Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802005974/wn6092sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802005974/wn6092Isup2.hkl |
CCDC reference: 185746
Crystals were obtained from the slow evaporation of an acetonitrile solution of Zn(S2COiPr)2 (Cox & Tiekink, 1999) and Ph2PCH2CH2PPh2 (Aldrich) in a 2:1 ratio. The colourless crystals were characterized spectroscopically and crystallographically. IR: (KBr) ν(C—S) 1037 and 1092, and ν(C—O) 1231 cm-1. 1H NMR: δ 1.35 (d, 6.0 Hz, 6H, CH3), 2.59 (br, 2H, P—CH2), 5.21 (sept, 6.2 Hz, 1H, CH), 7.34 - 7.53 p.p.m. (m, 10H, phenyl-H). 13C NMR: δ 21.2, 21.3 (CH3), 63.4 (P—CH2), 81.6 (CH), 128.8–132.9 (phenyl), 225.8 p.p.m. (CS2). 31P NMR: δ 10.0 p.p.m. cf. δ 12.1 p.p.m. for Ph2PCH2CH2PPh2.
The C-bound H atoms were placed in their geometrically calculated positions and included in the final refinement in as riding, with an overall displacement parameter Uiso = Ueq(C) for phenyl, 1.25Ueq(C) for methine and methylene H, and 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: DIRDIF92 PATTY (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Farrugia, 1997). |
[Zn2(C4H7OS2)4(C26H24P2)] | F(000) = 2216 |
Mr = 1070.00 | Dx = 1.446 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 14333 reflections |
a = 11.1205 (6) Å | θ = 1.4–30.0° |
b = 17.7659 (9) Å | µ = 1.42 mm−1 |
c = 24.9002 (13) Å | T = 183 K |
β = 92.712 (1)° | Block, colourless |
V = 4913.9 (4) Å3 | 0.31 × 0.23 × 0.10 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 14333 independent reflections |
Radiation source: fine-focus sealed tube | 9844 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
ω scans | θmax = 30.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −15→15 |
Tmin = 0.706, Tmax = 0.868 | k = −24→25 |
40815 measured reflections | l = −35→24 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0487P)2] where P = (Fo2 + 2Fc2)/3 |
14333 reflections | (Δ/σ)max = 0.001 |
524 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Zn2(C4H7OS2)4(C26H24P2)] | V = 4913.9 (4) Å3 |
Mr = 1070.00 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1205 (6) Å | µ = 1.42 mm−1 |
b = 17.7659 (9) Å | T = 183 K |
c = 24.9002 (13) Å | 0.31 × 0.23 × 0.10 mm |
β = 92.712 (1)° |
Bruker SMART CCD diffractometer | 14333 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 9844 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.868 | Rint = 0.048 |
40815 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.57 e Å−3 |
14333 reflections | Δρmin = −0.33 e Å−3 |
524 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 | ||
Zn1 | 0.60957 (2) | 0.520081 (15) | 0.372022 (12) | 0.02813 (8) | |
Zn2 | 0.89935 (2) | 0.588634 (15) | 0.118504 (12) | 0.02784 (8) | |
S1 | 0.42908 (6) | 0.46039 (3) | 0.34542 (3) | 0.03315 (15) | |
S2 | 0.43299 (6) | 0.60403 (4) | 0.40540 (3) | 0.03489 (15) | |
S3 | 0.71062 (6) | 0.50205 (4) | 0.45522 (3) | 0.03372 (15) | |
S4 | 0.77054 (6) | 0.41573 (3) | 0.35855 (3) | 0.03029 (14) | |
S5 | 0.77395 (6) | 0.60953 (3) | 0.04274 (2) | 0.02888 (13) | |
S6 | 0.74639 (6) | 0.69429 (3) | 0.14354 (2) | 0.03039 (14) | |
S7 | 1.08298 (5) | 0.64761 (3) | 0.13975 (3) | 0.03349 (15) | |
S8 | 1.06841 (5) | 0.51119 (4) | 0.07173 (3) | 0.03746 (16) | |
P1 | 0.68186 (5) | 0.61600 (3) | 0.31307 (2) | 0.02286 (12) | |
P2 | 0.82959 (5) | 0.48994 (3) | 0.17617 (2) | 0.02352 (13) | |
O1 | 0.23773 (15) | 0.52945 (10) | 0.37105 (8) | 0.0410 (5) | |
O2 | 0.86072 (17) | 0.39445 (10) | 0.45849 (8) | 0.0446 (5) | |
O3 | 0.62439 (16) | 0.71680 (10) | 0.05081 (7) | 0.0369 (4) | |
O4 | 1.26919 (15) | 0.57751 (10) | 0.10961 (8) | 0.0407 (5) | |
C1 | 0.3565 (2) | 0.53405 (13) | 0.37486 (10) | 0.0309 (5) | |
C2 | 0.1647 (2) | 0.59324 (16) | 0.38845 (14) | 0.0476 (8) | |
H2 | 0.2036 | 0.6165 | 0.4215 | 0.0610 (14)* | |
C3 | 0.0449 (3) | 0.5595 (2) | 0.40155 (16) | 0.0630 (10) | |
H3A | 0.0568 | 0.5232 | 0.4309 | 0.0732 (17)* | |
H3B | 0.0096 | 0.5339 | 0.3697 | 0.0732 (17)* | |
H3C | −0.0093 | 0.5996 | 0.4125 | 0.0732 (17)* | |
C4 | 0.1576 (3) | 0.64972 (19) | 0.34403 (17) | 0.0684 (11) | |
H4A | 0.2384 | 0.6690 | 0.3379 | 0.0732 (17)* | |
H4B | 0.1054 | 0.6914 | 0.3539 | 0.0732 (17)* | |
H4C | 0.1244 | 0.6258 | 0.3111 | 0.0732 (17)* | |
C5 | 0.7887 (2) | 0.43275 (13) | 0.42516 (10) | 0.0279 (5) | |
C6 | 0.9285 (3) | 0.32800 (16) | 0.44087 (13) | 0.0499 (8) | |
H6 | 0.8911 | 0.3084 | 0.4063 | 0.0610 (14)* | |
C7 | 0.9154 (3) | 0.27161 (18) | 0.48407 (16) | 0.0669 (10) | |
H7A | 0.8301 | 0.2592 | 0.4869 | 0.0732 (17)* | |
H7B | 0.9473 | 0.2924 | 0.5183 | 0.0732 (17)* | |
H7C | 0.9602 | 0.2260 | 0.4755 | 0.0732 (17)* | |
C8 | 1.0535 (3) | 0.3511 (2) | 0.43289 (16) | 0.0718 (11) | |
H8A | 1.0547 | 0.3882 | 0.4038 | 0.0732 (17)* | |
H8B | 1.1010 | 0.3070 | 0.4234 | 0.0732 (17)* | |
H8C | 1.0880 | 0.3733 | 0.4662 | 0.0732 (17)* | |
C9 | 0.7069 (2) | 0.67834 (12) | 0.07855 (9) | 0.0240 (5) | |
C10 | 0.5618 (2) | 0.78253 (13) | 0.07322 (10) | 0.0344 (6) | |
H10 | 0.5976 | 0.7951 | 0.1097 | 0.0610 (14)* | |
C11 | 0.4334 (3) | 0.7606 (2) | 0.07690 (14) | 0.0594 (9) | |
H11A | 0.4273 | 0.7191 | 0.1026 | 0.0732 (17)* | |
H11B | 0.4011 | 0.7445 | 0.0415 | 0.0732 (17)* | |
H11C | 0.3872 | 0.8038 | 0.0891 | 0.0732 (17)* | |
C12 | 0.5817 (3) | 0.84506 (16) | 0.03543 (13) | 0.0529 (8) | |
H12A | 0.6679 | 0.8563 | 0.0352 | 0.0732 (17)* | |
H12B | 0.5382 | 0.8898 | 0.0469 | 0.0732 (17)* | |
H12C | 0.5521 | 0.8305 | −0.0008 | 0.0732 (17)* | |
C13 | 1.1504 (2) | 0.57579 (13) | 0.10592 (11) | 0.0317 (5) | |
C14 | 1.3384 (2) | 0.51148 (17) | 0.09214 (14) | 0.0473 (8) | |
H14 | 1.2988 | 0.4891 | 0.0590 | 0.0610 (14)* | |
C15 | 1.3412 (3) | 0.45541 (18) | 0.13690 (17) | 0.0662 (11) | |
H15A | 1.2592 | 0.4381 | 0.1427 | 0.0732 (17)* | |
H15B | 1.3751 | 0.4790 | 0.1698 | 0.0732 (17)* | |
H15C | 1.3912 | 0.4124 | 0.1275 | 0.0732 (17)* | |
C16 | 1.4612 (3) | 0.5417 (2) | 0.07998 (16) | 0.0610 (10) | |
H16A | 1.4532 | 0.5780 | 0.0504 | 0.0732 (17)* | |
H16B | 1.5131 | 0.5001 | 0.0696 | 0.0732 (17)* | |
H16C | 1.4970 | 0.5667 | 0.1120 | 0.0732 (17)* | |
C17 | 0.7859 (2) | 0.58101 (12) | 0.26377 (9) | 0.0256 (5) | |
H17A | 0.8164 | 0.6239 | 0.2430 | 0.0610 (14)* | |
H17B | 0.8556 | 0.5566 | 0.2829 | 0.0610 (14)* | |
C18 | 0.7246 (2) | 0.52459 (12) | 0.22520 (9) | 0.0254 (5) | |
H18A | 0.6551 | 0.5490 | 0.2060 | 0.0610 (14)* | |
H18B | 0.6941 | 0.4816 | 0.2459 | 0.0610 (14)* | |
C19 | 0.5657 (2) | 0.66671 (13) | 0.27345 (9) | 0.0279 (5) | |
C20 | 0.5775 (3) | 0.74224 (14) | 0.26002 (11) | 0.0376 (6) | |
H20 | 0.6480 | 0.7693 | 0.2712 | 0.0488 (11)* | |
C21 | 0.4848 (3) | 0.77795 (17) | 0.22994 (12) | 0.0497 (8) | |
H21 | 0.4928 | 0.8294 | 0.2204 | 0.0488 (11)* | |
C22 | 0.3828 (3) | 0.73941 (18) | 0.21405 (12) | 0.0509 (8) | |
H22 | 0.3197 | 0.7644 | 0.1942 | 0.0488 (11)* | |
C23 | 0.3715 (3) | 0.66437 (18) | 0.22680 (12) | 0.0494 (8) | |
H23 | 0.3013 | 0.6373 | 0.2151 | 0.0488 (11)* | |
C24 | 0.4626 (2) | 0.62844 (15) | 0.25670 (11) | 0.0367 (6) | |
H24 | 0.4541 | 0.5768 | 0.2658 | 0.0488 (11)* | |
C25 | 0.7631 (2) | 0.68828 (12) | 0.35101 (9) | 0.0248 (5) | |
C26 | 0.8528 (2) | 0.73250 (14) | 0.33072 (11) | 0.0351 (6) | |
H26 | 0.8787 | 0.7236 | 0.2955 | 0.0488 (11)* | |
C27 | 0.9048 (3) | 0.78950 (14) | 0.36147 (12) | 0.0400 (6) | |
H27 | 0.9660 | 0.8198 | 0.3472 | 0.0488 (11)* | |
C28 | 0.8687 (2) | 0.80274 (14) | 0.41281 (11) | 0.0378 (6) | |
H28 | 0.9044 | 0.8422 | 0.4338 | 0.0488 (11)* | |
C29 | 0.7814 (3) | 0.75872 (15) | 0.43324 (11) | 0.0451 (7) | |
H29 | 0.7567 | 0.7675 | 0.4687 | 0.0488 (11)* | |
C30 | 0.7286 (2) | 0.70169 (14) | 0.40299 (11) | 0.0373 (6) | |
H30 | 0.6681 | 0.6713 | 0.4178 | 0.0488 (11)* | |
C31 | 0.7453 (2) | 0.41935 (12) | 0.13720 (10) | 0.0278 (5) | |
C32 | 0.7686 (2) | 0.41195 (13) | 0.08295 (10) | 0.0349 (6) | |
H32 | 0.8272 | 0.4430 | 0.0675 | 0.0488 (11)* | |
C33 | 0.7063 (3) | 0.35938 (16) | 0.05175 (12) | 0.0476 (7) | |
H33 | 0.7212 | 0.3549 | 0.0146 | 0.0488 (11)* | |
C34 | 0.6227 (3) | 0.31347 (16) | 0.07410 (13) | 0.0553 (9) | |
H34 | 0.5806 | 0.2772 | 0.0524 | 0.0488 (11)* | |
C35 | 0.5997 (3) | 0.31978 (16) | 0.12767 (13) | 0.0494 (8) | |
H35 | 0.5425 | 0.2875 | 0.1430 | 0.0488 (11)* | |
C36 | 0.6595 (2) | 0.37302 (14) | 0.15913 (11) | 0.0376 (6) | |
H36 | 0.6420 | 0.3781 | 0.1959 | 0.0488 (11)* | |
C37 | 0.9423 (2) | 0.43951 (13) | 0.21752 (9) | 0.0285 (5) | |
C38 | 0.9184 (3) | 0.37061 (15) | 0.24140 (11) | 0.0406 (7) | |
H38 | 0.8426 | 0.3469 | 0.2349 | 0.0488 (11)* | |
C39 | 1.0064 (3) | 0.33672 (17) | 0.27495 (12) | 0.0510 (8) | |
H39 | 0.9896 | 0.2902 | 0.2918 | 0.0488 (11)* | |
C40 | 1.1168 (3) | 0.36966 (18) | 0.28388 (12) | 0.0523 (8) | |
H40 | 1.1766 | 0.3457 | 0.3064 | 0.0488 (11)* | |
C41 | 1.1410 (3) | 0.43748 (18) | 0.26013 (13) | 0.0518 (8) | |
H41 | 1.2175 | 0.4604 | 0.2663 | 0.0488 (11)* | |
C42 | 1.0537 (3) | 0.47255 (15) | 0.22712 (11) | 0.0399 (6) | |
H42 | 1.0707 | 0.5196 | 0.2110 | 0.0488 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02816 (14) | 0.02712 (15) | 0.02866 (16) | −0.00205 (11) | −0.00335 (12) | 0.00422 (11) |
Zn2 | 0.02672 (14) | 0.02681 (14) | 0.02950 (16) | 0.00053 (11) | −0.00397 (12) | 0.00502 (12) |
S1 | 0.0314 (3) | 0.0250 (3) | 0.0422 (4) | 0.0000 (2) | −0.0064 (3) | −0.0052 (3) |
S2 | 0.0267 (3) | 0.0340 (3) | 0.0438 (4) | −0.0021 (2) | −0.0005 (3) | −0.0123 (3) |
S3 | 0.0392 (3) | 0.0359 (3) | 0.0256 (3) | 0.0112 (3) | −0.0022 (3) | −0.0031 (3) |
S4 | 0.0361 (3) | 0.0277 (3) | 0.0269 (3) | 0.0051 (2) | −0.0008 (3) | −0.0014 (2) |
S5 | 0.0379 (3) | 0.0272 (3) | 0.0214 (3) | 0.0117 (2) | −0.0002 (2) | −0.0013 (2) |
S6 | 0.0392 (3) | 0.0293 (3) | 0.0221 (3) | 0.0103 (3) | −0.0049 (2) | −0.0025 (2) |
S7 | 0.0303 (3) | 0.0250 (3) | 0.0446 (4) | 0.0011 (2) | −0.0046 (3) | −0.0066 (3) |
S8 | 0.0252 (3) | 0.0360 (3) | 0.0507 (4) | 0.0026 (3) | −0.0030 (3) | −0.0159 (3) |
P1 | 0.0285 (3) | 0.0207 (3) | 0.0194 (3) | 0.0030 (2) | 0.0011 (2) | −0.0006 (2) |
P2 | 0.0309 (3) | 0.0197 (3) | 0.0199 (3) | 0.0043 (2) | 0.0002 (2) | −0.0004 (2) |
O1 | 0.0266 (9) | 0.0413 (10) | 0.0545 (13) | −0.0038 (8) | −0.0035 (9) | −0.0117 (9) |
O2 | 0.0543 (12) | 0.0446 (11) | 0.0336 (11) | 0.0238 (9) | −0.0125 (9) | −0.0054 (9) |
O3 | 0.0485 (11) | 0.0390 (10) | 0.0222 (9) | 0.0241 (8) | −0.0086 (8) | −0.0062 (8) |
O4 | 0.0241 (9) | 0.0389 (10) | 0.0587 (13) | 0.0005 (8) | −0.0033 (9) | −0.0126 (9) |
C1 | 0.0289 (12) | 0.0306 (12) | 0.0327 (14) | −0.0008 (10) | −0.0035 (10) | −0.0021 (11) |
C2 | 0.0285 (14) | 0.0480 (17) | 0.066 (2) | 0.0028 (12) | 0.0012 (14) | −0.0162 (16) |
C3 | 0.0327 (16) | 0.073 (2) | 0.083 (3) | −0.0054 (15) | 0.0043 (17) | −0.016 (2) |
C4 | 0.0400 (17) | 0.062 (2) | 0.104 (3) | 0.0150 (16) | 0.0036 (19) | 0.000 (2) |
C5 | 0.0279 (12) | 0.0246 (11) | 0.0308 (13) | 0.0005 (9) | −0.0014 (10) | 0.0002 (10) |
C6 | 0.063 (2) | 0.0432 (16) | 0.0423 (17) | 0.0290 (15) | −0.0149 (15) | −0.0099 (14) |
C7 | 0.075 (2) | 0.0436 (18) | 0.081 (3) | 0.0125 (17) | −0.012 (2) | 0.0047 (18) |
C8 | 0.077 (3) | 0.069 (2) | 0.072 (3) | 0.035 (2) | 0.025 (2) | 0.000 (2) |
C9 | 0.0272 (11) | 0.0230 (11) | 0.0218 (11) | 0.0025 (9) | 0.0014 (9) | 0.0003 (9) |
C10 | 0.0448 (15) | 0.0333 (13) | 0.0246 (13) | 0.0227 (11) | −0.0042 (11) | −0.0062 (10) |
C11 | 0.0552 (19) | 0.071 (2) | 0.054 (2) | 0.0123 (17) | 0.0221 (17) | −0.0164 (18) |
C12 | 0.074 (2) | 0.0377 (15) | 0.0487 (19) | 0.0178 (15) | 0.0154 (17) | −0.0003 (14) |
C13 | 0.0260 (12) | 0.0301 (12) | 0.0385 (15) | 0.0001 (10) | −0.0029 (11) | −0.0011 (11) |
C14 | 0.0261 (13) | 0.0506 (17) | 0.065 (2) | 0.0056 (12) | 0.0014 (14) | −0.0161 (16) |
C15 | 0.0381 (17) | 0.0496 (19) | 0.110 (3) | 0.0042 (15) | −0.0008 (19) | 0.001 (2) |
C16 | 0.0288 (15) | 0.071 (2) | 0.084 (3) | 0.0063 (15) | 0.0075 (16) | −0.006 (2) |
C17 | 0.0303 (12) | 0.0246 (11) | 0.0218 (11) | 0.0033 (9) | 0.0000 (9) | −0.0014 (9) |
C18 | 0.0296 (12) | 0.0239 (11) | 0.0229 (12) | 0.0031 (9) | 0.0041 (9) | −0.0031 (9) |
C19 | 0.0359 (13) | 0.0268 (11) | 0.0213 (12) | 0.0119 (10) | 0.0041 (10) | 0.0014 (9) |
C20 | 0.0500 (16) | 0.0319 (13) | 0.0317 (14) | 0.0116 (12) | 0.0109 (12) | 0.0069 (11) |
C21 | 0.068 (2) | 0.0414 (16) | 0.0408 (17) | 0.0292 (15) | 0.0157 (15) | 0.0170 (13) |
C22 | 0.0539 (18) | 0.067 (2) | 0.0317 (16) | 0.0343 (17) | 0.0040 (14) | 0.0105 (15) |
C23 | 0.0469 (17) | 0.064 (2) | 0.0365 (17) | 0.0142 (15) | −0.0105 (14) | −0.0004 (15) |
C24 | 0.0409 (15) | 0.0381 (14) | 0.0304 (14) | 0.0074 (12) | −0.0053 (12) | 0.0023 (11) |
C25 | 0.0304 (12) | 0.0192 (10) | 0.0250 (12) | −0.0001 (9) | 0.0019 (9) | −0.0014 (9) |
C26 | 0.0457 (15) | 0.0313 (13) | 0.0293 (14) | −0.0056 (11) | 0.0128 (12) | −0.0047 (11) |
C27 | 0.0501 (16) | 0.0285 (13) | 0.0424 (16) | −0.0146 (12) | 0.0108 (13) | −0.0010 (12) |
C28 | 0.0512 (16) | 0.0249 (12) | 0.0368 (15) | −0.0094 (12) | −0.0012 (13) | −0.0035 (11) |
C29 | 0.0663 (19) | 0.0430 (15) | 0.0272 (14) | −0.0179 (14) | 0.0138 (14) | −0.0128 (12) |
C30 | 0.0451 (15) | 0.0368 (14) | 0.0309 (14) | −0.0155 (12) | 0.0123 (12) | −0.0084 (12) |
C31 | 0.0384 (13) | 0.0190 (10) | 0.0259 (12) | 0.0024 (10) | 0.0023 (10) | −0.0031 (9) |
C32 | 0.0485 (16) | 0.0269 (12) | 0.0297 (14) | −0.0023 (11) | 0.0060 (12) | −0.0042 (11) |
C33 | 0.073 (2) | 0.0408 (15) | 0.0294 (15) | −0.0111 (15) | 0.0089 (14) | −0.0085 (12) |
C34 | 0.083 (2) | 0.0391 (16) | 0.0447 (19) | −0.0229 (16) | 0.0074 (17) | −0.0177 (14) |
C35 | 0.0629 (19) | 0.0374 (15) | 0.0488 (19) | −0.0213 (14) | 0.0105 (16) | −0.0049 (14) |
C36 | 0.0504 (16) | 0.0293 (13) | 0.0340 (15) | −0.0049 (12) | 0.0092 (12) | −0.0043 (11) |
C37 | 0.0418 (14) | 0.0255 (11) | 0.0185 (11) | 0.0129 (10) | 0.0030 (10) | 0.0000 (9) |
C38 | 0.0492 (16) | 0.0381 (14) | 0.0356 (15) | 0.0176 (13) | 0.0127 (13) | 0.0111 (12) |
C39 | 0.074 (2) | 0.0456 (16) | 0.0346 (16) | 0.0300 (16) | 0.0172 (16) | 0.0169 (13) |
C40 | 0.069 (2) | 0.061 (2) | 0.0267 (15) | 0.0359 (17) | −0.0012 (15) | 0.0054 (14) |
C41 | 0.0518 (18) | 0.0583 (19) | 0.0432 (18) | 0.0162 (15) | −0.0198 (15) | −0.0049 (15) |
C42 | 0.0493 (16) | 0.0332 (13) | 0.0357 (15) | 0.0082 (12) | −0.0151 (13) | −0.0026 (12) |
Zn1—S1 | 2.3380 (7) | C14—C15 | 1.494 (5) |
Zn1—S2 | 2.6316 (7) | C14—C16 | 1.511 (4) |
Zn1—S3 | 2.3317 (7) | C14—H14 | 1.0000 |
Zn1—S4 | 2.6097 (7) | C15—H15A | 0.9800 |
Zn1—P1 | 2.4118 (7) | C15—H15B | 0.9800 |
Zn2—S5 | 2.3222 (7) | C15—H15C | 0.9800 |
Zn2—S6 | 2.6279 (6) | C16—H16A | 0.9800 |
Zn2—S7 | 2.3335 (7) | C16—H16B | 0.9800 |
Zn2—S8 | 2.6440 (7) | C16—H16C | 0.9800 |
Zn2—P2 | 2.4173 (7) | C17—C18 | 1.526 (3) |
S1—C1 | 1.719 (3) | C17—H17A | 0.9900 |
S2—C1 | 1.669 (2) | C17—H17B | 0.9900 |
S3—C5 | 1.700 (2) | C18—H18A | 0.9900 |
S4—C5 | 1.689 (3) | C18—H18B | 0.9900 |
S5—C9 | 1.706 (2) | C19—C24 | 1.380 (3) |
S6—C9 | 1.681 (2) | C19—C20 | 1.391 (3) |
S7—C13 | 1.720 (3) | C20—C21 | 1.397 (4) |
S8—C13 | 1.673 (2) | C20—H20 | 0.9500 |
P1—C25 | 1.810 (2) | C21—C22 | 1.368 (4) |
P1—C19 | 1.825 (2) | C21—H21 | 0.9500 |
P1—C17 | 1.835 (2) | C22—C23 | 1.378 (4) |
P2—C31 | 1.818 (2) | C22—H22 | 0.9500 |
P2—C37 | 1.820 (2) | C23—C24 | 1.385 (4) |
P2—C18 | 1.835 (2) | C23—H23 | 0.9500 |
O1—C1 | 1.323 (3) | C24—H24 | 0.9500 |
O1—C2 | 1.471 (3) | C25—C26 | 1.384 (3) |
O2—C5 | 1.315 (3) | C25—C30 | 1.388 (3) |
O2—C6 | 1.478 (3) | C26—C27 | 1.380 (3) |
O3—C9 | 1.314 (3) | C26—H26 | 0.9500 |
O3—C10 | 1.482 (3) | C27—C28 | 1.378 (4) |
O4—C13 | 1.320 (3) | C27—H27 | 0.9500 |
O4—C14 | 1.480 (3) | C28—C29 | 1.364 (4) |
C2—C4 | 1.493 (5) | C28—H28 | 0.9500 |
C2—C3 | 1.510 (4) | C29—C30 | 1.377 (3) |
C2—H2 | 1.0000 | C29—H29 | 0.9500 |
C3—H3A | 0.9800 | C30—H30 | 0.9500 |
C3—H3B | 0.9800 | C31—C36 | 1.391 (3) |
C3—H3C | 0.9800 | C31—C32 | 1.394 (3) |
C4—H4A | 0.9800 | C32—C33 | 1.380 (4) |
C4—H4B | 0.9800 | C32—H32 | 0.9500 |
C4—H4C | 0.9800 | C33—C34 | 1.374 (4) |
C6—C8 | 1.472 (5) | C33—H33 | 0.9500 |
C6—C7 | 1.482 (5) | C34—C35 | 1.375 (4) |
C6—H6 | 1.0000 | C34—H34 | 0.9500 |
C7—H7A | 0.9800 | C35—C36 | 1.379 (4) |
C7—H7B | 0.9800 | C35—H35 | 0.9500 |
C7—H7C | 0.9800 | C36—H36 | 0.9500 |
C8—H8A | 0.9800 | C37—C42 | 1.381 (4) |
C8—H8B | 0.9800 | C37—C38 | 1.392 (3) |
C8—H8C | 0.9800 | C38—C39 | 1.393 (4) |
C10—C12 | 1.479 (4) | C38—H38 | 0.9500 |
C10—C11 | 1.487 (4) | C39—C40 | 1.368 (5) |
C10—H10 | 1.0000 | C39—H39 | 0.9500 |
C11—H11A | 0.9800 | C40—C41 | 1.374 (4) |
C11—H11B | 0.9800 | C40—H40 | 0.9500 |
C11—H11C | 0.9800 | C41—C42 | 1.389 (4) |
C12—H12A | 0.9800 | C41—H41 | 0.9500 |
C12—H12B | 0.9800 | C42—H42 | 0.9500 |
C12—H12C | 0.9800 | ||
S1—Zn1—S2 | 72.73 (2) | H12B—C12—H12C | 109.5 |
S1—Zn1—S3 | 124.10 (3) | S7—C13—S8 | 121.20 (14) |
S1—Zn1—S4 | 103.08 (2) | S7—C13—O4 | 114.01 (18) |
S1—Zn1—P1 | 117.03 (2) | S8—C13—O4 | 124.79 (19) |
S2—Zn1—S3 | 97.62 (2) | O4—C14—C15 | 107.6 (3) |
S2—Zn1—S4 | 165.88 (2) | O4—C14—C16 | 105.3 (2) |
S2—Zn1—P1 | 93.84 (2) | C15—C14—C16 | 113.5 (3) |
S3—Zn1—P1 | 118.51 (3) | O4—C14—H14 | 110.1 |
S3—Zn1—S4 | 73.26 (2) | C15—C14—H14 | 110.1 |
S4—Zn1—P1 | 99.98 (2) | C16—C14—H14 | 110.1 |
S5—Zn2—S6 | 73.02 (2) | C14—C15—H15A | 109.5 |
S5—Zn2—S7 | 126.72 (3) | C14—C15—H15B | 109.5 |
S5—Zn2—S8 | 97.90 (2) | H15A—C15—H15B | 109.5 |
S5—Zn2—P2 | 113.66 (2) | C14—C15—H15C | 109.5 |
S6—Zn2—S7 | 101.23 (2) | H15A—C15—H15C | 109.5 |
S6—Zn2—S8 | 163.32 (2) | H15B—C15—H15C | 109.5 |
S6—Zn2—P2 | 98.49 (2) | C14—C16—H16A | 109.5 |
S7—Zn2—S8 | 72.59 (2) | C14—C16—H16B | 109.5 |
S7—Zn2—P2 | 119.54 (2) | H16A—C16—H16B | 109.5 |
S8—Zn2—P2 | 97.99 (2) | C14—C16—H16C | 109.5 |
Zn1—S1—C1 | 87.01 (8) | H16A—C16—H16C | 109.5 |
Zn1—S2—C1 | 78.79 (9) | H16B—C16—H16C | 109.5 |
Zn1—S3—C5 | 86.74 (9) | C18—C17—P1 | 111.51 (16) |
Zn1—S4—C5 | 78.32 (8) | C18—C17—H17A | 109.3 |
Zn2—S5—C9 | 87.15 (8) | P1—C17—H17A | 109.3 |
Zn2—S6—C9 | 78.10 (8) | C18—C17—H17B | 109.3 |
Zn2—S7—C13 | 87.31 (8) | P1—C17—H17B | 109.3 |
Zn2—S8—C13 | 78.51 (9) | H17A—C17—H17B | 108.0 |
C25—P1—C19 | 104.76 (11) | C17—C18—P2 | 111.10 (16) |
C25—P1—C17 | 105.94 (11) | C17—C18—H18A | 109.4 |
C19—P1—C17 | 104.96 (11) | P2—C18—H18A | 109.4 |
C25—P1—Zn1 | 110.86 (8) | C17—C18—H18B | 109.4 |
C19—P1—Zn1 | 115.46 (8) | P2—C18—H18B | 109.4 |
C17—P1—Zn1 | 114.00 (8) | H18A—C18—H18B | 108.0 |
C31—P2—C37 | 106.62 (11) | C24—C19—C20 | 119.3 (2) |
C31—P2—C18 | 104.98 (11) | C24—C19—P1 | 118.46 (18) |
C37—P2—C18 | 103.38 (11) | C20—C19—P1 | 122.3 (2) |
C31—P2—Zn2 | 110.80 (8) | C19—C20—C21 | 119.4 (3) |
C37—P2—Zn2 | 117.48 (9) | C19—C20—H20 | 120.3 |
C18—P2—Zn2 | 112.58 (7) | C21—C20—H20 | 120.3 |
C1—O1—C2 | 119.6 (2) | C22—C21—C20 | 120.6 (3) |
C5—O2—C6 | 122.0 (2) | C22—C21—H21 | 119.7 |
C9—O3—C10 | 122.73 (18) | C20—C21—H21 | 119.7 |
C13—O4—C14 | 119.61 (19) | C21—C22—C23 | 120.1 (3) |
S1—C1—S2 | 121.47 (14) | C21—C22—H22 | 120.0 |
S1—C1—O1 | 114.17 (18) | C23—C22—H22 | 120.0 |
S2—C1—O1 | 124.36 (19) | C22—C23—C24 | 119.8 (3) |
O1—C2—C4 | 108.1 (3) | C22—C23—H23 | 120.1 |
O1—C2—C3 | 105.2 (2) | C24—C23—H23 | 120.1 |
C4—C2—C3 | 114.2 (3) | C19—C24—C23 | 120.8 (3) |
O1—C2—H2 | 109.7 | C19—C24—H24 | 119.6 |
C4—C2—H2 | 109.7 | C23—C24—H24 | 119.6 |
C3—C2—H2 | 109.7 | C26—C25—C30 | 118.6 (2) |
C2—C3—H3A | 109.5 | C26—C25—P1 | 124.24 (19) |
C2—C3—H3B | 109.5 | C30—C25—P1 | 117.08 (18) |
H3A—C3—H3B | 109.5 | C27—C26—C25 | 120.3 (2) |
C2—C3—H3C | 109.5 | C27—C26—H26 | 119.8 |
H3A—C3—H3C | 109.5 | C25—C26—H26 | 119.8 |
H3B—C3—H3C | 109.5 | C28—C27—C26 | 120.4 (2) |
C2—C4—H4A | 109.5 | C28—C27—H27 | 119.8 |
C2—C4—H4B | 109.5 | C26—C27—H27 | 119.8 |
H4A—C4—H4B | 109.5 | C29—C28—C27 | 119.5 (2) |
C2—C4—H4C | 109.5 | C29—C28—H28 | 120.3 |
H4A—C4—H4C | 109.5 | C27—C28—H28 | 120.3 |
H4B—C4—H4C | 109.5 | C28—C29—C30 | 120.7 (3) |
S3—C5—S4 | 121.47 (14) | C28—C29—H29 | 119.7 |
S3—C5—O2 | 113.90 (18) | C30—C29—H29 | 119.7 |
S4—C5—O2 | 124.62 (18) | C29—C30—C25 | 120.4 (2) |
C8—C6—O2 | 108.4 (3) | C29—C30—H30 | 119.8 |
C8—C6—C7 | 114.3 (3) | C25—C30—H30 | 119.8 |
O2—C6—C7 | 104.8 (3) | C36—C31—C32 | 119.1 (2) |
C8—C6—H6 | 109.7 | C36—C31—P2 | 122.98 (19) |
O2—C6—H6 | 109.7 | C32—C31—P2 | 117.89 (18) |
C7—C6—H6 | 109.7 | C33—C32—C31 | 119.9 (2) |
C6—C7—H7A | 109.5 | C33—C32—H32 | 120.1 |
C6—C7—H7B | 109.5 | C31—C32—H32 | 120.1 |
H7A—C7—H7B | 109.5 | C34—C33—C32 | 120.3 (3) |
C6—C7—H7C | 109.5 | C34—C33—H33 | 119.8 |
H7A—C7—H7C | 109.5 | C32—C33—H33 | 119.8 |
H7B—C7—H7C | 109.5 | C33—C34—C35 | 120.4 (3) |
C6—C8—H8A | 109.5 | C33—C34—H34 | 119.8 |
C6—C8—H8B | 109.5 | C35—C34—H34 | 119.8 |
H8A—C8—H8B | 109.5 | C34—C35—C36 | 120.0 (3) |
C6—C8—H8C | 109.5 | C34—C35—H35 | 120.0 |
H8A—C8—H8C | 109.5 | C36—C35—H35 | 120.0 |
H8B—C8—H8C | 109.5 | C35—C36—C31 | 120.3 (3) |
S5—C9—S6 | 121.57 (13) | C35—C36—H36 | 119.9 |
S5—C9—O3 | 114.17 (17) | C31—C36—H36 | 119.9 |
S6—C9—O3 | 124.25 (17) | C42—C37—C38 | 119.2 (2) |
C12—C10—O3 | 105.4 (2) | C42—C37—P2 | 118.47 (18) |
C12—C10—C11 | 114.1 (2) | C38—C37—P2 | 122.3 (2) |
O3—C10—C11 | 106.7 (2) | C37—C38—C39 | 119.5 (3) |
C12—C10—H10 | 110.2 | C37—C38—H38 | 120.2 |
O3—C10—H10 | 110.2 | C39—C38—H38 | 120.2 |
C11—C10—H10 | 110.2 | C40—C39—C38 | 120.8 (3) |
C10—C11—H11A | 109.5 | C40—C39—H39 | 119.6 |
C10—C11—H11B | 109.5 | C38—C39—H39 | 119.6 |
H11A—C11—H11B | 109.5 | C39—C40—C41 | 119.8 (3) |
C10—C11—H11C | 109.5 | C39—C40—H40 | 120.1 |
H11A—C11—H11C | 109.5 | C41—C40—H40 | 120.1 |
H11B—C11—H11C | 109.5 | C40—C41—C42 | 120.2 (3) |
C10—C12—H12A | 109.5 | C40—C41—H41 | 119.9 |
C10—C12—H12B | 109.5 | C42—C41—H41 | 119.9 |
H12A—C12—H12B | 109.5 | C37—C42—C41 | 120.5 (3) |
C10—C12—H12C | 109.5 | C37—C42—H42 | 119.8 |
H12A—C12—H12C | 109.5 | C41—C42—H42 | 119.8 |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C4H7OS2)4(C26H24P2)] |
Mr | 1070.00 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 183 |
a, b, c (Å) | 11.1205 (6), 17.7659 (9), 24.9002 (13) |
β (°) | 92.712 (1) |
V (Å3) | 4913.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.42 |
Crystal size (mm) | 0.31 × 0.23 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.706, 0.868 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 40815, 14333, 9844 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.109, 0.97 |
No. of reflections | 14333 |
No. of parameters | 524 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.33 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), DIRDIF92 PATTY (Beurskens et al., 1992), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL.
Zn1—S1 | 2.3380 (7) | S5—C9 | 1.706 (2) |
Zn1—S2 | 2.6316 (7) | S6—C9 | 1.681 (2) |
Zn1—S3 | 2.3317 (7) | S7—C13 | 1.720 (3) |
Zn1—S4 | 2.6097 (7) | S8—C13 | 1.673 (2) |
Zn1—P1 | 2.4118 (7) | P1—C17 | 1.835 (2) |
Zn2—S5 | 2.3222 (7) | P2—C18 | 1.835 (2) |
Zn2—S6 | 2.6279 (6) | O1—C1 | 1.323 (3) |
Zn2—S7 | 2.3335 (7) | O1—C2 | 1.471 (3) |
Zn2—S8 | 2.6440 (7) | O2—C5 | 1.315 (3) |
Zn2—P2 | 2.4173 (7) | O2—C6 | 1.478 (3) |
S1—C1 | 1.719 (3) | O3—C9 | 1.314 (3) |
S2—C1 | 1.669 (2) | O3—C10 | 1.482 (3) |
S3—C5 | 1.700 (2) | O4—C13 | 1.320 (3) |
S4—C5 | 1.689 (3) | O4—C14 | 1.480 (3) |
S1—Zn1—S2 | 72.73 (2) | S8—Zn2—P2 | 97.99 (2) |
S1—Zn1—S3 | 124.10 (3) | Zn1—S1—C1 | 87.01 (8) |
S1—Zn1—S4 | 103.08 (2) | Zn1—S2—C1 | 78.79 (9) |
S1—Zn1—P1 | 117.03 (2) | Zn1—S3—C5 | 86.74 (9) |
S2—Zn1—S3 | 97.62 (2) | Zn1—S4—C5 | 78.32 (8) |
S2—Zn1—S4 | 165.88 (2) | Zn2—S5—C9 | 87.15 (8) |
S2—Zn1—P1 | 93.84 (2) | Zn2—S6—C9 | 78.10 (8) |
S3—Zn1—P1 | 118.51 (3) | Zn2—S7—C13 | 87.31 (8) |
S3—Zn1—S4 | 73.26 (2) | Zn2—S8—C13 | 78.51 (9) |
S4—Zn1—P1 | 99.98 (2) | S1—C1—S2 | 121.47 (14) |
S5—Zn2—S6 | 73.02 (2) | S1—C1—O1 | 114.17 (18) |
S5—Zn2—S7 | 126.72 (3) | S2—C1—O1 | 124.36 (19) |
S5—Zn2—S8 | 97.90 (2) | S3—C5—S4 | 121.47 (14) |
S5—Zn2—P2 | 113.66 (2) | S3—C5—O2 | 113.90 (18) |
S6—Zn2—S7 | 101.23 (2) | S4—C5—O2 | 124.62 (18) |
S6—Zn2—S8 | 163.32 (2) | S7—C13—S8 | 121.20 (14) |
S6—Zn2—P2 | 98.49 (2) | S7—C13—O4 | 114.01 (18) |
S7—Zn2—S8 | 72.59 (2) | S8—C13—O4 | 124.79 (19) |
S7—Zn2—P2 | 119.54 (2) |
It is well known that the oligomeric and polymeric arrays found for the bis-1,1-dithiolate structures of zinc, cadmium and mercury (Cox & Tiekink, 1997) are moderated upon the addition of base. One motivation for such adduct formation is to prepare more suitable precursors for chemical vapour deposition by reducing the aggregation between molecules. In this context, it has been demonstrated that the tetrameric structure of zinc(II) bis(O-isopropyldithiocarbonate), [Zn(S2COiPr)2]4, which features a 16-membered –[Zn—S—C—S]4– ring (Ito, 1972), is disrupted when an additional donor atom(s) is incorporated into the coordination sphere. Thus, isolated monomeric species are formed upon chelation with 1,10-phenanthroline (Klevtsova et al., 2001). In the same way, isolated dimeric units are found in the 1:2 adduct with 4,4'-bipyridyl, in which the latter is bidentate bridging (Klevtsova et al., 2000). As a continuation of previous studies in this area (Tiekink, 2001a,b; Jie & Tiekink, 2002; Dee & Tiekink, 2002), the title compound, (µ-Ph2PCH2CH2PPh2){Zn(S2COiPr)2}2, (I), has been investigated.
The dinuclear molecular structure of (I) (Fig. 1 and Table 1) has approximate Ci symmetry, with deviations from a centrosymmetric arrangement ascribed primarily to differences in the Zn-atom coordination geometries. Each Zn atom is coordinated by two xanthate (i.e. -S2COiPr) ligands which form asymmetric Zn—S bonds. The five-coordinate geometry is completed by a P atom of the bidentate bridging diphosphine ligand. The Zn—S bond distances fall into classes with bonds formed by atoms S1, S3, S5 and S7 [average 2.3314 (4) Å] being significantly shorter than those formed by the remaining S atoms [average 2.6283 (3) Å]. The Zn—P bond distances average 2.4145 (5) Å and are intermediate between the short and long Zn—S bonds. The asymmetry in the mode of coordination of the xanthate ligands is reflected in the magnitudes of the associated C—S bond distances (Table 1) that follow the expected trends. The coordination geometry lies between the two extremes of square pyramidal and trigonal bipyramidal, with the latter description being the preferred. This being the case, the axial positions about Zn1 are defined by the weakly coordinated S2 and S4 atoms [165.88 (2)°] and for the Zn2 atom the S6 and S8 atoms occupy the axial sites [163.32 (2)°]. Phosphine adducts are relatively rare for the 1,1-dithiolates of Zn, Cd and Hg. Relevant to the present study are the structures of centrosymmetric (µ2-depe){Zd(S2CNEt2)2}2, where depe is bis(diethylphosphino)ethane (Zeng et al., 1994) and the recently determined structure of (µ2-dppf){Cd(S2CNEt2)2}2, where dppf is bis(diphenylphosphino)ferrocene (Dee & Tiekink, 2002). In the former, the coordination geometry about Zn has been described as trigonal bipyramidal, whereas a square-pyramidal geometry was assigned to the Cd atom in the latter structure.
The lattice features interactions (Spek, 2000) of the type C—H···π, C—H···O and C—H···S. The closest C—H···π contact occurs between C27—H and the ring centroid of C37—C42 so that the H···ring centroid distance is 2.87 Å and the angle subtended at H is 131°; symmetry code: 2 - x, 1/2 + y, 1/2 - z. In this context, analogous intramolecular C—H···π contacts involving the Zn—S—C—S chelate rings are noted. The closest of these occurs between C42—H and the centroid of Zn2—S7—C13—S8 chelate ring with geometric parameters of 2.76 Å and 137°. Similar contacts have been described recently for the structure of the 2,2'-bipyridine adduct of Zn(S2CNnBu2)2(2,2'-bipyridine) (Tiekink, 2001b). The closest C—H···O contact of 2.59 Å occurs between C29—H and O3 with an angle of 162° subtended at H; symmetry code: x, 3/2 - y, 1/2 + z. The C29—H atom also forms the closest intermolecular C—H···S contact. This involves the same molecule as for the C—H···O interaction, but with the S5 atom so that H···S is 2.86 Å and the angle at H is 135°. In this sense, the H29 atom is bifurcated, bridging an O—C—S entity.