{4,4′,6,6′-Tetra­chloro-2,2′-[(spiro­[4.4]nonane-1,6-di­yl)bis­(nitrilo­methyl­idyne)]diphenolato-κ4O,N,N′,O′}nickel(II)

Ni, F.; Wu, Z.-Q.; Liang, L.; Zhou, X.-G.

doi:10.1107/S1600536808013792

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m903

doi:10.1107/S1600536808013792

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{4,4′,6,6′-Tetrachloro-2,2′-[(spiro[4.4]nonane-1,6-diyl)bis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}nickel(II)

Fan Ni,^a Zhi-Qing Wu,^a Lei Liang ^a and Xiang-Ge Zhou ^a ^*

^aInstitute of Homogeneous Catalysis, Department of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: scuzhouxg@163.com

(Received 28 March 2008; accepted 8 May 2008; online 13 June 2008)

The title compound, [Ni(C₂₃H₂₀Cl₄N₂O₂)], has an Ni^II ion in a square-planar coordination formed by two imine N and two phenolato O atoms.

Related literature

For related literature, see: Gaetani Manfredotti et al. (1983 ), de Castro et al. (2001 ); Lutz (2003 ); Hoshina et al. (2000 ); Gosden et al. (1978 , 1981 ); Healy & Pletcher (1980 ); Dahm & Peters (1996 ).

Experimental

Crystal data

[Ni(C₂₃H₂₀Cl₄N₂O₂)]
M_r = 556.92
Monoclinic, P 2₁ /n
a = 13.344 (2) Å
b = 12.073 (2) Å
c = 14.081 (2) Å
β = 97.181 (3)°
V = 2250.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 294 (2) K
0.22 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.761, T_max = 1.000 (expected range = 0.646–0.849)
20414 measured reflections
5196 independent reflections
3731 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.113
S = 1.01
5196 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013792/im2062sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013792/im2062Isup2.hkl

checkCIF report

Comment top

Nickel(II) complexes with N₂O₂ Schiff base ligands derived from salicylaldehyde have long been used as homogenous catalysts (Gosden et al., 1978, 1981; Healy & Pletcher, 1980). More recently, the preparation of metal-salen based modified electrodes by oxidative electropolymerization of the metal complexes prompted their use in heterogenous electrocatalysis (Dahm & Peters, 1996). Work in our laboratory has attempted to introduce spiro[4.4]nonane-1,6-diamine as backbone into the salen system and investigate its coordination feature.

The crystal structure of the title compound 1 is shown in Fig. 1, while bond lengths and angles are listed in the supplementary material. As shown in Fig.1, the mononuclear Ni^II ion is tetra-coordinated, showing a nearly perfectly square-planar coordination mode. The planes Ni1—N1—C10—C11—C12—O1 and Ni1—Ni2—C17—C18—C19—O2 are not coplanar due to the steric pressure of the spirocyclic ligand.

The O—Ni—O, N—Ni—N and N—Ni—O angles correspond very well with the familiar Ni-salen complexes based on 1,2-ethanediamine (Gaetani Manfredotti et al. 1983, Lutz, 2003), 1,2-cyclohexanediamine (Castro et al. 2001), and 1,2- diphenyl-1,2-ethanediamine (Hoshina et al. 2000). de Castro et al. found that the coordination geometry usually is tetrahedrally distorted the more the substituents in the imine bridge are bulkier or if the substitution is asymmetric. Here we attribute the intensive distortion to the spiro frame which reinforces the asymmetry.

A comparison with the three analogous nickel complexes above indicates that, in the present compound, both the Ni—O bonding distances [1.848 (2) / 1.846 (2), respectively] are in good agreement with those observed in similar Schiff base Ni complexes whereas the Ni—N bonding distances [1.892 (2) / 1.884 (2) Å, respectively] are slightly longer [reported values range from 1.843 (2) to 1.855 (2) Å].

Related literature top

For related literature, see: Gaetani Manfredotti et al. (1983), de Castro et al. (2001); Lutz (2003); Hoshina et al. (2000); Gosden et al. (1978, 1981); Healy & Pletcher (1980); Dahm & Peters (1996).

Experimental top

The title complex, [N,N'-Bis(3,5-dichloro-salicylidene)- spiro[4.4]nonane-1,6-diaminato]-nickel(II), was prepared by the reaction of a hot methanolic solution (30 mL) of nickel(II) acetate tetrahydrate (0.249 g, 1 mmol) with the Schiff base ligand N,N'-Bis(3,5-dichloro-salicylidene)-spiro[4.4]nonane-1,6-diamine (0.500 g, 1 mmol). The resulting green precipitate was collected by filtration and washed with methanol and ether (yield 38%). Dark green crystals of 1 were grown by slow diffusion of ether into a solution of 1 in dichloromethane.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of complex [Ni(C₂₃H₂₀Cl₄N₂O₂)], with displacement ellipsoids drawn at the 30% probability level.

{4,4',6,6'-Tetrachloro-2,2'-[(spiro[4.4]nonane-1,6- diyl)bis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N',O'}nickel(II) top

Crystal data top

[Ni(C₂₃H₂₀Cl₄N₂O₂)]	F(000) = 1136
M_r = 556.92	D_x = 1.644 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10509 reflections
a = 13.344 (2) Å	θ = 1–27.5°
b = 12.073 (2) Å	µ = 1.36 mm⁻¹
c = 14.081 (2) Å	T = 294 K
β = 97.181 (3)°	Prism, black
V = 2250.6 (6) Å³	0.22 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5196 independent reflections
Radiation source: fine-focus sealed tube	3731 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ϕ and ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
T_min = 0.761, T_max = 1.000	k = −15→15
20414 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.065P)²] where P = (F_o² + 2F_c²)/3
5196 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Ni(C₂₃H₂₀Cl₄N₂O₂)]	V = 2250.6 (6) Å³
M_r = 556.92	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.344 (2) Å	µ = 1.36 mm⁻¹
b = 12.073 (2) Å	T = 294 K
c = 14.081 (2) Å	0.22 × 0.20 × 0.12 mm
β = 97.181 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5196 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3731 reflections with I > 2σ(I)
T_min = 0.761, T_max = 1.000	R_int = 0.055
20414 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.113	H-atom parameters constrained
S = 1.01	Δρ_max = 0.55 e Å⁻³
5196 reflections	Δρ_min = −0.40 e Å⁻³
289 parameters

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.

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 > σ(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
Ni1	0.42863 (2)	0.43913 (3)	0.65679 (2)	0.02559 (11)
Cl1	0.10295 (6)	0.32950 (8)	0.53445 (7)	0.0554 (2)
Cl2	−0.05657 (6)	0.63477 (9)	0.75125 (8)	0.0661 (3)
Cl3	0.41217 (6)	0.10984 (6)	0.47916 (6)	0.0453 (2)
Cl4	0.78080 (7)	0.18824 (7)	0.37495 (7)	0.0568 (2)
O1	0.29376 (14)	0.39968 (17)	0.63812 (14)	0.0377 (5)
O2	0.43951 (13)	0.32517 (15)	0.57124 (13)	0.0327 (4)
N1	0.41147 (15)	0.52722 (18)	0.76468 (15)	0.0276 (5)
N2	0.55652 (15)	0.49892 (17)	0.64347 (15)	0.0267 (5)
C1	0.49859 (19)	0.5405 (2)	0.84037 (18)	0.0306 (6)
H1A	0.4785	0.5892	0.8904	0.037*
C2	0.5314 (2)	0.4293 (3)	0.8853 (2)	0.0416 (7)
H2A	0.5236	0.3704	0.8382	0.050*
H2B	0.4928	0.4110	0.9372	0.050*
C3	0.6429 (2)	0.4480 (3)	0.9227 (2)	0.0441 (8)
H3A	0.6505	0.4916	0.9810	0.053*
H3B	0.6786	0.3784	0.9344	0.053*
C4	0.6798 (2)	0.5111 (3)	0.8402 (2)	0.0410 (7)
H4A	0.6944	0.4605	0.7902	0.049*
H4B	0.7405	0.5526	0.8622	0.049*
C5	0.59263 (19)	0.5905 (2)	0.80250 (18)	0.0285 (6)
C6	0.58053 (19)	0.6042 (2)	0.69372 (18)	0.0274 (5)
H6A	0.5229	0.6537	0.6767	0.033*
C7	0.6754 (2)	0.6688 (2)	0.6779 (2)	0.0366 (6)
H7A	0.6677	0.7045	0.6157	0.044*
H7B	0.7343	0.6210	0.6833	0.044*
C8	0.6830 (2)	0.7548 (3)	0.7596 (2)	0.0480 (8)
H8A	0.6586	0.8264	0.7355	0.058*
H8B	0.7525	0.7627	0.7886	0.058*
C9	0.6165 (2)	0.7099 (3)	0.8331 (2)	0.0431 (7)
H9A	0.6526	0.7124	0.8973	0.052*
H9B	0.5549	0.7529	0.8317	0.052*
C10	0.32576 (19)	0.5653 (2)	0.78429 (19)	0.0295 (6)
H10A	0.3273	0.6123	0.8368	0.035*
C11	0.22883 (19)	0.5419 (2)	0.73250 (19)	0.0302 (6)
C12	0.21902 (19)	0.4569 (2)	0.66395 (19)	0.0304 (6)
C13	0.1189 (2)	0.4320 (2)	0.6213 (2)	0.0367 (6)
C14	0.0362 (2)	0.4869 (3)	0.6479 (2)	0.0421 (7)
H14A	−0.0285	0.4692	0.6193	0.051*
C15	0.0498 (2)	0.5684 (3)	0.7173 (2)	0.0397 (7)
C16	0.1439 (2)	0.5968 (2)	0.7601 (2)	0.0354 (6)
H16A	0.1517	0.6517	0.8068	0.043*
C17	0.6168 (2)	0.4638 (2)	0.58462 (18)	0.0290 (6)
H17A	0.6717	0.5085	0.5757	0.035*
C18	0.6061 (2)	0.3617 (2)	0.53205 (18)	0.0280 (6)
C19	0.51800 (19)	0.2961 (2)	0.53137 (18)	0.0278 (5)
C20	0.5172 (2)	0.1946 (2)	0.4804 (2)	0.0321 (6)
C21	0.5954 (2)	0.1621 (2)	0.4321 (2)	0.0355 (6)
H21A	0.5921	0.0955	0.3988	0.043*
C22	0.6801 (2)	0.2305 (2)	0.4335 (2)	0.0359 (6)
C23	0.6860 (2)	0.3287 (2)	0.48250 (19)	0.0324 (6)
H23A	0.7428	0.3734	0.4829	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02081 (18)	0.02942 (19)	0.02673 (19)	0.00060 (13)	0.00379 (13)	−0.00226 (14)
Cl1	0.0407 (4)	0.0607 (6)	0.0629 (5)	−0.0066 (4)	−0.0008 (4)	−0.0221 (4)
Cl2	0.0264 (4)	0.0838 (7)	0.0887 (7)	0.0125 (4)	0.0095 (4)	−0.0225 (6)
Cl3	0.0416 (4)	0.0319 (4)	0.0620 (5)	−0.0045 (3)	0.0044 (4)	−0.0038 (3)
Cl4	0.0631 (5)	0.0467 (5)	0.0688 (6)	0.0084 (4)	0.0402 (5)	−0.0077 (4)
O1	0.0227 (10)	0.0430 (11)	0.0477 (12)	−0.0003 (8)	0.0057 (8)	−0.0123 (9)
O2	0.0251 (9)	0.0325 (10)	0.0416 (11)	−0.0006 (8)	0.0077 (8)	−0.0089 (8)
N1	0.0216 (11)	0.0342 (12)	0.0274 (11)	−0.0005 (9)	0.0044 (9)	0.0002 (9)
N2	0.0244 (11)	0.0294 (12)	0.0262 (11)	0.0014 (9)	0.0030 (9)	0.0002 (9)
C1	0.0239 (13)	0.0420 (16)	0.0258 (13)	0.0021 (11)	0.0023 (10)	−0.0030 (11)
C2	0.0359 (16)	0.0485 (18)	0.0393 (17)	−0.0031 (13)	0.0006 (13)	0.0122 (14)
C3	0.0333 (16)	0.059 (2)	0.0385 (17)	0.0051 (14)	−0.0034 (13)	0.0139 (15)
C4	0.0268 (15)	0.0538 (19)	0.0418 (17)	0.0066 (13)	0.0012 (12)	0.0058 (15)
C5	0.0217 (12)	0.0345 (15)	0.0287 (14)	0.0004 (10)	0.0003 (10)	−0.0017 (11)
C6	0.0236 (13)	0.0274 (13)	0.0308 (14)	−0.0008 (10)	0.0020 (10)	−0.0008 (11)
C7	0.0332 (15)	0.0364 (16)	0.0406 (16)	−0.0072 (12)	0.0065 (12)	0.0014 (13)
C8	0.0472 (19)	0.0435 (18)	0.054 (2)	−0.0134 (15)	0.0088 (15)	−0.0082 (15)
C9	0.0445 (18)	0.0451 (18)	0.0392 (17)	−0.0112 (14)	0.0030 (13)	−0.0129 (14)
C10	0.0271 (13)	0.0315 (14)	0.0306 (14)	0.0006 (11)	0.0059 (11)	−0.0010 (11)
C11	0.0232 (13)	0.0360 (15)	0.0323 (14)	0.0008 (11)	0.0067 (11)	0.0031 (11)
C12	0.0239 (13)	0.0332 (15)	0.0350 (15)	−0.0011 (11)	0.0069 (11)	0.0024 (12)
C13	0.0312 (15)	0.0387 (16)	0.0393 (16)	−0.0040 (12)	0.0007 (12)	−0.0018 (13)
C14	0.0224 (14)	0.0531 (19)	0.0500 (18)	−0.0021 (13)	0.0015 (12)	−0.0004 (15)
C15	0.0233 (14)	0.0472 (18)	0.0493 (18)	0.0057 (12)	0.0077 (12)	0.0011 (14)
C16	0.0306 (15)	0.0394 (16)	0.0368 (16)	0.0069 (12)	0.0067 (12)	0.0010 (12)
C17	0.0269 (13)	0.0313 (14)	0.0292 (14)	−0.0031 (11)	0.0055 (11)	0.0014 (11)
C18	0.0301 (14)	0.0283 (14)	0.0259 (13)	0.0054 (11)	0.0043 (11)	0.0020 (11)
C19	0.0284 (13)	0.0278 (13)	0.0275 (13)	0.0039 (11)	0.0042 (11)	0.0019 (11)
C20	0.0324 (14)	0.0295 (14)	0.0339 (15)	0.0015 (11)	0.0017 (11)	0.0028 (11)
C21	0.0465 (17)	0.0272 (14)	0.0338 (15)	0.0060 (13)	0.0093 (13)	0.0000 (12)
C22	0.0398 (16)	0.0356 (16)	0.0348 (15)	0.0108 (13)	0.0146 (12)	0.0024 (12)
C23	0.0325 (15)	0.0343 (15)	0.0321 (15)	0.0014 (12)	0.0109 (12)	0.0052 (12)

Geometric parameters (Å, º) top

Ni1—O2	1.8463 (18)	C6—H6A	0.9800
Ni1—O1	1.8484 (19)	C7—C8	1.544 (4)
Ni1—N2	1.884 (2)	C7—H7A	0.9700
Ni1—N1	1.892 (2)	C7—H7B	0.9700
Cl1—C13	1.734 (3)	C8—C9	1.544 (4)
Cl2—C15	1.747 (3)	C8—H8A	0.9700
Cl3—C20	1.733 (3)	C8—H8B	0.9700
Cl4—C22	1.739 (3)	C9—H9A	0.9700
O1—C12	1.302 (3)	C9—H9B	0.9700
O2—C19	1.297 (3)	C10—C11	1.432 (4)
N1—C10	1.294 (3)	C10—H10A	0.9300
N1—C1	1.484 (3)	C11—C12	1.403 (4)
N2—C17	1.296 (3)	C11—C16	1.409 (4)
N2—C6	1.470 (3)	C12—C13	1.426 (4)
C1—C2	1.525 (4)	C13—C14	1.379 (4)
C1—C5	1.546 (4)	C14—C15	1.383 (4)
C1—H1A	0.9800	C14—H14A	0.9300
C2—C3	1.532 (4)	C15—C16	1.366 (4)
C2—H2A	0.9700	C16—H16A	0.9300
C2—H2B	0.9700	C17—C18	1.436 (4)
C3—C4	1.522 (4)	C17—H17A	0.9300
C3—H3A	0.9700	C18—C23	1.403 (4)
C3—H3B	0.9700	C18—C19	1.416 (4)
C4—C5	1.548 (4)	C19—C20	1.420 (4)
C4—H4A	0.9700	C20—C21	1.372 (4)
C4—H4B	0.9700	C21—C22	1.397 (4)
C5—C9	1.527 (4)	C21—H21A	0.9300
C5—C6	1.529 (4)	C22—C23	1.368 (4)
C6—C7	1.526 (4)	C23—H23A	0.9300

O2—Ni1—O1	82.52 (8)	H7A—C7—H7B	109.2
O2—Ni1—N2	94.27 (8)	C7—C8—C9	105.9 (2)
O1—Ni1—N2	164.28 (9)	C7—C8—H8A	110.6
O2—Ni1—N1	165.98 (9)	C9—C8—H8A	110.6
O1—Ni1—N1	92.62 (9)	C7—C8—H8B	110.6
N2—Ni1—N1	93.82 (9)	C9—C8—H8B	110.6
C12—O1—Ni1	126.14 (18)	H8A—C8—H8B	108.7
C19—O2—Ni1	128.15 (17)	C5—C9—C8	105.0 (2)
C10—N1—C1	116.2 (2)	C5—C9—H9A	110.7
C10—N1—Ni1	124.76 (18)	C8—C9—H9A	110.7
C1—N1—Ni1	118.34 (16)	C5—C9—H9B	110.7
C17—N2—C6	118.3 (2)	C8—C9—H9B	110.7
C17—N2—Ni1	125.51 (19)	H9A—C9—H9B	108.8
C6—N2—Ni1	115.40 (15)	N1—C10—C11	126.0 (3)
N1—C1—C2	111.2 (2)	N1—C10—H10A	117.0
N1—C1—C5	113.0 (2)	C11—C10—H10A	117.0
C2—C1—C5	106.5 (2)	C12—C11—C16	121.6 (2)
N1—C1—H1A	108.7	C12—C11—C10	119.7 (2)
C2—C1—H1A	108.7	C16—C11—C10	118.2 (3)
C5—C1—H1A	108.7	O1—C12—C11	124.8 (2)
C1—C2—C3	103.2 (2)	O1—C12—C13	118.7 (2)
C1—C2—H2A	111.1	C11—C12—C13	116.5 (2)
C3—C2—H2A	111.1	C14—C13—C12	121.6 (3)
C1—C2—H2B	111.1	C14—C13—Cl1	120.2 (2)
C3—C2—H2B	111.1	C12—C13—Cl1	118.3 (2)
H2A—C2—H2B	109.1	C13—C14—C15	119.7 (3)
C4—C3—C2	101.8 (2)	C13—C14—H14A	120.2
C4—C3—H3A	111.4	C15—C14—H14A	120.2
C2—C3—H3A	111.4	C16—C15—C14	121.5 (3)
C4—C3—H3B	111.4	C16—C15—Cl2	119.8 (2)
C2—C3—H3B	111.4	C14—C15—Cl2	118.7 (2)
H3A—C3—H3B	109.3	C15—C16—C11	119.1 (3)
C3—C4—C5	105.7 (2)	C15—C16—H16A	120.4
C3—C4—H4A	110.6	C11—C16—H16A	120.4
C5—C4—H4A	110.6	N2—C17—C18	125.5 (2)
C3—C4—H4B	110.6	N2—C17—H17A	117.3
C5—C4—H4B	110.6	C18—C17—H17A	117.3
H4A—C4—H4B	108.7	C23—C18—C19	121.3 (2)
C9—C5—C6	99.9 (2)	C23—C18—C17	117.9 (2)
C9—C5—C1	114.9 (2)	C19—C18—C17	120.9 (2)
C6—C5—C1	113.5 (2)	O2—C19—C18	124.0 (2)
C9—C5—C4	111.5 (2)	O2—C19—C20	119.8 (2)
C6—C5—C4	113.0 (2)	C18—C19—C20	116.1 (2)
C1—C5—C4	104.4 (2)	C21—C20—C19	122.6 (3)
N2—C6—C7	120.4 (2)	C21—C20—Cl3	119.4 (2)
N2—C6—C5	112.2 (2)	C19—C20—Cl3	118.0 (2)
C7—C6—C5	102.5 (2)	C20—C21—C22	119.2 (3)
N2—C6—H6A	107.0	C20—C21—H21A	120.4
C7—C6—H6A	107.0	C22—C21—H21A	120.4
C5—C6—H6A	107.0	C23—C22—C21	121.0 (2)
C6—C7—C8	102.3 (2)	C23—C22—Cl4	119.6 (2)
C6—C7—H7A	111.3	C21—C22—Cl4	119.4 (2)
C8—C7—H7A	111.3	C22—C23—C18	119.8 (3)
C6—C7—H7B	111.3	C22—C23—H23A	120.1
C8—C7—H7B	111.3	C18—C23—H23A	120.1

O2—Ni1—O1—C12	−167.0 (2)	C6—C5—C9—C8	−37.3 (3)
N2—Ni1—O1—C12	−87.9 (4)	C1—C5—C9—C8	−159.1 (2)
N1—Ni1—O1—C12	26.2 (2)	C4—C5—C9—C8	82.4 (3)
O1—Ni1—O2—C19	172.9 (2)	C7—C8—C9—C5	12.0 (3)
N2—Ni1—O2—C19	8.3 (2)	C1—N1—C10—C11	−165.9 (3)
N1—Ni1—O2—C19	−116.8 (4)	Ni1—N1—C10—C11	4.6 (4)
O2—Ni1—N1—C10	−88.5 (4)	N1—C10—C11—C12	11.5 (4)
O1—Ni1—N1—C10	−19.3 (2)	N1—C10—C11—C16	−175.7 (3)
N2—Ni1—N1—C10	146.4 (2)	Ni1—O1—C12—C11	−18.5 (4)
O2—Ni1—N1—C1	81.9 (4)	Ni1—O1—C12—C13	162.3 (2)
O1—Ni1—N1—C1	151.08 (19)	C16—C11—C12—O1	−177.0 (3)
N2—Ni1—N1—C1	−43.26 (19)	C10—C11—C12—O1	−4.5 (4)
O2—Ni1—N2—C17	4.1 (2)	C16—C11—C12—C13	2.2 (4)
O1—Ni1—N2—C17	−73.4 (4)	C10—C11—C12—C13	174.7 (2)
N1—Ni1—N2—C17	172.7 (2)	O1—C12—C13—C14	177.7 (3)
O2—Ni1—N2—C6	174.05 (17)	C11—C12—C13—C14	−1.5 (4)
O1—Ni1—N2—C6	96.6 (4)	O1—C12—C13—Cl1	−2.0 (4)
N1—Ni1—N2—C6	−17.40 (18)	C11—C12—C13—Cl1	178.8 (2)
C10—N1—C1—C2	109.6 (3)	C12—C13—C14—C15	0.2 (5)
Ni1—N1—C1—C2	−61.6 (3)	Cl1—C13—C14—C15	179.9 (2)
C10—N1—C1—C5	−130.8 (2)	C13—C14—C15—C16	0.5 (5)
Ni1—N1—C1—C5	58.1 (3)	C13—C14—C15—Cl2	−178.8 (2)
N1—C1—C2—C3	154.6 (2)	C14—C15—C16—C11	0.2 (5)
C5—C1—C2—C3	31.1 (3)	Cl2—C15—C16—C11	179.5 (2)
C1—C2—C3—C4	−42.6 (3)	C12—C11—C16—C15	−1.6 (4)
C2—C3—C4—C5	38.5 (3)	C10—C11—C16—C15	−174.2 (3)
N1—C1—C5—C9	107.9 (3)	C6—N2—C17—C18	178.2 (2)
C2—C1—C5—C9	−129.7 (3)	Ni1—N2—C17—C18	−12.2 (4)
N1—C1—C5—C6	−6.2 (3)	N2—C17—C18—C23	−170.7 (2)
C2—C1—C5—C6	116.1 (3)	N2—C17—C18—C19	8.5 (4)
N1—C1—C5—C4	−129.7 (2)	Ni1—O2—C19—C18	−13.3 (4)
C2—C1—C5—C4	−7.4 (3)	Ni1—O2—C19—C20	169.04 (18)
C3—C4—C5—C9	105.1 (3)	C23—C18—C19—O2	−176.0 (2)
C3—C4—C5—C6	−143.2 (2)	C17—C18—C19—O2	4.8 (4)
C3—C4—C5—C1	−19.4 (3)	C23—C18—C19—C20	1.8 (4)
C17—N2—C6—C7	−1.1 (4)	C17—C18—C19—C20	−177.4 (2)
Ni1—N2—C6—C7	−171.80 (19)	O2—C19—C20—C21	176.2 (2)
C17—N2—C6—C5	−121.8 (2)	C18—C19—C20—C21	−1.7 (4)
Ni1—N2—C6—C5	67.5 (2)	O2—C19—C20—Cl3	−3.3 (3)
C9—C5—C6—N2	179.9 (2)	C18—C19—C20—Cl3	178.82 (19)
C1—C5—C6—N2	−57.2 (3)	C19—C20—C21—C22	0.7 (4)
C4—C5—C6—N2	61.4 (3)	Cl3—C20—C21—C22	−179.8 (2)
C9—C5—C6—C7	49.4 (3)	C20—C21—C22—C23	0.2 (4)
C1—C5—C6—C7	172.2 (2)	C20—C21—C22—Cl4	178.4 (2)
C4—C5—C6—C7	−69.2 (3)	C21—C22—C23—C18	−0.1 (4)
N2—C6—C7—C8	−167.4 (2)	Cl4—C22—C23—C18	−178.3 (2)
C5—C6—C7—C8	−42.0 (3)	C19—C18—C23—C22	−1.0 (4)
C6—C7—C8—C9	18.2 (3)	C17—C18—C23—C22	178.3 (2)

Experimental details

Crystal data
Chemical formula	[Ni(C₂₃H₂₀Cl₄N₂O₂)]
M_r	556.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	13.344 (2), 12.073 (2), 14.081 (2)
β (°)	97.181 (3)
V (Å³)	2250.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.36
Crystal size (mm)	0.22 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.761, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20414, 5196, 3731
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.113, 1.01
No. of reflections	5196
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.40

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The project was sponsored by the Scientific Research Foundation for Returned Overseas Chinese Scholars 2005383–10-9, NSFC 20672075 and the Student Innovation Foundation of Sichuan University.

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