[1,2-Bis­(diisopropyl­phosphan­yl)ethane-κ2P,P′]dichloridonickel(II)

Castellanos-Blanco, N.Y.; García, J.J.; Flores-Alamo, M.

doi:10.1107/S1600536811021209

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m871

doi:10.1107/S1600536811021209

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[1,2-Bis(diisopropylphosphanyl)ethane-κ²P,P′]dichloridonickel(II)

Nahury Y. Castellanos-Blanco,^a Juventino J. García ^a and Marcos Flores-Alamo ^a ^*

^aFacultad de Química, Universidad Nacional Autónoma de México, México DF, 04510, Mexico
^*Correspondence e-mail: mfa@unam.mx

(Received 26 May 2011; accepted 2 June 2011; online 11 June 2011)

In the crystal structure of title compound, [NiCl₂(C₁₄H₃₂P₂)], the Ni^II atom lies on a twofold rotation axis and shows a slightly distorted square-planar coordination geometry, with a dihedral angle of 10.01 (8)° between the cis-Cl—Ni—Cl and cis-P—Ni—P planes. There is no significant intermolecular interaction except very weak C—H⋯Cl interactions. The crystal studied was a racemic twin.

Related literature

For the synthesis, see: Scott et al. (1990 ). For applications of nickel complexes to catalytic systems, see: Vicic & Jones (1997 ); Arévalo & García (2010 ). For related structures, see: Cañavera-Buelvas et al. (2011 ); Angulo et al. (2003 ); Dahlenburg & Kurth (2001 ).

Experimental

Crystal data

[NiCl₂(C₁₄H₃₂P₂)]
M_r = 391.95
Tetragonal, $[I \overline 4c 2]$
a = 14.2402 (2) Å
c = 18.4369 (7) Å
V = 3738.70 (16) Å³
Z = 8
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 122 K
0.17 × 0.14 × 0.07 mm

Data collection

Oxford Xcalibur Atlas Gemini diffractometer
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.975, T_max = 0.989
5823 measured reflections
1850 independent reflections
1547 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.070
S = 0.97
1850 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 832 Friedel pairs
Flack parameter: 0.53 (3)

Table 1
Selected bond lengths (Å)

Ni1—P1	2.1600 (9)
Ni1—Cl1	2.2150 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯Cl1ⁱ	0.98	2.94	3.808 (4)	148
C5—H5A⋯Cl1ⁱⁱ	0.98	2.91	3.777 (4)	148
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021209/is2724sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021209/is2724Isup2.hkl

checkCIF report

Comment top

The synthesis of the current complex [Ni (dippe)Cl₂] was documented 21 years ago (Scott et al., 1990) and still the corresponding X-ray structure of this compound has not been reported. This type of nickel complexes are useful starting materials for the preparation of catalysts and catalytic precursors, for a series of active catalyst in a wide variety of model reactions (Vicic & Jones, 1997) and catalytic systems (Arévalo & García, 2010).

In the title complex, [Ni(dippe)Cl₂], the Ni^II atom is coordinated by two P atoms of dippe ligand and two chloride anions (Fig. 1) into a slight distorted square-planar coordination geometry with a dihedral angle between the planes defined by the two cis-Cl–Ni–Cl and cis-P–Ni–P fragments [10.01 (8)°]. Additionally the Ni^II atom is situated 0.0837 (1) Å above the Cl1/P1/Cl1/P1 plane. These deviations from planarity, which can be attributed to some steric efect of the dippe ligand, are somewhat shorter than the distortion from ideal square-planar coordination geometry observed on [Ni (dippe)Cl₂](carbazole)₂ complex (Cañavera-Buelvas et al., 2011) with the NiCl2/NiP2 dihedral angle of 15.32° and somewhat larger than the distortion from ideal square-planar coordination geometry observed for related [Ni(dcpe)Cl₂] (Angulo et al., 2003) and [(1S,2S)-C₅H₈{P(C₆H₁₁)₂}₂NiCl₂] (Dahlenburg & Kurth, 2001) complexes, where the NiCl2/NiP2 dihedral angles of 3.96 and 5.37°, respectively.

In the crystal packing, there are two intermolecular contacts of the type hydrogen bond (Table 2) mainly between the carbon donor atom of the dippe to Cl1 chloride atom acceptor of the metallic complex, C5—H5A···Cl1 2.91 Å and C3—H3B···Cl1 2.94 Å.

Related literature top

For the synthesis, see: Scott et al. (1990). For applications of nickel complexes to catalytic systems, see: Vicic & Jones (1997); Arévalo & García (2010). For related structures, see: Cañavera-Buelvas et al. (2011); Angulo et al. (2003); Dahlenburg & Kurth (2001).

Experimental top

A concentrated THF solution of the complex [Ni(dippe)Cl₂], prepared according to the reported procedure (Scott et al., 1990), was stored in a freezer at -30 °C. After a couple of days suitable crystals for X-ray diffraction studies were obtained. NMR (25 °C): ³¹P{¹H} (CDCl₃, 121.32 MHz, 25 °C): δ 85.9 (s). NMR ¹H (CDCl₃,300 MHz, 25 °C): δ 1.30 (m, CH₃, 24H), 1.6 (m, CH₂, 4H), 2.48 (m, CH, 4H). Elemental analysis experimental (calculated): C 43.0 (42.9), H 8.24% (8.23%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.

[1,2-Bis(diisopropylphosphanyl)ethane-κ²P,P']dichloridonickel(II) top

Crystal data top

[NiCl₂(C₁₄H₃₂P₂)]	D_x = 1.393 Mg m⁻³
M_r = 391.95	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4c2	Cell parameters from 3046 reflections
a = 14.2402 (2) Å	θ = 3.4–26.0°
c = 18.4369 (7) Å	µ = 1.48 mm⁻¹
V = 3738.70 (16) Å³	T = 122 K
Z = 8	Prism, brown
F(000) = 1664	0.17 × 0.14 × 0.07 mm

Data collection top

Oxford Xcalibur Atlas Gemini diffractometer	1850 independent reflections
Graphite monochromator	1547 reflections with I > 2σ(I)
Detector resolution: 10.4685 pixels mm^-1	R_int = 0.030
ω scans	θ_max = 26.1°, θ_min = 3.4°
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010)	h = −16→17
T_min = 0.975, T_max = 0.989	k = −17→17
5823 measured reflections	l = −22→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0391P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
1850 reflections	Δρ_max = 0.80 e Å⁻³
92 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 832 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.53 (3)

Crystal data top

[NiCl₂(C₁₄H₃₂P₂)]	Z = 8
M_r = 391.95	Mo Kα radiation
Tetragonal, I4c2	µ = 1.48 mm⁻¹
a = 14.2402 (2) Å	T = 122 K
c = 18.4369 (7) Å	0.17 × 0.14 × 0.07 mm
V = 3738.70 (16) Å³

Data collection top

Oxford Xcalibur Atlas Gemini diffractometer	1850 independent reflections
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010)	1547 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.989	R_int = 0.030
5823 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.80 e Å⁻³
S = 0.97	Δρ_min = −0.23 e Å⁻³
1850 reflections	Absolute structure: Flack (1983), 832 Friedel pairs
92 parameters	Absolute structure parameter: 0.53 (3)
0 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5579 (3)	0.2802 (2)	0.4018 (2)	0.0423 (9)
H1	0.5088	0.2434	0.3754	0.051*
C2	0.5856 (3)	0.3616 (3)	0.3527 (3)	0.0708 (15)
H2A	0.5296	0.3982	0.3403	0.106*
H2B	0.6144	0.3371	0.3083	0.106*
H2C	0.6307	0.4019	0.3781	0.106*
C3	0.5142 (3)	0.3145 (3)	0.4703 (2)	0.0580 (13)
H3A	0.5614	0.3477	0.4993	0.087*
H3B	0.49	0.261	0.498	0.087*
H3C	0.4625	0.3573	0.4588	0.087*
C4	0.7002 (3)	0.1639 (3)	0.33272 (17)	0.0457 (10)
H4	0.7238	0.2221	0.3086	0.055*
C5	0.6214 (3)	0.1240 (3)	0.2847 (2)	0.0676 (12)
H5A	0.6454	0.1136	0.2355	0.101*
H5B	0.569	0.1686	0.283	0.101*
H5C	0.5995	0.0642	0.3049	0.101*
C6	0.7832 (3)	0.0972 (3)	0.3400 (2)	0.0554 (12)
H6A	0.7648	0.043	0.3695	0.083*
H6B	0.8356	0.1299	0.3634	0.083*
H6C	0.8025	0.0757	0.2918	0.083*
C7	0.5952 (2)	0.0942 (2)	0.45870 (15)	0.0292 (6)
H7A	0.5299	0.0924	0.4404	0.035*
H7B	0.6277	0.0369	0.4416	0.035*
P1	0.65506 (6)	0.19836 (6)	0.42220 (5)	0.0280 (2)
Cl1	0.83890 (6)	0.31965 (6)	0.58688 (5)	0.0349 (2)
Ni1	0.75392 (2)	0.25392 (2)	0.5	0.02082 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0335 (19)	0.0391 (19)	0.054 (3)	−0.0022 (16)	−0.0121 (19)	0.0064 (18)
C2	0.053 (3)	0.060 (3)	0.099 (4)	0.003 (2)	−0.009 (3)	0.038 (3)
C3	0.039 (2)	0.050 (2)	0.085 (4)	0.0139 (18)	−0.001 (2)	−0.006 (2)
C4	0.064 (3)	0.046 (2)	0.0270 (18)	−0.019 (2)	0.0057 (17)	−0.0057 (17)
C5	0.090 (4)	0.074 (4)	0.039 (2)	−0.015 (2)	−0.013 (2)	−0.016 (2)
C6	0.067 (3)	0.042 (2)	0.057 (3)	−0.004 (2)	0.022 (2)	−0.013 (2)
C7	0.0251 (18)	0.0270 (19)	0.0355 (16)	−0.0077 (12)	−0.0012 (17)	−0.0046 (17)
P1	0.0269 (4)	0.0268 (4)	0.0303 (5)	−0.0055 (3)	−0.0020 (4)	0.0005 (4)
Cl1	0.0306 (4)	0.0344 (5)	0.0397 (5)	−0.0094 (3)	−0.0042 (4)	−0.0077 (4)
Ni1	0.01688 (15)	0.01688 (15)	0.0287 (3)	−0.00262 (17)	0.00055 (18)	−0.00055 (18)

Geometric parameters (Å, º) top

C1—C3	1.491 (5)	C5—H5A	0.98
C1—C2	1.522 (6)	C5—H5B	0.98
C1—P1	1.847 (3)	C5—H5C	0.98
C1—H1	1.00	C6—H6A	0.98
C2—H2A	0.98	C6—H6B	0.98
C2—H2B	0.98	C6—H6C	0.98
C2—H2C	0.98	C7—C7ⁱ	1.523 (6)
C3—H3A	0.98	C7—P1	1.838 (3)
C3—H3B	0.98	C7—H7A	0.99
C3—H3C	0.98	C7—H7B	0.99
C4—C6	1.522 (6)	P1—Ni1	2.1600 (9)
C4—C5	1.538 (5)	Cl1—Ni1	2.2150 (8)
C4—P1	1.837 (3)	Ni1—P1ⁱ	2.1600 (9)
C4—H4	1.00	Ni1—Cl1ⁱ	2.2150 (8)

C3—C1—C2	111.2 (3)	C4—C5—H5C	109.5
C3—C1—P1	110.3 (3)	H5A—C5—H5C	109.5
C2—C1—P1	114.0 (3)	H5B—C5—H5C	109.5
C3—C1—H1	107	C4—C6—H6A	109.5
C2—C1—H1	107	C4—C6—H6B	109.5
P1—C1—H1	107	H6A—C6—H6B	109.5
C1—C2—H2A	109.5	C4—C6—H6C	109.5
C1—C2—H2B	109.5	H6A—C6—H6C	109.5
H2A—C2—H2B	109.5	H6B—C6—H6C	109.5
C1—C2—H2C	109.5	C7ⁱ—C7—P1	111.27 (13)
H2A—C2—H2C	109.5	C7ⁱ—C7—H7A	109.4
H2B—C2—H2C	109.5	P1—C7—H7A	109.4
C1—C3—H3A	109.5	C7ⁱ—C7—H7B	109.4
C1—C3—H3B	109.5	P1—C7—H7B	109.4
H3A—C3—H3B	109.5	H7A—C7—H7B	108
C1—C3—H3C	109.5	C4—P1—C7	105.97 (15)
H3A—C3—H3C	109.5	C4—P1—C1	104.33 (18)
H3B—C3—H3C	109.5	C7—P1—C1	103.68 (17)
C6—C4—C5	112.7 (4)	C4—P1—Ni1	117.79 (14)
C6—C4—P1	111.0 (3)	C7—P1—Ni1	110.76 (10)
C5—C4—P1	111.1 (3)	C1—P1—Ni1	113.10 (12)
C6—C4—H4	107.2	P1—Ni1—P1ⁱ	87.91 (5)
C5—C4—H4	107.2	P1—Ni1—Cl1	172.36 (3)
P1—C4—H4	107.2	P1ⁱ—Ni1—Cl1	89.73 (3)
C4—C5—H5A	109.5	P1—Ni1—Cl1ⁱ	89.73 (3)
C4—C5—H5B	109.5	P1ⁱ—Ni1—Cl1ⁱ	172.36 (3)
H5A—C5—H5B	109.5	Cl1—Ni1—Cl1ⁱ	93.51 (5)

C6—C4—P1—C7	−72.2 (3)	C2—C1—P1—C7	−164.7 (3)
C5—C4—P1—C7	54.2 (3)	C3—C1—P1—Ni1	−50.7 (3)
C6—C4—P1—C1	178.8 (3)	C2—C1—P1—Ni1	75.3 (3)
C5—C4—P1—C1	−54.9 (3)	C4—P1—Ni1—P1ⁱ	−129.91 (14)
C6—C4—P1—Ni1	52.4 (3)	C7—P1—Ni1—P1ⁱ	−7.74 (12)
C5—C4—P1—Ni1	178.8 (3)	C1—P1—Ni1—P1ⁱ	108.15 (14)
C7ⁱ—C7—P1—C4	153.8 (3)	C4—P1—Ni1—Cl1	158.0 (3)
C7ⁱ—C7—P1—C1	−96.6 (4)	C7—P1—Ni1—Cl1	−79.9 (3)
C7ⁱ—C7—P1—Ni1	25.0 (4)	C1—P1—Ni1—Cl1	36.0 (3)
C3—C1—P1—C4	−179.9 (3)	C4—P1—Ni1—Cl1ⁱ	42.82 (14)
C2—C1—P1—C4	−53.9 (4)	C7—P1—Ni1—Cl1ⁱ	164.99 (13)
C3—C1—P1—C7	69.4 (3)	C1—P1—Ni1—Cl1ⁱ	−79.12 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···Cl1ⁱⁱ	0.98	2.94	3.808 (4)	148
C5—H5A···Cl1ⁱⁱⁱ	0.98	2.91	3.777 (4)	148

Symmetry codes: (ii) x−1/2, −y+1/2, z; (iii) −x+3/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[NiCl₂(C₁₄H₃₂P₂)]
M_r	391.95
Crystal system, space group	Tetragonal, I4c2
Temperature (K)	122
a, c (Å)	14.2402 (2), 18.4369 (7)
V (Å³)	3738.70 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.17 × 0.14 × 0.07

Data collection
Diffractometer	Oxford Xcalibur Atlas Gemini diffractometer
Absorption correction	Analytical (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.975, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	5823, 1850, 1547
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.070, 0.97
No. of reflections	1850
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.23
Absolute structure	Flack (1983), 832 Friedel pairs
Absolute structure parameter	0.53 (3)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

P1—Ni1

2.1600 (9)

Cl1—Ni1

2.2150 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···Cl1ⁱ	0.98	2.94	3.808 (4)	148
C5—H5A···Cl1ⁱⁱ	0.98	2.91	3.777 (4)	148

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+3/2, −y+1/2, z−1/2.

Acknowledgements

We thank PAPIIT-DGAPA-UNAM (IN-201010) and CONACYT (080606) for their financial support of this work. We also thank Dr A. Arévalo for technical assistance.

References

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