Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015318/cv6052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015318/cv6052Isup2.hkl |
CCDC reference: 175343
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.033
- wR factor = 0.087
- Data-to-parameter ratio = 11.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 23.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared by adding oxygen to a suspension of Ni[P(C6H5)3]4 and two equivalents of ZnCl2 in toluene at 333 K. After filtration and removal of the solvent, colorless crystals were obtained by slowly cooling a saturated solution in tetrahydrofuran from 313 K to room temperature. NMR data validate the presence of two THF molecules in the crystal. All H atoms were located in the difference Fourier maps and refined freely except those located at the disordered THF solvent molecule. They were calculated in ideal positions and refined as a riding model.
Data collection: Kappa-CCD Control Software (Nonius, 2000); cell refinement: DENZO (Nonius, 2000); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1998); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: PLATON.
[ZnCl2(C18H15OP)2]·2C4H8O | Z = 2 |
Mr = 837.04 | F(000) = 872 |
Triclinic, P1 | Dx = 1.386 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6758 (1) Å | Cell parameters from 7093 reflections |
b = 12.9704 (1) Å | θ = 1.5–25.4° |
c = 15.2874 (2) Å | µ = 0.87 mm−1 |
α = 110.2721 (4)° | T = 123 K |
β = 109.8102 (5)° | Fragment, colorless |
γ = 92.8572 (4)° | 0.69 × 0.61 × 0.45 mm |
V = 2006.16 (4) Å3 |
Nonius κ-CCD diffractometer | 7358 independent reflections |
Radiation source: NONIUS FR 591 rotating anode | 6793 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 18 # 9 for binned mode pixels mm-1 | θmax = 25.4°, θmin = 1.5° |
ϕ and ω–rotation scans | h = −14→14 |
Absorption correction: multi-scan applied during the scaling procedure (Nonius, 2000) | k = −15→15 |
Tmin = 0.559, Tmax = 0.677 | l = −18→18 |
30256 measured reflections |
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)] = 0.033 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2) + (0.0454P)2 + 1.6738P] where P = (Fo2 + 2Fc2)/3 |
7357 reflections | (Δ/σ)max = 0.001 |
640 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[ZnCl2(C18H15OP)2]·2C4H8O | γ = 92.8572 (4)° |
Mr = 837.04 | V = 2006.16 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.6758 (1) Å | Mo Kα radiation |
b = 12.9704 (1) Å | µ = 0.87 mm−1 |
c = 15.2874 (2) Å | T = 123 K |
α = 110.2721 (4)° | 0.69 × 0.61 × 0.45 mm |
β = 109.8102 (5)° |
Nonius κ-CCD diffractometer | 7358 independent reflections |
Absorption correction: multi-scan applied during the scaling procedure (Nonius, 2000) | 6793 reflections with I > 2σ(I) |
Tmin = 0.559, Tmax = 0.677 | Rint = 0.046 |
30256 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.54 e Å−3 |
7357 reflections | Δρmin = −0.45 e Å−3 |
640 parameters |
Experimental. Diffractometer operator E. Herdtweck scanspeed 2 x 30 s per film repetition 1 713 films measured in 5 data sets set 1: phi-scan with delta_phi = 1.0 set 2 to set 5 omega-scan with delta_omega = 1.0 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R_factor_obs 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 | 0.64187 (2) | 0.32970 (2) | 0.24670 (2) | 0.0154 (1) | |
Cl1 | 0.66504 (5) | 0.47594 (4) | 0.38414 (4) | 0.0255 (2) | |
Cl2 | 0.47745 (4) | 0.28918 (4) | 0.10581 (4) | 0.0214 (1) | |
P1 | 0.84041 (4) | 0.32142 (4) | 0.13636 (4) | 0.0146 (1) | |
P2 | 0.68851 (4) | 0.16018 (4) | 0.36648 (4) | 0.0157 (1) | |
O1 | 0.65444 (12) | 0.19270 (11) | 0.27690 (10) | 0.0185 (4) | |
O2 | 0.79611 (12) | 0.34168 (11) | 0.22146 (10) | 0.0180 (4) | |
C11 | 0.82066 (18) | 0.43194 (15) | 0.09049 (14) | 0.0166 (5) | |
C12 | 0.70275 (19) | 0.45743 (18) | 0.05869 (16) | 0.0222 (6) | |
C13 | 0.6859 (2) | 0.54767 (18) | 0.03016 (16) | 0.0245 (6) | |
C14 | 0.7857 (2) | 0.61278 (17) | 0.03346 (15) | 0.0226 (6) | |
C15 | 0.9021 (2) | 0.58757 (17) | 0.06404 (16) | 0.0227 (6) | |
C16 | 0.92004 (19) | 0.49687 (17) | 0.09227 (15) | 0.0189 (6) | |
C21 | 0.76057 (17) | 0.19142 (16) | 0.03341 (15) | 0.0179 (5) | |
C22 | 0.70686 (19) | 0.10799 (17) | 0.05286 (17) | 0.0227 (6) | |
C23 | 0.6497 (2) | 0.00447 (18) | −0.02417 (18) | 0.0278 (7) | |
C24 | 0.6478 (2) | −0.01629 (18) | −0.11965 (17) | 0.0279 (7) | |
C25 | 0.7006 (2) | 0.06604 (19) | −0.13941 (17) | 0.0283 (7) | |
C26 | 0.7563 (2) | 0.17075 (18) | −0.06312 (16) | 0.0235 (6) | |
C31 | 1.00262 (17) | 0.31794 (16) | 0.18127 (15) | 0.0169 (5) | |
C32 | 1.05906 (19) | 0.26065 (17) | 0.11654 (16) | 0.0214 (6) | |
C33 | 1.1848 (2) | 0.26193 (19) | 0.15425 (17) | 0.0253 (7) | |
C34 | 1.2546 (2) | 0.3188 (2) | 0.25582 (18) | 0.0284 (7) | |
C35 | 1.1991 (2) | 0.37590 (19) | 0.32026 (17) | 0.0278 (7) | |
C36 | 1.07318 (19) | 0.37583 (17) | 0.28316 (16) | 0.0214 (6) | |
C41 | 0.56767 (18) | 0.16674 (17) | 0.41458 (14) | 0.0181 (6) | |
C42 | 0.5380 (2) | 0.27083 (18) | 0.45600 (16) | 0.0243 (6) | |
C43 | 0.4379 (2) | 0.2775 (2) | 0.48447 (17) | 0.0307 (7) | |
C44 | 0.3668 (2) | 0.1817 (2) | 0.47232 (18) | 0.0336 (8) | |
C45 | 0.3964 (2) | 0.0783 (2) | 0.43263 (18) | 0.0332 (8) | |
C46 | 0.4969 (2) | 0.07064 (19) | 0.40345 (16) | 0.0248 (6) | |
C51 | 0.82845 (18) | 0.24631 (16) | 0.46662 (15) | 0.0190 (6) | |
C52 | 0.9171 (2) | 0.29124 (18) | 0.44121 (17) | 0.0247 (6) | |
C53 | 1.0289 (2) | 0.3546 (2) | 0.51544 (18) | 0.0300 (7) | |
C54 | 1.0529 (2) | 0.37221 (18) | 0.61517 (17) | 0.0276 (7) | |
C55 | 0.9651 (2) | 0.32747 (18) | 0.64061 (16) | 0.0269 (7) | |
C56 | 0.8523 (2) | 0.26508 (17) | 0.56714 (15) | 0.0230 (6) | |
C61 | 0.71345 (18) | 0.01872 (16) | 0.32849 (15) | 0.0174 (5) | |
C62 | 0.7861 (2) | −0.02154 (18) | 0.39793 (17) | 0.0242 (6) | |
C63 | 0.8035 (2) | −0.13109 (19) | 0.36552 (18) | 0.0279 (7) | |
C64 | 0.7497 (2) | −0.20021 (18) | 0.26495 (18) | 0.0280 (7) | |
C65 | 0.6774 (2) | −0.16084 (18) | 0.19563 (18) | 0.0284 (7) | |
C66 | 0.6592 (2) | −0.05100 (17) | 0.22732 (16) | 0.0232 (6) | |
O81 | −0.0057 (2) | 0.86988 (15) | 0.12813 (14) | 0.0484 (7) | |
C82A | −0.0169 (4) | 0.9761 (3) | 0.1251 (3) | 0.0693 (13) | 0.531 (15) |
C83A | 0.0487 (13) | 1.0600 (5) | 0.2347 (5) | 0.054 (3) | 0.531 (15) |
C84A | 0.0433 (3) | 0.9979 (3) | 0.2937 (2) | 0.0539 (10) | 0.531 (15) |
C85 | 0.0405 (3) | 0.8799 (2) | 0.2300 (2) | 0.0400 (9) | |
C84B | 0.0433 (3) | 0.9979 (3) | 0.2937 (2) | 0.0539 (10) | 0.469 (15) |
C82B | −0.0169 (4) | 0.9761 (3) | 0.1251 (3) | 0.0693 (13) | 0.469 (15) |
C83B | −0.0284 (10) | 1.0467 (6) | 0.2213 (5) | 0.038 (2) | 0.469 (15) |
O71 | 0.3094 (2) | 0.73622 (17) | 0.26140 (16) | 0.0582 (8) | |
C72 | 0.2621 (2) | 0.6180 (3) | 0.2162 (2) | 0.0440 (9) | |
C73 | 0.3728 (2) | 0.5649 (2) | 0.24294 (19) | 0.0334 (7) | |
C74 | 0.4722 (3) | 0.6429 (2) | 0.2426 (2) | 0.0407 (8) | |
C75 | 0.4328 (3) | 0.7535 (2) | 0.2698 (3) | 0.0552 (10) | |
H121 | 0.638 (2) | 0.411 (2) | 0.0580 (18) | 0.029 (6)* | |
H131 | 0.605 (2) | 0.5625 (19) | 0.0066 (17) | 0.023 (6)* | |
H141 | 0.774 (2) | 0.673 (2) | 0.0143 (18) | 0.025 (6)* | |
H151 | 0.969 (2) | 0.634 (2) | 0.0702 (19) | 0.033 (7)* | |
H161 | 0.998 (2) | 0.4789 (18) | 0.1110 (16) | 0.018 (5)* | |
H221 | 0.707 (2) | 0.121 (2) | 0.118 (2) | 0.036 (7)* | |
H231 | 0.612 (2) | −0.049 (2) | −0.012 (2) | 0.034 (7)* | |
H241 | 0.6083 (19) | −0.0855 (18) | −0.1736 (17) | 0.014 (5)* | |
H251 | 0.700 (2) | 0.054 (2) | −0.205 (2) | 0.032 (7)* | |
H261 | 0.790 (2) | 0.225 (2) | −0.0743 (18) | 0.028 (6)* | |
H321 | 1.012 (2) | 0.2212 (19) | 0.0469 (18) | 0.020 (6)* | |
H331 | 1.222 (2) | 0.224 (2) | 0.1140 (19) | 0.027 (6)* | |
H341 | 1.343 (2) | 0.3189 (19) | 0.2793 (18) | 0.024 (6)* | |
H351 | 1.249 (2) | 0.418 (2) | 0.392 (2) | 0.031 (7)* | |
H361 | 1.036 (2) | 0.4167 (19) | 0.3275 (18) | 0.021 (6)* | |
H421 | 0.587 (2) | 0.334 (2) | 0.4651 (17) | 0.023 (6)* | |
H431 | 0.422 (2) | 0.344 (2) | 0.511 (2) | 0.033 (7)* | |
H441 | 0.299 (2) | 0.186 (2) | 0.4911 (19) | 0.035 (7)* | |
H451 | 0.347 (3) | 0.011 (2) | 0.425 (2) | 0.045 (8)* | |
H461 | 0.519 (2) | −0.003 (2) | 0.3783 (18) | 0.028 (6)* | |
H521 | 0.901 (2) | 0.276 (2) | 0.372 (2) | 0.039 (7)* | |
H531 | 1.090 (2) | 0.386 (2) | 0.4983 (19) | 0.032 (7)* | |
H541 | 1.123 (2) | 0.414 (2) | 0.6678 (19) | 0.026 (6)* | |
H551 | 0.979 (2) | 0.340 (2) | 0.709 (2) | 0.029 (6)* | |
H561 | 0.788 (2) | 0.234 (2) | 0.5829 (19) | 0.031 (6)* | |
H621 | 0.821 (2) | 0.021 (2) | 0.463 (2) | 0.024 (6)* | |
H631 | 0.852 (2) | −0.160 (2) | 0.410 (2) | 0.037 (7)* | |
H641 | 0.761 (2) | −0.273 (2) | 0.2450 (19) | 0.033 (7)* | |
H651 | 0.637 (2) | −0.208 (2) | 0.128 (2) | 0.037 (7)* | |
H661 | 0.612 (2) | −0.025 (2) | 0.1793 (19) | 0.027 (6)* | |
H821 | −0.10530 | 0.98190 | 0.09850 | 0.0830* | 0.531 (15) |
H841 | −0.03210 | 1.00370 | 0.30950 | 0.0650* | 0.531 (15) |
H842 | 0.11700 | 1.02520 | 0.35760 | 0.0650* | 0.531 (15) |
H851 | 0.12490 | 0.86240 | 0.24880 | 0.0480* | |
H852 | −0.01410 | 0.82720 | 0.23950 | 0.0480* | |
H822 | 0.02310 | 0.99020 | 0.08160 | 0.0830* | 0.531 (15) |
H831 | 0.13580 | 1.08880 | 0.24840 | 0.0650* | 0.531 (15) |
H832 | 0.00550 | 1.12390 | 0.24880 | 0.0650* | 0.531 (15) |
H823 | −0.09120 | 0.97040 | 0.06660 | 0.0830* | 0.469 (15) |
H824 | 0.05710 | 1.00910 | 0.11930 | 0.0830* | 0.469 (15) |
H833 | −0.11620 | 1.04070 | 0.21430 | 0.0450* | 0.469 (15) |
H834 | 0.00820 | 1.12620 | 0.24300 | 0.0450* | 0.469 (15) |
H843 | 0.12970 | 1.03990 | 0.33140 | 0.0650* | 0.469 (15) |
H844 | 0.00430 | 0.99990 | 0.34240 | 0.0650* | 0.469 (15) |
H721 | 0.223 (3) | 0.597 (3) | 0.146 (3) | 0.053 (9)* | |
H722 | 0.200 (3) | 0.607 (3) | 0.243 (3) | 0.075 (11)* | |
H731 | 0.362 (3) | 0.487 (3) | 0.195 (2) | 0.056 (9)* | |
H732 | 0.392 (2) | 0.562 (2) | 0.314 (2) | 0.038 (7)* | |
H741 | 0.551 (3) | 0.644 (3) | 0.290 (2) | 0.052 (9)* | |
H742 | 0.472 (3) | 0.622 (3) | 0.176 (3) | 0.053 (9)* | |
H751 | 0.490 (4) | 0.807 (4) | 0.338 (3) | 0.096 (13)* | |
H752 | 0.439 (3) | 0.795 (3) | 0.228 (3) | 0.074 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0171 (1) | 0.0153 (1) | 0.0144 (1) | 0.0033 (1) | 0.0065 (1) | 0.0059 (1) |
Cl1 | 0.0316 (3) | 0.0195 (2) | 0.0219 (3) | 0.0056 (2) | 0.0123 (2) | 0.0019 (2) |
Cl2 | 0.0187 (2) | 0.0225 (2) | 0.0207 (2) | 0.0022 (2) | 0.0028 (2) | 0.0103 (2) |
P1 | 0.0155 (2) | 0.0151 (2) | 0.0139 (2) | 0.0025 (2) | 0.0058 (2) | 0.0062 (2) |
P2 | 0.0197 (2) | 0.0150 (2) | 0.0135 (2) | 0.0036 (2) | 0.0070 (2) | 0.0061 (2) |
O1 | 0.0245 (7) | 0.0168 (7) | 0.0154 (7) | 0.0037 (5) | 0.0076 (6) | 0.0076 (6) |
O2 | 0.0190 (7) | 0.0213 (7) | 0.0159 (7) | 0.0032 (5) | 0.0080 (6) | 0.0085 (6) |
C11 | 0.0211 (10) | 0.0155 (9) | 0.0121 (9) | 0.0020 (7) | 0.0059 (8) | 0.0047 (7) |
C12 | 0.0202 (10) | 0.0231 (10) | 0.0269 (11) | 0.0036 (8) | 0.0095 (9) | 0.0133 (9) |
C13 | 0.0241 (11) | 0.0272 (11) | 0.0268 (11) | 0.0092 (9) | 0.0100 (9) | 0.0147 (9) |
C14 | 0.0355 (12) | 0.0181 (10) | 0.0184 (10) | 0.0079 (9) | 0.0123 (9) | 0.0095 (8) |
C15 | 0.0290 (11) | 0.0203 (10) | 0.0204 (10) | −0.0006 (9) | 0.0115 (9) | 0.0085 (8) |
C16 | 0.0209 (10) | 0.0210 (10) | 0.0157 (10) | 0.0038 (8) | 0.0071 (8) | 0.0081 (8) |
C21 | 0.0161 (9) | 0.0171 (9) | 0.0181 (10) | 0.0029 (7) | 0.0053 (8) | 0.0052 (8) |
C22 | 0.0271 (11) | 0.0188 (10) | 0.0254 (11) | 0.0049 (8) | 0.0124 (9) | 0.0098 (9) |
C23 | 0.0289 (11) | 0.0174 (10) | 0.0357 (13) | 0.0016 (9) | 0.0128 (10) | 0.0085 (9) |
C24 | 0.0221 (11) | 0.0193 (11) | 0.0275 (12) | 0.0018 (8) | 0.0016 (9) | −0.0001 (9) |
C25 | 0.0288 (11) | 0.0307 (12) | 0.0172 (11) | 0.0041 (9) | 0.0045 (9) | 0.0043 (9) |
C26 | 0.0252 (11) | 0.0248 (11) | 0.0190 (10) | 0.0021 (9) | 0.0068 (9) | 0.0088 (9) |
C31 | 0.0175 (9) | 0.0160 (9) | 0.0208 (10) | 0.0034 (7) | 0.0075 (8) | 0.0110 (8) |
C32 | 0.0240 (10) | 0.0234 (10) | 0.0201 (11) | 0.0059 (8) | 0.0097 (9) | 0.0108 (9) |
C33 | 0.0255 (11) | 0.0314 (12) | 0.0292 (12) | 0.0111 (9) | 0.0168 (10) | 0.0164 (10) |
C34 | 0.0167 (10) | 0.0384 (13) | 0.0348 (13) | 0.0077 (9) | 0.0075 (9) | 0.0213 (11) |
C35 | 0.0240 (11) | 0.0318 (12) | 0.0226 (12) | 0.0034 (9) | 0.0025 (9) | 0.0111 (10) |
C36 | 0.0240 (10) | 0.0212 (10) | 0.0202 (10) | 0.0054 (8) | 0.0083 (9) | 0.0094 (8) |
C41 | 0.0207 (10) | 0.0223 (10) | 0.0125 (9) | 0.0055 (8) | 0.0063 (8) | 0.0078 (8) |
C42 | 0.0310 (11) | 0.0236 (11) | 0.0205 (11) | 0.0076 (9) | 0.0109 (9) | 0.0095 (9) |
C43 | 0.0386 (13) | 0.0361 (13) | 0.0230 (11) | 0.0205 (11) | 0.0164 (10) | 0.0114 (10) |
C44 | 0.0291 (12) | 0.0513 (15) | 0.0275 (12) | 0.0114 (11) | 0.0187 (10) | 0.0152 (11) |
C45 | 0.0300 (12) | 0.0409 (14) | 0.0325 (13) | 0.0012 (10) | 0.0165 (10) | 0.0149 (11) |
C46 | 0.0277 (11) | 0.0259 (11) | 0.0210 (11) | 0.0034 (9) | 0.0112 (9) | 0.0076 (9) |
C51 | 0.0217 (10) | 0.0162 (9) | 0.0168 (10) | 0.0043 (8) | 0.0050 (8) | 0.0058 (8) |
C52 | 0.0247 (11) | 0.0293 (11) | 0.0200 (11) | 0.0017 (9) | 0.0056 (9) | 0.0126 (9) |
C53 | 0.0255 (11) | 0.0315 (12) | 0.0314 (12) | −0.0002 (9) | 0.0060 (10) | 0.0156 (10) |
C54 | 0.0261 (11) | 0.0208 (11) | 0.0260 (12) | 0.0024 (9) | 0.0010 (10) | 0.0065 (9) |
C55 | 0.0323 (12) | 0.0262 (11) | 0.0157 (11) | 0.0075 (9) | 0.0046 (9) | 0.0048 (9) |
C56 | 0.0280 (11) | 0.0222 (10) | 0.0186 (10) | 0.0049 (8) | 0.0092 (9) | 0.0072 (8) |
C61 | 0.0199 (9) | 0.0165 (9) | 0.0207 (10) | 0.0048 (7) | 0.0115 (8) | 0.0088 (8) |
C62 | 0.0312 (11) | 0.0253 (11) | 0.0186 (11) | 0.0092 (9) | 0.0109 (9) | 0.0095 (9) |
C63 | 0.0358 (12) | 0.0264 (11) | 0.0311 (12) | 0.0142 (10) | 0.0168 (10) | 0.0172 (10) |
C64 | 0.0345 (12) | 0.0180 (11) | 0.0381 (13) | 0.0101 (9) | 0.0220 (11) | 0.0098 (10) |
C65 | 0.0342 (12) | 0.0221 (11) | 0.0254 (12) | 0.0052 (9) | 0.0128 (10) | 0.0039 (9) |
C66 | 0.0266 (11) | 0.0207 (10) | 0.0220 (11) | 0.0048 (8) | 0.0089 (9) | 0.0081 (9) |
O81 | 0.0697 (13) | 0.0357 (10) | 0.0392 (11) | 0.0039 (9) | 0.0253 (10) | 0.0100 (8) |
C82A | 0.103 (3) | 0.069 (2) | 0.0462 (18) | 0.051 (2) | 0.0293 (19) | 0.0284 (17) |
C83A | 0.089 (8) | 0.029 (3) | 0.057 (4) | 0.014 (3) | 0.039 (4) | 0.020 (3) |
C84A | 0.0639 (19) | 0.0450 (17) | 0.0446 (17) | 0.0121 (14) | 0.0159 (15) | 0.0121 (14) |
C85 | 0.0464 (15) | 0.0385 (14) | 0.0507 (16) | 0.0140 (11) | 0.0279 (13) | 0.0252 (13) |
C84B | 0.0639 (19) | 0.0450 (17) | 0.0446 (17) | 0.0121 (14) | 0.0159 (15) | 0.0121 (14) |
C82B | 0.103 (3) | 0.069 (2) | 0.0462 (18) | 0.051 (2) | 0.0293 (19) | 0.0284 (17) |
C83B | 0.040 (5) | 0.036 (3) | 0.045 (4) | 0.016 (3) | 0.023 (3) | 0.016 (3) |
O71 | 0.0862 (17) | 0.0474 (12) | 0.0529 (13) | 0.0363 (11) | 0.0367 (12) | 0.0199 (10) |
C72 | 0.0319 (14) | 0.0630 (19) | 0.0266 (14) | 0.0044 (12) | 0.0101 (11) | 0.0067 (13) |
C73 | 0.0393 (13) | 0.0253 (12) | 0.0308 (13) | 0.0002 (10) | 0.0108 (11) | 0.0087 (10) |
C74 | 0.0348 (14) | 0.0456 (15) | 0.0373 (15) | −0.0020 (11) | 0.0064 (12) | 0.0194 (12) |
C75 | 0.0512 (18) | 0.0339 (15) | 0.0561 (19) | −0.0043 (13) | −0.0144 (15) | 0.0247 (14) |
Zn—Cl1 | 2.2108 (6) | C16—H161 | 0.92 (2) |
Zn—Cl2 | 2.2165 (6) | C22—H221 | 0.95 (3) |
Zn—O1 | 1.9851 (15) | C23—H231 | 0.91 (3) |
Zn—O2 | 1.9751 (15) | C24—H241 | 0.94 (2) |
P1—O2 | 1.5039 (15) | C25—H251 | 0.96 (3) |
P1—C11 | 1.794 (2) | C26—H261 | 0.88 (3) |
P1—C21 | 1.789 (2) | C32—H321 | 0.95 (2) |
P1—C31 | 1.791 (2) | C33—H331 | 0.90 (3) |
P2—O1 | 1.5031 (15) | C34—H341 | 0.97 (3) |
P2—C41 | 1.792 (2) | C35—H351 | 0.98 (3) |
P2—C51 | 1.789 (2) | C36—H361 | 0.95 (3) |
P2—C61 | 1.794 (2) | C42—H421 | 0.92 (3) |
O81—C82A | 1.405 (5) | C43—H431 | 0.88 (3) |
O81—C85 | 1.420 (3) | C44—H441 | 0.93 (3) |
O81—C82B | 1.405 (5) | C45—H451 | 0.97 (3) |
O71—C75 | 1.402 (5) | C46—H461 | 0.98 (3) |
O71—C72 | 1.434 (4) | C52—H521 | 0.95 (3) |
C11—C16 | 1.386 (3) | C53—H531 | 0.96 (3) |
C11—C12 | 1.394 (3) | C54—H541 | 0.90 (3) |
C12—C13 | 1.385 (3) | C55—H551 | 0.95 (3) |
C13—C14 | 1.381 (3) | C56—H561 | 0.97 (3) |
C14—C15 | 1.376 (3) | C62—H621 | 0.88 (3) |
C15—C16 | 1.389 (3) | C63—H631 | 0.93 (3) |
C21—C22 | 1.391 (3) | C64—H641 | 0.92 (3) |
C21—C26 | 1.388 (3) | C65—H651 | 0.93 (3) |
C22—C23 | 1.385 (3) | C66—H661 | 0.93 (3) |
C23—C24 | 1.382 (3) | C82A—C83A | 1.537 (8) |
C24—C25 | 1.377 (4) | C82B—C83B | 1.494 (9) |
C25—C26 | 1.388 (3) | C83A—C84A | 1.415 (8) |
C31—C36 | 1.388 (3) | C83B—C84B | 1.496 (9) |
C31—C32 | 1.395 (3) | C84A—C85 | 1.494 (5) |
C32—C33 | 1.380 (3) | C84B—C85 | 1.494 (5) |
C33—C34 | 1.381 (3) | C82A—H821 | 0.9903 |
C34—C35 | 1.383 (3) | C82A—H822 | 0.9900 |
C35—C36 | 1.385 (3) | C82B—H823 | 0.9898 |
C41—C46 | 1.386 (3) | C82B—H824 | 0.9894 |
C41—C42 | 1.395 (3) | C83A—H832 | 0.9896 |
C42—C43 | 1.375 (3) | C83A—H831 | 0.9905 |
C43—C44 | 1.379 (4) | C83B—H834 | 0.9894 |
C44—C45 | 1.382 (4) | C83B—H833 | 0.9901 |
C45—C46 | 1.386 (4) | C84A—H842 | 0.9901 |
C51—C56 | 1.394 (3) | C84A—H841 | 0.9885 |
C51—C52 | 1.390 (3) | C84B—H844 | 0.9899 |
C52—C53 | 1.382 (3) | C84B—H843 | 0.9900 |
C53—C54 | 1.385 (3) | C85—H851 | 0.9903 |
C54—C55 | 1.381 (4) | C85—H852 | 0.9914 |
C55—C56 | 1.383 (3) | C72—C73 | 1.496 (4) |
C61—C62 | 1.392 (3) | C73—C74 | 1.504 (4) |
C61—C66 | 1.386 (3) | C74—C75 | 1.491 (4) |
C62—C63 | 1.384 (4) | C72—H721 | 0.94 (4) |
C63—C64 | 1.377 (3) | C72—H722 | 0.97 (4) |
C64—C65 | 1.381 (3) | C73—H731 | 0.99 (4) |
C65—C66 | 1.390 (3) | C73—H732 | 1.05 (3) |
C12—H121 | 0.94 (3) | C74—H741 | 0.95 (3) |
C13—H131 | 0.95 (2) | C74—H742 | 0.96 (4) |
C14—H141 | 0.93 (3) | C75—H751 | 1.00 (4) |
C15—H151 | 0.92 (3) | C75—H752 | 0.98 (4) |
Cl1—Zn—Cl2 | 120.55 (2) | C35—C36—H361 | 119.7 (15) |
Cl1—Zn—O1 | 110.09 (4) | C41—C42—H421 | 119.1 (16) |
Cl1—Zn—O2 | 107.43 (4) | C43—C42—H421 | 121.0 (16) |
Cl2—Zn—O1 | 107.77 (4) | C44—C43—H431 | 121.8 (17) |
Cl2—Zn—O2 | 110.55 (4) | C42—C43—H431 | 118.0 (17) |
O1—Zn—O2 | 98.16 (6) | C43—C44—H441 | 120.4 (17) |
O2—P1—C11 | 111.29 (9) | C45—C44—H441 | 119.3 (17) |
O2—P1—C21 | 111.85 (9) | C44—C45—H451 | 120 (2) |
O2—P1—C31 | 109.09 (9) | C46—C45—H451 | 120 (2) |
C11—P1—C21 | 108.60 (10) | C45—C46—H461 | 118.9 (15) |
C11—P1—C31 | 107.51 (10) | C41—C46—H461 | 121.2 (15) |
C21—P1—C31 | 108.36 (10) | C51—C52—H521 | 119.4 (16) |
O1—P2—C41 | 111.83 (9) | C53—C52—H521 | 120.5 (16) |
O1—P2—C51 | 112.21 (9) | C52—C53—H531 | 120.4 (15) |
O1—P2—C61 | 108.73 (9) | C54—C53—H531 | 119.8 (15) |
C41—P2—C51 | 108.52 (10) | C53—C54—H541 | 124.7 (16) |
C41—P2—C61 | 107.94 (11) | C55—C54—H541 | 115.1 (16) |
C51—P2—C61 | 107.43 (10) | C54—C55—H551 | 121.5 (16) |
Zn—O1—P2 | 139.20 (9) | C56—C55—H551 | 117.9 (16) |
Zn—O2—P1 | 141.01 (9) | C55—C56—H561 | 122.4 (15) |
C82B—O81—C85 | 109.4 (2) | C51—C56—H561 | 118.2 (15) |
C82A—O81—C85 | 109.4 (2) | C61—C62—H621 | 121.6 (18) |
C72—O71—C75 | 108.2 (2) | C63—C62—H621 | 118.6 (18) |
C12—C11—C16 | 119.5 (2) | C62—C63—H631 | 121.6 (17) |
P1—C11—C16 | 121.95 (17) | C64—C63—H631 | 118.0 (17) |
P1—C11—C12 | 118.43 (17) | C65—C64—H641 | 120.6 (16) |
C11—C12—C13 | 120.0 (2) | C63—C64—H641 | 119.1 (16) |
C12—C13—C14 | 120.2 (2) | C64—C65—H651 | 120.9 (17) |
C13—C14—C15 | 120.2 (2) | C66—C65—H651 | 119.1 (17) |
C14—C15—C16 | 120.2 (2) | C61—C66—H661 | 121.2 (16) |
C11—C16—C15 | 120.0 (2) | C65—C66—H661 | 118.9 (16) |
P1—C21—C26 | 121.67 (17) | O81—C82A—C83A | 105.6 (4) |
P1—C21—C22 | 118.35 (16) | O81—C82B—C83B | 106.7 (4) |
C22—C21—C26 | 119.9 (2) | C82A—C83A—C84A | 104.6 (5) |
C21—C22—C23 | 119.8 (2) | C82B—C83B—C84B | 102.9 (6) |
C22—C23—C24 | 120.0 (2) | C83A—C84A—C85 | 105.0 (4) |
C23—C24—C25 | 120.4 (2) | C83B—C84B—C85 | 105.3 (3) |
C24—C25—C26 | 120.0 (2) | O81—C85—C84A | 107.2 (2) |
C21—C26—C25 | 119.8 (2) | O81—C85—C84B | 107.2 (2) |
P1—C31—C36 | 118.36 (17) | O81—C82A—H822 | 110.58 |
C32—C31—C36 | 119.8 (2) | C83A—C82A—H821 | 110.60 |
P1—C31—C32 | 121.80 (16) | O81—C82A—H821 | 110.61 |
C31—C32—C33 | 119.8 (2) | H821—C82A—H822 | 108.76 |
C32—C33—C34 | 120.3 (2) | C83A—C82A—H822 | 110.70 |
C33—C34—C35 | 120.2 (2) | O81—C82B—H824 | 110.33 |
C34—C35—C36 | 120.1 (2) | O81—C82B—H823 | 110.38 |
C31—C36—C35 | 119.9 (2) | H823—C82B—H824 | 108.70 |
C42—C41—C46 | 119.8 (2) | C83B—C82B—H823 | 110.35 |
P2—C41—C46 | 121.51 (17) | C83B—C82B—H824 | 110.42 |
P2—C41—C42 | 118.48 (18) | C82A—C83A—H831 | 110.75 |
C41—C42—C43 | 119.9 (2) | C84A—C83A—H831 | 110.84 |
C42—C43—C44 | 120.2 (2) | C84A—C83A—H832 | 110.87 |
C43—C44—C45 | 120.3 (2) | H831—C83A—H832 | 108.89 |
C44—C45—C46 | 119.9 (2) | C82A—C83A—H832 | 110.82 |
C41—C46—C45 | 119.9 (2) | C82B—C83B—H833 | 111.20 |
C52—C51—C56 | 120.0 (2) | C82B—C83B—H834 | 111.16 |
P2—C51—C52 | 117.87 (16) | H833—C83B—H834 | 109.16 |
P2—C51—C56 | 122.11 (17) | C84B—C83B—H834 | 111.17 |
C51—C52—C53 | 120.1 (2) | C84B—C83B—H833 | 111.19 |
C52—C53—C54 | 119.8 (2) | C83A—C84A—H841 | 110.76 |
C53—C54—C55 | 120.2 (2) | C83A—C84A—H842 | 110.78 |
C54—C55—C56 | 120.5 (2) | C85—C84A—H841 | 110.74 |
C51—C56—C55 | 119.4 (2) | C85—C84A—H842 | 110.70 |
P2—C61—C66 | 118.62 (17) | H841—C84A—H842 | 108.88 |
P2—C61—C62 | 121.53 (16) | C85—C84B—H844 | 110.71 |
C62—C61—C66 | 119.8 (2) | C85—C84B—H843 | 110.64 |
C61—C62—C63 | 119.8 (2) | H843—C84B—H844 | 108.83 |
C62—C63—C64 | 120.3 (2) | C83B—C84B—H843 | 110.65 |
C63—C64—C65 | 120.2 (2) | C83B—C84B—H844 | 110.72 |
C64—C65—C66 | 120.0 (2) | O81—C85—H852 | 110.29 |
C61—C66—C65 | 119.9 (2) | C84A—C85—H851 | 110.34 |
C11—C12—H121 | 116.7 (17) | C84A—C85—H852 | 110.28 |
C13—C12—H121 | 123.3 (17) | H851—C85—H852 | 108.52 |
C12—C13—H131 | 119.1 (16) | C84B—C85—H851 | 110.34 |
C14—C13—H131 | 120.7 (16) | C84B—C85—H852 | 110.28 |
C13—C14—H141 | 119.9 (16) | O81—C85—H851 | 110.23 |
C15—C14—H141 | 120.0 (16) | O71—C72—C73 | 105.4 (2) |
C14—C15—H151 | 119.7 (17) | C72—C73—C74 | 102.1 (2) |
C16—C15—H151 | 119.9 (17) | C73—C74—C75 | 104.1 (3) |
C15—C16—H161 | 120.0 (16) | O71—C75—C74 | 108.5 (3) |
C11—C16—H161 | 120.0 (16) | O71—C72—H721 | 108 (3) |
C21—C22—H221 | 121.2 (17) | O71—C72—H722 | 105 (2) |
C23—C22—H221 | 118.9 (17) | C73—C72—H721 | 112 (2) |
C22—C23—H231 | 119.7 (17) | C73—C72—H722 | 116 (2) |
C24—C23—H231 | 120.2 (17) | H721—C72—H722 | 109 (3) |
C23—C24—H241 | 121.7 (15) | C72—C73—H731 | 114 (2) |
C25—C24—H241 | 117.8 (15) | C72—C73—H732 | 109.7 (15) |
C24—C25—H251 | 122.1 (17) | C74—C73—H731 | 112 (2) |
C26—C25—H251 | 117.9 (17) | C74—C73—H732 | 112.4 (15) |
C21—C26—H261 | 118.7 (16) | H731—C73—H732 | 107 (3) |
C25—C26—H261 | 121.5 (16) | C73—C74—H741 | 110 (2) |
C31—C32—H321 | 120.6 (16) | C73—C74—H742 | 110 (2) |
C33—C32—H321 | 119.6 (15) | C75—C74—H741 | 113 (2) |
C34—C33—H331 | 118.9 (16) | C75—C74—H742 | 108 (2) |
C32—C33—H331 | 120.8 (16) | H741—C74—H742 | 112 (3) |
C33—C34—H341 | 117.9 (14) | O71—C75—H751 | 113 (3) |
C35—C34—H341 | 121.9 (14) | O71—C75—H752 | 109 (2) |
C34—C35—H351 | 120.2 (15) | C74—C75—H751 | 111 (3) |
C36—C35—H351 | 119.7 (15) | C74—C75—H752 | 115 (2) |
C31—C36—H361 | 120.4 (15) | H751—C75—H752 | 101 (4) |
Experimental details
Crystal data | |
Chemical formula | [ZnCl2(C18H15OP)2]·2C4H8O |
Mr | 837.04 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 11.6758 (1), 12.9704 (1), 15.2874 (2) |
α, β, γ (°) | 110.2721 (4), 109.8102 (5), 92.8572 (4) |
V (Å3) | 2006.16 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.87 |
Crystal size (mm) | 0.69 × 0.61 × 0.45 |
Data collection | |
Diffractometer | Nonius κ-CCD diffractometer |
Absorption correction | Multi-scan applied during the scaling procedure (Nonius, 2000) |
Tmin, Tmax | 0.559, 0.677 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30256, 7358, 6793 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.604 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.087, 1.05 |
No. of reflections | 7357 |
No. of parameters | 640 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.54, −0.45 |
Computer programs: Kappa-CCD Control Software (Nonius, 2000), DENZO (Nonius, 2000), DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1998), PLATON (Spek, 2000), PLATON.
Zn—Cl1 | 2.2108 (6) | P1—C21 | 1.789 (2) |
Zn—Cl2 | 2.2165 (6) | P1—C31 | 1.791 (2) |
Zn—O1 | 1.9851 (15) | P2—O1 | 1.5031 (15) |
Zn—O2 | 1.9751 (15) | P2—C41 | 1.792 (2) |
P1—O2 | 1.5039 (15) | P2—C51 | 1.789 (2) |
P1—C11 | 1.794 (2) | P2—C61 | 1.794 (2) |
Cl1—Zn—Cl2 | 120.55 (2) | C41—P2—C61 | 107.94 (11) |
Cl1—Zn—O1 | 110.09 (4) | C51—P2—C61 | 107.43 (10) |
Cl1—Zn—O2 | 107.43 (4) | Zn—O1—P2 | 139.20 (9) |
Cl2—Zn—O1 | 107.77 (4) | Zn—O2—P1 | 141.01 (9) |
Cl2—Zn—O2 | 110.55 (4) | P1—C11—C16 | 121.95 (17) |
O1—Zn—O2 | 98.16 (6) | P1—C11—C12 | 118.43 (17) |
O2—P1—C11 | 111.29 (9) | P1—C21—C26 | 121.67 (17) |
O2—P1—C21 | 111.85 (9) | P1—C21—C22 | 118.35 (16) |
O2—P1—C31 | 109.09 (9) | P1—C31—C36 | 118.36 (17) |
C11—P1—C21 | 108.60 (10) | P1—C31—C32 | 121.80 (16) |
C11—P1—C31 | 107.51 (10) | P2—C41—C46 | 121.51 (17) |
C21—P1—C31 | 108.36 (10) | P2—C41—C42 | 118.48 (18) |
O1—P2—C41 | 111.83 (9) | P2—C51—C52 | 117.87 (16) |
O1—P2—C51 | 112.21 (9) | P2—C51—C56 | 122.11 (17) |
O1—P2—C61 | 108.73 (9) | P2—C61—C66 | 118.62 (17) |
C41—P2—C51 | 108.52 (10) | P2—C61—C62 | 121.53 (16) |
Recently Mayer (1998) introduced the bond-strength concept, i.e. the importance of the thermodynamics of broken and formed bonds. Because of the importance of phosphine ligands in organometallic chemistry we decided to investigate a series of metal complexes with triphenylphosphine and triphenylphosphine oxide ligands structurally and computationally. In the course of our investigation of the coordination strength of triphenylphosphine and triphenylphosphine oxide, we have been able to redetermine the crystal structure of the title complex, (I). It has originally been reported without solvent molecules by Rose et al. (1980) and Kosky et al. (1982). Structures of the type [M{(C6H5)3PO}2Cl2] with M = CoII (Mangion, 1976) and M = CuII (Bertrand et al., 1971) had previously been investigated. Studies on the IR spectra of compounds with M = ZnII by Deacon & Green (1968, 1969), as well as the thermochemistry of M = ZnII, CdII, HgII investigated by Jorge et al. (1978) gives us valuable information whether the calculated bond strength are in good agreement with experimental data.
As can be seen in Fig. 1, the ZnII ion in the title compound has a slightly distorted tetrahedral coordination, where the metal is ligated by two O atoms and two Cl atoms. Compared to the C2-symmetrical structure, (II), reported by Rose et al. (1980), (I) shows no point symmetry, a result of the two solvent molecules present in the crystal. The THF molecules occupy the open space in the structure and are not bound to the central atom. Their incorporation also results in a slight flatening of the molecule in (I), as can seen by the larger Cl1—Zn—Cl2 angle of 120.55 (2)° and O1—Zn—O2 angle of 98.16 (6)° compared to 116.3 and 96.8° in (II). The biggest change in bond angles can be seen in the decrease of the Zn—O—P angle from 153.4° in (II) to 139.20 (9) and 141.01 (9)° in (I), whereas the effect on the O—P—C angles is negligible.
Furthermore the Cl—Zn—O—P torsion angles changed from -38.9° in (II) to -8.3 (2)° and -8.8 (2)° in (I). A comparison of the corresponding Zn—O—P—C torsion angles indicates a rotation of the triphenylphosphine group of about 20° in the present compound induced by the thf molecules in the structure, e.g. 78.3 (2) and 76.0 (2)° in (I) versus 54.7° in the earlier structure (II).