Di­chloro­bis­(tri­phenyl­phosphine oxide-κO)­nickel(II)

Moreno-Fuquen, R.; Cifuentes, O.; Naranjo, J.V.; Serratto, L.M.; Kennedy, A.R.

doi:10.1107/S1600536804029125

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 60| Part 12| December 2004| Pages m1861-m1862

https://doi.org/10.1107/S1600536804029125

Dichlorobis(triphenylphosphine oxide-κO)nickel(II)

Rodolfo Moreno-Fuquen,^a ^* Olga Cifuentes,^a Jaime Valderrama Naranjo,^b Luis Manuel Serratto ^a and Alan R. Kennedy ^c

^aDepartamento de Química, Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, ^bDepartamento de Física, Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, and ^cDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: rodolfu@telesat.com.co

(Received 28 October 2004; accepted 10 November 2004; online 20 November 2004)

The title nickel(II) complex, [NiCl₂(C₁₈H₁₅OP)₂], was prepared in order to determine the coordination of the Ni atom. The Ni atom lies on a twofold axis and is four-coordinated by two Cl atoms and two O atoms in a distorted tetrahedral coordination geometry. The Ni—Cl and Ni—O distances are 2.2151 (6) and 1.9662 (16) Å, respectively. The title compound is compared with the four-coordinated copper(II) analog; the two systems are isostructural.

Comment

In the period 1950–1960, there was a suggestion, based on the valence-bond theory, that paramagnetic nickel(II) complexes should be planar (Ballhausen & Liehr, 1959 ). This suggestion was difficult to verify due to the rather rare occurrence of tetrahedrally coordinated nickel(II) ions. Later, during the 1960s, some [(C₆H₅)₃PO]₂NiX₂, complexes (X = Cl, Br, I) were prepared (Cotton & Goodgame, 1960 ). Their electronic spectra, IR spectra and magnetic moments were recorded and analyzed in order to demonstrate that the nickel ion, in each case, was tetrahedrally coordinated (Cotton & Goodgame, 1960). Unfortunately, the purity of the [(C₆H₅)₃PO]₂NiCl₂ complex system was questioned and doubt of a tetrahedral array persisted. In order to elucidate the coordination of the nickel(II) ion in the [(C₆H₅)₃PO]₂NiCl₂ system, its crystal structure determination was undertaken.

A perspective view of the title molecule, (I), showing the atomic numbering scheme is given in Fig. 1. The Ni^II ion has C₂ site symmetry; C₂ is parallel to the c axis. The analogous dichlorobis(triphenylphosphine oxide)copper(II) system, (II) (Bertrand & Kalyanaraman, 1971 ), was taken as a reference and its internal parameters were compared to the parameters of the title complex. Within the tetrahedral geometry around the central Ni atom, complex (II) shows Cu—Cl and Cu—O bond lengths of 2.170 (2) and 1.958 (4) Å, respectively, while (I) shows Ni—Cl and Ni—O bond lengths of 2.2151 (6) and 1.9662 (16) Å, respectively. The Cl—Cu—Cl and O—Cu—O bond angles in (II) are 102.2 (1) and 93.0 (1)°, while in (I) the Cl—Ni—Cl and O—Ni—O bond angles are 116.17 (3) and 95.91 (10)°, respectively. The two systems are isostructural. The triphenylphosphine portion of the complex does not show any unusual features and the other bond lengths and angles of these systems are within expected ranges.

Figure 1
An ORTEP-3 plot (Farrugia, 1997

) of the title compound, with the atomic labeling scheme. Displacement ellipsoids are plotted at the 50% probability level. H atoms are shown as spheres of arbitrary radii. [Symmetry code: (i) ½ − x, ½ − y, z.]

Experimental

Reagents and solvents for the synthesis were purchased from the Aldrich Chemical Co. and were used without additional purification. Crystals of (I) were obtained following the synthesis previously reported by Cotton & Goodgame (1960). The product of this synthesis was recrystallized by slow evaporation of an acetonitrile solution at room temperature, in contact with oxygen. The pale-blue crystals had a melting point of 463 (1) K.

Crystal data

[NiCl₂(C₁₈H₁₅OP)₂]
M_r = 686.15
Orthorhombic, Fdd2
a = 20.6356 (3) Å
b = 32.5388 (6) Å
c = 9.7240 (1) Å
V = 6529.25 (17) Å³
Z = 8
D_x = 1.396 Mg m⁻³
Mo Kα radiation
Cell parameters from 3709 reflections
θ = 1.0–27.5°
μ = 0.89 mm⁻¹
T = 123 (2) K
Prism, pale blue
0.35 × 0.30 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997 ) T_min = 0.802, T_max = 0.868
7169 measured reflections
3686 independent reflections
3468 reflections with I > 2σ(I)
R_int = 0.021
θ_max = 27.5°
h = −26 → 26
k = −42 → 42
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.063
S = 1.07
3686 reflections
195 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0304P)² + 7.7683P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.00057 (6)
Absolute structure: Flack (1983 ), 1705 Friedel pairs
Flack parameter = 0.001 (1)

All H atoms were placed at geometrically idealized positions and were treated as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 2000 ); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804029125/ac6138sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804029125/ac6138Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 2000); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Dichlorobis(triphenylphosphine oxide-κO)nickel(II) top

Crystal data top

[NiCl₂(C₁₈H₁₅OP)₂]	D_x = 1.396 Mg m⁻³
M_r = 686.15	Melting point: 463(1) K
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 3709 reflections
a = 20.6356 (3) Å	θ = 1.0–27.5°
b = 32.5388 (6) Å	µ = 0.89 mm⁻¹
c = 9.7240 (1) Å	T = 123 K
V = 6529.25 (17) Å³	Prism, pale_blue
Z = 8	0.35 × 0.30 × 0.15 mm
F(000) = 2832

Data collection top

Nonius KappaCCD diffractometer	3686 independent reflections
Radiation source: fine-focus sealed tube	3468 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (DENZO; Otwinowski & Minor, 1997)	h = −26→26
T_min = 0.802, T_max = 0.868	k = −42→42
7169 measured reflections	l = −12→12

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0304P)² + 7.7683P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.063	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.45 e Å⁻³
3686 reflections	Δρ_min = −0.29 e Å⁻³
195 parameters	Extinction correction: SHELXL97
0 restraints	Extinction coefficient: 0.00057 (6)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.001 (1)

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Ni	0.2500	0.2500	0.0000	0.01108 (9)
P	0.16831 (3)	0.178349 (16)	0.18060 (7)	0.01842 (12)
Cl	0.32802 (3)	0.22015 (2)	−0.12042 (7)	0.03064 (14)
O1	0.21631 (7)	0.21054 (5)	0.13540 (17)	0.0254 (3)
C1	0.17605 (10)	0.13228 (7)	0.0797 (2)	0.0212 (4)
C2	0.12395 (11)	0.10513 (7)	0.0611 (3)	0.0269 (5)
H2	0.0837	0.1103	0.1052	0.032*
C3	0.13114 (12)	0.07063 (7)	−0.0219 (3)	0.0316 (5)
H3	0.0959	0.0522	−0.0342	0.038*
C4	0.18974 (12)	0.06317 (7)	−0.0865 (2)	0.0298 (5)
H4	0.1944	0.0399	−0.1447	0.036*
C5	0.24159 (12)	0.08943 (8)	−0.0666 (2)	0.0293 (5)
H5	0.2819	0.0838	−0.1097	0.035*
C6	0.23510 (10)	0.12386 (7)	0.0153 (2)	0.0247 (5)
H6	0.2709	0.1418	0.0279	0.030*
C7	0.08511 (10)	0.19434 (6)	0.1652 (2)	0.0199 (4)
C8	0.04882 (11)	0.20515 (7)	0.2806 (2)	0.0246 (5)
H8	0.0677	0.2040	0.3696	0.030*
C9	−0.01545 (10)	0.21768 (7)	0.2646 (3)	0.0290 (5)
H9	−0.0402	0.2251	0.3431	0.035*
C10	−0.04314 (10)	0.21945 (7)	0.1362 (3)	0.0269 (5)
H10	−0.0870	0.2278	0.1267	0.032*
C11	−0.00720 (10)	0.20909 (7)	0.0201 (2)	0.0262 (5)
H11	−0.0264	0.2105	−0.0685	0.031*
C12	0.05715 (11)	0.19661 (7)	0.0343 (2)	0.0239 (5)
H12	0.0819	0.1897	−0.0447	0.029*
C13	0.18248 (10)	0.16712 (7)	0.3592 (2)	0.0221 (4)
C14	0.15370 (12)	0.13430 (7)	0.4272 (3)	0.0304 (5)
H14	0.1273	0.1154	0.3780	0.036*
C15	0.16364 (14)	0.12914 (9)	0.5678 (3)	0.0394 (6)
H15	0.1441	0.1066	0.6142	0.047*
C16	0.20120 (16)	0.15620 (9)	0.6391 (3)	0.0447 (7)
H16	0.2068	0.1528	0.7355	0.054*
C17	0.23141 (18)	0.18867 (9)	0.5724 (3)	0.0477 (8)
H17	0.2582	0.2071	0.6226	0.057*
C18	0.22245 (14)	0.19416 (8)	0.4323 (3)	0.0361 (6)
H18	0.2434	0.2162	0.3861	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.00926 (14)	0.01456 (16)	0.00942 (15)	0.00033 (14)	0.000	0.000
P	0.0187 (2)	0.0189 (3)	0.0177 (3)	−0.0013 (2)	0.0003 (2)	0.0005 (2)
Cl	0.0214 (2)	0.0456 (3)	0.0249 (3)	0.0083 (2)	0.0051 (2)	−0.0055 (2)
O1	0.0229 (7)	0.0261 (8)	0.0272 (8)	−0.0050 (7)	0.0003 (7)	0.0044 (7)
C1	0.0232 (10)	0.0235 (10)	0.0168 (10)	0.0023 (9)	−0.0013 (8)	0.0015 (9)
C2	0.0220 (10)	0.0282 (12)	0.0306 (12)	0.0009 (9)	−0.0037 (9)	−0.0056 (10)
C3	0.0309 (11)	0.0286 (12)	0.0354 (14)	0.0012 (10)	−0.0123 (10)	−0.0086 (11)
C4	0.0425 (13)	0.0263 (12)	0.0205 (12)	0.0100 (10)	−0.0046 (10)	−0.0052 (9)
C5	0.0361 (12)	0.0308 (13)	0.0210 (11)	0.0102 (10)	0.0065 (10)	0.0032 (10)
C6	0.0248 (11)	0.0272 (11)	0.0221 (12)	0.0016 (8)	0.0016 (10)	0.0029 (10)
C7	0.0212 (10)	0.0175 (10)	0.0210 (11)	−0.0013 (8)	0.0022 (8)	−0.0001 (8)
C8	0.0240 (11)	0.0290 (12)	0.0208 (12)	−0.0011 (9)	−0.0021 (8)	−0.0011 (9)
C9	0.0219 (11)	0.0363 (13)	0.0286 (13)	0.0001 (9)	0.0065 (10)	−0.0039 (11)
C10	0.0200 (10)	0.0294 (12)	0.0312 (12)	0.0003 (9)	0.0004 (9)	0.0004 (10)
C11	0.0254 (11)	0.0287 (12)	0.0245 (12)	−0.0003 (9)	−0.0047 (9)	0.0001 (9)
C12	0.0254 (11)	0.0253 (11)	0.0209 (11)	0.0024 (9)	0.0026 (8)	−0.0016 (9)
C13	0.0231 (10)	0.0225 (11)	0.0205 (11)	0.0006 (9)	−0.0008 (9)	0.0000 (8)
C14	0.0372 (13)	0.0260 (12)	0.0280 (12)	−0.0017 (10)	0.0016 (11)	0.0033 (10)
C15	0.0572 (18)	0.0311 (14)	0.0298 (14)	0.0028 (12)	0.0059 (13)	0.0122 (11)
C16	0.0708 (19)	0.0422 (16)	0.0212 (12)	0.0152 (14)	−0.0080 (14)	0.0024 (12)
C17	0.069 (2)	0.0421 (17)	0.0315 (15)	−0.0025 (15)	−0.0210 (15)	−0.0056 (13)
C18	0.0475 (15)	0.0296 (13)	0.0311 (13)	−0.0093 (12)	−0.0115 (12)	0.0016 (11)

Geometric parameters (Å, º) top

Ni—O1ⁱ	1.9661 (15)	C8—C9	1.396 (3)
Ni—O1	1.9661 (15)	C8—H8	0.9500
Ni—Clⁱ	2.2152 (5)	C9—C10	1.374 (4)
Ni—Cl	2.2152 (5)	C9—H9	0.9500
P—O1	1.5072 (15)	C10—C11	1.392 (3)
P—C13	1.799 (2)	C10—H10	0.9500
P—C1	1.799 (2)	C11—C12	1.396 (3)
P—C7	1.800 (2)	C11—H11	0.9500
C1—C6	1.397 (3)	C12—H12	0.9500
C1—C2	1.403 (3)	C13—C14	1.389 (3)
C2—C3	1.390 (3)	C13—C18	1.400 (3)
C2—H2	0.9500	C14—C15	1.392 (4)
C3—C4	1.384 (4)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.363 (4)
C4—C5	1.383 (4)	C15—H15	0.9500
C4—H4	0.9500	C16—C17	1.388 (4)
C5—C6	1.381 (3)	C16—H16	0.9500
C5—H5	0.9500	C17—C18	1.386 (4)
C6—H6	0.9500	C17—H17	0.9500
C7—C8	1.394 (3)	C18—H18	0.9500
C7—C12	1.399 (3)

O1ⁱ—Ni—O1	95.92 (10)	C7—C8—C9	119.6 (2)
O1ⁱ—Ni—Clⁱ	108.95 (5)	C7—C8—H8	120.2
O1—Ni—Clⁱ	112.54 (5)	C9—C8—H8	120.2
O1ⁱ—Ni—Cl	112.54 (5)	C10—C9—C8	120.6 (2)
O1—Ni—Cl	108.95 (5)	C10—C9—H9	119.7
Clⁱ—Ni—Cl	116.17 (3)	C8—C9—H9	119.7
O1—P—C13	108.42 (10)	C9—C10—C11	120.3 (2)
O1—P—C1	111.20 (10)	C9—C10—H10	119.8
C13—P—C1	110.06 (10)	C11—C10—H10	119.8
O1—P—C7	113.68 (9)	C10—C11—C12	119.8 (2)
C13—P—C7	107.11 (10)	C10—C11—H11	120.1
C1—P—C7	106.27 (10)	C12—C11—H11	120.1
P—O1—Ni	151.84 (10)	C11—C12—C7	119.9 (2)
C6—C1—C2	119.1 (2)	C11—C12—H12	120.1
C6—C1—P	119.05 (17)	C7—C12—H12	120.1
C2—C1—P	121.80 (17)	C14—C13—C18	119.6 (2)
C3—C2—C1	120.1 (2)	C14—C13—P	123.11 (18)
C3—C2—H2	120.0	C18—C13—P	117.28 (18)
C1—C2—H2	120.0	C13—C14—C15	119.8 (2)
C4—C3—C2	119.9 (2)	C13—C14—H14	120.1
C4—C3—H3	120.1	C15—C14—H14	120.1
C2—C3—H3	120.1	C16—C15—C14	120.4 (3)
C5—C4—C3	120.3 (2)	C16—C15—H15	119.8
C5—C4—H4	119.9	C14—C15—H15	119.8
C3—C4—H4	119.9	C15—C16—C17	120.6 (3)
C6—C5—C4	120.5 (2)	C15—C16—H16	119.7
C6—C5—H5	119.8	C17—C16—H16	119.7
C4—C5—H5	119.8	C18—C17—C16	119.8 (3)
C5—C6—C1	120.1 (2)	C18—C17—H17	120.1
C5—C6—H6	119.9	C16—C17—H17	120.1
C1—C6—H6	119.9	C17—C18—C13	119.8 (3)
C8—C7—C12	119.81 (19)	C17—C18—H18	120.1
C8—C7—P	121.21 (16)	C13—C18—H18	120.1
C12—C7—P	118.96 (16)

C13—P—O1—Ni	−171.8 (2)	C13—P—C7—C12	−166.62 (17)
C1—P—O1—Ni	67.1 (2)	C1—P—C7—C12	−49.0 (2)
C7—P—O1—Ni	−52.8 (2)	C12—C7—C8—C9	0.8 (3)
O1ⁱ—Ni—O1—P	148.4 (3)	P—C7—C8—C9	179.55 (17)
Clⁱ—Ni—O1—P	35.1 (2)	C7—C8—C9—C10	0.0 (4)
Cl—Ni—O1—P	−95.3 (2)	C8—C9—C10—C11	−0.6 (4)
O1—P—C1—C6	24.3 (2)	C9—C10—C11—C12	0.4 (4)
C13—P—C1—C6	−95.91 (19)	C10—C11—C12—C7	0.4 (3)
C7—P—C1—C6	148.45 (18)	C8—C7—C12—C11	−1.0 (3)
O1—P—C1—C2	−154.12 (18)	P—C7—C12—C11	−179.76 (17)
C13—P—C1—C2	85.7 (2)	O1—P—C13—C14	−169.46 (19)
C7—P—C1—C2	−29.9 (2)	C1—P—C13—C14	−47.6 (2)
C6—C1—C2—C3	−0.8 (3)	C7—P—C13—C14	67.5 (2)
P—C1—C2—C3	177.60 (18)	O1—P—C13—C18	13.3 (2)
C1—C2—C3—C4	−0.2 (3)	C1—P—C13—C18	135.08 (19)
C2—C3—C4—C5	1.3 (4)	C7—P—C13—C18	−109.8 (2)
C3—C4—C5—C6	−1.5 (4)	C18—C13—C14—C15	1.5 (4)
C4—C5—C6—C1	0.4 (3)	P—C13—C14—C15	−175.8 (2)
C2—C1—C6—C5	0.7 (3)	C13—C14—C15—C16	0.3 (4)
P—C1—C6—C5	−177.74 (18)	C14—C15—C16—C17	−1.6 (5)
O1—P—C7—C8	−105.11 (19)	C15—C16—C17—C18	1.2 (5)
C13—P—C7—C8	14.6 (2)	C16—C17—C18—C13	0.6 (5)
C1—P—C7—C8	132.25 (18)	C14—C13—C18—C17	−1.9 (4)
O1—P—C7—C12	73.65 (19)	P—C13—C18—C17	175.5 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Acknowledgements

RMF acknowledges Universidad del Valle, Colombia, for partial support of this work.

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