Bis(cis-1,4-diphenyl-1,4-diphosphacyclo­hexane-κ²P,P′)platinum(II) bis­(tetra­fluorido­borate)

The title complex, [Pt(C₁₆H₁₈P₂)₂](BF₄)₂, possesses a crystallographically imposed center of symmetry occupied by a Pt^II ion, which is coordinated by four P atoms from two 1,4-diphenyl-1,4-diphosphacyclo­hexane ligands in a distorted square-planar geometry.

Key indicators

• Single-crystal X-ray study
• T = 373 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.016
• wR factor = 0.033
• Data-to-parameter ratio = 30.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         B1

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           33.17
           From the CIF: _reflns_number_total               6509
           Count of symmetry unique reflns         3802
           Completeness (_total/calc)            171.20%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2707
           Fraction of Friedel pairs measured     0.712
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Pt1         (9)       2.95

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The crystal structure of (I) consists of [Pt(C₁₆H₁₈P₂)₂]²⁺ cations and BF₄^- anions (Fig. 1). The cation shows a distorted square planar geometry around the metal center with two non-coordinating BF₄^- anions. The P—Pt—P bite angle observed in the structure is 72.908 (13)°. Additionally, the phenyl substituents on the phosphorus atoms are arranged in a parallel fashion, with a distance between the center of the phenyl rings of 3.727 Å and a dihedral angle of 2.15 (4)° between the rings. The parallel arrangement of phenyl rings is not, however, repeated in the unit cell between individual molecules. The parallel arrangement of the phenyl rings within the molecule was also observed in the previously reported analogous Pt^II an Pd(II) chloride complexes (Mason et al., 2006).

Related literature

The corresponding complexes with both Pt^II and Pd^II have been previously reported as chloride salts (Mason et al., 2006). For related literature, see: Brooks et al. (1989).

S2. Experimental

The synthesis of (I) was completed through reaction of the previously reported chloride salt with an excess of AgBF₄, followed by filtration to remove the solid AgCl (Mason et al., 2006, Brooks et al., 1989). Crystals where grown by slow vapor diffusion of diethylether into a saturated chloroform solution of (I).

S3. Refinement

All H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H distances in the range of 0.93–0.97Å, with U_iso(H) = 1.2 times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids. H–atoms are drawn as spheres with arbitrary radius.

Bis(cis-1,4-diphenyl-1,4-diphosphacyclohexane-κ²P,P')platinum(II) bis(tetrafluoridoborate)

Crystal data

[Pt(C16H18P2)2](BF4)2	Dx = 1.775 Mg m^−3
Mr = 913.20	Melting point: not measured K
Tetragonal, P41212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 4abw 2nw	Cell parameters from 8065 reflections
a = 10.83270 (15) Å	θ = 2.3–33.2°
c = 29.1244 (6) Å	µ = 4.36 mm^−1
V = 3417.67 (10) Å^3	T = 373 K
Z = 4	Prismatic, colorless
F(000) = 1792	0.47 × 0.25 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer	6509 independent reflections
Radiation source: fine-focus sealed tube	6151 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 33.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→16
Tmin = 0.281, Tmax = 0.647	k = −16→16
41078 measured reflections	l = −44→44

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.016	H-atom parameters constrained
wR(F^2) = 0.033	w = 1/[σ^2(Fo^2) + (0.0084P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.003
6509 reflections	Δρmax = 0.69 e Å^−3
213 parameters	Δρmin = −0.87 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (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 > 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
Pt1	0.832348 (5)	0.832348 (5)	0.0000	0.01048 (2)
P1	0.84079 (4)	1.00450 (4)	0.045922 (11)	0.01195 (6)
P2	0.84132 (4)	0.64859 (3)	−0.040032 (12)	0.01251 (7)
C1	0.97255 (15)	1.10328 (14)	0.05191 (5)	0.0148 (3)
C2	0.96273 (16)	1.23257 (15)	0.04781 (6)	0.0184 (3)
H2A	0.8872	1.2691	0.0411	0.022*
C3	1.06751 (18)	1.30451 (16)	0.05401 (6)	0.0234 (4)
H3A	1.0617	1.3900	0.0518	0.028*
C4	1.18032 (18)	1.25058 (17)	0.06340 (6)	0.0247 (4)
H4A	1.2497	1.2999	0.0676	0.030*
C5	1.19046 (15)	1.12267 (17)	0.06662 (6)	0.0221 (3)
H5A	1.2667	1.0865	0.0725	0.026*
C6	1.08678 (15)	1.04949 (15)	0.06097 (5)	0.0180 (3)
H6A	1.0934	0.9641	0.0632	0.022*
C7	0.80596 (14)	0.94231 (14)	0.10316 (5)	0.0150 (3)
H7A	0.8759	0.8950	0.1143	0.018*
H7B	0.7912	1.0097	0.1244	0.018*
C8	0.70129 (14)	1.09169 (15)	0.03316 (5)	0.0163 (3)
H8A	0.6819	1.1469	0.0584	0.020*
H8B	0.7130	1.1407	0.0056	0.020*
C9	0.85797 (14)	0.68966 (14)	−0.10070 (5)	0.0158 (3)
H9A	0.8950	0.6219	−0.1176	0.019*
H9B	0.7778	0.7074	−0.1140	0.019*
C10	0.99765 (16)	0.59454 (13)	−0.02600 (5)	0.0171 (3)
H10A	1.0004	0.5669	0.0057	0.021*
H10B	1.0192	0.5254	−0.0456	0.021*
C11	0.73590 (14)	0.52277 (14)	−0.03228 (5)	0.0152 (3)
C12	0.70222 (14)	0.49227 (15)	0.01255 (5)	0.0158 (3)
H12A	0.7375	0.5341	0.0371	0.019*
C13	0.61647 (15)	0.40002 (15)	0.02062 (5)	0.0180 (3)
H13A	0.5941	0.3799	0.0505	0.022*
C14	0.56379 (15)	0.33727 (16)	−0.01647 (6)	0.0192 (3)
H14A	0.5052	0.2762	−0.0112	0.023*
C15	0.59824 (17)	0.36542 (15)	−0.06104 (6)	0.0223 (4)
H15A	0.5640	0.3220	−0.0855	0.027*
C16	0.68378 (16)	0.45819 (14)	−0.06942 (5)	0.0200 (3)
H16A	0.7064	0.4775	−0.0994	0.024*
B1	1.00964 (16)	0.65886 (17)	0.10947 (5)	0.0167 (3)
F1	1.01041 (11)	0.72699 (9)	0.14989 (4)	0.0289 (2)
F2	1.07033 (10)	0.54795 (10)	0.11657 (4)	0.0334 (3)
F3	0.88695 (10)	0.63397 (11)	0.09696 (4)	0.0319 (3)
F4	1.06599 (11)	0.72618 (12)	0.07492 (4)	0.0350 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.01143 (2)	0.01143 (2)	0.00858 (3)	0.00085 (3)	0.00064 (2)	−0.00064 (2)
P1	0.01367 (15)	0.01235 (14)	0.00981 (13)	0.00177 (18)	−0.00029 (13)	−0.00078 (13)
P2	0.01565 (16)	0.01150 (16)	0.01038 (13)	0.00070 (17)	0.00073 (13)	−0.00081 (12)
C1	0.0182 (7)	0.0147 (7)	0.0114 (6)	−0.0019 (6)	0.0002 (5)	−0.0015 (5)
C2	0.0240 (8)	0.0171 (7)	0.0143 (7)	0.0012 (7)	0.0012 (6)	0.0002 (6)
C3	0.0348 (9)	0.0178 (8)	0.0177 (7)	−0.0063 (8)	0.0012 (7)	−0.0003 (6)
C4	0.0259 (9)	0.0275 (8)	0.0208 (7)	−0.0122 (8)	0.0007 (7)	−0.0016 (6)
C5	0.0172 (8)	0.0300 (8)	0.0190 (7)	−0.0040 (7)	−0.0025 (6)	−0.0013 (6)
C6	0.0197 (7)	0.0180 (7)	0.0165 (7)	0.0010 (7)	−0.0025 (6)	−0.0010 (6)
C7	0.0180 (7)	0.0175 (7)	0.0094 (6)	0.0006 (6)	−0.0012 (5)	−0.0007 (5)
C8	0.0183 (7)	0.0147 (6)	0.0158 (7)	0.0039 (6)	−0.0004 (5)	−0.0013 (5)
C9	0.0192 (7)	0.0165 (7)	0.0116 (6)	−0.0016 (6)	−0.0002 (5)	−0.0010 (5)
C10	0.0197 (7)	0.0142 (6)	0.0174 (6)	0.0037 (7)	−0.0004 (6)	0.0008 (5)
C11	0.0186 (7)	0.0125 (7)	0.0145 (6)	0.0016 (6)	0.0003 (5)	−0.0006 (5)
C12	0.0210 (7)	0.0154 (6)	0.0111 (5)	0.0010 (7)	−0.0018 (5)	−0.0008 (5)
C13	0.0216 (8)	0.0157 (7)	0.0168 (6)	0.0002 (6)	0.0004 (6)	0.0037 (6)
C14	0.0212 (7)	0.0143 (6)	0.0222 (7)	−0.0010 (7)	−0.0016 (6)	0.0014 (6)
C15	0.0280 (8)	0.0193 (7)	0.0196 (7)	−0.0043 (7)	−0.0037 (6)	−0.0041 (6)
C16	0.0257 (8)	0.0188 (7)	0.0154 (6)	−0.0020 (7)	−0.0001 (6)	−0.0014 (5)
B1	0.0159 (7)	0.0186 (8)	0.0157 (6)	−0.0001 (7)	0.0008 (6)	−0.0001 (6)
F1	0.0368 (6)	0.0281 (5)	0.0220 (5)	0.0017 (6)	0.0052 (5)	−0.0078 (4)
F2	0.0316 (6)	0.0203 (5)	0.0484 (7)	0.0082 (5)	−0.0111 (5)	−0.0084 (5)
F3	0.0193 (5)	0.0343 (6)	0.0422 (7)	−0.0048 (5)	−0.0082 (5)	0.0085 (5)
F4	0.0357 (6)	0.0486 (7)	0.0208 (5)	−0.0118 (6)	0.0064 (5)	0.0078 (5)

Geometric parameters (Å, º)

Pt1—P1	2.2967 (4)	C8—C10^i	1.555 (2)
Pt1—P1^i	2.2967 (4)	C8—H8A	0.9700
Pt1—P2	2.3089 (3)	C8—H8B	0.9700
Pt1—P2^i	2.3089 (3)	C9—C7^i	1.558 (2)
P1—C1	1.7924 (16)	C9—H9A	0.9700
P1—C8	1.8204 (16)	C9—H9B	0.9700
P1—C7	1.8372 (15)	C10—C8^i	1.555 (2)
P2—C11	1.7924 (16)	C10—H10A	0.9700
P2—C9	1.8309 (15)	C10—H10B	0.9700
P2—C10	1.8379 (17)	C11—C12	1.395 (2)
C1—C6	1.393 (2)	C11—C16	1.407 (2)
C1—C2	1.410 (2)	C12—C13	1.384 (2)
C2—C3	1.389 (2)	C12—H12A	0.9300
C2—H2A	0.9300	C13—C14	1.398 (2)
C3—C4	1.382 (3)	C13—H13A	0.9300
C3—H3A	0.9300	C14—C15	1.384 (2)
C4—C5	1.393 (3)	C14—H14A	0.9300
C4—H4A	0.9300	C15—C16	1.389 (2)
C5—C6	1.385 (2)	C15—H15A	0.9300
C5—H5A	0.9300	C16—H16A	0.9300
C6—H6A	0.9300	B1—F4	1.3845 (19)
C7—C9^i	1.558 (2)	B1—F2	1.385 (2)
C7—H7A	0.9700	B1—F1	1.3894 (18)
C7—H7B	0.9700	B1—F3	1.404 (2)
P1—Pt1—P1^i	105.93 (2)	C10^i—C8—P1	107.75 (11)
P1—Pt1—P2	172.928 (14)	C10^i—C8—H8A	110.2
P1^i—Pt1—P2	72.908 (13)	P1—C8—H8A	110.2
P1—Pt1—P2^i	72.908 (13)	C10^i—C8—H8B	110.2
P1^i—Pt1—P2^i	172.928 (13)	P1—C8—H8B	110.2
P2—Pt1—P2^i	109.12 (2)	H8A—C8—H8B	108.5
C1—P1—C8	111.79 (7)	C7^i—C9—P2	107.38 (10)
C1—P1—C7	107.11 (7)	C7^i—C9—H9A	110.2
C8—P1—C7	101.83 (7)	P2—C9—H9A	110.2
C1—P1—Pt1	124.97 (5)	C7^i—C9—H9B	110.2
C8—P1—Pt1	105.63 (5)	P2—C9—H9B	110.2
C7—P1—Pt1	102.85 (5)	H9A—C9—H9B	108.5
C11—P2—C9	111.66 (7)	C8^i—C10—P2	109.69 (10)
C11—P2—C10	108.47 (7)	C8^i—C10—H10A	109.7
C9—P2—C10	101.61 (7)	P2—C10—H10A	109.7
C11—P2—Pt1	124.41 (5)	C8^i—C10—H10B	109.7
C9—P2—Pt1	106.38 (5)	P2—C10—H10B	109.7
C10—P2—Pt1	101.61 (5)	H10A—C10—H10B	108.2
C6—C1—C2	119.91 (16)	C12—C11—C16	119.80 (14)
C6—C1—P1	118.43 (12)	C12—C11—P2	117.68 (12)
C2—C1—P1	121.66 (13)	C16—C11—P2	122.48 (12)
C3—C2—C1	119.01 (16)	C13—C12—C11	120.34 (14)
C3—C2—H2A	120.5	C13—C12—H12A	119.8
C1—C2—H2A	120.5	C11—C12—H12A	119.8
C4—C3—C2	120.76 (16)	C12—C13—C14	119.59 (14)
C4—C3—H3A	119.6	C12—C13—H13A	120.2
C2—C3—H3A	119.6	C14—C13—H13A	120.2
C3—C4—C5	120.23 (17)	C15—C14—C13	120.48 (15)
C3—C4—H4A	119.9	C15—C14—H14A	119.8
C5—C4—H4A	119.9	C13—C14—H14A	119.8
C6—C5—C4	119.84 (17)	C14—C15—C16	120.28 (15)
C6—C5—H5A	120.1	C14—C15—H15A	119.9
C4—C5—H5A	120.1	C16—C15—H15A	119.9
C5—C6—C1	120.24 (15)	C15—C16—C11	119.50 (15)
C5—C6—H6A	119.9	C15—C16—H16A	120.2
C1—C6—H6A	119.9	C11—C16—H16A	120.2
C9^i—C7—P1	109.84 (10)	F4—B1—F2	110.86 (14)
C9^i—C7—H7A	109.7	F4—B1—F1	109.47 (14)
P1—C7—H7A	109.7	F2—B1—F1	109.35 (12)
C9^i—C7—H7B	109.7	F4—B1—F3	109.26 (13)
P1—C7—H7B	109.7	F2—B1—F3	108.75 (14)
H7A—C7—H7B	108.2	F1—B1—F3	109.12 (13)

Symmetry code: (i) y, x, −z.