Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802007572/cm6006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802007572/cm6006Isup2.hkl |
CCDC reference: 185764
Yellow crystals were obtained from the slow evaporation of an CH3CN/CHCl3 (1/1) solution of [Zn(pyrdtc)2(4,7-Me2phen)] that had been prepared by refluxing equimolar amounts of Zn(pyrdtc) (Wang & Marshall, 1994) and 4,7-dimethyl-1,10-phenanthroline (Aldrich) in chloroform solution. M.p. 529–531 K. IR: (KBr) ν(C—S) 1005; ν(C—N) 1429 cm-1.
The C-bound H atoms were placed in calculated positions and included in the final refinement in the with an overall displacement parameter, Uiso, so that aromatic-H had Uiso, methylene-H had 1.25Uiso and methyl-H had 1.5Uiso.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2000).
Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976). |
[Zn(C5H8NS2)2(C14H12N2)] | F(000) = 2352 |
Mr = 566.11 | Dx = 1.467 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 10135 reflections |
a = 11.2558 (6) Å | θ = 2.2–30.0° |
b = 14.5078 (7) Å | µ = 1.31 mm−1 |
c = 31.3950 (17) Å | T = 193 K |
V = 5126.7 (5) Å3 | Block, yellow |
Z = 8 | 0.47 × 0.47 × 0.24 mm |
Bruker SMART CCD diffractometer | 7496 independent reflections |
Radiation source: fine-focus sealed tube | 6189 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 30.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −15→14 |
Tmin = 0.578, Tmax = 0.730 | k = −20→19 |
40758 measured reflections | l = −35→44 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0638P)2 + 1.6656P] where P = (Fo2 + 2Fc2)/3 |
7496 reflections | (Δ/σ)max < 0.001 |
301 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
[Zn(C5H8NS2)2(C14H12N2)] | V = 5126.7 (5) Å3 |
Mr = 566.11 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.2558 (6) Å | µ = 1.31 mm−1 |
b = 14.5078 (7) Å | T = 193 K |
c = 31.3950 (17) Å | 0.47 × 0.47 × 0.24 mm |
Bruker SMART CCD diffractometer | 7496 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 6189 reflections with I > 2σ(I) |
Tmin = 0.578, Tmax = 0.730 | Rint = 0.038 |
40758 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.84 e Å−3 |
7496 reflections | Δρmin = −0.26 e Å−3 |
301 parameters |
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. 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. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.04197 (2) | 0.155808 (16) | 0.133266 (7) | 0.02733 (8) | |
S1 | 0.12993 (5) | 0.31040 (3) | 0.119985 (17) | 0.03063 (11) | |
S2 | 0.18169 (5) | 0.14171 (3) | 0.070666 (17) | 0.03135 (12) | |
S3 | −0.15826 (5) | 0.19079 (4) | 0.100764 (18) | 0.03474 (12) | |
S4 | −0.06750 (5) | 0.00551 (4) | 0.122250 (17) | 0.03186 (12) | |
N1 | 0.28449 (15) | 0.30255 (11) | 0.05654 (5) | 0.0283 (3) | |
N2 | −0.27404 (15) | 0.03640 (11) | 0.08450 (6) | 0.0307 (3) | |
N3 | 0.17091 (15) | 0.08863 (11) | 0.17585 (5) | 0.0270 (3) | |
N4 | −0.01292 (15) | 0.19311 (11) | 0.19947 (6) | 0.0282 (3) | |
C1 | 0.20674 (17) | 0.25631 (13) | 0.07985 (6) | 0.0252 (4) | |
C2 | 0.3094 (2) | 0.40180 (14) | 0.06170 (7) | 0.0343 (4) | |
H2a | 0.3460 | 0.4146 | 0.0897 | 0.0541 (16)* | |
H2b | 0.2359 | 0.4388 | 0.0589 | 0.0541 (16)* | |
C3 | 0.3954 (2) | 0.42223 (16) | 0.02568 (8) | 0.0443 (6) | |
H3a | 0.3525 | 0.4402 | −0.0006 | 0.0541 (16)* | |
H3b | 0.4511 | 0.4722 | 0.0336 | 0.0541 (16)* | |
C4 | 0.4604 (2) | 0.33179 (19) | 0.01963 (9) | 0.0500 (6) | |
H4a | 0.4971 | 0.3283 | −0.0090 | 0.0541 (16)* | |
H4b | 0.5228 | 0.3236 | 0.0415 | 0.0541 (16)* | |
C5 | 0.3629 (2) | 0.26057 (15) | 0.02459 (7) | 0.0379 (5) | |
H5a | 0.3205 | 0.2505 | −0.0026 | 0.0541 (16)* | |
H5b | 0.3953 | 0.2011 | 0.0348 | 0.0541 (16)* | |
C6 | −0.17649 (17) | 0.07422 (14) | 0.10075 (6) | 0.0280 (4) | |
C7 | −0.2944 (2) | −0.06374 (14) | 0.08168 (8) | 0.0376 (5) | |
H7a | −0.3128 | −0.0902 | 0.1100 | 0.0541 (16)* | |
H7b | −0.2243 | −0.0957 | 0.0697 | 0.0541 (16)* | |
C8 | −0.4003 (2) | −0.07089 (16) | 0.05201 (8) | 0.0411 (5) | |
H8a | −0.3749 | −0.0717 | 0.0218 | 0.0541 (16)* | |
H8b | −0.4475 | −0.1269 | 0.0580 | 0.0541 (16)* | |
C9 | −0.4702 (2) | 0.01590 (17) | 0.06223 (9) | 0.0420 (5) | |
H9a | −0.5155 | 0.0089 | 0.0891 | 0.0541 (16)* | |
H9b | −0.5260 | 0.0315 | 0.0389 | 0.0541 (16)* | |
C10 | −0.37362 (19) | 0.08878 (15) | 0.06664 (7) | 0.0342 (4) | |
H10a | −0.3527 | 0.1156 | 0.0386 | 0.0541 (16)* | |
H10b | −0.3987 | 0.1388 | 0.0861 | 0.0541 (16)* | |
C11 | 0.2596 (2) | 0.03495 (15) | 0.16375 (7) | 0.0340 (4) | |
H11 | 0.2738 | 0.0273 | 0.1341 | 0.0433 (13)* | |
C12 | 0.3333 (2) | −0.01089 (15) | 0.19232 (7) | 0.0364 (5) | |
H12 | 0.3961 | −0.0483 | 0.1818 | 0.0433 (13)* | |
C13 | 0.31629 (19) | −0.00282 (13) | 0.23548 (7) | 0.0315 (4) | |
C14 | 0.22289 (17) | 0.05508 (13) | 0.24926 (6) | 0.0274 (4) | |
C15 | 0.15238 (16) | 0.09893 (12) | 0.21832 (6) | 0.0249 (4) | |
C16 | 0.05576 (17) | 0.15786 (13) | 0.23096 (6) | 0.0253 (4) | |
C17 | −0.10202 (18) | 0.24755 (15) | 0.21083 (7) | 0.0339 (4) | |
H17 | −0.1518 | 0.2721 | 0.1892 | 0.0433 (13)* | |
C18 | −0.12620 (19) | 0.27052 (15) | 0.25315 (8) | 0.0371 (5) | |
H18 | −0.1911 | 0.3100 | 0.2595 | 0.0433 (13)* | |
C19 | −0.05731 (18) | 0.23670 (15) | 0.28564 (7) | 0.0341 (4) | |
C20 | 0.03644 (17) | 0.17616 (14) | 0.27439 (7) | 0.0285 (4) | |
C21 | 0.1118 (2) | 0.13170 (16) | 0.30497 (7) | 0.0361 (5) | |
H21 | 0.0999 | 0.1439 | 0.3344 | 0.0433 (13)* | |
C22 | 0.1985 (2) | 0.07339 (16) | 0.29328 (7) | 0.0357 (5) | |
H22 | 0.2446 | 0.0437 | 0.3146 | 0.0433 (13)* | |
C23 | 0.3941 (2) | −0.05418 (16) | 0.26613 (8) | 0.0434 (6) | |
H23a | 0.4555 | −0.0877 | 0.2503 | 0.0649 (19)* | |
H23b | 0.3459 | −0.0980 | 0.2824 | 0.0649 (19)* | |
H23c | 0.4318 | −0.0104 | 0.2857 | 0.0649 (19)* | |
C24 | −0.0783 (2) | 0.2643 (2) | 0.33135 (8) | 0.0471 (6) | |
H24a | −0.1463 | 0.3064 | 0.3329 | 0.0649 (19)* | |
H24b | −0.0074 | 0.2952 | 0.3425 | 0.0649 (19)* | |
H24c | −0.0949 | 0.2092 | 0.3484 | 0.0649 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.02652 (13) | 0.02873 (13) | 0.02672 (13) | −0.00167 (8) | −0.00198 (8) | 0.00115 (9) |
S1 | 0.0282 (2) | 0.0279 (2) | 0.0357 (3) | −0.00158 (18) | 0.00372 (19) | −0.00485 (19) |
S2 | 0.0414 (3) | 0.0224 (2) | 0.0303 (2) | −0.00510 (19) | −0.0001 (2) | −0.00190 (18) |
S3 | 0.0379 (3) | 0.0289 (2) | 0.0374 (3) | −0.0066 (2) | −0.0063 (2) | 0.0026 (2) |
S4 | 0.0261 (2) | 0.0355 (3) | 0.0340 (3) | 0.00128 (19) | −0.00147 (18) | 0.0007 (2) |
N1 | 0.0311 (8) | 0.0227 (7) | 0.0310 (8) | −0.0022 (6) | 0.0028 (6) | −0.0018 (6) |
N2 | 0.0274 (8) | 0.0274 (8) | 0.0373 (9) | −0.0015 (7) | −0.0055 (7) | 0.0007 (7) |
N3 | 0.0286 (8) | 0.0285 (8) | 0.0240 (8) | −0.0001 (6) | −0.0012 (6) | −0.0038 (6) |
N4 | 0.0251 (8) | 0.0269 (8) | 0.0325 (9) | −0.0010 (6) | −0.0013 (6) | −0.0005 (7) |
C1 | 0.0250 (9) | 0.0242 (8) | 0.0263 (9) | 0.0003 (7) | −0.0036 (7) | −0.0015 (7) |
C2 | 0.0389 (11) | 0.0246 (9) | 0.0392 (12) | −0.0088 (8) | 0.0054 (9) | −0.0015 (8) |
C3 | 0.0548 (15) | 0.0389 (11) | 0.0392 (13) | −0.0156 (11) | 0.0096 (10) | 0.0029 (10) |
C4 | 0.0480 (15) | 0.0532 (14) | 0.0489 (15) | −0.0097 (11) | 0.0209 (11) | −0.0036 (12) |
C5 | 0.0463 (13) | 0.0337 (10) | 0.0336 (11) | −0.0011 (9) | 0.0124 (9) | −0.0037 (9) |
C6 | 0.0276 (9) | 0.0318 (9) | 0.0247 (9) | −0.0020 (7) | 0.0011 (7) | 0.0012 (7) |
C7 | 0.0358 (11) | 0.0264 (9) | 0.0506 (13) | −0.0031 (8) | −0.0087 (9) | −0.0010 (9) |
C8 | 0.0409 (13) | 0.0370 (11) | 0.0454 (13) | −0.0081 (9) | −0.0096 (10) | −0.0060 (10) |
C9 | 0.0305 (11) | 0.0439 (12) | 0.0516 (14) | −0.0017 (9) | −0.0104 (9) | −0.0008 (11) |
C10 | 0.0316 (10) | 0.0334 (10) | 0.0376 (11) | 0.0012 (8) | −0.0065 (8) | 0.0024 (9) |
C11 | 0.0366 (11) | 0.0357 (10) | 0.0298 (10) | 0.0060 (9) | −0.0034 (8) | −0.0096 (8) |
C12 | 0.0363 (11) | 0.0345 (10) | 0.0384 (11) | 0.0092 (9) | −0.0068 (9) | −0.0127 (9) |
C13 | 0.0343 (10) | 0.0234 (8) | 0.0368 (11) | 0.0015 (7) | −0.0104 (8) | −0.0048 (8) |
C14 | 0.0281 (9) | 0.0261 (9) | 0.0279 (9) | −0.0038 (7) | −0.0052 (7) | −0.0015 (7) |
C15 | 0.0236 (8) | 0.0241 (8) | 0.0270 (9) | −0.0031 (7) | −0.0025 (7) | −0.0023 (7) |
C16 | 0.0238 (9) | 0.0252 (8) | 0.0268 (9) | −0.0038 (7) | 0.0003 (6) | −0.0005 (7) |
C17 | 0.0277 (10) | 0.0313 (10) | 0.0426 (12) | 0.0016 (8) | −0.0026 (8) | −0.0004 (9) |
C18 | 0.0260 (10) | 0.0339 (10) | 0.0513 (13) | 0.0011 (8) | 0.0044 (9) | −0.0090 (10) |
C19 | 0.0281 (10) | 0.0353 (10) | 0.0388 (12) | −0.0078 (8) | 0.0080 (8) | −0.0082 (9) |
C20 | 0.0266 (9) | 0.0307 (9) | 0.0282 (10) | −0.0051 (7) | 0.0032 (7) | −0.0026 (8) |
C21 | 0.0371 (11) | 0.0476 (12) | 0.0237 (10) | −0.0024 (10) | 0.0001 (8) | −0.0014 (9) |
C22 | 0.0366 (11) | 0.0448 (12) | 0.0256 (10) | −0.0010 (9) | −0.0053 (8) | 0.0028 (8) |
C23 | 0.0468 (13) | 0.0357 (11) | 0.0476 (14) | 0.0116 (10) | −0.0192 (10) | −0.0050 (10) |
C24 | 0.0421 (13) | 0.0588 (15) | 0.0404 (13) | −0.0004 (12) | 0.0139 (10) | −0.0141 (11) |
Zn—S1 | 2.4868 (6) | C8—C9 | 1.519 (3) |
Zn—S2 | 2.5254 (6) | C8—H8A | 0.9900 |
Zn—S3 | 2.5256 (6) | C8—H8B | 0.9900 |
Zn—S4 | 2.5283 (6) | C9—C10 | 1.523 (3) |
Zn—N3 | 2.2008 (16) | C9—H9A | 0.9900 |
Zn—N4 | 2.2349 (17) | C9—H9B | 0.9900 |
S1—C1 | 1.718 (2) | C10—H10A | 0.9900 |
S2—C1 | 1.7107 (19) | C10—H10B | 0.9900 |
S3—C6 | 1.703 (2) | C11—C12 | 1.390 (3) |
S4—C6 | 1.719 (2) | C11—H11 | 0.9500 |
N1—C1 | 1.323 (2) | C12—C13 | 1.373 (3) |
N1—C2 | 1.476 (2) | C12—H12 | 0.9500 |
N1—C5 | 1.469 (3) | C13—C14 | 1.414 (3) |
N2—C6 | 1.329 (3) | C13—C23 | 1.500 (3) |
N2—C10 | 1.466 (3) | C14—C15 | 1.407 (3) |
N2—C7 | 1.473 (3) | C14—C22 | 1.434 (3) |
N3—C11 | 1.322 (3) | C15—C16 | 1.439 (3) |
N3—C15 | 1.358 (2) | C16—C20 | 1.406 (3) |
N4—C17 | 1.325 (3) | C17—C18 | 1.397 (3) |
N4—C16 | 1.355 (3) | C17—H17 | 0.9500 |
C2—C3 | 1.518 (3) | C18—C19 | 1.372 (3) |
C2—H2A | 0.9900 | C18—H18 | 0.9500 |
C2—H2B | 0.9900 | C19—C20 | 1.418 (3) |
C3—C4 | 1.514 (4) | C19—C24 | 1.509 (3) |
C3—H3A | 0.9900 | C20—C21 | 1.434 (3) |
C3—H3B | 0.9900 | C21—C22 | 1.343 (3) |
C4—C5 | 1.515 (3) | C21—H21 | 0.9500 |
C4—H4A | 0.9900 | C22—H22 | 0.9500 |
C4—H4B | 0.9900 | C23—H23A | 0.9800 |
C5—H5A | 0.9900 | C23—H23B | 0.9800 |
C5—H5B | 0.9900 | C23—H23C | 0.9800 |
C7—C8 | 1.516 (3) | C24—H24A | 0.9800 |
C7—H7A | 0.9900 | C24—H24B | 0.9800 |
C7—H7B | 0.9900 | C24—H24C | 0.9800 |
S1—Zn—S2 | 72.220 (17) | C9—C8—C7 | 102.78 (18) |
S1—Zn—S3 | 96.102 (19) | C9—C8—H8A | 111.2 |
S1—Zn—S4 | 161.60 (2) | C7—C8—H8A | 111.2 |
S1—Zn—N3 | 103.81 (5) | C9—C8—H8B | 111.2 |
S1—Zn—N4 | 92.73 (4) | C7—C8—H8B | 111.2 |
S2—Zn—S3 | 104.93 (2) | H8A—C8—H8B | 109.1 |
S2—Zn—S4 | 97.309 (18) | C8—C9—C10 | 102.96 (18) |
S2—Zn—N3 | 91.50 (4) | C8—C9—H9A | 111.2 |
S2—Zn—N4 | 156.28 (5) | C10—C9—H9A | 111.2 |
S3—Zn—S4 | 71.524 (18) | C8—C9—H9B | 111.2 |
S3—Zn—N3 | 157.36 (5) | C10—C9—H9B | 111.2 |
S3—Zn—N4 | 94.61 (5) | H9A—C9—H9B | 109.1 |
S4—Zn—N3 | 91.29 (4) | N2—C10—C9 | 102.76 (17) |
S4—Zn—N4 | 101.61 (4) | N2—C10—H10A | 111.2 |
N3—Zn—N4 | 74.01 (6) | C9—C10—H10A | 111.2 |
Zn—S1—C1 | 84.91 (7) | N2—C10—H10B | 111.2 |
Zn—S2—C1 | 83.85 (7) | C9—C10—H10B | 111.2 |
Zn—S3—C6 | 84.73 (7) | H10A—C10—H10B | 109.1 |
Zn—S4—C6 | 84.34 (7) | N3—C11—C12 | 123.15 (19) |
C1—N1—C2 | 124.02 (17) | N3—C11—H11 | 118.4 |
C1—N1—C5 | 124.40 (16) | C12—C11—H11 | 118.4 |
C2—N1—C5 | 111.44 (16) | C13—C12—C11 | 120.8 (2) |
C6—N2—C10 | 124.36 (17) | C13—C12—H12 | 119.6 |
C6—N2—C7 | 123.95 (17) | C11—C12—H12 | 119.6 |
C10—N2—C7 | 111.68 (16) | C12—C13—C14 | 117.15 (18) |
C11—N3—C15 | 117.57 (17) | C12—C13—C23 | 120.6 (2) |
C11—N3—Zn | 125.77 (14) | C14—C13—C23 | 122.2 (2) |
C15—N3—Zn | 116.52 (12) | C15—C14—C13 | 118.49 (18) |
C17—N4—C16 | 117.41 (18) | C15—C14—C22 | 118.28 (18) |
C17—N4—Zn | 127.13 (15) | C13—C14—C22 | 123.21 (18) |
C16—N4—Zn | 115.43 (13) | N3—C15—C14 | 122.81 (17) |
S1—C1—S2 | 118.98 (11) | N3—C15—C16 | 116.88 (17) |
S1—C1—N1 | 120.45 (14) | C14—C15—C16 | 120.31 (18) |
S2—C1—N1 | 120.57 (14) | N4—C16—C20 | 123.23 (18) |
N1—C2—C3 | 103.29 (17) | N4—C16—C15 | 117.01 (17) |
N1—C2—H2A | 111.1 | C20—C16—C15 | 119.76 (18) |
C3—C2—H2A | 111.1 | N4—C17—C18 | 123.1 (2) |
N1—C2—H2B | 111.1 | N4—C17—H17 | 118.5 |
C3—C2—H2B | 111.1 | C18—C17—H17 | 118.5 |
H2A—C2—H2B | 109.1 | C19—C18—C17 | 120.8 (2) |
C4—C3—C2 | 103.44 (18) | C19—C18—H18 | 119.6 |
C4—C3—H3A | 111.1 | C17—C18—H18 | 119.6 |
C2—C3—H3A | 111.1 | C18—C19—C20 | 117.2 (2) |
C4—C3—H3B | 111.1 | C18—C19—C24 | 121.6 (2) |
C2—C3—H3B | 111.1 | C20—C19—C24 | 121.2 (2) |
H3A—C3—H3B | 109.0 | C16—C20—C19 | 118.27 (19) |
C5—C4—C3 | 103.2 (2) | C16—C20—C21 | 118.22 (19) |
C5—C4—H4A | 111.1 | C19—C20—C21 | 123.5 (2) |
C3—C4—H4A | 111.1 | C22—C21—C20 | 122.0 (2) |
C5—C4—H4B | 111.1 | C22—C21—H21 | 119.0 |
C3—C4—H4B | 111.1 | C20—C21—H21 | 119.0 |
H4A—C4—H4B | 109.1 | C21—C22—C14 | 121.3 (2) |
N1—C5—C4 | 102.86 (18) | C21—C22—H22 | 119.4 |
N1—C5—H5A | 111.2 | C14—C22—H22 | 119.4 |
C4—C5—H5A | 111.2 | C13—C23—H23A | 109.5 |
N1—C5—H5B | 111.2 | C13—C23—H23B | 109.5 |
C4—C5—H5B | 111.2 | H23A—C23—H23B | 109.5 |
H5A—C5—H5B | 109.1 | C13—C23—H23C | 109.5 |
S3—C6—S4 | 119.32 (12) | H23A—C23—H23C | 109.5 |
S3—C6—N2 | 120.62 (15) | H23B—C23—H23C | 109.5 |
S4—C6—N2 | 120.05 (15) | C19—C24—H24A | 109.5 |
N2—C7—C8 | 103.09 (17) | C19—C24—H24B | 109.5 |
N2—C7—H7A | 111.1 | H24A—C24—H24B | 109.5 |
C8—C7—H7A | 111.1 | C19—C24—H24C | 109.5 |
N2—C7—H7B | 111.1 | H24A—C24—H24C | 109.5 |
C8—C7—H7B | 111.1 | H24B—C24—H24C | 109.5 |
H7A—C7—H7B | 109.1 |
Experimental details
Crystal data | |
Chemical formula | [Zn(C5H8NS2)2(C14H12N2)] |
Mr | 566.11 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 193 |
a, b, c (Å) | 11.2558 (6), 14.5078 (7), 31.3950 (17) |
V (Å3) | 5126.7 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.31 |
Crystal size (mm) | 0.47 × 0.47 × 0.24 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.578, 0.730 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40758, 7496, 6189 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.04 |
No. of reflections | 7496 |
No. of parameters | 301 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.84, −0.26 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), PATTY in DIRDIF92 (Beurskens et al., 1992), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97 and PLATON (Spek, 2000).
Zn—S1 | 2.4868 (6) | S1—C1 | 1.718 (2) |
Zn—S2 | 2.5254 (6) | S2—C1 | 1.7107 (19) |
Zn—S3 | 2.5256 (6) | S3—C6 | 1.703 (2) |
Zn—S4 | 2.5283 (6) | S4—C6 | 1.719 (2) |
Zn—N3 | 2.2008 (16) | N1—C1 | 1.323 (2) |
Zn—N4 | 2.2349 (17) | N2—C6 | 1.329 (3) |
S1—Zn—S2 | 72.220 (17) | S4—Zn—N4 | 101.61 (4) |
S1—Zn—S3 | 96.102 (19) | N3—Zn—N4 | 74.01 (6) |
S1—Zn—S4 | 161.60 (2) | Zn—S1—C1 | 84.91 (7) |
S1—Zn—N3 | 103.81 (5) | Zn—S2—C1 | 83.85 (7) |
S1—Zn—N4 | 92.73 (4) | Zn—S3—C6 | 84.73 (7) |
S2—Zn—S3 | 104.93 (2) | Zn—S4—C6 | 84.34 (7) |
S2—Zn—S4 | 97.309 (18) | S1—C1—S2 | 118.98 (11) |
S2—Zn—N3 | 91.50 (4) | S1—C1—N1 | 120.45 (14) |
S2—Zn—N4 | 156.28 (5) | S2—C1—N1 | 120.57 (14) |
S3—Zn—S4 | 71.524 (18) | S3—C6—S4 | 119.32 (12) |
S3—Zn—N3 | 157.36 (5) | S3—C6—N2 | 120.62 (15) |
S3—Zn—N4 | 94.61 (5) | S4—C6—N2 | 120.05 (15) |
S4—Zn—N3 | 91.29 (4) |
The addition of a Lewis base is known to disrupt the fascinating array of structural motifs observed in the zinc-triad 1,1-dithiolates, such as those containing dithiocarbamate (-S2CNR2) ligands (Cox & Tiekink, 1997). One possible advantage of disrupting the extended arrays is to provide more suitable precursors for chemical vapour deposition studies (e.g. Zeng, Hampden-Smith, Alam & Rheingold, 1994). Consequently, there have been a number of recent investigations into adduct formation of such species by various groups (e.g. Zeng, Hampden-Smith & Larson, 1994; Klevtsova et al., 2001), as well as by us (e.g. Beer et al., 2002; Tiekink, 2001a,b; Jie & Tiekink, 2002; Dee & Tiekink, 2002). It is in this context that the structure of the title compound, Zn(pyrdtc)2(4,7-Me2phen), (I), was investigated.
The Zn atom in (I) exists in a distorted octahedral geometry within a N2S4-donor set (Fig. 1). The dithiocarbamate ligands are chelating with slight asymmetry in their Zn—S bond distances for the S1/S2-chelate compared with the experimentally equivalent Zn—S bond distances formed by the S3/S4-chelate (Table 1). The near equivalence in the Zn—S bond distances is reflected in the associated C—S bonds. There is also some asymmetry in the Zn—N bond distances, with Zn—N3 being significantly shorter than Zn—N4. The reasons for the pattern in bond distances in not immediately apparent. The greatest distortion from the ideal octahedral geometry is manifested in the S2—Zn—N4 angle of 156.28 (5)°, probably reflecting the influence of three tight chelate angles in the structure, that range from 71.524 (18) to 74.01 (6)°. The overall molecular geometry is comparable to that reported recently for the 2,2'-bipyridine adduct of Zn(pyrdtc)2 (Jie & Tiekink, 2002) and related zinc bis(dithiocarbamate) diimine structures (e.g. Klevstova et al., 1999).
The crystal structure comprises essentially isolated molecules. Arguably, the most significant intermolecular contact is of the type C—H···π. This occurs between a methyl C—H and the ring centroid of the five-membered chelate ring formed by the 4,7-Me2phen moiety. The parameters associated with this interaction are H···ring centroid distance of 2.84 Å and an angle of 156° at H for symmetry operation 1/2 + x, y, 1/2 - z.