Two new polymorphs of the title compound, K[PtCl
3(C
6H
15O
4PS)], already known in the monoclinic form, were obtained by crystallization from acetone-
n-pentane solutions of different composition. Both polymorphs are orthorhombic in the space group
P2
12
12
1, with
Z' = 1 (solvent ratio 1:4) and 3 (solvent ratio 1:9). In both polymorphs, electrostatic interactions link K
+ cations and [PtCl
3(SMP)]
- anions [SMP is diethyl (methylsulfinylmethyl)phosphonate] in infinite chains, while adjacent chains are held together by weak C-H
Cl and C-H
O hydrogen-bond interactions.
Supporting information
CCDC references: 616118; 616119
K[PtCl3(SMP)] was prepared as reported by Laforgia et al. (2005). The polymorphs (Ib) and (Ic) were crystallized as follows. For the crystallization of (Ib), K[PtCl3(SMP)] (15 mg, 2.7 × 10−2 mmol) was dissolved in acetone (4 ml) and layered under n-pentane (16 ml). After one week at room temperature, crystals suitable for crystallographic analysis were obtained. They were characterized by elemental analysis, IR spectroscopy and X-ray crystallography; C6H15Cl3KO4PPtS (554.75), calculated: C 13.00, H 2.73%; found: C 13.25, H 2.64; IR (Medium?, cm−1): 2913 (νCH), 1253 (νPO), 1049 (νSO), 1013 (νPOR), 341 (νPtCl).
For the crystallization of (Ic), K[PtCl3(SMP)] (5 mg, 9 × 10−3 mmol) was dissolved in acetone (1 ml) and layered under n-pentane (9 ml). After one week at room temperature, crystals suitable for crystallographic analysis were obtained. They were characterized by elemental analysis, IR spectroscopy and X-ray crystallography; C6H15Cl3KO4PPtS (554.75), found C 13.31, H 2.78%; IR (Medium?, cm−1): 2913 (νCH), 1253 (νPO), 1049 (νSO), 1013 (νPOR), 341 (νPtCl).
H atoms were placed in calculated positions, with C—H = 0.96–0.97 Å [Please check added text], and refined with Uiso(H) = 1.2 (1.5 for the methyl H atoms) times Ueq(parent). Four restraints were used in the refinement of the structure of (Ib). These were associated with an –OCH2CH3 group, which was disordered over two orientations, DFIX 1.5 O4 C5 O4 C5A and DFIX 1.45 C5 C6 C5A C6. The coordinates of the disordered –OCH2CH3 group were refined with occupancies tied to sum to unity.
For both compounds, data collection: COSMO, APEX2 and BIS (Bruker, 2004); cell refinement: SAINT-IRIX (Bruker, 2004); data reduction: SAINT-IRIX; program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1983, 1995) and WinGX (Farrugia, 1999).
(Ib) potassium trichloro[diethyl (methylsulfinylmethyl)phosphonate-
κS]platinum(II)
top
Crystal data top
K[PtCl3(C6H15O4PS)] | F(000) = 1048 |
Mr = 554.75 | Dx = 2.288 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2Ac 2Ab | Cell parameters from 63182 reflections |
a = 8.1697 (2) Å | θ = 2.1–36.0° |
b = 13.2052 (3) Å | µ = 9.70 mm−1 |
c = 14.9286 (4) Å | T = 295 K |
V = 1610.54 (7) Å3 | Prism, yellow |
Z = 4 | 0.50 × 0.25 × 0.14 mm |
Data collection top
Bruker X8 APEX CCD area-detector diffractometer | 7591 independent reflections |
Radiation source: fine-focus sealed tube | 4342 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 36.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.017, Tmax = 0.437 | k = −21→21 |
63182 measured reflections | l = −24→24 |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0271P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.065 | (Δ/σ)max = 0.005 |
S = 0.87 | Δρmax = 2.63 e Å−3 |
7591 reflections | Δρmin = −1.30 e Å−3 |
167 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
10 restraints | Extinction coefficient: 0.00146 (12) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 3348 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.002 (6) |
Crystal data top
K[PtCl3(C6H15O4PS)] | V = 1610.54 (7) Å3 |
Mr = 554.75 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.1697 (2) Å | µ = 9.70 mm−1 |
b = 13.2052 (3) Å | T = 295 K |
c = 14.9286 (4) Å | 0.50 × 0.25 × 0.14 mm |
Data collection top
Bruker X8 APEX CCD area-detector diffractometer | 7591 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4342 reflections with I > 2σ(I) |
Tmin = 0.017, Tmax = 0.437 | Rint = 0.046 |
63182 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.065 | Δρmax = 2.63 e Å−3 |
S = 0.87 | Δρmin = −1.30 e Å−3 |
7591 reflections | Absolute structure: Flack (1983), with 3348 Friedel pairs |
167 parameters | Absolute structure parameter: 0.002 (6) |
10 restraints | |
Special details top
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. Hydrogen atoms were placed at calculated positions and refined given isotropic parameters equivalent to 1.2 (1.5 for the methyl H atoms) times those of the atom to which they were attached. Some 4 restraints were used in the refinement. These were associated with –OCH2CH3 group was disordered over two orientations DFIX 1.5 O4 C5 O4 C5A DFIX 1.45 C5 C6 C5A C6. The coordinates of disorder –OCH2CH3 group over two orientations were refined with the occupancies tied to sum to unity. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Pt | 0.45308 (2) | 0.695750 (14) | 0.327866 (12) | 0.03397 (6) | |
Cl1 | 0.26702 (16) | 0.80214 (13) | 0.39893 (8) | 0.0464 (3) | |
Cl2 | 0.65406 (17) | 0.81016 (12) | 0.36534 (10) | 0.0558 (3) | |
Cl3 | 0.24153 (17) | 0.58728 (12) | 0.29386 (11) | 0.0583 (4) | |
S | 0.62444 (16) | 0.59825 (11) | 0.25345 (9) | 0.0412 (3) | |
O1 | 0.7996 (4) | 0.6220 (3) | 0.2549 (3) | 0.0581 (11) | |
C1 | 0.5608 (8) | 0.5952 (5) | 0.1394 (3) | 0.0598 (16) | |
H1A | 0.5520 | 0.6631 | 0.1170 | 0.090* | |
H1B | 0.4563 | 0.5623 | 0.1351 | 0.090* | |
H1C | 0.6398 | 0.5585 | 0.1045 | 0.090* | |
C2 | 0.6011 (7) | 0.4677 (4) | 0.2821 (4) | 0.0489 (14) | |
H2A | 0.6559 | 0.4275 | 0.2367 | 0.059* | |
H2B | 0.4855 | 0.4512 | 0.2795 | 0.059* | |
P | 0.6781 (2) | 0.42996 (12) | 0.39025 (11) | 0.0533 (4) | |
O2 | 0.7827 (9) | 0.5083 (4) | 0.4340 (4) | 0.0931 (18) | |
O3 | 0.7738 (8) | 0.3273 (4) | 0.3746 (4) | 0.0923 (17) | |
O4 | 0.5314 (10) | 0.3944 (6) | 0.4422 (4) | 0.127 (2) | |
C3 | 0.9367 (9) | 0.3322 (7) | 0.3282 (6) | 0.095 (3) | |
H3A | 0.9475 | 0.2738 | 0.2892 | 0.114* | |
H3B | 0.9400 | 0.3923 | 0.2910 | 0.114* | |
C4 | 1.0741 (12) | 0.3343 (7) | 0.3896 (7) | 0.112 (3) | |
H4A | 1.0731 | 0.3968 | 0.4225 | 0.169* | |
H4B | 1.1743 | 0.3291 | 0.3564 | 0.169* | |
H4C | 1.0658 | 0.2785 | 0.4305 | 0.169* | |
C5 | 0.454 (2) | 0.4853 (16) | 0.4960 (11) | 0.147 (8) | 0.66 (2) |
H5A | 0.5218 | 0.5440 | 0.4840 | 0.176* | 0.66 (2) |
H5B | 0.3483 | 0.4988 | 0.4689 | 0.176* | 0.66 (2) |
C5A | 0.483 (4) | 0.4039 (19) | 0.5355 (12) | 0.099 (10) | 0.34 (2) |
H51A | 0.3978 | 0.3534 | 0.5437 | 0.119* | 0.34 (2) |
H52A | 0.5763 | 0.3798 | 0.5694 | 0.119* | 0.34 (2) |
C6 | 0.431 (2) | 0.4833 (13) | 0.5795 (10) | 0.200 (7) | |
H6A | 0.3514 | 0.4323 | 0.5937 | 0.300* | 0.66 (2) |
H6b | 0.3918 | 0.5482 | 0.5991 | 0.300* | 0.66 (2) |
H6C | 0.5321 | 0.4680 | 0.6092 | 0.300* | 0.66 (2) |
H6D | 0.5205 | 0.5130 | 0.6118 | 0.300* | 0.34 (2) |
H6E | 0.3470 | 0.4633 | 0.6209 | 0.300* | 0.34 (2) |
H6F | 0.3873 | 0.5319 | 0.5381 | 0.300* | 0.34 (2) |
K | 0.95429 (17) | 0.66900 (10) | 0.41928 (8) | 0.0561 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt | 0.03539 (9) | 0.03427 (9) | 0.03225 (8) | −0.00041 (9) | −0.00033 (9) | −0.00079 (9) |
Cl1 | 0.0508 (7) | 0.0445 (7) | 0.0438 (6) | 0.0059 (7) | 0.0045 (6) | −0.0084 (7) |
Cl2 | 0.0469 (7) | 0.0415 (7) | 0.0791 (9) | −0.0056 (7) | −0.0158 (7) | −0.0038 (8) |
Cl3 | 0.0403 (7) | 0.0571 (9) | 0.0776 (10) | −0.0097 (7) | 0.0084 (7) | −0.0249 (8) |
S | 0.0357 (6) | 0.0528 (8) | 0.0352 (7) | −0.0001 (6) | 0.0026 (6) | −0.0062 (6) |
O1 | 0.0356 (19) | 0.082 (3) | 0.057 (3) | −0.001 (2) | 0.0127 (19) | −0.006 (2) |
C1 | 0.057 (3) | 0.088 (4) | 0.035 (3) | 0.005 (4) | −0.003 (3) | −0.011 (3) |
C2 | 0.054 (3) | 0.040 (3) | 0.053 (3) | 0.006 (2) | 0.001 (3) | −0.018 (3) |
P | 0.0712 (11) | 0.0413 (9) | 0.0474 (9) | 0.0008 (8) | 0.0036 (8) | −0.0078 (7) |
O2 | 0.152 (6) | 0.056 (3) | 0.072 (3) | −0.008 (3) | −0.037 (4) | −0.003 (3) |
O3 | 0.126 (5) | 0.065 (4) | 0.086 (4) | 0.015 (3) | −0.004 (3) | −0.002 (3) |
O4 | 0.111 (5) | 0.180 (7) | 0.091 (4) | −0.026 (6) | 0.023 (4) | −0.004 (4) |
C3 | 0.078 (5) | 0.128 (7) | 0.078 (5) | 0.042 (5) | 0.023 (5) | −0.008 (5) |
C4 | 0.113 (8) | 0.108 (8) | 0.117 (8) | 0.016 (6) | −0.036 (6) | −0.005 (6) |
C5 | 0.107 (11) | 0.24 (2) | 0.091 (12) | 0.056 (15) | 0.000 (11) | 0.017 (14) |
C5A | 0.12 (2) | 0.13 (2) | 0.052 (14) | 0.046 (17) | 0.026 (13) | 0.011 (13) |
C6 | 0.244 (19) | 0.200 (16) | 0.157 (14) | 0.020 (16) | 0.066 (15) | −0.012 (12) |
K | 0.0384 (5) | 0.0750 (9) | 0.0549 (7) | −0.0001 (7) | 0.0049 (7) | −0.0077 (6) |
Geometric parameters (Å, º) top
Pt—S | 2.2027 (14) | C3—C4 | 1.449 (11) |
Pt—Cl2 | 2.3003 (14) | C3—H3A | 0.9700 |
Pt—Cl3 | 2.3014 (14) | C3—H3B | 0.9700 |
Pt—Cl1 | 2.3259 (14) | C4—H4A | 0.9600 |
S—O1 | 1.465 (4) | C4—H4B | 0.9600 |
S—C1 | 1.781 (5) | C4—H4C | 0.9600 |
S—C2 | 1.786 (6) | C5—C6 | 1.260 (14) |
C1—H1A | 0.9600 | C5—H5A | 0.9700 |
C1—H1B | 0.9600 | C5—H5B | 0.9700 |
C1—H1C | 0.9600 | C5A—C6 | 1.308 (16) |
C2—P | 1.804 (6) | C5A—H51A | 0.9700 |
C2—H2A | 0.9700 | C5A—H52A | 0.9700 |
C2—H2B | 0.9700 | C6—H6A | 0.9600 |
P—O2 | 1.492 (5) | C6—H6b | 0.9600 |
P—O4 | 1.503 (7) | C6—H6C | 0.9600 |
P—O3 | 1.582 (5) | C6—H6D | 0.9600 |
O3—C3 | 1.502 (9) | C6—H6E | 0.9600 |
O4—C5A | 1.454 (15) | C6—H6F | 0.9600 |
O4—C5 | 1.577 (15) | | |
| | | |
K···O1 | 2.829 (4) | K···Cl1ii | 3.139 (2) |
K···Cl2 | 3.184 (2) | K···Cl3i | 3.190 (2) |
K···O2 | 2.553 (6) | K···Cl2ii | 3.616 (2) |
K···Cl1i | 3.116 (2) | | |
| | | |
S—Pt—Cl2 | 93.03 (5) | C4—C3—H3A | 108.9 |
S—Pt—Cl3 | 90.13 (5) | O3—C3—H3A | 108.9 |
Cl2—Pt—Cl3 | 176.82 (6) | C4—C3—H3B | 108.9 |
S—Pt—Cl1 | 176.85 (5) | O3—C3—H3B | 108.9 |
Cl2—Pt—Cl1 | 87.64 (5) | H3A—C3—H3B | 107.7 |
Cl3—Pt—Cl1 | 89.19 (5) | C3—C4—H4A | 109.5 |
O1—S—C1 | 107.7 (3) | C3—C4—H4B | 109.5 |
O1—S—C2 | 107.9 (3) | H4A—C4—H4B | 109.5 |
C1—S—C2 | 100.1 (3) | C3—C4—H4C | 109.5 |
O1—S—Pt | 119.19 (19) | H4A—C4—H4C | 109.5 |
C1—S—Pt | 108.1 (2) | H4B—C4—H4C | 109.5 |
C2—S—Pt | 112.06 (19) | C6—C5—O4 | 123.2 (15) |
S—C1—H1A | 109.5 | C6—C5—H5A | 106.6 |
S—C1—H1B | 109.5 | O4—C5—H5A | 106.6 |
H1A—C1—H1B | 109.5 | C6—C5—H5B | 106.6 |
S—C1—H1C | 109.5 | O4—C5—H5B | 106.6 |
H1A—C1—H1C | 109.5 | H5A—C5—H5B | 106.6 |
H1B—C1—H1C | 109.5 | C6—C5A—O4 | 129.7 (19) |
S—C2—P | 116.4 (3) | C6—C5A—H51A | 105.1 |
S—C2—H2A | 108.2 | O4—C5A—H51A | 105.1 |
P—C2—H2A | 108.2 | C6—C5A—H52A | 105.1 |
S—C2—H2B | 108.2 | O4—C5A—H52A | 105.1 |
P—C2—H2B | 108.2 | H51A—C5A—H52A | 105.9 |
H2A—C2—H2B | 107.4 | C5—C6—H6A | 109.5 |
O2—P—O4 | 116.6 (4) | C5—C6—H6b | 109.5 |
O2—P—O3 | 112.1 (3) | H6A—C6—H6b | 109.5 |
O4—P—O3 | 101.7 (4) | C5—C6—H6C | 109.5 |
O2—P—C2 | 113.6 (3) | H6A—C6—H6C | 109.5 |
O4—P—C2 | 105.7 (4) | H6b—C6—H6C | 109.5 |
O3—P—C2 | 106.1 (3) | C5A—C6—H6D | 109.5 |
C3—O3—P | 118.0 (5) | C5A—C6—H6E | 109.5 |
C5A—O4—P | 133.3 (13) | H6D—C6—H6E | 109.5 |
C5A—O4—C5 | 49.0 (11) | C5A—C6—H6F | 109.5 |
P—O4—C5 | 110.2 (9) | H6D—C6—H6F | 109.5 |
C4—C3—O3 | 113.3 (7) | H6E—C6—H6F | 109.5 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Cl1iii | 0.97 | 2.69 | 3.639 (6) | 166 |
C3—H3A···O1iv | 0.97 | 2.95 | 3.726 (9) | 138 |
C1—H1C···O2v | 0.96 | 2.77 | 3.592 (8) | 144 |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+3/2, −y+1, z−1/2. |
(Ic) potassium trichloro[diethyl (methylsulfinylmethyl)phosphonate-
κS]platinum(II)
top
Crystal data top
K[PtCl3(C6H15O4PS)] | F(000) = 3144 |
Mr = 554.76 | Dx = 2.228 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2Ac 2Ab | Cell parameters from 169856 reflections |
a = 14.2518 (3) Å | θ = 1.6–37.6° |
b = 16.6754 (3) Å | µ = 9.44 mm−1 |
c = 20.8743 (3) Å | T = 295 K |
V = 4960.87 (15) Å3 | Acicular, yellow |
Z = 12 | 1.00 × 0.07 × 0.06 mm |
Data collection top
Bruker X8 APEX CCD area-detector diffractometer | 23275 independent reflections |
Radiation source: fine-focus sealed tube | 10272 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 37.6°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→24 |
Tmin = 0.121, Tmax = 0.437 | k = −28→27 |
169856 measured reflections | l = −34→33 |
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)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0238P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.85 | (Δ/σ)max = 0.003 |
23275 reflections | Δρmax = 3.73 e Å−3 |
469 parameters | Δρmin = −1.50 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with 10077 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.008 (3) |
Crystal data top
K[PtCl3(C6H15O4PS)] | V = 4960.87 (15) Å3 |
Mr = 554.76 | Z = 12 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 14.2518 (3) Å | µ = 9.44 mm−1 |
b = 16.6754 (3) Å | T = 295 K |
c = 20.8743 (3) Å | 1.00 × 0.07 × 0.06 mm |
Data collection top
Bruker X8 APEX CCD area-detector diffractometer | 23275 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 10272 reflections with I > 2σ(I) |
Tmin = 0.121, Tmax = 0.437 | Rint = 0.031 |
169856 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.067 | Δρmax = 3.73 e Å−3 |
S = 0.85 | Δρmin = −1.50 e Å−3 |
23275 reflections | Absolute structure: Flack (1983), with 10077 Friedel pairs |
469 parameters | Absolute structure parameter: −0.008 (3) |
0 restraints | |
Special details top
Experimental. no |
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. Hydrogen atoms were placed at calculated positions and refined given isotropic parameters equivalent to 1.2 (1.5 for the methyl H atoms) times those of the atom to which they were attached. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.755981 (15) | 0.296334 (13) | 0.822025 (9) | 0.03914 (5) | |
Cl1 | 0.88240 (11) | 0.28643 (11) | 0.75322 (7) | 0.0650 (4) | |
Cl2 | 0.81917 (11) | 0.41394 (9) | 0.85986 (7) | 0.0568 (4) | |
Cl3 | 0.69554 (15) | 0.18023 (9) | 0.77911 (8) | 0.0736 (5) | |
S1 | 0.63265 (9) | 0.30902 (8) | 0.88412 (6) | 0.0415 (3) | |
O1 | 0.6248 (3) | 0.3791 (2) | 0.92649 (17) | 0.0561 (11) | |
P1 | 0.51816 (12) | 0.40254 (9) | 0.79171 (7) | 0.0457 (4) | |
O2 | 0.6055 (3) | 0.4317 (2) | 0.76448 (17) | 0.0487 (10) | |
O3 | 0.4391 (3) | 0.3820 (3) | 0.74418 (19) | 0.0679 (13) | |
O4 | 0.4810 (3) | 0.4676 (3) | 0.8390 (2) | 0.0620 (12) | |
C1 | 0.6140 (5) | 0.2219 (4) | 0.9311 (3) | 0.068 (2) | |
H11 | 0.6665 | 0.2140 | 0.9592 | 0.102* | |
H12 | 0.6074 | 0.1762 | 0.9036 | 0.102* | |
H13 | 0.5579 | 0.2284 | 0.9561 | 0.102* | |
C2 | 0.5293 (4) | 0.3079 (3) | 0.8346 (2) | 0.0475 (15) | |
H21 | 0.4742 | 0.2994 | 0.8610 | 0.057* | |
H22 | 0.5333 | 0.2641 | 0.8041 | 0.057* | |
C5 | 0.3982 (6) | 0.4579 (5) | 0.8776 (5) | 0.108 (3) | |
H51 | 0.3545 | 0.4228 | 0.8556 | 0.129* | |
H52 | 0.4151 | 0.4328 | 0.9179 | 0.129* | |
C6 | 0.3542 (6) | 0.5320 (5) | 0.8900 (4) | 0.110 (3) | |
H61 | 0.3985 | 0.5681 | 0.9091 | 0.164* | |
H62 | 0.3026 | 0.5238 | 0.9189 | 0.164* | |
H63 | 0.3313 | 0.5543 | 0.8506 | 0.164* | |
C3 | 0.4253 (6) | 0.4282 (5) | 0.6847 (4) | 0.109 (3) | |
H31 | 0.4792 | 0.4628 | 0.6783 | 0.131* | |
H32 | 0.4225 | 0.3912 | 0.6489 | 0.131* | |
C4 | 0.3478 (9) | 0.4728 (6) | 0.6850 (5) | 0.172 (6) | |
H41 | 0.2939 | 0.4388 | 0.6896 | 0.257* | |
H42 | 0.3434 | 0.5020 | 0.6455 | 0.257* | |
H43 | 0.3502 | 0.5099 | 0.7202 | 0.257* | |
K1 | 0.76815 (10) | 0.45058 (7) | 0.70206 (5) | 0.0490 (3) | |
Pt1A | 0.793078 (15) | 0.301575 (14) | 0.121016 (9) | 0.03959 (5) | |
Cl1A | 0.85894 (12) | 0.28429 (11) | 0.02110 (7) | 0.0726 (5) | |
Cl2A | 0.88278 (12) | 0.41522 (10) | 0.13265 (8) | 0.0658 (5) | |
Cl3A | 0.70552 (13) | 0.18738 (9) | 0.10550 (7) | 0.0681 (4) | |
S1A | 0.72497 (10) | 0.32006 (8) | 0.21449 (6) | 0.0394 (3) | |
O1A | 0.7462 (3) | 0.3925 (2) | 0.25189 (15) | 0.0493 (10) | |
P1A | 0.55790 (11) | 0.40902 (10) | 0.16849 (8) | 0.0491 (4) | |
O2A | 0.6245 (3) | 0.4420 (2) | 0.12200 (17) | 0.0518 (10) | |
O3A | 0.4577 (3) | 0.3907 (3) | 0.1467 (2) | 0.0905 (17) | |
O4A | 0.5446 (3) | 0.4705 (3) | 0.2246 (2) | 0.0663 (13) | |
C1A | 0.7468 (5) | 0.2364 (3) | 0.2656 (2) | 0.0592 (17) | |
H11A | 0.8130 | 0.2317 | 0.2731 | 0.089* | |
H12A | 0.7242 | 0.1883 | 0.2455 | 0.089* | |
H13A | 0.7149 | 0.2441 | 0.3056 | 0.089* | |
C2A | 0.5995 (4) | 0.3179 (3) | 0.2050 (3) | 0.0455 (15) | |
H21A | 0.5820 | 0.2725 | 0.1784 | 0.055* | |
H22A | 0.5700 | 0.3112 | 0.2465 | 0.055* | |
C3A | 0.4276 (6) | 0.3724 (6) | 0.0847 (4) | 0.122 (4) | |
H31A | 0.4113 | 0.3160 | 0.0826 | 0.147* | |
H32A | 0.4787 | 0.3818 | 0.0549 | 0.147* | |
C4A | 0.3482 (7) | 0.4193 (6) | 0.0656 (4) | 0.139 (4) | |
H41A | 0.2979 | 0.4114 | 0.0955 | 0.209* | |
H42A | 0.3282 | 0.4029 | 0.0236 | 0.209* | |
H43A | 0.3652 | 0.4750 | 0.0647 | 0.209* | |
C5A | 0.4784 (7) | 0.4602 (6) | 0.2768 (4) | 0.108 (3) | |
H51A | 0.4440 | 0.4106 | 0.2706 | 0.130* | |
H52A | 0.5126 | 0.4560 | 0.3169 | 0.130* | |
C6A | 0.4160 (8) | 0.5231 (7) | 0.2806 (5) | 0.154 (5) | |
H61A | 0.4427 | 0.5652 | 0.3060 | 0.230* | |
H62A | 0.3588 | 0.5049 | 0.3001 | 0.230* | |
H63A | 0.4030 | 0.5428 | 0.2383 | 0.230* | |
K1A | 0.73604 (10) | 0.45737 (7) | 0.01396 (5) | 0.0545 (4) | |
Pt1B | 0.846264 (16) | 0.290004 (14) | 0.473729 (10) | 0.04572 (6) | |
Cl1B | 0.94678 (12) | 0.27236 (12) | 0.38719 (8) | 0.0800 (6) | |
Cl2B | 0.92146 (11) | 0.41035 (10) | 0.49244 (7) | 0.0594 (4) | |
Cl3B | 0.77868 (13) | 0.16744 (10) | 0.45425 (9) | 0.0796 (6) | |
S1B | 0.74049 (10) | 0.31265 (8) | 0.54847 (6) | 0.0435 (3) | |
O1B | 0.7402 (3) | 0.3904 (2) | 0.58158 (16) | 0.0596 (12) | |
P1B | 0.60752 (11) | 0.36321 (10) | 0.44389 (7) | 0.0466 (4) | |
O2B | 0.6862 (3) | 0.4176 (2) | 0.43261 (17) | 0.0524 (10) | |
O3B | 0.5901 (3) | 0.3043 (3) | 0.38629 (16) | 0.0595 (11) | |
O4B | 0.5101 (3) | 0.4020 (3) | 0.4532 (2) | 0.0683 (13) | |
C1B | 0.7377 (5) | 0.2364 (4) | 0.6087 (2) | 0.072 (2) | |
H11B | 0.7904 | 0.2428 | 0.6369 | 0.108* | |
H12B | 0.7405 | 0.1846 | 0.5887 | 0.108* | |
H13B | 0.6806 | 0.2408 | 0.6329 | 0.108* | |
C2B | 0.6251 (4) | 0.2996 (3) | 0.5146 (2) | 0.0474 (14) | |
H21B | 0.5782 | 0.3127 | 0.5466 | 0.057* | |
H22B | 0.6166 | 0.2438 | 0.5026 | 0.057* | |
C3B | 0.5116 (4) | 0.2456 (4) | 0.3896 (3) | 0.072 (2) | |
H31B | 0.4900 | 0.2410 | 0.4335 | 0.086* | |
H32B | 0.4597 | 0.2645 | 0.3636 | 0.086* | |
C4B | 0.5424 (6) | 0.1660 (4) | 0.3663 (3) | 0.087 (3) | |
H41B | 0.5636 | 0.1706 | 0.3227 | 0.131* | |
H42B | 0.4908 | 0.1291 | 0.3683 | 0.131* | |
H43B | 0.5929 | 0.1468 | 0.3926 | 0.131* | |
C5B | 0.4962 (7) | 0.4682 (7) | 0.4936 (5) | 0.153 (5) | |
H51B | 0.4817 | 0.4481 | 0.5360 | 0.184* | |
H52B | 0.5552 | 0.4970 | 0.4967 | 0.184* | |
C6b | 0.4295 (8) | 0.5212 (5) | 0.4775 (5) | 0.155 (5) | |
H61B | 0.3727 | 0.4931 | 0.4671 | 0.232* | |
H62B | 0.4498 | 0.5516 | 0.4410 | 0.232* | |
H63B | 0.4182 | 0.5567 | 0.5129 | 0.232* | |
K1B | 0.84078 (10) | 0.44627 (8) | 0.35408 (6) | 0.0533 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.04710 (12) | 0.03590 (11) | 0.03441 (10) | 0.00329 (12) | 0.00273 (10) | 0.00159 (10) |
Cl1 | 0.0594 (10) | 0.0802 (12) | 0.0553 (8) | 0.0171 (10) | 0.0183 (7) | 0.0020 (9) |
Cl2 | 0.0572 (11) | 0.0547 (10) | 0.0584 (9) | −0.0121 (8) | 0.0010 (8) | −0.0074 (7) |
Cl3 | 0.1045 (15) | 0.0470 (10) | 0.0693 (10) | −0.0131 (10) | 0.0124 (10) | −0.0165 (7) |
S1 | 0.0461 (8) | 0.0436 (8) | 0.0349 (7) | −0.0027 (7) | 0.0026 (6) | 0.0012 (7) |
O1 | 0.055 (3) | 0.062 (3) | 0.052 (2) | 0.006 (2) | 0.003 (2) | −0.017 (2) |
P1 | 0.0437 (10) | 0.0432 (9) | 0.0503 (9) | −0.0082 (8) | −0.0053 (7) | 0.0035 (7) |
O2 | 0.047 (2) | 0.047 (2) | 0.052 (2) | −0.009 (2) | 0.001 (2) | 0.0080 (18) |
O3 | 0.069 (3) | 0.074 (3) | 0.060 (3) | −0.025 (3) | −0.027 (2) | 0.019 (2) |
O4 | 0.052 (3) | 0.057 (3) | 0.077 (3) | −0.001 (2) | 0.009 (2) | −0.002 (2) |
C1 | 0.078 (5) | 0.074 (5) | 0.051 (4) | −0.001 (4) | 0.013 (3) | 0.035 (3) |
C2 | 0.052 (4) | 0.045 (4) | 0.045 (3) | −0.017 (3) | 0.001 (3) | 0.000 (3) |
C5 | 0.082 (6) | 0.082 (6) | 0.160 (8) | 0.017 (5) | 0.073 (6) | −0.005 (6) |
C6 | 0.075 (6) | 0.093 (6) | 0.160 (9) | 0.009 (5) | 0.028 (6) | −0.014 (6) |
C3 | 0.096 (7) | 0.115 (8) | 0.115 (7) | −0.031 (6) | −0.043 (6) | 0.021 (6) |
C4 | 0.267 (15) | 0.122 (9) | 0.125 (8) | 0.129 (10) | −0.007 (10) | 0.026 (7) |
K1 | 0.0647 (10) | 0.0443 (7) | 0.0380 (6) | −0.0039 (7) | 0.0100 (6) | −0.0019 (5) |
Pt1A | 0.03777 (11) | 0.04160 (12) | 0.03939 (10) | 0.00312 (11) | −0.00011 (9) | −0.00294 (11) |
Cl1A | 0.0715 (11) | 0.0954 (13) | 0.0510 (8) | 0.0075 (11) | 0.0170 (8) | −0.0149 (9) |
Cl2A | 0.0584 (11) | 0.0694 (11) | 0.0697 (11) | −0.0225 (9) | 0.0097 (9) | −0.0082 (9) |
Cl3A | 0.0817 (11) | 0.0494 (10) | 0.0731 (10) | −0.0115 (9) | −0.0031 (9) | −0.0135 (8) |
S1A | 0.0425 (9) | 0.0391 (8) | 0.0365 (7) | 0.0001 (6) | 0.0022 (6) | 0.0018 (6) |
O1A | 0.062 (3) | 0.044 (2) | 0.042 (2) | 0.004 (2) | 0.003 (2) | −0.0072 (17) |
P1A | 0.0368 (9) | 0.0552 (11) | 0.0553 (10) | −0.0007 (8) | −0.0027 (8) | 0.0083 (8) |
O2A | 0.049 (2) | 0.066 (3) | 0.041 (2) | −0.006 (2) | 0.0027 (19) | 0.014 (2) |
O3A | 0.061 (3) | 0.113 (4) | 0.098 (4) | −0.022 (3) | −0.018 (3) | 0.031 (3) |
O4A | 0.068 (3) | 0.066 (3) | 0.065 (3) | 0.011 (3) | 0.021 (3) | −0.005 (2) |
C1A | 0.071 (4) | 0.052 (4) | 0.054 (3) | 0.017 (4) | −0.002 (3) | 0.023 (3) |
C2A | 0.039 (3) | 0.051 (4) | 0.047 (3) | −0.010 (3) | 0.006 (3) | 0.007 (3) |
C3A | 0.084 (7) | 0.157 (10) | 0.126 (8) | −0.012 (7) | −0.016 (6) | −0.084 (7) |
C4A | 0.129 (9) | 0.158 (10) | 0.131 (8) | 0.048 (8) | −0.054 (7) | 0.009 (7) |
C5A | 0.133 (9) | 0.124 (8) | 0.067 (5) | 0.048 (7) | 0.016 (6) | 0.001 (5) |
C6A | 0.132 (10) | 0.186 (12) | 0.143 (10) | 0.075 (9) | 0.049 (8) | 0.012 (8) |
K1A | 0.0718 (10) | 0.0519 (8) | 0.0397 (7) | −0.0088 (7) | −0.0007 (7) | 0.0014 (5) |
Pt1B | 0.04379 (13) | 0.05108 (14) | 0.04230 (11) | 0.00651 (13) | −0.00938 (10) | 0.00077 (12) |
Cl1B | 0.0610 (11) | 0.1163 (16) | 0.0626 (10) | 0.0274 (10) | 0.0060 (9) | −0.0075 (10) |
Cl2B | 0.0526 (10) | 0.0703 (11) | 0.0553 (9) | −0.0166 (8) | −0.0126 (8) | 0.0118 (8) |
Cl3B | 0.0803 (14) | 0.0518 (10) | 0.1067 (14) | 0.0030 (9) | −0.0084 (11) | −0.0243 (9) |
S1B | 0.0525 (9) | 0.0429 (9) | 0.0351 (6) | −0.0086 (7) | −0.0029 (6) | 0.0033 (6) |
O1B | 0.085 (3) | 0.057 (3) | 0.037 (2) | −0.019 (2) | 0.006 (2) | −0.0096 (18) |
P1B | 0.0390 (9) | 0.0512 (10) | 0.0496 (9) | 0.0004 (8) | 0.0016 (7) | 0.0110 (7) |
O2B | 0.051 (3) | 0.052 (2) | 0.054 (2) | −0.004 (2) | −0.004 (2) | 0.0174 (19) |
O3B | 0.059 (3) | 0.080 (3) | 0.039 (2) | −0.012 (3) | 0.0105 (19) | 0.000 (2) |
O4B | 0.049 (3) | 0.079 (3) | 0.077 (3) | 0.012 (2) | 0.000 (2) | −0.008 (3) |
C1B | 0.098 (6) | 0.076 (5) | 0.041 (3) | −0.019 (4) | −0.009 (3) | 0.026 (3) |
C2B | 0.051 (4) | 0.054 (3) | 0.037 (3) | −0.011 (3) | 0.005 (2) | 0.007 (3) |
C3B | 0.049 (4) | 0.119 (6) | 0.048 (4) | −0.036 (4) | −0.006 (3) | −0.006 (4) |
C4B | 0.121 (7) | 0.083 (6) | 0.058 (4) | −0.038 (5) | −0.029 (5) | 0.016 (4) |
C5B | 0.104 (9) | 0.203 (12) | 0.152 (10) | 0.038 (8) | −0.017 (7) | −0.119 (9) |
C6b | 0.185 (12) | 0.095 (7) | 0.185 (11) | 0.071 (8) | −0.031 (10) | −0.020 (8) |
K1B | 0.0575 (8) | 0.0610 (9) | 0.0415 (7) | −0.0114 (7) | −0.0086 (6) | 0.0127 (6) |
Geometric parameters (Å, º) top
Pt1—S1 | 2.1942 (13) | C1A—H13A | 0.9600 |
Pt1—Cl2 | 2.2980 (15) | C2A—H21A | 0.9700 |
Pt1—Cl3 | 2.3007 (15) | C2A—H22A | 0.9700 |
Pt1—Cl1 | 2.3101 (14) | C3A—C4A | 1.432 (11) |
S1—O1 | 1.469 (4) | C3A—H31A | 0.9700 |
S1—C1 | 1.773 (5) | C3A—H32A | 0.9700 |
S1—C2 | 1.800 (5) | C4A—H41A | 0.9600 |
P1—O2 | 1.452 (4) | C4A—H42A | 0.9600 |
P1—O3 | 1.540 (4) | C4A—H43A | 0.9600 |
P1—O4 | 1.560 (4) | C5A—C6A | 1.377 (11) |
P1—C2 | 1.821 (6) | C5A—H51A | 0.9700 |
O3—C3 | 1.474 (8) | C5A—H52A | 0.9700 |
O4—C5 | 1.438 (8) | C6A—H61A | 0.9600 |
C1—H11 | 0.9600 | C6A—H62A | 0.9600 |
C1—H12 | 0.9600 | C6A—H63A | 0.9600 |
C1—H13 | 0.9600 | Pt1B—S1B | 2.2021 (14) |
C2—H21 | 0.9700 | Pt1B—Cl3B | 2.2956 (17) |
C2—H22 | 0.9700 | Pt1B—Cl2B | 2.3083 (16) |
C5—C6 | 1.409 (9) | Pt1B—Cl1B | 2.3243 (16) |
C5—H51 | 0.9700 | S1B—O1B | 1.469 (4) |
C5—H52 | 0.9700 | S1B—C1B | 1.789 (5) |
C6—H61 | 0.9600 | S1B—C2B | 1.804 (5) |
C6—H62 | 0.9600 | P1B—O2B | 1.461 (4) |
C6—H63 | 0.9600 | P1B—O4B | 1.544 (4) |
C3—C4 | 1.333 (11) | P1B—O3B | 1.572 (4) |
C3—H31 | 0.9700 | P1B—C2B | 1.834 (5) |
C3—H32 | 0.9700 | O3B—C3B | 1.488 (7) |
C4—H41 | 0.9600 | O4B—C5B | 1.404 (9) |
C4—H42 | 0.9600 | C1B—H11B | 0.9600 |
C4—H43 | 0.9600 | C1B—H12B | 0.9600 |
Pt1A—S1A | 2.2010 (13) | C1B—H13B | 0.9600 |
Pt1A—Cl2A | 2.2988 (15) | C2B—H21B | 0.9700 |
Pt1A—Cl3A | 2.2997 (15) | C2B—H22B | 0.9700 |
Pt1A—Cl1A | 2.3053 (14) | C3B—C4B | 1.479 (9) |
S1A—O1A | 1.470 (4) | C3B—H31B | 0.9700 |
S1A—C1A | 1.784 (5) | C3B—H32B | 0.9700 |
S1A—C2A | 1.800 (5) | C4B—H41B | 0.9600 |
P1A—O2A | 1.465 (4) | C4B—H42B | 0.9600 |
P1A—O3A | 1.529 (5) | C4B—H43B | 0.9600 |
P1A—O4A | 1.568 (4) | C5B—C6b | 1.339 (11) |
P1A—C2A | 1.800 (5) | C5B—H51B | 0.9700 |
O3A—C3A | 1.398 (8) | C5B—H52B | 0.9700 |
O4A—C5A | 1.451 (8) | C6b—H61B | 0.9600 |
C1A—H11A | 0.9600 | C6b—H62B | 0.9600 |
C1A—H12A | 0.9600 | C6b—H63B | 0.9600 |
| | | |
K1···O2 | 2.678 (4) | K1A···O1ii | 2.748 (4) |
K1···O1B | 2.737 (3) | K1A···O2Biii | 2.909 (4) |
K1···Cl1 | 3.359 (2) | K1A···O1Biii | 2.924 (4) |
K1···Cl2 | 3.428 (2) | K1A···Cl2Biii | 3.179 (2) |
K1···Cl2Ai | 3.426 (2) | K1B···Cl1B | 3.342 (2) |
K1···O1Ai | 2.823 (4) | K1B···Cl2B | 3.166 (2) |
K1···O2Ai | 2.888 (4) | K1B···O1A | 2.678 (4) |
K1···O4Ai | 3.013 (5) | K1B···O2B | 2.787 (4) |
K1A···Cl1A | 3.379 (2) | K1B···O2iii | 2.868 (4) |
K1A···Cl2A | 3.317 (2) | K1B···O4iii | 2.934 (4) |
K1A···O2A | 2.771 (4) | K1B···Cl2iii | 3.263 (2) |
K1A···Cl2ii | 3.504 (2) | | |
| | | |
S1—Pt1—Cl2 | 91.64 (5) | S1A—C2A—H21A | 109.5 |
S1—Pt1—Cl3 | 90.64 (6) | P1A—C2A—H22A | 109.5 |
Cl2—Pt1—Cl3 | 177.11 (6) | S1A—C2A—H22A | 109.5 |
S1—Pt1—Cl1 | 177.42 (5) | H21A—C2A—H22A | 108.1 |
Cl2—Pt1—Cl1 | 88.23 (6) | O3A—C3A—C4A | 112.5 (8) |
Cl3—Pt1—Cl1 | 89.41 (7) | O3A—C3A—H31A | 109.1 |
O1—S1—C1 | 107.9 (2) | C4A—C3A—H31A | 109.1 |
O1—S1—C2 | 107.0 (3) | O3A—C3A—H32A | 109.1 |
C1—S1—C2 | 100.7 (3) | C4A—C3A—H32A | 109.1 |
O1—S1—Pt1 | 119.54 (18) | H31A—C3A—H32A | 107.8 |
C1—S1—Pt1 | 111.6 (2) | C3A—C4A—H41A | 109.5 |
C2—S1—Pt1 | 108.36 (18) | C3A—C4A—H42A | 109.5 |
O2—P1—O3 | 116.7 (2) | H41A—C4A—H42A | 109.5 |
O2—P1—O4 | 107.8 (2) | C3A—C4A—H43A | 109.5 |
O3—P1—O4 | 108.3 (3) | H41A—C4A—H43A | 109.5 |
O2—P1—C2 | 114.0 (2) | H42A—C4A—H43A | 109.5 |
O3—P1—C2 | 100.8 (2) | C6A—C5A—O4A | 111.9 (8) |
O4—P1—C2 | 108.8 (2) | C6A—C5A—H51A | 109.2 |
C3—O3—P1 | 121.6 (4) | O4A—C5A—H51A | 109.2 |
C5—O4—P1 | 123.7 (4) | C6A—C5A—H52A | 109.2 |
S1—C1—H11 | 109.5 | O4A—C5A—H52A | 109.2 |
S1—C1—H12 | 109.5 | H51A—C5A—H52A | 107.9 |
H11—C1—H12 | 109.5 | C5A—C6A—H61A | 109.5 |
S1—C1—H13 | 109.5 | C5A—C6A—H62A | 109.5 |
H11—C1—H13 | 109.5 | H61A—C6A—H62A | 109.5 |
H12—C1—H13 | 109.5 | C5A—C6A—H63A | 109.5 |
S1—C2—P1 | 110.1 (3) | H61A—C6A—H63A | 109.5 |
S1—C2—H21 | 109.6 | H62A—C6A—H63A | 109.5 |
P1—C2—H21 | 109.6 | S1B—Pt1B—Cl3B | 89.48 (6) |
S1—C2—H22 | 109.6 | S1B—Pt1B—Cl2B | 92.80 (5) |
P1—C2—H22 | 109.6 | Cl3B—Pt1B—Cl2B | 177.14 (6) |
H21—C2—H22 | 108.1 | S1B—Pt1B—Cl1B | 173.88 (6) |
C6—C5—O4 | 111.8 (7) | Cl3B—Pt1B—Cl1B | 90.47 (7) |
C6—C5—H51 | 109.3 | Cl2B—Pt1B—Cl1B | 87.45 (7) |
O4—C5—H51 | 109.3 | O1B—S1B—C1B | 107.3 (3) |
C6—C5—H52 | 109.3 | O1B—S1B—C2B | 106.8 (3) |
O4—C5—H52 | 109.3 | C1B—S1B—C2B | 99.7 (3) |
H51—C5—H52 | 107.9 | O1B—S1B—Pt1B | 119.11 (18) |
C5—C6—H61 | 109.5 | C1B—S1B—Pt1B | 113.0 (2) |
C5—C6—H62 | 109.5 | C2B—S1B—Pt1B | 109.00 (17) |
H61—C6—H62 | 109.5 | O2B—P1B—O4B | 116.8 (2) |
C5—C6—H63 | 109.5 | O2B—P1B—O3B | 112.7 (2) |
H61—C6—H63 | 109.5 | O4B—P1B—O3B | 102.5 (2) |
H62—C6—H63 | 109.5 | O2B—P1B—C2B | 112.6 (2) |
C4—C3—O3 | 113.5 (9) | O4B—P1B—C2B | 105.3 (2) |
C4—C3—H31 | 108.9 | O3B—P1B—C2B | 105.9 (2) |
O3—C3—H31 | 108.9 | C3B—O3B—P1B | 119.6 (3) |
C4—C3—H32 | 108.9 | C5B—O4B—P1B | 122.1 (5) |
O3—C3—H32 | 108.9 | S1B—C1B—H11B | 109.5 |
H31—C3—H32 | 107.7 | S1B—C1B—H12B | 109.5 |
C3—C4—H41 | 109.5 | H11B—C1B—H12B | 109.5 |
C3—C4—H42 | 109.5 | S1B—C1B—H13B | 109.5 |
H41—C4—H42 | 109.5 | H11B—C1B—H13B | 109.5 |
C3—C4—H43 | 109.5 | H12B—C1B—H13B | 109.5 |
H41—C4—H43 | 109.5 | S1B—C2B—P1B | 111.7 (3) |
H42—C4—H43 | 109.5 | S1B—C2B—H21B | 109.3 |
S1A—Pt1A—Cl2A | 92.07 (5) | P1B—C2B—H21B | 109.3 |
S1A—Pt1A—Cl3A | 90.09 (5) | S1B—C2B—H22B | 109.3 |
Cl2A—Pt1A—Cl3A | 177.83 (6) | P1B—C2B—H22B | 109.3 |
S1A—Pt1A—Cl1A | 177.63 (6) | H21B—C2B—H22B | 107.9 |
Cl2A—Pt1A—Cl1A | 88.41 (6) | C4B—C3B—O3B | 110.6 (5) |
Cl3A—Pt1A—Cl1A | 89.42 (6) | C4B—C3B—H31B | 109.5 |
O1A—S1A—C1A | 106.8 (2) | O3B—C3B—H31B | 109.5 |
O1A—S1A—C2A | 106.3 (2) | C4B—C3B—H32B | 109.5 |
C1A—S1A—C2A | 102.9 (3) | O3B—C3B—H32B | 109.5 |
O1A—S1A—Pt1A | 119.68 (16) | H31B—C3B—H32B | 108.1 |
C1A—S1A—Pt1A | 110.1 (2) | C3B—C4B—H41B | 109.5 |
C2A—S1A—Pt1A | 109.72 (19) | C3B—C4B—H42B | 109.5 |
O2A—P1A—O3A | 118.9 (3) | H41B—C4B—H42B | 109.5 |
O2A—P1A—O4A | 109.2 (3) | C3B—C4B—H43B | 109.5 |
O3A—P1A—O4A | 103.9 (3) | H41B—C4B—H43B | 109.5 |
O2A—P1A—C2A | 112.6 (2) | H42B—C4B—H43B | 109.5 |
O3A—P1A—C2A | 105.3 (3) | C6B—C5B—O4B | 117.9 (9) |
O4A—P1A—C2A | 106.0 (3) | C6b—C5B—H51B | 107.8 |
C3A—O3A—P1A | 127.3 (5) | O4B—C5B—H51B | 107.8 |
C5A—O4A—P1A | 124.2 (5) | C6b—C5B—H52B | 107.8 |
S1A—C1A—H11A | 109.5 | O4B—C5B—H52B | 107.8 |
S1A—C1A—H12A | 109.5 | H51B—C5B—H52B | 107.2 |
H11A—C1A—H12A | 109.5 | C5B—C6b—H61B | 109.5 |
S1A—C1A—H13A | 109.5 | C5B—C6b—H62B | 109.5 |
H11A—C1A—H13A | 109.5 | H61B—C6b—H62B | 109.5 |
H12A—C1A—H13A | 109.5 | C5B—C6b—H63B | 109.5 |
P1A—C2A—S1A | 110.9 (3) | H61B—C6b—H63B | 109.5 |
P1A—C2A—H21A | 109.5 | H62B—C6b—H63B | 109.5 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x, y, z−1; (iii) −x+3/2, −y+1, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H13A···O3B | 0.96 | 2.65 | 3.552 (7) | 157 |
C2A—H22A···O3B | 0.97 | 2.93 | 3.794 (6) | 148 |
C5A—H52A···O4B | 0.97 | 2.98 | 3.833 (9) | 147 |
C1—H13···Cl1Aiv | 0.96 | 2.88 | 3.770 (7) | 154 |
C3B—H32B···Cl1iv | 0.97 | 2.81 | 3.544 (6) | 133 |
C3A—H31A···Cl1Av | 0.97 | 2.83 | 3.559 (8) | 132 |
C3—H32···Cl1Biv | 0.97 | 2.85 | 3.678 (10) | 144 |
C5—H51···Cl3Aiv | 0.97 | 2.92 | 3.679 (8) | 136 |
C1B—H11B···Cl1 | 0.96 | 2.85 | 3.748 (6) | 155 |
C2B—H21B···Cl1Biv | 0.97 | 2.73 | 3.478 (5) | 135 |
Symmetry codes: (iv) x−1/2, −y+1/2, −z+1; (v) x−1/2, −y+1/2, −z. |
Experimental details
| (Ib) | (Ic) |
Crystal data |
Chemical formula | K[PtCl3(C6H15O4PS)] | K[PtCl3(C6H15O4PS)] |
Mr | 554.75 | 554.76 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 8.1697 (2), 13.2052 (3), 14.9286 (4) | 14.2518 (3), 16.6754 (3), 20.8743 (3) |
V (Å3) | 1610.54 (7) | 4960.87 (15) |
Z | 4 | 12 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 9.70 | 9.44 |
Crystal size (mm) | 0.50 × 0.25 × 0.14 | 1.00 × 0.07 × 0.06 |
|
Data collection |
Diffractometer | Bruker X8 APEX CCD area-detector diffractometer | Bruker X8 APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.017, 0.437 | 0.121, 0.437 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 63182, 7591, 4342 | 169856, 23275, 10272 |
Rint | 0.046 | 0.031 |
(sin θ/λ)max (Å−1) | 0.826 | 0.859 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.065, 0.87 | 0.050, 0.067, 0.85 |
No. of reflections | 7591 | 23275 |
No. of parameters | 167 | 469 |
No. of restraints | 10 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.63, −1.30 | 3.73, −1.50 |
Absolute structure | Flack (1983), with 3348 Friedel pairs | Flack (1983), with 10077 Friedel pairs |
Absolute structure parameter | 0.002 (6) | −0.008 (3) |
Selected interatomic distances (Å) for (Ib) topK···O1 | 2.829 (4) | K···Cl1ii | 3.139 (2) |
K···Cl2 | 3.184 (2) | K···Cl3i | 3.190 (2) |
K···O2 | 2.553 (6) | K···Cl2ii | 3.616 (2) |
K···Cl1i | 3.116 (2) | | |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, −z+1. |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Cl1iii | 0.97 | 2.69 | 3.639 (6) | 166 |
C3—H3A···O1iv | 0.97 | 2.95 | 3.726 (9) | 138 |
C1—H1C···O2v | 0.96 | 2.77 | 3.592 (8) | 144 |
Symmetry codes: (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, y−1/2, −z+1/2; (v) −x+3/2, −y+1, z−1/2. |
Selected interatomic distances (Å) for (Ic) topK1···O2 | 2.678 (4) | K1A···O1ii | 2.748 (4) |
K1···O1B | 2.737 (3) | K1A···O2Biii | 2.909 (4) |
K1···Cl1 | 3.359 (2) | K1A···O1Biii | 2.924 (4) |
K1···Cl2 | 3.428 (2) | K1A···Cl2Biii | 3.179 (2) |
K1···Cl2Ai | 3.426 (2) | K1B···Cl1B | 3.342 (2) |
K1···O1Ai | 2.823 (4) | K1B···Cl2B | 3.166 (2) |
K1···O2Ai | 2.888 (4) | K1B···O1A | 2.678 (4) |
K1···O4Ai | 3.013 (5) | K1B···O2B | 2.787 (4) |
K1A···Cl1A | 3.379 (2) | K1B···O2iii | 2.868 (4) |
K1A···Cl2A | 3.317 (2) | K1B···O4iii | 2.934 (4) |
K1A···O2A | 2.771 (4) | K1B···Cl2iii | 3.263 (2) |
K1A···Cl2ii | 3.504 (2) | | |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) x, y, z−1; (iii) −x+3/2, −y+1, z−1/2. |
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H13A···O3B | 0.96 | 2.65 | 3.552 (7) | 157 |
C2A—H22A···O3B | 0.97 | 2.93 | 3.794 (6) | 148 |
C5A—H52A···O4B | 0.97 | 2.98 | 3.833 (9) | 147 |
C1—H13···Cl1Aiv | 0.96 | 2.88 | 3.770 (7) | 154 |
C3B—H32B···Cl1iv | 0.97 | 2.81 | 3.544 (6) | 133 |
C3A—H31A···Cl1Av | 0.97 | 2.83 | 3.559 (8) | 132 |
C3—H32···Cl1Biv | 0.97 | 2.85 | 3.678 (10) | 144 |
C5—H51···Cl3Aiv | 0.97 | 2.92 | 3.679 (8) | 136 |
C1B—H11B···Cl1 | 0.96 | 2.85 | 3.748 (6) | 155 |
C2B—H21B···Cl1Biv | 0.97 | 2.73 | 3.478 (5) | 135 |
Symmetry codes: (iv) x−1/2, −y+1/2, −z+1; (v) x−1/2, −y+1/2, −z. |
Several compounds form different crystalline structures having the same molecular composition. This phenomenon, known as polymorphism, can stem from different possible ways of optimizing the intra and intermolecular interactions within the crystal packing. Several drugs used in clinical medicine show this peculiar behaviour. For instance, chloramfenicol palmitate exists in three crystalline forms and phenylbutazone in as many as five different polymorphic structures. Although the mode of interaction with the biological target(s) does not change, different polymorphic structures of a given drug can show a variety of chemico-physical properties (rate of dissolution in physiological media, bioavailability etc.) which can significantly influence the success of the pharmacological treatment (Aguiar et al., 1967; Foppoli et al., 2003; Kaliszan, 1986). It is generally accepted that, among different polymorphs, the best form is that with the greatest bioavailability, which usually coincides with the least stable crystalline form at room temperature.
Recently, we have proposed new PtII compounds containing diethyl[(methylsulfinyl)methyl]phosphonate, SMP (Laforgia et al., 2004), as antitumour drugs which may have a selective tropism for bone tissue (thanks to the phosphonate moiety) and which have shown interesting MMP inhibition activity (MMP is membrane metalloproteinase; Sasanelli et al., 2006). Our investigation has already led to the isolation and characterization of a monoclinic species, (Ia), K[PtCl3(SMP)] (Laforgia et al., 2005). We now report the crystallographic analysis of two new orthorhombic polymorphs. The monoclinic form (space group P21/a, Z' = 1), (Ia) was obtained from a mixture of H2O–acetone–CHCl3 (Ratio?). However, if acetone–pentane is used as solvent, two orthorhombic polymorphs, having space group P212121 and with Z' = 1 for (Ib) (solvent ratio 1:4) or 3 for (Ic) (solvent ratio 1:9), are obtained.
The bond lengths in the orthorhombic polymorphs (Ib) and (Ic) are very similar to those found in the monoclinic polymorph (Ia), and do not require further discussion. In contrast, the patterns of the supramolecular aggregations are very different for (Ia), (Ib) and (Ic), and these will be discussed here.
The simpler orthorhombic polymorph, (Ib) (Fig. 1), has Z' = 1 in space group P212121. Each complex anion is linked to three K+ cations by way of the three Cl− ligands (Cl1, Cl2, and Cl3) and the S═O and P═O O atoms of the SMP ligand (O1 and O2). Similar to the case of (Ia), the P═O O atom interacts with only one K+ cation. Atoms Cl1 and Cl2 interact with two K+ cations, while atom Cl3 interacts with only one K+ cation (Fig. 1). Each K+ cation is trapped in an irregular seven-donor cage formed by five Cl and two O atoms of three different anions, namely atoms Cl2, O1, and O2 of one platinum unit (Pt), atoms Cl1 and Cl3 of the second platinum unit (PtA), and atoms Cl1 and Cl2 of the third platinum unit (PtB). The K···O and K···Cl distances are reported in Table 1.
Electrostatic interactions link cations and anions in an infinite chain extending along the a direction (Fig. 2). Adjacent chains are held together by hydrogen-bond interactions of different strengths involving Cl1 atoms of one chain and C2 atoms of an adjacent chain, and atoms O2 and O1 of one chain and atoms C3 and C1 of an adjacent chain (Table 2). A view of the crystal packing along the a direction is shown in Fig. 3. In this polymorph, one ethyl group (C5/C5A and C6) is disordered, probably because it lacks significant intermolecular interactions.
The second orthorhombic polymorph, (Ic), has Z' = 3 in space group P212121. Each independent anion interacts with three K+ cations by way of atoms Cl1, Cl2, O1 and O2 (Fig. 4). In two of the three independent anions (Pt1 and Pt1A), the ester atom O4 is also involved in electrostatic interactions with the K+ cations. In particular, two anions (Pt1A and Pt1B) have one K+ cation interacting with the S═ O and P═O O atoms of the SMP ligand and the Cl ligand cis to the sulfoxide [as observed in (Ia) and (Ib)], while the third anion (Pt), having the S═O and P═O O atoms more distant [O1···O2 = 3.505 (5) Å, compared with O1A···O2A = 3.323 (5) Å and O1B···O2B = 3.235 (5) Å), has its K+ cation interacting with the P═O O atom of the SMP ligand and with the Cl1 and Cl2 ligands which are cis and trans to the coordinated sulfoxide (Fig. 4). In general, atom Cl1 interacts with only one cation and atom Cl2 with two cations (three in the case of Pt). Two independent K+ cations are trapped in an irregular eight-donor cage formed by three Cl and five O atoms of three different anions in the case of K1, and by four Cl and four O atoms of three different anions in the case of K1A. The third cation, K1B, is trapped in a seven-donor cage formed by three Cl and four O atoms. The K···O and K···Cl distances for cations K1, K1A and K1B are given in Table 3.
Intra-chain hydrogen-bonding interactions of different strengths are also present. These involve Cl and O atoms on one hand (Cl1, O4B and O3B) and C atoms on the other hand (C1B, C1A, C2A and C5A). Infinite chains of anions and cations extend along the c direction (Fig. 5). Adjacent chains are held together by hydrogen-bond interactions involving atoms Cl1, Cl1A, Cl1B and Cl3A of one chain, and atoms C1, C2B, C3B, C3A, C3 and C5 of adjacent chains (Table 4). A view of the crystal packing along the c direction is shown in Fig. 5.
In conclusion, this work has shown that it is possible to isolate the complex K[PtCl3(SMP)] in three different crystalline forms, one of which has already been reported (Laforgia et al., 2005). The solvent of crystallization [H2O–acetone–CHCl3 (Ratio?) for (Ia), and acetone–n-pentane in the ratios 1:4 and 1:9 for (Ib) and (Ic), respectively] appears to be responsible for the different crystalline packings. In all cases, strong interactions between anions and cations lead to chains extending in one direction. The chains are held together in the crystal structure by weak hydrogen-bond interactions involving Cl or O atoms of one chain and CH atoms of adjacent chains. In the case of (Ic), there are also hydrogen bonds of this type within each chain. The P═O O atom interacts with only one K+ cation in (Ia) and (Ib) (the same K+ cation also interacts with the S═O O atom and with the Cl− cis to the sulfoxide), and with two K+ cations in (Ic) (one K+ cation also interacts with atoms Cl1 and Cl2, and the other interacts with atoms Cl2 and O1 in Pt and PtB, and with atoms Cl2 and O4 in PtA). Moreover, in the structures of (Ia) and (Ib), all three Cl atoms of the complex anion are involved in interactions with K+ cations, while in the structure of (Ic), one Cl atom (Cl3 of all three independent anions) does not interact with any K+ cations. The different mode of interaction of the [PtCl3(SMP)]− anion with the cations revealed in this investigation can also provide useful information for elucidating the mechanism of the biological activity of this type of compound, particularly the inhibition of MMP activity.