Download citation
Download citation
link to html
The asymmetric unit in the crystal structure of the title compound, [Zn2(C16H14N2S2)2]2·0.18C2H6OS·0.82CH3OH, con­sists of two ordered bis­{[mu]-2,2'-[(butane-2,3-diyl­idene)bis­(aza­nylyl­idene)]di­benzene­thiol­ato}dizinc(II) mol­ecules and a disordered solvent combination at the same location which refined to 18.1 (7)% dimethyl sulfoxide and 81.9 (7)% methanol. The compound has a metallic cluster structure formed by the joining together of two zinc(II) complex mol­ecules, forming a rhomboidal Zn2S2 arrangement. This complex was previously suggested on the basis of nonstructural evidence to be a monomer [Jadamus, Fernando & Freiser (1964). J. Am. Chem. Soc. 86, 3056-3059]. Each ZnII atom is five-coordinated and exhibits distorted trigonal bipyramidal geometry. The structure may be of inter­est with respect to zinc-thiol­ate bonds, the coordination chemistry of Schiff bases and the folding of proteins. The structure displays weak inter­molecular C-H...S, C-H...O and C-H...N inter­actions, and contains a unique bonding arrangement of the ligands around the Zn2S2 rhomboid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023524/sk3509sup1.cif
Contains datablocks I, New_Global_Publ_Block

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023524/sk3509Isup2.hkl
Contains datablock I

CCDC reference: 969446

Introduction top

Bis(benzthia­zolines) undergo rearrangement by certain metal ions to yield a Schiff base chelate (Jadamus et al., 1964). The synthesis of the complex bis­(di­acetyl)­bis­(2-mercaptoanil)zinc(II) or {2,2'-[(butane-2,3-diyl­idene)bis­(aza­nylyl­idene)]di­benzene­thiol­ato}zinc(II), Zn(o-SPhNCMe)2, was reported on the basis of elemental analysis and electronic absorption spectra to result in a monomeric complex consisting of a Schiff base chelated to a metal atom (Jadamus et al., 1964). The structure of the closely related complex Zn(o-SPhNHCHMe).MeOH, for which the solid-state structure had been obtained, was also reported as being monomeric (Tsagkalidis & Rehder, 1996). This complex displayed an S—Zn—S angle of 141.15 (7)° and a hydrogen bond between one of the Zn-coordinated thiol­ate S atoms and the –OH group of the methanol solvent molecule. It was noted that `biologically active zinc sites in enzymes tend to vary between tetra- and penta­coordination in geometrical arrangements largely deviating from ideal polyhedral' (Tsagkalidis & Rehder, 1996). A monomer was also evident in the crystal structure of Zn(o-SPhNHCH2)2 (Shaban, 2011) and this complex did feature an S—Zn—S angle of 138.20 (3)°. The reason for this, in both cases, is probably the twisted nature of the ethyl­enic group which can accommodate the aforementioned large S—Zn—S angle.

Experimental top

Synthesis and crystallization top

The title zinc complex was prepared according to the literature method of Jadamus et al. (1964) resulting in a fibrous red precipitate. Crystals of the material were grown by slow diffusion of methanol into a saturated solution of the compound in a mixture of DMSO and MeOH (1:1 v/v) using a straight glass tube.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The nature of the disordered solvent molecules was discerned via difference maps and the molecules (di­methyl sulfoxide and methanol) were refined with the sum of their occupancies constrained to unity. The O—H distance was restrained to be 0.84 (1) Å, with Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions, with C—H distances of 0.98 and 0.95 Å for aromatic and methyl H atoms, and with Uiso(H) = 1.2Ueq(aromatic C) or 1.5Ueq(methyl C).

Results and discussion top

Crystals of the title compound, bis­{µ-2,2'-[(butane-2,3-diyl­idene)bis­(aza­nylyl­idene)]di­benzene­thiol­ato}dizinc(II)–di­methyl sulfoxide–methanol (2/0.18/0.82), (I), were obtained during our examination of the Zn2+-ion-induced rearrangement of 2,2'-bis­(2-methyl­benzo­thia­zoline) (see Scheme). The IR spectra of the ligand (after washing with H2O2) and that of (I) (Fig. 1), illustrate the disappearance of the ν(NH) stretch at 3387 cm-1, together with slight changes in the fingerprint region of the spectrum. We found that crystals of (I) had limited solubility which hindered characterization in solution.

In contrast to the findings for compounds closely related to Zn(o-SPhNCMe)2, and somewhat in disagreement with the claims that had been put forward for the complex itself in the report of Jadamus et al. (1964), we find that the title compound consists in the solid state of two Schiff base complexes linked together forming a dimeric Zn2S2 rhomboid, with the Zn atoms displaying distorted trigonal bipyramidal geometries (Fig. 2 and Table 2). The axial atoms and the angle for each Zn atom in the molecules are: N1—Zn1—S2 = 157.93 (12)°, N4—Zn2—S3 = 159.75 (12)°, N6—Zn3—S5 = 160.63 (11)° and N8—Zn4—S8 = 160.73 (12)° (Table 2). The τ parameters (a way of estimating the distortion with a perfect square-pyramidal geometry being 0 and trigonal bipyramidal being 1; Addison et al., 1984) for the Zn atoms are not equal, with the values for Zn1 and Zn2 being 0.36 and 0.37, respectively, whereas the values for Zn3 and Zn4 are 0.46 and 0.43, respectively. The equivalent S—Zn—S bond angles to those mentioned above are 115.47 (5), 111.68 (5), 112.05 (5) and 111.50 (5)° for Zn1–Zn4, respectively, and much smaller. These differences result in different orientations of the ligands in the two structures, as is evident in the imprecise overlay presented in Fig. 3. The Zn—S bond lengths within the Zn2S2 rhomboids in the two molecules average from 2.380 (9) and 2.49 (1) Å for the shorter and longer sides, respectively. The Zn—S(bidentate) distances are shorter and average 2.306 (7) Å (Table 2).

Similar to the structure of a related monomer (Tsagkalidis & Rehder, 1996), one of these S atoms, i.e., S6 is hydrogen bonded to a methanol solvent molecule refined to 81.9 (7)% occupancy with 18.1 (7)% occupied by a di­methyl sulfoxide molecule Table 3. The methanol O atom (O1B) is also involved in weak inter­actions with two other H atoms of an adjacent dimer (Table 3). The DMSO solvent molecule is also secured by weak hydrogen-bonding inter­actions, with atom O1A linked to H50 and H28 of adjacent dimers and atom S1A linked to H28. Additional weak inter­actions are also observed between adjacent dimers, as evidenced in the listings for atoms S1, S3 and S7 in Table 3. The acute and obtuse angles within the squares average 87.4 (3) and 92.6 (4)°, respectively, for the S- and Zn-centered angles in Zn1—S2—Zn2—S3, and are slightly more distorted at 86.1 (3) and 93.9 (6)° for the S- and Zn-centered angles in Zn3—S5—Zn4—S8. The two Zn—N bond lengths were significantly different at each Zn atom (Table 2). An intriguing aspect of the two molecules in the asymmetric unit is the fact that the two 2,2'-[(butane-2,3-diyl­idene)bis­(aza­nylyl­idene)]di­benzene­thiol­ate ligands are bonded on the same side (i.e. cis) to one another with respect to the Zn2S2 rhomboid. In this arrangement, there is a C2 axis located perpendicular to the Zn2S2 rhomboid. This is in contrast to other related structures where a trans arrangement, due to a center of inversion in the middle of the rhomboid, was observed (Anselmo et al., 2012; Almaraz et al., 2008; Buncic et al., 2010; Cowley et al., 2002; Shaban, 2011; Tuntulani et al., 1992).

Related literature top

For synthesis, see Jadamus et al. (1964). For discussion of distortion from a square pyramidal geometry to trigonal bipyramidal, see: Addison et al. (1984). For related structures consisting of zinc bonded by S2N2 chelating ligands see Tsagkalidis & Rehder (1996) for a monomer, and for dimers see Anselmo et al. (2012), Almaraz et al. (2008), Buncic et al. (2010), Cowley et al. (2002), Shaban (2011), Tuntulani et al. (1992).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SADABS (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL-2013 (Sheldrick, 2013); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. The FT–IR spectra of 2,2'-bis(2-methylbenzothiazoline) (after washing with H2O2) and the title complex, (I).
[Figure 2] Fig. 2. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
[Figure 3] Fig. 3. POV-RAY-rendered Mercury (Macrae et al., 2008) drawing of the two independent molecules in the asymmetric unit of (I), with the Zn4, S8, Zn3, and S5 atoms from one molecule, i.e. an overlay of the Zn2S2 cores (light; red in the electronic version of the paper), overlayed with the Zn1, S2, Zn2 and S3 atoms of the other molecule (dark; blue).
Bis{µ-2,2'-[(butane-2,3-diylidene)bis(azanylylidene)]dibenzenethiolato}dizinc(II)–dimethyl sulfoxide–methanol (2/0.18/0.82) top
Crystal data top
[Zn2(C16H14N2S2)2]2·0.18C2H6OS·0.82CH4OZ = 2
Mr = 1495.4F(000) = 1532.7
Triclinic, P1Dx = 1.611 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 11.757 (4) ÅCell parameters from 5099 reflections
b = 16.145 (6) Åθ = 2.2–28.3°
c = 17.376 (6) ŵ = 1.87 mm1
α = 92.254 (5)°T = 100 K
β = 91.897 (6)°Plate, colorless
γ = 110.427 (5)°0.25 × 0.23 × 0.01 mm
V = 3084.6 (19) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer
15164 independent reflections
Radiation source: sealed x-ray tube10524 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
ω scansθmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1515
Tmin = 0.654, Tmax = 0.746k = 2121
37532 measured reflectionsl = 2323
Refinement top
Refinement on F27 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.066H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + 12.0817P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
15164 reflectionsΔρmax = 0.73 e Å3
814 parametersΔρmin = 0.81 e Å3
Crystal data top
[Zn2(C16H14N2S2)2]2·0.18C2H6OS·0.82CH4Oγ = 110.427 (5)°
Mr = 1495.4V = 3084.6 (19) Å3
Triclinic, P1Z = 2
a = 11.757 (4) ÅMo Kα radiation
b = 16.145 (6) ŵ = 1.87 mm1
c = 17.376 (6) ÅT = 100 K
α = 92.254 (5)°0.25 × 0.23 × 0.01 mm
β = 91.897 (6)°
Data collection top
Bruker SMART APEX CCD
diffractometer
15164 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
10524 reflections with I > 2σ(I)
Tmin = 0.654, Tmax = 0.746Rint = 0.067
37532 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0667 restraints
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + 12.0817P]
where P = (Fo2 + 2Fc2)/3
15164 reflectionsΔρmax = 0.73 e Å3
814 parametersΔρmin = 0.81 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.77100 (5)0.12340 (4)0.55796 (3)0.01389 (12)
Zn20.97449 (5)0.32972 (4)0.59098 (3)0.01453 (13)
N10.6854 (4)0.0531 (3)0.4533 (2)0.0137 (8)
N20.6109 (4)0.1590 (3)0.5387 (2)0.0128 (8)
N30.8779 (4)0.3881 (3)0.5159 (2)0.0137 (8)
N40.9705 (4)0.4426 (3)0.6570 (2)0.0137 (8)
S10.80927 (12)0.00491 (8)0.58078 (7)0.0170 (3)
S20.80970 (12)0.22695 (8)0.66511 (7)0.0152 (3)
S30.93968 (12)0.22249 (8)0.48562 (7)0.0150 (2)
S41.16690 (12)0.36639 (9)0.64742 (8)0.0195 (3)
C10.8038 (5)0.0362 (3)0.4821 (3)0.0164 (10)
C20.8652 (5)0.0926 (3)0.4576 (3)0.0198 (11)
H20.90880.11330.49460.024*
C30.8629 (5)0.1186 (4)0.3795 (3)0.0258 (13)
H30.90350.15760.36380.031*
C40.8017 (5)0.0874 (4)0.3256 (3)0.0248 (12)
H40.8010.10450.27260.03*
C50.7413 (5)0.0317 (3)0.3478 (3)0.0201 (11)
H50.70210.00890.30970.024*
C60.7370 (4)0.0084 (3)0.4257 (3)0.0150 (10)
C70.5944 (4)0.0695 (3)0.4247 (3)0.0140 (10)
C80.5121 (5)0.0234 (3)0.3568 (3)0.0174 (11)
H8A0.54060.05570.31050.026*
H8B0.42930.02130.36580.026*
H8C0.51250.0370.34960.026*
C90.5660 (4)0.1424 (3)0.4682 (3)0.0124 (9)
C100.4964 (5)0.1880 (3)0.4247 (3)0.0163 (10)
H10A0.51680.18950.37050.024*
H10B0.51720.24870.44660.024*
H10C0.40910.1560.42850.024*
C110.5911 (5)0.2222 (3)0.5909 (3)0.0133 (10)
C120.4839 (5)0.2405 (3)0.5919 (3)0.0177 (11)
H120.41880.20960.5560.021*
C130.4701 (5)0.3026 (3)0.6440 (3)0.0194 (11)
H130.39630.31430.64380.023*
C140.5652 (5)0.3482 (3)0.6970 (3)0.0177 (11)
H140.55830.39370.73080.021*
C150.6695 (5)0.3272 (3)0.7004 (3)0.0169 (11)
H150.73290.35780.73750.02*
C160.6840 (5)0.2614 (3)0.6501 (3)0.0148 (10)
C170.8560 (4)0.2667 (3)0.4245 (3)0.0150 (10)
C180.8134 (4)0.2240 (3)0.3520 (3)0.0159 (10)
H180.82560.170.33930.019*
C190.7545 (5)0.2577 (4)0.2986 (3)0.0201 (11)
H190.72560.22660.25020.024*
C200.7375 (5)0.3372 (4)0.3155 (3)0.0217 (12)
H200.69970.36180.27810.026*
C210.7756 (5)0.3799 (4)0.3866 (3)0.0193 (11)
H210.76380.43440.39780.023*
C220.8316 (4)0.3453 (3)0.4432 (3)0.0136 (10)
C230.8361 (4)0.4416 (3)0.5533 (3)0.0151 (10)
C240.7245 (5)0.4620 (4)0.5322 (3)0.0197 (11)
H24A0.74610.51280.49950.029*
H24B0.68950.47610.57920.029*
H24C0.66490.41050.50410.029*
C250.9080 (4)0.4853 (3)0.6267 (3)0.0147 (10)
C260.9015 (5)0.5728 (3)0.6539 (3)0.0216 (11)
H26A0.88230.60250.60980.032*
H26B0.97990.60990.67860.032*
H26C0.83790.56330.69120.032*
C271.0491 (5)0.4672 (3)0.7237 (3)0.0163 (10)
C281.0337 (5)0.5174 (3)0.7869 (3)0.0224 (12)
H280.96730.5380.78650.027*
C291.1155 (5)0.5374 (3)0.8506 (3)0.0230 (12)
H291.10670.57330.89290.028*
C301.2102 (5)0.5045 (3)0.8521 (3)0.0228 (12)
H301.26640.51870.89530.027*
C311.2232 (5)0.4513 (3)0.7910 (3)0.0202 (11)
H311.28660.42750.79390.024*
Zn30.41800 (6)0.30363 (4)0.16001 (3)0.01718 (13)
Zn40.57297 (5)0.18855 (4)0.07942 (3)0.01522 (13)
N50.2625 (4)0.2490 (3)0.0825 (2)0.0175 (9)
N60.2693 (4)0.2633 (3)0.2340 (2)0.0135 (8)
N70.4144 (4)0.0818 (3)0.0343 (2)0.0145 (9)
N80.6096 (4)0.1704 (3)0.0377 (2)0.0155 (9)
S50.53022 (12)0.32299 (9)0.04626 (7)0.0178 (3)
S60.48520 (13)0.42718 (9)0.24273 (8)0.0218 (3)
S70.77557 (12)0.20710 (9)0.10127 (7)0.0172 (3)
S80.46991 (12)0.17128 (8)0.19587 (7)0.0165 (3)
C321.1447 (5)0.4317 (3)0.7248 (3)0.0162 (10)
C330.4037 (5)0.2820 (3)0.0205 (3)0.0165 (10)
C340.4249 (5)0.2865 (3)0.0992 (3)0.0204 (11)
H340.50610.30520.11510.024*
C350.3300 (5)0.2642 (3)0.1545 (3)0.0224 (12)
H350.34630.26660.20770.027*
C360.2114 (5)0.2384 (4)0.1320 (3)0.0253 (12)
H360.14630.22570.16960.03*
C370.1877 (5)0.2310 (4)0.0542 (3)0.0228 (12)
H370.1060.2130.03910.027*
C380.2821 (5)0.2497 (3)0.0022 (3)0.0170 (11)
C390.1666 (5)0.2015 (3)0.1152 (3)0.0155 (10)
C400.0580 (5)0.1277 (4)0.0798 (3)0.0211 (11)
H40A0.00760.15020.06820.032*
H40B0.03050.08050.11610.032*
H40C0.08030.10410.03210.032*
C410.1642 (5)0.2219 (3)0.2011 (3)0.0161 (10)
C420.0443 (5)0.1980 (4)0.2372 (3)0.0234 (12)
H42A0.0160.20560.20050.035*
H42B0.0520.23660.28360.035*
H42C0.0180.13620.25130.035*
C430.3002 (4)0.2968 (3)0.3113 (3)0.0143 (10)
C440.2396 (5)0.2566 (3)0.3756 (3)0.0167 (10)
H440.17070.20370.36890.02*
C450.2803 (5)0.2942 (3)0.4486 (3)0.0183 (11)
H450.23790.26770.49210.022*
C460.3826 (5)0.3701 (3)0.4591 (3)0.0197 (11)
H460.41010.39560.50960.024*
C470.4440 (5)0.4082 (3)0.3966 (3)0.0183 (11)
H470.51550.45920.40450.022*
C480.4040 (5)0.3739 (3)0.3211 (3)0.0160 (10)
C490.8146 (5)0.2436 (3)0.0087 (3)0.0154 (10)
C500.9351 (5)0.2970 (3)0.0031 (3)0.0188 (11)
H500.99370.31340.0390.023*
C510.9688 (5)0.3259 (4)0.0757 (3)0.0230 (12)
H511.05080.36170.08290.028*
C520.8861 (5)0.3037 (4)0.1378 (3)0.0262 (13)
H520.91060.32430.18720.031*
C530.7669 (5)0.2512 (4)0.1275 (3)0.0212 (11)
H530.70960.23630.17020.025*
C540.7292 (5)0.2195 (3)0.0555 (3)0.0185 (11)
C550.5228 (5)0.1159 (3)0.0802 (3)0.0160 (10)
C560.5272 (5)0.0860 (4)0.1628 (3)0.0231 (12)
H56A0.49880.12240.1970.035*
H56B0.47480.02390.17130.035*
H56C0.6110.09240.17390.035*
C570.4049 (5)0.0767 (3)0.0401 (3)0.0159 (10)
C580.2908 (5)0.0402 (3)0.0902 (3)0.0191 (11)
H58A0.30070.07230.13770.029*
H58B0.2230.0470.06270.029*
H58C0.2740.02270.10320.029*
C590.3217 (5)0.0453 (3)0.0852 (3)0.0145 (10)
C600.2216 (5)0.0329 (3)0.0670 (3)0.0194 (11)
H600.21160.06030.01660.023*
C610.1376 (5)0.0706 (4)0.1212 (3)0.0229 (12)
H610.07070.12330.10760.028*
C620.1506 (5)0.0317 (4)0.1952 (3)0.0250 (12)
H620.09170.05690.23180.03*
C630.2497 (5)0.0441 (3)0.2157 (3)0.0198 (11)
H630.25810.07060.26630.024*
C640.3386 (5)0.0823 (3)0.1617 (3)0.0167 (10)
C1B0.2468 (16)0.4851 (11)0.0939 (8)0.049 (4)0.819 (7)
H1B10.18390.51020.08210.073*0.819 (7)
H1B20.2380.43560.0570.073*0.819 (7)
H1B30.32720.53070.09030.073*0.819 (7)
O1B0.2346 (7)0.4548 (6)0.1692 (5)0.062 (2)0.819 (7)
H1B0.302 (5)0.453 (7)0.185 (6)0.093*0.819 (7)
O1A0.172 (2)0.3999 (15)0.1380 (16)0.062 (2)0.181 (7)
S1A0.2543 (16)0.4906 (12)0.1232 (8)0.036 (4)0.181 (7)
C1A0.357 (3)0.469 (2)0.0575 (18)0.054 (10)0.181 (7)
H1A10.43820.48750.08240.08*0.181 (7)
H1A20.35870.50220.01120.08*0.181 (7)
H1A30.32850.40560.0430.08*0.181 (7)
C2A0.164 (3)0.523 (2)0.0528 (16)0.054 (10)0.181 (7)
H2A10.1250.47330.01540.08*0.181 (7)
H2A20.21690.57350.0260.08*0.181 (7)
H2A30.10220.53980.07870.08*0.181 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0144 (3)0.0116 (3)0.0150 (3)0.0040 (2)0.0000 (2)0.0006 (2)
Zn20.0145 (3)0.0118 (3)0.0176 (3)0.0054 (2)0.0008 (2)0.0017 (2)
N10.017 (2)0.0089 (19)0.0128 (19)0.0014 (17)0.0025 (16)0.0006 (15)
N20.012 (2)0.0113 (19)0.0157 (19)0.0052 (17)0.0014 (16)0.0004 (16)
N30.016 (2)0.011 (2)0.0141 (19)0.0043 (17)0.0009 (16)0.0045 (16)
N40.010 (2)0.012 (2)0.020 (2)0.0045 (17)0.0024 (16)0.0012 (16)
S10.0167 (7)0.0134 (6)0.0217 (6)0.0058 (5)0.0005 (5)0.0031 (5)
S20.0169 (7)0.0163 (6)0.0134 (5)0.0069 (5)0.0012 (5)0.0006 (5)
S30.0148 (7)0.0150 (6)0.0158 (6)0.0059 (5)0.0014 (5)0.0001 (5)
S40.0139 (7)0.0202 (7)0.0247 (7)0.0073 (5)0.0027 (5)0.0050 (5)
C10.016 (3)0.014 (2)0.018 (2)0.003 (2)0.006 (2)0.0001 (19)
C20.017 (3)0.009 (2)0.033 (3)0.005 (2)0.004 (2)0.001 (2)
C30.024 (3)0.018 (3)0.038 (3)0.012 (2)0.005 (2)0.008 (2)
C40.024 (3)0.025 (3)0.026 (3)0.011 (3)0.002 (2)0.009 (2)
C50.018 (3)0.020 (3)0.022 (3)0.006 (2)0.003 (2)0.003 (2)
C60.012 (3)0.009 (2)0.021 (2)0.002 (2)0.0021 (19)0.0062 (19)
C70.009 (2)0.015 (2)0.013 (2)0.001 (2)0.0011 (18)0.0011 (19)
C80.014 (3)0.020 (3)0.016 (2)0.004 (2)0.0074 (19)0.001 (2)
C90.009 (2)0.008 (2)0.019 (2)0.0003 (19)0.0053 (18)0.0038 (18)
C100.014 (3)0.020 (3)0.016 (2)0.008 (2)0.0009 (19)0.000 (2)
C110.017 (3)0.011 (2)0.012 (2)0.005 (2)0.0014 (18)0.0009 (18)
C120.018 (3)0.016 (3)0.018 (2)0.006 (2)0.003 (2)0.001 (2)
C130.019 (3)0.019 (3)0.023 (3)0.010 (2)0.008 (2)0.003 (2)
C140.022 (3)0.014 (2)0.017 (2)0.007 (2)0.005 (2)0.0019 (19)
C150.023 (3)0.016 (2)0.014 (2)0.010 (2)0.001 (2)0.0001 (19)
C160.016 (3)0.013 (2)0.016 (2)0.004 (2)0.0063 (19)0.0015 (19)
C170.013 (3)0.016 (2)0.013 (2)0.001 (2)0.0028 (18)0.0024 (19)
C180.009 (2)0.017 (3)0.020 (2)0.002 (2)0.0048 (19)0.003 (2)
C190.010 (3)0.031 (3)0.016 (2)0.003 (2)0.0022 (19)0.003 (2)
C200.015 (3)0.028 (3)0.020 (3)0.003 (2)0.003 (2)0.013 (2)
C210.015 (3)0.021 (3)0.024 (3)0.009 (2)0.002 (2)0.008 (2)
C220.009 (2)0.014 (2)0.018 (2)0.003 (2)0.0004 (18)0.0037 (19)
C230.010 (2)0.010 (2)0.026 (3)0.0034 (19)0.004 (2)0.0047 (19)
C240.013 (3)0.023 (3)0.029 (3)0.012 (2)0.009 (2)0.005 (2)
C250.012 (3)0.014 (2)0.021 (2)0.007 (2)0.0095 (19)0.0041 (19)
C260.023 (3)0.017 (3)0.024 (3)0.006 (2)0.003 (2)0.000 (2)
C270.015 (3)0.010 (2)0.020 (2)0.001 (2)0.004 (2)0.0004 (19)
C280.025 (3)0.014 (3)0.024 (3)0.002 (2)0.003 (2)0.001 (2)
C290.033 (3)0.010 (2)0.021 (3)0.001 (2)0.002 (2)0.000 (2)
C300.019 (3)0.015 (3)0.024 (3)0.008 (2)0.004 (2)0.003 (2)
C310.015 (3)0.016 (3)0.024 (3)0.001 (2)0.002 (2)0.006 (2)
Zn30.0150 (3)0.0170 (3)0.0166 (3)0.0023 (2)0.0028 (2)0.0039 (2)
Zn40.0135 (3)0.0171 (3)0.0125 (3)0.0025 (2)0.0006 (2)0.0024 (2)
N50.017 (2)0.019 (2)0.018 (2)0.0082 (19)0.0001 (17)0.0036 (17)
N60.017 (2)0.012 (2)0.0143 (19)0.0079 (17)0.0001 (16)0.0009 (16)
N70.015 (2)0.013 (2)0.0140 (19)0.0027 (17)0.0001 (16)0.0010 (16)
N80.019 (2)0.015 (2)0.0122 (19)0.0048 (18)0.0017 (16)0.0024 (16)
S50.0155 (7)0.0172 (6)0.0173 (6)0.0017 (5)0.0025 (5)0.0013 (5)
S60.0210 (7)0.0156 (6)0.0229 (6)0.0006 (5)0.0055 (5)0.0056 (5)
S70.0150 (7)0.0220 (7)0.0135 (6)0.0050 (5)0.0014 (5)0.0004 (5)
S80.0156 (7)0.0180 (6)0.0125 (5)0.0019 (5)0.0000 (5)0.0016 (5)
C320.017 (3)0.013 (2)0.015 (2)0.001 (2)0.0004 (19)0.0005 (19)
C330.015 (3)0.010 (2)0.023 (3)0.002 (2)0.001 (2)0.0027 (19)
C340.021 (3)0.019 (3)0.020 (3)0.004 (2)0.007 (2)0.004 (2)
C350.031 (3)0.021 (3)0.014 (2)0.007 (2)0.004 (2)0.003 (2)
C360.031 (3)0.021 (3)0.021 (3)0.005 (3)0.005 (2)0.002 (2)
C370.024 (3)0.022 (3)0.022 (3)0.009 (2)0.001 (2)0.003 (2)
C380.019 (3)0.013 (2)0.018 (2)0.003 (2)0.004 (2)0.0007 (19)
C390.014 (3)0.015 (2)0.017 (2)0.006 (2)0.0006 (19)0.0038 (19)
C400.017 (3)0.024 (3)0.021 (3)0.006 (2)0.002 (2)0.002 (2)
C410.011 (3)0.017 (3)0.016 (2)0.001 (2)0.0029 (19)0.0003 (19)
C420.012 (3)0.036 (3)0.024 (3)0.009 (2)0.000 (2)0.001 (2)
C430.011 (2)0.016 (2)0.016 (2)0.006 (2)0.0028 (19)0.0050 (19)
C440.013 (3)0.016 (2)0.025 (3)0.010 (2)0.003 (2)0.001 (2)
C450.018 (3)0.021 (3)0.021 (3)0.012 (2)0.005 (2)0.004 (2)
C460.025 (3)0.018 (3)0.019 (2)0.013 (2)0.004 (2)0.004 (2)
C470.018 (3)0.012 (2)0.025 (3)0.006 (2)0.003 (2)0.000 (2)
C480.017 (3)0.014 (2)0.015 (2)0.005 (2)0.0006 (19)0.0073 (19)
C490.015 (3)0.014 (2)0.017 (2)0.004 (2)0.0038 (19)0.0022 (19)
C500.019 (3)0.018 (3)0.019 (2)0.005 (2)0.002 (2)0.001 (2)
C510.021 (3)0.021 (3)0.027 (3)0.007 (2)0.007 (2)0.005 (2)
C520.033 (4)0.022 (3)0.019 (3)0.003 (3)0.008 (2)0.008 (2)
C530.025 (3)0.021 (3)0.019 (3)0.010 (2)0.001 (2)0.003 (2)
C540.024 (3)0.019 (3)0.013 (2)0.008 (2)0.005 (2)0.001 (2)
C550.019 (3)0.019 (3)0.011 (2)0.009 (2)0.0002 (19)0.0015 (19)
C560.031 (3)0.027 (3)0.011 (2)0.009 (3)0.003 (2)0.000 (2)
C570.015 (3)0.016 (2)0.016 (2)0.006 (2)0.0042 (19)0.0026 (19)
C580.023 (3)0.018 (3)0.015 (2)0.006 (2)0.003 (2)0.001 (2)
C590.014 (3)0.011 (2)0.016 (2)0.001 (2)0.0014 (19)0.0016 (18)
C600.022 (3)0.018 (3)0.016 (2)0.005 (2)0.003 (2)0.004 (2)
C610.014 (3)0.019 (3)0.029 (3)0.003 (2)0.002 (2)0.003 (2)
C620.019 (3)0.020 (3)0.033 (3)0.001 (2)0.004 (2)0.007 (2)
C630.017 (3)0.022 (3)0.019 (2)0.004 (2)0.006 (2)0.004 (2)
C640.017 (3)0.013 (2)0.019 (2)0.003 (2)0.002 (2)0.0019 (19)
C1B0.050 (7)0.035 (6)0.053 (10)0.008 (5)0.012 (8)0.008 (7)
O1B0.052 (5)0.115 (7)0.043 (4)0.055 (5)0.019 (3)0.036 (4)
O1A0.052 (5)0.115 (7)0.043 (4)0.055 (5)0.019 (3)0.036 (4)
S1A0.031 (7)0.037 (7)0.038 (10)0.012 (5)0.001 (7)0.007 (7)
C1A0.09 (3)0.08 (2)0.025 (13)0.07 (2)0.012 (14)0.022 (14)
C2A0.09 (3)0.08 (2)0.025 (13)0.07 (2)0.012 (14)0.022 (14)
Geometric parameters (Å, º) top
Zn1—N12.128 (4)Zn4—S72.3111 (16)
Zn1—N22.171 (4)Zn4—S82.3689 (15)
Zn1—S12.3139 (16)Zn4—S52.4773 (17)
Zn1—S22.3742 (14)N5—C391.286 (6)
Zn1—S32.4861 (15)N5—C381.423 (6)
Zn2—N42.130 (4)N6—C411.282 (6)
Zn2—N32.151 (4)N6—C431.415 (6)
Zn2—S42.3027 (16)N7—C571.291 (6)
Zn2—S32.3922 (15)N7—C591.405 (6)
Zn2—S22.5011 (15)N8—C551.279 (6)
N1—C71.278 (6)N8—C541.404 (7)
N1—C61.410 (6)S5—C331.770 (5)
N2—C91.299 (6)S6—C481.763 (5)
N2—C111.422 (6)S7—C491.755 (5)
N3—C231.298 (6)S8—C641.767 (5)
N3—C221.412 (6)C33—C341.398 (7)
N4—C251.284 (6)C33—C381.415 (7)
N4—C271.412 (6)C34—C351.385 (7)
S1—C11.761 (5)C34—H340.95
S2—C161.766 (5)C35—C361.383 (8)
S3—C171.756 (5)C35—H350.95
S4—C321.759 (5)C36—C371.391 (7)
C1—C21.406 (7)C36—H360.95
C1—C61.419 (7)C37—C381.398 (7)
C2—C31.402 (7)C37—H370.95
C2—H20.95C39—C401.502 (7)
C3—C41.377 (8)C39—C411.519 (6)
C3—H30.95C40—H40A0.98
C4—C51.378 (7)C40—H40B0.98
C4—H40.95C40—H40C0.98
C5—C61.397 (7)C41—C421.493 (7)
C5—H50.95C42—H42A0.98
C7—C81.496 (6)C42—H42B0.98
C7—C91.512 (6)C42—H42C0.98
C8—H8A0.98C43—C441.401 (7)
C8—H8B0.98C43—C481.406 (7)
C8—H8C0.98C44—C451.381 (7)
C9—C101.486 (7)C44—H440.95
C10—H10A0.98C45—C461.386 (7)
C10—H10B0.98C45—H450.95
C10—H10C0.98C46—C471.370 (7)
C11—C121.393 (7)C46—H460.95
C11—C161.430 (7)C47—C481.403 (7)
C12—C131.379 (6)C47—H470.95
C12—H120.95C49—C501.405 (7)
C13—C141.394 (7)C49—C541.422 (7)
C13—H130.95C50—C511.385 (7)
C14—C151.382 (7)C50—H500.95
C14—H140.95C51—C521.376 (8)
C15—C161.408 (6)C51—H510.95
C15—H150.95C52—C531.383 (8)
C17—C181.401 (6)C52—H520.95
C17—C221.423 (7)C53—C541.396 (7)
C18—C191.379 (7)C53—H530.95
C18—H180.95C55—C561.503 (6)
C19—C201.387 (8)C55—C571.515 (7)
C19—H190.95C56—H56A0.98
C20—C211.373 (7)C56—H56B0.98
C20—H200.95C56—H56C0.98
C21—C221.404 (7)C57—C581.495 (7)
C21—H210.95C58—H58A0.98
C23—C241.498 (7)C58—H58B0.98
C23—C251.510 (7)C58—H58C0.98
C24—H24A0.98C59—C601.409 (7)
C24—H24B0.98C59—C641.414 (6)
C24—H24C0.98C60—C611.386 (7)
C25—C261.501 (6)C60—H600.95
C26—H26A0.98C61—C621.389 (7)
C26—H26B0.98C61—H610.95
C26—H26C0.98C62—C631.387 (7)
C27—C281.393 (7)C62—H620.95
C27—C321.428 (7)C63—C641.419 (7)
C28—C291.393 (8)C63—H630.95
C28—H280.95C1B—O1B1.408 (14)
C29—C301.390 (8)C1B—H1B10.98
C29—H290.95C1B—H1B20.98
C30—C311.386 (7)C1B—H1B30.98
C30—H300.95O1B—H1B0.850 (15)
C31—C321.404 (7)O1A—S1A1.484 (10)
C31—H310.95S1A—C1A1.795 (10)
Zn3—N52.134 (4)S1A—C2A1.799 (10)
Zn3—N62.134 (4)C1A—H1A10.98
Zn3—S62.2952 (15)C1A—H1A20.98
Zn3—S52.3831 (15)C1A—H1A30.98
Zn3—S82.5133 (17)C2A—H2A10.98
Zn4—N82.125 (4)C2A—H2A20.98
Zn4—N72.148 (4)C2A—H2A30.98
N1—Zn1—N274.85 (15)N7—Zn4—S884.74 (11)
N1—Zn1—S183.74 (12)S7—Zn4—S8111.50 (5)
N2—Zn1—S1136.24 (11)N8—Zn4—S589.08 (12)
N1—Zn1—S2157.93 (12)N7—Zn4—S5103.73 (12)
N2—Zn1—S283.41 (11)S7—Zn4—S5115.80 (5)
S1—Zn1—S2115.47 (5)S8—Zn4—S594.51 (5)
N1—Zn1—S390.45 (11)C39—N5—C38126.7 (4)
N2—Zn1—S3108.88 (11)C39—N5—Zn3113.6 (3)
S1—Zn1—S3109.00 (5)C38—N5—Zn3117.5 (3)
S2—Zn1—S393.03 (5)C41—N6—C43129.3 (4)
N4—Zn2—N376.04 (16)C41—N6—Zn3116.2 (3)
N4—Zn2—S484.31 (12)C43—N6—Zn3113.8 (3)
N3—Zn2—S4137.85 (12)C57—N7—C59127.3 (4)
N4—Zn2—S3159.75 (12)C57—N7—Zn4112.7 (3)
N3—Zn2—S383.72 (11)C59—N7—Zn4117.3 (3)
S4—Zn2—S3111.68 (5)C55—N8—C54130.0 (4)
N4—Zn2—S292.08 (12)C55—N8—Zn4116.5 (3)
N3—Zn2—S2103.25 (12)C54—N8—Zn4113.4 (3)
S4—Zn2—S2114.53 (6)C33—S5—Zn396.89 (17)
S3—Zn2—S292.22 (5)C33—S5—Zn4103.54 (17)
C7—N1—C6128.5 (4)Zn3—S5—Zn486.33 (5)
C7—N1—Zn1117.7 (3)C48—S6—Zn394.82 (16)
C6—N1—Zn1113.8 (3)C49—S7—Zn493.55 (18)
C9—N2—C11123.9 (4)C64—S8—Zn496.85 (17)
C9—N2—Zn1113.4 (3)C64—S8—Zn3102.24 (18)
C11—N2—Zn1118.7 (3)Zn4—S8—Zn385.82 (5)
C23—N3—C22125.1 (4)C31—C32—C27117.4 (5)
C23—N3—Zn2112.1 (3)C31—C32—S4119.9 (4)
C22—N3—Zn2118.8 (3)C27—C32—S4122.7 (4)
C25—N4—C27128.0 (4)C34—C33—C38118.6 (5)
C25—N4—Zn2116.0 (3)C34—C33—S5118.3 (4)
C27—N4—Zn2115.5 (3)C38—C33—S5123.0 (4)
C1—S1—Zn193.75 (18)C35—C34—C33121.5 (5)
C16—S2—Zn198.49 (16)C35—C34—H34119.3
C16—S2—Zn2104.77 (17)C33—C34—H34119.3
Zn1—S2—Zn287.36 (5)C36—C35—C34119.8 (5)
C17—S3—Zn297.14 (17)C36—C35—H35120.1
C17—S3—Zn199.37 (17)C34—C35—H35120.1
Zn2—S3—Zn187.31 (5)C35—C36—C37119.9 (5)
C32—S4—Zn295.79 (18)C35—C36—H36120.1
C2—C1—C6118.0 (4)C37—C36—H36120.1
C2—C1—S1119.5 (4)C36—C37—C38121.0 (5)
C6—C1—S1122.5 (4)C36—C37—H37119.5
C3—C2—C1121.0 (5)C38—C37—H37119.5
C3—C2—H2119.5C37—C38—C33119.0 (5)
C1—C2—H2119.5C37—C38—N5122.7 (5)
C4—C3—C2119.7 (5)C33—C38—N5117.7 (4)
C4—C3—H3120.1N5—C39—C40128.5 (4)
C2—C3—H3120.1N5—C39—C41115.5 (4)
C3—C4—C5120.6 (5)C40—C39—C41116.0 (4)
C3—C4—H4119.7C39—C40—H40A109.5
C5—C4—H4119.7C39—C40—H40B109.5
C4—C5—C6120.7 (5)H40A—C40—H40B109.5
C4—C5—H5119.6C39—C40—H40C109.5
C6—C5—H5119.6H40A—C40—H40C109.5
C5—C6—N1124.6 (5)H40B—C40—H40C109.5
C5—C6—C1119.8 (4)N6—C41—C42127.0 (4)
N1—C6—C1114.9 (4)N6—C41—C39114.1 (4)
N1—C7—C8128.0 (4)C42—C41—C39118.8 (4)
N1—C7—C9114.5 (4)C41—C42—H42A109.5
C8—C7—C9117.5 (4)C41—C42—H42B109.5
C7—C8—H8A109.5H42A—C42—H42B109.5
C7—C8—H8B109.5C41—C42—H42C109.5
H8A—C8—H8B109.5H42A—C42—H42C109.5
C7—C8—H8C109.5H42B—C42—H42C109.5
H8A—C8—H8C109.5C44—C43—C48120.3 (4)
H8B—C8—H8C109.5C44—C43—N6124.9 (4)
N2—C9—C10128.5 (4)C48—C43—N6114.7 (4)
N2—C9—C7114.5 (4)C45—C44—C43119.8 (5)
C10—C9—C7116.9 (4)C45—C44—H44120.1
C9—C10—H10A109.5C43—C44—H44120.1
C9—C10—H10B109.5C44—C45—C46120.5 (5)
H10A—C10—H10B109.5C44—C45—H45119.7
C9—C10—H10C109.5C46—C45—H45119.7
H10A—C10—H10C109.5C47—C46—C45119.9 (5)
H10B—C10—H10C109.5C47—C46—H46120.1
C12—C11—N2124.1 (4)C45—C46—H46120.1
C12—C11—C16119.4 (4)C46—C47—C48121.6 (5)
N2—C11—C16116.2 (4)C46—C47—H47119.2
C13—C12—C11121.4 (5)C48—C47—H47119.2
C13—C12—H12119.3C47—C48—C43117.9 (5)
C11—C12—H12119.3C47—C48—S6119.6 (4)
C12—C13—C14119.6 (5)C43—C48—S6122.5 (4)
C12—C13—H13120.2C50—C49—C54118.5 (5)
C14—C13—H13120.2C50—C49—S7119.0 (4)
C15—C14—C13120.0 (5)C54—C49—S7122.5 (4)
C15—C14—H14120C51—C50—C49120.3 (5)
C13—C14—H14120C51—C50—H50119.9
C14—C15—C16121.6 (5)C49—C50—H50119.9
C14—C15—H15119.2C52—C51—C50121.3 (5)
C16—C15—H15119.2C52—C51—H51119.3
C15—C16—C11117.4 (5)C50—C51—H51119.3
C15—C16—S2119.6 (4)C51—C52—C53119.4 (5)
C11—C16—S2122.9 (4)C51—C52—H52120.3
C18—C17—C22117.6 (5)C53—C52—H52120.3
C18—C17—S3118.5 (4)C52—C53—C54121.2 (5)
C22—C17—S3124.0 (4)C52—C53—H53119.4
C19—C18—C17122.1 (5)C54—C53—H53119.4
C19—C18—H18118.9C53—C54—N8125.9 (5)
C17—C18—H18118.9C53—C54—C49119.3 (5)
C18—C19—C20119.9 (5)N8—C54—C49114.7 (4)
C18—C19—H19120N8—C55—C56127.3 (5)
C20—C19—H19120N8—C55—C57114.4 (4)
C21—C20—C19119.6 (5)C56—C55—C57118.3 (4)
C21—C20—H20120.2C55—C56—H56A109.5
C19—C20—H20120.2C55—C56—H56B109.5
C20—C21—C22121.7 (5)H56A—C56—H56B109.5
C20—C21—H21119.2C55—C56—H56C109.5
C22—C21—H21119.2H56A—C56—H56C109.5
C21—C22—N3124.3 (4)H56B—C56—H56C109.5
C21—C22—C17119.0 (4)N7—C57—C58127.3 (5)
N3—C22—C17116.4 (4)N7—C57—C55115.7 (4)
N3—C23—C24127.0 (5)C58—C57—C55117.0 (4)
N3—C23—C25115.1 (4)C57—C58—H58A109.5
C24—C23—C25117.9 (4)C57—C58—H58B109.5
C23—C24—H24A109.5H58A—C58—H58B109.5
C23—C24—H24B109.5C57—C58—H58C109.5
H24A—C24—H24B109.5H58A—C58—H58C109.5
C23—C24—H24C109.5H58B—C58—H58C109.5
H24A—C24—H24C109.5N7—C59—C60123.2 (4)
H24B—C24—H24C109.5N7—C59—C64117.8 (4)
N4—C25—C26128.1 (5)C60—C59—C64118.5 (4)
N4—C25—C23114.4 (4)C61—C60—C59121.2 (5)
C26—C25—C23117.4 (4)C61—C60—H60119.4
C25—C26—H26A109.5C59—C60—H60119.4
C25—C26—H26B109.5C60—C61—C62120.3 (5)
H26A—C26—H26B109.5C60—C61—H61119.9
C25—C26—H26C109.5C62—C61—H61119.9
H26A—C26—H26C109.5C63—C62—C61120.0 (5)
H26B—C26—H26C109.5C63—C62—H62120
C28—C27—N4124.4 (5)C61—C62—H62120
C28—C27—C32120.7 (5)C62—C63—C64120.6 (5)
N4—C27—C32114.8 (4)C62—C63—H63119.7
C27—C28—C29120.1 (5)C64—C63—H63119.7
C27—C28—H28119.9C59—C64—C63119.2 (5)
C29—C28—H28119.9C59—C64—S8123.3 (4)
C30—C29—C28119.8 (5)C63—C64—S8117.4 (4)
C30—C29—H29120.1O1B—C1B—H1B1109.5
C28—C29—H29120.1O1B—C1B—H1B2109.5
C31—C30—C29120.6 (5)H1B1—C1B—H1B2109.5
C31—C30—H30119.7O1B—C1B—H1B3109.5
C29—C30—H30119.7H1B1—C1B—H1B3109.5
C30—C31—C32121.3 (5)H1B2—C1B—H1B3109.5
C30—C31—H31119.3C1B—O1B—H1B108 (7)
C32—C31—H31119.3O1A—S1A—C1A101.9 (8)
N5—Zn3—N676.04 (16)O1A—S1A—C2A101.5 (8)
N5—Zn3—S6133.08 (12)C1A—S1A—C2A96.9 (19)
N6—Zn3—S683.58 (11)S1A—C1A—H1A1109.5
N5—Zn3—S584.75 (12)S1A—C1A—H1A2109.5
N6—Zn3—S5160.63 (11)H1A1—C1A—H1A2109.5
S6—Zn3—S5112.05 (5)S1A—C1A—H1A3109.5
N5—Zn3—S8103.73 (12)H1A1—C1A—H1A3109.5
N6—Zn3—S888.98 (11)H1A2—C1A—H1A3109.5
S6—Zn3—S8117.84 (6)S1A—C2A—H2A1109.5
S5—Zn3—S893.23 (5)S1A—C2A—H2A2109.5
N8—Zn4—N776.02 (16)H2A1—C2A—H2A2109.5
N8—Zn4—S783.59 (12)S1A—C2A—H2A3109.5
N7—Zn4—S7134.94 (12)H2A1—C2A—H2A3109.5
N8—Zn4—S8160.73 (12)H2A2—C2A—H2A3109.5
Zn1—S1—C1—C2155.8 (4)Zn3—S5—C33—C34175.2 (4)
Zn1—S1—C1—C625.7 (4)Zn4—S5—C33—C3496.9 (4)
C6—C1—C2—C31.6 (8)Zn3—S5—C33—C381.1 (4)
S1—C1—C2—C3179.8 (4)Zn4—S5—C33—C3886.7 (4)
C1—C2—C3—C41.2 (8)C38—C33—C34—C353.2 (8)
C2—C3—C4—C50.8 (9)S5—C33—C34—C35173.3 (4)
C3—C4—C5—C62.4 (9)C33—C34—C35—C361.2 (8)
C4—C5—C6—N1175.0 (5)C34—C35—C36—C372.9 (8)
C4—C5—C6—C15.2 (8)C35—C36—C37—C380.3 (8)
C7—N1—C6—C533.0 (8)C36—C37—C38—C334.1 (8)
Zn1—N1—C6—C5148.8 (4)C36—C37—C38—N5175.5 (5)
C7—N1—C6—C1156.8 (5)C34—C33—C38—C375.7 (7)
Zn1—N1—C6—C121.4 (5)S5—C33—C38—C37170.6 (4)
C2—C1—C6—C54.7 (7)C34—C33—C38—N5177.6 (5)
S1—C1—C6—C5176.7 (4)S5—C33—C38—N51.3 (7)
C2—C1—C6—N1175.5 (4)C39—N5—C38—C3729.5 (8)
S1—C1—C6—N16.0 (6)Zn3—N5—C38—C37168.1 (4)
C6—N1—C7—C84.6 (9)C39—N5—C38—C33159.0 (5)
Zn1—N1—C7—C8173.6 (4)Zn3—N5—C38—C333.4 (6)
C6—N1—C7—C9178.0 (4)C38—N5—C39—C408.2 (9)
Zn1—N1—C7—C93.8 (5)Zn3—N5—C39—C40154.9 (4)
C11—N2—C9—C105.8 (8)C38—N5—C39—C41173.1 (5)
Zn1—N2—C9—C10151.6 (4)Zn3—N5—C39—C4123.9 (5)
C11—N2—C9—C7177.2 (4)C43—N6—C41—C420.0 (9)
Zn1—N2—C9—C725.4 (5)Zn3—N6—C41—C42170.6 (4)
N1—C7—C9—N220.0 (6)C43—N6—C41—C39176.1 (4)
C8—C7—C9—N2157.7 (4)Zn3—N6—C41—C395.4 (6)
N1—C7—C9—C10157.4 (4)N5—C39—C41—N620.0 (7)
C8—C7—C9—C1024.9 (6)C40—C39—C41—N6158.9 (5)
C9—N2—C11—C1233.9 (7)N5—C39—C41—C42156.4 (5)
Zn1—N2—C11—C12169.8 (4)C40—C39—C41—C4224.7 (7)
C9—N2—C11—C16152.6 (5)C41—N6—C43—C4435.5 (8)
Zn1—N2—C11—C163.7 (6)Zn3—N6—C43—C44153.7 (4)
N2—C11—C12—C13180.0 (5)C41—N6—C43—C48148.0 (5)
C16—C11—C12—C136.7 (8)Zn3—N6—C43—C4822.8 (5)
C11—C12—C13—C140.1 (8)C48—C43—C44—C451.6 (7)
C12—C13—C14—C154.1 (8)N6—C43—C44—C45178.0 (4)
C13—C14—C15—C161.4 (8)C43—C44—C45—C461.7 (7)
C14—C15—C16—C115.2 (7)C44—C45—C46—C470.1 (8)
C14—C15—C16—S2171.6 (4)C45—C46—C47—C481.9 (8)
C12—C11—C16—C159.1 (7)C46—C47—C48—C431.9 (8)
N2—C11—C16—C15177.1 (4)C46—C47—C48—S6178.8 (4)
C12—C11—C16—S2167.6 (4)C44—C43—C48—C470.1 (7)
N2—C11—C16—S26.2 (6)N6—C43—C48—C47176.6 (4)
Zn1—S2—C16—C15178.3 (4)C44—C43—C48—S6179.4 (4)
Zn2—S2—C16—C1588.8 (4)N6—C43—C48—S62.7 (6)
Zn1—S2—C16—C115.1 (4)Zn3—S6—C48—C47156.4 (4)
Zn2—S2—C16—C1194.6 (4)Zn3—S6—C48—C4322.9 (4)
Zn2—S3—C17—C18180.0 (4)Zn4—S7—C49—C50155.6 (4)
Zn1—S3—C17—C1891.5 (4)Zn4—S7—C49—C5425.8 (4)
Zn2—S3—C17—C222.0 (4)C54—C49—C50—C510.5 (7)
Zn1—S3—C17—C2290.5 (4)S7—C49—C50—C51179.2 (4)
C22—C17—C18—C192.7 (7)C49—C50—C51—C520.3 (8)
S3—C17—C18—C19175.4 (4)C50—C51—C52—C530.3 (8)
C17—C18—C19—C201.0 (8)C51—C52—C53—C540.6 (8)
C18—C19—C20—C212.4 (8)C52—C53—C54—N8176.0 (5)
C19—C20—C21—C220.1 (8)C52—C53—C54—C491.5 (8)
C20—C21—C22—N3176.9 (5)C55—N8—C54—C5330.6 (9)
C20—C21—C22—C173.9 (8)Zn4—N8—C54—C53151.5 (4)
C23—N3—C22—C2129.6 (8)C55—N8—C54—C49154.7 (5)
Zn2—N3—C22—C21174.7 (4)Zn4—N8—C54—C4923.2 (5)
C23—N3—C22—C17157.3 (5)C50—C49—C54—C531.4 (7)
Zn2—N3—C22—C171.6 (6)S7—C49—C54—C53180.0 (4)
C18—C17—C22—C215.1 (7)C50—C49—C54—N8176.5 (4)
S3—C17—C22—C21172.9 (4)S7—C49—C54—N84.9 (6)
C18—C17—C22—N3178.6 (4)C54—N8—C55—C562.7 (9)
S3—C17—C22—N30.6 (6)Zn4—N8—C55—C56175.1 (4)
C22—N3—C23—C246.8 (8)C54—N8—C55—C57179.1 (5)
Zn2—N3—C23—C24150.3 (4)Zn4—N8—C55—C573.1 (6)
C22—N3—C23—C25174.8 (4)C59—N7—C57—C587.9 (8)
Zn2—N3—C23—C2528.1 (5)Zn4—N7—C57—C58152.6 (4)
C27—N4—C25—C260.0 (8)C59—N7—C57—C55174.9 (4)
Zn2—N4—C25—C26171.2 (4)Zn4—N7—C57—C5524.6 (5)
C27—N4—C25—C23177.9 (4)N8—C55—C57—N719.1 (7)
Zn2—N4—C25—C236.7 (5)C56—C55—C57—N7159.2 (5)
N3—C23—C25—N424.0 (6)N8—C55—C57—C58158.4 (5)
C24—C23—C25—N4154.5 (5)C56—C55—C57—C5823.3 (7)
N3—C23—C25—C26154.1 (5)C57—N7—C59—C6030.2 (8)
C24—C23—C25—C2627.3 (6)Zn4—N7—C59—C60170.2 (4)
C25—N4—C27—C2831.0 (8)C57—N7—C59—C64158.6 (5)
Zn2—N4—C27—C28157.7 (4)Zn4—N7—C59—C641.0 (6)
C25—N4—C27—C32152.9 (5)N7—C59—C60—C61174.6 (5)
Zn2—N4—C27—C3218.4 (5)C64—C59—C60—C613.4 (8)
N4—C27—C28—C29179.2 (5)C59—C60—C61—C620.1 (9)
C32—C27—C28—C293.3 (8)C60—C61—C62—C631.5 (9)
C27—C28—C29—C302.2 (8)C61—C62—C63—C640.3 (8)
C28—C29—C30—C310.6 (8)N7—C59—C64—C63176.8 (5)
C29—C30—C31—C322.5 (8)C60—C59—C64—C635.1 (8)
C30—C31—C32—C271.4 (7)N7—C59—C64—S80.2 (7)
C30—C31—C32—S4178.2 (4)C60—C59—C64—S8171.5 (4)
C28—C27—C32—C311.5 (7)C62—C63—C64—C593.6 (8)
N4—C27—C32—C31177.8 (4)C62—C63—C64—S8173.2 (4)
C28—C27—C32—S4178.9 (4)Zn4—S8—C64—C590.6 (5)
N4—C27—C32—S42.7 (6)Zn3—S8—C64—C5986.6 (4)
Zn2—S4—C32—C31161.6 (4)Zn4—S8—C64—C63176.0 (4)
Zn2—S4—C32—C2718.9 (4)Zn3—S8—C64—C6396.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···S60.850 (15)2.507 (10)3.350 (7)172 (9)
C26—H26C···O1Bi0.982.593.484 (9)151
C28—H28···O1Bi0.952.563.444 (9)155
C28—H28···O1Ai0.952.573.42 (3)149
C50—H50···O1Aii0.952.623.54 (3)165
C28—H28···S1Ai0.952.993.740 (18)137
C8—H8B···S1iii0.982.913.880 (5)170
C10—H10C···S1iii0.982.853.768 (5)156
C63—H63···S1iii0.952.933.663 (5)135
C2—H2···S3iv0.952.933.742 (6)144
C42—H42A···S7v0.982.963.929 (6)172
C58—H58C···S7vi0.982.833.787 (5)166
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) x+2, y, z+1; (v) x1, y, z; (vi) x+1, y, z.

Experimental details

Crystal data
Chemical formula[Zn2(C16H14N2S2)2]2·0.18C2H6OS·0.82CH4O
Mr1495.4
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)11.757 (4), 16.145 (6), 17.376 (6)
α, β, γ (°)92.254 (5), 91.897 (6), 110.427 (5)
V3)3084.6 (19)
Z2
Radiation typeMo Kα
µ (mm1)1.87
Crystal size (mm)0.25 × 0.23 × 0.01
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.654, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
37532, 15164, 10524
Rint0.067
(sin θ/λ)max1)0.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.116, 1.11
No. of reflections15164
No. of parameters814
No. of restraints7
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + 12.0817P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.73, 0.81

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SADABS (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL-2013 (Sheldrick, 2013), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Selected geometric parameters (Å, º) top
Zn1—N12.128 (4)Zn3—N52.134 (4)
Zn1—N22.171 (4)Zn3—N62.134 (4)
Zn1—S12.3139 (16)Zn3—S62.2952 (15)
Zn1—S22.3742 (14)Zn3—S52.3831 (15)
Zn1—S32.4861 (15)Zn3—S82.5133 (17)
Zn2—N42.130 (4)Zn4—N82.125 (4)
Zn2—N32.151 (4)Zn4—N72.148 (4)
Zn2—S42.3027 (16)Zn4—S72.3111 (16)
Zn2—S32.3922 (15)Zn4—S82.3689 (15)
Zn2—S22.5011 (15)Zn4—S52.4773 (17)
N1—Zn1—N274.85 (15)N5—Zn3—N676.04 (16)
N1—Zn1—S183.74 (12)N5—Zn3—S6133.08 (12)
N2—Zn1—S1136.24 (11)N6—Zn3—S683.58 (11)
N1—Zn1—S2157.93 (12)N5—Zn3—S584.75 (12)
N2—Zn1—S283.41 (11)N6—Zn3—S5160.63 (11)
S1—Zn1—S2115.47 (5)S6—Zn3—S5112.05 (5)
N1—Zn1—S390.45 (11)N5—Zn3—S8103.73 (12)
N2—Zn1—S3108.88 (11)N6—Zn3—S888.98 (11)
S1—Zn1—S3109.00 (5)S6—Zn3—S8117.84 (6)
S2—Zn1—S393.03 (5)S5—Zn3—S893.23 (5)
N4—Zn2—N376.04 (16)N8—Zn4—N776.02 (16)
N4—Zn2—S484.31 (12)N8—Zn4—S783.59 (12)
N3—Zn2—S4137.85 (12)N7—Zn4—S7134.94 (12)
N4—Zn2—S3159.75 (12)N8—Zn4—S8160.73 (12)
N3—Zn2—S383.72 (11)N7—Zn4—S884.74 (11)
S4—Zn2—S3111.68 (5)S7—Zn4—S8111.50 (5)
N4—Zn2—S292.08 (12)N8—Zn4—S589.08 (12)
N3—Zn2—S2103.25 (12)N7—Zn4—S5103.73 (12)
S4—Zn2—S2114.53 (6)S7—Zn4—S5115.80 (5)
S3—Zn2—S292.22 (5)S8—Zn4—S594.51 (5)
Zn1—S2—Zn287.36 (5)Zn3—S5—Zn486.33 (5)
Zn2—S3—Zn187.31 (5)Zn4—S8—Zn385.82 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1B—H1B···S60.850 (15)2.507 (10)3.350 (7)172 (9)
C26—H26C···O1Bi0.982.593.484 (9)151
C28—H28···O1Bi0.952.563.444 (9)155
C28—H28···O1Ai0.952.573.42 (3)149
C50—H50···O1Aii0.952.623.54 (3)165
C28—H28···S1Ai0.952.993.740 (18)137
C8—H8B···S1iii0.982.913.880 (5)170
C10—H10C···S1iii0.982.853.768 (5)156
C63—H63···S1iii0.952.933.663 (5)135
C2—H2···S3iv0.952.933.742 (6)144
C42—H42A···S7v0.982.963.929 (6)172
C58—H58C···S7vi0.982.833.787 (5)166
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) x+2, y, z+1; (v) x1, y, z; (vi) x+1, y, z.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds