Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199013803/fr1238sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199013803/fr1238Isup2.sft | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199013803/fr1238IIsup3.sft |
CCDC references: 140946; 140947
For (I), a solution of cis-bis(dimethyl sulfoxide)(1,1-cyclobutanedicarboxylato)platinum(II) (0.502 g, 0.95 mmol) and 3,6-dihydro-1,2-oxazinium chloride (0.239 g, 1.95 mmol) in water (30 ml) was stirred at room temperature for 0.5 h. The yellow crystals which formed were collected by filtration, washed with several portions of distilled water, and dried at 323 K and 2666.45 Pa to provide cis-dichloro(3,6-dihydro-1,2-oxazine-N)(dimethyl sulfoxide-S)platinum(II) (0.269 g). For (II), to a stirred solution of cis-bis(dimethyl sulfoxide)(1,1-cyclobutanedicarboxylato)platinum(II) (0.314 g, 0.60 mmol) in water (20 ml) was added, dropwise, a solution of 3,6-dihydro-1,2-oxazine (0.149 g, 1.23 mmol) in water (5.0 ml) (pH adjusted to 4.0 with aqueous hydrochloric acid solution). The resulting solution was stirred at 328 K for 2 h and then allowed to stand at room temperature for 2 d. The volume of solution was reduced by rotary evaporation of the solvent at reduced pressure. The solid product was collected, washed repeatedly with distilled water, and dried at 323 K and 2666.45 Pa to provide trans-dichloro(3,6-dihydro-1,2-oxazine-N)(dimethyl sulfoxide-S)platinum(II) (0.167 g).
The minimum and maximum points on the final difference electron-density map were 1.03 and 1.27 Å, respectively, from the Pt atom. The minimum and maximum peaks in the final difference electron-density map were 1.02 Å from Pt and 1.63 Å from H9, respectively.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1991); program(s) used to solve structure: MITHRIL (Gilmore, 1983); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
[PtCl2(C4H7NO)(C2H6OS)] | Z = 2 |
Mr = 429.23 | F(000) = 400 |
Triclinic, P1 | Dx = 2.403 Mg m−3 |
a = 8.177 (4) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 8.517 (4) Å | Cell parameters from 22 reflections |
c = 10.297 (4) Å | θ = 20.6–22.4° |
α = 105.84 (3)° | µ = 12.6 mm−1 |
β = 104.42 (3)° | T = 296 K |
γ = 111.16 (3)° | Slab, pale yellow |
V = 593.2 (5) Å3 | 0.25 × 0.12 × 0.10 mm |
Rigaku AFC6S diffractometer | 1820 reflections with I > 3σ(I) |
Radiation source: X-ray tube | Rint = 0.013 |
Graphite monochromator | θmax = 25.0° |
ω–2θ scans | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→9 |
Tmin = 0.190, Tmax = 0.284 | l = −12→11 |
2249 measured reflections | 3 standard reflections every 150 reflections |
2089 independent reflections | intensity decay: 2.3% |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters not refined |
wR(F2) = 0.059 | Weighting scheme based on measured s.u.'s w = 4Fo2/σ2(Fo2) |
S = 2.23 | (Δ/σ)max = 0.001 |
2087 reflections | Δρmax = 0.73 e Å−3 |
118 parameters | Δρmin = −1.75 e Å−3 |
[PtCl2(C4H7NO)(C2H6OS)] | γ = 111.16 (3)° |
Mr = 429.23 | V = 593.2 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.177 (4) Å | Mo Kα radiation |
b = 8.517 (4) Å | µ = 12.6 mm−1 |
c = 10.297 (4) Å | T = 296 K |
α = 105.84 (3)° | 0.25 × 0.12 × 0.10 mm |
β = 104.42 (3)° |
Rigaku AFC6S diffractometer | 1820 reflections with I > 3σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.190, Tmax = 0.284 | 3 standard reflections every 150 reflections |
2249 measured reflections | intensity decay: 2.3% |
2089 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters not refined |
S = 2.23 | Δρmax = 0.73 e Å−3 |
2087 reflections | Δρmin = −1.75 e Å−3 |
118 parameters |
Refinement. The minimum and maximum points on the final difference electron density map were 1.03 and 1.27 Å, respectively, from the Pt atom. H atoms were located on difference electron-density maps and their positions idealized (X—H 0.95 Å) with Biso values set at 1.2 times Beq of the attached atom at the time of their inclusion. |
x | y | z | Uiso*/Ueq | ||
Pt | 0.24440 (5) | 0.21118 (4) | 0.24855 (3) | 0.03340 (9) | |
Cl1 | 0.2700 (4) | 0.0318 (3) | 0.3774 (3) | 0.0608 (8) | |
Cl2 | 0.3838 (3) | 0.0909 (3) | 0.1045 (3) | 0.0513 (7) | |
S | 0.1078 (3) | 0.3257 (3) | 0.3807 (2) | 0.0384 (6) | |
O1 | 0.4130 (7) | 0.5031 (7) | 0.1580 (6) | 0.049 (2) | |
O2 | 0.0728 (8) | 0.4734 (8) | 0.3483 (6) | 0.049 (2) | |
N | 0.2241 (9) | 0.3738 (8) | 0.1355 (7) | 0.037 (2) | |
C1 | 0.405 (1) | 0.651 (1) | 0.1163 (10) | 0.052 (3) | |
C2 | 0.255 (1) | 0.580 (1) | −0.0310 (10) | 0.048 (3) | |
C3 | 0.122 (1) | 0.408 (1) | −0.0957 (9) | 0.045 (3) | |
C4 | 0.104 (1) | 0.279 (1) | −0.0232 (8) | 0.042 (2) | |
C5 | −0.112 (1) | 0.153 (1) | 0.358 (1) | 0.060 (3) | |
C6 | 0.244 (1) | 0.412 (1) | 0.5716 (9) | 0.061 (3) | |
H1 | 0.1700 | 0.4447 | 0.1787 | 0.0448 | |
H2 | 0.3788 | 0.7272 | 0.1861 | 0.0627 | |
H3 | 0.5246 | 0.7223 | 0.1153 | 0.0627 | |
H4 | 0.2550 | 0.6598 | −0.0795 | 0.0576 | |
H5 | 0.0334 | 0.3650 | −0.1927 | 0.0543 | |
H6 | −0.0247 | 0.2163 | −0.0357 | 0.0509 | |
H7 | 0.1424 | 0.1921 | −0.0674 | 0.0509 | |
H8 | −0.1603 | 0.2040 | 0.4242 | 0.0716 | |
H9 | −0.0940 | 0.0561 | 0.3769 | 0.0716 | |
H10 | −0.2010 | 0.1057 | 0.2603 | 0.0716 | |
H11 | 0.3500 | 0.5275 | 0.6014 | 0.0735 | |
H12 | 0.2880 | 0.3277 | 0.5904 | 0.0735 | |
H13 | 0.1671 | 0.4256 | 0.6249 | 0.0735 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.0378 (2) | 0.0339 (2) | 0.0299 (2) | 0.0156 (1) | 0.0139 (1) | 0.0153 (1) |
Cl1 | 0.091 (2) | 0.061 (1) | 0.055 (1) | 0.045 (1) | 0.032 (1) | 0.039 (1) |
Cl2 | 0.060 (1) | 0.049 (1) | 0.064 (2) | 0.032 (1) | 0.039 (1) | 0.027 (1) |
S | 0.041 (1) | 0.050 (1) | 0.027 (1) | 0.021 (1) | 0.0143 (10) | 0.0187 (10) |
O1 | 0.035 (3) | 0.047 (3) | 0.050 (4) | 0.007 (3) | 0.007 (3) | 0.025 (3) |
O2 | 0.071 (4) | 0.062 (4) | 0.046 (4) | 0.046 (3) | 0.033 (3) | 0.036 (3) |
N | 0.042 (4) | 0.044 (4) | 0.031 (4) | 0.020 (3) | 0.017 (3) | 0.020 (3) |
C1 | 0.052 (6) | 0.045 (5) | 0.058 (6) | 0.015 (4) | 0.018 (5) | 0.030 (5) |
C2 | 0.052 (6) | 0.056 (6) | 0.051 (6) | 0.025 (5) | 0.028 (5) | 0.036 (5) |
C3 | 0.056 (6) | 0.061 (6) | 0.033 (5) | 0.031 (5) | 0.023 (4) | 0.028 (4) |
C4 | 0.041 (5) | 0.040 (5) | 0.032 (5) | 0.011 (4) | 0.007 (4) | 0.011 (4) |
C5 | 0.052 (6) | 0.065 (6) | 0.062 (6) | 0.020 (5) | 0.029 (5) | 0.029 (5) |
C6 | 0.066 (6) | 0.087 (7) | 0.020 (4) | 0.040 (6) | 0.009 (4) | 0.007 (4) |
Pt—Cl1 | 2.310 (2) | N—H1 | 0.95 |
Pt—Cl2 | 2.325 (2) | C1—H2 | 0.95 |
Pt—S | 2.207 (2) | C1—H3 | 0.95 |
Pt—N | 2.062 (6) | C2—H4 | 0.95 |
S—O2 | 1.489 (5) | C3—H5 | 0.95 |
S—C5 | 1.776 (9) | C4—H6 | 0.95 |
S—C6 | 1.783 (8) | C4—H7 | 0.95 |
O1—N | 1.452 (7) | C5—H8 | 0.95 |
O1—C1 | 1.458 (9) | C5—H9 | 0.95 |
N—C4 | 1.480 (9) | C5—H10 | 0.95 |
C1—C2 | 1.49 (1) | C6—H11 | 0.95 |
C2—C3 | 1.32 (1) | C6—H12 | 0.95 |
C3—C4 | 1.47 (1) | C6—H13 | 0.95 |
Cl1—Pt—Cl2 | 90.07 (8) | C2—C1—H2 | 109 |
Cl1—Pt—S | 91.08 (8) | C2—C1—H3 | 109 |
Cl1—Pt—N | 179.4 (2) | H2—C1—H3 | 109 |
Cl2—Pt—S | 178.61 (8) | C1—C2—H4 | 119 |
Cl2—Pt—N | 90.1 (2) | C3—C2—H4 | 119 |
S—Pt—N | 88.8 (2) | C2—C3—H5 | 119 |
Pt—S—O2 | 113.8 (2) | C4—C3—H5 | 119 |
Pt—S—C5 | 111.7 (3) | N—C4—H6 | 109 |
Pt—S—C6 | 111.2 (3) | N—C4—H7 | 109 |
O2—S—C5 | 107.9 (4) | C3—C4—H6 | 109 |
O2—S—C6 | 108.9 (4) | C3—C4—H7 | 109 |
C5—S—C6 | 102.7 (4) | H6—C4—H7 | 109 |
N—O1—C1 | 110.2 (5) | S—C5—H8 | 109 |
Pt—N—O1 | 109.8 (4) | S—C5—H9 | 109 |
Pt—N—C4 | 117.1 (5) | S—C5—H10 | 109 |
O1—N—C4 | 109.4 (5) | H8—C5—H9 | 109 |
O1—C1—C2 | 111.6 (7) | H8—C5—H10 | 109 |
C1—C2—C3 | 121.5 (8) | H9—C5—H10 | 109 |
C2—C3—C4 | 122.3 (8) | S—C6—H11 | 110 |
N—C4—C3 | 112.1 (6) | S—C6—H12 | 110 |
Pt—N—H1 | 107 | S—C6—H13 | 110 |
O1—N—H1 | 107 | H11—C6—H12 | 109 |
C4—N—H1 | 107 | H11—C6—H13 | 109 |
O1—C1—H2 | 109 | H12—C6—H13 | 109 |
O1—C1—H3 | 109 | ||
Pt—N—O1—C1 | −163.4 (5) | O1—N—C4—C3 | −46.4 (8) |
Pt—N—C4—C3 | −172.1 (5) | O1—C1—C2—C3 | 15 (1) |
Cl1—Pt—S—O2 | 174.8 (3) | O2—S—Pt—N | −4.6 (3) |
Cl1—Pt—S—C5 | −62.6 (4) | N—Pt—S—C5 | 118.0 (4) |
Cl1—Pt—S—C6 | 51.4 (4) | N—Pt—S—C6 | −128.0 (4) |
Cl2—Pt—N—O1 | −63.3 (4) | N—O1—C1—C2 | −49.6 (8) |
Cl2—Pt—N—C4 | 62.2 (5) | N—C4—C3—C2 | 12 (1) |
S—Pt—N—O1 | 117.5 (4) | C1—O1—N—C4 | 66.8 (7) |
S—Pt—N—C4 | −117.0 (5) | C1—C2—C3—C4 | 4 (1) |
[PtCl2(C4H7NO)(C2H6OS)] | Dx = 2.442 Mg m−3 |
Mr = 429.23 | Mo Kα radiation, λ = 0.7107 Å |
Orthorhombic, Pbca | Cell parameters from 20 reflections |
a = 16.532 (3) Å | θ = 15.5–20.3° |
b = 13.868 (2) Å | µ = 12.8 mm−1 |
c = 10.182 (4) Å | T = 296 K |
V = 2334 (1) Å3 | Hexagonal plate, pale yellow |
Z = 8 | 0.30 × 0.10 × 0.03 mm |
F(000) = 1600 |
Rigaku AFC6S diffractometer | 1277 reflections with I > 3σ(I) |
Radiation source: X-ray tube | Rint = 0.00 |
Graphite monochromator | θmax = 25.0° |
ω–2θ scans | h = 0→19 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→16 |
Tmin = 0.242, Tmax = 0.681 | l = −12→0 |
2053 measured reflections | 3 standard reflections every 150 reflections |
2053 independent reflections | intensity decay: −0.1% |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.032 | Weighting scheme based on measured s.u.'s w = 4Fo2/σ2(Fo2) |
wR(F2) = 0.074 | (Δ/σ)max = 0.001 |
S = 1.71 | Δρmax = 1.95 e Å−3 |
2049 reflections | Δρmin = −2.09 e Å−3 |
119 parameters | Extinction correction: Zachariasen (1968) type 2 Gaussian isotropic |
0 restraints | Extinction coefficient: 0.00000010 (5) |
[PtCl2(C4H7NO)(C2H6OS)] | V = 2334 (1) Å3 |
Mr = 429.23 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 16.532 (3) Å | µ = 12.8 mm−1 |
b = 13.868 (2) Å | T = 296 K |
c = 10.182 (4) Å | 0.30 × 0.10 × 0.03 mm |
Rigaku AFC6S diffractometer | 1277 reflections with I > 3σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.00 |
Tmin = 0.242, Tmax = 0.681 | 3 standard reflections every 150 reflections |
2053 measured reflections | intensity decay: −0.1% |
2053 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters not refined |
S = 1.71 | Δρmax = 1.95 e Å−3 |
2049 reflections | Δρmin = −2.09 e Å−3 |
119 parameters |
Refinement. The minimum and maximum peaks in the final difference map were 1.02 Å from Pt and 1.63 Å from H9, respectively. H atoms were located on difference electron-density maps and their positions idealized (X—H 0.95 Å) with Biso values set at 1.2 times Beq of the attached atom at the time of their inclusion. |
x | y | z | Uiso*/Ueq | ||
Pt | 0.04257 (3) | 0.07117 (3) | 0.72831 (4) | 0.0280 (1) | |
Cl1 | 0.1433 (2) | 0.1845 (2) | 0.7486 (4) | 0.0478 (10) | |
Cl2 | −0.0533 (2) | −0.0483 (2) | 0.7217 (4) | 0.0457 (9) | |
S | −0.0391 (2) | 0.1812 (2) | 0.6393 (3) | 0.0358 (9) | |
O1 | 0.1921 (5) | −0.0372 (5) | 0.7407 (10) | 0.040 (2) | |
O2 | −0.0767 (5) | 0.2498 (5) | 0.7326 (9) | 0.046 (2) | |
N | 0.1173 (6) | −0.0308 (6) | 0.8133 (10) | 0.035 (3) | |
C1 | 0.2384 (8) | −0.1211 (8) | 0.779 (1) | 0.046 (4) | |
C2 | 0.2459 (9) | −0.1305 (9) | 0.922 (2) | 0.053 (5) | |
C3 | 0.2007 (9) | −0.081 (1) | 1.006 (1) | 0.056 (5) | |
C4 | 0.1360 (10) | −0.0145 (9) | 0.954 (1) | 0.047 (4) | |
C5 | −0.118 (1) | 0.1284 (9) | 0.542 (1) | 0.061 (5) | |
C6 | 0.0137 (9) | 0.249 (1) | 0.518 (2) | 0.064 (5) | |
H1 | 0.0909 | −0.0914 | 0.8066 | 0.0419 | |
H2 | 0.2911 | −0.1161 | 0.7418 | 0.0551 | |
H3 | 0.2124 | −0.1770 | 0.7452 | 0.0551 | |
H4 | 0.2850 | −0.1740 | 0.9555 | 0.0630 | |
H5 | 0.2091 | −0.0875 | 1.0976 | 0.0669 | |
H6 | 0.1537 | 0.0502 | 0.9643 | 0.0572 | |
H7 | 0.0880 | −0.0243 | 1.0034 | 0.0572 | |
H8 | −0.0952 | 0.0785 | 0.4895 | 0.0728 | |
H9 | −0.1578 | 0.1025 | 0.5982 | 0.0728 | |
H10 | −0.1406 | 0.1764 | 0.4873 | 0.0728 | |
H11 | −0.0242 | 0.2816 | 0.4636 | 0.0766 | |
H12 | 0.0480 | 0.2944 | 0.5593 | 0.0766 | |
H13 | 0.0453 | 0.2063 | 0.4655 | 0.0766 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.0253 (3) | 0.0279 (2) | 0.0308 (3) | 0.0011 (2) | 0.0000 (3) | −0.0041 (2) |
Cl1 | 0.035 (2) | 0.035 (1) | 0.072 (3) | −0.009 (1) | −0.004 (2) | −0.003 (2) |
Cl2 | 0.030 (2) | 0.038 (2) | 0.069 (2) | −0.005 (1) | −0.003 (2) | 0.001 (2) |
S | 0.038 (2) | 0.033 (1) | 0.036 (2) | 0.006 (2) | −0.006 (2) | −0.006 (1) |
O1 | 0.029 (5) | 0.036 (4) | 0.053 (6) | 0.008 (4) | 0.004 (5) | 0.006 (5) |
O2 | 0.054 (5) | 0.046 (4) | 0.038 (5) | 0.013 (4) | −0.016 (5) | −0.007 (4) |
N | 0.023 (6) | 0.034 (5) | 0.047 (7) | 0.002 (5) | −0.006 (6) | 0.000 (5) |
C1 | 0.025 (7) | 0.041 (7) | 0.07 (1) | 0.008 (6) | 0.002 (9) | 0.006 (8) |
C2 | 0.042 (10) | 0.046 (9) | 0.07 (1) | 0.001 (8) | −0.012 (10) | 0.000 (8) |
C3 | 0.06 (1) | 0.063 (9) | 0.049 (9) | −0.011 (9) | −0.019 (8) | 0.004 (9) |
C4 | 0.06 (1) | 0.059 (8) | 0.023 (8) | 0.001 (8) | 0.004 (8) | −0.003 (7) |
C5 | 0.06 (1) | 0.051 (8) | 0.07 (1) | −0.001 (8) | −0.037 (10) | 0.006 (8) |
C6 | 0.08 (1) | 0.055 (7) | 0.052 (9) | 0.00 (1) | 0.00 (1) | 0.017 (7) |
Pt—Cl1 | 2.300 (3) | N—H1 | 0.95 |
Pt—Cl2 | 2.294 (3) | C1—H2 | 0.95 |
Pt—S | 2.230 (3) | C1—H3 | 0.95 |
Pt—N | 2.067 (9) | C2—H4 | 0.95 |
S—O2 | 1.480 (8) | C3—H5 | 0.95 |
S—C5 | 1.79 (1) | C4—H6 | 0.95 |
S—C6 | 1.78 (1) | C4—H7 | 0.95 |
O1—N | 1.44 (1) | C5—H8 | 0.95 |
O1—C1 | 1.44 (1) | C5—H9 | 0.95 |
N—C4 | 1.48 (1) | C5—H10 | 0.95 |
C1—C2 | 1.47 (2) | C6—H11 | 0.95 |
C2—C3 | 1.33 (2) | C6—H12 | 0.95 |
C3—C4 | 1.51 (2) | C6—H13 | 0.95 |
Cl1—Pt—Cl2 | 175.5 (1) | C2—C1—H2 | 109 |
Cl1—Pt—S | 90.4 (1) | C2—C1—H3 | 109 |
Cl1—Pt—N | 89.8 (3) | H2—C1—H3 | 109 |
Cl2—Pt—S | 93.7 (1) | C1—C2—H4 | 118 |
Cl2—Pt—N | 86.1 (3) | C3—C2—H4 | 118 |
S—Pt—N | 179.1 (3) | C2—C3—H5 | 120 |
Pt—S—O2 | 115.7 (4) | C4—C3—H5 | 120 |
Pt—S—C5 | 112.5 (4) | N—C4—H6 | 108 |
Pt—S—C6 | 110.2 (5) | N—C4—H7 | 108 |
O2—S—C5 | 108.2 (6) | C3—C4—H6 | 109 |
O2—S—C6 | 108.3 (6) | C3—C4—H7 | 109 |
C5—S—C6 | 100.8 (7) | H6—C4—H7 | 109 |
N—O1—C1 | 111.5 (9) | S—C5—H8 | 109 |
Pt—N—O1 | 109.9 (6) | S—C5—H9 | 109 |
Pt—N—C4 | 115.2 (8) | S—C5—H10 | 109 |
O1—N—C4 | 109 (1) | H8—C5—H9 | 110 |
O1—C1—C2 | 112 (1) | H8—C5—H10 | 109 |
C1—C2—C3 | 123 (1) | H9—C5—H10 | 110 |
C2—C3—C4 | 119 (1) | S—C6—H11 | 109 |
N—C4—C3 | 113 (1) | S—C6—H12 | 109 |
Pt—N—H1 | 107 | S—C6—H13 | 109 |
O1—N—H1 | 108 | H11—C6—H12 | 110 |
C4—N—H1 | 107 | H11—C6—H13 | 109 |
O1—C1—H2 | 109 | H12—C6—H13 | 110 |
O1—C1—H3 | 109 | ||
Pt—N—O1—C1 | −167.5 (7) | Cl2—Pt—S—C6 | −136.2 (6) |
Pt—N—C4—C3 | −170.9 (9) | Cl2—Pt—N—O1 | 126.3 (6) |
Cl1—Pt—S—O2 | −77.5 (4) | Cl2—Pt—N—C4 | −110.2 (9) |
Cl1—Pt—S—C5 | 157.4 (6) | O1—N—C4—C3 | −47 (1) |
Cl1—Pt—S—C6 | 45.8 (6) | O1—C1—C2—C3 | 14 (2) |
Cl1—Pt—N—O1 | −55.6 (6) | N—O1—C1—C2 | −48 (1) |
Cl1—Pt—N—C4 | 67.9 (9) | N—C4—C3—C2 | 14 (2) |
Cl2—Pt—S—O2 | 100.5 (4) | C1—O1—N—C4 | 65 (1) |
Cl2—Pt—S—C5 | −24.6 (6) | C1—C2—C3—C4 | 2 (2) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [PtCl2(C4H7NO)(C2H6OS)] | [PtCl2(C4H7NO)(C2H6OS)] |
Mr | 429.23 | 429.23 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 8.177 (4), 8.517 (4), 10.297 (4) | 16.532 (3), 13.868 (2), 10.182 (4) |
α, β, γ (°) | 105.84 (3), 104.42 (3), 111.16 (3) | 90, 90, 90 |
V (Å3) | 593.2 (5) | 2334 (1) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 12.6 | 12.8 |
Crystal size (mm) | 0.25 × 0.12 × 0.10 | 0.30 × 0.10 × 0.03 |
Data collection | ||
Diffractometer | Rigaku AFC6S diffractometer | Rigaku AFC6S diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.190, 0.284 | 0.242, 0.681 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 2249, 2089, 1820 | 2053, 2053, 1277 |
Rint | 0.013 | 0.00 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.059, 2.23 | 0.032, 0.074, 1.71 |
No. of reflections | 2087 | 2049 |
No. of parameters | 118 | 119 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.73, −1.75 | 1.95, −2.09 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1991), MITHRIL (Gilmore, 1983), TEXSAN, ORTEPII (Johnson, 1976).
Pt—Cl1 | 2.310 (2) | O1—N | 1.452 (7) |
Pt—Cl2 | 2.325 (2) | O1—C1 | 1.458 (9) |
Pt—S | 2.207 (2) | N—C4 | 1.480 (9) |
Pt—N | 2.062 (6) | C1—C2 | 1.49 (1) |
S—O2 | 1.489 (5) | C2—C3 | 1.32 (1) |
S—C5 | 1.776 (9) | C3—C4 | 1.47 (1) |
S—C6 | 1.783 (8) | ||
Cl1—Pt—Cl2 | 90.07 (8) | Pt—S—C6 | 111.2 (3) |
Cl1—Pt—S | 91.08 (8) | O2—S—C5 | 107.9 (4) |
Cl1—Pt—N | 179.4 (2) | O2—S—C6 | 108.9 (4) |
Cl2—Pt—S | 178.61 (8) | C5—S—C6 | 102.7 (4) |
Cl2—Pt—N | 90.1 (2) | N—O1—C1 | 110.2 (5) |
S—Pt—N | 88.8 (2) | Pt—N—O1 | 109.8 (4) |
Pt—S—O2 | 113.8 (2) | Pt—N—C4 | 117.1 (5) |
Pt—S—C5 | 111.7 (3) | O1—N—C4 | 109.4 (5) |
Pt—Cl1 | 2.300 (3) | O1—N | 1.44 (1) |
Pt—Cl2 | 2.294 (3) | O1—C1 | 1.44 (1) |
Pt—S | 2.230 (3) | N—C4 | 1.48 (1) |
Pt—N | 2.067 (9) | C1—C2 | 1.47 (2) |
S—O2 | 1.480 (8) | C2—C3 | 1.33 (2) |
S—C5 | 1.79 (1) | C3—C4 | 1.51 (2) |
S—C6 | 1.78 (1) | ||
Cl1—Pt—Cl2 | 175.5 (1) | Pt—S—C6 | 110.2 (5) |
Cl1—Pt—S | 90.4 (1) | O2—S—C5 | 108.2 (6) |
Cl1—Pt—N | 89.8 (3) | O2—S—C6 | 108.3 (6) |
Cl2—Pt—S | 93.7 (1) | C5—S—C6 | 100.8 (7) |
Cl2—Pt—N | 86.1 (3) | N—O1—C1 | 111.5 (9) |
S—Pt—N | 179.1 (3) | Pt—N—O1 | 109.9 (6) |
Pt—S—O2 | 115.7 (4) | Pt—N—C4 | 115.2 (8) |
Pt—S—C5 | 112.5 (4) | O1—N—C4 | 109 (1) |
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Since the discovery of the antitumor activity of cis-diamminedichloroplatinum(II) (cisplatin), a large number of square-planar platinum complexes have been studied as potential chemotherapeutic drugs which might maintain the efficacy of cisplatin without the undesirable side effects (Lippard, 1982; Rosenberg, 1985). Typically, these complexes consist of two inert cis ammine ligands and two labile cis ligands which act as leaving groups in the body, thus allowing the platinum to coordinate to the DNA of cancer cells. One complex which has achieved widespread use as an alternative to cisplatin is cis-diammine(1,1-cyclobutanedicarboxylato)platinum(II) (carboplatin). The use of 1,2-oxazines as nitrogen ligands could lead to novel compounds with increased antitumor activity or decreased toxicity due to the demonstrated biological activity of the oxazine and the easily cleaved N—O bond in the oxazine ring. Compounds (I) and (II) were obtained from an unsuccessful effort to synthesize cis-bis(3,6-dihydro-1,2-oxazine)1,1-cyclobutanedicarboxylatoplatinum(II) through an intermediate DMSO complex. They represent new members of a modest family of square planar [PtCl2(DMSO)(amine)] complexes whose structural features they share.
The cis isomer (I) of dichloro(3,6-dihydro-1,2-oxazine-N)(dimethyl sulfoxide-S)platinum(II) is shown in Fig. 1. The Pt coordination geometry (Table 1) is quite regular, with all angles within 1.4° of their ideal values. The mean devation from the PtCl2SN least squares plane is 0.011 (3) Å. The Pt—Cl distance opposite the DMSO ligand is 0.015 (3) Å longer than that opposite the oxazine ligand. This is consistent with what is observed in most of the reported cis-[PtCl2(DMSO)(amine)] complexes (Melanson & Rochon, 1977; Belsky et al., 1990, 1991; Rochon et al., 1990, 1994; Neuse et al., 1995; Caldwell et al., 1995; Cornia et al., 1997). The Pt—S and Pt—N distances are also within the reported ranges [2.184 (3)–2.225 (2) and 1.950 (6)–2.06 (1) Å, respectively], including those of two platinum 1,3-oxazine complexes (Albinati et al., 1989; Michelin et al., 1994). The pyramidal DMSO ligand is positioned so that the S═O bond is nearly coplanar with the square plane [torsion angle O2–S–Pt–N −4.6 (3)°], while the S—C bonds are staggered between the Pt—Cl1 bond [torsion angle Cl1—Pt—S—C5 − 62.6 (4)°]. This arrangement is also observed when the amine ligand is 2-picoline (Melanson & Rochon, 1977), pyridine (Belsky et al., 1991), cylopentylamine (Caldwell et al., 1995), tert-butylamine (Neuse et al., 1995), and thiazole (Cornia et al., 1997). For acetonitrile, two structures have been reported, one with S═ O eclipsing Pt—N (Rochon et al., 1990) and one with an S—C bond approximately aligned with Pt—N (Belsky et al., 1990). The latter conformation is also found in the propionitrile complex (Rochon et al., 1994). The S═O bond at 1.489 (5) Å is significantly shorter than that in the free molecule at 278 K [1.531 (5) Å] (Davies, 1981), but is at the high end of the range found in similar Pt complexes [1.44 (3)–1.48 (1) Å]. As in the free DMSO, the O—S—C angles are larger than the C—S—C angle, though the difference is smaller in the complex. The oxazine molecule shows bond distances and angles consistent with those found in non-coordinated 1,2-oxazine derivatives (Riddell et al., 1974; Holzapfel et al., 1987). It is positioned so that the N—O1 and N—C4 bonds are staggered about Cl2 [torsion angles Cl2—Pt—N—C4 62.2 (5) and Cl2–Pt–N–O1 − 63.3 (4) Å].
The trans isomer (II) is shown in Fig. 2. The Pt coordination geometry (Table 2) is slightly less regular than that of the cis isomer in that the Cl—Pt—Cl angle is closed 4.5° from ideal, causing a similar ca 3–4° distortion in the Cl2—Pt—S and Cl2—Pt—N angles. The mean deviation from the PtCl2SN plane is 0.021 (4) Å, with the two chloride ligands displaced 0.041 (4) and 0.035 (4) Å to the same side of the plane. As is the case in trans-[PtCl2(DMSO)(amine)] complexes (Melanson & Rochon, 1978; Caruso et al., 1980; Viossat et al., 1991; Lovqvist & Oskarsson, 1992; Cornia et al., 1997), the Pt—Cl bond distances are closer to one another than in (I) and within experimental error. The Pt—S distance [2.230 (3) Å] is nearly 0.01 Å longer than the longest reported distance for this type of complex, while the Pt—N distance [2.067 (9) Å] is to the high end of the reported range [2.03 (1)–2.08 (2) Å] as is the S—O bond length. The DMSO ligand is positioned quite differently from that in (I). The S═O bond is almost perpendicular to the square plane [torsion angle Cl2–Pt–S–O2 100.5 (4)°], while the S—C5 bond is the closest to being in the plane [torsion angle Cl2—Pt—S—C5 − 24.6 (6)°]. A similar arrangement is found in trans-[PtCl2(DMSO)(NH3)] (Viossat et al., 1991), while other skewed orientations with the S═O group directed away from the square plane are found in the pyridine (Caruso et al., 1980), piperidine (Lovqvist & Oskarsson, 1992) and thiazole (Cornia et al., 1997) complexes. Only the cytidine complex (Melanson & Rochon, 1978) differs in having the S═O bond eclipsing an adjacent ligand as in (I). The bond distances and angles within the oxazine ligand do not differ significantly from those in (I). The conformation of the ring is also essentially the same [torsion angles for (I) and (II), respectively: N—C4—C3—C2 12 (1), 14 (2)°; N—O1—C1—C2 − 49.6 (8), −48 (1)°]. The ring is positioned similarly to that in the cis isomer with the N—O1 and N—C4 bonds rotated away from the adjacent Cl ligands [torsion angles Cl1—Pt—N—O1 − 55.6 (6) and Cl1—Pt—N—C4 67.9 (9)°].