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The crystal structure of cis-[PtCl2(C6H15As)2], (I), is isostructural with a previously reported structure of cis-[PtCl2(C6H15P)2], (II). A new polymorph of (II) is also reported here. Selected geometrical parameters in the arsine complex are Pt-Cl 2.3412 (12) and 2.3498 (13), Pt-As 2.3563 (6) and 2.3630 (6) Å, Cl-Pt-Cl 88.74 (5), As-Pt-As 97.85 (2), and Cl-Pt-As 171.37 (4) and 177.45 (4)°. Corresponding parameters in the phosphine complex are Pt-Cl 2.364 (2) and 2.374 (2), Pt-P 2.264 (2) and 2.262 (2) Å, Cl-Pt-Cl 85.66 (9), P-Pt-P 98.39 (7), and Cl-Pt-P 170.26 (7) and 176.82 (8)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101016043/sk1505sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016043/sk1505Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101016043/sk1505IIsup3.hkl
Contains datablock II

CCDC references: 179260; 179261

Comment top

Although dihalo–bisphosphine complexes of platinum(II) are well documented in the literature, very few crystallographic studies are reported for the analogous arsine complexes. Some complexes with a trans geometry have been documented (Otto & Roodt 1997; Johansson et al., 2000), but only one complex of this nature, with a cis geometry, viz. cis-[PtCl2(AsPh3)2] (Otto & Johansson, 2001), has appeared so far in the literature. Crystallographic studies on these complexes are important for understanding the coordination mode of the ligands involved, especially to establish their respective trans influences.

As part of our systematic investigation on these systems, crystals of cis-dichlorobis(triethylarsine)platinum(II), (I), were obtained and the structure solved. We have also redetermined the structure of the analogous cis-dichlorobis(triethylphosphine)platinum(II) complex, (II), for which only a preliminary report was found (Caldwell et al., 1977), but for which no geometrical parameters were available. Compound (I) is isostructural with the polymorph reported by Caldwell et al. (1977), while (II) was found to be a new polymorph of the previously reported complex.

Both complexes have a distorted square-planar geometry with the neutral ligands in a cis configuration, see Figs. 1 and 2. They crystallize on general positions in the monoclinic space groups P21/n and Cc for (I) and (II), respectively, resulting in the chemically equivalent ligands being crystallographically different.

In (I), the Pt—As1 and Pt—As2 bond distances of 2.3563 (6) and 2.3630 (6) Å are significantly different (see Table 1), while Pt—Cl1 and Pt—Cl2 are more similar at 2.3412 (12) and 2.3498 (13) Å, respectively. The As1—Pt—Cl1 angle of 171.37 (4)° differs by 6.08 (4)° from the As2—Pt—Cl2 angle of 177.45 (4)°, while the As2—Pt—Cl1 and Cl1—Pt—Cl2 angles are close to 90° at 90.11 (4) and 88.74 (5)°, respectively. The As1—Pt—As2 and As1—Pt—Cl2 angles of 97.85 (2) and 83.18 (4)° suggest that As1 is sterically repelled from As2 to compensate for the crowding between these two large ligands. These angles can be understood by studying the Cl—Pt—As—C torsion angles describing the orientation of the arsine ligands around the Pt—As bonds. Each As ligand has one substituent, C111 and C211, almost in the coordination plane with Cl2—Pt—As1—C111 and Cl1—Pt—As2—C211 torsion angles of 177.4 (2) and -7.68 (19)°, respectively. In the case of As2, C211 points towards Cl1, while on As1, C111 points towards As2. The compression in the As1—Pt—Cl1 angle is thus facilitated by the resulting staggered conformation of As1 with respect to Cl2, as illustrated by the Cl2—Pt—As—C121 and Cl2—Pt—As—C131 torsion angles of -60.69 (17) and 52.0 (2)°, respectively. A consequence of this effect is that As2 is orientated with its remaining two substituents in a staggered conformation with respect to As1, as indicated by the As1—Pt—As2—C221 and As1—Pt—As2—C231 torsion angles of -68.20 (17) and 53.83 (16)°, respectively.

In (II), both the Pt—Cl1 and Pt—Cl2 distances of 2.364 (2) and 2.374 (2) Å and the Pt—P1 and Pt—P2 distances of 2.264 (2) and 2.2616 (18) Å (see Table 2) are quite similar for the respective ligands. Due to the shorter Pt—P bond distance, compared with Pt—As, a larger repulsion between the PEt3 ligands results in a P1—Pt—P2 angle of 98.39 (7)°. The P2—Pt—Cl1 angle is close to that obtained for (I) of 91.33 (17)°, while both the Cl1—Pt—Cl2 and Cl2—Pt—P1 angles are compressed to 85.66 (9) and 84.63 (9)°, respectively. The orientation of P1 was very similar to that found for As1 in (I) with a Cl2—Pt—P1—C111 torsion angle of 176.7 (4)°, while the Cl1—Pt—P2—C211 torsion angle differed by more than 7° from the corresponding angle in (I) with a value of -0.1 (4)°. A staggered conformation was observed for P1 with respect to Cl2 [similar to As1 in (I)], as shown by the Cl2—Pt—P1—C121 and Cl2—Pt—P1—C131 torsion angles of -60.5 (4) and 53.8 (3)°, respectively. A similar behaviour was exhibited by P2 with respect to P1, with P1—Pt—P2—C221 and P1—Pt—P2—C232 torsion angles of -61.8 (4) and 61.5 (4)°, respectively.

The expected elongation of ca 0.1 Å is observed for the As—C bond distances [average 1.949 (5) Å] compared with the P—C distances [average 1.827 (9) Å] in correspondences with the increase in the atomic radii. Furthermore, the average C—As—C angle of 102.6 (2)° is slightly smaller than the average C—P—C angle of 104.0 (5)°, in accordance with the normal geometry for these ligands.

The ethyl substituents have different orientations in the solid state (see Figs. 1 and 2) resulting in different effective steric demands. A modified calculation of the Tolman cone-angles (Tolman, 1977) was used to calculate the effective cone-angles for the ligands (Otto et al., 2000). The effective cone angle is based on Tolman's model but the crystallographically obtained geometry is used without any modifications. A van der Waals radius of 1.2 Å for hydrogen and calculated C—H bond distances of 0.97 Å for CH2 and 0.96 Å for CH3 were used. In (I), the effective cone angles for As1 and As2 were calculated as 144 and 155°, while in (II), values of 146 and 147° were obtained for P1 and P2. Values for the effective cone angles, obtained in this way, can thus give a qualitative indication of the similarity/difference between the packing modes of ligands in different crystallographic environments. The larger value for As2, as compared to the other three ligands, can be attributed to the orientation of C211 and C212 which is almost perpendicular to the coordination plane. In the other ligands, this group is bent to point away from the coordination plane and thus resulting in the smaller and comparable values. The accepted value for the Tolman cone angle for PEt3 is 132°, but this value is calculated using models in which the steric demand for all the substituents were minimized according to the original definition (Tolman, 1977). This is, however, not the case when calculating the effective cone angle thus resulting in the larger values being obtained for the latter.

In Table 3, the title compounds are compared with related complexes, illustrating the effect of phosphine, arsine and stibine ligands on the geometrical parameters. The increase observed in the Pt—L bond distances when going from P to As to Sb donor ligands is consistent with the increase in the atomic radii of these elements. In the PEt3 and AsEt3 structures, an elongation is observed in the Pt—Cl bond distances trans to the phosphine ligand compared with those trans to the arsine. This is in agreement with the established trans influence series for these ligands (Otto & Johansson, 2001). In the Pt—Cl bond distances trans to the triphenyl-substituted ligands, a clear tendency is, however, not observed with the bond distances effected to the same extent by packing forces (within the same molecule) than by the trans influences of the respective L ligands.

Related literature top

For related literature, see: Caldwell et al. (1977); Johansson et al. (2000); Otto & Johansson (2001); Otto & Roodt (1997); Otto et al. (2000); Parshall (1970); Tolman (1977).

Experimental top

For the preparation of cis-[PtCl2(AsEt3)2], AsEt3 (0.043 ml, 0.30 mmol) was added to a nitrogen-flushed solution of cis/trans-[PtCl2(SMe2)2] (50 mg, 0.13 mmol) in dry dichloromethane. After 1 h, the solvent was removed while a positive nitrogen pressure was maintained. The crude product was washed with ether and recrystallized from dichloromethane. cis-[PtCl2(PEt3)2], (II), was prepared according to the literature procedure of Parshall (1970) and recrystallized from a mixture of acetone and dichloromethane.

Refinement top

For both complexes, the H atoms were refined as riding with C—H distances of 0.96 or 0.97 Å. Both the minimum and maximum residual electron density for both structures are located within 1.5 Å of the Pt atom.

Computing details top

For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of cis-[PtCl2(AsEt3)2] showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. The H atoms are of arbitrary size.
[Figure 2] Fig. 2. The structure of cis-[PtCl2(PEt3)2] showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. The H atoms are of arbitrary size.
(I) cis-dichlorobis(triethylarsine)platinum(II) top
Crystal data top
[PtCl2(C6H15As)2]F(000) = 1120
Mr = 590.19Dx = 2.100 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.0566 (16) ÅCell parameters from 6559 reflections
b = 17.754 (4) Åθ = 2.3–30.9°
c = 13.083 (3) ŵ = 11.31 mm1
β = 94.20 (3)°T = 293 K
V = 1866.4 (6) Å3Rectangular, colourless
Z = 40.12 × 0.11 × 0.04 mm
Data collection top
Siemens SMART CCD
diffractometer
5905 independent reflections
Radiation source: rotating anode4285 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
ω scansθmax = 31.9°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 1111
Tmin = 0.328, Tmax = 0.651k = 2524
19330 measured reflectionsl = 1917
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.0281P)2]
where P = (Fo2 + 2Fc2)/3
5905 reflections(Δ/σ)max = 0.002
162 parametersΔρmax = 1.14 e Å3
0 restraintsΔρmin = 2.05 e Å3
Crystal data top
[PtCl2(C6H15As)2]V = 1866.4 (6) Å3
Mr = 590.19Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.0566 (16) ŵ = 11.31 mm1
b = 17.754 (4) ÅT = 293 K
c = 13.083 (3) Å0.12 × 0.11 × 0.04 mm
β = 94.20 (3)°
Data collection top
Siemens SMART CCD
diffractometer
5905 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
4285 reflections with I > 2σ(I)
Tmin = 0.328, Tmax = 0.651Rint = 0.071
19330 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 0.93Δρmax = 1.14 e Å3
5905 reflectionsΔρmin = 2.05 e Å3
162 parameters
Special details top

Experimental. For both complexes, the intensity data were collected on a Siemens SMART CCD diffractometer using an exposure time of 15 s per frame for (I) and 20 s per frame for (II). A total of 1890 frames with a frame width of 0.25° were collected for (I) and 2250 frames with a frame width of 0.20° were collected for (II). A completeness of 98.9% was accomplished up to θ = 30.50° for (I), while the completeness was 99.0% at θ = 30.51° for (II). The first 50 frames were recollected at the end of each data collection to check for decay; no decay was found for either data collection.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt0.23175 (2)0.197343 (9)0.191580 (13)0.02951 (6)
As10.34578 (5)0.07684 (2)0.22491 (3)0.03068 (10)
As20.48241 (6)0.26115 (2)0.16514 (4)0.03327 (11)
Cl10.08491 (18)0.31085 (7)0.17214 (12)0.0565 (4)
Cl20.01854 (15)0.13713 (8)0.22449 (12)0.0573 (4)
C1110.5813 (6)0.0591 (2)0.2122 (4)0.0434 (12)
H11A0.60460.06830.14150.059 (5)*
H11B0.64390.09580.25420.059 (5)*
C1120.6456 (7)0.0192 (3)0.2422 (5)0.0681 (18)
H11C0.63880.02640.31450.092 (5)*
H11D0.75940.02380.22580.092 (5)*
H11E0.57920.05650.20530.092 (5)*
C1210.3091 (7)0.0442 (3)0.3639 (4)0.0455 (12)
H12A0.19030.04270.37170.059 (5)*
H12B0.35200.00650.37390.059 (5)*
C1220.3904 (10)0.0946 (4)0.4449 (4)0.081 (2)
H12C0.50830.09570.43830.092 (5)*
H12D0.36900.07560.51140.092 (5)*
H12E0.34600.14450.43680.092 (5)*
C1310.2339 (7)0.0035 (3)0.1456 (4)0.0482 (13)
H13A0.28850.05090.16360.059 (5)*
H13B0.11990.00700.16430.059 (5)*
C1320.2333 (9)0.0077 (4)0.0309 (5)0.0701 (18)
H13C0.18110.05490.01250.092 (5)*
H13D0.17270.03260.00360.092 (5)*
H13E0.34570.00790.01110.092 (5)*
C2110.4630 (7)0.3668 (3)0.1233 (4)0.0542 (14)
H21A0.39130.39250.16840.059 (5)*
H21B0.57210.39000.13210.059 (5)*
C2120.3950 (9)0.3786 (3)0.0145 (5)0.0706 (18)
H21C0.47480.36150.03130.092 (5)*
H21D0.37290.43120.00310.092 (5)*
H21E0.29360.35050.00230.092 (5)*
C2210.6271 (6)0.2693 (3)0.2907 (4)0.0514 (14)
H22A0.66230.21930.31280.059 (5)*
H22B0.72570.29770.27660.059 (5)*
C2220.5421 (9)0.3078 (3)0.3771 (5)0.0688 (18)
H22C0.52400.36000.36060.092 (5)*
H22D0.61160.30380.43970.092 (5)*
H22E0.43710.28380.38550.092 (5)*
C2310.6287 (6)0.2227 (3)0.0649 (4)0.0400 (11)
H23A0.70110.26310.04540.059 (5)*
H23B0.69850.18340.09670.059 (5)*
C2320.5369 (8)0.1912 (3)0.0309 (5)0.0606 (16)
H23C0.46770.15000.01270.092 (5)*
H23D0.61590.17370.07700.092 (5)*
H23E0.46900.22990.06370.092 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.02428 (9)0.03401 (9)0.03033 (9)0.00395 (7)0.00265 (6)0.00006 (7)
As10.0277 (2)0.0305 (2)0.0341 (2)0.00035 (17)0.00402 (18)0.00045 (18)
As20.0317 (2)0.0325 (2)0.0359 (2)0.00120 (18)0.00457 (19)0.00042 (19)
Cl10.0492 (8)0.0485 (7)0.0729 (10)0.0213 (6)0.0117 (7)0.0099 (6)
Cl20.0249 (6)0.0626 (8)0.0854 (10)0.0004 (6)0.0094 (6)0.0121 (7)
C1110.034 (3)0.034 (2)0.064 (3)0.005 (2)0.013 (2)0.006 (2)
C1120.049 (3)0.058 (3)0.100 (5)0.025 (3)0.022 (3)0.030 (3)
C1210.049 (3)0.048 (3)0.040 (3)0.001 (2)0.010 (2)0.007 (2)
C1220.129 (7)0.073 (4)0.040 (3)0.008 (4)0.003 (4)0.002 (3)
C1310.048 (3)0.041 (3)0.055 (3)0.005 (2)0.005 (2)0.008 (2)
C1320.081 (5)0.077 (4)0.051 (4)0.012 (4)0.004 (3)0.016 (3)
C2110.064 (4)0.036 (3)0.064 (4)0.001 (2)0.015 (3)0.004 (3)
C2120.095 (5)0.053 (3)0.065 (4)0.017 (3)0.017 (4)0.016 (3)
C2210.043 (3)0.051 (3)0.057 (3)0.001 (2)0.010 (3)0.004 (3)
C2220.078 (5)0.084 (4)0.044 (3)0.002 (3)0.002 (3)0.019 (3)
C2310.034 (3)0.044 (2)0.044 (3)0.001 (2)0.013 (2)0.005 (2)
C2320.071 (4)0.059 (3)0.053 (4)0.002 (3)0.019 (3)0.011 (3)
Geometric parameters (Å, º) top
Pt—Cl12.3412 (12)C131—H13A0.9700
Pt—Cl22.3498 (13)C131—H13B0.9700
Pt—As12.3563 (6)C132—H13C0.9600
Pt—As22.3630 (6)C132—H13D0.9600
As1—C1111.942 (5)C132—H13E0.9600
As1—C1311.946 (4)C211—C2121.501 (8)
As1—C1211.952 (5)C211—H21A0.9700
As2—C2211.949 (5)C211—H21B0.9700
As2—C2311.950 (5)C212—H21C0.9600
As2—C2111.957 (5)C212—H21D0.9600
C111—C1121.525 (6)C212—H21E0.9600
C111—H11A0.9700C221—C2221.525 (8)
C111—H11B0.9700C221—H22A0.9700
C112—H11C0.9600C221—H22B0.9700
C112—H11D0.9600C222—H22C0.9600
C112—H11E0.9600C222—H22D0.9600
C121—C1221.500 (7)C222—H22E0.9600
C121—H12A0.9700C231—C2321.515 (7)
C121—H12B0.9700C231—H23A0.9700
C122—H12C0.9600C231—H23B0.9700
C122—H12D0.9600C232—H23C0.9600
C122—H12E0.9600C232—H23D0.9600
C131—C1321.514 (8)C232—H23E0.9600
Cl1—Pt—Cl288.74 (5)C132—C131—H13B108.9
As1—Pt—As297.85 (2)As1—C131—H13B108.9
As1—Pt—Cl1171.37 (4)H13A—C131—H13B107.7
As2—Pt—Cl2177.45 (4)C131—C132—H13C109.5
As1—Pt—Cl283.18 (4)C131—C132—H13D109.5
As2—Pt—Cl190.11 (4)H13C—C132—H13D109.5
C111—As1—C131104.6 (2)C131—C132—H13E109.5
C111—As1—C121104.3 (2)H13C—C132—H13E109.5
C131—As1—C121100.5 (2)H13D—C132—H13E109.5
C111—As1—Pt120.08 (13)C212—C211—As2114.5 (4)
C131—As1—Pt114.09 (15)C212—C211—H21A108.6
C121—As1—Pt111.00 (15)As2—C211—H21A108.6
C221—As2—C231103.9 (2)C212—C211—H21B108.6
C221—As2—C211101.2 (2)As2—C211—H21B108.6
C231—As2—C211100.8 (2)H21A—C211—H21B107.6
C221—As2—Pt112.16 (17)C211—C212—H21C109.5
C231—As2—Pt119.72 (14)C211—C212—H21D109.5
C211—As2—Pt116.67 (18)H21C—C212—H21D109.5
C112—C111—As1116.2 (4)C211—C212—H21E109.5
C112—C111—H11A108.2H21C—C212—H21E109.5
As1—C111—H11A108.2H21D—C212—H21E109.5
C112—C111—H11B108.2C222—C221—As2112.7 (4)
As1—C111—H11B108.2C222—C221—H22A109.1
H11A—C111—H11B107.4As2—C221—H22A109.1
C111—C112—H11C109.5C222—C221—H22B109.1
C111—C112—H11D109.5As2—C221—H22B109.1
H11C—C112—H11D109.5H22A—C221—H22B107.8
C111—C112—H11E109.5C221—C222—H22C109.5
H11C—C112—H11E109.5C221—C222—H22D109.5
H11D—C112—H11E109.5H22C—C222—H22D109.5
C122—C121—As1113.2 (4)C221—C222—H22E109.5
C122—C121—H12A108.9H22C—C222—H22E109.5
As1—C121—H12A108.9H22D—C222—H22E109.5
C122—C121—H12B108.9C232—C231—As2113.8 (4)
As1—C121—H12B108.9C232—C231—H23A108.8
H12A—C121—H12B107.8As2—C231—H23A108.8
C121—C122—H12C109.5C232—C231—H23B108.8
C121—C122—H12D109.5As2—C231—H23B108.8
H12C—C122—H12D109.5H23A—C231—H23B107.7
C121—C122—H12E109.5C231—C232—H23C109.5
H12C—C122—H12E109.5C231—C232—H23D109.5
H12D—C122—H12E109.5H23C—C232—H23D109.5
C132—C131—As1113.6 (4)C231—C232—H23E109.5
C132—C131—H13A108.9H23C—C232—H23E109.5
As1—C131—H13A108.9H23D—C232—H23E109.5
Cl2—Pt—As1—C111177.4 (2)As1—Pt—As2—C211175.68 (19)
Cl2—Pt—As1—C12160.69 (17)As1—Pt—As2—C22168.20 (17)
Cl2—Pt—As1—C13152.0 (2)As1—Pt—As2—C23153.83 (16)
Cl1—Pt—As2—C2117.68 (19)As2—Pt—As1—C1114.96 (19)
Cl1—Pt—As2—C221108.44 (17)As2—Pt—As1—C121116.96 (17)
Cl1—Pt—As2—C231129.54 (17)As2—Pt—As1—C131130.3 (2)
(II) cis-dichlorobis(triethylphosphine)platinum(II) top
Crystal data top
[PtCl2(C6H15P)2]F(000) = 976
Mr = 502.29Dx = 1.837 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 19.773 (4) ÅCell parameters from 6951 reflections
b = 7.5310 (15) Åθ = 2.3–31.7°
c = 13.726 (3) ŵ = 8.18 mm1
β = 117.31 (3)°T = 293 K
V = 1816.1 (6) Å3Rectangular, colourless
Z = 40.35 × 0.30 × 0.18 mm
Data collection top
Siemens SMART CCD
diffractometer
4284 independent reflections
Radiation source: rotating anode4059 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω scansθmax = 32.0°, θmin = 2.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2822
Tmin = 0.092, Tmax = 0.229k = 1011
9281 measured reflectionsl = 1917
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0648P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4284 reflectionsΔρmax = 0.98 e Å3
162 parametersΔρmin = 2.06 e Å3
2 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.035 (10), 1109 Friedel pairs
Crystal data top
[PtCl2(C6H15P)2]V = 1816.1 (6) Å3
Mr = 502.29Z = 4
Monoclinic, CcMo Kα radiation
a = 19.773 (4) ŵ = 8.18 mm1
b = 7.5310 (15) ÅT = 293 K
c = 13.726 (3) Å0.35 × 0.30 × 0.18 mm
β = 117.31 (3)°
Data collection top
Siemens SMART CCD
diffractometer
4284 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
4059 reflections with I > 2σ(I)
Tmin = 0.092, Tmax = 0.229Rint = 0.053
9281 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.092Δρmax = 0.98 e Å3
S = 1.02Δρmin = 2.06 e Å3
4284 reflectionsAbsolute structure: Flack (1983)
162 parametersAbsolute structure parameter: 0.035 (10), 1109 Friedel pairs
2 restraints
Special details top

Experimental. For both complexes, the intensity data were collected on a Siemens SMART CCD diffractometer using an exposure time of 15 s per frame for (I) and 20 s per frame for (II). A total of 1890 frames with a frame width of 0.25° were collected for (I) and 2250 frames with a frame width of 0.20° were collected for (II). A completeness of 98.9% was accomplished up to θ = 30.50° for (I), while the completeness was 99.0% at θ = 30.51° for (II). The first 50 frames were recollected at the end of each data collection to check for decay; no decay was found for either data collection.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt0.08960 (2)0.33029 (2)0.14145 (2)0.02873 (7)
P10.03044 (11)0.3783 (3)0.00820 (15)0.0323 (3)
P20.15326 (11)0.4669 (2)0.06151 (15)0.0310 (3)
Cl10.20485 (12)0.2581 (3)0.29721 (16)0.0456 (4)
Cl20.02913 (17)0.1786 (3)0.2319 (2)0.0523 (6)
C1110.0511 (5)0.5107 (13)0.1136 (8)0.049 (2)
H11A0.02580.62450.08970.056 (6)*
H11B0.02850.45170.15440.056 (6)*
C1120.1338 (6)0.5451 (17)0.1910 (10)0.064 (3)
H11C0.15840.43530.22350.113 (11)*
H11D0.13750.62560.24750.113 (11)*
H11E0.15820.59660.15110.113 (11)*
C1210.0784 (6)0.1672 (9)0.0468 (9)0.0429 (19)
H12A0.07710.09630.01300.056 (6)*
H12B0.13130.19070.09710.056 (6)*
C1220.0438 (7)0.0607 (13)0.1061 (10)0.064 (3)
H12C0.04880.12540.16940.113 (11)*
H12D0.06970.05100.12880.113 (11)*
H12E0.00910.04020.05790.113 (11)*
C1310.0886 (6)0.4812 (12)0.0646 (8)0.0488 (19)
H13A0.14100.48560.00790.056 (6)*
H13B0.08690.40730.12350.056 (6)*
C1320.0632 (11)0.6688 (13)0.1085 (15)0.073 (4)
H13C0.01130.66610.16450.113 (11)*
H13D0.09500.71340.13890.113 (11)*
H13E0.06740.74480.04980.113 (11)*
C2110.2563 (5)0.4640 (12)0.1434 (7)0.0455 (17)
H21A0.26930.52260.21270.056 (6)*
H21B0.27290.34150.15940.056 (6)*
C2120.3006 (6)0.5532 (15)0.0900 (9)0.055 (2)
H21C0.28260.50930.01660.113 (11)*
H21D0.35380.52690.13180.113 (11)*
H21E0.29310.67940.08800.113 (11)*
C2210.1378 (6)0.3677 (13)0.0688 (8)0.0455 (18)
H22A0.08360.36110.11750.056 (6)*
H22B0.16060.44300.10320.056 (6)*
C2220.1726 (11)0.1801 (12)0.0526 (13)0.071 (4)
H22C0.22670.18930.02510.113 (11)*
H22D0.15100.11840.12140.113 (11)*
H22E0.16170.11590.00100.113 (11)*
C2310.1332 (6)0.7041 (11)0.0355 (9)0.047 (2)
H23A0.16430.75310.00420.056 (6)*
H23B0.08020.72040.01720.056 (6)*
C2320.1498 (10)0.8042 (15)0.1424 (14)0.074 (4)
H23C0.13260.73440.18520.113 (11)*
H23D0.12360.91610.12470.113 (11)*
H23E0.20360.82440.18360.113 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt0.02999 (12)0.03011 (10)0.02696 (10)0.00048 (11)0.01382 (8)0.00179 (11)
P10.0290 (9)0.0342 (7)0.0346 (8)0.0027 (7)0.0154 (7)0.0041 (7)
P20.0317 (8)0.0308 (7)0.0311 (8)0.0016 (6)0.0150 (7)0.0018 (6)
Cl10.0347 (9)0.0601 (12)0.0355 (9)0.0036 (8)0.0104 (7)0.0104 (8)
Cl20.0498 (14)0.0678 (14)0.0450 (12)0.0028 (9)0.0265 (11)0.0167 (8)
C1110.032 (4)0.065 (5)0.048 (5)0.007 (4)0.016 (3)0.022 (4)
C1120.043 (5)0.083 (6)0.060 (6)0.015 (5)0.018 (4)0.033 (5)
C1210.029 (4)0.044 (4)0.047 (5)0.007 (3)0.010 (4)0.003 (3)
C1220.073 (7)0.040 (4)0.079 (7)0.004 (4)0.034 (6)0.015 (4)
C1310.047 (5)0.059 (5)0.047 (5)0.012 (4)0.027 (4)0.003 (3)
C1320.096 (12)0.057 (7)0.083 (10)0.015 (5)0.054 (10)0.006 (4)
C2110.037 (4)0.056 (4)0.042 (4)0.001 (3)0.017 (3)0.009 (3)
C2120.042 (5)0.071 (6)0.053 (5)0.016 (4)0.023 (4)0.002 (4)
C2210.048 (5)0.049 (4)0.044 (4)0.001 (4)0.025 (4)0.005 (3)
C2220.106 (13)0.053 (6)0.074 (9)0.007 (5)0.057 (9)0.022 (4)
C2310.048 (5)0.034 (3)0.058 (5)0.008 (3)0.025 (4)0.001 (3)
C2320.096 (11)0.046 (5)0.091 (10)0.010 (5)0.052 (9)0.016 (5)
Geometric parameters (Å, º) top
Pt—P12.264 (2)C131—H13A0.9700
Pt—P22.2616 (18)C131—H13B0.9700
Pt—Cl12.364 (2)C132—H13C0.9600
Pt—Cl22.374 (2)C132—H13D0.9600
P1—C1111.824 (8)C132—H13E0.9600
P1—C1311.827 (9)C211—C2121.531 (12)
P1—C1211.827 (7)C211—H21A0.9700
P2—C2111.821 (9)C211—H21B0.9700
P2—C2311.829 (9)C212—H21C0.9600
P2—C2211.831 (9)C212—H21D0.9600
C111—C1121.509 (13)C212—H21E0.9600
C111—H11A0.9700C221—C2221.542 (14)
C111—H11B0.9700C221—H22A0.9700
C112—H11C0.9600C221—H22B0.9700
C112—H11D0.9600C222—H22C0.9600
C112—H11E0.9600C222—H22D0.9600
C121—C1221.511 (15)C222—H22E0.9600
C121—H12A0.9700C231—C2321.545 (17)
C121—H12B0.9700C231—H23A0.9700
C122—H12C0.9600C231—H23B0.9700
C122—H12D0.9600C232—H23C0.9600
C122—H12E0.9600C232—H23D0.9600
C131—C1321.528 (15)C232—H23E0.9600
Cl1—Pt—Cl285.66 (9)C132—C131—H13B108.8
P1—Pt—P298.39 (7)P1—C131—H13B108.8
P1—Pt—Cl1170.26 (7)H13A—C131—H13B107.7
P2—Pt—Cl2176.82 (8)C131—C132—H13C109.5
P1—Pt—Cl284.63 (9)C131—C132—H13D109.5
P2—Pt—Cl191.33 (7)H13C—C132—H13D109.5
C111—P1—C131103.7 (4)C131—C132—H13E109.5
C111—P1—C121104.0 (5)H13C—C132—H13E109.5
C131—P1—C121103.7 (5)H13D—C132—H13E109.5
C111—P1—Pt122.6 (3)C212—C211—P2115.0 (6)
C131—P1—Pt110.8 (3)C212—C211—H21A108.5
C121—P1—Pt110.4 (3)P2—C211—H21A108.5
C211—P2—C231102.3 (4)C212—C211—H21B108.5
C211—P2—C221103.6 (5)P2—C211—H21B108.5
C231—P2—C221106.5 (5)H21A—C211—H21B107.5
C211—P2—Pt114.2 (3)C211—C212—H21C109.5
C231—P2—Pt114.8 (3)C211—C212—H21D109.5
C221—P2—Pt114.1 (3)H21C—C212—H21D109.5
C112—C111—P1117.0 (6)C211—C212—H21E109.5
C112—C111—H11A108.1H21C—C212—H21E109.5
P1—C111—H11A108.1H21D—C212—H21E109.5
C112—C111—H11B108.1C222—C221—P2111.6 (8)
P1—C111—H11B108.1C222—C221—H22A109.3
H11A—C111—H11B107.3P2—C221—H22A109.3
C111—C112—H11C109.5C222—C221—H22B109.3
C111—C112—H11D109.5P2—C221—H22B109.3
H11C—C112—H11D109.5H22A—C221—H22B108.0
C111—C112—H11E109.5C221—C222—H22C109.5
H11C—C112—H11E109.5C221—C222—H22D109.5
H11D—C112—H11E109.5H22C—C222—H22D109.5
C122—C121—P1114.0 (7)C221—C222—H22E109.5
C122—C121—H12A108.7H22C—C222—H22E109.5
P1—C121—H12A108.7H22D—C222—H22E109.5
C122—C121—H12B108.7C232—C231—P2111.0 (8)
P1—C121—H12B108.7C232—C231—H23A109.4
H12A—C121—H12B107.6P2—C231—H23A109.4
C121—C122—H12C109.5C232—C231—H23B109.4
C121—C122—H12D109.5P2—C231—H23B109.4
H12C—C122—H12D109.5H23A—C231—H23B108.0
C121—C122—H12E109.5C231—C232—H23C109.5
H12C—C122—H12E109.5C231—C232—H23D109.5
H12D—C122—H12E109.5H23C—C232—H23D109.5
C132—C131—P1113.8 (8)C231—C232—H23E109.5
C132—C131—H13A108.8H23C—C232—H23E109.5
P1—C131—H13A108.8H23D—C232—H23E109.5
Cl2—Pt—P1—C111176.7 (4)P1—Pt—P2—C211179.3 (3)
Cl2—Pt—P1—C12160.5 (4)P1—Pt—P2—C22161.8 (4)
Cl2—Pt—P1—C13153.8 (3)P1—Pt—P2—C23161.5 (4)
Cl1—Pt—P2—C2110.1 (4)P2—Pt—P1—C1114.3 (4)
Cl1—Pt—P2—C221118.8 (4)P2—Pt—P1—C121118.5 (4)
Cl1—Pt—P2—C231117.9 (4)P2—Pt—P1—C131127.2 (3)

Experimental details

(I)(II)
Crystal data
Chemical formula[PtCl2(C6H15As)2][PtCl2(C6H15P)2]
Mr590.19502.29
Crystal system, space groupMonoclinic, P21/nMonoclinic, Cc
Temperature (K)293293
a, b, c (Å)8.0566 (16), 17.754 (4), 13.083 (3)19.773 (4), 7.5310 (15), 13.726 (3)
β (°) 94.20 (3) 117.31 (3)
V3)1866.4 (6)1816.1 (6)
Z44
Radiation typeMo KαMo Kα
µ (mm1)11.318.18
Crystal size (mm)0.12 × 0.11 × 0.040.35 × 0.30 × 0.18
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Siemens SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.328, 0.6510.092, 0.229
No. of measured, independent and
observed [I > 2σ(I)] reflections
19330, 5905, 4285 9281, 4284, 4059
Rint0.0710.053
(sin θ/λ)max1)0.7440.746
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.072, 0.93 0.034, 0.092, 1.02
No. of reflections59054284
No. of parameters162162
No. of restraints02
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.14, 2.050.98, 2.06
Absolute structure?Flack (1983)
Absolute structure parameter?0.035 (10), 1109 Friedel pairs

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1999), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
Pt—Cl12.3412 (12)As1—C1311.946 (4)
Pt—Cl22.3498 (13)As1—C1211.952 (5)
Pt—As12.3563 (6)As2—C2211.949 (5)
Pt—As22.3630 (6)As2—C2311.950 (5)
As1—C1111.942 (5)As2—C2111.957 (5)
Cl1—Pt—Cl288.74 (5)C111—As1—C131104.6 (2)
As1—Pt—As297.85 (2)C111—As1—C121104.3 (2)
As1—Pt—Cl1171.37 (4)C131—As1—C121100.5 (2)
As2—Pt—Cl2177.45 (4)C221—As2—C231103.9 (2)
As1—Pt—Cl283.18 (4)C221—As2—C211101.2 (2)
As2—Pt—Cl190.11 (4)C231—As2—C211100.8 (2)
Cl2—Pt—As1—C111177.4 (2)As1—Pt—As2—C211175.68 (19)
Cl2—Pt—As1—C12160.69 (17)As1—Pt—As2—C22168.20 (17)
Cl2—Pt—As1—C13152.0 (2)As1—Pt—As2—C23153.83 (16)
Cl1—Pt—As2—C2117.68 (19)As2—Pt—As1—C1114.96 (19)
Cl1—Pt—As2—C221108.44 (17)As2—Pt—As1—C121116.96 (17)
Cl1—Pt—As2—C231129.54 (17)As2—Pt—As1—C131130.3 (2)
Selected geometric parameters (Å, º) for (II) top
Pt—P12.264 (2)P1—C1311.827 (9)
Pt—P22.2616 (18)P1—C1211.827 (7)
Pt—Cl12.364 (2)P2—C2111.821 (9)
Pt—Cl22.374 (2)P2—C2311.829 (9)
P1—C1111.824 (8)P2—C2211.831 (9)
Cl1—Pt—Cl285.66 (9)C111—P1—C131103.7 (4)
P1—Pt—P298.39 (7)C111—P1—C121104.0 (5)
P1—Pt—Cl1170.26 (7)C131—P1—C121103.7 (5)
P2—Pt—Cl2176.82 (8)C211—P2—C231102.3 (4)
P1—Pt—Cl284.63 (9)C211—P2—C221103.6 (5)
P2—Pt—Cl191.33 (7)C231—P2—C221106.5 (5)
Cl2—Pt—P1—C111176.7 (4)P1—Pt—P2—C211179.3 (3)
Cl2—Pt—P1—C12160.5 (4)P1—Pt—P2—C22161.8 (4)
Cl2—Pt—P1—C13153.8 (3)P1—Pt—P2—C23161.5 (4)
Cl1—Pt—P2—C2110.1 (4)P2—Pt—P1—C1114.3 (4)
Cl1—Pt—P2—C221118.8 (4)P2—Pt—P1—C121118.5 (4)
Cl1—Pt—P2—C231117.9 (4)P2—Pt—P1—C131127.2 (3)
Comparative X-ray data for cis-[PtCl2(L)2] complexes top
LPt-L1 (Å)Pt-L2 (Å)Pt-Cl1 (Å)Pt-Cl2 (Å)Footnote
PEt32.264 (2)2.2616 (18)2.364 (2)2.374 (2)(i)
AsEt32.3563 (6)2.3630 (6)2.3412 (12)2.3498 (13)(ii)
PPh32.267 (3)2.244 (3)2.329 (3)2.360 (3)(iii)
AsPh32.3599 (9)2.3770 (9)2.3515 (18)2.3251 (18)(iv)
SbPh32.491 (1)2.510 (1)2.354 (3)2.326 (4)(v)
(i) This work, (ii) This work, (iii) Anderson et al. (1982), (iv) Otto & Johansson (2001), (v) Wendt, Scodinun & Elding (1997).
 

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