Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100020023/gd1116sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100020023/gd1116Isup2.hkl |
CCDC reference: 162558
Complex (I) was prepared as its nitrate salt in 71% yield following the general method of Lowe & Vilaivan (1996). Triethylammonium diethylphosphinothioate was prepared as described previously by Reynolds et al. (1983). Dissolution of the nitrate salt in water followed by the addition of excess sodium tetraphenylborate afforded a yellow precipitate which was redissolved by the addition of acetonitrile. Evaporation of this water/acetonitrile solution afforded single crystals of (I) (m.p. > 503 K). Spectroscopic analysis: 1H NMR (200 MHz, d6-DMSO, δ, p.p.m.): 1.12 (6H, t), 4.01 (4H, quin), 8.02 (2H, dd), 8.51 (2H, dd), 8.57 (2H, d), 9.00 (2H, s), 9.23 (2H, d); 31P NMR (101 MHz, d6-DMSO, δ, p.p.m.) 31.93 (J195Pt-31P = 88 Hz); elemental analysis calculated (for hexafluorophosphate salt): C 29.3, H 2.6, N 5.4%; found: C 29.4, H 2.6, N 5.4%.
H atoms were placed geometrically after each cycle. The short C28—C280 bond is probably a consequence of librational disorder, but it could not be reliably modelled on this basis.
Data collection: XPRESS (MacScience, 1989); cell refinement: DENZO; data reduction: DENZO (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin, Prout, Carruthers & Betteridge, 1996); molecular graphics: CAMERON (Watkin, Prout & Pearce, 1996); software used to prepare material for publication: CRYSTALS.
[Pt(C15H10ClN3)(C4H10O3PS)](C24H20B) | F(000) = 1896.0 |
Mr = 951.20 | Dx = 1.62 Mg m−3 |
Monoclinic, P21/n | Melting point: not measured K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71069 Å |
a = 10.7550 (5) Å | Cell parameters from 16185 reflections |
b = 13.5230 (3) Å | θ = 0–27° |
c = 26.764 (1) Å | µ = 3.82 mm−1 |
β = 87.356 (2)° | T = 190 K |
V = 3888.4 Å3 | Prism, yellow |
Z = 4 | 0.8 × 0.2 × 0.2 mm |
Enraf-nonius DIP2000 diffractometer | 5773 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.05 |
ω scans | θmax = 26.6°, θmin = 0.0° |
Absorption correction: multi-scan DENZO (Otwinowski & Minor, 1996) | h = −13→13 |
Tmin = 0.46, Tmax = 0.46 | k = 0→16 |
7838 measured reflections | l = 0→33 |
7838 independent reflections |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters not refined |
wR(F2) = 0.037 | Chebychev polynomial with 3 parameters (Carruthers & Watkin, 1979) 1.66 0.505 1.28 |
S = 1.03 | (Δ/σ)max < 0.001 |
5773 reflections | Δρmax = 1.69 e Å−3 |
487 parameters | Δρmin = −0.84 e Å−3 |
[Pt(C15H10ClN3)(C4H10O3PS)](C24H20B) | V = 3888.4 Å3 |
Mr = 951.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.7550 (5) Å | µ = 3.82 mm−1 |
b = 13.5230 (3) Å | T = 190 K |
c = 26.764 (1) Å | 0.8 × 0.2 × 0.2 mm |
β = 87.356 (2)° |
Enraf-nonius DIP2000 diffractometer | 7838 independent reflections |
Absorption correction: multi-scan DENZO (Otwinowski & Minor, 1996) | 5773 reflections with I > 3σ(I) |
Tmin = 0.46, Tmax = 0.46 | Rint = 0.05 |
7838 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 487 parameters |
wR(F2) = 0.037 | H-atom parameters not refined |
S = 1.03 | Δρmax = 1.69 e Å−3 |
5773 reflections | Δρmin = −0.84 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Pt1 | 0.818682 (14) | 0.021608 (12) | 0.035006 (5) | 0.0332 | |
Cl12 | 0.70224 (12) | 0.1349 (1) | −0.18851 (4) | 0.0547 | |
S21 | 0.85760 (11) | −0.01859 (9) | 0.11721 (4) | 0.0445 | |
P22 | 0.71700 (9) | 0.06262 (9) | 0.14998 (4) | 0.0372 | |
O23 | 0.5934 (3) | 0.0481 (2) | 0.12959 (12) | 0.0450 | |
O24 | 0.7176 (3) | 0.0408 (3) | 0.20754 (12) | 0.0492 | |
O27 | 0.7660 (3) | 0.1719 (2) | 0.14592 (13) | 0.0495 | |
N2 | 0.7884 (3) | 0.0525 (3) | −0.03440 (12) | 0.0365 | |
N5 | 0.9434 (3) | 0.1321 (3) | 0.02400 (13) | 0.0401 | |
N16 | 0.6797 (3) | −0.0760 (2) | 0.02372 (12) | 0.0374 | |
C3 | 0.8553 (4) | 0.1259 (3) | −0.05681 (15) | 0.0368 | |
C4 | 0.9460 (4) | 0.1697 (3) | −0.02342 (16) | 0.0388 | |
C6 | 1.0205 (4) | 0.1697 (4) | 0.05733 (17) | 0.0493 | |
C7 | 1.1009 (5) | 0.2474 (4) | 0.0444 (2) | 0.0572 | |
C8 | 1.1031 (4) | 0.2853 (4) | −0.0030 (2) | 0.0570 | |
C9 | 1.0249 (4) | 0.2450 (4) | −0.03800 (18) | 0.0478 | |
C10 | 0.8317 (4) | 0.1523 (3) | −0.10539 (16) | 0.0408 | |
C11 | 0.7375 (4) | 0.1020 (3) | −0.12879 (15) | 0.0389 | |
C13 | 0.6693 (4) | 0.0275 (3) | −0.10530 (15) | 0.0367 | |
C14 | 0.6973 (4) | 0.0033 (3) | −0.05698 (16) | 0.0351 | |
C15 | 0.6348 (4) | −0.0708 (3) | −0.02327 (15) | 0.0370 | |
C17 | 0.6261 (4) | −0.1383 (3) | 0.05680 (16) | 0.0436 | |
C18 | 0.5274 (5) | −0.1980 (3) | 0.04506 (18) | 0.0487 | |
C19 | 0.4839 (4) | −0.1944 (3) | −0.00247 (18) | 0.0474 | |
C20 | 0.5382 (4) | −0.1295 (3) | −0.03740 (17) | 0.0428 | |
C25 | 0.6224 (5) | −0.0229 (4) | 0.23231 (18) | 0.0548 | |
C26 | 0.6418 (7) | −0.1284 (5) | 0.2197 (2) | 0.0763 | |
C28 | 0.6870 (6) | 0.2500 (5) | 0.1663 (3) | 0.0780 | |
C29 | 0.6268 (3) | 0.4748 (3) | −0.15966 (15) | 0.0345 | |
C30 | 0.5943 (4) | 0.5028 (3) | −0.20755 (16) | 0.0423 | |
C31 | 0.4891 (4) | 0.4675 (4) | −0.22983 (16) | 0.0442 | |
C32 | 0.4124 (4) | 0.4010 (4) | −0.20442 (18) | 0.0459 | |
C33 | 0.4402 (4) | 0.3717 (4) | −0.15770 (19) | 0.0481 | |
C34 | 0.5455 (4) | 0.4083 (3) | −0.13517 (16) | 0.0417 | |
C36 | 0.7334 (4) | 0.5075 (3) | −0.07264 (16) | 0.0364 | |
C37 | 0.6558 (4) | 0.5713 (3) | −0.04498 (17) | 0.0434 | |
C38 | 0.6308 (5) | 0.5603 (4) | 0.00578 (19) | 0.0515 | |
C39 | 0.6854 (5) | 0.4872 (4) | 0.03252 (18) | 0.0501 | |
C40 | 0.7609 (5) | 0.4212 (5) | 0.0063 (2) | 0.0713 | |
C41 | 0.7839 (5) | 0.4317 (5) | −0.04469 (19) | 0.0642 | |
C42 | 0.8731 (3) | 0.4471 (3) | −0.15289 (15) | 0.0343 | |
C43 | 0.8674 (4) | 0.3736 (3) | −0.18968 (18) | 0.0436 | |
C44 | 0.9693 (5) | 0.3135 (4) | −0.2028 (2) | 0.0529 | |
C45 | 1.0807 (4) | 0.3245 (4) | −0.1797 (2) | 0.0550 | |
C46 | 1.0909 (4) | 0.3975 (4) | −0.1439 (2) | 0.0523 | |
C47 | 0.9897 (4) | 0.4572 (3) | −0.13064 (17) | 0.0429 | |
C48 | 0.7742 (4) | 0.6310 (3) | −0.15192 (14) | 0.0351 | |
C49 | 0.6748 (4) | 0.6979 (3) | −0.15197 (16) | 0.0399 | |
C50 | 0.6873 (4) | 0.7958 (3) | −0.16670 (18) | 0.0475 | |
C51 | 0.8023 (5) | 0.8315 (4) | −0.18273 (19) | 0.0510 | |
C52 | 0.9034 (4) | 0.7697 (4) | −0.18385 (19) | 0.0511 | |
C53 | 0.8894 (4) | 0.6711 (3) | −0.16949 (17) | 0.0427 | |
C280 | 0.7269 (8) | 0.3438 (5) | 0.1484 (3) | 0.0888 | |
B35 | 0.7533 (4) | 0.5156 (4) | −0.13416 (18) | 0.0350 | |
H61 | 1.0192 | 0.1418 | 0.0917 | 0.0573* | |
H71 | 1.1576 | 0.2751 | 0.0694 | 0.0684* | |
H81 | 1.1605 | 0.3412 | −0.0129 | 0.0690* | |
H91 | 1.0259 | 0.2714 | −0.0729 | 0.0568* | |
H101 | 0.8809 | 0.2059 | −0.1230 | 0.0474* | |
H131 | 0.6016 | −0.0074 | −0.1226 | 0.0430* | |
H171 | 0.6589 | −0.1413 | 0.0918 | 0.0503* | |
H181 | 0.4875 | −0.2438 | 0.0713 | 0.0574* | |
H191 | 0.4147 | −0.2383 | −0.0118 | 0.0555* | |
H201 | 0.5071 | −0.1259 | −0.0721 | 0.0508* | |
H251 | 0.6269 | −0.0139 | 0.2692 | 0.0660* | |
H252 | 0.5389 | −0.0017 | 0.2215 | 0.0660* | |
H261 | 0.5764 | −0.1687 | 0.2372 | 0.0889* | |
H262 | 0.7261 | −0.1494 | 0.2303 | 0.0889* | |
H263 | 0.6381 | −0.1372 | 0.1826 | 0.0889* | |
H301 | 0.6487 | 0.5512 | −0.2262 | 0.0505* | |
H311 | 0.4693 | 0.4903 | −0.2638 | 0.0536* | |
H321 | 0.3357 | 0.3748 | −0.2200 | 0.0542* | |
H331 | 0.3856 | 0.3224 | −0.1391 | 0.0568* | |
H341 | 0.5634 | 0.3861 | −0.1006 | 0.0504* | |
H371 | 0.6158 | 0.6275 | −0.0623 | 0.0526* | |
H381 | 0.5717 | 0.6067 | 0.0234 | 0.0598* | |
H391 | 0.6704 | 0.4822 | 0.0695 | 0.0591* | |
H401 | 0.8005 | 0.3666 | 0.0244 | 0.0825* | |
H411 | 0.8381 | 0.3815 | −0.0622 | 0.0756* | |
H431 | 0.7887 | 0.3641 | −0.2073 | 0.0508* | |
H441 | 0.9616 | 0.2618 | −0.2294 | 0.0616* | |
H451 | 1.1528 | 0.2801 | −0.1888 | 0.0654* | |
H461 | 1.1722 | 0.4070 | −0.1277 | 0.0602* | |
H471 | 0.9998 | 0.5087 | −0.1046 | 0.0515* | |
H491 | 0.5903 | 0.6737 | −0.1404 | 0.0480* | |
H501 | 0.6121 | 0.8402 | −0.1652 | 0.0570* | |
H511 | 0.8119 | 0.9025 | −0.1937 | 0.0602* | |
H521 | 0.9881 | 0.7942 | −0.1955 | 0.0614* | |
H531 | 0.9632 | 0.6264 | −0.1715 | 0.0510* | |
H2801 | 0.6735 | 0.3983 | 0.1633 | 0.0918* | |
H2802 | 0.8164 | 0.3574 | 0.1578 | 0.0918* | |
H2803 | 0.7248 | 0.3470 | 0.1111 | 0.0918* | |
H281 | 0.6916 | 0.2496 | 0.2041 | 0.0500* | |
H282 | 0.6000 | 0.2392 | 0.1574 | 0.0500* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.03424 (9) | 0.0327 (1) | 0.03306 (9) | 0.00364 (7) | −0.00512 (5) | −0.00252 (7) |
Cl12 | 0.0641 (7) | 0.0628 (8) | 0.0378 (5) | −0.0147 (6) | −0.0100 (5) | 0.0076 (5) |
S21 | 0.0460 (6) | 0.0488 (6) | 0.0393 (5) | 0.0133 (5) | −0.0084 (4) | −0.0010 (5) |
P22 | 0.0359 (5) | 0.0380 (6) | 0.0382 (5) | 0.0004 (4) | −0.0068 (4) | −0.0016 (5) |
O23 | 0.0397 (15) | 0.0507 (19) | 0.0454 (16) | −0.0030 (13) | −0.0101 (12) | −0.0008 (14) |
O24 | 0.0541 (18) | 0.055 (2) | 0.0397 (16) | −0.0012 (15) | −0.0104 (13) | −0.0024 (14) |
O27 | 0.0431 (16) | 0.0404 (17) | 0.065 (2) | −0.0011 (14) | 0.0007 (14) | −0.0028 (15) |
N2 | 0.0395 (17) | 0.0358 (18) | 0.0345 (16) | −0.0004 (15) | −0.0045 (13) | −0.0054 (14) |
N5 | 0.0365 (17) | 0.043 (2) | 0.0411 (18) | −0.0022 (15) | −0.0060 (14) | −0.0041 (15) |
N16 | 0.0482 (19) | 0.0268 (17) | 0.0375 (17) | 0.0010 (14) | −0.0045 (14) | 0.0009 (13) |
C3 | 0.0342 (19) | 0.035 (2) | 0.040 (2) | 0.0016 (16) | 0.0025 (16) | −0.0017 (17) |
C4 | 0.0324 (19) | 0.041 (2) | 0.043 (2) | 0.0031 (17) | −0.0016 (16) | −0.0052 (18) |
C6 | 0.043 (2) | 0.062 (3) | 0.043 (2) | −0.001 (2) | −0.0075 (18) | −0.010 (2) |
C7 | 0.049 (3) | 0.064 (3) | 0.060 (3) | −0.015 (2) | −0.013 (2) | −0.011 (2) |
C8 | 0.046 (3) | 0.056 (3) | 0.070 (3) | −0.011 (2) | −0.007 (2) | −0.008 (3) |
C9 | 0.043 (2) | 0.049 (3) | 0.052 (3) | −0.002 (2) | −0.0016 (19) | −0.001 (2) |
C10 | 0.036 (2) | 0.045 (2) | 0.041 (2) | −0.0059 (17) | 0.0036 (16) | −0.0042 (18) |
C11 | 0.040 (2) | 0.041 (2) | 0.036 (2) | −0.0011 (18) | −0.0018 (16) | −0.0021 (17) |
C13 | 0.041 (2) | 0.034 (2) | 0.0355 (19) | −0.0003 (17) | −0.0012 (15) | −0.0058 (17) |
C14 | 0.0330 (18) | 0.035 (2) | 0.037 (2) | 0.0033 (15) | −0.0029 (15) | −0.0060 (16) |
C15 | 0.043 (2) | 0.029 (2) | 0.040 (2) | 0.0015 (17) | −0.0026 (16) | 0.0017 (17) |
C17 | 0.059 (3) | 0.032 (2) | 0.040 (2) | −0.0016 (19) | −0.0025 (19) | −0.0010 (17) |
C18 | 0.064 (3) | 0.033 (2) | 0.048 (2) | −0.007 (2) | 0.002 (2) | 0.0023 (19) |
C19 | 0.052 (3) | 0.033 (2) | 0.058 (3) | −0.0094 (19) | −0.005 (2) | −0.0001 (19) |
C20 | 0.043 (2) | 0.038 (2) | 0.048 (2) | −0.0020 (18) | −0.0044 (18) | 0.0009 (19) |
C25 | 0.067 (3) | 0.055 (3) | 0.042 (2) | 0.004 (3) | 0.004 (2) | −0.001 (2) |
C26 | 0.111 (5) | 0.056 (3) | 0.060 (3) | −0.001 (3) | 0.017 (3) | 0.003 (3) |
C28 | 0.063 (3) | 0.050 (3) | 0.119 (5) | −0.003 (3) | 0.020 (3) | −0.020 (3) |
C29 | 0.0297 (17) | 0.033 (2) | 0.040 (2) | −0.0010 (16) | 0.0021 (14) | −0.0047 (17) |
C30 | 0.036 (2) | 0.051 (3) | 0.039 (2) | −0.0043 (18) | 0.0020 (16) | 0.0004 (18) |
C31 | 0.041 (2) | 0.054 (3) | 0.038 (2) | −0.0006 (19) | −0.0054 (17) | −0.0041 (19) |
C32 | 0.034 (2) | 0.050 (3) | 0.054 (3) | −0.0015 (18) | −0.0080 (18) | −0.009 (2) |
C33 | 0.038 (2) | 0.046 (3) | 0.061 (3) | −0.0104 (19) | −0.0066 (19) | 0.004 (2) |
C34 | 0.038 (2) | 0.042 (2) | 0.044 (2) | −0.0052 (18) | −0.0038 (17) | 0.0049 (18) |
C36 | 0.0299 (18) | 0.038 (2) | 0.042 (2) | −0.0042 (16) | −0.0054 (15) | 0.0004 (17) |
C37 | 0.044 (2) | 0.038 (2) | 0.048 (2) | 0.0031 (19) | 0.0032 (17) | −0.0009 (19) |
C38 | 0.056 (3) | 0.043 (2) | 0.055 (3) | 0.003 (2) | 0.010 (2) | −0.006 (2) |
C39 | 0.047 (2) | 0.065 (3) | 0.039 (2) | −0.004 (2) | 0.0017 (18) | −0.001 (2) |
C40 | 0.061 (3) | 0.099 (5) | 0.054 (3) | 0.032 (3) | 0.004 (2) | 0.023 (3) |
C41 | 0.065 (3) | 0.078 (4) | 0.048 (3) | 0.035 (3) | 0.010 (2) | 0.013 (3) |
C42 | 0.0285 (17) | 0.036 (2) | 0.0379 (19) | −0.0026 (15) | 0.0022 (14) | 0.0041 (16) |
C43 | 0.037 (2) | 0.040 (2) | 0.053 (3) | −0.0014 (18) | 0.0024 (18) | 0.0018 (19) |
C44 | 0.054 (3) | 0.041 (3) | 0.062 (3) | −0.001 (2) | 0.012 (2) | −0.001 (2) |
C45 | 0.042 (2) | 0.049 (3) | 0.072 (3) | 0.014 (2) | 0.017 (2) | 0.012 (2) |
C46 | 0.030 (2) | 0.059 (3) | 0.068 (3) | 0.006 (2) | 0.0024 (19) | 0.015 (2) |
C47 | 0.0312 (19) | 0.049 (3) | 0.048 (2) | 0.0027 (17) | −0.0008 (16) | 0.0046 (19) |
C48 | 0.036 (2) | 0.036 (2) | 0.0333 (18) | −0.0037 (16) | −0.0053 (15) | −0.0013 (16) |
C49 | 0.034 (2) | 0.041 (2) | 0.044 (2) | −0.0015 (17) | −0.0014 (16) | 0.0006 (18) |
C50 | 0.046 (2) | 0.038 (2) | 0.059 (3) | 0.0038 (19) | −0.004 (2) | 0.001 (2) |
C51 | 0.062 (3) | 0.035 (2) | 0.055 (3) | −0.000 (2) | −0.003 (2) | 0.005 (2) |
C52 | 0.045 (2) | 0.045 (3) | 0.062 (3) | −0.008 (2) | 0.010 (2) | 0.004 (2) |
C53 | 0.036 (2) | 0.040 (2) | 0.052 (2) | −0.0010 (18) | 0.0024 (17) | 0.0009 (19) |
C280 | 0.124 (6) | 0.042 (3) | 0.097 (5) | 0.014 (3) | 0.027 (4) | 0.012 (3) |
B35 | 0.0294 (19) | 0.033 (2) | 0.043 (2) | −0.0014 (18) | −0.0004 (16) | −0.001 (2) |
Pt1—S21 | 2.3230 (11) | C29—C34 | 1.396 (6) |
Pt1—N2 | 1.946 (3) | C29—B35 | 1.646 (6) |
Pt1—N5 | 2.020 (4) | C30—C31 | 1.387 (6) |
Pt1—N16 | 2.027 (3) | C30—H301 | 1.00 |
Cl12—C11 | 1.718 (4) | C31—C32 | 1.379 (7) |
S21—P22 | 2.0346 (16) | C31—H311 | 0.99 |
P22—O23 | 1.473 (3) | C32—C33 | 1.358 (7) |
P22—O24 | 1.569 (3) | C32—H321 | 1.01 |
P22—O27 | 1.571 (3) | C33—C34 | 1.397 (6) |
O24—C25 | 1.471 (6) | C33—H331 | 1.01 |
O27—C28 | 1.447 (6) | C34—H341 | 1.00 |
N2—C3 | 1.351 (5) | C36—C37 | 1.390 (6) |
N2—C14 | 1.350 (5) | C36—C41 | 1.394 (7) |
N5—C4 | 1.367 (6) | C36—B35 | 1.654 (6) |
N5—C6 | 1.346 (6) | C37—C38 | 1.381 (6) |
N16—C15 | 1.369 (5) | C37—H371 | 1.00 |
N16—C17 | 1.334 (5) | C38—C39 | 1.369 (8) |
C3—C4 | 1.477 (6) | C38—H381 | 1.00 |
C3—C10 | 1.383 (6) | C39—C40 | 1.376 (8) |
C4—C9 | 1.371 (6) | C39—H391 | 1.00 |
C6—C7 | 1.394 (7) | C40—C41 | 1.384 (7) |
C6—H61 | 0.99 | C40—H401 | 0.99 |
C7—C8 | 1.369 (8) | C41—H411 | 1.00 |
C7—H71 | 1.00 | C42—C43 | 1.403 (6) |
C8—C9 | 1.397 (7) | C42—C47 | 1.420 (6) |
C8—H81 | 1.00 | C42—B35 | 1.646 (6) |
C9—H91 | 1.00 | C43—C44 | 1.396 (6) |
C10—C11 | 1.393 (6) | C43—H431 | 1.00 |
C10—H101 | 1.00 | C44—C45 | 1.383 (8) |
C11—C13 | 1.380 (6) | C44—H441 | 1.00 |
C13—C14 | 1.381 (6) | C45—C46 | 1.382 (8) |
C13—H131 | 1.00 | C45—H451 | 1.00 |
C14—C15 | 1.489 (6) | C46—C47 | 1.388 (6) |
C15—C20 | 1.374 (6) | C46—H461 | 1.00 |
C17—C18 | 1.381 (7) | C47—H471 | 1.00 |
C17—H171 | 1.02 | C48—C49 | 1.401 (6) |
C18—C19 | 1.376 (7) | C48—C53 | 1.413 (6) |
C18—H181 | 1.02 | C48—B35 | 1.643 (6) |
C19—C20 | 1.391 (6) | C49—C50 | 1.386 (6) |
C19—H191 | 0.99 | C49—H491 | 1.00 |
C20—H201 | 1.00 | C50—C51 | 1.377 (7) |
C25—C26 | 1.479 (8) | C50—H501 | 1.01 |
C25—H251 | 1.00 | C51—C52 | 1.370 (7) |
C25—H252 | 1.00 | C51—H511 | 1.01 |
C26—H261 | 0.99 | C52—C53 | 1.394 (6) |
C26—H262 | 1.00 | C52—H521 | 1.01 |
C26—H263 | 1.00 | C53—H531 | 1.00 |
C28—C280 | 1.415 (9) | C280—H2801 | 1.01 |
C28—H281 | 1.02 | C280—H2802 | 1.02 |
C28—H282 | 0.99 | C280—H2803 | 1.00 |
C29—C30 | 1.396 (6) | ||
S21—Pt1—N2 | 178.6 (1) | H281—C28—H282 | 109 |
S21—Pt1—N5 | 99.4 (1) | C30—C29—C34 | 115.3 (4) |
N2—Pt1—N5 | 80.87 (14) | C30—C29—B35 | 122.4 (4) |
S21—Pt1—N16 | 98.9 (1) | C34—C29—B35 | 122.2 (4) |
N2—Pt1—N16 | 80.82 (14) | C29—C30—C31 | 123.0 (4) |
N5—Pt1—N16 | 161.61 (14) | C29—C30—H301 | 118 |
Pt1—S21—P22 | 96.84 (5) | C31—C30—H301 | 119 |
S21—P22—O23 | 115.69 (15) | C30—C31—C32 | 119.6 (4) |
S21—P22—O24 | 106.56 (14) | C30—C31—H311 | 120 |
O23—P22—O24 | 112.52 (19) | C32—C31—H311 | 120 |
S21—P22—O27 | 103.76 (13) | C31—C32—C33 | 119.5 (4) |
O23—P22—O27 | 113.92 (19) | C31—C32—H321 | 121 |
O24—P22—O27 | 103.22 (19) | C33—C32—H321 | 120 |
P22—O24—C25 | 121.2 (3) | C32—C33—C34 | 120.7 (4) |
P22—O27—C28 | 118.2 (3) | C32—C33—H331 | 120 |
Pt1—N2—C3 | 118.2 (3) | C34—C33—H331 | 119 |
Pt1—N2—C14 | 118.6 (3) | C29—C34—C33 | 121.9 (4) |
C3—N2—C14 | 123.1 (4) | C29—C34—H341 | 119 |
Pt1—N5—C4 | 113.3 (3) | C33—C34—H341 | 119 |
Pt1—N5—C6 | 127.5 (3) | C37—C36—C41 | 114.2 (4) |
C4—N5—C6 | 119.2 (4) | C37—C36—B35 | 122.4 (4) |
Pt1—N16—C15 | 113.4 (3) | C41—C36—B35 | 123.2 (4) |
Pt1—N16—C17 | 127.7 (3) | C36—C37—C38 | 122.8 (4) |
C15—N16—C17 | 118.8 (4) | C36—C37—H371 | 119 |
N2—C3—C4 | 112.3 (4) | C38—C37—H371 | 118 |
N2—C3—C10 | 119.3 (4) | C37—C38—C39 | 121.6 (4) |
C4—C3—C10 | 128.4 (4) | C37—C38—H381 | 119 |
N5—C4—C3 | 115.3 (4) | C39—C38—H381 | 119 |
N5—C4—C9 | 121.8 (4) | C38—C39—C40 | 117.3 (4) |
C3—C4—C9 | 122.9 (4) | C38—C39—H391 | 121 |
N5—C6—C7 | 121.0 (5) | C40—C39—H391 | 122 |
N5—C6—H61 | 119 | C39—C40—C41 | 120.7 (5) |
C7—C6—H61 | 120 | C39—C40—H401 | 120 |
C6—C7—C8 | 119.7 (4) | C41—C40—H401 | 120 |
C6—C7—H71 | 121 | C36—C41—C40 | 123.3 (5) |
C8—C7—H71 | 120 | C36—C41—H411 | 119 |
C7—C8—C9 | 119.4 (5) | C40—C41—H411 | 118 |
C7—C8—H81 | 121 | C43—C42—C47 | 115.5 (4) |
C9—C8—H81 | 120 | C43—C42—B35 | 123.6 (3) |
C4—C9—C8 | 118.9 (5) | C47—C42—B35 | 120.8 (4) |
C4—C9—H91 | 121 | C42—C43—C44 | 122.1 (4) |
C8—C9—H91 | 120 | C42—C43—H431 | 119 |
C3—C10—C11 | 117.8 (4) | C44—C43—H431 | 119 |
C3—C10—H101 | 121 | C43—C44—C45 | 120.7 (5) |
C11—C10—H101 | 121 | C43—C44—H441 | 120 |
Cl12—C11—C10 | 119.2 (3) | C45—C44—H441 | 120 |
Cl12—C11—C13 | 118.5 (3) | C44—C45—C46 | 119.0 (4) |
C10—C11—C13 | 122.3 (4) | C44—C45—H451 | 120 |
C11—C13—C14 | 117.7 (4) | C46—C45—H451 | 120 |
C11—C13—H131 | 121 | C45—C46—C47 | 120.4 (4) |
C14—C13—H131 | 121 | C45—C46—H461 | 119 |
N2—C14—C13 | 119.8 (4) | C47—C46—H461 | 120 |
N2—C14—C15 | 112.2 (4) | C42—C47—C46 | 122.3 (4) |
C13—C14—C15 | 128.0 (4) | C42—C47—H471 | 119 |
N16—C15—C14 | 115.0 (3) | C46—C47—H471 | 119 |
N16—C15—C20 | 121.8 (4) | C49—C48—C53 | 114.1 (4) |
C14—C15—C20 | 123.3 (4) | C49—C48—B35 | 121.3 (3) |
N16—C17—C18 | 122.1 (4) | C53—C48—B35 | 124.5 (4) |
N16—C17—H171 | 119 | C48—C49—C50 | 123.6 (4) |
C18—C17—H171 | 119 | C48—C49—H491 | 118 |
C17—C18—C19 | 119.2 (4) | C50—C49—H491 | 118 |
C17—C18—H181 | 120 | C49—C50—C51 | 119.8 (4) |
C19—C18—H181 | 121 | C49—C50—H501 | 119 |
C18—C19—C20 | 119.5 (4) | C51—C50—H501 | 121 |
C18—C19—H191 | 120 | C50—C51—C52 | 119.6 (4) |
C20—C19—H191 | 120 | C50—C51—H511 | 120 |
C15—C20—C19 | 118.6 (4) | C52—C51—H511 | 120 |
C15—C20—H201 | 121 | C51—C52—C53 | 120.1 (4) |
C19—C20—H201 | 120 | C51—C52—H521 | 121 |
O24—C25—C26 | 112.0 (4) | C53—C52—H521 | 119 |
O24—C25—H251 | 108 | C48—C53—C52 | 122.8 (4) |
C26—C25—H251 | 109 | C48—C53—H531 | 118 |
O24—C25—H252 | 109 | C52—C53—H531 | 119 |
C26—C25—H252 | 109 | C28—C280—H2801 | 111 |
H251—C25—H252 | 110 | C28—C280—H2802 | 111 |
C25—C26—H261 | 110 | H2801—C280—H2802 | 107 |
C25—C26—H262 | 109 | C28—C280—H2803 | 111 |
H261—C26—H262 | 110 | H2801—C280—H2803 | 109 |
C25—C26—H263 | 109 | H2802—C280—H2803 | 108 |
H261—C26—H263 | 110 | C29—B35—C36 | 108.6 (3) |
H262—C26—H263 | 109 | C29—B35—C42 | 109.6 (3) |
O27—C28—C280 | 111.3 (5) | C36—B35—C42 | 109.2 (3) |
O27—C28—H281 | 109 | C29—B35—C48 | 107.6 (3) |
C280—C28—H281 | 108 | C36—B35—C48 | 111.1 (3) |
O27—C28—H282 | 110 | C42—B35—C48 | 110.6 (3) |
C280—C28—H282 | 109 |
Experimental details
Crystal data | |
Chemical formula | [Pt(C15H10ClN3)(C4H10O3PS)](C24H20B) |
Mr | 951.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 190 |
a, b, c (Å) | 10.7550 (5), 13.5230 (3), 26.764 (1) |
β (°) | 87.356 (2) |
V (Å3) | 3888.4 |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.82 |
Crystal size (mm) | 0.8 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Enraf-nonius DIP2000 diffractometer |
Absorption correction | Multi-scan DENZO (Otwinowski & Minor, 1996) |
Tmin, Tmax | 0.46, 0.46 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 7838, 7838, 5773 |
Rint | 0.05 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.037, 1.03 |
No. of reflections | 5773 |
No. of parameters | 487 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.69, −0.84 |
Computer programs: XPRESS (MacScience, 1989), DENZO (Otwinowski & Minor, 1996), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin, Prout, Carruthers & Betteridge, 1996), CAMERON (Watkin, Prout & Pearce, 1996), CRYSTALS.
Pt1—S21 | 2.3230 (11) | P22—O24 | 1.569 (3) |
Pt1—N2 | 1.946 (3) | P22—O27 | 1.571 (3) |
Pt1—N5 | 2.020 (4) | O24—C25 | 1.471 (6) |
Pt1—N16 | 2.027 (3) | O27—C28 | 1.447 (6) |
S21—P22 | 2.0346 (16) | C25—C26 | 1.479 (8) |
P22—O23 | 1.473 (3) | C28—C280 | 1.415 (9) |
S21—Pt1—N2 | 178.6 (1) | S21—P22—O24 | 106.56 (14) |
S21—Pt1—N5 | 99.4 (1) | O23—P22—O24 | 112.52 (19) |
N2—Pt1—N5 | 80.87 (14) | S21—P22—O27 | 103.76 (13) |
S21—Pt1—N16 | 98.9 (1) | O23—P22—O27 | 113.92 (19) |
N2—Pt1—N16 | 80.82 (14) | O24—P22—O27 | 103.22 (19) |
N5—Pt1—N16 | 161.61 (14) | P22—O24—C25 | 121.2 (3) |
Pt1—S21—P22 | 96.84 (5) | P22—O27—C28 | 118.2 (3) |
S21—P22—O23 | 115.69 (15) |
Platinum(II) complexes of 2,2':6',2''-terpyridine ligands are of interest due to their photophysical properties (Tzeng et al., 1999), fast ligand-substitution kinetics (Mureinik & Bidani, 1978; Carr et al., 2000), and antitumour (Lowe, Droz, Vilaivan, Weaver, Park et al., 1999) and antiparasitic activity (Lowe, Droz, Vilaivan, Weaver, Tweedale et al., 1999). Intercalation into nucleic acids (McCoubrey et al., 1996) and irreversible enzyme inhibition (Bonse et al., 2000) have been implicated as possible modes of action of this class of compounds in vivo. Oligo(deoxy)ribonucleotides containing phosphinothioate linkages have been proposed as potential antisense or antigene agents, due to their resistance to enzymatic hydrolysis in vivo (Eckstein, 2000). Binding of platinum complexes to the phosphinothioate linkage of oligonucleotides has been reported by Elmroth & Lippard (1995), and crosslinking of oligonucleotides using binuclear platinum complexes has also been reported (Gruff & Orgel, 1991). In addition, phosphinothioates have been used as chemoprotective agents for platinum antitumour agents (Thompson et al., 1995). We describe herein the first single-crystal X-ray structure of a mononuclear platinum(II)-phosphinothioate complex, (I). \sch
The distorted square planar geometry of the Pt centre in (I) [N5—Pt1—N16 161.61 (14)°; Fig. 1] is in agreement with other reported (terpyridine)platinum(II) complexes (Chernega et al., 1996; Jennette et al., 1976; Tzeng et al., 1999). The Pt1—S21—P22 bond angle of 96.84 (5)° is quite acute and compares with the equivalent Pt—S—P angles of 107.0 (1) and 104.6 (1)° in a related PtII—ZnII bridged dialkylphosphinothioate complex reported by Poat et al. (1990).
The N5—Pt1—S21—P22 torsion angle of 97.0 (3)° illustrates the necessity for the phosphinothioate ligand to adopt a conformation which avoids non-bonding contacts with atoms H6 and H6'' (H61 and H171 in the present atom-labelling scheme) of the terpyridine ligand. This torsion angle leads to the P centre being displaced significantly from the (terpyridine)platinum(II) plane. Thus, intercalation of this complex into double-stranded nucleic acids would almost certainly lead to steric interactions between the phosphinothioate group and adjacent base-pairs. Interestingly, O23 is displaced 2.58 (2) Å from the mean plane defined by Pt1, N5, N2, N16 and S21, which may facilitate hydrogen-bonding interactions between O23 and the adjacent base-pairs of DNA upon intercalation.
The crystal structure of (I) shows that the cations are arranged in a stacked manner in the solid state (Fig. 2). This has been observed previously with (terpyridine)platinum(II) complexes (Chernega et al., 1996; Tzeng et al., 1999), and is a good indication of the ability of these compounds to intercalate and also to stack in solution (Jennette et al., 1976). The intramolecular (or inter?) stacking distance [3.59 (5) Å between the equivalent mean planes described above] and antiparallel orientation are consistent with previously reported structures. The intermolecular Pt1—Pt1' distance is 4.29 (5) Å.
Finally, the structural parameters for the present platinum(II)-phosphinothioate complex will prove useful in predicting how the (terpyridine)platinum(II) fragment will bind to nucleic acids containing the phosphinothioate linkage.