8213 (3)	0.0568 (14)
H10A	0.2643	0.5100	0.8144	0.050 (8)*
H10B	0.3143	0.4406	0.8556	0.050 (8)*
H10C	0.3316	0.4668	0.7783	0.050 (8)*
C11	0.1254 (2)	0.7454 (3)	0.55252 (19)	0.0285 (8)
C12	0.0531 (2)	0.7492 (3)	0.5848 (2)	0.0311 (8)
C13	0.0284 (3)	0.8346 (3)	0.6115 (3)	0.0543 (14)
H13	0.0555	0.8902	0.6081	0.055 (10)*
C14	−0.0370 (3)	0.8365 (4)	0.6436 (4)	0.0678 (18)
C15	−0.0792 (2)	0.7542 (4)	0.6456 (3)	0.0510 (13)
C16	−0.0545 (2)	0.6694 (3)	0.6170 (2)	0.0346 (10)
C17	0.0122 (2)	0.6669 (3)	0.5871 (2)	0.0303 (9)
H17	0.0296	0.6099	0.5685	0.055 (10)*
C18	−0.0156 (8)	0.9929 (11)	0.6886 (11)	0.105 (7)	0.5
H18A	0.0263	0.9640	0.7076	0.150*	0.5
H18B	−0.0362	1.0354	0.7222	0.150*	0.5
H18C	−0.0034	1.0285	0.6476	0.150*	0.5
C18X	−0.0416 (9)	1.0071 (7)	0.6374 (11)	0.125 (10)	0.5
H18D	−0.0647	1.0612	0.6583	0.150*	0.5
H18E	−0.0525	1.0053	0.5887	0.150*	0.5
H18F	0.0087	1.0127	0.6436	0.150*	0.5
C19	−0.1488 (4)	0.7388 (4)	0.7465 (3)	0.083 (2)
H19A	−0.1422	0.6712	0.7537	0.16 (2)*
H19B	−0.1941	0.7577	0.7646	0.16 (2)*
H19C	−0.1120	0.7736	0.7701	0.16 (2)*
C20	−0.0818 (3)	0.5103 (3)	0.5803 (3)	0.0539 (13)
H20A	−0.0760	0.5286	0.5326	0.080 (11)*
H20B	−0.1193	0.4639	0.5839	0.080 (11)*
H20C	−0.0384	0.4828	0.5973	0.080 (11)*
S1	0.28196 (19)	0.41693 (19)	0.50269 (16)	0.0463 (8)	0.5
C21	0.2543 (11)	0.4155 (12)	0.5903 (6)	0.063 (4)	0.5
H21A	0.2050	0.3983	0.5925	0.41 (13)*	0.5
H21B	0.2609	0.4779	0.6102	0.41 (13)*	0.5
H21C	0.2818	0.3694	0.6157	0.41 (13)*	0.5
C22	0.3713 (4)	0.4506 (6)	0.5154 (4)	0.036 (2)	0.5
H22A	0.3945	0.4560	0.4712	0.048 (15)*	0.5
H22B	0.3949	0.4029	0.5430	0.048 (15)*	0.5
H22C	0.3731	0.5113	0.5389	0.048 (15)*	0.5
S1X	0.28535 (16)	0.4397 (2)	0.5380 (2)	0.0522 (8)	0.5
C21X	0.2680 (8)	0.3248 (7)	0.5050 (8)	0.106 (6)	0.5
H21D	0.2948	0.3152	0.4632	0.200*	0.5
H21E	0.2183	0.3189	0.4948	0.200*	0.5
H21F	0.2814	0.2775	0.5387	0.200*	0.5
C22X	0.2319 (13)	0.4262 (19)	0.6110 (9)	0.108 (8)	0.5
H22D	0.2329	0.4843	0.6379	0.200*	0.5
H22E	0.2493	0.3740	0.6388	0.200*	0.5
H22F	0.1841	0.4129	0.5967	0.200*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0257 (2)	0.0168 (2)	0.0209 (2)	−0.00103 (18)	−0.00125 (15)	0.00041 (18)
O1	0.0544 (19)	0.0325 (16)	0.0259 (14)	−0.0037 (13)	−0.0117 (13)	0.0000 (12)
O2	0.0537 (19)	0.0335 (16)	0.0318 (16)	−0.0030 (14)	−0.0144 (14)	0.0102 (13)
O3	0.135 (4)	0.051 (2)	0.053 (2)	−0.034 (2)	−0.049 (2)	0.0011 (19)
O4	0.106 (3)	0.081 (3)	0.0316 (19)	−0.026 (2)	−0.030 (2)	0.0061 (17)
O5	0.070 (2)	0.0471 (19)	0.0270 (16)	−0.0041 (16)	−0.0104 (15)	0.0134 (14)
O6	0.0342 (16)	0.0344 (17)	0.058 (2)	0.0025 (13)	0.0159 (15)	0.0036 (14)
O7	0.0322 (16)	0.0381 (16)	0.0469 (18)	−0.0089 (13)	0.0113 (14)	−0.0097 (14)
O8	0.084 (3)	0.058 (3)	0.221 (6)	−0.008 (2)	0.099 (4)	−0.045 (3)
O9	0.0320 (18)	0.093 (3)	0.100 (3)	0.0028 (19)	0.027 (2)	−0.003 (2)
O10	0.0393 (17)	0.052 (2)	0.051 (2)	−0.0156 (15)	0.0073 (15)	0.0000 (16)
O11	0.0460 (18)	0.0218 (15)	0.065 (2)	−0.0007 (13)	−0.0023 (16)	−0.0019 (14)
C1	0.0228 (18)	0.032 (2)	0.0244 (19)	−0.0026 (15)	0.0003 (14)	0.0024 (16)
C2	0.029 (2)	0.038 (2)	0.0218 (19)	−0.0023 (16)	−0.0043 (15)	0.0040 (16)
C3	0.054 (3)	0.037 (2)	0.029 (2)	−0.010 (2)	−0.013 (2)	0.0055 (19)
C4	0.075 (4)	0.040 (3)	0.041 (3)	−0.017 (2)	−0.027 (3)	0.002 (2)
C5	0.065 (3)	0.051 (3)	0.024 (2)	−0.010 (2)	−0.015 (2)	0.0036 (19)
C6	0.042 (2)	0.039 (2)	0.024 (2)	−0.002 (2)	−0.0019 (17)	0.0061 (18)
C7	0.033 (2)	0.031 (2)	0.0226 (18)	−0.0009 (17)	−0.0007 (15)	0.0025 (17)
C8	0.40 (5)	0.070 (13)	0.057 (15)	−0.13 (2)	−0.075 (19)	0.016 (10)
C8X	0.21 (2)	0.045 (9)	0.053 (12)	−0.041 (10)	−0.088 (15)	−0.001 (7)
C9	0.107 (6)	0.076 (5)	0.067 (4)	−0.008 (4)	−0.060 (4)	0.001 (3)
C10	0.090 (4)	0.043 (3)	0.038 (3)	−0.019 (3)	−0.003 (3)	0.017 (2)
C11	0.0263 (18)	0.034 (2)	0.0251 (19)	−0.0007 (18)	−0.0027 (15)	−0.0019 (18)
C12	0.0296 (19)	0.037 (2)	0.0272 (19)	0.0007 (19)	0.0032 (15)	0.0012 (18)
C13	0.037 (3)	0.043 (3)	0.083 (4)	−0.009 (2)	0.024 (3)	−0.013 (3)
C14	0.047 (3)	0.052 (3)	0.105 (5)	0.004 (2)	0.037 (3)	−0.019 (3)
C15	0.028 (2)	0.061 (3)	0.064 (3)	0.001 (2)	0.015 (2)	0.004 (3)
C16	0.024 (2)	0.046 (3)	0.034 (2)	−0.0021 (17)	−0.0006 (17)	0.0056 (19)
C17	0.028 (2)	0.037 (2)	0.026 (2)	−0.0003 (16)	−0.0024 (16)	0.0027 (17)
C18	0.073 (11)	0.087 (12)	0.153 (18)	0.007 (9)	0.007 (11)	−0.064 (12)
C18X	0.098 (13)	0.027 (6)	0.25 (3)	−0.001 (7)	0.113 (16)	−0.038 (11)
C19	0.080 (5)	0.068 (4)	0.101 (6)	−0.004 (3)	0.057 (4)	0.003 (4)
C20	0.049 (3)	0.052 (3)	0.061 (3)	−0.022 (2)	−0.004 (3)	0.002 (3)
S1	0.0740 (19)	0.0196 (13)	0.0452 (17)	0.0047 (12)	0.0011 (15)	−0.0029 (11)
C21	0.092 (11)	0.051 (7)	0.047 (9)	−0.008 (7)	0.032 (7)	0.033 (7)
C22	0.047 (5)	0.038 (5)	0.024 (4)	0.020 (4)	−0.007 (4)	−0.001 (3)
S1X	0.0506 (15)	0.0197 (13)	0.086 (3)	0.0076 (11)	0.0008 (19)	0.0125 (16)
C21X	0.148 (15)	0.018 (5)	0.152 (15)	0.011 (7)	0.004 (12)	−0.004 (7)
C22X	0.14 (2)	0.142 (17)	0.047 (10)	0.008 (14)	0.040 (10)	0.048 (10)

Geometric parameters (Å, º) top

Zn1—O11	1.966 (3)	C9—H9A	0.9600
Zn1—O6	2.019 (3)	C9—H9B	0.9600
Zn1—O7ⁱ	2.034 (3)	C9—H9C	0.9600
Zn1—O2ⁱ	2.037 (3)	C10—H10A	0.9600
Zn1—O1	2.042 (3)	C10—H10B	0.9600
Zn1—Zn1ⁱ	2.9399 (9)	C10—H10C	0.9600
O1—C1	1.252 (4)	C11—C12	1.501 (5)
O2—C1	1.240 (4)	C12—C13	1.378 (6)
O2—Zn1ⁱ	2.037 (3)	C12—C17	1.382 (5)
O3—C4	1.372 (6)	C13—C14	1.380 (6)
O3—C8	1.435 (9)	C13—H13	0.9300
O3—C8X	1.439 (9)	C14—C15	1.396 (7)
O4—C5	1.380 (5)	C15—C16	1.384 (6)
O4—C9	1.431 (6)	C16—C17	1.386 (5)
O5—C6	1.360 (5)	C17—H17	0.9300
O5—C10	1.425 (5)	C18—H18A	0.9600
O6—C11	1.244 (5)	C18—H18B	0.9600
O7—C11	1.249 (5)	C18—H18C	0.9600
O7—Zn1ⁱ	2.034 (3)	C18X—H18D	0.9600
O8—C14	1.368 (6)	C18X—H18E	0.9600
O8—C18	1.464 (8)	C18X—H18F	0.9600
O8—C18X	1.476 (8)	C19—H19A	0.9600
O9—C15	1.371 (5)	C19—H19B	0.9600
O9—C19	1.439 (6)	C19—H19C	0.9600
O10—C16	1.358 (5)	C20—H20A	0.9600
O10—C20	1.435 (5)	C20—H20B	0.9600
O11—S1	1.474 (4)	C20—H20C	0.9600
O11—S1X	1.614 (4)	S1—C21	1.765 (9)
C1—C2	1.511 (5)	S1—C22	1.766 (7)
C2—C3	1.381 (6)	C21—H21A	0.9600
C2—C7	1.382 (5)	C21—H21B	0.9600
C3—C4	1.388 (6)	C21—H21C	0.9600
C3—H3	0.9300	C22—H22A	0.9600
C4—C5	1.392 (6)	C22—H22B	0.9600
C5—C6	1.397 (6)	C22—H22C	0.9600
C6—C7	1.394 (5)	S1X—C22X	1.741 (9)
C7—H7	0.9300	S1X—C21X	1.753 (8)
C8—H8A	0.9600	C21X—H21D	0.9600
C8—H8B	0.9600	C21X—H21E	0.9600
C8—H8C	0.9600	C21X—H21F	0.9600
C8X—H8D	0.9600	C22X—H22D	0.9600
C8X—H8E	0.9600	C22X—H22E	0.9600
C8X—H8F	0.9600	C22X—H22F	0.9600

O11—Zn1—O6	100.72 (12)	O6—C11—C12	116.9 (4)
O11—Zn1—O7ⁱ	99.65 (12)	O7—C11—C12	117.1 (4)
O6—Zn1—O7ⁱ	159.55 (13)	C13—C12—C17	121.1 (4)
O11—Zn1—O2ⁱ	97.09 (13)	C13—C12—C11	119.5 (4)
O6—Zn1—O2ⁱ	87.56 (13)	C17—C12—C11	119.3 (4)
O7ⁱ—Zn1—O2ⁱ	88.14 (13)	C12—C13—C14	119.1 (4)
O11—Zn1—O1	103.43 (12)	C12—C13—H13	120.5
O6—Zn1—O1	88.39 (13)	C14—C13—H13	120.5
O7ⁱ—Zn1—O1	88.67 (12)	O8—C14—C13	123.6 (5)
O2ⁱ—Zn1—O1	159.48 (12)	O8—C14—C15	115.9 (4)
O11—Zn1—Zn1ⁱ	172.42 (10)	C13—C14—C15	120.4 (5)
O6—Zn1—Zn1ⁱ	83.57 (8)	O9—C15—C16	120.7 (4)
O7ⁱ—Zn1—Zn1ⁱ	75.99 (9)	O9—C15—C14	119.3 (4)
O2ⁱ—Zn1—Zn1ⁱ	76.73 (9)	C16—C15—C14	119.9 (4)
O1—Zn1—Zn1ⁱ	82.82 (8)	O10—C16—C15	115.8 (4)
C1—O1—Zn1	123.0 (3)	O10—C16—C17	124.7 (4)
C1—O2—Zn1ⁱ	131.5 (3)	C15—C16—C17	119.5 (4)
C4—O3—C8	111.7 (11)	C12—C17—C16	119.9 (4)
C4—O3—C8X	119.2 (9)	C12—C17—H17	120.0
C5—O4—C9	115.6 (5)	C16—C17—H17	120.0
C6—O5—C10	116.9 (3)	O8—C18—H18A	109.5
C11—O6—Zn1	122.7 (3)	O8—C18—H18B	109.5
C11—O7—Zn1ⁱ	131.8 (3)	H18A—C18—H18B	109.5
C14—O8—C18	114.3 (8)	O8—C18—H18C	109.5
C14—O8—C18X	113.6 (7)	H18A—C18—H18C	109.5
C15—O9—C19	113.9 (5)	H18B—C18—H18C	109.5
C16—O10—C20	117.1 (3)	O8—C18X—H18D	109.5
S1—O11—Zn1	140.8 (2)	O8—C18X—H18E	109.5
S1X—O11—Zn1	116.4 (2)	H18D—C18X—H18E	109.5
O2—C1—O1	125.8 (4)	O8—C18X—H18F	109.5
O2—C1—C2	116.9 (3)	H18D—C18X—H18F	109.5
O1—C1—C2	117.3 (3)	H18E—C18X—H18F	109.5
C3—C2—C7	121.4 (4)	O9—C19—H19A	109.5
C3—C2—C1	118.7 (3)	O9—C19—H19B	109.5
C7—C2—C1	119.9 (3)	H19A—C19—H19B	109.5
C2—C3—C4	119.0 (4)	O9—C19—H19C	109.5
C2—C3—H3	120.5	H19A—C19—H19C	109.5
C4—C3—H3	120.5	H19B—C19—H19C	109.5
O3—C4—C3	123.6 (4)	O10—C20—H20A	109.5
O3—C4—C5	116.0 (4)	O10—C20—H20B	109.5
C3—C4—C5	120.4 (4)	H20A—C20—H20B	109.5
O4—C5—C4	121.6 (4)	O10—C20—H20C	109.5
O4—C5—C6	118.3 (4)	H20A—C20—H20C	109.5
C4—C5—C6	120.0 (4)	H20B—C20—H20C	109.5
O5—C6—C7	124.3 (4)	O11—S1—C21	98.0 (6)
O5—C6—C5	116.5 (4)	O11—S1—C22	105.3 (3)
C7—C6—C5	119.2 (4)	C21—S1—C22	98.9 (7)
C2—C7—C6	119.8 (4)	S1—C21—H21A	109.5
C2—C7—H7	120.1	S1—C21—H21B	109.5
C6—C7—H7	120.1	H21A—C21—H21B	109.5
O3—C8—H8A	109.5	S1—C21—H21C	109.5
O3—C8—H8B	109.5	H21A—C21—H21C	109.5
H8A—C8—H8B	109.5	H21B—C21—H21C	109.5
O3—C8—H8C	109.5	S1—C22—H22A	109.5
H8A—C8—H8C	109.5	S1—C22—H22B	109.5
H8B—C8—H8C	109.5	H22A—C22—H22B	109.5
O3—C8X—H8D	109.5	S1—C22—H22C	109.5
O3—C8X—H8E	109.5	H22A—C22—H22C	109.5
H8D—C8X—H8E	109.5	H22B—C22—H22C	109.5
O3—C8X—H8F	109.5	O11—S1X—C22X	109.7 (9)
H8D—C8X—H8F	109.5	O11—S1X—C21X	100.7 (5)
H8E—C8X—H8F	109.5	C22X—S1X—C21X	95.0 (10)
O4—C9—H9A	109.5	S1X—C21X—H21D	109.5
O4—C9—H9B	109.5	S1X—C21X—H21E	109.5
H9A—C9—H9B	109.5	H21D—C21X—H21E	109.5
O4—C9—H9C	109.5	S1X—C21X—H21F	109.5
H9A—C9—H9C	109.5	H21D—C21X—H21F	109.5
H9B—C9—H9C	109.5	H21E—C21X—H21F	109.5
O5—C10—H10A	109.5	S1X—C22X—H22D	109.5
O5—C10—H10B	109.5	S1X—C22X—H22E	109.5
H10A—C10—H10B	109.5	H22D—C22X—H22E	109.5
O5—C10—H10C	109.5	S1X—C22X—H22F	109.5
H10A—C10—H10C	109.5	H22D—C22X—H22F	109.5
H10B—C10—H10C	109.5	H22E—C22X—H22F	109.5
O6—C11—O7	126.0 (4)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₁₀H₁₁O₅)₄(C₂H₆OS)₂]
M_r	1131.75
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	18.854 (2), 13.937 (2), 19.249 (2)
β (°)	90.082 (3)
V (Å³)	5058.0 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.6 × 0.4 × 0.4

Data collection
Diffractometer	Siemens SMART CCD 1000 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.555, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	29984, 6234, 4049
R_int	0.121
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.164, 1.03
No. of reflections	6234
No. of parameters	378
No. of restraints	19
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.79

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), XPMA (Zsolnai, 1996) and ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).

Acknowledgements

The authors gratefully acknowledge financial support for their work from the Karlsruhe Institute for Technology.

References

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