Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029466/ng6201sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029466/ng6201Isup2.hkl |
CCDC reference: 287669
Key indicators
- Single-crystal X-ray study
- T = 223 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.057
- wR factor = 0.137
- Data-to-parameter ratio = 24.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.89 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 4.00 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.54 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C2 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C4' PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.29 PLAT301_ALERT_3_C Main Residue Disorder ......................... 12.00 Perc. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
The title compound was prepared by refluxing the parent zinc dithiophosphate with 4-pyridinealdazine (Aldrich) using a literature procedure (Lai et al., 2004a). Colourless crystals were isolated in 65% yield by slow evaporation of a chloroform–acetonitrile (3:1 (v/v) solution of the compound (m.p. 377–379 K). Analysis found: C 50.38, H 6.34%; C36H54N4O4P2S4Zn requires: C 50.14, H 6.31%. IR (KBr disk): ν(C—O) 1153 (m), ν(P—O) 968 (s), ν(P—S)asymm 658 (m), ν(P—S)symm 523 (m) cm−1.
H atoms were included in the riding-model approximation, with aromatic C—H = 0.94 Å, methine C—H = 0.99 Å and methylene C—H = 0.98 Å, and with Uiso(H) = 1.2Ueq(C). The C1–C6 cyclohexyl group was disordered and two sites were discerned for atoms C5 and C6. As the occupancy for each site refined to nearly 50%, the occupancies of the disordered atoms were fixed at 50%.
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.
[Zn(C12H22O2PS2)2(C12H10N4)] | Dx = 1.356 Mg m−3 |
Mr = 862.38 | Melting point = 377–379 K |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 6234 reflections |
a = 18.3340 (8) Å | θ = 2.4–25.8° |
b = 12.0404 (5) Å | µ = 0.90 mm−1 |
c = 19.1304 (8) Å | T = 223 K |
V = 4223.0 (3) Å3 | Block, yellow |
Z = 4 | 0.52 × 0.36 × 0.26 mm |
F(000) = 1816 |
Bruker SMART area-detector diffractometer | 6155 independent reflections |
Radiation source: medium-focus sealed tube | 4886 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 30.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS, Bruker, 2000) | h = −25→25 |
Tmin = 0.565, Tmax = 0.792 | k = −14→16 |
39717 measured reflections | l = −26→26 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0635P)2 + 1.9949P] where P = (Fo2 + 2Fc2)/3 |
6155 reflections | (Δ/σ)max < 0.001 |
253 parameters | Δρmax = 0.92 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
[Zn(C12H22O2PS2)2(C12H10N4)] | V = 4223.0 (3) Å3 |
Mr = 862.38 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 18.3340 (8) Å | µ = 0.90 mm−1 |
b = 12.0404 (5) Å | T = 223 K |
c = 19.1304 (8) Å | 0.52 × 0.36 × 0.26 mm |
Bruker SMART area-detector diffractometer | 6155 independent reflections |
Absorption correction: multi-scan (SADABS, Bruker, 2000) | 4886 reflections with I > 2σ(I) |
Tmin = 0.565, Tmax = 0.792 | Rint = 0.049 |
39717 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.92 e Å−3 |
6155 reflections | Δρmin = −0.23 e Å−3 |
253 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 | Occ. (<1) | |
Zn | 0.5000 | 0.48584 (3) | 0.7500 | 0.03079 (11) | |
S1 | 0.36497 (4) | 0.46900 (5) | 0.74253 (3) | 0.03848 (15) | |
S2 | 0.48669 (4) | 0.33984 (6) | 0.64643 (4) | 0.04344 (17) | |
P1 | 0.38187 (4) | 0.36064 (5) | 0.66535 (3) | 0.03481 (15) | |
O2 | 0.33669 (12) | 0.39099 (14) | 0.59734 (9) | 0.0494 (5) | |
N1 | 0.50840 (11) | 0.61737 (16) | 0.67173 (10) | 0.0318 (4) | |
N2 | 0.49444 (12) | 0.96364 (18) | 0.52840 (12) | 0.0424 (5) | |
C1 | 0.36590 (15) | 0.1762 (2) | 0.73787 (13) | 0.0403 (6) | |
H1 | 0.4142 | 0.2061 | 0.7513 | 0.048* | |
C2 | 0.3811 (3) | 0.0635 (3) | 0.71081 (16) | 0.0794 (13) | |
H2A | 0.4216 | 0.0668 | 0.6774 | 0.095* | |
H2B | 0.3380 | 0.0354 | 0.6861 | 0.095* | |
C3 | 0.4007 (3) | −0.0156 (3) | 0.7705 (2) | 0.0846 (14) | |
H3A | 0.4096 | −0.0899 | 0.7514 | 0.102* | |
H3B | 0.4458 | 0.0099 | 0.7929 | 0.102* | |
C4 | 0.34220 (19) | −0.0219 (2) | 0.82339 (17) | 0.0552 (8) | 0.50 |
H4A | 0.3517 | −0.0807 | 0.8576 | 0.066* | 0.50 |
H4B | 0.2945 | −0.0343 | 0.8017 | 0.066* | 0.50 |
C5 | 0.3472 (7) | 0.0960 (9) | 0.8574 (5) | 0.081 (4) | 0.50 |
H5A | 0.3150 | 0.1007 | 0.8983 | 0.097* | 0.50 |
H5B | 0.3973 | 0.1114 | 0.8725 | 0.097* | 0.50 |
C6 | 0.3231 (7) | 0.1805 (10) | 0.8009 (6) | 0.078 (4) | 0.50 |
H6A | 0.3263 | 0.2556 | 0.8204 | 0.093* | 0.50 |
H6B | 0.2719 | 0.1665 | 0.7890 | 0.093* | 0.50 |
O1 | 0.34203 (10) | 0.24598 (14) | 0.68023 (9) | 0.0419 (4) | 0.50 |
C4' | 0.34220 (19) | −0.0219 (2) | 0.82339 (17) | 0.0552 (8) | 0.50 |
H4'1 | 0.3621 | −0.0558 | 0.8659 | 0.066* | 0.50 |
H4'2 | 0.3037 | −0.0710 | 0.8058 | 0.066* | 0.50 |
C5' | 0.3091 (5) | 0.0863 (10) | 0.8421 (5) | 0.060 (2) | 0.50 |
H5'1 | 0.3414 | 0.1236 | 0.8755 | 0.072* | 0.50 |
H5'2 | 0.2628 | 0.0720 | 0.8660 | 0.072* | 0.50 |
C6' | 0.2948 (5) | 0.1645 (9) | 0.7827 (6) | 0.047 (2) | 0.50 |
H6'1 | 0.2803 | 0.2373 | 0.8009 | 0.057* | 0.50 |
H6'2 | 0.2550 | 0.1359 | 0.7536 | 0.057* | 0.50 |
O1' | 0.34203 (10) | 0.24598 (14) | 0.68023 (9) | 0.0419 (4) | 0.50 |
C7 | 0.31081 (14) | 0.50087 (19) | 0.57852 (12) | 0.0368 (5) | |
H7 | 0.3010 | 0.5439 | 0.6216 | 0.044* | |
C8 | 0.24043 (17) | 0.4848 (3) | 0.53899 (16) | 0.0518 (7) | |
H8A | 0.2488 | 0.4348 | 0.4993 | 0.062* | |
H8B | 0.2042 | 0.4503 | 0.5697 | 0.062* | |
C9 | 0.21125 (17) | 0.5954 (3) | 0.51241 (16) | 0.0589 (8) | |
H9A | 0.1971 | 0.6415 | 0.5524 | 0.071* | |
H9B | 0.1675 | 0.5820 | 0.4841 | 0.071* | |
C10 | 0.26649 (18) | 0.6567 (2) | 0.46922 (16) | 0.0571 (8) | |
H10A | 0.2468 | 0.7294 | 0.4559 | 0.069* | |
H10B | 0.2764 | 0.6149 | 0.4263 | 0.069* | |
C11 | 0.3371 (2) | 0.6725 (3) | 0.50988 (18) | 0.0626 (9) | |
H11A | 0.3282 | 0.7210 | 0.5501 | 0.075* | |
H11B | 0.3734 | 0.7085 | 0.4799 | 0.075* | |
C12 | 0.36655 (15) | 0.5611 (2) | 0.53515 (16) | 0.0486 (6) | |
H12A | 0.3798 | 0.5154 | 0.4947 | 0.058* | |
H12B | 0.4106 | 0.5734 | 0.5631 | 0.058* | |
C13 | 0.55511 (13) | 0.61015 (19) | 0.61883 (12) | 0.0355 (5) | |
H13 | 0.5868 | 0.5488 | 0.6171 | 0.043* | |
C14 | 0.55932 (14) | 0.68874 (19) | 0.56618 (13) | 0.0371 (5) | |
H14 | 0.5921 | 0.6795 | 0.5289 | 0.045* | |
C15 | 0.51456 (13) | 0.78096 (19) | 0.56927 (12) | 0.0332 (5) | |
C16 | 0.46576 (14) | 0.78913 (18) | 0.62449 (12) | 0.0349 (5) | |
H16 | 0.4346 | 0.8508 | 0.6283 | 0.042* | |
C17 | 0.46358 (14) | 0.70568 (18) | 0.67361 (12) | 0.0342 (5) | |
H17 | 0.4293 | 0.7107 | 0.7100 | 0.041* | |
C18 | 0.51922 (14) | 0.8674 (2) | 0.51543 (13) | 0.0354 (5) | |
H18 | 0.5403 | 0.8516 | 0.4718 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0474 (2) | 0.02128 (18) | 0.02365 (18) | 0.000 | 0.00074 (15) | 0.000 |
S1 | 0.0513 (4) | 0.0333 (3) | 0.0309 (3) | −0.0008 (3) | −0.0006 (2) | −0.0033 (2) |
S2 | 0.0554 (4) | 0.0307 (3) | 0.0441 (4) | −0.0004 (3) | 0.0075 (3) | 0.0010 (3) |
P1 | 0.0529 (4) | 0.0230 (3) | 0.0285 (3) | −0.0013 (2) | −0.0050 (3) | 0.0021 (2) |
O2 | 0.0852 (14) | 0.0275 (9) | 0.0356 (9) | 0.0066 (9) | −0.0194 (9) | −0.0011 (7) |
N1 | 0.0499 (11) | 0.0222 (9) | 0.0232 (8) | 0.0018 (8) | 0.0023 (8) | 0.0021 (7) |
N2 | 0.0629 (14) | 0.0280 (11) | 0.0363 (11) | 0.0016 (9) | 0.0044 (10) | 0.0124 (9) |
C1 | 0.0527 (15) | 0.0342 (13) | 0.0339 (12) | −0.0116 (11) | −0.0034 (10) | 0.0077 (10) |
C2 | 0.153 (4) | 0.0448 (18) | 0.0405 (16) | 0.035 (2) | 0.029 (2) | 0.0138 (14) |
C3 | 0.121 (3) | 0.067 (2) | 0.065 (2) | 0.047 (2) | 0.040 (2) | 0.0328 (19) |
C4 | 0.070 (2) | 0.0384 (15) | 0.0569 (18) | 0.0004 (13) | 0.0131 (15) | 0.0173 (13) |
C5 | 0.175 (12) | 0.041 (4) | 0.026 (3) | −0.002 (7) | 0.019 (6) | 0.006 (3) |
C6 | 0.135 (12) | 0.034 (4) | 0.064 (7) | 0.007 (6) | 0.043 (7) | 0.006 (4) |
O1 | 0.0560 (11) | 0.0281 (9) | 0.0417 (9) | −0.0068 (8) | −0.0099 (8) | 0.0062 (7) |
C4' | 0.070 (2) | 0.0384 (15) | 0.0569 (18) | 0.0004 (13) | 0.0131 (15) | 0.0173 (13) |
C5' | 0.080 (6) | 0.060 (5) | 0.041 (5) | −0.001 (4) | 0.018 (4) | 0.010 (4) |
C6' | 0.052 (4) | 0.032 (4) | 0.057 (6) | 0.000 (3) | 0.015 (3) | 0.005 (3) |
O1' | 0.0560 (11) | 0.0281 (9) | 0.0417 (9) | −0.0068 (8) | −0.0099 (8) | 0.0062 (7) |
C7 | 0.0546 (14) | 0.0262 (11) | 0.0296 (11) | 0.0069 (10) | −0.0070 (10) | −0.0024 (9) |
C8 | 0.0555 (17) | 0.0512 (17) | 0.0485 (15) | −0.0079 (13) | −0.0087 (13) | 0.0058 (13) |
C9 | 0.0550 (17) | 0.068 (2) | 0.0537 (17) | 0.0172 (15) | −0.0144 (14) | −0.0047 (16) |
C10 | 0.079 (2) | 0.0377 (15) | 0.0547 (16) | 0.0071 (14) | −0.0267 (16) | 0.0078 (13) |
C11 | 0.079 (2) | 0.0415 (16) | 0.068 (2) | −0.0104 (15) | −0.0286 (17) | 0.0169 (15) |
C12 | 0.0499 (15) | 0.0439 (15) | 0.0519 (16) | 0.0009 (12) | −0.0092 (12) | 0.0051 (13) |
C13 | 0.0505 (14) | 0.0253 (11) | 0.0307 (11) | 0.0057 (9) | 0.0063 (10) | 0.0038 (9) |
C14 | 0.0508 (14) | 0.0284 (12) | 0.0322 (11) | 0.0024 (10) | 0.0078 (10) | 0.0060 (9) |
C15 | 0.0473 (13) | 0.0220 (10) | 0.0303 (11) | −0.0023 (9) | −0.0017 (9) | 0.0056 (9) |
C16 | 0.0495 (14) | 0.0210 (10) | 0.0343 (11) | 0.0051 (9) | 0.0009 (10) | 0.0024 (9) |
C17 | 0.0520 (14) | 0.0230 (10) | 0.0277 (10) | 0.0042 (9) | 0.0058 (10) | 0.0017 (8) |
C18 | 0.0457 (13) | 0.0285 (11) | 0.0319 (11) | −0.0027 (9) | 0.0003 (9) | 0.0084 (9) |
Zn—S1 | 2.4880 (7) | C4'—H4'2 | 0.9800 |
Zn—S2 | 2.6600 (7) | C5'—C6' | 1.498 (16) |
Zn—N1 | 2.1850 (18) | C5'—H5'1 | 0.9800 |
P1—S1 | 1.9946 (9) | C5'—H5'2 | 0.9800 |
P1—S2 | 1.9716 (10) | C6'—H6'1 | 0.9800 |
P1—O1 | 1.5876 (18) | C6'—H6'2 | 0.9800 |
P1—O2 | 1.5849 (18) | C7—C8 | 1.508 (4) |
O2—C7 | 1.451 (3) | C7—C12 | 1.503 (4) |
N1—C13 | 1.328 (3) | C7—H7 | 0.9900 |
N1—C17 | 1.344 (3) | C8—C9 | 1.522 (4) |
N2—N2i | 1.410 (4) | C8—H8A | 0.9800 |
N2—C18 | 1.270 (3) | C8—H8B | 0.9800 |
C1—C6 | 1.439 (13) | C9—C10 | 1.501 (5) |
C1—O1' | 1.454 (3) | C9—H9A | 0.9800 |
C1—O1 | 1.454 (3) | C9—H9B | 0.9800 |
C1—C2 | 1.478 (4) | C10—C11 | 1.523 (4) |
C1—C6' | 1.566 (11) | C10—H10A | 0.9800 |
C1—H1 | 0.9900 | C10—H10B | 0.9800 |
C2—C3 | 1.530 (4) | C11—C12 | 1.524 (4) |
C2—H2A | 0.9800 | C11—H11A | 0.9800 |
C2—H2B | 0.9800 | C11—H11B | 0.9800 |
C3—C4 | 1.477 (5) | C12—H12A | 0.9800 |
C3—H3A | 0.9800 | C12—H12B | 0.9800 |
C3—H3B | 0.9800 | C13—C14 | 1.384 (3) |
C4—C5 | 1.565 (11) | C13—H13 | 0.9400 |
C4—H4A | 0.9800 | C14—C15 | 1.382 (3) |
C4—H4B | 0.9800 | C14—H14 | 0.9400 |
C5—C6 | 1.549 (16) | C15—C16 | 1.388 (3) |
C5—H5A | 0.9800 | C15—C18 | 1.467 (3) |
C5—H5B | 0.9800 | C16—C17 | 1.376 (3) |
C6—H6A | 0.9800 | C16—H16 | 0.9400 |
C6—H6B | 0.9800 | C17—H17 | 0.9400 |
C4'—C5' | 1.481 (12) | C18—H18 | 0.9400 |
C4'—H4'1 | 0.9800 | ||
S1—Zn—S2 | 79.17 (2) | C5'—C4'—H4'1 | 108.6 |
S1—Zn—N1 | 95.15 (5) | C3—C4'—H4'1 | 108.6 |
S1—Zn—S1ii | 170.66 (3) | C5'—C4'—H4'2 | 108.6 |
S1—Zn—S2ii | 94.60 (2) | C3—C4'—H4'2 | 108.6 |
S1—Zn—N1ii | 91.62 (5) | H4'1—C4'—H4'2 | 107.6 |
S2—Zn—N1 | 88.57 (5) | C4'—C5'—C6' | 116.2 (8) |
S2—Zn—S2ii | 97.27 (3) | C4'—C5'—H5'1 | 108.2 |
S2—Zn—N1ii | 169.43 (5) | C6'—C5'—H5'1 | 108.2 |
N1ii—Zn—N1 | 87.09 (10) | C4'—C5'—H5'2 | 108.2 |
Zn—S1—P1 | 86.63 (3) | C6'—C5'—H5'2 | 108.2 |
Zn—S2—P1 | 82.46 (3) | H5'1—C5'—H5'2 | 107.4 |
S1—P1—S2 | 111.74 (4) | C5'—C6'—C1 | 109.0 (8) |
Zn—N1—C13 | 121.33 (15) | C5'—C6'—H6'1 | 109.9 |
Zn—N1—C17 | 120.79 (15) | C1—C6'—H6'1 | 109.9 |
C13—N1—C17 | 117.79 (19) | C5'—C6'—H6'2 | 109.9 |
C18—N2—N2i | 111.4 (3) | C1—C6'—H6'2 | 109.9 |
O2—P1—O1' | 96.16 (10) | H6'1—C6'—H6'2 | 108.3 |
O2—P1—O1 | 96.16 (10) | C1—O1'—P1 | 120.02 (15) |
O2—P1—S2 | 112.83 (9) | O2—C7—C8 | 106.7 (2) |
O1'—P1—S2 | 111.77 (8) | O2—C7—C12 | 110.8 (2) |
O1—P1—S2 | 111.77 (8) | C8—C7—C12 | 111.5 (2) |
O2—P1—S1 | 112.06 (8) | O2—C7—H7 | 109.3 |
O1'—P1—S1 | 111.38 (8) | C8—C7—H7 | 109.3 |
O1—P1—S1 | 111.38 (8) | C12—C7—H7 | 109.3 |
C7—O2—P1 | 125.79 (15) | C7—C8—C9 | 110.9 (2) |
C6—C1—O1' | 116.7 (6) | C7—C8—H8A | 109.5 |
C6—C1—O1 | 116.7 (6) | C9—C8—H8A | 109.5 |
C6—C1—C2 | 115.4 (5) | C7—C8—H8B | 109.5 |
O1'—C1—C2 | 108.8 (2) | C9—C8—H8B | 109.5 |
O1—C1—C2 | 108.8 (2) | H8A—C8—H8B | 108.1 |
O1'—C1—C6' | 102.5 (5) | C8—C9—C10 | 112.1 (3) |
O1—C1—C6' | 102.5 (5) | C8—C9—H9A | 109.2 |
C2—C1—C6' | 105.4 (5) | C10—C9—H9A | 109.2 |
C6—C1—H1 | 104.9 | C8—C9—H9B | 109.2 |
O1'—C1—H1 | 104.9 | C10—C9—H9B | 109.2 |
O1—C1—H1 | 104.9 | H9A—C9—H9B | 107.9 |
C2—C1—H1 | 104.9 | C11—C10—C9 | 110.7 (2) |
C6'—C1—H1 | 129.3 | C11—C10—H10A | 109.5 |
C1—C2—C3 | 110.7 (3) | C9—C10—H10A | 109.5 |
C1—C2—H2A | 109.5 | C11—C10—H10B | 109.5 |
C3—C2—H2A | 109.5 | C9—C10—H10B | 109.5 |
C1—C2—H2B | 109.5 | H10A—C10—H10B | 108.1 |
C3—C2—H2B | 109.5 | C12—C11—C10 | 110.7 (2) |
H2A—C2—H2B | 108.1 | C12—C11—H11A | 109.5 |
C4'—C3—C2 | 111.9 (3) | C10—C11—H11A | 109.5 |
C4—C3—C2 | 111.9 (3) | C12—C11—H11B | 109.5 |
C4'—C3—H3A | 109.2 | C10—C11—H11B | 109.5 |
C4—C3—H3A | 109.2 | H11A—C11—H11B | 108.1 |
C2—C3—H3A | 109.2 | C7—C12—C11 | 111.0 (3) |
C4'—C3—H3B | 109.2 | C7—C12—H12A | 109.4 |
C4—C3—H3B | 109.2 | C11—C12—H12A | 109.4 |
C2—C3—H3B | 109.2 | C7—C12—H12B | 109.4 |
H3A—C3—H3B | 107.9 | C11—C12—H12B | 109.4 |
C3—C4—C5 | 101.3 (5) | H12A—C12—H12B | 108.0 |
C3—C4—H4A | 111.5 | N1—C13—C14 | 123.1 (2) |
C5—C4—H4A | 111.5 | N1—C13—H13 | 118.5 |
C3—C4—H4B | 111.5 | C14—C13—H13 | 118.5 |
C5—C4—H4B | 111.5 | C13—C14—C15 | 119.0 (2) |
H4A—C4—H4B | 109.3 | C13—C14—H14 | 120.5 |
C6—C5—C4 | 106.8 (7) | C15—C14—H14 | 120.5 |
C6—C5—H5A | 110.4 | C14—C15—C16 | 118.2 (2) |
C4—C5—H5A | 110.4 | C14—C15—C18 | 120.4 (2) |
C6—C5—H5B | 110.4 | C16—C15—C18 | 121.5 (2) |
C4—C5—H5B | 110.4 | C17—C16—C15 | 119.1 (2) |
H5A—C5—H5B | 108.6 | C17—C16—H16 | 120.4 |
C1—C6—C5 | 114.0 (9) | C15—C16—H16 | 120.4 |
C1—C6—H6A | 108.8 | N1—C17—C16 | 122.8 (2) |
C5—C6—H6A | 108.8 | N1—C17—H17 | 118.6 |
C1—C6—H6B | 108.8 | C16—C17—H17 | 118.6 |
C5—C6—H6B | 108.8 | N2—C18—C15 | 119.3 (2) |
H6A—C6—H6B | 107.7 | N2—C18—H18 | 120.3 |
C1—O1—P1 | 120.02 (15) | C15—C18—H18 | 120.3 |
C5'—C4'—C3 | 114.7 (5) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C12H22O2PS2)2(C12H10N4)] |
Mr | 862.38 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 223 |
a, b, c (Å) | 18.3340 (8), 12.0404 (5), 19.1304 (8) |
V (Å3) | 4223.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.90 |
Crystal size (mm) | 0.52 × 0.36 × 0.26 |
Data collection | |
Diffractometer | Bruker SMART area-detector diffractometer |
Absorption correction | Multi-scan (SADABS, Bruker, 2000) |
Tmin, Tmax | 0.565, 0.792 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39717, 6155, 4886 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.137, 1.10 |
No. of reflections | 6155 |
No. of parameters | 253 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.23 |
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.
Zn—S1 | 2.4880 (7) | P1—O2 | 1.5849 (18) |
Zn—S2 | 2.6600 (7) | N1—C13 | 1.328 (3) |
Zn—N1 | 2.1850 (18) | N1—C17 | 1.344 (3) |
P1—S1 | 1.9946 (9) | N2—N2i | 1.410 (4) |
P1—S2 | 1.9716 (10) | N2—C18 | 1.270 (3) |
P1—O1 | 1.5876 (18) | ||
S1—Zn—S2 | 79.17 (2) | N1ii—Zn—N1 | 87.09 (10) |
S1—Zn—N1 | 95.15 (5) | Zn—S1—P1 | 86.63 (3) |
S1—Zn—S1ii | 170.66 (3) | Zn—S2—P1 | 82.46 (3) |
S1—Zn—S2ii | 94.60 (2) | S1—P1—S2 | 111.74 (4) |
S1—Zn—N1ii | 91.62 (5) | Zn—N1—C13 | 121.33 (15) |
S2—Zn—N1 | 88.57 (5) | Zn—N1—C17 | 120.79 (15) |
S2—Zn—S2ii | 97.27 (3) | C13—N1—C17 | 117.79 (19) |
S2—Zn—N1ii | 169.43 (5) | C18—N2—N2i | 111.4 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, y, −z+3/2. |
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Interest in crystal structures related to the polymeric title complex, [Zn{S2P(OCy)2}2{4-NC5H4C(H)═NN═C(H)C5H4N-4}]n, (I), arises from the desire to rationalize the formation of polymer topologies based on the steric requirements of the respective ligands, i.e. dithiolate-bound R groups and/or the dipyridyl-type ligands themselves (Lai et al., 2002, 2004a; Tiekink, 2003; Lai & Tiekink, 2004).
The immediate coordination geometry about the Zn atom (Fig. 1) is defined by four S atoms, derived from two chelating dithiophosphate ligands, and two N atoms, derived from two µ2-bridging dipyridyl-type ligands. There is crystallographic symmetry in the structure so that the Zn atom is located on a twofold axis and each dipyridyl-type ligand is disposed about a centre of inversion. The cis-N2S4 donor set defines an octahedral geometry with the major distortion being due to the restricted bite distance of the dithiophosphate ligand, i.e. the S1—Zn—S2 chelate angle is 79.17 (2)°. Other geometric parameters are as expected (Table 1).
The cis disposition of the N-donor atoms gives rise to a polymer with a zigzag topology (Fig. 2). The polymer is aligned along the c axis and a small twist in the dipyridyl-type ligand is noted, as seen in the N2—C18—C15—C16 torsion angle of 19.8 (4)°. It is noteworthy that in the absence of any obvious steric hindrance in the structure of (I), a zigzag polymer is found, an observation consistent with the majority of structures of the general formula [Zn{S2P(OR)2}2(bridging dipyridyl-type ligand)]n. Thus, for each of the [Zn{S2P(OR)2}2(4-NC5H4C5H4N-4)]n, for R = Et (Zhu et al., 1996) and R = iPr (Glinskaya et al., 2000), and [Zn{S2P(OR)2}2(4-NC5H4CH2CH2C5H4N-4)]n, R = iPr and Cy (Lai et al., 2004a) structures, a zigzag topology is found. By contrast, in the two cases where steric influences become a factor in polymer formation, a linear chain is formed, i.e. [Zn{S2P(OCy)2}2{4-NC5H4C(H)═C(H)C5H4N-4}]n (Lai et al., 2004a) and [Zn{S2P(OiBu)2}2(4-NC5H4CH2CH2C5H4N-4)]n (Lai et al., 2004b).