[1,2-Bis­(diisopropyl­phosphan­yl)ethane-κ2P,P′]dichloridonickel(II)–9H-carbazole (1/2)

Cañavera-Buelvas, F.; Flores-Alamo, M.; García, J.J.

doi:10.1107/S1600536811010555

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m501

doi:10.1107/S1600536811010555

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[1,2-Bis(diisopropylphosphanyl)ethane-κ²P,P′]dichloridonickel(II)–9H-carbazole (1/2)

Farah Cañavera-Buelvas,^a Marcos Flores-Alamo ^a and Juventino J. García ^a ^*

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

(Received 4 March 2011; accepted 21 March 2011; online 26 March 2011)

In the title compound, [NiCl₂(C₁₄H₃₂P₂)]·2C₁₂H₉N, the neutral [Ni(dppe)Cl₂] complex [dppe is 1,2-bis(diisopropylphosphanyl)ethane] consists of a tetracoordinated Ni²⁺ cation and has a crystallographic twofold axis passing through the metal atom and the mid-point of the CH₂—CH₂ bond of the dppe ligand. The metal atom shows slight tetrahedral distortion from an ideal square-planar coordination geometry, as reflected in the dihedral angle between NiCl₂ and NiP₂ planes of 15.32 (2)°. The 9H-carbazole ring system is essentially planar (r.m.s. deviation = 0.022 Å). In the crystal packing, there are two symmetry-related 9H-carbazole molecules between two adjacent Ni^II complexes, with an angle between the carbazole mean planes of ca 77°.

Related literature

For the use of nickel complexes of the type [Ni(dppe)Cl₂] as starting materials and precursors in metal-mediated and catalytic systems, respectively, see: Vicic & Jones (1997 ); Arévalo & García (2010 ). For details of tetrahedral distortion and motifs, see: Angulo et al. (2003 ); Dahlenburg & Kurth (2001 ); Etter et al. (1990 ).

Experimental

Crystal data

[NiCl₂(C₁₄H₃₂P₂)]·2C₁₂H₉N
M_r = 726.35
Monoclinic, C 2/c
a = 22.5830 (5) Å
b = 8.4374 (2) Å
c = 18.9630 (5) Å
β = 101.544 (2)°
V = 3540.15 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 122 K
0.42 × 0.16 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini diffractometer
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); based on expressions derived by Clark & Reid (1995 )] T_min = 0.851, T_max = 0.987
12792 measured reflections
3484 independent reflections
2908 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.065
S = 1.05
3484 reflections
211 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—Cl1	2.2221 (4)
Ni1—P1	2.1581 (5)

P1ⁱ—Ni1—P1	88.61 (3)
P1ⁱ—Ni1—Cl1ⁱ	168.757 (16)
P1ⁱ—Ni1—Cl1	89.797 (16)
Cl1ⁱ—Ni1—Cl1	93.87 (2)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 I, global. DOI: 10.1107/S1600536811010555/bh2344sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010555/bh2344Isup2.hkl

checkCIF report

Comment top

The nickel complexes of the type [Ni(dppe)Cl₂] are useful starting materials for the preparation of catalysts and catalytic precursors, for an interesting series of active catalyst in a wide variety of stoichiometric (Vicic & Jones, 1997) and catalytic systems (Arévalo & García, 2010). The synthesis of the current complex [Ni (dppe)Cl₂](carbazole)₂ (see Scheme) can be envisaged as the preparation of a model compound relevant to hydrodenitrogenation and N—H activation process.

In the asymmetric unit, the tetracoordinated [Ni(dppe)Cl₂] complex has a 2-fold axis passing through the metal and the centre of the methylene—methylene bond (Fig. 1). The metal center shows slight tetrahedral distortion from ideal square-planar coordination geometry, with the angle between the normals to the planes defined by the two cis-Cl–Ni–Cl and cis-P–Ni–P fragments [15.32 (2)°] being larger than the limiting value of 0° for square-planar coordination. Additionally, the metal ion is situated 0.1144 (1) Å above the Cl1/P1/Cl1ⁱ/P1ⁱ plane [symmetry code: (i) -x, y, 1/2 - z]. These deviations from planarity, which can safely be attributed to some steric congestion by intermolecular contacts between the metallic complex and the 9H-carbazole molecules (Fig. 2), are 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 are 3.96 and 5.37°, respectively. The Ni–P bond lengths in the title compound are equal, by symmetry. Probably as a consequence of the steric bulk of the 9H-carbazole molecules, the Ni–Cl distance, 2.2221 (4) Å, tends to be slightly longer than those in the analogues nickel complexes.

In the crystal packing, there are two 9H-carbazole molecules between two adjacent nickel complexes, with an angle between the carbazole mean planes of ca. 77°. There are two types of intermolecular contacts: one of the van der Waals type N—H···Cl [2.65 (2) Å] is formed from N1 donor atom of the 9H-carbazole to Cl1 chloride atom acceptor of the metallic complex; and other of the type C—H···N [2.645 (1) Å] involving C19 in the dppe ligand and N1 in 9H-carbazole. These van der Waals interactions lead to infinite ribbons based on R¹₂(5) motifs (Etter et al., 1990), as illustrated in Fig. 2.

Related literature top

For the use of nickel complexes of the type [Ni(dppe)Cl₂] as starting materials and precursors in stoichiometric and catalytic systems, respectively, see: Vicic & Jones (1997); Arévalo & García (2010). For details of tetrahedral distortion and motifs see: Angulo et al. (2003); Dahlenburg & Kurth (2001); Etter et al. (1990).

Experimental top

A THF solution of [Ni(dppe)H]₂ (Vicic & Jones, 1997) (0.100 g, 0.15 mmol) was added with 9H-carbazole (0. 261 g, 1.56 mmol) and heated to 80 °C for 10 h. After this time, the solution changed from wine red color to brown. The solvent was eliminated under reduced pressure and the resulting solid dissolved in dichloromethane (DCM). Slow evaporation at room temperature of DCM afforded crystals suitable for X-ray diffraction. NMR: ³¹P{¹H} (acetone-d₆,121.32 MHz, 25 °C): d 57.2. NMR ¹H (acetone-d₆, 300 MHz, 25 °C): d 8.13 (d, J_H—H=7.8, 1H), d 7.54 (d, J_H—H=7.8, 1H), d 7.39 (dd, J_H—H=7.8, J_H—H=7.2, 1H), d 7.18 (dd, J_H—H=7.2, J_H—H=7.8, 1H), d 2.5 (m, CH, 2H), d 1.7 (m, CH₂, 2H), d 1.35 (m, CH₃, 12H). Elemental analysis (calc.): C 62.9 (62.83), H 6.90 (6.93), N 3.82% (3.85%).

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 for the title compound. Displacement ellipsoids are draw at the 50% probability level and H atoms are shown as circles of arbitrary size. Symmetry code for i labeled atoms: -x, y, -z + 1/2.
	Fig. 2. Intermolecular van der Waals contacts (dashed lines) in the crystal structure, forming infinite ribbons including R¹₂(5) motifs.

[1,2-Bis(diisopropylphosphanyl)ethane- κ²P,P']dichloridonickel(II)–9H-carbazole (1/2) top

Crystal data top

[NiCl₂(C₁₄H₃₂P₂)]·2C₁₂H₉N	F(000) = 1536
M_r = 726.35	D_x = 1.363 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7654 reflections
a = 22.5830 (5) Å	θ = 3.3–26.0°
b = 8.4374 (2) Å	µ = 0.82 mm⁻¹
c = 18.9630 (5) Å	T = 122 K
β = 101.544 (2)°	Prism, orange
V = 3540.15 (15) Å³	0.42 × 0.16 × 0.02 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini diffractometer	3484 independent reflections
Radiation source: fine-focus sealed tube	2908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.4685 pixels mm^-1	θ_max = 26.1°, θ_min = 3.5°
ω scans	h = −27→27
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009); based on expressions derived by Clark & Reid (1995)]	k = −10→10
T_min = 0.851, T_max = 0.987	l = −18→23
12792 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0343P)² + 0.7966P] where P = (F_o² + 2F_c²)/3
3484 reflections	(Δ/σ)_max = 0.001
211 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³
0 constraints

Crystal data top

[NiCl₂(C₁₄H₃₂P₂)]·2C₁₂H₉N	V = 3540.15 (15) Å³
M_r = 726.35	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.5830 (5) Å	µ = 0.82 mm⁻¹
b = 8.4374 (2) Å	T = 122 K
c = 18.9630 (5) Å	0.42 × 0.16 × 0.02 mm
β = 101.544 (2)°

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini diffractometer	3484 independent reflections
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2009); based on expressions derived by Clark & Reid (1995)]	2908 reflections with I > 2σ(I)
T_min = 0.851, T_max = 0.987	R_int = 0.027
12792 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.62 e Å⁻³
3484 reflections	Δρ_min = −0.26 e Å⁻³
211 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.13521 (7)	0.51654 (19)	0.17978 (9)	0.0162 (4)
C2	0.10421 (8)	0.4878 (2)	0.10949 (9)	0.0208 (4)
H2	0.0704	0.4185	0.0998	0.025*
C3	0.12477 (8)	0.5644 (2)	0.05455 (10)	0.0237 (4)
H3	0.1046	0.5469	0.0062	0.028*
C4	0.17440 (8)	0.6668 (2)	0.06818 (10)	0.0231 (4)
H4	0.1873	0.7177	0.0291	0.028*
C5	0.20488 (8)	0.6947 (2)	0.13744 (10)	0.0207 (4)
H5	0.2385	0.7648	0.1464	0.025*
C6	0.18570 (7)	0.61860 (19)	0.19446 (9)	0.0163 (4)
C7	0.20640 (7)	0.61872 (19)	0.27183 (9)	0.0164 (4)
C8	0.25374 (8)	0.6941 (2)	0.31818 (10)	0.0218 (4)
H8	0.2812	0.7597	0.2996	0.026*
C9	0.26007 (8)	0.6719 (2)	0.39150 (10)	0.0251 (4)
H9	0.2922	0.7226	0.4235	0.03*
C10	0.21966 (8)	0.5759 (2)	0.41916 (10)	0.0236 (4)
H10	0.2246	0.5635	0.4698	0.028*
C11	0.17264 (8)	0.4985 (2)	0.37428 (9)	0.0195 (4)
H11	0.1453	0.4334	0.3933	0.023*
C12	0.16687 (7)	0.51933 (19)	0.30049 (9)	0.0164 (4)
C13	0.12297 (7)	0.9420 (2)	0.35115 (9)	0.0193 (4)
H13	0.1382	0.8312	0.361	0.023*
C14	0.14981 (8)	1.0047 (2)	0.28869 (10)	0.0247 (4)
H14A	0.136	1.1137	0.2776	0.037*
H14B	0.1366	0.9377	0.2463	0.037*
H14C	0.194	1.0031	0.3022	0.037*
C15	0.14581 (8)	1.0381 (2)	0.41930 (10)	0.0247 (4)
H15A	0.19	1.0448	0.428	0.037*
H15B	0.1335	0.9862	0.4603	0.037*
H15C	0.1286	1.145	0.4134	0.037*
C16	0.01068 (8)	0.9163 (2)	0.40785 (9)	0.0213 (4)
H16	0.0272	1.0094	0.4381	0.026*
C17	0.03308 (9)	0.7674 (2)	0.45155 (11)	0.0316 (5)
H17A	0.0223	0.7741	0.499	0.047*
H17B	0.0771	0.7595	0.4573	0.047*
H17C	0.0141	0.6734	0.4262	0.047*
C18	−0.05797 (8)	0.9302 (2)	0.39410 (10)	0.0268 (4)
H18A	−0.0761	0.8401	0.3649	0.04*
H18B	−0.0705	1.0292	0.3684	0.04*
H18C	−0.0714	0.9301	0.4401	0.04*
C19	0.02934 (8)	0.7388 (2)	0.27707 (10)	0.0251 (4)
H19A	0.0633	0.7196	0.2523	0.03*
H19B	0.029	0.6525	0.3124	0.03*
Cl1	−0.025597 (18)	1.29303 (5)	0.16367 (2)	0.01865 (11)
N1	0.12485 (7)	0.45582 (17)	0.24411 (8)	0.0174 (3)
Ni1	0	1.11320 (3)	0.25	0.01164 (9)
P1	0.039792 (19)	0.93016 (5)	0.32401 (2)	0.01575 (11)
H1N	0.0953 (9)	0.405 (2)	0.2501 (10)	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0171 (8)	0.0132 (8)	0.0203 (9)	0.0045 (7)	0.0080 (7)	0.0006 (7)
C2	0.0194 (9)	0.0193 (9)	0.0239 (10)	−0.0008 (7)	0.0046 (8)	−0.0053 (7)
C3	0.0245 (10)	0.0283 (10)	0.0183 (10)	0.0045 (8)	0.0045 (8)	−0.0027 (8)
C4	0.0257 (10)	0.0252 (9)	0.0214 (10)	0.0059 (8)	0.0114 (8)	0.0056 (8)
C5	0.0188 (9)	0.0181 (9)	0.0272 (10)	0.0014 (7)	0.0091 (8)	0.0037 (8)
C6	0.0143 (8)	0.0140 (8)	0.0214 (9)	0.0033 (7)	0.0060 (7)	0.0007 (7)
C7	0.0149 (8)	0.0147 (8)	0.0205 (9)	0.0027 (7)	0.0054 (7)	0.0006 (7)
C8	0.0184 (9)	0.0204 (9)	0.0274 (10)	−0.0012 (8)	0.0061 (8)	0.0000 (8)
C9	0.0198 (9)	0.0280 (10)	0.0248 (10)	0.0000 (8)	−0.0016 (8)	−0.0049 (8)
C10	0.0268 (10)	0.0265 (10)	0.0169 (9)	0.0076 (8)	0.0029 (8)	0.0026 (7)
C11	0.0221 (9)	0.0161 (9)	0.0222 (10)	0.0029 (7)	0.0089 (8)	0.0036 (7)
C12	0.0172 (8)	0.0127 (8)	0.0198 (9)	0.0039 (7)	0.0047 (7)	−0.0006 (7)
C13	0.0157 (8)	0.0182 (9)	0.0218 (9)	0.0040 (7)	−0.0020 (7)	0.0012 (7)
C14	0.0183 (9)	0.0281 (10)	0.0274 (10)	0.0031 (8)	0.0037 (8)	0.0027 (8)
C15	0.0173 (9)	0.0268 (10)	0.0270 (10)	−0.0005 (8)	−0.0027 (8)	−0.0019 (8)
C16	0.0212 (9)	0.0252 (10)	0.0165 (9)	−0.0046 (8)	0.0013 (7)	0.0039 (7)
C17	0.0337 (11)	0.0314 (11)	0.0278 (11)	−0.0026 (9)	0.0016 (9)	0.0124 (9)
C18	0.0220 (9)	0.0363 (11)	0.0219 (10)	−0.0054 (8)	0.0042 (8)	0.0041 (8)
C19	0.0311 (10)	0.0137 (8)	0.0276 (10)	0.0010 (8)	−0.0014 (8)	−0.0001 (8)
Cl1	0.0204 (2)	0.0144 (2)	0.0208 (2)	0.00193 (16)	0.00338 (17)	0.00393 (16)
N1	0.0162 (7)	0.0158 (7)	0.0218 (8)	−0.0033 (6)	0.0074 (6)	−0.0011 (6)
Ni1	0.01075 (15)	0.00869 (15)	0.01507 (16)	0	0.00161 (11)	0
P1	0.0167 (2)	0.0120 (2)	0.0169 (2)	−0.00081 (17)	−0.00073 (17)	0.00090 (17)

Geometric parameters (Å, º) top

C1—N1	1.386 (2)	C13—H13	1
C1—C2	1.397 (2)	C14—H14A	0.98
C1—C6	1.411 (2)	C14—H14B	0.98
C2—C3	1.383 (3)	C14—H14C	0.98
C2—H2	0.95	C15—H15A	0.98
C3—C4	1.398 (3)	C15—H15B	0.98
C3—H3	0.95	C15—H15C	0.98
C4—C5	1.376 (2)	C16—C18	1.524 (2)
C4—H4	0.95	C16—C17	1.534 (2)
C5—C6	1.399 (2)	C16—P1	1.8418 (18)
C5—H5	0.95	C16—H16	1
C6—C7	1.448 (2)	C17—H17A	0.98
C7—C8	1.394 (2)	C17—H17B	0.98
C7—C12	1.411 (2)	C17—H17C	0.98
C8—C9	1.382 (3)	C18—H18A	0.98
C8—H8	0.95	C18—H18B	0.98
C9—C10	1.399 (3)	C18—H18C	0.98
C9—H9	0.95	C19—C19ⁱ	1.505 (3)
C10—C11	1.384 (2)	C19—P1	1.8362 (18)
C10—H10	0.95	C19—H19A	0.99
C11—C12	1.390 (2)	C19—H19B	0.99
C11—H11	0.95	Ni1—Cl1	2.2221 (4)
C12—N1	1.387 (2)	N1—H1N	0.821 (19)
C13—C15	1.525 (2)	Ni1—P1ⁱ	2.1581 (5)
C13—C14	1.529 (3)	Ni1—P1	2.1581 (5)
C13—P1	1.8482 (17)	Ni1—Cl1ⁱ	2.2221 (4)

N1—C1—C2	129.44 (16)	H14B—C14—H14C	109.5
N1—C1—C6	108.91 (15)	C13—C15—H15A	109.5
C2—C1—C6	121.65 (16)	C13—C15—H15B	109.5
C3—C2—C1	117.26 (16)	H15A—C15—H15B	109.5
C3—C2—H2	121.4	C13—C15—H15C	109.5
C1—C2—H2	121.4	H15A—C15—H15C	109.5
C2—C3—C4	121.82 (17)	H15B—C15—H15C	109.5
C2—C3—H3	119.1	C18—C16—C17	111.69 (15)
C4—C3—H3	119.1	C18—C16—P1	111.96 (12)
C5—C4—C3	120.79 (17)	C17—C16—P1	112.49 (13)
C5—C4—H4	119.6	C18—C16—H16	106.8
C3—C4—H4	119.6	C17—C16—H16	106.8
C4—C5—C6	119.09 (17)	P1—C16—H16	106.8
C4—C5—H5	120.5	C16—C17—H17A	109.5
C6—C5—H5	120.5	C16—C17—H17B	109.5
C5—C6—C1	119.38 (16)	H17A—C17—H17B	109.5
C5—C6—C7	134.09 (16)	C16—C17—H17C	109.5
C1—C6—C7	106.53 (14)	H17A—C17—H17C	109.5
C8—C7—C12	119.53 (16)	H17B—C17—H17C	109.5
C8—C7—C6	133.67 (16)	C16—C18—H18A	109.5
C12—C7—C6	106.80 (14)	C16—C18—H18B	109.5
C9—C8—C7	118.98 (16)	H18A—C18—H18B	109.5
C9—C8—H8	120.5	C16—C18—H18C	109.5
C7—C8—H8	120.5	H18A—C18—H18C	109.5
C8—C9—C10	120.79 (17)	H18B—C18—H18C	109.5
C8—C9—H9	119.6	C19ⁱ—C19—P1	109.93 (8)
C10—C9—H9	119.6	C19ⁱ—C19—H19A	109.7
C11—C10—C9	121.37 (17)	P1—C19—H19A	109.7
C11—C10—H10	119.3	C19ⁱ—C19—H19B	109.7
C9—C10—H10	119.3	P1—C19—H19B	109.7
C10—C11—C12	117.70 (16)	H19A—C19—H19B	108.2
C10—C11—H11	121.1	C1—N1—C12	109.01 (14)
C12—C11—H11	121.1	C1—N1—H1N	126.9 (13)
N1—C12—C11	129.69 (15)	C12—N1—H1N	123.1 (13)
N1—C12—C7	108.71 (14)	P1ⁱ—Ni1—P1	88.61 (3)
C11—C12—C7	121.60 (16)	P1ⁱ—Ni1—Cl1ⁱ	168.757 (16)
C15—C13—C14	110.67 (15)	P1—Ni1—Cl1ⁱ	89.797 (16)
C15—C13—P1	114.66 (12)	P1ⁱ—Ni1—Cl1	89.797 (16)
C14—C13—P1	109.96 (12)	P1—Ni1—Cl1	168.758 (16)
C15—C13—H13	107.1	Cl1ⁱ—Ni1—Cl1	93.87 (2)
C14—C13—H13	107.1	C19—P1—C16	109.21 (9)
P1—C13—H13	107.1	C19—P1—C13	101.97 (8)
C13—C14—H14A	109.5	C16—P1—C13	106.35 (8)
C13—C14—H14B	109.5	C19—P1—Ni1	108.52 (6)
H14A—C14—H14B	109.5	C16—P1—Ni1	115.65 (6)
C13—C14—H14C	109.5	C13—P1—Ni1	114.22 (6)
H14A—C14—H14C	109.5

N1—C1—C2—C3	−179.52 (17)	C6—C1—N1—C12	1.32 (18)
C6—C1—C2—C3	−0.4 (3)	C11—C12—N1—C1	177.09 (17)
C1—C2—C3—C4	−0.1 (3)	C7—C12—N1—C1	−2.04 (18)
C2—C3—C4—C5	0.2 (3)	C19ⁱ—C19—P1—C16	93.81 (18)
C3—C4—C5—C6	0.3 (3)	C19ⁱ—C19—P1—C13	−153.95 (17)
C4—C5—C6—C1	−0.7 (2)	C19ⁱ—C19—P1—Ni1	−33.06 (19)
C4—C5—C6—C7	179.56 (17)	C18—C16—P1—C19	−79.07 (14)
N1—C1—C6—C5	−179.89 (15)	C17—C16—P1—C19	47.67 (15)
C2—C1—C6—C5	0.8 (2)	C18—C16—P1—C13	171.60 (13)
N1—C1—C6—C7	−0.11 (18)	C17—C16—P1—C13	−61.66 (14)
C2—C1—C6—C7	−179.40 (15)	C18—C16—P1—Ni1	43.64 (14)
C5—C6—C7—C8	−0.7 (3)	C17—C16—P1—Ni1	170.38 (11)
C1—C6—C7—C8	179.53 (18)	C15—C13—P1—C19	−151.39 (13)
C5—C6—C7—C12	178.62 (18)	C14—C13—P1—C19	83.17 (14)
C1—C6—C7—C12	−1.10 (18)	C15—C13—P1—C16	−37.02 (15)
C12—C7—C8—C9	−1.3 (2)	C14—C13—P1—C16	−162.46 (12)
C6—C7—C8—C9	178.01 (17)	C15—C13—P1—Ni1	91.77 (13)
C7—C8—C9—C10	−0.2 (3)	C14—C13—P1—Ni1	−33.67 (14)
C8—C9—C10—C11	0.8 (3)	P1ⁱ—Ni1—P1—C19	10.07 (6)
C9—C10—C11—C12	0.0 (3)	Cl1ⁱ—Ni1—P1—C19	178.94 (7)
C10—C11—C12—N1	179.44 (16)	Cl1—Ni1—P1—C19	−71.87 (12)
C10—C11—C12—C7	−1.5 (2)	P1ⁱ—Ni1—P1—C16	−113.00 (7)
C8—C7—C12—N1	−178.60 (15)	Cl1ⁱ—Ni1—P1—C16	55.87 (6)
C6—C7—C12—N1	1.93 (18)	Cl1—Ni1—P1—C16	165.06 (10)
C8—C7—C12—C11	2.2 (2)	P1ⁱ—Ni1—P1—C13	123.06 (7)
C6—C7—C12—C11	−177.29 (15)	Cl1ⁱ—Ni1—P1—C13	−68.07 (6)
C2—C1—N1—C12	−179.46 (16)	Cl1—Ni1—P1—C13	41.12 (12)

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[NiCl₂(C₁₄H₃₂P₂)]·2C₁₂H₉N
M_r	726.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	122
a, b, c (Å)	22.5830 (5), 8.4374 (2), 18.9630 (5)
β (°)	101.544 (2)
V (Å³)	3540.15 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.42 × 0.16 × 0.02

Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini diffractometer
Absorption correction	Analytical [CrysAlis PRO (Oxford Diffraction, 2009); based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.851, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	12792, 3484, 2908
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.065, 1.05
No. of reflections	3484
No. of parameters	211
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.26

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 geometric parameters (Å, º) top

Ni1—Cl1	2.2221 (4)	Ni1—P1	2.1581 (5)

P1ⁱ—Ni1—P1	88.61 (3)	P1ⁱ—Ni1—Cl1	89.797 (16)
P1ⁱ—Ni1—Cl1ⁱ	168.757 (16)	Cl1ⁱ—Ni1—Cl1	93.87 (2)

Symmetry code: (i) −x, y, −z+1/2.

Acknowledgements

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

References

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