trans-Dibromidobis(triphenyl­phosphane)platinum(II) chloro­form monosolvate

Abstract

Both the platininum complex and the solvent mol­ecule of the title compound, [PtBr₂(C₁₈H₁₅P)₂]·CHCl₃, are located on a twofold rotation axis. The CH unit and the Cl atoms of the CHCl₃ mol­ecule are disordered over two equally occupied positions. The complex shows a trans square-planar geometry about the Pt atom.

Related literature

For the dichloro­methane solvate analogue of the title structure, see: Sharma et al. (2003 ▶). For the structure of the cis isomer of the title complex, see: Rigamonti et al. (2010 ▶). For the low temperature structure of the chloro­form solvate of the cis isomer of the title complex, see: Waddell et al. (2010 ▶). For more information on the effect of the trans influence of ligands on platinum-phospho­rus complexes, see: Allen et al. (1970 ▶); Appleton et al. (1973 ▶).

Experimental

Crystal data

• [PtBr₂(C₁₈H₁₅P)₂]·CHCl₃

• M _r = 998.82

• Monoclinic,

• a = 12.2581 (11) Å

• b = 14.5375 (13) Å

• c = 20.1433 (18) Å

• β = 92.402 (6)°

• V = 3586.4 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 6.48 mm⁻¹

• T = 125 K

• 0.20 × 0.12 × 0.09 mm

Data collection

• Rigaku SCXmini diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.364, T _max = 0.600

• 14789 measured reflections

• 3161 independent reflections

• 2495 reflections with I > 2σ(I)

• R _int = 0.043

Refinement

• R[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 0.047

• S = 1.09

• 3161 reflections

• 218 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.58 e Å⁻³

• Δρ_min = −0.71 e Å⁻³

Data collection: SCXmini Benchtop Crystallography System Software (Rigaku, 2006b ▶); cell refinement: PROCESS-AUTO (Rigaku, 1998 ▶); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Crystal­Structure (Rigaku, 2006a ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The trans-Bis(triphenylphosphane)dibromoplatinum(II) molecule in the title structure bears a close resemblance to that of the dichloromethane solvate of the same complex (Sharma et al. 2003). The geometry about platinum is similar in both structures. As would be expected, due to the different trans infuences of triphenylphosphane and bromide (Allen et al. 1970; Appleton et al. 1973), the Pt—Br distances are observed to be shorter and the Pt—P distances longer in the title structure than those of the structures of the cis isomer of the complex (Rigamonti et al. 2010; Waddell et al. 2010). A twofold disorder is observed in the chloroform molecule.

Experimental

trans-bis(benzonitrile)platinum(II) dibromide (0.5 g, 0.9 mmol) was vigorously stirred in acetone (20 ml), to which triphenylphosphane (0.472 g, 1.8 mmol) dissolved in acetone (20 ml) was added, affording a yellow precipitate. Crystals were grown for X-ray crystallography via slow diffusion of hexane into a solution of the product in chloroform. Yield: 0.726 g (0.8 mmol), 92%.

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).

Figures

Fig. 1.

The structure of the title compound with displacement ellipsoids drawn at the 50% probability level, hydrogen atoms and the disordered CHCl3 omitted for clarity. Symmetry operator for generating equivalent atoms (A): -x + 1,y,-z + 1/2.

Crystal data

[PtBr2(C18H15P)2]·CHCl3	F(000) = 1928
Mr = 998.82	Dx = 1.85 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 14699 reflections
a = 12.2581 (11) Å	θ = 3–27.4°
b = 14.5375 (13) Å	µ = 6.48 mm−1
c = 20.1433 (18) Å	T = 125 K
β = 92.402 (6)°	Prism, yellow
V = 3586.4 (6) Å3	0.2 × 0.12 × 0.09 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	3161 independent reflections
graphite	2495 reflections with I > 2σ(I)
Detector resolution: 6.85 pixels mm-1	Rint = 0.043
ω scans	θmax = 25°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.364, Tmax = 0.600	k = −17→17
14789 measured reflections	l = −23→23

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.047	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0095P)2 + 13.9423P] where P = (Fo2 + 2Fc2)/3
3161 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.71 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Pt1	0.5	0.247997 (17)	0.25	0.01380 (6)
Br1	0.67746 (3)	0.24647 (3)	0.199294 (18)	0.02189 (10)
Cl1	0.06034 (12)	0.09593 (10)	0.19017 (7)	0.0479 (3)
Cl2	−0.0238 (3)	0.26606 (18)	0.2359 (2)	0.0593 (12)	0.5
P1	0.40680 (8)	0.24595 (8)	0.14711 (5)	0.0152 (2)
C1	0.4819 (3)	0.2713 (2)	0.07256 (19)	0.0166 (9)
C2	0.5531 (4)	0.2057 (3)	0.0482 (2)	0.0276 (11)
H2	0.5621	0.1485	0.0706	0.033*
C3	0.6107 (4)	0.2230 (3)	−0.0081 (2)	0.0330 (12)
H3	0.6581	0.1774	−0.0245	0.04*
C4	0.5996 (4)	0.3062 (3)	−0.0405 (2)	0.0276 (11)
H4	0.6405	0.3183	−0.0786	0.033*
C5	0.5295 (4)	0.3713 (3)	−0.0178 (2)	0.0274 (11)
H5	0.5203	0.428	−0.0408	0.033*
C6	0.4719 (3)	0.3544 (3)	0.0389 (2)	0.0231 (10)
H6	0.4249	0.4006	0.0549	0.028*
C7	0.3475 (3)	0.1333 (2)	0.1283 (2)	0.0153 (9)
C8	0.3484 (3)	0.0654 (3)	0.1772 (2)	0.0181 (10)
H8	0.381	0.0775	0.2199	0.022*
C9	0.3014 (4)	−0.0204 (3)	0.1635 (2)	0.0246 (10)
H9	0.3021	−0.0664	0.1969	0.03*
C10	0.2541 (4)	−0.0387 (3)	0.1017 (2)	0.0243 (10)
H10	0.22	−0.0964	0.0932	0.029*
C11	0.2563 (4)	0.0275 (3)	0.0518 (2)	0.0278 (11)
H11	0.2259	0.014	0.0087	0.033*
C12	0.3027 (4)	0.1131 (3)	0.0648 (2)	0.0248 (10)
H12	0.3041	0.1581	0.0307	0.03*
C13	0.2975 (3)	0.3308 (3)	0.14371 (19)	0.0171 (9)
C14	0.1927 (3)	0.3134 (3)	0.1176 (2)	0.0250 (10)
H14	0.1743	0.254	0.1009	0.03*
C15	0.1145 (4)	0.3834 (3)	0.1160 (2)	0.0330 (12)
H15	0.0427	0.3715	0.0985	0.04*
C16	0.1417 (4)	0.4701 (3)	0.1400 (2)	0.0359 (13)
H16	0.0882	0.5174	0.1392	0.043*
C17	0.2453 (4)	0.4882 (3)	0.1649 (2)	0.0346 (12)
H17	0.2639	0.5481	0.1804	0.041*
C18	0.3229 (4)	0.4186 (3)	0.1673 (2)	0.0253 (11)
H18	0.3943	0.431	0.1854	0.03*
C19	0.0326 (8)	0.1586 (7)	0.2592 (6)	0.035 (3)	0.5
H19	0.093 (8)	0.172 (7)	0.280 (5)	0.04 (3)*	0.5

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Pt1	0.01756 (11)	0.01119 (10)	0.01270 (11)	0	0.00113 (8)	0
Br1	0.0228 (2)	0.0222 (2)	0.0209 (2)	−0.0013 (2)	0.00405 (17)	−0.0001 (2)
Cl1	0.0518 (8)	0.0557 (8)	0.0375 (8)	−0.0015 (7)	0.0168 (7)	−0.0071 (7)
Cl2	0.064 (3)	0.0486 (16)	0.068 (4)	0.0134 (16)	0.031 (2)	0.0093 (17)
P1	0.0188 (5)	0.0119 (4)	0.0148 (5)	0.0016 (5)	0.0016 (4)	0.0005 (5)
C1	0.017 (2)	0.020 (2)	0.013 (2)	−0.0013 (16)	−0.0015 (17)	0.0012 (16)
C2	0.033 (3)	0.026 (2)	0.024 (3)	0.005 (2)	0.006 (2)	0.004 (2)
C3	0.034 (3)	0.039 (3)	0.027 (3)	0.012 (2)	0.009 (2)	−0.006 (2)
C4	0.027 (3)	0.039 (3)	0.017 (2)	−0.007 (2)	0.006 (2)	0.001 (2)
C5	0.037 (3)	0.025 (2)	0.019 (2)	−0.006 (2)	0.000 (2)	0.007 (2)
C6	0.028 (2)	0.022 (2)	0.020 (2)	−0.0002 (19)	0.003 (2)	−0.0006 (19)
C7	0.020 (2)	0.0112 (19)	0.015 (2)	0.0001 (17)	0.0033 (18)	−0.0007 (17)
C8	0.022 (2)	0.016 (2)	0.016 (2)	0.0024 (18)	0.0012 (19)	0.0003 (18)
C9	0.034 (3)	0.016 (2)	0.024 (3)	−0.0021 (19)	0.011 (2)	0.0025 (19)
C10	0.027 (2)	0.020 (2)	0.027 (3)	−0.0042 (19)	0.005 (2)	−0.007 (2)
C11	0.034 (3)	0.029 (2)	0.020 (2)	−0.004 (2)	−0.002 (2)	−0.009 (2)
C12	0.035 (3)	0.017 (2)	0.022 (3)	−0.0028 (19)	0.000 (2)	0.0037 (19)
C13	0.024 (2)	0.018 (2)	0.010 (2)	0.0035 (18)	0.0066 (18)	0.0023 (17)
C14	0.027 (3)	0.026 (2)	0.022 (2)	0.0026 (19)	0.004 (2)	0.001 (2)
C15	0.024 (3)	0.048 (3)	0.028 (3)	0.012 (2)	0.005 (2)	0.015 (2)
C16	0.043 (3)	0.038 (3)	0.028 (3)	0.028 (2)	0.012 (2)	0.014 (2)
C17	0.062 (4)	0.020 (2)	0.023 (3)	0.016 (2)	0.009 (3)	0.001 (2)
C18	0.032 (3)	0.023 (2)	0.021 (3)	0.002 (2)	−0.003 (2)	0.002 (2)
C19	0.022 (7)	0.052 (6)	0.030 (7)	−0.003 (4)	−0.006 (6)	0.001 (5)

Geometric parameters (Å, °)

Pt1—P1	2.3245 (9)	C8—C9	1.396 (5)
Pt1—P1i	2.3245 (9)	C8—H8	0.95
Pt1—Br1	2.4417 (4)	C9—C10	1.376 (6)
Pt1—Br1i	2.4417 (4)	C9—H9	0.95
Cl1—C19	1.708 (12)	C10—C11	1.392 (6)
Cl1—C19ii	1.807 (11)	C10—H10	0.95
Cl2—Cl2ii	0.796 (6)	C11—C12	1.390 (6)
Cl2—C19ii	1.569 (11)	C11—H11	0.95
Cl2—C19	1.763 (10)	C12—H12	0.95
P1—C13	1.820 (4)	C13—C14	1.391 (6)
P1—C7	1.825 (4)	C13—C18	1.393 (6)
P1—C1	1.831 (4)	C14—C15	1.397 (6)
C1—C6	1.389 (5)	C14—H14	0.95
C1—C2	1.394 (6)	C15—C16	1.386 (7)
C2—C3	1.385 (6)	C15—H15	0.95
C2—H2	0.95	C16—C17	1.371 (7)
C3—C4	1.378 (6)	C16—H16	0.95
C3—H3	0.95	C17—C18	1.389 (6)
C4—C5	1.370 (6)	C17—H17	0.95
C4—H4	0.95	C18—H18	0.95
C5—C6	1.389 (6)	C19—C19ii	0.865 (18)
C5—H5	0.95	C19—Cl2ii	1.569 (10)
C6—H6	0.95	C19—Cl1ii	1.807 (11)
C7—C8	1.395 (5)	C19—H19	0.86 (9)
C7—C12	1.400 (6)
P1—Pt1—P1i	178.54 (6)	C9—C10—C11	120.0 (4)
P1—Pt1—Br1	92.30 (3)	C9—C10—H10	120
P1i—Pt1—Br1	87.69 (3)	C11—C10—H10	120
P1—Pt1—Br1i	87.69 (3)	C12—C11—C10	120.1 (4)
P1i—Pt1—Br1i	92.30 (3)	C12—C11—H11	119.9
Br1—Pt1—Br1i	178.96 (3)	C10—C11—H11	119.9
Cl2ii—Cl2—C19ii	90.3 (4)	C11—C12—C7	120.1 (4)
Cl2ii—Cl2—C19	62.9 (3)	C11—C12—H12	119.9
C13—P1—C7	108.31 (19)	C7—C12—H12	119.9
C13—P1—C1	103.16 (18)	C14—C13—C18	119.1 (4)
C7—P1—C1	102.66 (17)	C14—C13—P1	123.9 (3)
C13—P1—Pt1	111.00 (13)	C18—C13—P1	117.0 (3)
C7—P1—Pt1	111.91 (13)	C13—C14—C15	119.9 (4)
C1—P1—Pt1	118.91 (13)	C13—C14—H14	120.1
C6—C1—C2	117.8 (4)	C15—C14—H14	120.1
C6—C1—P1	122.5 (3)	C16—C15—C14	120.0 (4)
C2—C1—P1	119.6 (3)	C16—C15—H15	120
C3—C2—C1	120.8 (4)	C14—C15—H15	120
C3—C2—H2	119.6	C17—C16—C15	120.5 (4)
C1—C2—H2	119.6	C17—C16—H16	119.8
C4—C3—C2	120.3 (4)	C15—C16—H16	119.8
C4—C3—H3	119.9	C16—C17—C18	119.7 (4)
C2—C3—H3	119.9	C16—C17—H17	120.1
C5—C4—C3	119.9 (4)	C18—C17—H17	120.1
C5—C4—H4	120.1	C17—C18—C13	120.8 (4)
C3—C4—H4	120.1	C17—C18—H18	119.6
C4—C5—C6	120.1 (4)	C13—C18—H18	119.6
C4—C5—H5	120	C19ii—C19—Cl2ii	87.8 (4)
C6—C5—H5	120	C19ii—C19—Cl1	82.2 (13)
C5—C6—C1	121.1 (4)	Cl2ii—C19—Cl1	126.8 (7)
C5—C6—H6	119.4	C19ii—C19—Cl2	62.8 (3)
C1—C6—H6	119.4	Cl1—C19—Cl2	110.2 (6)
C8—C7—C12	119.2 (4)	C19ii—C19—Cl1ii	69.5 (12)
C8—C7—P1	119.8 (3)	Cl2ii—C19—Cl1ii	114.8 (7)
C12—C7—P1	121.0 (3)	Cl1—C19—Cl1ii	110.0 (5)
C7—C8—C9	120.1 (4)	Cl2—C19—Cl1ii	110.3 (6)
C7—C8—H8	120	C19ii—C19—H19	166 (7)
C9—C8—H8	120	Cl2ii—C19—H19	78 (7)
C10—C9—C8	120.4 (4)	Cl1—C19—H19	109 (7)
C10—C9—H9	119.8	Cl2—C19—H19	104 (7)
C8—C9—H9	119.8	Cl1ii—C19—H19	113 (7)

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2.