The structures of the title compounds, [PtCl
2(C
7H
5N
3O
2S)
2]·4C
3H
7NO, (I), and [Pt(C
3H
5N
3S)
4][PtCl
6]·2C
3H
7NO, (II), respectively, comprise square-planar Pt
II centres. In the cation and anion of (II), the Pt atoms lie on independent inversion centres. For (I), the metal atom is N-bonded to two
trans organic ligands and also bonded to two Cl atoms, whereas in (II), the Pt atom is
N-bonded to four organic ligands, the charge being balanced by the presence of an additional [PtCl
6]
2− species (from the starting material). Both structures contain dimethylformamide solvate molecules, four in the asymmetric unit of (I) and one in (II), which are involved in the hydrogen-bonding network
via N—H
X and C—H
X associations.
Supporting information
CCDC references: 173348; 173349
Complexes (I) and (II) were prepared by dissolving (upon heating) 1:2 molar
amounts of chloroplatinic acid with, respectively,
2-amino-6-nitro-1,3,4-benzothiazole for (I) and
2-amino-5-methyl-1,3,4-thiadiazole for (II) in dry DMF. Crystals were
separated from the reaction solutions after three weeks.
All H atoms were included in the refinement at calculated positions as riding
models, with C—H distances set to either 0.98 (CH3) or 0.95 Å (CHO) and
the N—H distance set to 0.88 Å.
For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.
(I)
trans-Bis(2-amino-6-nitro-1,3-benzothiazole-
N)dichloroplatinum(II)
tetrakis(
N,
N'-dimethylformamide) solvate
top
Crystal data top
[PtCl2(C7H5N3O2S)2]·4C3H7NO | Z = 2 |
Mr = 948.77 | F(000) = 944 |
Triclinic, P1 | Dx = 1.757 Mg m−3 |
a = 11.137 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.671 (3) Å | Cell parameters from 29063 reflections |
c = 14.409 (3) Å | θ = 2.9–27.5° |
α = 64.28 (3)° | µ = 4.24 mm−1 |
β = 85.77 (3)° | T = 150 K |
γ = 78.28 (3)° | Needle, yellow |
V = 1793.4 (6) Å3 | 0.28 × 0.08 × 0.05 mm |
Data collection top
Enraf-Nonius KappaCCD area-detector diffractometer | 8177 independent reflections |
Radiation source: Enraf-Nonius FR591 rotating anode | 7229 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −14→12 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −16→16 |
Tmin = 0.389, Tmax = 0.816 | l = −18→18 |
29010 measured reflections | |
Refinement top
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0561P)2 + 0.4358P] where P = (Fo2 + 2Fc2)/3 |
8177 reflections | (Δ/σ)max < 0.001 |
451 parameters | Δρmax = 2.45 e Å−3 |
0 restraints | Δρmin = −2.61 e Å−3 |
Crystal data top
[PtCl2(C7H5N3O2S)2]·4C3H7NO | γ = 78.28 (3)° |
Mr = 948.77 | V = 1793.4 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.137 (2) Å | Mo Kα radiation |
b = 12.671 (3) Å | µ = 4.24 mm−1 |
c = 14.409 (3) Å | T = 150 K |
α = 64.28 (3)° | 0.28 × 0.08 × 0.05 mm |
β = 85.77 (3)° | |
Data collection top
Enraf-Nonius KappaCCD area-detector diffractometer | 8177 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 7229 reflections with I > 2σ(I) |
Tmin = 0.389, Tmax = 0.816 | Rint = 0.066 |
29010 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.04 | Δρmax = 2.45 e Å−3 |
8177 reflections | Δρmin = −2.61 e Å−3 |
451 parameters | |
Special details top
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the
entire data set is used to refine the cell, which is indexed from all observed
reflections in a 10 degree phi range. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | −0.160112 (11) | −0.205099 (11) | −0.111809 (10) | 0.02204 (7) | |
Cl1 | −0.11420 (10) | −0.02908 (9) | −0.23411 (8) | 0.0336 (2) | |
Cl2 | −0.20186 (10) | −0.38565 (9) | 0.00743 (8) | 0.0297 (2) | |
S1A | −0.36404 (9) | −0.22879 (9) | −0.36415 (8) | 0.0270 (2) | |
C2A | −0.3327 (4) | −0.1810 (3) | −0.2736 (3) | 0.0244 (8) | |
N21A | −0.4126 (3) | −0.0990 (3) | −0.2575 (3) | 0.0329 (8) | |
H21A | −0.3966 | −0.0754 | −0.2114 | 0.041* | |
H22A | −0.4822 | −0.0678 | −0.2928 | 0.041* | |
N3A | −0.2238 (3) | −0.2345 (3) | −0.2241 (3) | 0.0225 (7) | |
C4A | −0.0455 (4) | −0.3862 (4) | −0.2236 (3) | 0.0268 (8) | |
H4A | −0.0023 | −0.3785 | −0.1731 | 0.033* | |
C5A | 0.0062 (3) | −0.4667 (4) | −0.2627 (3) | 0.0276 (8) | |
H5A | 0.0850 | −0.5149 | −0.2397 | 0.035* | |
C6A | −0.0594 (4) | −0.4759 (3) | −0.3367 (3) | 0.0266 (8) | |
N61A | −0.0071 (3) | −0.5663 (3) | −0.3740 (3) | 0.0311 (8) | |
O61A | 0.1001 (3) | −0.6158 (3) | −0.3510 (3) | 0.0477 (9) | |
O62A | −0.0724 (3) | −0.5890 (3) | −0.4239 (3) | 0.0368 (7) | |
C7A | −0.1743 (3) | −0.4078 (3) | −0.3740 (3) | 0.0252 (8) | |
H7A | −0.2169 | −0.4161 | −0.4245 | 0.032* | |
C8A | −0.2238 (3) | −0.3279 (3) | −0.3343 (3) | 0.0238 (8) | |
C9A | −0.1604 (3) | −0.3166 (3) | −0.2581 (3) | 0.0224 (8) | |
S1B | −0.06255 (9) | −0.08434 (9) | 0.12527 (8) | 0.0265 (2) | |
C2B | −0.1449 (4) | −0.0933 (3) | 0.0310 (3) | 0.0234 (8) | |
N21B | −0.2500 (3) | −0.0201 (3) | −0.0031 (3) | 0.0292 (8) | |
H21B | −0.2924 | −0.0240 | −0.0503 | 0.036* | |
H22B | −0.2781 | 0.0328 | 0.0213 | 0.036* | |
N3B | −0.0926 (3) | −0.1771 (3) | 0.0005 (3) | 0.0224 (7) | |
C4B | 0.0961 (4) | −0.3334 (3) | 0.0398 (3) | 0.0248 (8) | |
H4B | 0.0745 | −0.3614 | −0.0070 | 0.031* | |
C5B | 0.2039 (4) | −0.3858 (3) | 0.0959 (3) | 0.0279 (8) | |
H5B | 0.2576 | −0.4501 | 0.0883 | 0.035* | |
C6B | 0.2334 (4) | −0.3436 (3) | 0.1639 (3) | 0.0272 (8) | |
N61B | 0.3476 (3) | −0.4010 (3) | 0.2251 (3) | 0.0339 (8) | |
O61B | 0.4177 (3) | −0.4785 (3) | 0.2082 (3) | 0.0445 (8) | |
O62B | 0.3688 (3) | −0.3687 (3) | 0.2905 (3) | 0.0415 (8) | |
C7B | 0.1588 (4) | −0.2506 (4) | 0.1792 (3) | 0.0282 (8) | |
H7B | 0.1811 | −0.2236 | 0.2264 | 0.035* | |
C8B | 0.0511 (4) | −0.1994 (3) | 0.1229 (3) | 0.0240 (8) | |
C9B | 0.0185 (4) | −0.2388 (3) | 0.0517 (3) | 0.0238 (8) | |
O1 | 0.4341 (3) | 0.9599 (3) | 0.1499 (3) | 0.0436 (8) | |
C2 | 0.5201 (4) | 0.8771 (4) | 0.1930 (4) | 0.0379 (10) | |
H2 | 0.5537 | 0.8727 | 0.2536 | 0.047* | |
N3 | 0.5688 (3) | 0.7949 (3) | 0.1625 (3) | 0.0314 (8) | |
C4 | 0.5230 (4) | 0.7973 (4) | 0.0705 (4) | 0.0403 (11) | |
H41 | 0.4396 | 0.7809 | 0.0819 | 0.050* | |
H42 | 0.5763 | 0.7365 | 0.0536 | 0.050* | |
H43 | 0.5221 | 0.8762 | 0.0133 | 0.050* | |
C5 | 0.6671 (4) | 0.6983 (5) | 0.2196 (4) | 0.0488 (13) | |
H51 | 0.6867 | 0.7055 | 0.2815 | 0.061* | |
H52 | 0.7398 | 0.7021 | 0.1764 | 0.061* | |
H53 | 0.6414 | 0.6219 | 0.2395 | 0.061* | |
O6 | 0.6988 (4) | 0.1256 (3) | 0.1005 (3) | 0.0509 (9) | |
C7 | 0.7374 (5) | 0.1697 (4) | 0.1494 (4) | 0.0421 (11) | |
H7 | 0.8137 | 0.1308 | 0.1850 | 0.053* | |
N8 | 0.6799 (4) | 0.2688 (4) | 0.1564 (3) | 0.0435 (10) | |
C9 | 0.5640 (6) | 0.3344 (5) | 0.1010 (5) | 0.0605 (15) | |
H91 | 0.5775 | 0.4085 | 0.0430 | 0.076* | |
H92 | 0.5045 | 0.3534 | 0.1478 | 0.076* | |
H93 | 0.5323 | 0.2854 | 0.0751 | 0.076* | |
C10 | 0.7272 (7) | 0.3155 (6) | 0.2178 (5) | 0.0694 (18) | |
H101 | 0.6680 | 0.3178 | 0.2711 | 0.087* | |
H102 | 0.7407 | 0.3964 | 0.1738 | 0.087* | |
H103 | 0.8050 | 0.2643 | 0.2505 | 0.087* | |
O11 | 0.6319 (4) | 1.0135 (5) | 0.3672 (4) | 0.0849 (17) | |
C12 | 0.7240 (5) | 0.9343 (6) | 0.3826 (4) | 0.0571 (15) | |
H12 | 0.7186 | 0.8719 | 0.3643 | 0.071* | |
N13 | 0.8284 (3) | 0.9294 (4) | 0.4221 (3) | 0.0396 (9) | |
C14 | 0.8390 (8) | 1.0180 (7) | 0.4558 (7) | 0.101 (3) | |
H141 | 0.7570 | 1.0615 | 0.4605 | 0.127* | |
H142 | 0.8874 | 1.0738 | 0.4063 | 0.127* | |
H143 | 0.8797 | 0.9793 | 0.5236 | 0.127* | |
C15 | 0.9337 (5) | 0.8367 (4) | 0.4377 (5) | 0.0559 (15) | |
H151 | 0.9129 | 0.7772 | 0.4184 | 0.070* | |
H152 | 0.9591 | 0.7984 | 0.5105 | 0.070* | |
H153 | 1.0009 | 0.8710 | 0.3951 | 0.070* | |
O16 | 0.4064 (4) | 0.3089 (4) | 0.5284 (3) | 0.0635 (11) | |
C17 | 0.4907 (5) | 0.3602 (5) | 0.4881 (4) | 0.0464 (12) | |
H17 | 0.4695 | 0.4417 | 0.4405 | 0.058* | |
N18 | 0.6084 (4) | 0.3138 (4) | 0.5041 (3) | 0.0424 (9) | |
C19 | 0.6488 (8) | 0.1959 (6) | 0.5792 (6) | 0.097 (3) | |
H191 | 0.6394 | 0.1940 | 0.6481 | 0.122* | |
H192 | 0.7353 | 0.1690 | 0.5683 | 0.122* | |
H193 | 0.5996 | 0.1431 | 0.5734 | 0.122* | |
C20 | 0.7005 (7) | 0.3862 (8) | 0.4600 (6) | 0.090 (3) | |
H201 | 0.6627 | 0.4639 | 0.4066 | 0.112* | |
H202 | 0.7645 | 0.3461 | 0.4295 | 0.112* | |
H203 | 0.7368 | 0.3978 | 0.5140 | 0.112* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.02358 (10) | 0.01978 (10) | 0.02515 (10) | −0.00329 (6) | −0.00220 (6) | −0.01179 (7) |
Cl1 | 0.0441 (6) | 0.0273 (5) | 0.0285 (5) | −0.0152 (4) | −0.0053 (4) | −0.0067 (4) |
Cl2 | 0.0393 (5) | 0.0218 (5) | 0.0297 (5) | −0.0095 (4) | 0.0008 (4) | −0.0110 (4) |
S1A | 0.0241 (5) | 0.0286 (5) | 0.0304 (5) | 0.0005 (4) | −0.0066 (4) | −0.0159 (4) |
C2A | 0.027 (2) | 0.0187 (18) | 0.025 (2) | −0.0022 (15) | −0.0046 (16) | −0.0073 (16) |
N21A | 0.0308 (18) | 0.0306 (19) | 0.040 (2) | 0.0046 (15) | −0.0097 (16) | −0.0210 (17) |
N3A | 0.0189 (15) | 0.0218 (16) | 0.0286 (18) | −0.0028 (12) | 0.0000 (13) | −0.0130 (14) |
C4A | 0.0242 (19) | 0.035 (2) | 0.028 (2) | −0.0031 (16) | −0.0050 (16) | −0.0201 (18) |
C5A | 0.0226 (19) | 0.031 (2) | 0.031 (2) | 0.0005 (15) | −0.0024 (16) | −0.0161 (17) |
C6A | 0.027 (2) | 0.025 (2) | 0.031 (2) | −0.0030 (15) | 0.0030 (16) | −0.0164 (17) |
N61A | 0.035 (2) | 0.0318 (19) | 0.0296 (19) | −0.0030 (15) | 0.0009 (15) | −0.0177 (16) |
O61A | 0.0329 (18) | 0.059 (2) | 0.059 (2) | 0.0175 (15) | −0.0146 (15) | −0.0416 (19) |
O62A | 0.0379 (17) | 0.0395 (18) | 0.046 (2) | −0.0043 (13) | −0.0037 (14) | −0.0309 (16) |
C7A | 0.0241 (18) | 0.029 (2) | 0.026 (2) | −0.0094 (15) | 0.0031 (15) | −0.0138 (17) |
C8A | 0.0253 (19) | 0.0218 (18) | 0.023 (2) | −0.0038 (14) | 0.0018 (15) | −0.0090 (15) |
C9A | 0.0247 (19) | 0.0218 (19) | 0.0226 (19) | −0.0082 (15) | 0.0011 (15) | −0.0096 (15) |
S1B | 0.0295 (5) | 0.0248 (5) | 0.0297 (5) | −0.0011 (4) | −0.0046 (4) | −0.0170 (4) |
C2B | 0.0255 (19) | 0.0223 (19) | 0.027 (2) | −0.0087 (15) | −0.0020 (15) | −0.0126 (16) |
N21B | 0.0255 (17) | 0.0307 (18) | 0.037 (2) | 0.0004 (14) | −0.0051 (15) | −0.0217 (16) |
N3B | 0.0220 (16) | 0.0207 (16) | 0.0286 (18) | −0.0056 (12) | 0.0022 (13) | −0.0138 (14) |
C4B | 0.030 (2) | 0.0199 (18) | 0.028 (2) | −0.0061 (15) | 0.0010 (16) | −0.0132 (16) |
C5B | 0.028 (2) | 0.0220 (19) | 0.032 (2) | −0.0020 (15) | 0.0031 (17) | −0.0115 (17) |
C6B | 0.026 (2) | 0.0239 (19) | 0.027 (2) | −0.0042 (15) | −0.0032 (16) | −0.0066 (16) |
N61B | 0.0287 (18) | 0.0298 (19) | 0.036 (2) | −0.0024 (15) | −0.0054 (15) | −0.0078 (16) |
O61B | 0.0302 (17) | 0.0394 (19) | 0.061 (2) | 0.0072 (14) | −0.0085 (15) | −0.0239 (17) |
O62B | 0.0378 (17) | 0.0420 (18) | 0.045 (2) | 0.0008 (14) | −0.0143 (15) | −0.0206 (16) |
C7B | 0.031 (2) | 0.028 (2) | 0.027 (2) | −0.0071 (16) | −0.0019 (17) | −0.0122 (17) |
C8B | 0.0254 (19) | 0.0169 (18) | 0.027 (2) | −0.0021 (14) | −0.0013 (15) | −0.0074 (15) |
C9B | 0.030 (2) | 0.0210 (19) | 0.022 (2) | −0.0064 (15) | 0.0003 (16) | −0.0099 (16) |
O1 | 0.0394 (18) | 0.0444 (19) | 0.051 (2) | 0.0122 (14) | −0.0143 (15) | −0.0307 (17) |
C2 | 0.030 (2) | 0.045 (3) | 0.042 (3) | 0.0010 (19) | −0.0060 (19) | −0.024 (2) |
N3 | 0.0265 (17) | 0.0310 (18) | 0.033 (2) | 0.0022 (14) | −0.0028 (14) | −0.0131 (16) |
C4 | 0.038 (2) | 0.041 (3) | 0.046 (3) | 0.0015 (19) | −0.007 (2) | −0.025 (2) |
C5 | 0.039 (3) | 0.052 (3) | 0.045 (3) | 0.018 (2) | −0.011 (2) | −0.020 (2) |
O6 | 0.060 (2) | 0.050 (2) | 0.058 (2) | −0.0044 (17) | 0.0002 (18) | −0.040 (2) |
C7 | 0.051 (3) | 0.039 (3) | 0.038 (3) | −0.011 (2) | 0.006 (2) | −0.017 (2) |
N8 | 0.062 (3) | 0.038 (2) | 0.039 (2) | −0.0162 (19) | 0.014 (2) | −0.0229 (18) |
C9 | 0.065 (4) | 0.054 (3) | 0.058 (4) | 0.004 (3) | 0.012 (3) | −0.028 (3) |
C10 | 0.105 (5) | 0.059 (4) | 0.068 (4) | −0.039 (4) | 0.010 (4) | −0.039 (3) |
O11 | 0.039 (2) | 0.125 (4) | 0.052 (3) | −0.006 (3) | −0.013 (2) | −0.005 (3) |
C12 | 0.051 (3) | 0.075 (4) | 0.041 (3) | −0.033 (3) | 0.000 (2) | −0.012 (3) |
N13 | 0.031 (2) | 0.045 (2) | 0.049 (2) | −0.0032 (16) | −0.0048 (17) | −0.027 (2) |
C14 | 0.119 (6) | 0.076 (5) | 0.135 (7) | 0.023 (4) | −0.070 (6) | −0.076 (5) |
C15 | 0.044 (3) | 0.035 (3) | 0.068 (4) | −0.003 (2) | 0.019 (3) | −0.009 (3) |
O16 | 0.051 (2) | 0.093 (3) | 0.072 (3) | −0.020 (2) | −0.004 (2) | −0.056 (3) |
C17 | 0.052 (3) | 0.040 (3) | 0.047 (3) | −0.003 (2) | −0.018 (2) | −0.019 (2) |
N18 | 0.045 (2) | 0.045 (2) | 0.035 (2) | −0.0057 (18) | −0.0083 (17) | −0.0151 (18) |
C19 | 0.104 (6) | 0.067 (5) | 0.070 (5) | 0.041 (4) | 0.012 (4) | −0.008 (4) |
C20 | 0.079 (5) | 0.141 (7) | 0.080 (5) | −0.067 (5) | 0.012 (4) | −0.057 (5) |
Geometric parameters (Å, º) top
Pt1—Cl1 | 2.2935 (14) | C2—N3 | 1.305 (5) |
Pt1—Cl2 | 2.3031 (13) | C2—H2 | 0.95 |
Pt1—N3A | 2.015 (3) | N3—C4 | 1.442 (6) |
Pt1—N3B | 2.023 (3) | N3—C5 | 1.445 (5) |
S1A—C2A | 1.740 (4) | C4—H41 | 0.98 |
S1A—C8A | 1.742 (4) | C4—H42 | 0.98 |
C2A—N21A | 1.315 (5) | C4—H43 | 0.98 |
C2A—N3A | 1.346 (5) | C5—H51 | 0.98 |
N21A—H21A | 0.88 | C5—H52 | 0.98 |
N21A—H22A | 0.88 | C5—H53 | 0.98 |
N3A—C9A | 1.382 (5) | O6—C7 | 1.216 (6) |
C4A—C5A | 1.379 (5) | C7—N8 | 1.331 (6) |
C4A—C9A | 1.385 (6) | C7—H7 | 0.95 |
C4A—H4A | 0.95 | N8—C10 | 1.435 (6) |
C5A—C6A | 1.393 (6) | N8—C9 | 1.461 (8) |
C5A—H5A | 0.95 | C9—H91 | 0.98 |
C6A—C7A | 1.387 (6) | C9—H92 | 0.98 |
C6A—N61A | 1.469 (5) | C9—H93 | 0.98 |
N61A—O62A | 1.213 (5) | C10—H101 | 0.98 |
N61A—O61A | 1.226 (5) | C10—H102 | 0.98 |
C7A—C8A | 1.373 (5) | C10—H103 | 0.98 |
C7A—H7A | 0.95 | O11—C12 | 1.238 (8) |
C8A—C9A | 1.421 (5) | C12—N13 | 1.310 (7) |
S1B—C8B | 1.737 (4) | C12—H12 | 0.95 |
S1B—C2B | 1.749 (4) | N13—C14 | 1.429 (7) |
C2B—N21B | 1.312 (5) | N13—C15 | 1.433 (6) |
C2B—N3B | 1.333 (5) | C14—H141 | 0.98 |
N21B—H21B | 0.88 | C14—H142 | 0.98 |
N21B—H22B | 0.88 | C14—H143 | 0.98 |
N3B—C9B | 1.388 (5) | C15—H151 | 0.98 |
C4B—C5B | 1.375 (6) | C15—H152 | 0.98 |
C4B—C9B | 1.396 (5) | C15—H153 | 0.98 |
C4B—H4B | 0.95 | O16—C17 | 1.217 (7) |
C5B—C6B | 1.389 (6) | C17—N18 | 1.316 (7) |
C5B—H5B | 0.95 | C17—H17 | 0.95 |
C6B—C7B | 1.388 (6) | N18—C19 | 1.414 (7) |
C6B—N61B | 1.469 (5) | N18—C20 | 1.441 (8) |
N61B—O61B | 1.225 (5) | C19—H191 | 0.98 |
N61B—O62B | 1.232 (5) | C19—H192 | 0.98 |
C7B—C8B | 1.374 (6) | C19—H193 | 0.98 |
C7B—H7B | 0.95 | C20—H201 | 0.98 |
C8B—C9B | 1.417 (5) | C20—H202 | 0.98 |
O1—C2 | 1.231 (5) | C20—H203 | 0.98 |
| | | |
N3A—Pt1—N3B | 178.80 (11) | N3—C2—H2 | 117.2 |
N3A—Pt1—Cl1 | 89.41 (10) | C2—N3—C4 | 120.0 (4) |
N3B—Pt1—Cl1 | 90.51 (10) | C2—N3—C5 | 122.0 (4) |
N3A—Pt1—Cl2 | 89.24 (10) | C4—N3—C5 | 117.9 (4) |
N3B—Pt1—Cl2 | 90.80 (10) | N3—C4—H41 | 109.5 |
Cl1—Pt1—Cl2 | 177.75 (3) | N3—C4—H42 | 109.5 |
C2A—S1A—C8A | 89.75 (19) | H41—C4—H42 | 109.5 |
N21A—C2A—N3A | 124.9 (4) | N3—C4—H43 | 109.5 |
N21A—C2A—S1A | 120.3 (3) | H41—C4—H43 | 109.5 |
N3A—C2A—S1A | 114.8 (3) | H42—C4—H43 | 109.5 |
C2A—N21A—H21A | 120.0 | N3—C5—H51 | 109.5 |
C2A—N21A—H22A | 120.0 | N3—C5—H52 | 109.5 |
H21A—N21A—H22A | 120.0 | H51—C5—H52 | 109.5 |
C2A—N3A—C9A | 111.2 (3) | N3—C5—H53 | 109.5 |
C2A—N3A—Pt1 | 125.5 (3) | H51—C5—H53 | 109.5 |
C9A—N3A—Pt1 | 123.2 (3) | H52—C5—H53 | 109.5 |
C5A—C4A—C9A | 120.0 (4) | O6—C7—N8 | 124.3 (5) |
C5A—C4A—H4A | 120.0 | O6—C7—H7 | 117.8 |
C9A—C4A—H4A | 120.0 | N8—C7—H7 | 117.8 |
C4A—C5A—C6A | 118.7 (4) | C7—N8—C10 | 122.4 (5) |
C4A—C5A—H5A | 120.7 | C7—N8—C9 | 120.4 (4) |
C6A—C5A—H5A | 120.7 | C10—N8—C9 | 117.3 (5) |
C7A—C6A—C5A | 123.6 (3) | N8—C9—H91 | 109.5 |
C7A—C6A—N61A | 117.8 (3) | N8—C9—H92 | 109.5 |
C5A—C6A—N61A | 118.5 (3) | H91—C9—H92 | 109.5 |
O62A—N61A—O61A | 123.9 (3) | N8—C9—H93 | 109.5 |
O62A—N61A—C6A | 118.5 (3) | H91—C9—H93 | 109.5 |
O61A—N61A—C6A | 117.5 (3) | H92—C9—H93 | 109.5 |
C8A—C7A—C6A | 116.8 (4) | N8—C10—H101 | 109.5 |
C8A—C7A—H7A | 121.6 | N8—C10—H102 | 109.5 |
C6A—C7A—H7A | 121.6 | H101—C10—H102 | 109.5 |
C7A—C8A—C9A | 121.4 (4) | N8—C10—H103 | 109.5 |
C7A—C8A—S1A | 128.8 (3) | H101—C10—H103 | 109.5 |
C9A—C8A—S1A | 109.8 (3) | H102—C10—H103 | 109.5 |
N3A—C9A—C4A | 126.0 (3) | O11—C12—N13 | 125.4 (6) |
N3A—C9A—C8A | 114.4 (3) | O11—C12—H12 | 117.3 |
C4A—C9A—C8A | 119.6 (3) | N13—C12—H12 | 117.3 |
C8B—S1B—C2B | 89.43 (19) | C12—N13—C14 | 119.3 (5) |
N21B—C2B—N3B | 125.7 (4) | C12—N13—C15 | 123.8 (5) |
N21B—C2B—S1B | 119.2 (3) | C14—N13—C15 | 116.9 (5) |
N3B—C2B—S1B | 115.1 (3) | N13—C14—H141 | 109.5 |
C2B—N21B—H21B | 120.0 | N13—C14—H142 | 109.5 |
C2B—N21B—H22B | 120.0 | H141—C14—H142 | 109.5 |
H21B—N21B—H22B | 120.0 | N13—C14—H143 | 109.5 |
C2B—N3B—C9B | 111.1 (3) | H141—C14—H143 | 109.5 |
C2B—N3B—Pt1 | 124.8 (3) | H142—C14—H143 | 109.5 |
C9B—N3B—Pt1 | 124.0 (3) | N13—C15—H151 | 109.5 |
C5B—C4B—C9B | 119.7 (4) | N13—C15—H152 | 109.5 |
C5B—C4B—H4B | 120.2 | H151—C15—H152 | 109.5 |
C9B—C4B—H4B | 120.2 | N13—C15—H153 | 109.5 |
C4B—C5B—C6B | 119.1 (4) | H151—C15—H153 | 109.5 |
C4B—C5B—H5B | 120.4 | H152—C15—H153 | 109.5 |
C6B—C5B—H5B | 120.4 | O16—C17—N18 | 126.3 (5) |
C7B—C6B—C5B | 123.3 (4) | O16—C17—H17 | 116.9 |
C7B—C6B—N61B | 117.6 (4) | N18—C17—H17 | 116.9 |
C5B—C6B—N61B | 119.1 (4) | C17—N18—C19 | 120.8 (5) |
O61B—N61B—O62B | 123.1 (4) | C17—N18—C20 | 121.4 (6) |
O61B—N61B—C6B | 118.3 (4) | C19—N18—C20 | 116.9 (6) |
O62B—N61B—C6B | 118.6 (3) | N18—C19—H191 | 109.5 |
C8B—C7B—C6B | 116.9 (4) | N18—C19—H192 | 109.5 |
C8B—C7B—H7B | 121.5 | H191—C19—H192 | 109.5 |
C6B—C7B—H7B | 121.5 | N18—C19—H193 | 109.5 |
C7B—C8B—C9B | 121.5 (4) | H191—C19—H193 | 109.5 |
C7B—C8B—S1B | 128.4 (3) | H192—C19—H193 | 109.5 |
C9B—C8B—S1B | 110.1 (3) | N18—C20—H201 | 109.5 |
N3B—C9B—C4B | 126.2 (4) | N18—C20—H202 | 109.5 |
N3B—C9B—C8B | 114.3 (3) | H201—C20—H202 | 109.5 |
C4B—C9B—C8B | 119.4 (4) | N18—C20—H203 | 109.5 |
O1—C2—N3 | 125.5 (4) | H201—C20—H203 | 109.5 |
O1—C2—H2 | 117.2 | H202—C20—H203 | 109.5 |
| | | |
C8A—S1A—C2A—N21A | −179.3 (4) | N21B—C2B—N3B—Pt1 | 3.3 (6) |
C8A—S1A—C2A—N3A | 0.4 (3) | S1B—C2B—N3B—Pt1 | −176.93 (18) |
N21A—C2A—N3A—C9A | −179.9 (4) | Cl1—Pt1—N3B—C2B | 69.9 (3) |
S1A—C2A—N3A—C9A | 0.4 (4) | Cl2—Pt1—N3B—C2B | −111.9 (3) |
N21A—C2A—N3A—Pt1 | 1.7 (6) | Cl1—Pt1—N3B—C9B | −106.2 (3) |
S1A—C2A—N3A—Pt1 | −177.96 (18) | Cl2—Pt1—N3B—C9B | 71.9 (3) |
Cl1—Pt1—N3A—C2A | −76.8 (3) | C9B—C4B—C5B—C6B | 0.2 (6) |
Cl2—Pt1—N3A—C2A | 105.0 (3) | C4B—C5B—C6B—C7B | 0.4 (6) |
Cl1—Pt1—N3A—C9A | 105.1 (3) | C4B—C5B—C6B—N61B | 179.0 (4) |
Cl2—Pt1—N3A—C9A | −73.1 (3) | C7B—C6B—N61B—O61B | −175.9 (4) |
C9A—C4A—C5A—C6A | 0.0 (6) | C5B—C6B—N61B—O61B | 5.5 (6) |
C4A—C5A—C6A—C7A | 0.3 (6) | C7B—C6B—N61B—O62B | 3.7 (6) |
C4A—C5A—C6A—N61A | −176.6 (4) | C5B—C6B—N61B—O62B | −174.9 (4) |
C7A—C6A—N61A—O62A | −10.0 (6) | C5B—C6B—C7B—C8B | −0.1 (6) |
C5A—C6A—N61A—O62A | 167.2 (4) | N61B—C6B—C7B—C8B | −178.7 (4) |
C7A—C6A—N61A—O61A | 171.2 (4) | C6B—C7B—C8B—C9B | −0.7 (6) |
C5A—C6A—N61A—O61A | −11.7 (6) | C6B—C7B—C8B—S1B | 178.8 (3) |
C5A—C6A—C7A—C8A | 0.0 (6) | C2B—S1B—C8B—C7B | 179.5 (4) |
N61A—C6A—C7A—C8A | 177.0 (3) | C2B—S1B—C8B—C9B | −1.0 (3) |
C6A—C7A—C8A—C9A | −0.6 (6) | C2B—N3B—C9B—C4B | 178.9 (4) |
C6A—C7A—C8A—S1A | 179.5 (3) | Pt1—N3B—C9B—C4B | −4.5 (6) |
C2A—S1A—C8A—C7A | 178.8 (4) | C2B—N3B—C9B—C8B | −0.4 (5) |
C2A—S1A—C8A—C9A | −1.1 (3) | Pt1—N3B—C9B—C8B | 176.2 (3) |
C2A—N3A—C9A—C4A | 179.5 (4) | C5B—C4B—C9B—N3B | 179.8 (4) |
Pt1—N3A—C9A—C4A | −2.1 (6) | C5B—C4B—C9B—C8B | −0.9 (6) |
C2A—N3A—C9A—C8A | −1.3 (5) | C7B—C8B—C9B—N3B | −179.4 (4) |
Pt1—N3A—C9A—C8A | 177.1 (3) | S1B—C8B—C9B—N3B | 1.0 (4) |
C5A—C4A—C9A—N3A | 178.6 (4) | C7B—C8B—C9B—C4B | 1.2 (6) |
C5A—C4A—C9A—C8A | −0.6 (6) | S1B—C8B—C9B—C4B | −178.3 (3) |
C7A—C8A—C9A—N3A | −178.3 (3) | O1—C2—N3—C4 | 0.8 (7) |
S1A—C8A—C9A—N3A | 1.6 (4) | O1—C2—N3—C5 | −177.9 (5) |
C7A—C8A—C9A—C4A | 0.9 (6) | O6—C7—N8—C10 | 178.0 (5) |
S1A—C8A—C9A—C4A | −179.2 (3) | O6—C7—N8—C9 | −1.8 (8) |
C8B—S1B—C2B—N21B | −179.4 (4) | O11—C12—N13—C14 | 3.2 (9) |
C8B—S1B—C2B—N3B | 0.8 (3) | O11—C12—N13—C15 | −179.3 (5) |
N21B—C2B—N3B—C9B | 179.9 (4) | O16—C17—N18—C19 | −4.7 (9) |
S1B—C2B—N3B—C9B | −0.4 (4) | O16—C17—N18—C20 | −173.6 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1i | 0.88 | 1.98 | 2.778 (5) | 150 |
N21A—H22A···O11i | 0.88 | 1.89 | 2.765 (6) | 175 |
N21B—H21B···O1i | 0.88 | 2.00 | 2.804 (5) | 151 |
N21B—H22B···O6ii | 0.88 | 1.94 | 2.794 (5) | 164 |
C7A—H7A···O16iii | 0.95 | 2.47 | 3.212 (6) | 135 |
C17—H17···O62Biv | 0.95 | 2.54 | 3.455 (6) | 162 |
C4—H43···O1v | 0.98 | 2.47 | 3.416 (7) | 163 |
C5—H51···O61Avi | 0.98 | 2.49 | 3.050 (6) | 116 |
C9—H93···O6 | 0.98 | 2.37 | 2.766 (6) | 104 |
C14—H141···O11 | 0.98 | 2.33 | 2.738 (8) | 104 |
C15—H153···Cl1vii | 0.98 | 2.75 | 3.675 (5) | 158 |
C20—H203···O62Aviii | 0.98 | 2.43 | 3.271 (7) | 144 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y, −z; (iv) x, y+1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z; (viii) x+1, y+1, z+1. |
(II) Tetrakis(2-amino-5-methyl-1,3,4-thiadiazole-N
4)platinum(II)
hexachloroplatinate(IV) bis(
N,
N'-dimethylformamide) solvate
top
Crystal data top
[Pt(C3H5N3S)4][PtCl6]·2C3H7NO | Z = 1 |
Mr = 604.86 | F(000) = 578 |
Triclinic, P1 | Dx = 2.196 Mg m−3 |
a = 9.0397 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3009 (4) Å | Cell parameters from 4414 reflections |
c = 11.5241 (5) Å | θ = 2.9–27.5° |
α = 109.027 (2)° | µ = 8.35 mm−1 |
β = 91.850 (3)° | T = 150 K |
γ = 91.785 (3)° | Prism, yellow |
V = 914.61 (7) Å3 | 0.08 × 0.03 × 0.01 mm |
Data collection top
Enraf-Nonius KappaCCD area-detector diffractometer | 3838 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 2804 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −11→8 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −12→11 |
Tmin = 0.573, Tmax = 0.921 | l = −12→14 |
6735 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.037P)2 + 8.3603P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
3838 reflections | Δρmax = 2.38 e Å−3 |
216 parameters | Δρmin = −2.59 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0032 (6) |
Crystal data top
[Pt(C3H5N3S)4][PtCl6]·2C3H7NO | γ = 91.785 (3)° |
Mr = 604.86 | V = 914.61 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.0397 (4) Å | Mo Kα radiation |
b = 9.3009 (4) Å | µ = 8.35 mm−1 |
c = 11.5241 (5) Å | T = 150 K |
α = 109.027 (2)° | 0.08 × 0.03 × 0.01 mm |
β = 91.850 (3)° | |
Data collection top
Enraf-Nonius KappaCCD area-detector diffractometer | 3838 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 2804 reflections with I > 2σ(I) |
Tmin = 0.573, Tmax = 0.921 | Rint = 0.050 |
6735 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.38 e Å−3 |
3838 reflections | Δρmin = −2.59 e Å−3 |
216 parameters | |
Special details top
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the
entire data set is used to refine the cell, which is indexed from all observed
reflections in a 10 degree phi range. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.5000 | 0.0000 | 0.0000 | 0.02032 (19) | |
S1A | 0.0590 (3) | 0.2190 (3) | 0.0761 (3) | 0.0374 (7) | |
C2A | 0.2283 (10) | 0.1555 (11) | 0.1090 (9) | 0.028 (2) | |
N21A | 0.2830 (10) | 0.1813 (11) | 0.2214 (8) | 0.041 (2) | |
H21A | 0.3717 | 0.1508 | 0.2333 | 0.051* | |
H22A | 0.2310 | 0.2290 | 0.2846 | 0.051* | |
N3A | 0.2967 (8) | 0.0859 (9) | 0.0095 (7) | 0.0227 (17) | |
N4A | 0.2198 (9) | 0.0767 (10) | −0.1009 (8) | 0.0320 (19) | |
C5A | 0.0949 (12) | 0.1401 (12) | −0.0784 (10) | 0.035 (2) | |
C51A | −0.0132 (13) | 0.1465 (15) | −0.1786 (11) | 0.045 (3) | |
H51A | 0.0247 | 0.0908 | −0.2589 | 0.056* | |
H52A | −0.0257 | 0.2529 | −0.1729 | 0.056* | |
H53A | −0.1090 | 0.1001 | −0.1694 | 0.056* | |
S1B | 0.2650 (3) | −0.4579 (3) | −0.0546 (3) | 0.0405 (7) | |
C2B | 0.3313 (12) | −0.3017 (12) | −0.0935 (10) | 0.035 (2) | |
N21B | 0.3028 (12) | −0.2907 (12) | −0.2049 (9) | 0.049 (3) | |
H21B | 0.3366 | −0.2107 | −0.2222 | 0.062* | |
H22B | 0.2502 | −0.3634 | −0.2607 | 0.062* | |
N3B | 0.4072 (8) | −0.2033 (8) | −0.0023 (7) | 0.0207 (16) | |
N4B | 0.4274 (10) | −0.2472 (11) | 0.0985 (8) | 0.036 (2) | |
C5B | 0.3593 (12) | −0.3759 (13) | 0.0866 (11) | 0.039 (3) | |
C51B | 0.3581 (14) | −0.4500 (15) | 0.1837 (11) | 0.048 (3) | |
H51B | 0.4420 | −0.4088 | 0.2425 | 0.060* | |
H52B | 0.3662 | −0.5601 | 0.1457 | 0.060* | |
H53B | 0.2653 | −0.4296 | 0.2267 | 0.060* | |
Pt2 | 0.0000 | −0.5000 | 0.5000 | 0.0304 (2) | |
Cl1 | 0.0261 (3) | −0.2431 (3) | 0.6136 (2) | 0.0385 (6) | |
Cl2 | −0.0225 (3) | −0.4432 (3) | 0.3190 (2) | 0.0400 (6) | |
Cl3 | 0.2550 (3) | −0.5131 (3) | 0.4835 (3) | 0.0426 (7) | |
O1 | 0.5456 (10) | 0.1095 (12) | 0.3245 (8) | 0.057 (2) | |
C2 | 0.6069 (19) | 0.037 (4) | 0.361 (2) | 0.156 (14) | |
H2 | 0.6081 | −0.0542 | 0.2933 | 0.195* | |
N3 | 0.6777 (11) | 0.0067 (13) | 0.4430 (9) | 0.046 (3) | |
C4 | 0.726 (3) | 0.114 (3) | 0.5545 (17) | 0.153 (12) | |
H41 | 0.7497 | 0.2113 | 0.5422 | 0.191* | |
H42 | 0.8146 | 0.0787 | 0.5865 | 0.191* | |
H43 | 0.6475 | 0.1273 | 0.6135 | 0.191* | |
C5 | 0.712 (4) | −0.149 (3) | 0.408 (3) | 0.201 (18) | |
H51 | 0.6744 | −0.1932 | 0.4684 | 0.252* | |
H52 | 0.8202 | −0.1571 | 0.4058 | 0.252* | |
H53 | 0.6668 | −0.2035 | 0.3269 | 0.252* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.0172 (3) | 0.0247 (3) | 0.0183 (3) | 0.00356 (19) | 0.0021 (2) | 0.0056 (2) |
S1A | 0.0272 (14) | 0.0485 (17) | 0.0351 (15) | 0.0148 (12) | 0.0050 (12) | 0.0104 (13) |
C2A | 0.019 (5) | 0.040 (6) | 0.028 (5) | 0.010 (4) | 0.008 (4) | 0.012 (4) |
N21A | 0.032 (5) | 0.061 (6) | 0.027 (5) | 0.021 (5) | 0.009 (4) | 0.010 (4) |
N3A | 0.021 (4) | 0.029 (4) | 0.018 (4) | 0.002 (3) | 0.002 (3) | 0.008 (3) |
N4A | 0.028 (5) | 0.036 (5) | 0.028 (4) | 0.002 (4) | 0.001 (4) | 0.005 (4) |
C5A | 0.028 (6) | 0.041 (6) | 0.038 (6) | 0.004 (5) | −0.005 (5) | 0.016 (5) |
C51A | 0.036 (6) | 0.062 (8) | 0.039 (7) | 0.011 (6) | −0.006 (5) | 0.019 (6) |
S1B | 0.0391 (16) | 0.0362 (15) | 0.0462 (17) | −0.0052 (12) | −0.0027 (13) | 0.0144 (13) |
C2B | 0.031 (6) | 0.032 (6) | 0.041 (6) | 0.004 (5) | 0.007 (5) | 0.011 (5) |
N21B | 0.067 (7) | 0.051 (6) | 0.030 (5) | −0.002 (5) | −0.010 (5) | 0.014 (5) |
N3B | 0.018 (4) | 0.019 (4) | 0.021 (4) | −0.002 (3) | −0.002 (3) | 0.002 (3) |
N4B | 0.029 (5) | 0.043 (5) | 0.039 (5) | −0.001 (4) | −0.002 (4) | 0.016 (4) |
C5B | 0.028 (6) | 0.045 (7) | 0.047 (7) | 0.010 (5) | 0.007 (5) | 0.018 (5) |
C51B | 0.051 (8) | 0.056 (8) | 0.044 (7) | 0.004 (6) | 0.008 (6) | 0.026 (6) |
Pt2 | 0.0301 (3) | 0.0348 (4) | 0.0236 (3) | 0.0018 (2) | 0.0036 (2) | 0.0057 (2) |
Cl1 | 0.0427 (15) | 0.0356 (14) | 0.0316 (14) | 0.0027 (11) | 0.0036 (12) | 0.0030 (11) |
Cl2 | 0.0462 (16) | 0.0462 (16) | 0.0262 (13) | −0.0011 (12) | 0.0021 (11) | 0.0100 (12) |
Cl3 | 0.0374 (15) | 0.0457 (16) | 0.0395 (15) | 0.0026 (12) | 0.0059 (12) | 0.0063 (13) |
O1 | 0.042 (5) | 0.092 (7) | 0.048 (5) | 0.010 (5) | −0.004 (4) | 0.040 (5) |
C2 | 0.045 (10) | 0.34 (4) | 0.20 (2) | 0.048 (16) | 0.041 (13) | 0.24 (3) |
N3 | 0.040 (6) | 0.073 (7) | 0.034 (5) | 0.013 (5) | 0.001 (4) | 0.027 (5) |
C4 | 0.17 (2) | 0.19 (3) | 0.060 (12) | −0.10 (2) | 0.031 (13) | −0.011 (14) |
C5 | 0.25 (4) | 0.088 (17) | 0.30 (4) | 0.07 (2) | 0.21 (3) | 0.08 (2) |
Geometric parameters (Å, º) top
Pt2—Cl1 | 2.320 (3) | C2B—N21B | 1.338 (14) |
Pt2—Cl2 | 2.317 (3) | N21B—H21B | 0.88 |
Pt2—Cl3 | 2.323 (3) | N21B—H22B | 0.88 |
Pt1—N3A | 2.019 (7) | N3B—N4B | 1.360 (11) |
Pt1—N3B | 2.037 (7) | N4B—C5B | 1.293 (15) |
S1A—C2A | 1.732 (9) | C5B—C51B | 1.493 (15) |
S1A—C5A | 1.736 (11) | C51B—H51B | 0.98 |
C2A—N3A | 1.305 (11) | C51B—H52B | 0.98 |
C2A—N21A | 1.315 (13) | C51B—H53B | 0.98 |
N21A—H21A | 0.88 | O1—C2 | 1.060 (18) |
N21A—H22A | 0.88 | C2—N3 | 1.238 (19) |
N3A—N4A | 1.406 (11) | C2—H2 | 0.95 |
N4A—C5A | 1.284 (13) | N3—C4 | 1.39 (2) |
C5A—C51A | 1.507 (15) | N3—C5 | 1.42 (2) |
C51A—H51A | 0.98 | C4—H41 | 0.98 |
C51A—H52A | 0.98 | C4—H42 | 0.98 |
C51A—H53A | 0.98 | C4—H43 | 0.98 |
S1B—C5B | 1.737 (13) | C5—H51 | 0.98 |
S1B—C2B | 1.748 (11) | C5—H52 | 0.98 |
C2B—N3B | 1.304 (13) | C5—H53 | 0.98 |
| | | |
N3A—Pt1—N3Ai | 180.0 (4) | N21B—C2B—S1B | 121.5 (9) |
N3A—Pt1—N3Bi | 90.2 (3) | C2B—N21B—H21B | 120.0 |
N3A—Pt1—N3B | 89.8 (3) | C2B—N21B—H22B | 120.0 |
N3Bi—Pt1—N3B | 180.0 (4) | H21B—N21B—H22B | 120.0 |
Cl1—Pt2—Cl1ii | 180.0 | C2B—N3B—N4B | 114.6 (8) |
Cl2ii—Pt2—Cl2 | 180.0 | C2B—N3B—Pt1 | 126.6 (7) |
Cl3—Pt2—Cl3ii | 180.0 | N4B—N3B—Pt1 | 118.7 (6) |
Cl2—Pt2—Cl1 | 90.87 (10) | C5B—N4B—N3B | 112.5 (9) |
Cl2—Pt2—Cl1ii | 89.13 (10) | N4B—C5B—C51B | 124.5 (11) |
Cl2—Pt2—Cl3 | 90.74 (10) | N4B—C5B—S1B | 113.9 (8) |
Cl1—Pt2—Cl3 | 90.66 (10) | C51B—C5B—S1B | 121.7 (9) |
Cl2—Pt2—Cl3ii | 89.26 (10) | C5B—C51B—H51B | 109.5 |
Cl1—Pt2—Cl3ii | 89.34 (10) | C5B—C51B—H52B | 109.5 |
C2A—S1A—C5A | 87.5 (5) | H51B—C51B—H52B | 109.5 |
N3A—C2A—N21A | 124.6 (8) | C5B—C51B—H53B | 109.5 |
N3A—C2A—S1A | 112.0 (7) | H51B—C51B—H53B | 109.5 |
N21A—C2A—S1A | 123.4 (7) | H52B—C51B—H53B | 109.5 |
C2A—N21A—H21A | 120.0 | O1—C2—N3 | 154 (3) |
C2A—N21A—H22A | 120.0 | O1—C2—H2 | 102.9 |
H21A—N21A—H22A | 120.0 | N3—C2—H2 | 102.9 |
C2A—N3A—N4A | 114.8 (7) | C2—N3—C4 | 124 (2) |
C2A—N3A—Pt1 | 126.8 (6) | C2—N3—C5 | 113 (2) |
N4A—N3A—Pt1 | 118.3 (5) | C4—N3—C5 | 123 (2) |
C5A—N4A—N3A | 110.2 (8) | N3—C4—H41 | 109.5 |
N4A—C5A—C51A | 122.6 (10) | N3—C4—H42 | 109.5 |
N4A—C5A—S1A | 115.4 (8) | H41—C4—H42 | 109.5 |
C51A—C5A—S1A | 122.0 (8) | N3—C4—H43 | 109.5 |
C5A—C51A—H51A | 109.5 | H41—C4—H43 | 109.5 |
C5A—C51A—H52A | 109.5 | H42—C4—H43 | 109.5 |
H51A—C51A—H52A | 109.5 | N3—C5—H51 | 109.5 |
C5A—C51A—H53A | 109.5 | N3—C5—H52 | 109.5 |
H51A—C51A—H53A | 109.5 | H51—C5—H52 | 109.5 |
H52A—C51A—H53A | 109.5 | N3—C5—H53 | 109.5 |
C5B—S1B—C2B | 87.0 (6) | H51—C5—H53 | 109.5 |
N3B—C2B—N21B | 126.7 (10) | H52—C5—H53 | 109.5 |
N3B—C2B—S1B | 111.8 (8) | | |
| | | |
C5A—S1A—C2A—N3A | 0.7 (8) | C5B—S1B—C2B—N21B | 177.4 (9) |
C5A—S1A—C2A—N21A | 177.8 (10) | N21B—C2B—N3B—N4B | −176.0 (10) |
N21A—C2A—N3A—N4A | −177.4 (10) | S1B—C2B—N3B—N4B | 4.5 (10) |
S1A—C2A—N3A—N4A | −0.3 (11) | N21B—C2B—N3B—Pt1 | 2.0 (15) |
N21A—C2A—N3A—Pt1 | 0.1 (15) | S1B—C2B—N3B—Pt1 | −177.5 (4) |
S1A—C2A—N3A—Pt1 | 177.3 (5) | N3A—Pt1—N3B—C2B | 72.9 (8) |
N3Bi—Pt1—N3A—C2A | −89.5 (9) | N3Ai—Pt1—N3B—C2B | −107.1 (8) |
N3B—Pt1—N3A—C2A | 90.5 (9) | N3A—Pt1—N3B—N4B | −109.1 (6) |
N3Bi—Pt1—N3A—N4A | 88.0 (7) | N3Ai—Pt1—N3B—N4B | 70.9 (6) |
N3B—Pt1—N3A—N4A | −92.0 (7) | C2B—N3B—N4B—C5B | −3.8 (11) |
C2A—N3A—N4A—C5A | −0.4 (12) | Pt1—N3B—N4B—C5B | 178.0 (7) |
Pt1—N3A—N4A—C5A | −178.2 (7) | N3B—N4B—C5B—C51B | −178.2 (9) |
N3A—N4A—C5A—C51A | −179.3 (10) | N3B—N4B—C5B—S1B | 1.2 (11) |
N3A—N4A—C5A—S1A | 0.9 (12) | C2B—S1B—C5B—N4B | 1.0 (8) |
C2A—S1A—C5A—N4A | −0.9 (9) | C2B—S1B—C5B—C51B | −179.6 (9) |
C2A—S1A—C5A—C51A | 179.3 (10) | O1—C2—N3—C4 | −11 (5) |
C5B—S1B—C2B—N3B | −3.1 (8) | O1—C2—N3—C5 | 173 (4) |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y−1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1 | 0.88 | 1.98 | 2.816 (12) | 158 |
N21A—H22A···Cl1iii | 0.88 | 2.62 | 3.389 (9) | 146 |
N21A—H22A···Cl3iv | 0.88 | 2.72 | 3.430 (10) | 139 |
N21B—H21B···O1i | 0.88 | 2.04 | 2.849 (14) | 153 |
N21B—H22B···Cl2v | 0.88 | 2.61 | 3.399 (12) | 150 |
N21B—H22B···Cl3vi | 0.88 | 2.82 | 3.516 (10) | 137 |
N21B—H22B···Cl1vi | 0.88 | 2.91 | 3.341 (10) | 112 |
C4—H41···Cl1vii | 0.98 | 2.82 | 3.44 (2) | 122 |
Symmetry codes: (i) −x+1, −y, −z; (iii) −x, −y, −z+1; (iv) x, y+1, z; (v) −x, −y−1, −z; (vi) x, y, z−1; (vii) −x+1, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [PtCl2(C7H5N3O2S)2]·4C3H7NO | [Pt(C3H5N3S)4][PtCl6]·2C3H7NO |
Mr | 948.77 | 604.86 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 11.137 (2), 12.671 (3), 14.409 (3) | 9.0397 (4), 9.3009 (4), 11.5241 (5) |
α, β, γ (°) | 64.28 (3), 85.77 (3), 78.28 (3) | 109.027 (2), 91.850 (3), 91.785 (3) |
V (Å3) | 1793.4 (6) | 914.61 (7) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 4.24 | 8.35 |
Crystal size (mm) | 0.28 × 0.08 × 0.05 | 0.08 × 0.03 × 0.01 |
|
Data collection |
Diffractometer | Enraf-Nonius KappaCCD area-detector diffractometer | Enraf-Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.389, 0.816 | 0.573, 0.921 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29010, 8177, 7229 | 6735, 3838, 2804 |
Rint | 0.066 | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.094, 1.04 | 0.048, 0.135, 1.07 |
No. of reflections | 8177 | 3838 |
No. of parameters | 451 | 216 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.45, −2.61 | 2.38, −2.59 |
Selected geometric parameters (Å, º) for (I) topPt1—Cl1 | 2.2935 (14) | Pt1—N3A | 2.015 (3) |
Pt1—Cl2 | 2.3031 (13) | Pt1—N3B | 2.023 (3) |
| | | |
N3A—Pt1—N3B | 178.80 (11) | C9A—N3A—Pt1 | 123.2 (3) |
Cl1—Pt1—Cl2 | 177.75 (3) | C2B—N3B—Pt1 | 124.8 (3) |
C2A—N3A—Pt1 | 125.5 (3) | C9B—N3B—Pt1 | 124.0 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1i | 0.88 | 1.98 | 2.778 (5) | 150 |
N21A—H22A···O11i | 0.88 | 1.89 | 2.765 (6) | 175 |
N21B—H21B···O1i | 0.88 | 2.00 | 2.804 (5) | 151 |
N21B—H22B···O6ii | 0.88 | 1.94 | 2.794 (5) | 164 |
C7A—H7A···O16iii | 0.95 | 2.47 | 3.212 (6) | 135 |
C17—H17···O62Biv | 0.95 | 2.54 | 3.455 (6) | 162 |
C4—H43···O1v | 0.98 | 2.47 | 3.416 (7) | 163 |
C5—H51···O61Avi | 0.98 | 2.49 | 3.050 (6) | 116 |
C9—H93···O6 | 0.98 | 2.37 | 2.766 (6) | 104 |
C14—H141···O11 | 0.98 | 2.33 | 2.738 (8) | 104 |
C15—H153···Cl1vii | 0.98 | 2.75 | 3.675 (5) | 158 |
C20—H203···O62Aviii | 0.98 | 2.43 | 3.271 (7) | 144 |
Symmetry codes: (i) −x, −y+1, −z; (ii) x−1, y, z; (iii) −x, −y, −z; (iv) x, y+1, z; (v) −x+1, −y+2, −z; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z; (viii) x+1, y+1, z+1. |
Selected bond lengths (Å) for (II) topPt2—Cl1 | 2.320 (3) | Pt1—N3A | 2.019 (7) |
Pt2—Cl2 | 2.317 (3) | Pt1—N3B | 2.037 (7) |
Pt2—Cl3 | 2.323 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21A—H21A···O1 | 0.88 | 1.98 | 2.816 (12) | 158 |
N21A—H22A···Cl1i | 0.88 | 2.62 | 3.389 (9) | 146 |
N21A—H22A···Cl3ii | 0.88 | 2.72 | 3.430 (10) | 139 |
N21B—H21B···O1iii | 0.88 | 2.04 | 2.849 (14) | 153 |
N21B—H22B···Cl2iv | 0.88 | 2.61 | 3.399 (12) | 150 |
N21B—H22B···Cl3v | 0.88 | 2.82 | 3.516 (10) | 137 |
N21B—H22B···Cl1v | 0.88 | 2.91 | 3.341 (10) | 112 |
C4—H41···Cl1vi | 0.98 | 2.82 | 3.44 (2) | 122 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, −y, −z; (iv) −x, −y−1, −z; (v) x, y, z−1; (vi) −x+1, −y, −z+1. |
The structures of many metal complexes of 2-amino-1,3-thiazole derivatives, where the metal is directly bound to the ligand, are known and include most of the d-block transition metal first row (i.e. Mn–Zn), plus a few other metals (such as Mo, Hg and Cd). In all but a few of these cases, the thiazoles bind to the metal via N3. Our current interest in studying the hydrogen-bonding features of 2-amino-1,3-thiazoles has led us to investigate such aspects in their metal complexes, especially when the main hydrogen-bond acceptor atom (N3) is bound to the metal. Interestingly, a Cambridge Structural Database (CSD) search (Fletcher et al., 1996) reveals that there are 13 reported single-crystal structures of 1,3-thiazole complexes with Pt, but none for any 2-amino (i.e. NH2) analogues. However, by mixing chloroplatinic acid with a series of thiazole derivatives we expected to produce [bis(thiazolium)]2+[PtCl6]2-. Several similar complexes of this type with 2-amino-1,3-thiazole derivatives are known and include anions such as [CuCl4]2- (Fernandez et al., 1996), [ZnCl4]2- (Kubiak & Glowiak, 1984), [Cd4Cl11]4-, [BiI4]-, [Bi2Br10]4- and [Sb4Br16]4-. In each of these complexes, N—H···Cl interactions dominate the hydrogen-bond network. Instead, our syntheses yielded (I) and (II), which have Pt coordination to N3 but also contain solvent N,N'-dimethylformamide (DMF) molecules that are intricately involved via hydrogen-bond interactions.
The structures of (I) and (II) both contain square-planar PtII complexes, which is interesting because the Pt from the starting material has undergone reductive elimination. Selected Pt bonds are listed in Table 1, while hydrogen-bond geometries are given in Table 2. In (I), the organic ligands are trans across the Pt atom but oriented in the same direction; the charge (and coordination) being balanced by two bound Cl atoms (Fig. 1). The thiazoles are essentially coplanar [dihedral angle 4.5 (1)°] and are involved with three of the four DMF molecules in strong N—H···O hydrogen-bonding associations from the 2-amino groups (Fig. 2). This packing arrangement may explain the specific orientation of the two thiazoles. Several C—H···O short contacts are also listed in Table 2, with the majority of C—H donors being from the N-methyl groups on the DMF molecules.
Complex (II) has one PtII cation species surrounded by four N-bound organic ligands and one PtCl62- anion to balance the charge (Fig. 3). Again, the Pt complex has undergone formal reductive elimination, although it is interesting to encounter a mixed-valence system. The cation has two symmetry-unique thiazoles [dihedral angle 89.9 (8)°], whereas the anion has three crystallographically unique Cl atoms; both Pt centres reside on inversion centres. Complex (II) contains only one DMF molecule and this is involved in hydrogen-bonding associations although the majority of hydrogen-bonding interactions from the 2-amino H atoms use the chlorides as acceptors (Fig. 4). The DMF molecules neatly reside between the inner-facing 2-amino H atoms; the outer-facing H atoms both associate via three-centre interactions to adjacent Cl atoms. The N-attachment of the organic ligands in complexes (I) and (II) leaves an outer-facing S atom that is susceptible to close contact from another large atom. In (I), S1B is 3.649 (5) Å from a related atom (i.e. S1B at -x, -y, -z) and is also 3.459 (5) Å from Cl1(-x, -y, -z). S1A is 3.050 (5) Å from O16(-x, -y, -z), while S1B is 3.273 (5) Å from O6(-1 + x, y, z). In (II), S1A has the greater number of close contacts and is 3.78 (1) Å from S1B(-x, -y, -z), 3.62 (1) Å from Cl1(-x, -y, 1 - z), and 3.58 (1) Å from Cl2(x, -1 - y, z), while S1B is 3.54 (1) Å from Cl2(-x, -1 - y, -z). In both structures, the distances between the closest DMF O atom and the organic-bound Pt atom are 3.766 (5) Å (symmetry code: -x, 1 - y, -z) for (I) and 3.55 (1) Å (symmetry code: 1 - x, -y, -z) for (II).