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The charge density of the title compound was determined at 90 K, using a spherical crystal of 150 µm diameter. The proper treatment of the Zn atom in the pseudo-tetrahedral environment is considered in detail. A satisfactory refinement is only obtained when anharmonic Gram–Charlier parameters are included as variables in the refinement. A successful combined anharmonic/multipole refinement indicates a small polarization of the 4s shell in the anisotropic environment. One of the two toluenethiols is approximately π-stacked with the phenanthroline ligand. A bond path is found connecting the two ligands. In addition the Zn—S bond to this ligand is slightly extended compared with the same bond to the second toluenethiol. A separate photocrystallographic and theoretical study indicates the long wavelength emission of the title compound to be due to a ligand-to-ligand charge transfer (LLCT) from a toluenethiol to the phenanthroline ligand. The charge-density results do not provide a basis for deciding which of the thiole ligands is the source of the transferred electron density. This result is in agreement with the theoretical calculations, which show comparable oscillator strengths for charge transfer from either of the ligands.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768110009687/pi5004sup1.cif
Contains datablock ZnSMe

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768110009687/pi5004ZnSMesup2.hkl
Contains datablock ZnSMe

CCDC reference: 782726

Computing details top

Data reduction: SORTAV Blessing 1997; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).

(ZnSMe) top
Crystal data top
C26H22N2S2ZnF(000) = 1016
Mr = 491.99Dx = 1.446 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9906 reflections
a = 9.9280 (4) Åθ = 27.7–52.1°
b = 19.9226 (8) ŵ = 1.29 mm1
c = 12.0100 (5) ÅT = 90 K
β = 107.924 (1)°Sphere, pale yellow
V = 2260.18 (16) Å30.15 mm (radius)
Z = 4
Data collection top
Bruker SMART Apex II CCD Detector
diffractometer
26207 independent reflections
Radiation source: rotating anode21306 reflections with > 3σ(I)
Graphite monochromatorRint = 0.0000
φ scansθmax = 52.3°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements)
spherical
h = 2221
Tmin = 0.754, Tmax = 0.781k = 044
293231 measured reflectionsl = 026
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.014Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.017H-atom parameters constrained
S = 0.92 w = 1/[σ2(Fo2) + (0.0379P)2 + 0.141P]
where P = (Fo2 + 2Fc2)/3
21306 reflections(Δ/σ)max = 0.00003
837 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.36 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*/Ueq
Zn(1)0.287310 (7)0.507532 (3)0.230086 (5)0.012
S(1)0.226142 (7)0.616984 (3)0.204640 (5)0.015
S(2)0.222559 (8)0.434642 (3)0.350058 (6)0.017
N(1)0.50274 (3)0.493770 (12)0.24780 (2)0.013
N(2)0.27238 (3)0.454914 (12)0.07355 (2)0.012
C(1)0.61377 (3)0.512840 (12)0.33614 (2)0.016
C(2)0.75334 (3)0.496864 (14)0.34102 (3)0.019
C(3)0.77728 (3)0.459483 (14)0.25200 (3)0.018
C(4)0.66055 (3)0.437642 (12)0.15836 (2)0.014
C(5)0.67406 (3)0.396265 (14)0.06430 (3)0.018
C(6)0.55733 (3)0.374143 (14)0.02115 (3)0.017
C(7)0.41754 (3)0.392513 (12)0.02074 (2)0.014
C(8)0.29357 (3)0.369352 (14)0.10547 (2)0.017
C(9)0.16322 (3)0.389250 (14)0.09842 (2)0.017
C(10)0.15747 (3)0.432398 (13)0.00754 (2)0.015
C(11)0.40109 (3)0.434829 (10)0.068215 (18)0.011
C(12)0.52446 (3)0.456736 (10)0.160153 (19)0.012
C(13)0.18199 (2)0.639192 (11)0.33256 (2)0.012
C(14)0.09253 (3)0.599965 (12)0.37673 (2)0.014
C(15)0.05412 (3)0.621549 (12)0.47327 (2)0.014
C(16)0.10297 (3)0.682432 (12)0.52901 (2)0.013
C(17)0.19224 (3)0.721347 (12)0.48491 (2)0.015
C(18)0.23139 (3)0.700267 (12)0.38847 (2)0.015
C(19)0.27536 (3)0.361333 (12)0.28908 (2)0.014
C(20)0.17496 (3)0.324279 (14)0.20372 (2)0.016
C(21)0.21519 (3)0.269380 (14)0.14935 (2)0.016
C(22)0.35699 (3)0.249743 (12)0.17769 (2)0.015
C(23)0.45697 (3)0.285552 (13)0.26540 (2)0.015
C(24)0.41715 (3)0.340316 (13)0.32100 (2)0.015
C(25)0.06010 (4)0.705248 (14)0.63267 (2)0.02
C(26)0.39901 (4)0.192671 (17)0.11325 (3)0.024
H(1)0.5962140.5416830.4069220.019079
H(2)0.8413970.5136390.4138350.022576
H(3)0.8842290.4471960.2541120.021758
H(5)0.7783770.3825230.0611080.02113
H(6)0.5702740.3423180.0901420.020734
H(8)0.3005190.3364160.1750970.020423
H(9)0.0667740.37180.1622170.0209
H(10)0.0546220.4480320.0033620.018393
H(14)0.0529230.5525870.3354860.016232
H(15)0.0151190.5905090.5057860.016901
H(17)0.2316620.76870.5263410.017732
H(18)0.3007050.731460.3563370.017343
H(20)0.0644270.3385350.1795040.019136
H(21)0.1352350.2413660.0842030.019609
H(23)0.5671170.2705350.2906940.018315
H(24)0.4963530.3667960.38930.017956
H(261)0.4890870.166910.1665440.03478
H(251)0.0627570.7581180.6425060.04148
H(253)0.0418370.6878540.629690.04539
H(262)0.3144180.1586680.0784280.04149
H(263)0.4314250.2121840.0435830.03674
H(252)0.1326370.6846630.7089280.03658
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn(1)0.01443 (3)0.01229 (3)0.01206 (3)0.001129 (19)0.00620 (2)0.001416 (17)
S(1)0.01847 (2)0.013401 (19)0.01460 (2)0.002679 (16)0.009212 (17)0.000825 (15)
S(2)0.02446 (3)0.01439 (2)0.01657 (2)0.000138 (19)0.01276 (2)0.001199 (16)
N(1)0.01337 (7)0.01281 (6)0.01200 (7)0.00014 (6)0.00404 (6)0.00201 (6)
N(2)0.01208 (7)0.01422 (7)0.01120 (6)0.00110 (6)0.00402 (6)0.00150 (5)
C(1)0.01633 (9)0.01521 (8)0.01471 (8)0.00132 (6)0.00263 (7)0.00329 (6)
C(2)0.01480 (9)0.01797 (9)0.02071 (10)0.00170 (7)0.00115 (8)0.00317 (8)
C(3)0.01261 (9)0.01763 (8)0.02312 (10)0.00017 (7)0.00388 (8)0.00152 (8)
C(4)0.01233 (8)0.01391 (7)0.01702 (8)0.00097 (6)0.00578 (6)0.00055 (6)
C(5)0.01543 (9)0.01855 (9)0.02114 (9)0.00264 (7)0.00910 (8)0.00271 (8)
C(6)0.01828 (10)0.01873 (9)0.01730 (8)0.00281 (7)0.00908 (8)0.00357 (7)
C(7)0.01601 (9)0.01465 (7)0.01149 (6)0.00171 (6)0.00571 (6)0.00189 (6)
C(8)0.01970 (10)0.01917 (9)0.01183 (7)0.00106 (7)0.00411 (7)0.00400 (7)
C(9)0.01700 (10)0.02072 (9)0.01271 (7)0.00010 (7)0.00166 (7)0.00317 (7)
C(10)0.01309 (8)0.01858 (8)0.01357 (7)0.00124 (6)0.00285 (6)0.00175 (6)
C(11)0.01266 (7)0.01219 (6)0.01033 (6)0.00118 (5)0.00461 (5)0.00081 (5)
C(12)0.01203 (7)0.01163 (6)0.01193 (6)0.00054 (5)0.00457 (6)0.00064 (5)
C(13)0.01334 (7)0.01192 (6)0.01266 (6)0.00036 (6)0.00555 (6)0.00041 (5)
C(14)0.01597 (8)0.01245 (6)0.01386 (7)0.00220 (6)0.00687 (6)0.00258 (5)
C(15)0.01675 (8)0.01352 (7)0.01385 (7)0.00318 (6)0.00735 (6)0.00242 (6)
C(16)0.01614 (8)0.01310 (7)0.01173 (6)0.00150 (6)0.00543 (6)0.00201 (5)
C(17)0.01771 (8)0.01281 (7)0.01485 (7)0.00322 (6)0.00637 (7)0.00261 (6)
C(18)0.01627 (8)0.01297 (7)0.01599 (7)0.00243 (6)0.00745 (7)0.00128 (6)
C(19)0.01770 (9)0.01339 (7)0.01295 (7)0.00010 (6)0.00669 (6)0.00058 (6)
C(20)0.01550 (9)0.01690 (8)0.01597 (8)0.00023 (7)0.00544 (7)0.00154 (7)
C(21)0.01682 (9)0.01601 (8)0.01556 (8)0.00100 (7)0.00391 (7)0.00286 (7)
C(22)0.01799 (9)0.01283 (7)0.01434 (7)0.00070 (6)0.00512 (7)0.00112 (6)
C(23)0.01597 (9)0.01448 (7)0.01495 (7)0.00102 (6)0.00412 (7)0.00022 (6)
C(24)0.01729 (9)0.01429 (7)0.01304 (7)0.00094 (7)0.00412 (6)0.00114 (6)
C(25)0.02845 (12)0.01906 (9)0.01543 (8)0.00325 (8)0.01132 (8)0.00465 (6)
C(26)0.02708 (12)0.01935 (9)0.02427 (11)0.00420 (9)0.00693 (9)0.00719 (8)
Geometric parameters (Å, º) top
ZN(1)—S(1)2.2589 (1)C(13)—C(14)1.4039 (3)
ZN(1)—S(2)2.2734 (1)C(13)—C(18)1.4033 (3)
S(1)—C(13)1.7784 (2)C(14)—C(15)1.3953 (3)
S(2)—C(19)1.7834 (3)C(14)—H(14)1.0822 (2)
N(1)—C(1)1.3287 (3)C(15)—C(16)1.3981 (3)
N(1)—C(12)1.3559 (3)C(15)—H(15)1.0829 (2)
N(2)—C(10)1.3294 (3)C(16)—C(17)1.3985 (4)
N(2)—C(11)1.3592 (3)C(16)—C(25)1.5046 (4)
C(1)—C(2)1.4052 (4)C(17)—C(18)1.3950 (4)
C(1)—H(1)1.0837 (3)C(17)—H(17)1.0821 (2)
C(2)—C(3)1.3822 (5)C(18)—H(18)1.0827 (3)
C(2)—H(2)1.0818 (3)C(19)—C(20)1.4002 (4)
C(3)—C(4)1.4124 (4)C(19)—C(24)1.4042 (4)
C(3)—H(3)1.0823 (3)C(20)—C(21)1.3938 (4)
C(4)—C(5)1.4376 (4)C(20)—H(20)1.0831 (3)
C(4)—C(12)1.4102 (3)C(21)—C(22)1.3985 (4)
C(5)—C(6)1.3632 (4)C(21)—H(21)1.0824 (3)
C(5)—H(5)1.0833 (3)C(22)—C(23)1.4001 (4)
C(6)—C(7)1.4367 (4)C(22)—C(26)1.5048 (4)
C(6)—H(6)1.0820 (3)C(23)—C(24)1.3982 (4)
C(7)—C(8)1.4115 (4)C(23)—H(23)1.0831 (3)
C(7)—C(11)1.4094 (3)C(24)—H(24)1.0828 (3)
C(8)—C(9)1.3808 (4)C(25)—H(251)1.0593 (3)
C(8)—H(8)1.0817 (3)C(25)—H(253)1.0599 (3)
C(9)—C(10)1.4043 (4)C(25)—H(252)1.0581 (3)
C(9)—H(9)1.0832 (3)C(26)—H(261)1.0585 (3)
C(10)—H(10)1.0833 (3)C(26)—H(262)1.0597 (4)
C(11)—C(12)1.4414 (3)C(26)—H(263)1.0586 (4)
S(1)—ZN(1)—S(2)125.850 (3)C(13)—C(14)—H(14)119.71 (2)
ZN(1)—S(1)—C(13)104.523 (8)C(15)—C(14)—H(14)119.70 (2)
ZN(1)—S(2)—C(19)94.972 (8)C(14)—C(15)—C(16)121.47 (2)
C(1)—N(1)—C(12)118.97 (2)C(14)—C(15)—H(15)119.33 (2)
C(10)—N(2)—C(11)118.25 (2)C(16)—C(15)—H(15)119.20 (2)
N(1)—C(1)—C(2)122.25 (3)C(15)—C(16)—C(17)117.81 (2)
N(1)—C(1)—H(1)118.93 (3)C(15)—C(16)—C(25)120.90 (2)
C(2)—C(1)—H(1)118.82 (3)C(17)—C(16)—C(25)121.30 (2)
C(1)—C(2)—C(3)119.46 (3)C(16)—C(17)—C(18)121.23 (2)
C(1)—C(2)—H(2)120.32 (3)C(16)—C(17)—H(17)119.40 (2)
C(3)—C(2)—H(2)120.21 (3)C(18)—C(17)—H(17)119.37 (2)
C(2)—C(3)—C(4)119.18 (3)C(13)—C(18)—C(17)120.84 (2)
C(2)—C(3)—H(3)120.31 (3)C(13)—C(18)—H(18)119.60 (2)
C(4)—C(3)—H(3)120.51 (3)C(17)—C(18)—H(18)119.55 (2)
C(3)—C(4)—C(5)123.38 (3)S(2)—C(19)—C(20)119.96 (2)
C(3)—C(4)—C(12)117.38 (2)S(2)—C(19)—C(24)121.92 (2)
C(5)—C(4)—C(12)119.22 (2)C(20)—C(19)—C(24)118.07 (2)
C(4)—C(5)—C(6)120.91 (3)C(19)—C(20)—C(21)120.98 (3)
C(4)—C(5)—H(5)119.61 (3)C(19)—C(20)—H(20)119.50 (3)
C(6)—C(5)—H(5)119.48 (3)C(21)—C(20)—H(20)119.52 (3)
C(5)—C(6)—C(7)120.89 (2)C(20)—C(21)—C(22)121.17 (3)
C(5)—C(6)—H(6)119.49 (3)C(20)—C(21)—H(21)119.42 (3)
C(7)—C(6)—H(6)119.63 (3)C(22)—C(21)—H(21)119.41 (3)
C(6)—C(7)—C(8)122.90 (2)C(21)—C(22)—C(23)117.91 (2)
C(6)—C(7)—C(11)119.50 (2)C(21)—C(22)—C(26)120.25 (3)
C(8)—C(7)—C(11)117.60 (2)C(23)—C(22)—C(26)121.83 (3)
C(7)—C(8)—C(9)119.19 (2)C(22)—C(23)—C(24)121.18 (3)
C(7)—C(8)—H(8)120.45 (3)C(22)—C(23)—H(23)119.41 (2)
C(9)—C(8)—H(8)120.36 (3)C(24)—C(23)—H(23)119.41 (3)
C(8)—C(9)—C(10)119.11 (3)C(19)—C(24)—C(23)120.62 (2)
C(8)—C(9)—H(9)120.37 (3)C(19)—C(24)—H(24)119.66 (2)
C(10)—C(9)—H(9)120.51 (3)C(23)—C(24)—H(24)119.73 (3)
N(2)—C(10)—C(9)123.02 (3)C(16)—C(25)—H(251)112.90 (2)
N(2)—C(10)—H(10)118.53 (2)C(16)—C(25)—H(253)112.56 (2)
C(9)—C(10)—H(10)118.45 (2)C(16)—C(25)—H(252)107.98 (3)
N(2)—C(11)—C(7)122.81 (2)H(251)—C(25)—H(253)108.64 (3)
N(2)—C(11)—C(12)117.67 (2)H(251)—C(25)—H(252)107.57 (2)
C(7)—C(11)—C(12)119.50 (2)H(253)—C(25)—H(252)106.91 (2)
N(1)—C(12)—C(4)122.73 (2)C(22)—C(26)—H(261)111.82 (3)
N(1)—C(12)—C(11)117.31 (2)C(22)—C(26)—H(262)112.00 (3)
C(4)—C(12)—C(11)119.93 (2)C(22)—C(26)—H(263)109.20 (3)
S(1)—C(13)—C(14)122.734 (18)H(261)—C(26)—H(262)110.37 (3)
S(1)—C(13)—C(18)119.100 (18)H(261)—C(26)—H(263)104.49 (3)
C(14)—C(13)—C(18)118.06 (2)H(262)—C(26)—H(263)108.64 (3)
C(13)—C(14)—C(15)120.59 (2)
 

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