Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106018932/av3009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106018932/av3009Isup2.hkl |
CCDC reference: 616124
The title complex was obtained by the reaction between a warm (about 313 K) ethanol solution containing 0.5 mmol of each of [Ni(L)NH3]·2H2O (L, dianion 2,4-pentandione S-methylisothiosemicarbazone) (Leovac et al., 1993) and 2-(diphenyl-phosphino)benzaldehyde.
All H atoms are found in a difference Fourier map, but they were placed at geometrically calculated positions and refined using a riding model. H atoms from methyl groups are treated with HFIX 137 instruction. Isotropic displacement parameters are equal to 1.2 (or 1.5 for methyl groups) times the equivalent isotropic displacement parameter of the parent atom.
Data collection: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
[Ni(C28H30N3O2PS)] | Z = 4 |
Mr = 562.29 | F(000) = 1176 |
Triclinic, P1 | Dx = 1.350 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.974 (3) Å | Cell parameters from 25 reflections |
b = 12.531 (2) Å | θ = 12.0–15.9° |
c = 20.827 (7) Å | µ = 0.86 mm−1 |
α = 89.81 (2)° | T = 293 K |
β = 73.56 (2)° | Prism, black |
γ = 68.26 (2)° | 0.36 × 0.30 × 0.26 mm |
V = 2765.9 (12) Å3 |
Enraf–Nonius CAD-4 diffractometer | Rint = 0.025 |
ω/2θ scans | θmax = 26.0°, θmin = 1.0° |
Absorption correction: gaussian (PLATON; Spek, 2003) | h = 0→14 |
Tmin = 0.756, Tmax = 0.820 | k = −13→15 |
11363 measured reflections | l = −24→25 |
10824 independent reflections | 3 standard reflections every 60 min |
6782 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.729P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.117 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.43 e Å−3 |
10824 reflections | Δρmin = −0.28 e Å−3 |
657 parameters |
[Ni(C28H30N3O2PS)] | γ = 68.26 (2)° |
Mr = 562.29 | V = 2765.9 (12) Å3 |
Triclinic, P1 | Z = 4 |
a = 11.974 (3) Å | Mo Kα radiation |
b = 12.531 (2) Å | µ = 0.86 mm−1 |
c = 20.827 (7) Å | T = 293 K |
α = 89.81 (2)° | 0.36 × 0.30 × 0.26 mm |
β = 73.56 (2)° |
Enraf–Nonius CAD-4 diffractometer | 6782 reflections with I > 2σ(I) |
Absorption correction: gaussian (PLATON; Spek, 2003) | Rint = 0.025 |
Tmin = 0.756, Tmax = 0.820 | 3 standard reflections every 60 min |
11363 measured reflections | intensity decay: none |
10824 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.43 e Å−3 |
10824 reflections | Δρmin = −0.28 e Å−3 |
657 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. |
x | y | z | Uiso*/Ueq | ||
Ni1a | 0.18357 (4) | 0.26223 (4) | 0.11535 (2) | 0.04047 (12) | |
P1a | 0.31500 (8) | 0.34566 (7) | 0.06963 (5) | 0.0404 (2) | |
S1a | 0.08343 (12) | 0.28575 (12) | 0.33548 (6) | 0.0770 (3) | |
O1a | 0.1816 (2) | 0.2243 (2) | 0.03069 (12) | 0.0544 (6) | |
O2a | 0.4019 (2) | 0.2517 (2) | 0.18981 (13) | 0.0523 (6) | |
N1a | 0.0596 (3) | 0.2092 (2) | 0.16089 (15) | 0.0476 (7) | |
N2a | 0.0294 (3) | 0.2197 (3) | 0.23164 (16) | 0.0545 (8) | |
N3a | 0.1861 (3) | 0.2932 (2) | 0.20187 (14) | 0.0453 (7) | |
C1a | 0.1014 (3) | 0.2635 (3) | 0.24861 (18) | 0.0487 (9) | |
C2a | −0.0456 (5) | 0.2431 (5) | 0.3729 (2) | 0.1071 (19) | |
H72a | −0.1210 | 0.2974 | 0.3659 | 0.161* | |
H82a | −0.0572 | 0.2414 | 0.4204 | 0.161* | |
H92a | −0.0275 | 0.1675 | 0.3527 | 0.161* | |
C3a | −0.1043 (4) | 0.1309 (4) | 0.1803 (3) | 0.0874 (15) | |
H73a | −0.0664 | 0.0696 | 0.2046 | 0.131* | |
H83a | −0.1455 | 0.1051 | 0.1540 | 0.131* | |
H93a | −0.1650 | 0.1965 | 0.2116 | 0.131* | |
C4a | −0.0031 (3) | 0.1650 (3) | 0.1341 (2) | 0.0562 (10) | |
C5a | 0.0207 (4) | 0.1508 (3) | 0.0645 (2) | 0.0597 (10) | |
H5a | −0.0267 | 0.1188 | 0.0489 | 0.072* | |
C6a | 0.1063 (4) | 0.1793 (3) | 0.0175 (2) | 0.0575 (10) | |
C7a | 0.1237 (5) | 0.1626 (5) | −0.0567 (2) | 0.0913 (16) | |
H77a | 0.1098 | 0.2355 | −0.0746 | 0.137* | |
H87a | 0.0644 | 0.1326 | −0.0635 | 0.137* | |
H97a | 0.2080 | 0.1091 | −0.0792 | 0.137* | |
C8a | 0.5649 (4) | 0.0689 (4) | 0.1812 (3) | 0.0984 (18) | |
H78a | 0.5931 | 0.0641 | 0.1329 | 0.148* | |
H88a | 0.5834 | −0.0076 | 0.1946 | 0.148* | |
H98a | 0.6075 | 0.1064 | 0.1998 | 0.148* | |
C9a | 0.4277 (4) | 0.1361 (4) | 0.2061 (2) | 0.0769 (13) | |
H79a | 0.3845 | 0.1012 | 0.1854 | 0.092* | |
H89a | 0.3975 | 0.1362 | 0.2545 | 0.092* | |
C10a | 0.2752 (3) | 0.3299 (3) | 0.22051 (18) | 0.0469 (8) | |
H10a | 0.2570 | 0.3345 | 0.2696 | 0.056* | |
C11a | 0.2951 (3) | 0.4617 (3) | 0.12956 (17) | 0.0424 (8) | |
C12a | 0.2708 (3) | 0.4458 (3) | 0.19806 (18) | 0.0441 (8) | |
C13a | 0.2467 (4) | 0.5355 (3) | 0.24436 (19) | 0.0559 (10) | |
H13a | 0.2299 | 0.5253 | 0.2899 | 0.067* | |
C14a | 0.2471 (4) | 0.6410 (3) | 0.2243 (2) | 0.0613 (11) | |
H14a | 0.2301 | 0.7012 | 0.2562 | 0.074* | |
C15a | 0.2726 (4) | 0.6566 (3) | 0.1571 (2) | 0.0564 (10) | |
H15a | 0.2743 | 0.7269 | 0.1436 | 0.068* | |
C16a | 0.2957 (3) | 0.5681 (3) | 0.10981 (19) | 0.0475 (9) | |
H16a | 0.3117 | 0.5794 | 0.0645 | 0.057* | |
C17a | 0.4827 (3) | 0.2564 (3) | 0.03803 (17) | 0.0445 (8) | |
C18a | 0.5731 (3) | 0.2924 (3) | 0.0487 (2) | 0.0580 (10) | |
H18a | 0.5483 | 0.3612 | 0.0756 | 0.070* | |
C19a | 0.7001 (4) | 0.2261 (4) | 0.0194 (2) | 0.0744 (13) | |
H19a | 0.7606 | 0.2508 | 0.0263 | 0.089* | |
C20a | 0.7362 (4) | 0.1255 (4) | −0.0192 (3) | 0.0829 (15) | |
H20a | 0.8217 | 0.0813 | −0.0387 | 0.099* | |
C21a | 0.6483 (4) | 0.0876 (3) | −0.0300 (2) | 0.0775 (14) | |
H21a | 0.6745 | 0.0182 | −0.0567 | 0.093* | |
C22a | 0.5202 (4) | 0.1526 (3) | −0.0011 (2) | 0.0608 (10) | |
H22a | 0.4604 | 0.1270 | −0.0080 | 0.073* | |
C23a | 0.2844 (3) | 0.4195 (3) | −0.00269 (17) | 0.0441 (8) | |
C24a | 0.3805 (4) | 0.4111 (3) | −0.06106 (19) | 0.0581 (10) | |
H24a | 0.4633 | 0.3635 | −0.0646 | 0.070* | |
C25a | 0.3545 (5) | 0.4726 (4) | −0.1139 (2) | 0.0768 (13) | |
H25a | 0.4201 | 0.4674 | −0.1522 | 0.092* | |
C26a | 0.2329 (5) | 0.5411 (4) | −0.1101 (2) | 0.0780 (14) | |
H26a | 0.2155 | 0.5815 | −0.1460 | 0.094* | |
C27a | 0.1369 (4) | 0.5497 (4) | −0.0531 (3) | 0.0774 (14) | |
H27a | 0.0543 | 0.5965 | −0.0504 | 0.093* | |
C28a | 0.1616 (4) | 0.4895 (3) | 0.0005 (2) | 0.0624 (11) | |
H28a | 0.0955 | 0.4960 | 0.0388 | 0.075* | |
Ni1b | 0.47224 (4) | 0.22627 (4) | 0.55006 (2) | 0.04287 (12) | |
P1b | 0.44638 (8) | 0.31256 (8) | 0.64687 (5) | 0.0410 (2) | |
S1b | 0.86028 (9) | −0.00663 (9) | 0.44389 (6) | 0.0647 (3) | |
O1b | 0.3025 (2) | 0.3056 (2) | 0.56445 (13) | 0.0584 (7) | |
O2b | 0.7068 (2) | 0.2921 (2) | 0.55316 (13) | 0.0529 (6) | |
N1b | 0.5004 (3) | 0.1400 (2) | 0.47082 (14) | 0.0462 (7) | |
N2b | 0.6262 (3) | 0.0644 (3) | 0.43833 (15) | 0.0514 (7) | |
N3b | 0.6450 (2) | 0.1468 (2) | 0.53222 (15) | 0.0464 (7) | |
C1b | 0.6958 (3) | 0.0765 (3) | 0.47384 (18) | 0.0457 (8) | |
C2b | 0.8721 (5) | −0.0792 (4) | 0.3670 (2) | 0.0952 (16) | |
H72b | 0.8481 | −0.0233 | 0.3366 | 0.143* | |
H82b | 0.8170 | −0.1205 | 0.3762 | 0.143* | |
H92b | 0.9575 | −0.1325 | 0.3467 | 0.143* | |
C3b | 0.4549 (4) | 0.0583 (4) | 0.3800 (2) | 0.0722 (13) | |
H73b | 0.4919 | −0.0200 | 0.3893 | 0.108* | |
H83b | 0.5157 | 0.0753 | 0.3450 | 0.108* | |
H93b | 0.3826 | 0.0678 | 0.3657 | 0.108* | |
C4b | 0.4152 (4) | 0.1390 (3) | 0.44241 (19) | 0.0525 (9) | |
C5b | 0.2877 (4) | 0.2136 (4) | 0.4708 (2) | 0.0606 (11) | |
H5b | 0.2318 | 0.2101 | 0.4485 | 0.073* | |
C6b | 0.2380 (4) | 0.2895 (4) | 0.5272 (2) | 0.0589 (10) | |
C7b | 0.0991 (4) | 0.3631 (4) | 0.5535 (2) | 0.0817 (14) | |
H77b | 0.0874 | 0.4430 | 0.5589 | 0.123* | |
H87b | 0.0637 | 0.3411 | 0.5963 | 0.123* | |
H97b | 0.0578 | 0.3522 | 0.5223 | 0.123* | |
C8b | 0.7661 (4) | 0.4513 (3) | 0.5540 (2) | 0.0684 (12) | |
H78b | 0.6791 | 0.5010 | 0.5740 | 0.103* | |
H88b | 0.7869 | 0.4484 | 0.5058 | 0.103* | |
H98b | 0.8186 | 0.4810 | 0.5692 | 0.103* | |
C9b | 0.7874 (4) | 0.3313 (3) | 0.5742 (2) | 0.0616 (11) | |
H79b | 0.8745 | 0.2799 | 0.5531 | 0.074* | |
H89b | 0.7696 | 0.3330 | 0.6226 | 0.074* | |
C10b | 0.7229 (3) | 0.1750 (3) | 0.56487 (18) | 0.0477 (9) | |
H10b | 0.8113 | 0.1242 | 0.5433 | 0.057* | |
C11b | 0.5674 (3) | 0.2242 (3) | 0.68338 (17) | 0.0414 (8) | |
C12b | 0.6884 (3) | 0.1611 (3) | 0.63893 (19) | 0.0454 (8) | |
C13b | 0.7785 (4) | 0.0831 (3) | 0.6648 (2) | 0.0551 (10) | |
H13b | 0.8589 | 0.0410 | 0.6360 | 0.066* | |
C14b | 0.7503 (4) | 0.0673 (3) | 0.7322 (2) | 0.0624 (11) | |
H14b | 0.8110 | 0.0136 | 0.7482 | 0.075* | |
C15b | 0.6326 (4) | 0.1308 (3) | 0.7759 (2) | 0.0608 (11) | |
H15b | 0.6144 | 0.1216 | 0.8215 | 0.073* | |
C16b | 0.5405 (4) | 0.2090 (3) | 0.75158 (19) | 0.0508 (9) | |
H16b | 0.4607 | 0.2512 | 0.7810 | 0.061* | |
C17b | 0.4437 (3) | 0.4584 (3) | 0.64893 (17) | 0.0438 (8) | |
C18b | 0.4721 (3) | 0.5054 (3) | 0.69862 (19) | 0.0515 (9) | |
H18b | 0.4992 | 0.4602 | 0.7309 | 0.062* | |
C19b | 0.4605 (4) | 0.6202 (3) | 0.7010 (2) | 0.0650 (11) | |
H19b | 0.4796 | 0.6518 | 0.7348 | 0.078* | |
C20b | 0.4203 (4) | 0.6865 (3) | 0.6526 (2) | 0.0687 (12) | |
H20b | 0.4105 | 0.7637 | 0.6544 | 0.082* | |
C21b | 0.3951 (4) | 0.6394 (3) | 0.6023 (2) | 0.0648 (11) | |
H21b | 0.3705 | 0.6841 | 0.5692 | 0.078* | |
C22b | 0.4059 (3) | 0.5259 (3) | 0.6000 (2) | 0.0559 (10) | |
H22b | 0.3878 | 0.4945 | 0.5657 | 0.067* | |
C23b | 0.2961 (3) | 0.3270 (3) | 0.70847 (17) | 0.0438 (8) | |
C24b | 0.2011 (3) | 0.4324 (3) | 0.7349 (2) | 0.0589 (10) | |
H24b | 0.2139 | 0.4997 | 0.7236 | 0.071* | |
C25b | 0.0861 (4) | 0.4396 (4) | 0.7782 (2) | 0.0746 (13) | |
H25b | 0.0227 | 0.5115 | 0.7964 | 0.089* | |
C26b | 0.0659 (4) | 0.3408 (4) | 0.7944 (2) | 0.0718 (12) | |
H26b | −0.0114 | 0.3455 | 0.8232 | 0.086* | |
C27b | 0.1601 (4) | 0.2348 (4) | 0.7679 (2) | 0.0698 (12) | |
H27b | 0.1468 | 0.1676 | 0.7789 | 0.084* | |
C28b | 0.2750 (4) | 0.2278 (3) | 0.7247 (2) | 0.0616 (11) | |
H28b | 0.3383 | 0.1558 | 0.7066 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1a | 0.0369 (2) | 0.0392 (2) | 0.0457 (3) | −0.01682 (19) | −0.01027 (19) | 0.00625 (19) |
P1a | 0.0357 (4) | 0.0391 (5) | 0.0444 (5) | −0.0154 (4) | −0.0080 (4) | 0.0066 (4) |
S1a | 0.0872 (8) | 0.1019 (9) | 0.0473 (6) | −0.0501 (7) | −0.0102 (6) | 0.0166 (6) |
O1a | 0.0564 (16) | 0.0553 (15) | 0.0548 (16) | −0.0253 (13) | −0.0169 (13) | 0.0036 (12) |
O2a | 0.0477 (14) | 0.0541 (15) | 0.0643 (17) | −0.0242 (12) | −0.0245 (13) | 0.0233 (13) |
N1a | 0.0389 (16) | 0.0434 (16) | 0.063 (2) | −0.0199 (13) | −0.0132 (15) | 0.0100 (14) |
N2a | 0.0526 (19) | 0.061 (2) | 0.054 (2) | −0.0322 (16) | −0.0089 (15) | 0.0134 (16) |
N3a | 0.0451 (16) | 0.0520 (17) | 0.0435 (17) | −0.0252 (14) | −0.0119 (13) | 0.0106 (14) |
C1a | 0.045 (2) | 0.046 (2) | 0.051 (2) | −0.0167 (17) | −0.0094 (17) | 0.0126 (17) |
C2a | 0.104 (4) | 0.143 (5) | 0.069 (3) | −0.069 (4) | 0.011 (3) | 0.021 (3) |
C3a | 0.071 (3) | 0.106 (4) | 0.106 (4) | −0.062 (3) | −0.020 (3) | 0.018 (3) |
C4a | 0.043 (2) | 0.042 (2) | 0.083 (3) | −0.0165 (17) | −0.019 (2) | 0.004 (2) |
C5a | 0.053 (2) | 0.050 (2) | 0.083 (3) | −0.0223 (19) | −0.028 (2) | 0.002 (2) |
C6a | 0.059 (2) | 0.046 (2) | 0.069 (3) | −0.0128 (19) | −0.030 (2) | −0.0046 (19) |
C7a | 0.106 (4) | 0.107 (4) | 0.070 (3) | −0.044 (3) | −0.035 (3) | −0.010 (3) |
C8a | 0.070 (3) | 0.078 (3) | 0.122 (5) | −0.009 (3) | −0.018 (3) | 0.043 (3) |
C9a | 0.070 (3) | 0.064 (3) | 0.097 (4) | −0.024 (2) | −0.028 (3) | 0.039 (3) |
C10a | 0.050 (2) | 0.053 (2) | 0.044 (2) | −0.0240 (18) | −0.0186 (17) | 0.0111 (17) |
C11a | 0.0357 (17) | 0.0445 (19) | 0.048 (2) | −0.0191 (15) | −0.0092 (15) | 0.0039 (16) |
C12a | 0.0435 (19) | 0.0443 (19) | 0.053 (2) | −0.0228 (16) | −0.0194 (17) | 0.0090 (16) |
C13a | 0.065 (3) | 0.065 (3) | 0.047 (2) | −0.034 (2) | −0.0192 (19) | 0.0058 (19) |
C14a | 0.068 (3) | 0.052 (2) | 0.070 (3) | −0.031 (2) | −0.020 (2) | −0.005 (2) |
C15a | 0.062 (2) | 0.046 (2) | 0.071 (3) | −0.0299 (19) | −0.021 (2) | 0.0107 (19) |
C16a | 0.046 (2) | 0.047 (2) | 0.050 (2) | −0.0220 (17) | −0.0093 (17) | 0.0078 (17) |
C17a | 0.0368 (18) | 0.0423 (19) | 0.048 (2) | −0.0112 (15) | −0.0095 (16) | 0.0145 (16) |
C18a | 0.046 (2) | 0.052 (2) | 0.073 (3) | −0.0166 (18) | −0.018 (2) | 0.013 (2) |
C19a | 0.041 (2) | 0.068 (3) | 0.108 (4) | −0.017 (2) | −0.019 (2) | 0.031 (3) |
C20a | 0.046 (3) | 0.067 (3) | 0.105 (4) | −0.004 (2) | −0.002 (3) | 0.025 (3) |
C21a | 0.072 (3) | 0.041 (2) | 0.088 (3) | −0.002 (2) | −0.004 (3) | 0.001 (2) |
C22a | 0.056 (2) | 0.046 (2) | 0.069 (3) | −0.0146 (19) | −0.009 (2) | 0.006 (2) |
C23a | 0.0448 (19) | 0.0360 (18) | 0.050 (2) | −0.0139 (15) | −0.0142 (17) | 0.0061 (15) |
C24a | 0.057 (2) | 0.058 (2) | 0.048 (2) | −0.0133 (19) | −0.0102 (19) | 0.0120 (19) |
C25a | 0.096 (4) | 0.072 (3) | 0.046 (2) | −0.021 (3) | −0.013 (2) | 0.011 (2) |
C26a | 0.112 (4) | 0.065 (3) | 0.074 (3) | −0.036 (3) | −0.051 (3) | 0.028 (2) |
C27a | 0.067 (3) | 0.061 (3) | 0.118 (4) | −0.022 (2) | −0.052 (3) | 0.035 (3) |
C28a | 0.048 (2) | 0.054 (2) | 0.081 (3) | −0.0176 (19) | −0.017 (2) | 0.020 (2) |
Ni1b | 0.0356 (2) | 0.0517 (3) | 0.0456 (3) | −0.0203 (2) | −0.0142 (2) | 0.0087 (2) |
P1b | 0.0355 (5) | 0.0431 (5) | 0.0455 (5) | −0.0160 (4) | −0.0128 (4) | 0.0093 (4) |
S1b | 0.0444 (5) | 0.0672 (7) | 0.0716 (7) | −0.0217 (5) | −0.0009 (5) | −0.0073 (5) |
O1b | 0.0367 (13) | 0.0740 (18) | 0.0647 (17) | −0.0190 (13) | −0.0188 (13) | 0.0083 (14) |
O2b | 0.0446 (14) | 0.0579 (15) | 0.0652 (17) | −0.0283 (12) | −0.0184 (12) | 0.0124 (13) |
N1b | 0.0523 (18) | 0.0511 (17) | 0.0444 (17) | −0.0296 (15) | −0.0156 (14) | 0.0133 (14) |
N2b | 0.0557 (19) | 0.0546 (18) | 0.0475 (18) | −0.0286 (16) | −0.0115 (15) | 0.0071 (14) |
N3b | 0.0342 (15) | 0.0548 (18) | 0.0507 (18) | −0.0179 (13) | −0.0126 (13) | 0.0017 (15) |
C1b | 0.045 (2) | 0.043 (2) | 0.048 (2) | −0.0230 (16) | −0.0047 (17) | 0.0084 (16) |
C2b | 0.077 (3) | 0.095 (4) | 0.086 (4) | −0.021 (3) | 0.001 (3) | −0.030 (3) |
C3b | 0.099 (4) | 0.087 (3) | 0.062 (3) | −0.062 (3) | −0.036 (3) | 0.016 (2) |
C4b | 0.069 (3) | 0.057 (2) | 0.053 (2) | −0.040 (2) | −0.029 (2) | 0.0223 (19) |
C5b | 0.061 (3) | 0.074 (3) | 0.072 (3) | −0.041 (2) | −0.039 (2) | 0.027 (2) |
C6b | 0.049 (2) | 0.065 (3) | 0.077 (3) | −0.030 (2) | −0.030 (2) | 0.027 (2) |
C7b | 0.045 (2) | 0.099 (4) | 0.110 (4) | −0.032 (2) | −0.033 (3) | 0.029 (3) |
C8b | 0.056 (2) | 0.071 (3) | 0.088 (3) | −0.039 (2) | −0.017 (2) | 0.015 (2) |
C9b | 0.060 (2) | 0.069 (3) | 0.068 (3) | −0.037 (2) | −0.020 (2) | 0.009 (2) |
C10b | 0.0339 (18) | 0.050 (2) | 0.055 (2) | −0.0136 (16) | −0.0106 (16) | 0.0024 (17) |
C11b | 0.0422 (18) | 0.0392 (18) | 0.050 (2) | −0.0203 (15) | −0.0182 (16) | 0.0090 (15) |
C12b | 0.0405 (19) | 0.0410 (19) | 0.063 (2) | −0.0184 (16) | −0.0243 (18) | 0.0044 (17) |
C13b | 0.048 (2) | 0.050 (2) | 0.076 (3) | −0.0196 (18) | −0.030 (2) | 0.011 (2) |
C14b | 0.068 (3) | 0.049 (2) | 0.088 (3) | −0.024 (2) | −0.049 (3) | 0.025 (2) |
C15b | 0.083 (3) | 0.061 (3) | 0.063 (3) | −0.042 (2) | −0.041 (2) | 0.025 (2) |
C16b | 0.056 (2) | 0.046 (2) | 0.059 (2) | −0.0268 (18) | −0.0225 (19) | 0.0103 (18) |
C17b | 0.0368 (18) | 0.047 (2) | 0.049 (2) | −0.0185 (16) | −0.0119 (16) | 0.0118 (16) |
C18b | 0.054 (2) | 0.052 (2) | 0.050 (2) | −0.0225 (18) | −0.0145 (18) | 0.0118 (18) |
C19b | 0.076 (3) | 0.059 (3) | 0.070 (3) | −0.039 (2) | −0.019 (2) | 0.006 (2) |
C20b | 0.067 (3) | 0.048 (2) | 0.090 (3) | −0.029 (2) | −0.012 (2) | 0.015 (2) |
C21b | 0.062 (3) | 0.057 (3) | 0.081 (3) | −0.028 (2) | −0.024 (2) | 0.032 (2) |
C22b | 0.052 (2) | 0.064 (3) | 0.062 (3) | −0.0273 (19) | −0.027 (2) | 0.023 (2) |
C23b | 0.0370 (18) | 0.053 (2) | 0.043 (2) | −0.0188 (16) | −0.0120 (15) | 0.0067 (16) |
C24b | 0.041 (2) | 0.054 (2) | 0.072 (3) | −0.0120 (18) | −0.0118 (19) | 0.012 (2) |
C25b | 0.041 (2) | 0.078 (3) | 0.083 (3) | −0.008 (2) | −0.005 (2) | 0.013 (3) |
C26b | 0.046 (2) | 0.102 (4) | 0.064 (3) | −0.033 (3) | −0.006 (2) | 0.008 (3) |
C27b | 0.069 (3) | 0.079 (3) | 0.067 (3) | −0.047 (3) | −0.006 (2) | 0.004 (2) |
C28b | 0.054 (2) | 0.056 (2) | 0.066 (3) | −0.024 (2) | 0.000 (2) | −0.004 (2) |
Ni1a—O1a | 1.836 (3) | Ni1b—O1b | 1.835 (2) |
Ni1a—N3a | 1.856 (3) | Ni1b—N1b | 1.852 (3) |
Ni1a—N1a | 1.864 (3) | Ni1b—N3b | 1.857 (3) |
Ni1a—P1a | 2.2001 (10) | Ni1b—P1b | 2.1780 (12) |
P1a—C23a | 1.819 (4) | P1b—C17b | 1.816 (3) |
P1a—C17a | 1.820 (3) | P1b—C11b | 1.826 (3) |
P1a—C11a | 1.821 (3) | P1b—C23b | 1.836 (3) |
S1a—C1a | 1.771 (4) | S1b—C1b | 1.773 (4) |
S1a—C2a | 1.791 (5) | S1b—C2b | 1.789 (5) |
O1a—C6a | 1.314 (4) | O1b—C6b | 1.303 (4) |
O2a—C10a | 1.423 (4) | O2b—C9b | 1.399 (4) |
O2a—C9a | 1.427 (4) | O2b—C10b | 1.437 (4) |
N1a—C4a | 1.315 (4) | N1b—C4b | 1.320 (4) |
N1a—N2a | 1.408 (4) | N1b—N2b | 1.412 (4) |
N2a—C1a | 1.302 (4) | N2b—C1b | 1.307 (4) |
N3a—C1a | 1.354 (4) | N3b—C1b | 1.347 (4) |
N3a—C10a | 1.450 (4) | N3b—C10b | 1.437 (4) |
C2a—H72a | 0.9600 | C2b—H72b | 0.9600 |
C2a—H82a | 0.9600 | C2b—H82b | 0.9600 |
C2a—H92a | 0.9600 | C2b—H92b | 0.9600 |
C3a—C4a | 1.515 (5) | C3b—C4b | 1.497 (5) |
C3a—H73a | 0.9600 | C3b—H73b | 0.9600 |
C3a—H83a | 0.9600 | C3b—H83b | 0.9600 |
C3a—H93a | 0.9600 | C3b—H93b | 0.9600 |
C4a—C5a | 1.394 (5) | C4b—C5b | 1.411 (5) |
C5a—C6a | 1.355 (5) | C5b—C6b | 1.353 (6) |
C5a—H5a | 0.9300 | C5b—H5b | 0.9300 |
C6a—C7a | 1.503 (5) | C6b—C7b | 1.506 (5) |
C7a—H77a | 0.9600 | C7b—H77b | 0.9600 |
C7a—H87a | 0.9600 | C7b—H87b | 0.9600 |
C7a—H97a | 0.9600 | C7b—H97b | 0.9600 |
C8a—C9a | 1.474 (6) | C8b—C9b | 1.508 (5) |
C8a—H78a | 0.9600 | C8b—H78b | 0.9600 |
C8a—H88a | 0.9600 | C8b—H88b | 0.9600 |
C8a—H98a | 0.9600 | C8b—H98b | 0.9600 |
C9a—H79a | 0.9700 | C9b—H79b | 0.9700 |
C9a—H89a | 0.9700 | C9b—H89b | 0.9700 |
C10a—C12a | 1.511 (5) | C10b—C12b | 1.507 (5) |
C10a—H10a | 0.9800 | C10b—H10b | 0.9800 |
C11a—C16a | 1.395 (4) | C11b—C16b | 1.394 (5) |
C11a—C12a | 1.402 (5) | C11b—C12b | 1.407 (5) |
C12a—C13a | 1.374 (5) | C12b—C13b | 1.397 (5) |
C13a—C14a | 1.387 (5) | C13b—C14b | 1.381 (5) |
C13a—H13a | 0.9300 | C13b—H13b | 0.9300 |
C14a—C15a | 1.374 (5) | C14b—C15b | 1.377 (6) |
C14a—H14a | 0.9300 | C14b—H14b | 0.9300 |
C15a—C16a | 1.380 (5) | C15b—C16b | 1.394 (5) |
C15a—H15a | 0.9300 | C15b—H15b | 0.9300 |
C16a—H16a | 0.9300 | C16b—H16b | 0.9300 |
C17a—C18a | 1.386 (5) | C17b—C18b | 1.373 (5) |
C17a—C22a | 1.387 (5) | C17b—C22b | 1.389 (5) |
C18a—C19a | 1.385 (5) | C18b—C19b | 1.393 (5) |
C18a—H18a | 0.9300 | C18b—H18b | 0.9300 |
C19a—C20a | 1.353 (6) | C19b—C20b | 1.383 (6) |
C19a—H19a | 0.9300 | C19b—H19b | 0.9300 |
C20a—C21a | 1.375 (6) | C20b—C21b | 1.361 (6) |
C20a—H20a | 0.9300 | C20b—H20b | 0.9300 |
C21a—C22a | 1.391 (5) | C21b—C22b | 1.380 (5) |
C21a—H21a | 0.9300 | C21b—H21b | 0.9300 |
C22a—H22a | 0.9300 | C22b—H22b | 0.9300 |
C23a—C28a | 1.388 (5) | C23b—C24b | 1.370 (5) |
C23a—C24a | 1.390 (5) | C23b—C28b | 1.381 (5) |
C24a—C25a | 1.382 (5) | C24b—C25b | 1.387 (5) |
C24a—H24a | 0.9300 | C24b—H24b | 0.9300 |
C25a—C26a | 1.369 (6) | C25b—C26b | 1.370 (6) |
C25a—H25a | 0.9300 | C25b—H25b | 0.9300 |
C26a—C27a | 1.371 (6) | C26b—C27b | 1.373 (6) |
C26a—H26a | 0.9300 | C26b—H26b | 0.9300 |
C27a—C28a | 1.385 (6) | C27b—C28b | 1.385 (5) |
C27a—H27a | 0.9300 | C27b—H27b | 0.9300 |
C28a—H28a | 0.9300 | C28b—H28b | 0.9300 |
O1a—Ni1a—N3a | 177.14 (12) | O1b—Ni1b—N1b | 95.85 (13) |
O1a—Ni1a—N1a | 95.34 (13) | O1b—Ni1b—N3b | 177.92 (12) |
N3a—Ni1a—N1a | 82.79 (13) | N1b—Ni1b—N3b | 82.64 (13) |
O1a—Ni1a—P1a | 88.92 (8) | O1b—Ni1b—P1b | 87.09 (9) |
N3a—Ni1a—P1a | 93.17 (9) | N1b—Ni1b—P1b | 174.70 (9) |
N1a—Ni1a—P1a | 172.77 (9) | N3b—Ni1b—P1b | 94.53 (10) |
C23a—P1a—C17a | 102.62 (16) | C17b—P1b—C11b | 108.06 (15) |
C23a—P1a—C11a | 103.22 (16) | C17b—P1b—C23b | 103.91 (16) |
C17a—P1a—C11a | 107.56 (16) | C11b—P1b—C23b | 104.93 (16) |
C23a—P1a—Ni1a | 114.21 (12) | C17b—P1b—Ni1b | 117.72 (12) |
C17a—P1a—Ni1a | 118.51 (11) | C11b—P1b—Ni1b | 109.86 (12) |
C11a—P1a—Ni1a | 109.42 (11) | C23b—P1b—Ni1b | 111.48 (12) |
C1a—S1a—C2a | 101.6 (2) | C1b—S1b—C2b | 100.8 (2) |
C6a—O1a—Ni1a | 125.3 (3) | C6b—O1b—Ni1b | 125.3 (3) |
C10a—O2a—C9a | 114.3 (3) | C9b—O2b—C10b | 114.4 (3) |
C4a—N1a—N2a | 117.1 (3) | C4b—N1b—N2b | 116.4 (3) |
C4a—N1a—Ni1a | 127.0 (3) | C4b—N1b—Ni1b | 127.1 (3) |
N2a—N1a—Ni1a | 115.9 (2) | N2b—N1b—Ni1b | 116.5 (2) |
C1a—N2a—N1a | 108.3 (3) | C1b—N2b—N1b | 107.5 (3) |
C1a—N3a—C10a | 121.1 (3) | C1b—N3b—C10b | 121.2 (3) |
C1a—N3a—Ni1a | 111.5 (2) | C1b—N3b—Ni1b | 111.5 (2) |
C10a—N3a—Ni1a | 127.0 (2) | C10b—N3b—Ni1b | 125.5 (2) |
N2a—C1a—N3a | 121.6 (3) | N2b—C1b—N3b | 121.7 (3) |
N2a—C1a—S1a | 117.8 (3) | N2b—C1b—S1b | 117.6 (3) |
N3a—C1a—S1a | 120.6 (3) | N3b—C1b—S1b | 120.7 (3) |
S1a—C2a—H72a | 109.5 | S1b—C2b—H72b | 109.5 |
S1a—C2a—H82a | 109.5 | S1b—C2b—H82b | 109.5 |
H72a—C2a—H82a | 109.5 | H72b—C2b—H82b | 109.5 |
S1a—C2a—H92a | 109.5 | S1b—C2b—H92b | 109.5 |
H72a—C2a—H92a | 109.5 | H72b—C2b—H92b | 109.5 |
H82a—C2a—H92a | 109.5 | H82b—C2b—H92b | 109.5 |
C4a—C3a—H73a | 109.5 | C4b—C3b—H73b | 109.5 |
C4a—C3a—H83a | 109.5 | C4b—C3b—H83b | 109.5 |
H73a—C3a—H83a | 109.5 | H73b—C3b—H83b | 109.5 |
C4a—C3a—H93a | 109.5 | C4b—C3b—H93b | 109.5 |
H73a—C3a—H93a | 109.5 | H73b—C3b—H93b | 109.5 |
H83a—C3a—H93a | 109.5 | H83b—C3b—H93b | 109.5 |
N1a—C4a—C5a | 121.2 (4) | N1b—C4b—C5b | 120.1 (4) |
N1a—C4a—C3a | 118.9 (4) | N1b—C4b—C3b | 119.5 (4) |
C5a—C4a—C3a | 120.0 (4) | C5b—C4b—C3b | 120.4 (4) |
C6a—C5a—C4a | 126.3 (4) | C6b—C5b—C4b | 126.9 (4) |
C6a—C5a—H5a | 116.8 | C6b—C5b—H5b | 116.5 |
C4a—C5a—H5a | 116.8 | C4b—C5b—H5b | 116.5 |
O1a—C6a—C5a | 124.8 (4) | O1b—C6b—C5b | 124.6 (4) |
O1a—C6a—C7a | 112.7 (4) | O1b—C6b—C7b | 113.3 (4) |
C5a—C6a—C7a | 122.5 (4) | C5b—C6b—C7b | 122.1 (4) |
C6a—C7a—H77a | 109.5 | C6b—C7b—H77b | 109.5 |
C6a—C7a—H87a | 109.5 | C6b—C7b—H87b | 109.5 |
H77a—C7a—H87a | 109.5 | H77b—C7b—H87b | 109.5 |
C6a—C7a—H97a | 109.5 | C6b—C7b—H97b | 109.5 |
H77a—C7a—H97a | 109.5 | H77b—C7b—H97b | 109.5 |
H87a—C7a—H97a | 109.5 | H87b—C7b—H97b | 109.5 |
C9a—C8a—H78a | 109.5 | C9b—C8b—H78b | 109.5 |
C9a—C8a—H88a | 109.5 | C9b—C8b—H88b | 109.5 |
H78a—C8a—H88a | 109.5 | H78b—C8b—H88b | 109.5 |
C9a—C8a—H98a | 109.5 | C9b—C8b—H98b | 109.5 |
H78a—C8a—H98a | 109.5 | H78b—C8b—H98b | 109.5 |
H88a—C8a—H98a | 109.5 | H88b—C8b—H98b | 109.5 |
O2a—C9a—C8a | 109.1 (3) | O2b—C9b—C8b | 108.1 (3) |
O2a—C9a—H79a | 109.9 | O2b—C9b—H79b | 110.1 |
C8a—C9a—H79a | 109.9 | C8b—C9b—H79b | 110.1 |
O2a—C9a—H89a | 109.9 | O2b—C9b—H89b | 110.1 |
C8a—C9a—H89a | 109.9 | C8b—C9b—H89b | 110.1 |
H79a—C9a—H89a | 108.3 | H79b—C9b—H89b | 108.4 |
O2a—C10a—N3a | 111.7 (3) | N3b—C10b—O2b | 105.6 (3) |
O2a—C10a—C12a | 105.1 (3) | N3b—C10b—C12b | 112.2 (3) |
N3a—C10a—C12a | 112.8 (3) | O2b—C10b—C12b | 112.0 (3) |
O2a—C10a—H10a | 109.0 | N3b—C10b—H10b | 109.0 |
N3a—C10a—H10a | 109.0 | O2b—C10b—H10b | 109.0 |
C12a—C10a—H10a | 109.0 | C12b—C10b—H10b | 109.0 |
C16a—C11a—C12a | 119.3 (3) | C16b—C11b—C12b | 119.8 (3) |
C16a—C11a—P1a | 121.9 (3) | C16b—C11b—P1b | 122.4 (3) |
C12a—C11a—P1a | 118.7 (2) | C12b—C11b—P1b | 117.5 (3) |
C13a—C12a—C11a | 119.3 (3) | C13b—C12b—C11b | 118.4 (4) |
C13a—C12a—C10a | 120.3 (3) | C13b—C12b—C10b | 119.5 (3) |
C11a—C12a—C10a | 120.3 (3) | C11b—C12b—C10b | 122.0 (3) |
C12a—C13a—C14a | 121.0 (4) | C14b—C13b—C12b | 121.3 (4) |
C12a—C13a—H13a | 119.5 | C14b—C13b—H13b | 119.3 |
C14a—C13a—H13a | 119.5 | C12b—C13b—H13b | 119.3 |
C15a—C14a—C13a | 119.9 (4) | C15b—C14b—C13b | 120.1 (4) |
C15a—C14a—H14a | 120.1 | C15b—C14b—H14b | 119.9 |
C13a—C14a—H14a | 120.1 | C13b—C14b—H14b | 119.9 |
C14a—C15a—C16a | 120.1 (3) | C14b—C15b—C16b | 119.9 (4) |
C14a—C15a—H15a | 119.9 | C14b—C15b—H15b | 120.1 |
C16a—C15a—H15a | 119.9 | C16b—C15b—H15b | 120.1 |
C15a—C16a—C11a | 120.4 (3) | C11b—C16b—C15b | 120.4 (4) |
C15a—C16a—H16a | 119.8 | C11b—C16b—H16b | 119.8 |
C11a—C16a—H16a | 119.8 | C15b—C16b—H16b | 119.8 |
C18a—C17a—C22a | 119.7 (3) | C18b—C17b—C22b | 119.2 (3) |
C18a—C17a—P1a | 121.9 (3) | C18b—C17b—P1b | 122.3 (3) |
C22a—C17a—P1a | 118.3 (3) | C22b—C17b—P1b | 118.4 (3) |
C19a—C18a—C17a | 120.1 (4) | C17b—C18b—C19b | 120.6 (4) |
C19a—C18a—H18a | 119.9 | C17b—C18b—H18b | 119.7 |
C17a—C18a—H18a | 119.9 | C19b—C18b—H18b | 119.7 |
C20a—C19a—C18a | 120.0 (4) | C20b—C19b—C18b | 119.2 (4) |
C20a—C19a—H19a | 120.0 | C20b—C19b—H19b | 120.4 |
C18a—C19a—H19a | 120.0 | C18b—C19b—H19b | 120.4 |
C19a—C20a—C21a | 120.9 (4) | C21b—C20b—C19b | 120.4 (4) |
C19a—C20a—H20a | 119.6 | C21b—C20b—H20b | 119.8 |
C21a—C20a—H20a | 119.6 | C19b—C20b—H20b | 119.8 |
C20a—C21a—C22a | 120.2 (4) | C20b—C21b—C22b | 120.5 (4) |
C20a—C21a—H21a | 119.9 | C20b—C21b—H21b | 119.8 |
C22a—C21a—H21a | 119.9 | C22b—C21b—H21b | 119.8 |
C17a—C22a—C21a | 119.1 (4) | C21b—C22b—C17b | 120.1 (4) |
C17a—C22a—H22a | 120.5 | C21b—C22b—H22b | 119.9 |
C21a—C22a—H22a | 120.5 | C17b—C22b—H22b | 119.9 |
C28a—C23a—C24a | 118.1 (3) | C24b—C23b—C28b | 119.0 (3) |
C28a—C23a—P1a | 119.5 (3) | C24b—C23b—P1b | 122.4 (3) |
C24a—C23a—P1a | 122.4 (3) | C28b—C23b—P1b | 118.4 (3) |
C25a—C24a—C23a | 120.9 (4) | C23b—C24b—C25b | 120.6 (4) |
C25a—C24a—H24a | 119.6 | C23b—C24b—H24b | 119.7 |
C23a—C24a—H24a | 119.6 | C25b—C24b—H24b | 119.7 |
C26a—C25a—C24a | 120.4 (4) | C26b—C25b—C24b | 120.1 (4) |
C26a—C25a—H25a | 119.8 | C26b—C25b—H25b | 120.0 |
C24a—C25a—H25a | 119.8 | C24b—C25b—H25b | 120.0 |
C25a—C26a—C27a | 119.5 (4) | C25b—C26b—C27b | 119.7 (4) |
C25a—C26a—H26a | 120.3 | C25b—C26b—H26b | 120.1 |
C27a—C26a—H26a | 120.3 | C27b—C26b—H26b | 120.1 |
C26a—C27a—C28a | 120.8 (4) | C26b—C27b—C28b | 120.1 (4) |
C26a—C27a—H27a | 119.6 | C26b—C27b—H27b | 119.9 |
C28a—C27a—H27a | 119.6 | C28b—C27b—H27b | 119.9 |
C27a—C28a—C23a | 120.4 (4) | C23b—C28b—C27b | 120.4 (4) |
C27a—C28a—H28a | 119.8 | C23b—C28b—H28b | 119.8 |
C23a—C28a—H28a | 119.8 | C27b—C28b—H28b | 119.8 |
O1a—Ni1a—P1a—C23a | 36.62 (14) | O1b—Ni1b—P1b—C17b | −82.10 (15) |
N3a—Ni1a—P1a—C23a | −145.34 (15) | N3b—Ni1b—P1b—C17b | 96.59 (15) |
O1a—Ni1a—P1a—C17a | −84.50 (16) | O1b—Ni1b—P1b—C11b | 153.70 (14) |
N3a—Ni1a—P1a—C17a | 93.54 (16) | N3b—Ni1b—P1b—C11b | −27.61 (15) |
O1a—Ni1a—P1a—C11a | 151.74 (14) | O1b—Ni1b—P1b—C23b | 37.82 (15) |
N3a—Ni1a—P1a—C11a | −30.22 (15) | N3b—Ni1b—P1b—C23b | −143.49 (15) |
N1a—Ni1a—O1a—C6a | 2.3 (3) | N1b—Ni1b—O1b—C6b | 3.3 (3) |
P1a—Ni1a—O1a—C6a | −171.8 (3) | P1b—Ni1b—O1b—C6b | −172.3 (3) |
O1a—Ni1a—N1a—C4a | −2.0 (3) | O1b—Ni1b—N1b—C4b | −4.1 (3) |
N3a—Ni1a—N1a—C4a | −179.8 (3) | N3b—Ni1b—N1b—C4b | 177.4 (3) |
O1a—Ni1a—N1a—N2a | 179.0 (2) | O1b—Ni1b—N1b—N2b | 178.1 (2) |
N3a—Ni1a—N1a—N2a | 1.2 (2) | N3b—Ni1b—N1b—N2b | −0.5 (2) |
C4a—N1a—N2a—C1a | 179.3 (3) | C4b—N1b—N2b—C1b | −179.3 (3) |
Ni1a—N1a—N2a—C1a | −1.6 (4) | Ni1b—N1b—N2b—C1b | −1.2 (3) |
N1a—Ni1a—N3a—C1a | −0.5 (2) | N1b—Ni1b—N3b—C1b | 2.0 (2) |
P1a—Ni1a—N3a—C1a | 173.5 (2) | P1b—Ni1b—N3b—C1b | 177.5 (2) |
N1a—Ni1a—N3a—C10a | 171.8 (3) | N1b—Ni1b—N3b—C10b | 166.8 (3) |
P1a—Ni1a—N3a—C10a | −14.3 (3) | P1b—Ni1b—N3b—C10b | −17.7 (3) |
N1a—N2a—C1a—N3a | 1.2 (5) | N1b—N2b—C1b—N3b | 3.2 (4) |
N1a—N2a—C1a—S1a | −179.8 (2) | N1b—N2b—C1b—S1b | −178.8 (2) |
C10a—N3a—C1a—N2a | −173.1 (3) | C10b—N3b—C1b—N2b | −169.2 (3) |
Ni1a—N3a—C1a—N2a | −0.3 (4) | Ni1b—N3b—C1b—N2b | −3.7 (4) |
C10a—N3a—C1a—S1a | 7.9 (4) | C10b—N3b—C1b—S1b | 12.9 (4) |
Ni1a—N3a—C1a—S1a | −179.29 (18) | Ni1b—N3b—C1b—S1b | 178.37 (17) |
C2a—S1a—C1a—N2a | −3.3 (4) | C2b—S1b—C1b—N2b | 2.4 (3) |
C2a—S1a—C1a—N3a | 175.7 (3) | C2b—S1b—C1b—N3b | −179.6 (3) |
N2a—N1a—C4a—C5a | −179.7 (3) | N2b—N1b—C4b—C5b | −178.8 (3) |
Ni1a—N1a—C4a—C5a | 1.3 (5) | Ni1b—N1b—C4b—C5b | 3.4 (5) |
N2a—N1a—C4a—C3a | 1.3 (5) | N2b—N1b—C4b—C3b | 1.3 (5) |
Ni1a—N1a—C4a—C3a | −177.7 (3) | Ni1b—N1b—C4b—C3b | −176.5 (3) |
N1a—C4a—C5a—C6a | −0.3 (6) | N1b—C4b—C5b—C6b | −0.9 (6) |
C3a—C4a—C5a—C6a | 178.7 (4) | C3b—C4b—C5b—C6b | 179.1 (4) |
Ni1a—O1a—C6a—C5a | −2.0 (5) | Ni1b—O1b—C6b—C5b | −2.0 (5) |
Ni1a—O1a—C6a—C7a | 177.6 (3) | Ni1b—O1b—C6b—C7b | 176.9 (3) |
C4a—C5a—C6a—O1a | 0.7 (6) | C4b—C5b—C6b—O1b | 0.2 (7) |
C4a—C5a—C6a—C7a | −178.9 (4) | C4b—C5b—C6b—C7b | −178.7 (4) |
C10a—O2a—C9a—C8a | −170.4 (4) | C10b—O2b—C9b—C8b | 175.9 (3) |
C9a—O2a—C10a—N3a | −58.8 (4) | C1b—N3b—C10b—O2b | 105.6 (3) |
C9a—O2a—C10a—C12a | 178.5 (3) | Ni1b—N3b—C10b—O2b | −57.8 (4) |
C1a—N3a—C10a—O2a | 116.0 (3) | C1b—N3b—C10b—C12b | −132.1 (3) |
Ni1a—N3a—C10a—O2a | −55.6 (4) | Ni1b—N3b—C10b—C12b | 64.5 (4) |
C1a—N3a—C10a—C12a | −125.8 (3) | C9b—O2b—C10b—N3b | −172.6 (3) |
Ni1a—N3a—C10a—C12a | 62.6 (4) | C9b—O2b—C10b—C12b | 65.0 (4) |
C23a—P1a—C11a—C16a | −16.7 (3) | C17b—P1b—C11b—C16b | 92.3 (3) |
C17a—P1a—C11a—C16a | 91.4 (3) | C23b—P1b—C11b—C16b | −18.1 (3) |
Ni1a—P1a—C11a—C16a | −138.7 (3) | Ni1b—P1b—C11b—C16b | −138.1 (3) |
C23a—P1a—C11a—C12a | 159.4 (3) | C17b—P1b—C11b—C12b | −94.1 (3) |
C17a—P1a—C11a—C12a | −92.6 (3) | C23b—P1b—C11b—C12b | 155.4 (3) |
Ni1a—P1a—C11a—C12a | 37.4 (3) | Ni1b—P1b—C11b—C12b | 35.5 (3) |
C16a—C11a—C12a—C13a | 0.7 (5) | C16b—C11b—C12b—C13b | 0.8 (5) |
P1a—C11a—C12a—C13a | −175.4 (3) | P1b—C11b—C12b—C13b | −172.9 (2) |
C16a—C11a—C12a—C10a | −177.3 (3) | C16b—C11b—C12b—C10b | −179.5 (3) |
P1a—C11a—C12a—C10a | 6.5 (4) | P1b—C11b—C12b—C10b | 6.8 (4) |
O2a—C10a—C12a—C13a | −115.5 (4) | N3b—C10b—C12b—C13b | 119.8 (3) |
N3a—C10a—C12a—C13a | 122.5 (4) | O2b—C10b—C12b—C13b | −121.6 (3) |
O2a—C10a—C12a—C11a | 62.6 (4) | N3b—C10b—C12b—C11b | −59.9 (4) |
N3a—C10a—C12a—C11a | −59.4 (4) | O2b—C10b—C12b—C11b | 58.7 (4) |
C11a—C12a—C13a—C14a | −0.5 (6) | C11b—C12b—C13b—C14b | 0.2 (5) |
C10a—C12a—C13a—C14a | 177.5 (3) | C10b—C12b—C13b—C14b | −179.5 (3) |
C12a—C13a—C14a—C15a | −0.4 (6) | C12b—C13b—C14b—C15b | −1.5 (6) |
C13a—C14a—C15a—C16a | 1.1 (6) | C13b—C14b—C15b—C16b | 1.7 (6) |
C14a—C15a—C16a—C11a | −0.9 (6) | C12b—C11b—C16b—C15b | −0.6 (5) |
C12a—C11a—C16a—C15a | 0.0 (5) | P1b—C11b—C16b—C15b | 172.8 (3) |
P1a—C11a—C16a—C15a | 176.0 (3) | C14b—C15b—C16b—C11b | −0.7 (5) |
C23a—P1a—C17a—C18a | 95.5 (3) | C11b—P1b—C17b—C18b | −31.6 (3) |
C11a—P1a—C17a—C18a | −13.0 (3) | C23b—P1b—C17b—C18b | 79.5 (3) |
Ni1a—P1a—C17a—C18a | −137.7 (3) | Ni1b—P1b—C17b—C18b | −156.7 (3) |
C23a—P1a—C17a—C22a | −80.7 (3) | C11b—P1b—C17b—C22b | 151.4 (3) |
C11a—P1a—C17a—C22a | 170.8 (3) | C23b—P1b—C17b—C22b | −97.5 (3) |
Ni1a—P1a—C17a—C22a | 46.2 (3) | Ni1b—P1b—C17b—C22b | 26.3 (3) |
C22a—C17a—C18a—C19a | 1.1 (6) | C22b—C17b—C18b—C19b | 1.4 (5) |
P1a—C17a—C18a—C19a | −174.9 (3) | P1b—C17b—C18b—C19b | −175.6 (3) |
C17a—C18a—C19a—C20a | −0.6 (6) | C17b—C18b—C19b—C20b | −0.2 (6) |
C18a—C19a—C20a—C21a | 0.1 (7) | C18b—C19b—C20b—C21b | −1.5 (6) |
C19a—C20a—C21a—C22a | 0.0 (7) | C19b—C20b—C21b—C22b | 1.8 (6) |
C18a—C17a—C22a—C21a | −1.1 (6) | C20b—C21b—C22b—C17b | −0.5 (6) |
P1a—C17a—C22a—C21a | 175.1 (3) | C18b—C17b—C22b—C21b | −1.1 (5) |
C20a—C21a—C22a—C17a | 0.6 (6) | P1b—C17b—C22b—C21b | 176.0 (3) |
C17a—P1a—C23a—C28a | 174.6 (3) | C17b—P1b—C23b—C24b | 12.3 (4) |
C11a—P1a—C23a—C28a | −73.6 (3) | C11b—P1b—C23b—C24b | 125.6 (3) |
Ni1a—P1a—C23a—C28a | 45.1 (3) | Ni1b—P1b—C23b—C24b | −115.5 (3) |
C17a—P1a—C23a—C24a | −7.2 (3) | C17b—P1b—C23b—C28b | −172.7 (3) |
C11a—P1a—C23a—C24a | 104.6 (3) | C11b—P1b—C23b—C28b | −59.3 (3) |
Ni1a—P1a—C23a—C24a | −136.8 (3) | Ni1b—P1b—C23b—C28b | 59.5 (3) |
C28a—C23a—C24a—C25a | 1.2 (6) | C28b—C23b—C24b—C25b | 1.1 (6) |
P1a—C23a—C24a—C25a | −177.0 (3) | P1b—C23b—C24b—C25b | 176.1 (3) |
C23a—C24a—C25a—C26a | −1.4 (7) | C23b—C24b—C25b—C26b | −0.9 (7) |
C24a—C25a—C26a—C27a | 1.0 (7) | C24b—C25b—C26b—C27b | 0.5 (7) |
C25a—C26a—C27a—C28a | −0.3 (7) | C25b—C26b—C27b—C28b | −0.3 (7) |
C26a—C27a—C28a—C23a | 0.2 (7) | C24b—C23b—C28b—C27b | −0.9 (6) |
C24a—C23a—C28a—C27a | −0.6 (6) | P1b—C23b—C28b—C27b | −176.1 (3) |
P1a—C23a—C28a—C27a | 177.6 (3) | C26b—C27b—C28b—C23b | 0.5 (7) |
Experimental details
Crystal data | |
Chemical formula | [Ni(C28H30N3O2PS)] |
Mr | 562.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 11.974 (3), 12.531 (2), 20.827 (7) |
α, β, γ (°) | 89.81 (2), 73.56 (2), 68.26 (2) |
V (Å3) | 2765.9 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.36 × 0.30 × 0.26 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Gaussian (PLATON; Spek, 2003) |
Tmin, Tmax | 0.756, 0.820 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11363, 10824, 6782 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.117, 1.01 |
No. of reflections | 10824 |
No. of parameters | 657 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.28 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Ni1a—O1a | 1.836 (3) | Ni1b—O1b | 1.835 (2) |
Ni1a—N3a | 1.856 (3) | Ni1b—N1b | 1.852 (3) |
Ni1a—N1a | 1.864 (3) | Ni1b—N3b | 1.857 (3) |
Ni1a—P1a | 2.2001 (10) | Ni1b—P1b | 2.1780 (12) |
O1a—C6a | 1.314 (4) | O1b—C6b | 1.303 (4) |
N1a—C4a | 1.315 (4) | N1b—C4b | 1.320 (4) |
N1a—N2a | 1.408 (4) | N1b—N2b | 1.412 (4) |
N2a—C1a | 1.302 (4) | N2b—C1b | 1.307 (4) |
N3a—C1a | 1.354 (4) | N3b—C1b | 1.347 (4) |
C4a—C5a | 1.394 (5) | C4b—C5b | 1.411 (5) |
C5a—C6a | 1.355 (5) | C5b—C6b | 1.353 (6) |
O1a—Ni1a—N1a | 95.34 (13) | O1b—Ni1b—N1b | 95.85 (13) |
N3a—Ni1a—N1a | 82.79 (13) | N1b—Ni1b—N3b | 82.64 (13) |
O1a—Ni1a—P1a | 88.92 (8) | O1b—Ni1b—P1b | 87.09 (9) |
N3a—Ni1a—P1a | 93.17 (9) | N3b—Ni1b—P1b | 94.53 (10) |
Q | q2 | q3 | θ | ϕ | |
[NiL1]a | 0.714 (4) | 0.714 (4) | -0.005 (3) | 90.4 (2) | 178.7 (3) |
[NiL1]b | 0.696 (4) | 0.696 (4) | 0.018 (3) | 88.5 (2) | -178.7 (3) |
[NiL2] | 0.70 | 0.70 | -0.03 | 92.3 | 179.4 |
Ω is the mid-point of an aromatic ring; β is the angle between the line connecting the H atom and Ω and the normal to the ring. |
C—H···Ω | H···Ω | C···Ω | β | C—H···Ω | Ω symmetry code | ||
[NiL1]a | C8a—H78a···Ω1a | 2.91 | 3.85 | 4.2 | 146 | x,y,z | |
C14a—H14a···Ω2 b | 2.79 | 3.67 | 10.1 | 140 | 1 − x,1 − y,1 − z | ||
C21a—H21a···Ω3a | 2.90 | 3.69 | 13.5 | 130 | 1 − x,-y,-z | ||
C27a—H27a···Ω3a | 2.65 | 3.55 | 19.3 | 141 | -x,1 − y,-z | ||
[NiL1]b | C3b—H73b···Ω4 b | 2.84 | 3.60 | 24.0 | 128 | 1 − x,-y,1 − z | |
C8b—H78b···Ω1 b | 2.61 | 3.64 | 0.4 | 159 | x,y,z | ||
C21b—H21b···Ω4 b | 2.68 | 3.52 | 7.0 | 135 | 1 − x,1 − y,1 − z | ||
C25b—H25b···Ω4a | 2.66 | 3.67 | 15.3 | 157 | -x,1 − y,1 − z | ||
C26b—H26b···Ω2a | 2.79 | 3.61 | 10.6 | 133 | -x,1 − y,1 − z | ||
[NiL2] | C8c—H78c···Ω1c | 3.06 | 4.00 | 26.2 | 146 | x,y,z | |
C9c—H79c···Ω5c | 3.01 | 3.87 | 25.3 | 137 | -1 + x,y,z | ||
C19c—H19c···Ω2c | 3.00 | 3.95 | 11.5 | 147 | 1 − x,1 − y,1 − z | ||
C21c—H21c···Ω6c | 2.97 | 3.79 | 16.9 | 134 | -x,-y,1 − z |
Ω1a is the centroid of the C17a–C22a ring; (Ω2a), the C11a–C16a ring; (Ω3a), ring B; (Ω4a), ring A; (Ω1 b), the C17b—C22b ring; (Ω2 b), the C11b–C16b ring; (Ω4 b), ring A; (Ω1c), the C17c–C22c ring; (Ω2c), the C11c–C16c ring; (Ω5c), the C23c–C28c ring; (Ω6c), the C5c–C31c ring. |
Transition metal complexes with thiosemicarbazide-based ligands have been very extensively investigated because of their interesting structural properties and biological activities (Campbell, 1975; Padhye & Kauffman, 1985; West et al., 1991; Casas et al., 2000; Beraldo & Gambino, 2004). This work is a part of our systematic study of transition metal complexes containing thiosemicarbazide-based ligands, aimed at investigating their structural properties and the influence of the thiosemicarbazide substituents on the properties of the complexes (Leovac et al., 2000; Bogdanović et al., 2001; Leovac et al., 2002).
Among the more than 150 crystal structures of metal complexes with isothiosemicarbazide-based ligands (ITSC), the title compound, [NiL1], (I), represents a rare example of a transition metal complex involving a P atom in its coordination sphere. Only one other metal complex, [NiL2], [Ni(C30H28N3O2PS)], (II), with an ITSC ligand possessing a P atom as one of ligator atoms, has hitherto been reported (Bogdanović et al., 1998).
The asymmetric unit of the [NiL1] complex (Fig. 1) contains two crystallographically independent molecules, [NiL1]a and [NiL1]b. These molecules are of the same composition but have slightly different conformations. The mutual orientation of the molecules is shown in Fig. 2, from which it can be seen that the angle between the coordination plane of molecules [NiL1]a and [NiL1]b is 56.4 (1)°. The square-planar coordination geometry of the Ni atom is significantly deformed. Atoms Ni1, O1, N1 and N3 are nearly coplanar, but atoms P1 deviate from the mean plane by 0.278 (4), 0.203 (4) and 0.280 (3) Å for the molecules [NiL1]a, [NiL1]b and [NiL2], respectively. The L1 ligands are coordinated to the Ni atom through four atoms (O1, N1, P1 and N3), forming three fused chelate rings (Fig. 1), one being five-membered (ring A; Ni1/N1/N2/C1/N3), and two six-membered, ring B (Ni1/N1/C4–C6/O1) and ring C (Ni1/N3/C10/C12/C11/P1). Rings A and B are nearly planar, with delocalized π bonds (Table 1). However, ring C is non-planar, adopting a boat conformation with atoms Ni1, N3, C11 and C12 approximately coplanar. The conformational parameters (Cremer & Pople, 1975) of all three complex molecules, [NiL1]a, [NiL1]b and [NiL2] (Table 2), are very similar. This non-planar form of a six-membered chelate ring in metal complexes with ITSC ligands is unusual and could be caused by (a) the addition of EtOH across the azomethine N3═C10 bonds and/or (b) the presence of P atoms, which tends to decrease the Ni1—P1—C11 angles, as described by Brčeski et al. (2003).
The conformation of ring C in similar square-planar metal complexes [(III) in the scheme above] that possess a triphenylphosphine fragment and two condensed chelate rings were also analyzed. In almost all of the 29 examples fiund in the Cambridge Structural Database (version of April 2005; Allen, 2002), the six-membered rings were more or less non-planar, with an average value of 22.3° for the largest C—P—M—N torsion angle (C1—P—M—N). On the other hand, the most planar part of the rings was the P—C1—C2—C3 fragment, (III), with a mean P—C1—C2—C3 torsion angle of 5.7°. As shown in Fig. 3, a direct relation exists between the values of the C1—P—M—N torsion angle and the displacement of the P atom (ΔP) from the mean plane of the chelate ring. The rings are the most puckered when the N—C3 and C3—C2 bonds are single bonds, which enables additional rotation around them. For this reason, four of the six highest ΔP values are found for [NiL1], described in this work, and the previously published [NiL2] (Bogdanović et al., 1998) and [PtL3]CHCl3, [Pt(C44H32N2O2P2)](CCl3H) (Burger et al., 2003), all of which are labeled by circles in Fig. 3.
It was considered worthwhile to analyze the orientation of the ethoxy –O2—C9H2—C8H3 group. Although the rotation around the O2—C9 and C9—C8 single bonds is not restricted, the orientation of the ethoxy group is very similar in all of the three compared molecules [NiL1]a, [NiL1]b and [NiL2]. An explanation for this structural behavior can be found in intramolecular C—H···π interactions between the C8 methyl group and the Ph2 phenyl ring (Fig. 2), which was not observed in the previously published crystal structure of [NiL2] (Bogdanović et al., 1998). The geometrical parameters of this interaction for the [NiL1]a, [NiL1]b and [NiL2] complexes are listed in Table 3.
There are no intermolecular hydrogen bonds or significant π–π interactions with participation of the phenyl rings from the triphenylphosphine fragment in the crystal of the [NiL1] complex. However, numerous intermolecular C—H···π interactions are found in the crystal packing. The geometrical parameters listed in Table 3 were calculated for normalized C—H distances (1.08 Å) as is usual for the analysis of C—H···π interactions (Desiraju & Steiner, 1999). Four interactions have a H···Ω distance (where Ω is the midpoint of the ring) shorter than 2.70 Å. It is known that chelate rings with π delocalized bonds are able to participate in C—H···π interactions as π acceptors (Bogdanović et al., 2002), which was here observed in the case of rings A and B in [NiL1]b. The [NiL1]b molecule forms as many as seven intermolecular interactions (four as C—H donor and three as π acceptor). Generally speaking, it can be concluded that C—H···π interactions play a dominant role in the crystal packing.
The existence of C—H···π interactions in (III), as well as the mutual position of the three phenyl rings bonded to one P atom, was also analyzed. Almost all of the 29 structures lack significant intermolecular hydrogen bonds (25 in total) but form C—H···π interactions with phenyl or chelate rings acting as π acceptors. Comparing the angle between the mean planes of the phenyl rings bonded to the P atom and taking into account their position relative to the coordination plane, it was found that the conformations of the triphenylphosphine structural part in all 29 crystal structures, including the structures presented in this work, are very similar. Such a mutual position of the phenyl rings avoids short and destabilizing H···H contacts of their H atoms in the ortho positions. Nevertheless, it is interesting to note the existence of three short H···C contacts between an H atom in the ortho position and a C atom bonded to the P atom from a neighboring phenyl group. These H···C distances range from 2.5 to 2.8 Å, with C—H···C angles of about 110°. A similar orientation of the phenyl rings exists in uncoordinated triphenylphosphine and its derivatives (Daly, 1964; Dunne & Orpen, 1991; Chekhlov, 1993; Bruckmann et al., 1995; Kooijman et al., 1998; Ziemer et al., 2000), suggesting the presented mutual orientation of phenyl rings is the most stable.