Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014109/oa1096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014109/oa1096Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014109/oa1096IIsup3.hkl |
CCDC references: 142733; 142734
Each isomer was isolated by the following procedure: an aqueous solution of Hdmbarb (0.937 g, 6.001 mmol) was added to the yellow eluate containing [Pt(en)(OH)2], prepared from [Pt(en)(ONO2)2] (1.135 g, 2.993 mmol). After rotoevaporation to 30 ml it was allowed to stand at 278 K for 2 d to form pale-yellow crystals of (I) (0.600 g, 35% yield). Analysis found: C 29.34, H 4.00, N 14.82%; calculated for C14H22N6O6Pt: C 29.74, H 3.92, N 14.86%. 1H NMR (0.01 mol dm−3 in D2O, 300 MHz): δ 5.66 (s, 1H, CH), 4.40 (s, 1H, CH), 3.08 (s, 3H, CH3), 2.99 (s, 3H, CH3), 2.92 (s, 6H, CH3), 2.49 (m, 4H, CH2) p.p.m.; 13C{1H} NMR (75.5 MHz): δ 176.33 (C14, C16), 167.12 (C26), 165.73 (C24), 153.96, 153.23 (C12, C22), 80.07 (C25), 49.39, 45.49 (C1, C2), 47.20 (C15), 27.67, 27.63, 27.53, 26.34 (C11, C13, C21, C23). Another aqueous solution of [Pt(en)(OH)2] prepared from [Pt(en)(ONO2)2] (0.379 g, 0.999 mmol) was rotoevaporated to 10 ml, and was added to 10 ml of an aqueous solution of Hdmbarb (0.312 g, 1.998 mmol). After standing at room temperature for 14 days, yellow crystals of (II) were obtained (0.336 g, 56% yield). Analysis found: C 27.84, H 4.34, N 14.04%; calculated for C14H26N6O8Pt: C 27.96, H 4.36, N 13.97%. 1H NMR (0.01 mol dm−3 in D2O, 300 MHz): δ 4.13 (s, 2H, CH), 3.07 (s, 12H, CH3), 2.43 (s, 4H, CH2), 13C{1H} NMR (75.5 MHz): δ 176.80 (C14, C16, C24, C26), 154.17 (C12, C22), 47.21 (C1, C2, C15, C25), 27.69 (C11, C13, C21, C23).
Compound (I) is more soluble in H2O than (II): up to 0.015 mol dm−3 for (I) and less than 0.01 mol dm−3 for (II) at room temperature. Both compounds were air-stable in the solid state, but (I) dissolved in H2O has been changed into (II) in two weeks. It was difficult to recrystallize (I) from H2O because of the contamination of (II), while (II) could be recrystallized from H2O.
For both compounds H atoms other than those on H2O were included as riding models and positions of the H atoms on H2O in (II) were refined with O—H restrained at 0.82 (3) Å; Uiso(H) = 1.2Ueq(parent atom). The site-occupancy parameters of disordered ethylene chains in (II), were refined to 0.84 (1) for C1 and C2, and 0.16 (1) for C10 and C20.
For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN PROCESS (Molecular Structure Corporation, 1993b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
[Pt(C2H8N2)(C6H7N2O3)2] | Z = 2 |
Mr = 565.47 | F(000) = 548 |
Triclinic, P1 | Dx = 2.036 Mg m−3 Dm = 2.04 Mg m−3 Dm measured by flotation in CCl4/CHBr3 |
a = 9.505 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.2518 (9) Å | Cell parameters from 25 reflections |
c = 9.464 (2) Å | θ = 16.9–17.5° |
α = 103.10 (1)° | µ = 7.65 mm−1 |
β = 110.52 (1)° | T = 296 K |
γ = 87.93 (1)° | Thin plate, pale yellow |
V = 922.2 (2) Å3 | 0.20 × 0.10 × 0.07 mm |
Rigaku AFC7R diffractometer | 4663 reflections with I > 2σ(I) |
Radiation source: rotating Mo anticathode | Rint = 0.029 |
Graphite monochromator | θmax = 30.0°, θmin = 2.3° |
ω/2θ scans | h = −13→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −15→15 |
Tmin = 0.294, Tmax = 0.585 | l = −12→13 |
5685 measured reflections | 3 standard reflections every 150 reflections |
5383 independent reflections | intensity decay: 0.9% |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0258P)2 + 0.5877P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
5383 reflections | Δρmax = 1.17 e Å−3 |
245 parameters | Δρmin = −1.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0023 (2) |
[Pt(C2H8N2)(C6H7N2O3)2] | γ = 87.93 (1)° |
Mr = 565.47 | V = 922.2 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.505 (2) Å | Mo Kα radiation |
b = 11.2518 (9) Å | µ = 7.65 mm−1 |
c = 9.464 (2) Å | T = 296 K |
α = 103.10 (1)° | 0.20 × 0.10 × 0.07 mm |
β = 110.52 (1)° |
Rigaku AFC7R diffractometer | 4663 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.294, Tmax = 0.585 | 3 standard reflections every 150 reflections |
5685 measured reflections | intensity decay: 0.9% |
5383 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.17 e Å−3 |
5383 reflections | Δρmin = −1.14 e Å−3 |
245 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Pt | 0.536793 (17) | 0.341507 (13) | 0.292565 (16) | 0.02565 (5) | |
O12 | 1.0320 (5) | 0.1670 (4) | 0.4841 (5) | 0.0697 (12) | |
O14 | 0.7685 (5) | 0.3327 (4) | 0.0803 (4) | 0.0586 (10) | |
O16 | 0.8300 (4) | 0.5307 (3) | 0.5862 (4) | 0.0485 (8) | |
O22 | 0.6747 (4) | −0.0157 (3) | 0.7665 (4) | 0.0509 (9) | |
O24 | 0.6351 (3) | 0.2269 (3) | 0.4347 (3) | 0.0354 (6) | |
O26 | 0.4055 (4) | 0.3242 (3) | 0.8130 (3) | 0.0399 (7) | |
N1 | 0.3161 (4) | 0.2813 (3) | 0.2493 (4) | 0.0311 (7) | |
H1 | 0.3109 | 0.1997 | 0.2365 | 0.037* | |
H2 | 0.2876 | 0.3157 | 0.3300 | 0.037* | |
N2 | 0.4338 (4) | 0.4354 (3) | 0.1295 (4) | 0.0329 (7) | |
H7 | 0.4761 | 0.5115 | 0.1589 | 0.039* | |
H8 | 0.4449 | 0.3984 | 0.0394 | 0.039* | |
N11 | 0.9318 (4) | 0.3495 (4) | 0.5363 (4) | 0.0387 (8) | |
N13 | 0.8904 (5) | 0.2415 (4) | 0.2790 (5) | 0.0447 (9) | |
N21 | 0.5280 (5) | 0.1487 (3) | 0.7792 (4) | 0.0366 (8) | |
N23 | 0.6525 (4) | 0.1078 (3) | 0.6006 (4) | 0.0318 (7) | |
C1 | 0.2156 (5) | 0.3166 (4) | 0.1069 (5) | 0.0406 (10) | |
H3 | 0.1129 | 0.3194 | 0.1052 | 0.049* | |
H4 | 0.2180 | 0.2574 | 0.0157 | 0.049* | |
C2 | 0.2708 (5) | 0.4413 (4) | 0.1078 (5) | 0.0383 (9) | |
H5 | 0.2152 | 0.4635 | 0.0106 | 0.046* | |
H6 | 0.2563 | 0.5023 | 0.1915 | 0.046* | |
C11 | 1.0067 (6) | 0.3541 (6) | 0.7020 (6) | 0.0568 (14) | |
H111 | 1.0679 | 0.2848 | 0.7148 | 0.068* | |
H112 | 0.9323 | 0.3526 | 0.7490 | 0.068* | |
H113 | 1.0689 | 0.4279 | 0.7508 | 0.068* | |
C12 | 0.9547 (5) | 0.2470 (4) | 0.4346 (6) | 0.0445 (11) | |
C13 | 0.9206 (7) | 0.1357 (5) | 0.1731 (8) | 0.0677 (17) | |
H131 | 0.8697 | 0.1424 | 0.0681 | 0.081* | |
H132 | 0.8850 | 0.0624 | 0.1880 | 0.081* | |
H133 | 1.0269 | 0.1329 | 0.1938 | 0.081* | |
C14 | 0.8011 (5) | 0.3322 (4) | 0.2170 (5) | 0.0390 (10) | |
C15 | 0.7476 (5) | 0.4199 (4) | 0.3248 (5) | 0.0319 (8) | |
H15 | 0.7334 | 0.4984 | 0.2943 | 0.038* | |
C16 | 0.8374 (5) | 0.4397 (4) | 0.4896 (5) | 0.0342 (8) | |
C21 | 0.4850 (7) | 0.1102 (5) | 0.8964 (6) | 0.0554 (14) | |
H211 | 0.4200 | 0.1684 | 0.9295 | 0.067* | |
H212 | 0.5735 | 0.1055 | 0.9836 | 0.067* | |
H213 | 0.4332 | 0.0315 | 0.8532 | 0.067* | |
C22 | 0.6214 (5) | 0.0747 (4) | 0.7180 (5) | 0.0354 (9) | |
C23 | 0.7497 (6) | 0.0287 (4) | 0.5340 (6) | 0.0473 (11) | |
H231 | 0.7637 | 0.0603 | 0.4535 | 0.057* | |
H232 | 0.7038 | −0.0523 | 0.4914 | 0.057* | |
H233 | 0.8455 | 0.0262 | 0.6133 | 0.057* | |
C24 | 0.5974 (4) | 0.2120 (4) | 0.5465 (4) | 0.0288 (7) | |
C25 | 0.5121 (5) | 0.2863 (3) | 0.6163 (4) | 0.0302 (8) | |
H25 | 0.4764 | 0.3567 | 0.5823 | 0.036* | |
C26 | 0.4767 (5) | 0.2590 (4) | 0.7389 (4) | 0.0311 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.03179 (8) | 0.02414 (8) | 0.02707 (8) | 0.00483 (5) | 0.01500 (5) | 0.01076 (5) |
O12 | 0.056 (2) | 0.060 (3) | 0.095 (3) | 0.030 (2) | 0.026 (2) | 0.028 (2) |
O14 | 0.078 (3) | 0.068 (3) | 0.0430 (19) | −0.001 (2) | 0.0351 (19) | 0.0153 (18) |
O16 | 0.054 (2) | 0.0437 (19) | 0.0465 (19) | 0.0031 (15) | 0.0232 (16) | −0.0005 (15) |
O22 | 0.077 (3) | 0.0315 (16) | 0.0486 (19) | 0.0145 (16) | 0.0204 (18) | 0.0221 (14) |
O24 | 0.0383 (16) | 0.0381 (16) | 0.0429 (16) | 0.0141 (12) | 0.0219 (13) | 0.0247 (13) |
O26 | 0.055 (2) | 0.0375 (16) | 0.0335 (15) | 0.0099 (14) | 0.0231 (14) | 0.0100 (12) |
N1 | 0.0337 (17) | 0.0283 (16) | 0.0360 (17) | 0.0040 (13) | 0.0151 (14) | 0.0121 (13) |
N2 | 0.049 (2) | 0.0282 (16) | 0.0264 (15) | 0.0034 (14) | 0.0176 (15) | 0.0089 (13) |
N11 | 0.0318 (18) | 0.045 (2) | 0.042 (2) | 0.0052 (15) | 0.0144 (16) | 0.0128 (16) |
N13 | 0.043 (2) | 0.041 (2) | 0.057 (2) | 0.0065 (17) | 0.031 (2) | 0.0034 (18) |
N21 | 0.058 (2) | 0.0277 (17) | 0.0317 (17) | 0.0061 (16) | 0.0211 (17) | 0.0146 (14) |
N23 | 0.0377 (18) | 0.0248 (16) | 0.0370 (18) | 0.0072 (13) | 0.0150 (15) | 0.0132 (13) |
C1 | 0.040 (2) | 0.043 (2) | 0.036 (2) | −0.0017 (19) | 0.0075 (18) | 0.0115 (18) |
C2 | 0.040 (2) | 0.041 (2) | 0.036 (2) | 0.0097 (18) | 0.0103 (18) | 0.0181 (18) |
C11 | 0.042 (3) | 0.073 (4) | 0.051 (3) | 0.002 (3) | 0.007 (2) | 0.023 (3) |
C12 | 0.029 (2) | 0.043 (3) | 0.067 (3) | 0.0089 (18) | 0.022 (2) | 0.017 (2) |
C13 | 0.067 (4) | 0.048 (3) | 0.090 (5) | 0.011 (3) | 0.045 (3) | −0.006 (3) |
C14 | 0.038 (2) | 0.042 (2) | 0.043 (2) | −0.0058 (18) | 0.0232 (19) | 0.0055 (19) |
C15 | 0.036 (2) | 0.0283 (19) | 0.040 (2) | 0.0043 (15) | 0.0200 (17) | 0.0152 (16) |
C16 | 0.031 (2) | 0.035 (2) | 0.042 (2) | 0.0008 (16) | 0.0189 (18) | 0.0089 (17) |
C21 | 0.099 (5) | 0.041 (3) | 0.044 (3) | 0.007 (3) | 0.042 (3) | 0.019 (2) |
C22 | 0.050 (3) | 0.0231 (18) | 0.0317 (19) | −0.0013 (17) | 0.0096 (18) | 0.0097 (15) |
C23 | 0.051 (3) | 0.041 (3) | 0.057 (3) | 0.018 (2) | 0.024 (2) | 0.019 (2) |
C24 | 0.0286 (18) | 0.0287 (18) | 0.0302 (18) | 0.0021 (14) | 0.0080 (15) | 0.0128 (15) |
C25 | 0.039 (2) | 0.0236 (17) | 0.0315 (19) | 0.0073 (15) | 0.0142 (16) | 0.0118 (15) |
C26 | 0.036 (2) | 0.0277 (19) | 0.0292 (18) | 0.0008 (15) | 0.0103 (16) | 0.0086 (15) |
Pt—N1 | 2.098 (3) | O22—C22 | 1.231 (5) |
Pt—N2 | 2.015 (3) | O24—C24 | 1.275 (5) |
Pt—C15 | 2.112 (4) | O26—C26 | 1.245 (5) |
Pt—O24 | 2.041 (3) | N1—H1 | 0.90 |
N1—C1 | 1.483 (5) | N1—H2 | 0.90 |
N2—C2 | 1.491 (6) | N2—H7 | 0.90 |
C1—C2 | 1.513 (6) | N2—H8 | 0.90 |
N11—C11 | 1.467 (6) | C1—H3 | 0.97 |
N11—C12 | 1.389 (6) | C1—H4 | 0.97 |
N11—C16 | 1.376 (6) | C2—H5 | 0.97 |
N13—C12 | 1.370 (7) | C2—H6 | 0.97 |
N13—C13 | 1.463 (6) | C11—H111 | 0.96 |
N13—C14 | 1.402 (6) | C11—H112 | 0.96 |
C14—C15 | 1.464 (6) | C11—H113 | 0.96 |
C15—C16 | 1.460 (6) | C13—H131 | 0.96 |
O12—C12 | 1.212 (6) | C13—H132 | 0.96 |
O14—C14 | 1.222 (5) | C13—H133 | 0.96 |
O16—C16 | 1.227 (5) | C15—H15 | 0.98 |
N21—C22 | 1.380 (6) | C21—H211 | 0.96 |
N21—C26 | 1.401 (5) | C21—H212 | 0.96 |
N21—C21 | 1.461 (5) | C21—H213 | 0.96 |
N23—C22 | 1.374 (5) | C23—H231 | 0.96 |
N23—C24 | 1.397 (5) | C23—H232 | 0.96 |
N23—C23 | 1.463 (5) | C23—H233 | 0.96 |
C24—C25 | 1.368 (5) | C25—H25 | 0.93 |
C25—C26 | 1.413 (5) | ||
N1—Pt—N2 | 83.2 (1) | C1—N1—H2 | 110.0 |
N1—Pt—C15 | 173.2 (1) | Pt—N1—H2 | 110.0 |
N1—Pt—O24 | 94.8 (1) | H1—N1—H2 | 108.4 |
N2—Pt—C15 | 90.4 (1) | C2—N2—H7 | 109.8 |
N2—Pt—O24 | 172.6 (1) | Pt—N2—H7 | 109.8 |
C15—Pt—O24 | 91.9 (1) | C2—N2—H8 | 109.8 |
Pt—C15—C14 | 103.4 (3) | Pt—N2—H8 | 109.8 |
Pt—C15—C16 | 107.2 (3) | H7—N2—H8 | 108.2 |
Pt—O24—C24 | 125.1 (3) | N1—C1—H3 | 110.2 |
Pt—N1—C1 | 108.4 (3) | C2—C1—H3 | 110.2 |
Pt—N2—C2 | 109.5 (2) | N1—C1—H4 | 110.2 |
N1—C1—C2 | 107.7 (3) | C2—C1—H4 | 110.2 |
N2—C2—C1 | 107.9 (3) | H3—C1—H4 | 108.5 |
C12—N13—C14 | 123.7 (4) | N2—C2—H5 | 110.1 |
C12—N13—C13 | 117.4 (5) | C1—C2—H5 | 110.1 |
C14—N13—C13 | 118.9 (5) | N2—C2—H6 | 110.1 |
C16—N11—C12 | 123.6 (4) | C1—C2—H6 | 110.1 |
C16—N11—C11 | 119.9 (4) | H5—C2—H6 | 108.4 |
C12—N11—C11 | 116.3 (4) | N13—C13—H131 | 109.5 |
O12—C12—N13 | 121.9 (5) | N13—C13—H132 | 109.5 |
O12—C12—N11 | 120.2 (5) | H131—C13—H132 | 109.5 |
N13—C12—N11 | 117.8 (4) | N13—C13—H133 | 109.5 |
O16—C16—N11 | 119.5 (4) | H131—C13—H133 | 109.5 |
N11—C16—C15 | 117.2 (4) | H132—C13—H133 | 109.5 |
O14—C14—N13 | 120.4 (4) | N11—C11—H111 | 109.5 |
N13—C14—C15 | 115.6 (4) | N11—C11—H112 | 109.5 |
O14—C14—C15 | 124.0 (5) | H111—C11—H112 | 109.5 |
C14—C15—C16 | 117.1 (4) | N11—C11—H113 | 109.5 |
O16—C16—C15 | 123.2 (4) | H111—C11—H113 | 109.5 |
C22—N21—C26 | 124.0 (3) | H112—C11—H113 | 109.5 |
C22—N21—C21 | 117.2 (4) | C16—C15—H15 | 109.6 |
C26—N21—C21 | 118.8 (4) | C14—C15—H15 | 109.6 |
C22—N23—C24 | 123.0 (3) | Pt—C15—H15 | 109.6 |
C22—N23—C23 | 116.6 (3) | N21—C21—H211 | 109.5 |
C24—N23—C23 | 120.4 (3) | N21—C21—H212 | 109.5 |
O22—C22—N23 | 121.7 (4) | H211—C21—H212 | 109.5 |
O22—C22—N21 | 121.9 (4) | N21—C21—H213 | 109.5 |
N23—C22—N21 | 116.4 (3) | H211—C21—H213 | 109.5 |
O24—C24—N23 | 114.3 (3) | H212—C21—H213 | 109.5 |
C25—C24—N23 | 118.6 (3) | N23—C23—H231 | 109.5 |
O26—C26—N21 | 118.3 (4) | N23—C23—H232 | 109.5 |
N21—C26—C25 | 116.0 (4) | H231—C23—H232 | 109.5 |
O24—C24—C25 | 127.1 (4) | N23—C23—H233 | 109.5 |
C24—C25—C26 | 121.7 (4) | H231—C23—H233 | 109.5 |
O26—C26—C25 | 125.8 (4) | H232—C23—H233 | 109.5 |
C1—N1—H1 | 110.0 | C24—C25—H25 | 119.1 |
Pt—N1—H1 | 110.0 | C26—C25—H25 | 119.1 |
N2—Pt—O24—C24 | −121.8 (9) | O24—Pt—C15—C14 | 81.3 (3) |
N1—Pt—O24—C24 | −48.1 (3) | N1—Pt—C15—C14 | −112.8 (12) |
C15—Pt—O24—C24 | 130.2 (3) | C12—N13—C14—O14 | 167.4 (4) |
N2—Pt—N1—C1 | 12.0 (3) | C13—N13—C14—O14 | −11.1 (7) |
O24—Pt—N1—C1 | −160.9 (3) | C12—N13—C14—C15 | −14.8 (6) |
C15—Pt—N1—C1 | 33.3 (13) | C13—N13—C14—C15 | 166.6 (4) |
O24—Pt—N2—C2 | 91.3 (10) | C16—C15—C14—O14 | −156.6 (4) |
N1—Pt—N2—C2 | 16.9 (3) | Pt—C15—C14—O14 | 85.7 (5) |
C15—Pt—N2—C2 | −160.6 (3) | C16—C15—C14—N13 | 25.7 (5) |
Pt—N1—C1—C2 | −37.9 (4) | Pt—C15—C14—N13 | −91.9 (4) |
Pt—N2—C2—C1 | −42.5 (4) | C24—N23—C22—O22 | −178.0 (4) |
N1—C1—C2—N2 | 53.1 (4) | C23—N23—C22—O22 | 1.2 (6) |
C14—N13—C12—O12 | −179.7 (5) | C24—N23—C22—N21 | 1.6 (6) |
C13—N13—C12—O12 | −1.1 (7) | C23—N23—C22—N21 | −179.2 (4) |
C14—N13—C12—N11 | −1.1 (7) | C26—N21—C22—O22 | 173.3 (4) |
C13—N13—C12—N11 | 177.4 (4) | C21—N21—C22—O22 | −4.6 (7) |
C16—N11—C12—O12 | −175.2 (4) | C26—N21—C22—N23 | −6.3 (6) |
C11—N11—C12—O12 | 0.6 (7) | C21—N21—C22—N23 | 175.8 (4) |
C16—N11—C12—N13 | 6.3 (6) | Pt—O24—C24—C25 | −16.4 (6) |
C11—N11—C12—N13 | −178.0 (4) | Pt—O24—C24—N23 | 164.2 (3) |
C12—N11—C16—O16 | −175.9 (4) | C22—N23—C24—O24 | −178.6 (4) |
C11—N11—C16—O16 | 8.5 (6) | C23—N23—C24—O24 | 2.2 (6) |
C12—N11—C16—C15 | 5.4 (6) | C22—N23—C24—C25 | 1.9 (6) |
C11—N11—C16—C15 | −170.2 (4) | C23—N23—C24—C25 | −177.2 (4) |
O16—C16—C15—C14 | 159.9 (4) | O24—C24—C25—C26 | 179.4 (4) |
N11—C16—C15—C14 | −21.5 (5) | N23—C24—C25—C26 | −1.2 (6) |
O16—C16—C15—Pt | −84.6 (4) | C22—N21—C26—O26 | −172.8 (4) |
N11—C16—C15—Pt | 94.1 (4) | C21—N21—C26—O26 | 5.1 (6) |
N2—Pt—C15—C16 | 144.0 (3) | C22—N21—C26—C25 | 6.9 (6) |
O24—Pt—C15—C16 | −43.0 (3) | C21—N21—C26—C25 | −175.1 (4) |
N1—Pt—C15—C16 | 122.8 (11) | C24—C25—C26—O26 | 176.7 (4) |
N2—Pt—C15—C14 | −91.7 (3) | C24—C25—C26—N21 | −3.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O22i | 0.90 | 2.06 | 2.958 (5) | 172 |
N1—H2···O16ii | 0.90 | 2.17 | 2.939 (5) | 142 |
N2—H7···O26ii | 0.90 | 2.11 | 2.998 (5) | 167 |
N2—H8···O26iii | 0.90 | 2.02 | 2.893 (4) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1. |
[Pt(C2H8N2)(C6H7N2O3)2]·2H2O | F(000) = 1176 |
Mr = 601.50 | Dx = 2.049 Mg m−3 Dm = 2.04 Mg m−3 Dm measured by flotation in CCl4/CHBr3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 12.840 (2) Å | Cell parameters from 25 reflections |
b = 10.7834 (9) Å | θ = 19.1–19.9° |
c = 14.727 (2) Å | µ = 7.25 mm−1 |
β = 107.051 (9)° | T = 296 K |
V = 1949.5 (4) Å3 | Prism, yellow |
Z = 4 | 0.16 × 0.16 × 0.07 mm |
Rigaku AFC7R diffractometer | 4415 reflections with I > 2σ(I) |
Radiation source: rotating Mo anticathode | Rint = 0.026 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
ω/2θ scans | h = 0→18 |
Absorption correction: ψ scan (North et al., 1968) | k = −15→0 |
Tmin = 0.390, Tmax = 0.631 | l = −20→19 |
5892 measured reflections | 3 standard reflections every 150 reflections |
5664 independent reflections | intensity decay: 0.9% |
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)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.065 | w = 1/[σ2(Fo2) + (0.0275P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.003 |
5664 reflections | Δρmax = 0.88 e Å−3 |
284 parameters | Δρmin = −0.94 e Å−3 |
4 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00092 (9) |
[Pt(C2H8N2)(C6H7N2O3)2]·2H2O | V = 1949.5 (4) Å3 |
Mr = 601.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.840 (2) Å | µ = 7.25 mm−1 |
b = 10.7834 (9) Å | T = 296 K |
c = 14.727 (2) Å | 0.16 × 0.16 × 0.07 mm |
β = 107.051 (9)° |
Rigaku AFC7R diffractometer | 4415 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.026 |
Tmin = 0.390, Tmax = 0.631 | 3 standard reflections every 150 reflections |
5892 measured reflections | intensity decay: 0.9% |
5664 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 4 restraints |
wR(F2) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.88 e Å−3 |
5664 reflections | Δρmin = −0.94 e Å−3 |
284 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pt | 0.729256 (11) | 0.195623 (13) | 0.579509 (9) | 0.02254 (5) | |
O12 | 1.0368 (3) | 0.1008 (3) | 0.4434 (3) | 0.0523 (9) | |
O14 | 0.9398 (3) | 0.4185 (4) | 0.6000 (3) | 0.0533 (9) | |
O16 | 0.6889 (3) | 0.2418 (4) | 0.3382 (2) | 0.0459 (8) | |
O22 | 0.3835 (3) | 0.2825 (4) | 0.6845 (3) | 0.0525 (10) | |
O24 | 0.6224 (3) | 0.4887 (3) | 0.5682 (2) | 0.0398 (7) | |
O26 | 0.4661 (3) | 0.1183 (3) | 0.4317 (2) | 0.0418 (8) | |
O1 | 1.0471 (4) | 0.3422 (4) | 0.3168 (4) | 0.0695 (13) | |
H11 | 1.108 (3) | 0.310 (6) | 0.327 (5) | 0.083* | |
H12 | 1.063 (6) | 0.412 (4) | 0.340 (5) | 0.083* | |
O2 | 0.2689 (4) | 0.1927 (4) | 0.8260 (4) | 0.0746 (14) | |
H21 | 0.305 (6) | 0.240 (6) | 0.804 (5) | 0.089* | |
H22 | 0.307 (5) | 0.134 (5) | 0.855 (4) | 0.089* | |
N1 | 0.6697 (3) | 0.0893 (3) | 0.6718 (2) | 0.0293 (7) | |
H1 | 0.6359 | 0.1388 | 0.7035 | 0.035* | |
H2 | 0.6208 | 0.0341 | 0.6383 | 0.035* | |
N2 | 0.8719 (3) | 0.0964 (3) | 0.6454 (2) | 0.0318 (7) | |
H7 | 0.9053 | 0.0743 | 0.6020 | 0.038* | |
H8 | 0.9179 | 0.1442 | 0.6894 | 0.038* | |
N11 | 0.8601 (3) | 0.1640 (3) | 0.3930 (3) | 0.0360 (9) | |
N13 | 0.9870 (3) | 0.2583 (4) | 0.5237 (3) | 0.0367 (8) | |
N21 | 0.4327 (3) | 0.1915 (3) | 0.5646 (3) | 0.0319 (7) | |
N23 | 0.5151 (3) | 0.3778 (3) | 0.6361 (2) | 0.0314 (8) | |
C1 | 0.7621 (5) | 0.0219 (6) | 0.7413 (5) | 0.0343 (13) | 0.840 (12) |
H3 | 0.7969 | 0.0760 | 0.7941 | 0.041* | 0.840 (12) |
H4 | 0.7344 | −0.0503 | 0.7661 | 0.041* | 0.840 (12) |
C2 | 0.8427 (4) | −0.0173 (5) | 0.6915 (4) | 0.0335 (14) | 0.840 (12) |
H5 | 0.8111 | −0.0797 | 0.6440 | 0.040* | 0.840 (12) |
H6 | 0.9071 | −0.0519 | 0.7365 | 0.040* | 0.840 (12) |
C10 | 0.747 (3) | −0.011 (3) | 0.708 (2) | 0.028 (7)* | 0.160 (12) |
H30 | 0.7432 | −0.0728 | 0.6596 | 0.033* | 0.160 (12) |
H40 | 0.7325 | −0.0507 | 0.7623 | 0.033* | 0.160 (12) |
C20 | 0.859 (2) | 0.050 (2) | 0.7380 (17) | 0.025 (6)* | 0.160 (12) |
H50 | 0.8613 | 0.1179 | 0.7817 | 0.030* | 0.160 (12) |
H60 | 0.9154 | −0.0095 | 0.7676 | 0.030* | 0.160 (12) |
C11 | 0.8411 (5) | 0.0824 (6) | 0.3094 (4) | 0.0589 (15) | |
H111 | 0.8963 | 0.0194 | 0.3216 | 0.071* | |
H112 | 0.8437 | 0.1305 | 0.2553 | 0.071* | |
H113 | 0.7708 | 0.0441 | 0.2969 | 0.071* | |
C12 | 0.9655 (4) | 0.1692 (4) | 0.4527 (3) | 0.0350 (10) | |
C13 | 1.1026 (4) | 0.2786 (6) | 0.5757 (4) | 0.0636 (18) | |
H131 | 1.1458 | 0.2710 | 0.5326 | 0.076* | |
H132 | 1.1258 | 0.2179 | 0.6252 | 0.076* | |
H133 | 1.1116 | 0.3602 | 0.6030 | 0.076* | |
C14 | 0.9096 (4) | 0.3347 (4) | 0.5420 (3) | 0.0322 (9) | |
C15 | 0.7955 (3) | 0.3076 (4) | 0.4924 (3) | 0.0277 (8) | |
H15 | 0.7551 | 0.3859 | 0.4800 | 0.033* | |
C16 | 0.7753 (4) | 0.2393 (4) | 0.4025 (3) | 0.0322 (9) | |
C21 | 0.3463 (4) | 0.0982 (5) | 0.5553 (4) | 0.0440 (11) | |
H211 | 0.3435 | 0.0447 | 0.5026 | 0.053* | |
H212 | 0.2774 | 0.1393 | 0.5449 | 0.053* | |
H213 | 0.3617 | 0.0499 | 0.6125 | 0.053* | |
C22 | 0.4406 (4) | 0.2843 (4) | 0.6320 (3) | 0.0352 (10) | |
C23 | 0.5185 (4) | 0.4761 (5) | 0.7054 (4) | 0.0481 (13) | |
H231 | 0.5672 | 0.5404 | 0.6982 | 0.058* | |
H232 | 0.5437 | 0.4424 | 0.7684 | 0.058* | |
H233 | 0.4468 | 0.5099 | 0.6950 | 0.058* | |
C24 | 0.5752 (3) | 0.3907 (4) | 0.5714 (3) | 0.0283 (8) | |
C25 | 0.5786 (3) | 0.2826 (4) | 0.5119 (3) | 0.0271 (8) | |
H25 | 0.5805 | 0.3122 | 0.4495 | 0.032* | |
C26 | 0.4900 (3) | 0.1931 (4) | 0.4978 (3) | 0.0285 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt | 0.02121 (8) | 0.02483 (8) | 0.02221 (7) | 0.00130 (6) | 0.00738 (5) | −0.00083 (6) |
O12 | 0.052 (2) | 0.044 (2) | 0.070 (2) | 0.0140 (18) | 0.0320 (19) | 0.0010 (18) |
O14 | 0.045 (2) | 0.056 (2) | 0.061 (2) | −0.0119 (18) | 0.0181 (17) | −0.0272 (19) |
O16 | 0.0354 (18) | 0.069 (2) | 0.0298 (16) | −0.0067 (17) | 0.0049 (14) | 0.0065 (16) |
O22 | 0.053 (2) | 0.062 (3) | 0.056 (2) | −0.0054 (19) | 0.0377 (19) | −0.0109 (18) |
O24 | 0.0382 (18) | 0.0294 (16) | 0.0532 (19) | −0.0027 (14) | 0.0157 (15) | −0.0042 (14) |
O26 | 0.0394 (19) | 0.049 (2) | 0.0376 (17) | −0.0076 (15) | 0.0116 (14) | −0.0142 (15) |
O1 | 0.067 (3) | 0.051 (3) | 0.077 (3) | 0.000 (2) | 0.000 (3) | −0.004 (2) |
O2 | 0.064 (3) | 0.046 (3) | 0.116 (4) | 0.013 (2) | 0.029 (3) | 0.023 (3) |
N1 | 0.0240 (16) | 0.0343 (19) | 0.0300 (16) | −0.0009 (15) | 0.0085 (13) | 0.0024 (15) |
N2 | 0.0255 (17) | 0.035 (2) | 0.0362 (18) | 0.0052 (15) | 0.0116 (14) | 0.0057 (16) |
N11 | 0.043 (2) | 0.036 (2) | 0.0340 (19) | −0.0038 (17) | 0.0193 (17) | −0.0070 (15) |
N13 | 0.0283 (19) | 0.045 (2) | 0.037 (2) | 0.0011 (17) | 0.0095 (15) | −0.0037 (17) |
N21 | 0.0277 (18) | 0.0333 (19) | 0.0360 (18) | −0.0020 (15) | 0.0114 (14) | −0.0048 (16) |
N23 | 0.0297 (18) | 0.0338 (19) | 0.0315 (18) | 0.0051 (15) | 0.0105 (14) | −0.0043 (15) |
C1 | 0.036 (3) | 0.036 (3) | 0.030 (3) | 0.003 (2) | 0.008 (2) | 0.007 (3) |
C2 | 0.035 (3) | 0.031 (3) | 0.035 (3) | 0.006 (2) | 0.011 (2) | 0.007 (2) |
C11 | 0.067 (4) | 0.061 (4) | 0.055 (3) | −0.010 (3) | 0.027 (3) | −0.025 (3) |
C12 | 0.037 (2) | 0.035 (2) | 0.039 (2) | 0.0028 (18) | 0.021 (2) | 0.0049 (18) |
C13 | 0.031 (3) | 0.094 (5) | 0.062 (4) | −0.001 (3) | 0.009 (2) | −0.025 (3) |
C14 | 0.032 (2) | 0.031 (2) | 0.037 (2) | −0.0012 (17) | 0.0154 (18) | −0.0056 (17) |
C15 | 0.027 (2) | 0.029 (2) | 0.0291 (19) | −0.0002 (17) | 0.0120 (15) | 0.0025 (16) |
C16 | 0.032 (2) | 0.037 (2) | 0.031 (2) | −0.0034 (18) | 0.0136 (18) | 0.0047 (17) |
C21 | 0.029 (2) | 0.054 (3) | 0.052 (3) | −0.007 (2) | 0.017 (2) | −0.004 (2) |
C22 | 0.029 (2) | 0.040 (3) | 0.036 (2) | 0.0041 (18) | 0.0096 (18) | −0.0018 (19) |
C23 | 0.057 (3) | 0.044 (3) | 0.048 (3) | 0.000 (2) | 0.023 (2) | −0.017 (2) |
C24 | 0.0227 (19) | 0.031 (2) | 0.031 (2) | 0.0052 (16) | 0.0073 (15) | −0.0002 (16) |
C25 | 0.0231 (19) | 0.033 (2) | 0.0256 (18) | 0.0065 (16) | 0.0081 (15) | 0.0023 (15) |
C26 | 0.0201 (18) | 0.036 (2) | 0.0272 (17) | 0.0033 (17) | 0.0035 (14) | 0.0010 (17) |
Pt—N1 | 2.087 (3) | O26—C26 | 1.232 (5) |
Pt—N2 | 2.098 (3) | O1—H11 | 0.83 (3) |
Pt—C15 | 2.114 (4) | O1—H12 | 0.83 (3) |
Pt—C25 | 2.117 (4) | O2—H21 | 0.82 (3) |
C1—C2 | 1.495 (8) | O2—H22 | 0.84 (3) |
C10—C20 | 1.52 (4) | N1—H1 | 0.90 |
N1—C10 | 1.46 (3) | N1—H2 | 0.90 |
N1—C1 | 1.507 (6) | N2—H7 | 0.90 |
N2—C2 | 1.501 (6) | N2—H8 | 0.90 |
N2—C20 | 1.51 (2) | C1—H3 | 0.97 |
N11—C11 | 1.475 (6) | C1—H4 | 0.97 |
N11—C12 | 1.382 (6) | C2—H5 | 0.97 |
N11—C16 | 1.397 (6) | C2—H6 | 0.97 |
N13—C12 | 1.387 (6) | C10—H30 | 0.97 |
N13—C13 | 1.474 (6) | C10—H40 | 0.97 |
N13—C14 | 1.377 (6) | C20—H50 | 0.97 |
C14—C15 | 1.462 (6) | C20—H60 | 0.97 |
C15—C16 | 1.470 (6) | C11—H111 | 0.96 |
O12—C12 | 1.214 (5) | C11—H112 | 0.96 |
O14—C14 | 1.225 (5) | C11—H113 | 0.96 |
O16—C16 | 1.230 (5) | C13—H131 | 0.96 |
N21—C21 | 1.474 (6) | C13—H132 | 0.96 |
N21—C22 | 1.393 (6) | C13—H133 | 0.96 |
N21—C26 | 1.390 (5) | C15—H15 | 0.98 |
N23—C22 | 1.379 (6) | C21—H211 | 0.96 |
N23—C23 | 1.463 (5) | C21—H212 | 0.96 |
N23—C24 | 1.396 (5) | C21—H213 | 0.96 |
C24—C25 | 1.467 (6) | C23—H231 | 0.96 |
C25—C26 | 1.460 (6) | C23—H232 | 0.96 |
O22—C22 | 1.212 (5) | C23—H233 | 0.96 |
O24—C24 | 1.226 (5) | C25—H25 | 0.98 |
N1—Pt—N2 | 81.7 (1) | H1—N1—H2 | 108.2 |
N1—Pt—C15 | 177.0 (1) | C2—N2—H7 | 109.9 |
N1—Pt—C25 | 95.2 (1) | C20—N2—H7 | 139.2 |
N2—Pt—C15 | 96.9 (1) | Pt—N2—H7 | 109.9 |
N2—Pt—C25 | 175.6 (1) | C2—N2—H8 | 109.9 |
C15—Pt—C25 | 86.4 (2) | C20—N2—H8 | 76.2 |
Pt—C15—C14 | 109.5 (3) | Pt—N2—H8 | 109.9 |
Pt—C15—C16 | 105.3 (3) | H7—N2—H8 | 108.3 |
Pt—C25—C24 | 104.8 (3) | C2—C1—H3 | 109.9 |
Pt—C25—C26 | 109.9 (3) | N1—C1—H3 | 109.9 |
Pt—N1—C1 | 110.0 (3) | C2—C1—H4 | 109.9 |
Pt—N2—C2 | 109.0 (3) | N1—C1—H4 | 109.9 |
N1—C1—C2 | 108.8 (4) | H3—C1—H4 | 108.3 |
N2—C2—C1 | 107.0 (4) | C1—C2—H5 | 110.3 |
Pt—N1—C10 | 107.8 (12) | N2—C2—H5 | 110.3 |
Pt—N2—C20 | 105.9 (10) | C1—C2—H6 | 110.3 |
N1—C10—C20 | 106 (2) | N2—C2—H6 | 110.3 |
N2—C20—C10 | 103 (2) | H5—C2—H6 | 108.6 |
C12—N11—C16 | 124.0 (4) | N1—C10—H30 | 110.6 |
C12—N11—C11 | 116.5 (4) | C20—C10—H30 | 110.6 |
C16—N11—C11 | 119.2 (4) | N1—C10—H40 | 110.6 |
C14—N13—C12 | 124.6 (4) | C20—C10—H40 | 110.6 |
C14—N13—C13 | 118.9 (4) | H30—C10—H40 | 108.7 |
C12—N13—C13 | 116.2 (4) | N2—C20—H50 | 111.1 |
O12—C12—N11 | 122.3 (4) | C10—C20—H50 | 111.1 |
O12—C12—N13 | 121.0 (5) | N2—C20—H60 | 111.1 |
N11—C12—N13 | 116.6 (4) | C10—C20—H60 | 111.1 |
O16—C16—N11 | 119.3 (4) | H50—C20—H60 | 109.1 |
N11—C16—C15 | 116.4 (4) | N13—C13—H131 | 109.5 |
N13—C14—C15 | 117.2 (4) | N13—C13—H132 | 109.5 |
O14—C14—N13 | 118.6 (4) | H131—C13—H132 | 109.5 |
O14—C14—C15 | 124.1 (4) | N13—C13—H133 | 109.5 |
C14—C15—C16 | 115.9 (4) | H131—C13—H133 | 109.5 |
O16—C16—C15 | 124.3 (4) | H132—C13—H133 | 109.5 |
C26—N21—C22 | 123.5 (4) | N11—C11—H111 | 109.5 |
C26—N21—C21 | 118.9 (4) | N11—C11—H112 | 109.5 |
C22—N21—C21 | 116.9 (4) | H111—C11—H112 | 109.5 |
C22—N23—C24 | 123.9 (4) | N11—C11—H113 | 109.5 |
C22—N23—C23 | 115.9 (4) | H111—C11—H113 | 109.5 |
C24—N23—C23 | 119.6 (4) | H112—C11—H113 | 109.5 |
O22—C22—N23 | 121.8 (4) | C14—C15—H15 | 108.6 |
O22—C22—N21 | 120.8 (4) | C16—C15—H15 | 108.6 |
N23—C22—N21 | 117.4 (4) | Pt—C15—H15 | 108.6 |
O24—C24—N23 | 119.4 (4) | N21—C21—H211 | 109.5 |
N23—C24—C25 | 116.6 (4) | N21—C21—H212 | 109.5 |
O26—C26—N21 | 119.3 (4) | H211—C21—H212 | 109.5 |
N21—C26—C25 | 117.4 (4) | N21—C21—H213 | 109.5 |
O24—C24—C25 | 124.0 (4) | H211—C21—H213 | 109.5 |
C24—C25—C26 | 116.8 (4) | H212—C21—H213 | 109.5 |
O26—C26—C25 | 123.3 (4) | N23—C23—H231 | 109.5 |
C22—O22—H21 | 165 (2) | N23—C23—H232 | 109.5 |
H11—O1—H12 | 101 (7) | H231—C23—H232 | 109.5 |
H21—O2—H22 | 111 (7) | N23—C23—H233 | 109.5 |
C10—N1—H1 | 128.9 | H231—C23—H233 | 109.5 |
C1—N1—H1 | 109.7 | H232—C23—H233 | 109.5 |
Pt—N1—H1 | 109.7 | C26—C25—H25 | 108.4 |
C10—N1—H2 | 90.2 | C24—C25—H25 | 108.4 |
C1—N1—H2 | 109.7 | Pt—C25—H25 | 108.4 |
Pt—N1—H2 | 109.7 | ||
N2—Pt—N1—C10 | −14.5 (14) | C25—Pt—C15—C16 | −85.2 (3) |
C15—Pt—N1—C10 | −77 (3) | C12—N13—C14—O14 | −172.5 (4) |
C25—Pt—N1—C10 | 162.3 (14) | C13—N13—C14—O14 | 1.1 (7) |
N2—Pt—N1—C1 | 9.4 (4) | C12—N13—C14—C15 | 9.3 (7) |
C15—Pt—N1—C1 | −53 (3) | C13—N13—C14—C15 | −177.1 (4) |
C25—Pt—N1—C1 | −173.8 (4) | C16—C15—C14—O14 | 157.5 (5) |
N1—Pt—N2—C2 | 19.1 (3) | Pt—C15—C14—O14 | −83.6 (5) |
C15—Pt—N2—C2 | −163.6 (3) | C16—C15—C14—N13 | −24.4 (6) |
C25—Pt—N2—C2 | −27.2 (19) | Pt—C15—C14—N13 | 94.6 (4) |
N1—Pt—N2—C20 | −20.6 (11) | H21—O22—C22—N23 | −105 (7) |
C15—Pt—N2—C20 | 156.7 (11) | O2—O22—C22—N23 | −129.7 (10) |
C25—Pt—N2—C20 | −67 (2) | H21—O22—C22—N21 | 75 (7) |
C10—N1—C1—C2 | 52 (3) | O2—O22—C22—N21 | 50.6 (13) |
Pt—N1—C1—C2 | −36.6 (6) | C24—N23—C22—O22 | −173.6 (4) |
N1—C1—C2—N2 | 53.0 (6) | C23—N23—C22—O22 | −1.8 (7) |
C20—N2—C2—C1 | 47.6 (16) | C24—N23—C22—N21 | 6.1 (6) |
Pt—N2—C2—C1 | −44.1 (5) | C23—N23—C22—N21 | 177.9 (4) |
C1—N1—C10—C20 | −53 (3) | C26—N21—C22—O22 | 175.1 (4) |
Pt—N1—C10—C20 | 47 (2) | C21—N21—C22—O22 | 4.9 (7) |
C2—N2—C20—C10 | −50.2 (17) | C26—N21—C22—N23 | −4.6 (6) |
Pt—N2—C20—C10 | 50 (2) | C21—N21—C22—N23 | −174.8 (4) |
N1—C10—C20—N2 | −65 (2) | C22—N23—C24—O24 | 165.2 (4) |
C16—N11—C12—O12 | 178.6 (4) | C23—N23—C24—O24 | −6.3 (6) |
C11—N11—C12—O12 | −7.8 (7) | C22—N23—C24—C25 | −15.7 (6) |
C16—N11—C12—N13 | −2.3 (6) | C23—N23—C24—C25 | 172.8 (4) |
C11—N11—C12—N13 | 171.3 (4) | O24—C24—C25—C26 | −157.9 (4) |
C14—N13—C12—O12 | −176.4 (4) | N23—C24—C25—C26 | 23.1 (5) |
C13—N13—C12—O12 | 9.9 (7) | O24—C24—C25—Pt | 80.2 (4) |
C14—N13—C12—N11 | 4.5 (7) | N23—C24—C25—Pt | −98.8 (3) |
C13—N13—C12—N11 | −169.3 (5) | N1—Pt—C25—C26 | −39.7 (3) |
C12—N11—C16—O16 | 168.9 (4) | N2—Pt—C25—C26 | 6.2 (19) |
C11—N11—C16—O16 | −4.5 (7) | C15—Pt—C25—C26 | 142.9 (3) |
C12—N11—C16—C15 | −13.4 (6) | N1—Pt—C25—C24 | 86.6 (3) |
C11—N11—C16—C15 | 173.2 (4) | N2—Pt—C25—C24 | 132.5 (17) |
O16—C16—C15—C14 | −156.2 (4) | C15—Pt—C25—C24 | −90.8 (3) |
N11—C16—C15—C14 | 26.2 (6) | C22—N21—C26—O26 | −168.8 (4) |
O16—C16—C15—Pt | 82.6 (5) | C21—N21—C26—O26 | 1.3 (6) |
N11—C16—C15—Pt | −95.0 (4) | C22—N21—C26—C25 | 12.9 (6) |
N1—Pt—C15—C14 | 28 (3) | C21—N21—C26—C25 | −177.0 (4) |
N2—Pt—C15—C14 | −33.5 (3) | C24—C25—C26—O26 | 160.0 (4) |
C25—Pt—C15—C14 | 149.5 (3) | Pt—C25—C26—O26 | −80.9 (4) |
N1—Pt—C15—C16 | 154 (3) | C24—C25—C26—N21 | −21.9 (5) |
N2—Pt—C15—C16 | 91.7 (3) | Pt—C25—C26—N21 | 97.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O16i | 0.90 | 2.29 | 3.005 (5) | 136 |
N1—H2···O26ii | 0.90 | 2.08 | 2.969 (5) | 169 |
N2—H7···O12iii | 0.90 | 2.20 | 2.915 (5) | 136 |
N2—H8···O1i | 0.90 | 2.11 | 2.923 (6) | 149 |
O1—H11···O2iv | 0.83 (3) | 2.06 (4) | 2.837 (7) | 154 (7) |
O1—H12···O14v | 0.83 (3) | 2.03 (3) | 2.840 (6) | 165 (7) |
O2—H21···O22 | 0.82 (3) | 2.31 (5) | 3.040 (6) | 149 (7) |
O2—H22···O24vi | 0.84 (3) | 1.99 (3) | 2.819 (5) | 171 (7) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+2, −y, −z+1; (iv) x+1, −y+1/2, z−1/2; (v) −x+2, −y+1, −z+1; (vi) −x+1, y−1/2, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Pt(C2H8N2)(C6H7N2O3)2] | [Pt(C2H8N2)(C6H7N2O3)2]·2H2O |
Mr | 565.47 | 601.50 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 9.505 (2), 11.2518 (9), 9.464 (2) | 12.840 (2), 10.7834 (9), 14.727 (2) |
α, β, γ (°) | 103.10 (1), 110.52 (1), 87.93 (1) | 90, 107.051 (9), 90 |
V (Å3) | 922.2 (2) | 1949.5 (4) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 7.65 | 7.25 |
Crystal size (mm) | 0.20 × 0.10 × 0.07 | 0.16 × 0.16 × 0.07 |
Data collection | ||
Diffractometer | Rigaku AFC7R diffractometer | Rigaku AFC7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.294, 0.585 | 0.390, 0.631 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5685, 5383, 4663 | 5892, 5664, 4415 |
Rint | 0.029 | 0.026 |
(sin θ/λ)max (Å−1) | 0.704 | 0.704 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.061, 1.03 | 0.027, 0.065, 1.02 |
No. of reflections | 5383 | 5664 |
No. of parameters | 245 | 284 |
No. of restraints | 0 | 4 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.17, −1.14 | 0.88, −0.94 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a), MSC/AFC Diffractometer Control Software, TEXSAN PROCESS (Molecular Structure Corporation, 1993b), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
Pt—N1 | 2.098 (3) | O14—C14 | 1.222 (5) |
Pt—N2 | 2.015 (3) | O16—C16 | 1.227 (5) |
Pt—C15 | 2.112 (4) | C24—C25 | 1.368 (5) |
Pt—O24 | 2.041 (3) | C25—C26 | 1.413 (5) |
C14—C15 | 1.464 (6) | O22—C22 | 1.231 (5) |
C15—C16 | 1.460 (6) | O24—C24 | 1.275 (5) |
O12—C12 | 1.212 (6) | O26—C26 | 1.245 (5) |
N1—Pt—N2 | 83.2 (1) | Pt—O24—C24 | 125.1 (3) |
N1—Pt—C15 | 173.2 (1) | O14—C14—C15 | 124.0 (5) |
N1—Pt—O24 | 94.8 (1) | C14—C15—C16 | 117.1 (4) |
N2—Pt—C15 | 90.4 (1) | O16—C16—C15 | 123.2 (4) |
N2—Pt—O24 | 172.6 (1) | O24—C24—C25 | 127.1 (4) |
C15—Pt—O24 | 91.9 (1) | C24—C25—C26 | 121.7 (4) |
Pt—C15—C14 | 103.4 (3) | O26—C26—C25 | 125.8 (4) |
Pt—C15—C16 | 107.2 (3) | ||
Pt—O24—C24—C25 | −16.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O22i | 0.90 | 2.06 | 2.958 (5) | 172 |
N1—H2···O16ii | 0.90 | 2.17 | 2.939 (5) | 142 |
N2—H7···O26ii | 0.90 | 2.11 | 2.998 (5) | 167 |
N2—H8···O26iii | 0.90 | 2.02 | 2.893 (4) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1. |
Pt—N1 | 2.087 (3) | O14—C14 | 1.225 (5) |
Pt—N2 | 2.098 (3) | O16—C16 | 1.230 (5) |
Pt—C15 | 2.114 (4) | C24—C25 | 1.467 (6) |
Pt—C25 | 2.117 (4) | C25—C26 | 1.460 (6) |
C14—C15 | 1.462 (6) | O22—C22 | 1.212 (5) |
C15—C16 | 1.470 (6) | O24—C24 | 1.226 (5) |
O12—C12 | 1.214 (5) | O26—C26 | 1.232 (5) |
N1—Pt—N2 | 81.7 (1) | Pt—C25—C24 | 104.8 (3) |
N1—Pt—C15 | 177.0 (1) | Pt—C25—C26 | 109.9 (3) |
N1—Pt—C25 | 95.2 (1) | O14—C14—C15 | 124.1 (4) |
N2—Pt—C15 | 96.9 (1) | C14—C15—C16 | 115.9 (4) |
N2—Pt—C25 | 175.6 (1) | O16—C16—C15 | 124.3 (4) |
C15—Pt—C25 | 86.4 (2) | O24—C24—C25 | 124.0 (4) |
Pt—C15—C14 | 109.5 (3) | C24—C25—C26 | 116.8 (4) |
Pt—C15—C16 | 105.3 (3) | O26—C26—C25 | 123.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O16i | 0.90 | 2.29 | 3.005 (5) | 136 |
N1—H2···O26ii | 0.90 | 2.08 | 2.969 (5) | 169 |
N2—H7···O12iii | 0.90 | 2.20 | 2.915 (5) | 136 |
N2—H8···O1i | 0.90 | 2.11 | 2.923 (6) | 149 |
O1—H11···O2iv | 0.83 (3) | 2.06 (4) | 2.837 (7) | 154 (7) |
O1—H12···O14v | 0.83 (3) | 2.03 (3) | 2.840 (6) | 165 (7) |
O2—H21···O22 | 0.82 (3) | 2.31 (5) | 3.040 (6) | 149 (7) |
O2—H22···O24vi | 0.84 (3) | 1.99 (3) | 2.819 (5) | 171 (7) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x+2, −y, −z+1; (iv) x+1, −y+1/2, z−1/2; (v) −x+2, −y+1, −z+1; (vi) −x+1, y−1/2, −z+3/2. |
Some water-soluble palladium(II) and platinum(II) complexes involved with ambidentate β-diketonate have been known as organometallic compounds, in those the monodentate β-diketonato ligand is bound to the Pd or Pt atoms at a central C atom, e.g. K[PtCl(acac-C)(acac-O,O')] (Hacac = 2,4-pentanedione) (Mason, Robertson & Pauling, 1969). By using a cyclic β-diketone, 1,3-cyclohexanedione (Hchdo), in place of ambidentate Hacac, we have recently reported the monoalkylplatinum(II) compound [Pt(en)(chdo-C)(chdo-O)]·3H2O (3) (en = 1,2-diaminoethane), crystallized from a solution containing a 1:2 molar ratio of [Pt(en)(OH)2] and Hchdo (Yuge & Miyamoto, 1999); two monodentate chdo− ligands are bound to the Pt coordination center at an sp3-carbon and at an enolate oxygen. Any other compounds such as the dialkyl have not been obtained from the solution. The water-soluble dialkylplatinum(II) compound [Pt(en)(dmbarb-C)2]·2H2O (II) via [Pt(en)(dmbarb-C)(dmbarb-O)] (I) was isolated, replacing Hchdo with 1,3-dimethylbarbituric acid (Hdmbarb) as another potential monodentate ligand.
As shown in Figs. 1 and 2, the Pt complexes of (I) and (II) are found to be linkage isomers; two crystallographically independent dmbarb− anions coordinate to the Pt atom as monodentate ligands in common. In (I) one of the dmbarb− anions is bound at C15 and the other at O24 of the deprotonated enol, similarly to chdo− anions in (3). On the contrary in (II) both dmbarb− anions coordinate to the Pt atom at C15 and C25 atoms. The C-bound β-diketonate or O-bound enolate forms of the dmba− anions were confirmed by the bond lengths and angles. The angles about the donor C atoms are almost tetrahedral: 103.4 (3), 107.2 (3) and 117.1 (4)° for C15 in (I), 109.5 (3), 105.3 (3) and 115.9 (4) ° for C15 in (II) and 104.8 (3), 109.9 (3) and 116.8 (4) ° for C25 in (II). In (I) the enol O24—C24 bond length of 1.275 (5) Å are apparently longer than the carbonyl O22═C22 of 1.231 (5) and O26═C26 of 1.245 (5) Å. The Pt—C bond lengths, 2.112 (4) Å for (I), and 2.114 (4) and 2.117 (4) Å for (II), are comparable with that of (3), 2.123 (4) Å. Due to trans influence of the sp3-carbon atoms, the Pt—N bond lengths at trans to the Pt—C, 2.098 (3) Å for (I) and 2.087 (3) and 2.098 (3) Å for (II), are longer than that at trans to the Pt—O in (I), 2.015 (3) Å, as observed in (3) [2.070 (3) and 2.025 (3) Å]. The dmbarb− ligands in both compounds are approximately planar within 0.04 Å, except for the sp3-carbon atoms, C15 in (I) and C15 and C25 in (II), with the respective deviations of 0.288 (6), 0.309 (6) and 0.242 (6) Å from the least-square planes. Ignoring the sp3-carbon atoms from the molecular planes of the dmbarb− ligands, the C-bound are almost perpendicular to the Pt coordination planes with the dihedral angles of 88.8 (1)° for (I), and 85.5 (1) and 84.9 (1)° for (II); the angle for the O-bound in (I) is 59.5 (1)°. In (I) the two-dimensional hydrogen-bond network was formed along the bc plane by the amino N1 and N2 atoms of the en chelate and the carbonyl O16, O22 and O26 atoms of the dmbarb− ligands (Table 2), while the closer three-dimensional framework was built up in (II) by the amino groups, the carbonyl groups and water molecules (Table 4).
The 1H– and 13C-NMR spectra of (I) and (II) in D2O solutions show that the molecular structures in the solutions are consistent with those in the solid state, and that (I) changes into (II) in two weeks at room temperature. No changes have been found in the spectrum of (II) afterward, at least for a month. Accordingly the dialkylplatinum(II) compound (II) should be a thermodynamically stable species in an aqueous solution, compared with the monoalkyl (I).