Crystal structure of cis-[1,2-bis­(di­phenyl­phosphan­yl)ethene-κ2P,P′]di­chlorido­platinum(II) chloro­form disolvate: a new polymorph

Mugemana, J.; Bender, J.; Staples, R.J.; Biros, S.M.

doi:10.1107/S2056989018008836

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Volume 74| Part 7| July 2018| Pages 998-1001

https://doi.org/10.1107/S2056989018008836

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Crystal structure of cis-[1,2-bis(diphenylphosphanyl)ethene-κ²P,P′]dichloridoplatinum(II) chloroform disolvate: a new polymorph

Jimmy Mugemana,^a John Bender,^a Richard J. Staples ^b and Shannon M. Biros ^a ^*

^aDepartment of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA, and ^bCenter for Crystallographic Research, Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
^*Correspondence e-mail: biross@gvsu.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 May 2018; accepted 15 June 2018; online 21 June 2018)

The title compound, [PtCl₂(C₂₆H₂₂P₂)]·2CHCl₃ (I), is the third monoclinic polymorph of this platinum(II) complex involving the bidentate ligand cis-1,2-bis(diphenylphosphanyl)ethylene (cis-dppe) [for the others, see: Oberhauser et al. (1998a ). Inorg. Chim. Acta, 274, 143–154, and Oberhauser et al. (1995 ). Inorg. Chim. Acta, 238, 35–43]. The structure of compound (I) was solved in the space group P2₁/c, with one complex molecule in the asymmetric unit along with two solvate chloroform molecules. The Pt^II atom is ligated by two P and two Cl atoms in the equatorial plane and has a perfect square-planar coordination sphere. In the crystal, the complex molecule is linked to the chloroform solvate molecules by C—H⋯Cl hydrogen bonds and face-on C—Cl⋯π interactions. There are also weak offset π–π interactions present [intercentroid distances are 3.770 (6) and 4.096 (6) Å], linking the molecules to form supramolecular sheets that lie in the bc plane.

Keywords: crystal structure; polymorph; cis-dppe; C—H⋯Cl hydrogen bonding; face-on C—Cl⋯π interactions; offset π–π interactions.

CCDC reference: 1849747

1. Chemical context

The rigid compound cis-1,2-bis(diphenylphosphanyl)ethylene (cis-dppe) has been widely exploited as a bidentate ligand for transition metals. A selection of recent examples include complexes involving iron(II) (Song et al., 2018 ), copper(I) (Trivedi et al., 2017 ), gold(I) (Yao & Yam, 2015 ), nickel(II) (Schallenberg et al., 2014 ), nickel(III) (Hwang et al., 2015 ), and palladium(II) and platinum(II) (Song et al., 2017 ; Oberhauser et al., 1998a). The phosphorus atoms of this ligand have also been modified to give the corresponding oxide, sulfide and selenide derivatives (Morse et al., 2016 ; Duncan & Gallagher, 1981 ; Colquhoun et al., 1979 ; Aguiar & Daigle, 1964 ). Hence, structural studies of the parent bisphosphine are relevant to a wide array of researchers.

2. Structural commentary

The molecular structures of the cis-dppe ligand and the title compound (I) are shown in Fig. 1. This Pt–ligand complex features a square-planar geometry around the Pt^II metal center with bidentate coordination by the phosphorus atoms of the cis-dppe ligand. The metal coordination sphere is completed by two chloride anions.

Figure 1
A view of the molecular structure of the title compound, with the atom labeling. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms bonded to the ligand have been omitted for clarity.

As for the previously reported polymorphs of compound (I), structure HINCIQ (Oberhauser et al., 1998a) was solved in space group P2₁/n without solvent in the unit cell, while structure ZOLYII (Oberhauser et al., 1995) was solved in the space group P2₁/m as a chloroform and methylene chloride solvate. The latter complex molecule possesses mirror symmetry with the mirror bisecting the Pt atom and central C=C bond of the cis-dppe ligand. Selected bond distances and bond angles for the title compound (I), and the two other monoclinic polymorphs are given in Table 1.

Table 1
Selected bond distances (Å), bond angles (°) and the fourfold coordination descriptor, τ₄^a, for the three polymorphs of [(cis-dppe)Pt(Cl)₂]

Compound	(I)	HINCIQ^b	ZOLYII^c
Pt1—Cl1	2.358 (2)	2.36482)	2.360 (2)
Pt1—Cl2	2.363 (2)	2.366 (3)	2.360 (2)
Pt1—P1	2.217 (2)	2.216 (2)	2.211 (2)
Pt1—P2	2.210 (2)	2.219 (2)	2.211 (2)
P1—Pt1—Cl2	177.58 (7)	176.35 (10)	177.92 (9)
P2—Pt1—Cl1	178.38 (7)	175.81 (10)	177.92 (9)
τ₄	0.02	0.05	0.0
Notes: (a) Yang et al. (2007); (b) Oberhauser et al. (1998a); (c) Oberhauser et al. (1995).

When comparing these two structures to the title compound, the bond lengths and angles around the Pt^II center of all three structures are, unsurprisingly, quite similar. The Pt—P bond lengths range from 2.210 (2) to 2.219 (2) Å, while the Pt—Cl bond lengths range from 2.358 (2) to 2.366 (3) Å. The P—Pt—P bond angles range from 86.66 (11) to 87.08 (5)°, while the Cl—Pt—Cl bond angles range from 90.33 (7) to 91.03 (5)°. The τ₄ descriptor for fourfold coordination (where, for the extreme forms τ_{4 =} 0.00 for square-planar, 1.00 for tetrahedral and 0.85 for trigonal–pyramidal; Yang et al., 2007 ) of the Pt atoms range from 0.02 for compound (I), 0.05 for HINCIQ and 0.0 for ZOLYII, indicating perfect square-planar coordination spheres for each Pt atom.

3. Supramolecular features

In the crystal of (I), the metal–ligand complex is linked to the chloroform solvate molecules by C—H⋯Cl hydrogen bonds and Cl⋯π interactions. The hydrogen atoms of both chloroform molecules are engaged in weak hydrogen bonds with the metal-bound chlorine atoms (Fig. 2 and Table 2). The D⋯A distances range from 3.616 (9) to 3.789 (10) Å, while the D—H⋯A bond angles range from 132 to 158°. Three face-on Cl⋯π interactions (Imai et al., 2008 ) are also present involving the chlorine atoms of the chloroform molecules and the aromatic rings of the cis-dppe ligand (Fig. 2 and Table 3). The Cl⋯ring centroid distances for these interactions range from 3.242 (5) to 3.441 (7) Å, while the C—Cl⋯ring centroid angles range from 139.2 (5) to 160.3 (4)°.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1S—H1S⋯Cl1	1.00	3.04	3.782 (11)	132
C1S—H1S⋯Cl2	1.00	2.84	3.789 (10)	158
C2S—H2S⋯Cl1ⁱ	1.00	2.80	3.616 (9)	139
C2S—H2S⋯Cl2ⁱ	1.00	2.77	3.649 (9)	147
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 3
Face-on Cl⋯π interactions (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the phenyl rings C3–C8, C9–C14 and C15–C20, respectively.

C—Cl⋯Cg	C—Cl	Cl⋯Cg	C⋯Cg	C—Cl⋯Cg
C1S—Cl1S⋯Cg1	1.706 (11)	3.441 (7)	4.862 (11)	139.2 (5)
C2S—Cl4S⋯Cg2	1.737 (8)	3.242 (5)	4.775 (9)	145.4 (3)
C2S—Cl6S⋯Cg3	1.735 (8)	3.349 (5)	5.017 (9)	160.3 (4)

Figure 2
A view along the b axis of the title compound showing the C—H⋯Cl hydrogen bonds (blue dotted lines) and chlorine⋯π interactions (red dashed lines) found in the crystal lattice [symmetry code: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

The complex molecules are also linked by weak offset π–π interactions, forming sheets that lie in the bc plane, as shown in Fig. 3. The intercentroid distances are Cg2⋯Cg2ⁱⁱ = 4.096 (6) Å [Cg2 is the centroid of ring C9–C14, α = 0.0 (5)°, interplanar distance = 3.917 (4) Å, slippage = 1.20 Å, symmetry code (ii) −x + 2, −y, −z + 1], and Cg3⋯Cg4ⁱⁱⁱ = 3.770 (6) Å [Cg3 and Cg4 are the centroids of rings C15–C20 and C21–C26, respectively, α = 5.3 (5)°, interplanar distances are 3.326 (4) and 3.439 (4) Å, slippage = 1.544 Å, symmetry code (iii) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ].

Figure 3
A view along the a axis of the weak offset π–π interactions (purple dashed lines) between aromatic rings of the title compound, resulting in the formation of supramolecular sheets. Chloroform solvent molecules have been omitted for clarity.

The closely related polymorph ZOLYII, which contains one CH₂Cl₂ solvent molecule and one CHCl₃ solvent molecule in the unit cell, also shows Cl⋯π interactions. However, the methylene chloride solvent molecule is not engaged in a hydrogen bond with a chlorine atom of the Pt^II complex, and is disordered in the crystal lattice.

4. Database survey

The Cambridge Structural Database (CSD, version 5.39, February 2018; Groom et al., 2016 ) contains 21 structures in which the cis-dppe ligand is coordinated to a Pt^II center. In addition to the two polymorphs described above, the most similar cis-dppe–Pt^II coordination complexes include AFEXEO (Vaz et al., 2002 ) and FOQPUW (Lobana et al., 2000 ), where the Pt^II center is bound by two thiolate ligands (–SPh and –SPy, respectively). Another structure related to the title compound is KADQEL (Oberhauser et al., 1998b ) in which the Pt^II center is coordinated by two acetonitrile molecules. Finally, structure ZOLYOO (Oberhauser et al., 1995) contains one Pt^II center coordinated by two cis-dppe ligands with two outer sphere tetraphenylborate molecules as counter-anions. In each of these structures, the bond lengths and angles are similar to those described above for the title compound.

5. Synthesis and crystallization

The title compound was prepared serendipitously by mixing 20.5 mg of cis-1,2-dppeSe₂ (Colquhoun et al., 1979) with 8 mg of Pt(NCPh)₂Cl₂ in CDCl₃ (0.7 ml) in a NMR tube. This solution was left to stand at room temperature, and colorless needle-like crystals of compound (I) were obtained within a few days.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The hydrogen atoms were placed in calculated positions and refined as riding: C—H = 0.95–1.00 Å with U_iso(H) = 1.2U_eq(C).

Table 4
Experimental details

Crystal data
Chemical formula	[PtCl₂(C₂₆H₂₂P₂)]·2CHCl₃
M_r	901.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.1441 (10), 18.0870 (17), 16.9621 (16)
β (°)	106.2465 (10)
V (Å³)	3282.4 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.04
Crystal size (mm)	0.26 × 0.14 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.503, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	26503, 6039, 3360
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.122, 1.03
No. of reflections	6039
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.44, −1.01
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ; Bourhis et al., 2015 ), CrystalMaker (Palmer, 2007 ).

Supporting information

CCDC reference: 1849747

Crystal structure: contains datablocks Global, I. DOI: https://doi.org/10.1107/S2056989018008836/su5444sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018008836/su5444Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009; Bourhis et al., 2015); software used to prepare material for publication: CrystalMaker (Palmer, 2007).

cis-[1,2-Bis(diphenylphosphanyl)ethene-κ²P,P']dichloridoplatinum(II) chloroform disolvate top

Crystal data top

[PtCl₂(C₂₆H₂₂P₂)]·2CHCl₃	F(000) = 1744
M_r = 901.10	D_x = 1.823 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.1441 (10) Å	Cell parameters from 6541 reflections
b = 18.0870 (17) Å	θ = 2.2–25.4°
c = 16.9621 (16) Å	µ = 5.04 mm⁻¹
β = 106.2465 (10)°	T = 173 K
V = 3282.4 (5) Å³	Needle, colorless
Z = 4	0.26 × 0.14 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	3360 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.069
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θ_max = 25.4°, θ_min = 1.7°
T_min = 0.502, T_max = 0.745	h = −13→13
26503 measured reflections	k = −21→21
6039 independent reflections	l = −20→19

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0396P)² + 10.564P] where P = (F_o² + 2F_c²)/3
6039 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 3.44 e Å⁻³
0 restraints	Δρ_min = −1.00 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Pt1	0.76626 (2)	0.25106 (2)	0.26582 (2)	0.02442 (12)
Cl1	0.75592 (19)	0.15899 (10)	0.16572 (12)	0.0322 (5)
Cl2	0.7627 (2)	0.34405 (10)	0.16732 (12)	0.0346 (5)
P1	0.77172 (19)	0.16744 (11)	0.36235 (12)	0.0246 (5)
P2	0.78048 (19)	0.33570 (10)	0.36196 (12)	0.0243 (5)
C1	0.7832 (8)	0.2162 (5)	0.4579 (5)	0.0316 (19)
H1	0.7851	0.1901	0.5068	0.038*
C2	0.7887 (7)	0.2879 (5)	0.4572 (5)	0.0319 (19)
H2	0.7970	0.3151	0.5063	0.038*
C3	0.9055 (8)	0.1058 (4)	0.3861 (5)	0.031 (2)
C4	1.0070 (9)	0.1237 (5)	0.4509 (6)	0.053 (3)
H4	1.0036	0.1654	0.4843	0.064*
C5	1.1147 (11)	0.0803 (6)	0.4674 (7)	0.068 (3)
H5	1.1841	0.0911	0.5132	0.082*
C6	1.1195 (11)	0.0210 (6)	0.4160 (6)	0.063 (3)
H6	1.1943	−0.0068	0.4237	0.075*
C7	1.0156 (11)	0.0033 (5)	0.3545 (7)	0.059 (3)
H7	1.0171	−0.0391	0.3217	0.071*
C8	0.9087 (9)	0.0453 (5)	0.3388 (5)	0.044 (2)
H8	0.8375	0.0322	0.2952	0.053*
C9	0.6333 (8)	0.1110 (4)	0.3461 (5)	0.032 (2)
C10	0.5226 (8)	0.1331 (4)	0.2901 (5)	0.037 (2)
H10	0.5219	0.1758	0.2575	0.044*
C11	0.4138 (9)	0.0937 (5)	0.2815 (6)	0.050 (2)
H11	0.3384	0.1090	0.2430	0.060*
C12	0.4156 (11)	0.0322 (6)	0.3292 (7)	0.063 (3)
H12	0.3404	0.0055	0.3241	0.075*
C13	0.5234 (12)	0.0087 (5)	0.3838 (7)	0.059 (3)
H13	0.5233	−0.0345	0.4157	0.071*
C14	0.6331 (10)	0.0481 (5)	0.3925 (6)	0.051 (3)
H14	0.7084	0.0318	0.4304	0.061*
C15	0.6507 (8)	0.3979 (4)	0.3499 (5)	0.0290 (19)
C16	0.5387 (9)	0.3850 (5)	0.2923 (6)	0.046 (2)
H16	0.5307	0.3446	0.2554	0.055*
C17	0.4375 (10)	0.4306 (6)	0.2880 (7)	0.066 (3)
H17	0.3607	0.4217	0.2474	0.079*
C18	0.4464 (12)	0.4881 (7)	0.3410 (8)	0.066 (4)
H18	0.3761	0.5188	0.3381	0.079*
C19	0.5565 (13)	0.5010 (6)	0.3980 (8)	0.069 (4)
H19	0.5627	0.5414	0.4348	0.083*
C20	0.6601 (10)	0.4571 (5)	0.4042 (6)	0.054 (3)
H20	0.7366	0.4670	0.4446	0.065*
C21	0.9205 (8)	0.3907 (5)	0.3809 (5)	0.035 (2)
C22	0.9220 (9)	0.4607 (5)	0.3500 (6)	0.051 (3)
H22	0.8456	0.4828	0.3200	0.061*
C23	1.0324 (11)	0.4998 (6)	0.3615 (6)	0.060 (3)
H23	1.0318	0.5488	0.3414	0.072*
C24	1.1423 (10)	0.4664 (7)	0.4025 (6)	0.061 (3)
H24	1.2188	0.4922	0.4094	0.073*
C25	1.1440 (10)	0.3972 (7)	0.4336 (8)	0.085 (4)
H25	1.2209	0.3755	0.4633	0.101*
C26	1.0345 (9)	0.3588 (6)	0.4219 (7)	0.062 (3)
H26	1.0364	0.3097	0.4421	0.074*
Cl1S	1.1237 (5)	0.1975 (3)	0.2977 (2)	0.1431 (18)
Cl2S	1.0900 (3)	0.1895 (2)	0.1275 (2)	0.1086 (13)
Cl3S	1.1475 (6)	0.3253 (3)	0.2052 (5)	0.226 (4)
C1S	1.0756 (10)	0.2471 (5)	0.2089 (7)	0.066 (3)
H1S	0.9848	0.2583	0.1995	0.079*
Cl4S	0.4561 (3)	0.16565 (15)	0.48152 (18)	0.0731 (8)
Cl5S	0.3791 (3)	0.25490 (16)	0.59773 (16)	0.0679 (8)
Cl6S	0.4741 (3)	0.32216 (15)	0.47379 (18)	0.0681 (8)
C2S	0.4841 (8)	0.2468 (4)	0.5386 (5)	0.040 (2)
H2S	0.5708	0.2447	0.5764	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.02528 (18)	0.02567 (17)	0.02229 (17)	0.00053 (16)	0.00661 (12)	0.00026 (16)
Cl1	0.0440 (13)	0.0263 (10)	0.0265 (11)	0.0004 (9)	0.0104 (10)	−0.0046 (9)
Cl2	0.0494 (14)	0.0302 (10)	0.0260 (11)	−0.0040 (10)	0.0132 (10)	0.0034 (9)
P1	0.0261 (12)	0.0261 (11)	0.0201 (11)	0.0019 (9)	0.0040 (9)	0.0028 (9)
P2	0.0289 (12)	0.0234 (10)	0.0209 (11)	0.0004 (9)	0.0075 (10)	−0.0012 (9)
C1	0.035 (5)	0.039 (5)	0.022 (5)	0.004 (4)	0.009 (4)	−0.002 (4)
C2	0.026 (5)	0.046 (5)	0.023 (5)	0.004 (4)	0.004 (4)	−0.004 (4)
C3	0.029 (5)	0.031 (4)	0.035 (5)	0.013 (4)	0.011 (4)	0.011 (4)
C4	0.053 (7)	0.050 (6)	0.057 (7)	0.006 (5)	0.016 (6)	−0.002 (5)
C5	0.064 (8)	0.078 (8)	0.056 (7)	0.020 (6)	0.005 (6)	0.013 (6)
C6	0.067 (8)	0.072 (8)	0.046 (7)	0.038 (6)	0.010 (6)	0.013 (6)
C7	0.081 (9)	0.054 (6)	0.051 (7)	0.031 (6)	0.031 (7)	0.011 (5)
C8	0.050 (6)	0.050 (5)	0.030 (5)	0.010 (5)	0.009 (5)	−0.005 (4)
C9	0.032 (5)	0.033 (5)	0.031 (5)	−0.001 (4)	0.008 (4)	0.000 (4)
C10	0.043 (6)	0.036 (5)	0.034 (5)	−0.009 (4)	0.015 (5)	−0.009 (4)
C11	0.036 (6)	0.066 (7)	0.048 (6)	−0.013 (5)	0.014 (5)	−0.004 (5)
C12	0.075 (9)	0.067 (7)	0.059 (7)	−0.035 (7)	0.040 (7)	−0.024 (6)
C13	0.092 (10)	0.040 (6)	0.055 (7)	−0.007 (6)	0.037 (7)	0.001 (5)
C14	0.075 (8)	0.042 (5)	0.039 (6)	−0.010 (5)	0.021 (5)	−0.002 (5)
C15	0.034 (5)	0.029 (4)	0.031 (5)	0.005 (4)	0.021 (4)	0.005 (4)
C16	0.040 (6)	0.057 (6)	0.044 (6)	0.002 (5)	0.015 (5)	0.003 (5)
C17	0.048 (7)	0.070 (8)	0.079 (9)	0.022 (6)	0.019 (6)	0.035 (7)
C18	0.066 (8)	0.071 (8)	0.077 (9)	0.044 (7)	0.046 (7)	0.045 (7)
C19	0.107 (10)	0.048 (6)	0.073 (8)	0.042 (7)	0.058 (8)	0.014 (6)
C20	0.062 (7)	0.045 (6)	0.051 (7)	0.024 (5)	0.010 (6)	−0.002 (5)
C21	0.039 (5)	0.040 (5)	0.026 (5)	−0.006 (4)	0.008 (4)	−0.002 (4)
C22	0.044 (6)	0.055 (6)	0.052 (7)	−0.011 (5)	0.010 (5)	0.002 (5)
C23	0.080 (9)	0.055 (7)	0.046 (7)	−0.026 (6)	0.022 (7)	−0.004 (5)
C24	0.047 (7)	0.089 (9)	0.047 (7)	−0.031 (6)	0.017 (6)	−0.006 (6)
C25	0.034 (6)	0.102 (10)	0.098 (10)	−0.007 (7)	−0.014 (7)	0.019 (8)
C26	0.032 (6)	0.059 (6)	0.085 (8)	−0.005 (5)	0.000 (6)	0.015 (6)
Cl1S	0.165 (4)	0.189 (5)	0.087 (3)	0.079 (4)	0.054 (3)	0.043 (3)
Cl2S	0.075 (2)	0.157 (4)	0.097 (3)	−0.018 (2)	0.029 (2)	−0.011 (3)
Cl3S	0.276 (7)	0.097 (3)	0.395 (10)	−0.060 (4)	0.244 (7)	−0.033 (5)
C1S	0.053 (6)	0.077 (7)	0.075 (8)	0.018 (6)	0.028 (6)	0.019 (7)
Cl4S	0.104 (2)	0.0567 (16)	0.0630 (18)	−0.0037 (16)	0.0315 (17)	−0.0171 (14)
Cl5S	0.0672 (17)	0.095 (2)	0.0518 (16)	0.0031 (17)	0.0334 (14)	−0.0059 (16)
Cl6S	0.0653 (18)	0.0624 (17)	0.080 (2)	0.0084 (14)	0.0262 (16)	0.0302 (15)
C2S	0.044 (5)	0.038 (5)	0.038 (5)	0.009 (5)	0.013 (4)	0.002 (5)

Geometric parameters (Å, º) top

Pt1—Cl1	2.3580 (18)	C12—C13	1.363 (14)
Pt1—Cl2	2.3632 (19)	C13—C14	1.387 (14)
Pt1—P1	2.2173 (19)	C15—C16	1.372 (12)
Pt1—P2	2.2099 (19)	C15—C20	1.397 (11)
P1—C1	1.818 (8)	C16—C17	1.383 (12)
P1—C3	1.814 (8)	C17—C18	1.360 (15)
P1—C9	1.806 (8)	C18—C19	1.353 (16)
P2—C2	1.812 (8)	C19—C20	1.382 (13)
P2—C15	1.798 (8)	C21—C22	1.371 (12)
P2—C21	1.803 (8)	C21—C26	1.392 (12)
C1—C2	1.297 (11)	C22—C23	1.384 (13)
C3—C4	1.377 (12)	C23—C24	1.368 (14)
C3—C8	1.364 (11)	C24—C25	1.355 (15)
C4—C5	1.396 (13)	C25—C26	1.370 (13)
C5—C6	1.393 (14)	Cl1S—C1S	1.706 (11)
C6—C7	1.362 (14)	Cl2S—C1S	1.773 (11)
C7—C8	1.376 (12)	Cl3S—C1S	1.636 (11)
C9—C10	1.388 (11)	Cl4S—C2S	1.737 (8)
C9—C14	1.383 (11)	Cl5S—C2S	1.748 (9)
C10—C11	1.379 (11)	Cl6S—C2S	1.735 (8)
C11—C12	1.373 (13)

Cl1—Pt1—Cl2	90.33 (6)	C14—C9—P1	121.0 (7)
P1—Pt1—Cl1	92.04 (7)	C14—C9—C10	118.9 (8)
P1—Pt1—Cl2	177.58 (7)	C11—C10—C9	120.7 (8)
P2—Pt1—Cl1	178.38 (7)	C12—C11—C10	119.3 (10)
P2—Pt1—Cl2	90.70 (7)	C13—C12—C11	121.2 (10)
P2—Pt1—P1	86.91 (7)	C12—C13—C14	119.7 (10)
C1—P1—Pt1	107.9 (3)	C9—C14—C13	120.2 (10)
C3—P1—Pt1	115.7 (3)	C16—C15—P2	121.2 (7)
C3—P1—C1	104.6 (4)	C16—C15—C20	119.0 (8)
C9—P1—Pt1	115.3 (3)	C20—C15—P2	119.7 (7)
C9—P1—C1	104.8 (4)	C15—C16—C17	120.2 (10)
C9—P1—C3	107.5 (4)	C18—C17—C16	120.9 (11)
C2—P2—Pt1	107.6 (3)	C19—C18—C17	119.2 (10)
C15—P2—Pt1	117.4 (3)	C18—C19—C20	121.8 (11)
C15—P2—C2	103.8 (3)	C19—C20—C15	118.9 (10)
C15—P2—C21	107.7 (4)	C22—C21—P2	123.0 (7)
C21—P2—Pt1	113.2 (3)	C22—C21—C26	117.9 (8)
C21—P2—C2	106.3 (4)	C26—C21—P2	118.9 (7)
C2—C1—P1	117.9 (7)	C21—C22—C23	121.5 (10)
C1—C2—P2	119.6 (7)	C24—C23—C22	118.7 (10)
C4—C3—P1	118.2 (7)	C25—C24—C23	121.2 (10)
C8—C3—P1	121.1 (7)	C24—C25—C26	119.8 (11)
C8—C3—C4	120.5 (8)	C25—C26—C21	120.8 (10)
C3—C4—C5	119.7 (9)	Cl1S—C1S—Cl2S	107.7 (6)
C6—C5—C4	119.3 (11)	Cl3S—C1S—Cl1S	116.9 (8)
C7—C6—C5	119.2 (10)	Cl3S—C1S—Cl2S	109.0 (6)
C6—C7—C8	121.5 (10)	Cl4S—C2S—Cl5S	110.2 (5)
C3—C8—C7	119.5 (9)	Cl6S—C2S—Cl4S	109.9 (5)
C10—C9—P1	119.9 (6)	Cl6S—C2S—Cl5S	111.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1S—H1S···Cl1	1.00	3.04	3.782 (11)	132
C1S—H1S···Cl2	1.00	2.84	3.789 (10)	158
C2S—H2S···Cl1ⁱ	1.00	2.80	3.616 (9)	139
C2S—H2S···Cl2ⁱ	1.00	2.77	3.649 (9)	147

Symmetry code: (i) x, −y+1/2, z+1/2.

Selected bond distances (Å), bond angles (°) and the fourfold coordination descriptor, τ₄^a, for the three polymorphs of [(cis-dppe)Pt(Cl)₂] top

Compound	(I)	HINCIQ^b	ZOLYII^c
Pt1—Cl1	2.358 (2)	2.36482)	2.360 (2)
Pt1—Cl2	2.363 (2)	2.366 (3)	2.360 (2)
Pt1—P1	2.217 (2)	2.216 (2)	2.211 (2)
Pt1—P2	2.210 (2)	2.219 (2)	2.211 (2)
P1—Pt1—Cl2	177.58 (7)	176.35 (10)	177.92 (9)
P2—Pt1—Cl1	178.38 (7)	175.81 (10)	177.92 (9)
τ₄	0.02	0.05	0.0

Notes: (a) Yang et al. (2007); (b) Oberhauser et al. (1998a); (c) Oberhauser et al. (1995).

Face-on Cl···π interactions (Å, °) top

Cg1, Cg2 and Cg3 are the centroids of the phenyl rings C3–C8, C9–C14 and C15–C20, respectively.

C—Cl···Cg	C—Cl	Cl···Cg	C···Cg	C—Cl···Cg
C1S—Cl1S···Cg1	1.706 (11)	3.441 (7)	4.862 (11)	139.2 (5)
C2S—Cl4S···Cg2	1.737 (8)	3.242 (5)	4.775 (9)	145.4 (3)
C2S—Cl6S···Cg3	1.735 (8)	3.349 (5)	5.017 (9)	160.3 (4)

Acknowledgements

The authors thank Pfizer, Inc. for the donation of a Varian INOVA 400 FT NMR. The CCD-based X-ray diffractometers at Michigan State University were upgraded and/or replaced by departmental funds.

Funding information

Funding for this research was provided by: National Science Foundation [grant Nos. CCLI CHE-0087655, MRI CHE-1725699 and REU CHE-1559886 (to J. Mugemana)]; GVSU OURS, CSCE and the Chemistry Department's Weldon Fund.

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