cis-Dichloridobis(dimethoxy­phenyl­phosphino)platinum(II)

The title compound, [PtCl₂(C₈H₁₁O₂P)₂], resides on a crystallographic twofold rotation axis and adopts a cis-square-planar geometry. Mol­ecules are linked by C—H...Cl inter­actions forming one-dimensional chains along the [010] direction.

Key indicators

• Single-crystal X-ray study
• T = 125 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.021
• wR factor = 0.043
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

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Alert level A
DIFF019_ALERT_1_A  _diffrn_standards_number is missing
            Number of standards used in measurement.
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.
DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

   3 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
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   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The title complex (I) is comparable to similar platinum dichloride complexes containing trimethoxy phosphite; [PtCl₂(P(OMe)₃)₂] (Bao et al., 1987) and triphenyl phosphine [PtCl₂(PPh₃)₂] (Fun et al., 2006). The central platinum atom in (I) can be seen to bear a closer resemblance to the triphenyl phosphine complex. These measurement are also similar when compared to the structure of the complex [PtCl₂(P(OMe)Ph₂)₂] (Slawin et al., 2007) with the exception of the P—Pt—P bond angle which is unusually large.

Related literature

For related literature on PtCl₂L₂ complexes, see: Bao et al. (1987); Fun et al. (2006); Slawin et al. (2007).

S2. Experimental

1 g (2.67 mmol) of PtCl₂(COD) was dissolved in the minimum volume of dichloromethane in a round-bottomed flask. To this, 0.840 ml (5.34 mmol) of dimethylphenylphosphonite was added. The solution was then stirred for 0.5 h at room temperature. The product was precipitated via slow diffusion of hexane and was then filtered off and dried under vacuum, [PtCl₂(P(OMe)₂Ph)₂] (1.86 mmol,ca 69%). ³¹P-{¹H} NMR: δ 91.2 p.p.m. J{Pt—P} 4819 Hz.

S3. Refinement

All H atoms were included in calculated positions (C—H distances are 0.96 Å for methyl H atoms, 0.97 Å for methylene H atoms and 0.98 Å for methine H atoms) and were refined as riding atoms with U_iso(H) = 1.2 U_eq(parent atom, methylene and methine H atoms) or U_iso(H) = 1.5 U_eq(parent atom, methyl H atoms).

Computing details

Data collection: SCXmini (Rigaku/MSC, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure (Rigaku/MSC, 2006); software used to prepare material for publication: CrystalStructure.

Figures

Fig. 1. The structure of (1) with displacement ellipsoids drawn at the 50% probability level, H atoms omitted for clarity.

cis-Dichloridobis(dimethoxyphenylphosphino)platinum(II)

Crystal data

[PtCl2(C8H11O2P)2]	F(000) = 1168
Mr = 606.27	Dx = 1.967 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6759 reflections
a = 10.9734 (7) Å	θ = 3.0–27.5°
b = 9.2290 (6) Å	µ = 7.29 mm^−1
c = 20.7002 (14) Å	T = 125 K
β = 102.398 (2)°	Prism, colourless
V = 2047.5 (2) Å^3	0.20 × 0.16 × 0.07 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	1869 independent reflections
Radiation source: fine-focus sealed tube	1772 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 25.3°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.261, Tmax = 0.602	k = −11→10
5869 measured reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.043	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0167P)^2 + 0.5089P] where P = (Fo^2 + 2Fc^2)/3
1869 reflections	(Δ/σ)max = 0.007
117 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.69 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.5000	0.40682 (2)	0.2500	0.01234 (7)
Cl1	0.59209 (8)	0.58930 (10)	0.32480 (4)	0.0204 (2)
P1	0.40029 (8)	0.25413 (10)	0.17390 (4)	0.0141 (2)
C1	0.4614 (3)	0.2496 (4)	0.09966 (17)	0.0156 (8)
C2	0.4028 (3)	0.3176 (4)	0.04180 (18)	0.0217 (9)
H2A	0.3264	0.3677	0.0397	0.026*
C3	0.4560 (3)	0.3125 (5)	−0.01343 (19)	0.0270 (10)
H3A	0.4166	0.3598	−0.0532	0.032*
C4	0.5671 (4)	0.2379 (4)	−0.01014 (19)	0.0300 (10)
H4A	0.6027	0.2337	−0.0481	0.036*
C5	0.6258 (4)	0.1707 (5)	0.0466 (2)	0.0314 (10)
H5A	0.7017	0.1200	0.0480	0.038*
C6	0.5744 (3)	0.1764 (4)	0.10287 (19)	0.0244 (9)
H6A	0.6158	0.1312	0.1428	0.029*
O1	0.3959 (2)	0.0909 (2)	0.19814 (12)	0.0195 (6)
C7	0.3218 (4)	−0.0145 (4)	0.15439 (19)	0.0261 (9)
H7A	0.2341	−0.0059	0.1573	0.039*
H7B	0.3518	−0.1124	0.1676	0.039*
H7C	0.3294	0.0037	0.1088	0.039*
O2	0.2590 (2)	0.2966 (3)	0.14365 (11)	0.0170 (5)
C8	0.1756 (3)	0.3272 (5)	0.18759 (19)	0.0266 (10)
H8A	0.1804	0.2485	0.2198	0.040*
H8B	0.0899	0.3353	0.1617	0.040*
H8C	0.2001	0.4185	0.2109	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01451 (11)	0.01079 (12)	0.01187 (12)	0.000	0.00317 (8)	0.000
Cl1	0.0245 (5)	0.0150 (5)	0.0195 (5)	−0.0003 (4)	−0.0004 (4)	−0.0036 (4)
P1	0.0172 (5)	0.0127 (5)	0.0125 (5)	−0.0014 (4)	0.0033 (4)	0.0006 (4)
C1	0.0178 (17)	0.012 (2)	0.017 (2)	−0.0047 (14)	0.0040 (16)	−0.0026 (15)
C2	0.022 (2)	0.023 (2)	0.019 (2)	0.0008 (16)	0.0039 (18)	−0.0017 (17)
C3	0.031 (2)	0.035 (3)	0.012 (2)	−0.0028 (19)	−0.0005 (18)	0.0011 (18)
C4	0.037 (2)	0.036 (3)	0.020 (2)	−0.003 (2)	0.012 (2)	−0.0060 (19)
C5	0.023 (2)	0.040 (3)	0.034 (3)	0.0069 (19)	0.013 (2)	0.001 (2)
C6	0.024 (2)	0.027 (2)	0.022 (2)	0.0081 (17)	0.0031 (18)	0.0058 (18)
O1	0.0272 (13)	0.0134 (14)	0.0167 (14)	−0.0058 (11)	0.0021 (11)	−0.0003 (11)
C7	0.040 (2)	0.015 (2)	0.022 (2)	−0.0068 (18)	0.004 (2)	−0.0039 (17)
O2	0.0157 (12)	0.0190 (15)	0.0167 (14)	−0.0006 (10)	0.0048 (11)	−0.0002 (11)
C8	0.022 (2)	0.031 (3)	0.030 (2)	−0.0002 (17)	0.0135 (19)	0.0001 (19)

Geometric parameters (Å, º)

Pt1—P1	2.2190 (9)	C4—C5	1.362 (5)
Pt1—P1^i	2.2190 (9)	C4—H4A	0.9500
Pt1—Cl1	2.3629 (9)	C5—C6	1.400 (5)
Pt1—Cl1^i	2.3629 (9)	C5—H5A	0.9500
P1—O1	1.592 (2)	C6—H6A	0.9500
P1—O2	1.591 (2)	O1—C7	1.453 (4)
P1—C1	1.804 (3)	C7—H7A	0.9800
C1—C2	1.382 (5)	C7—H7B	0.9800
C1—C6	1.402 (5)	C7—H7C	0.9800
C2—C3	1.392 (5)	O2—C8	1.450 (4)
C2—H2A	0.9500	C8—H8A	0.9800
C3—C4	1.388 (5)	C8—H8B	0.9800
C3—H3A	0.9500	C8—H8C	0.9800
P1—Pt1—P1^i	101.16 (5)	C5—C4—H4A	119.5
P1—Pt1—Cl1	173.78 (3)	C3—C4—H4A	119.5
P1^i—Pt1—Cl1	84.90 (3)	C4—C5—C6	120.0 (4)
P1—Pt1—Cl1^i	84.90 (3)	C4—C5—H5A	120.0
P1^i—Pt1—Cl1^i	173.78 (3)	C6—C5—H5A	120.0
Cl1—Pt1—Cl1^i	89.08 (4)	C5—C6—C1	119.3 (4)
O1—P1—O2	105.34 (13)	C5—C6—H6A	120.3
O1—P1—C1	106.75 (15)	C1—C6—H6A	120.3
O2—P1—C1	100.32 (14)	C7—O1—P1	119.2 (2)
O1—P1—Pt1	114.89 (10)	O1—C7—H7A	109.5
O2—P1—Pt1	114.40 (10)	O1—C7—H7B	109.5
C1—P1—Pt1	113.76 (11)	H7A—C7—H7B	109.5
C2—C1—C6	120.1 (3)	O1—C7—H7C	109.5
C2—C1—P1	122.6 (3)	H7A—C7—H7C	109.5
C6—C1—P1	117.3 (3)	H7B—C7—H7C	109.5
C1—C2—C3	119.8 (3)	C8—O2—P1	119.6 (2)
C1—C2—H2A	120.1	O2—C8—H8A	109.5
C3—C2—H2A	120.1	O2—C8—H8B	109.5
C4—C3—C2	119.7 (4)	H8A—C8—H8B	109.5
C4—C3—H3A	120.2	O2—C8—H8C	109.5
C2—C3—H3A	120.2	H8A—C8—H8C	109.5
C5—C4—C3	121.1 (4)	H8B—C8—H8C	109.5
P1^i—Pt1—P1—O1	14.27 (10)	P1—C1—C2—C3	178.7 (3)
Cl1^i—Pt1—P1—O1	−167.15 (11)	C1—C2—C3—C4	0.6 (6)
P1^i—Pt1—P1—O2	136.32 (11)	C2—C3—C4—C5	−0.7 (6)
Cl1^i—Pt1—P1—O2	−45.10 (10)	C3—C4—C5—C6	−0.1 (7)
P1^i—Pt1—P1—C1	−109.19 (13)	C4—C5—C6—C1	1.1 (6)
Cl1^i—Pt1—P1—C1	69.39 (13)	C2—C1—C6—C5	−1.3 (6)
O1—P1—C1—C2	129.0 (3)	P1—C1—C6—C5	−179.6 (3)
O2—P1—C1—C2	19.4 (3)	O2—P1—O1—C7	46.7 (3)
Pt1—P1—C1—C2	−103.2 (3)	C1—P1—O1—C7	−59.3 (3)
O1—P1—C1—C6	−52.7 (3)	Pt1—P1—O1—C7	173.6 (2)
O2—P1—C1—C6	−162.3 (3)	O1—P1—O2—C8	75.5 (3)
Pt1—P1—C1—C6	75.1 (3)	C1—P1—O2—C8	−173.8 (3)
C6—C1—C2—C3	0.4 (5)	Pt1—P1—O2—C8	−51.6 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···Cl1^ii	0.98	2.82	3.778 (4)	166

Symmetry code: (ii) −x+1, y−1, −z+1/2.