Bis{4-chloro-6-formyl-2-[(E)-2-(1H-imidazol-4-yl-κN)ethyl-imino-methyl-κN]phenolato-κO}nickel(II).

In the title compound, [Ni(C(13)H(11)ClN(3)O(2))(2)], the Ni(II) atom is located on a twofold rotation axis and is six-coordinated by four N atoms and two phenolate O atoms from the two equal Schiff base ligands in a distorted octa-hedral coordination geometry. The complex mol-ecules are connected by C-H⋯Cl, C-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For related literature on transition metal–Schiff base complexes, see: Casella & Gullotti (1986 ▶); Hodnett & Dunn (1970 ▶); Kim et al. (2005 ▶); May et al. (2004 ▶). For literature related to the synthesis, see: Taniguchi (1984 ▶).

Experimental

Crystal data

[Ni(C13H11ClN3O2)2]

M = 612.11

Tetragonal,

a = 13.5883 (16) Å

c = 14.0392 (16) Å

V = 2592.2 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.00 mm−1

T = 293 (2) K

0.10 × 0.04 × 0.02 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.901, T max = 0.978

21136 measured reflections

2294 independent reflections

1253 reflections with I > 2σ(I)

R int = 0.154

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.081

S = 0.82

2294 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶), 920 Friedel pairs

Flack parameter: 0.02 (3)

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808031577/hy2154sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031577/hy2154Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C13H11ClN3O2)2]	Dx = 1.568 Mg m−3
Mr = 612.11	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 1360 reflections
Hall symbol: P 4nw 2abw	θ = 2.6–15.1°
a = 13.5883 (16) Å	µ = 1.00 mm−1
c = 14.0392 (16) Å	T = 293 K
V = 2592.2 (5) Å3	Needle, red
Z = 4	0.10 × 0.04 × 0.02 mm
F(000) = 1256

Bruker SMART APEX CCD area-detector diffractometer	2294 independent reflections
Radiation source: fine-focus sealed tube	1253 reflections with I > 2σ(I)
graphite	Rint = 0.154
φ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
Tmin = 0.901, Tmax = 0.978	k = −16→16
21136 measured reflections	l = −14→16

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)] = 0.045	H-atom parameters constrained
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0298P)2] where P = (Fo2 + 2Fc2)/3
S = 0.82	(Δ/σ)max = 0.003
2294 reflections	Δρmax = 0.35 e Å−3
177 parameters	Δρmin = −0.24 e Å−3
0 restraints	Absolute structure: Flack (1983), 920 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (3)

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. The reason of the large Rintvalue is the poor quality and small size of the crystal sample. Although many efforts were made to select better crystal for experiment, each time we failed.

	x	y	z	Uiso*/Ueq
Ni1	0.23545 (4)	0.23545 (4)	0.0000	0.0433 (3)
C1	0.2375 (4)	0.0575 (3)	0.1277 (3)	0.0428 (12)
C2	0.2104 (4)	0.0113 (4)	0.2139 (4)	0.0564 (15)
C3	0.2586 (4)	−0.0728 (4)	0.2478 (4)	0.0656 (14)
H3	0.2381	−0.1026	0.3041	0.079*
C4	0.3356 (4)	−0.1106 (4)	0.1977 (5)	0.0642 (17)
C5	0.3666 (4)	−0.0659 (4)	0.1150 (4)	0.0593 (15)
H5	0.4202	−0.0920	0.0825	0.071*
C6	0.3205 (4)	0.0165 (3)	0.0790 (4)	0.0455 (13)
C7	0.1300 (4)	0.0521 (5)	0.2722 (4)	0.0800 (19)
H7	0.1037	0.1125	0.2545	0.096*
C8	0.3581 (3)	0.0522 (4)	−0.0096 (4)	0.0519 (13)
H8	0.4055	0.0129	−0.0384	0.062*
C9	0.3904 (4)	0.1472 (4)	−0.1444 (4)	0.0700 (17)
H9A	0.4022	0.0839	−0.1743	0.084*
H9B	0.4539	0.1760	−0.1294	0.084*
C10	0.3368 (4)	0.2136 (4)	−0.2143 (3)	0.0636 (15)
H10A	0.3701	0.2112	−0.2754	0.076*
H10B	0.2704	0.1892	−0.2233	0.076*
C11	0.3326 (4)	0.3166 (4)	−0.1810 (4)	0.0500 (14)
C12	0.3728 (4)	0.4001 (4)	−0.2169 (4)	0.0620 (16)
H12	0.4097	0.4056	−0.2724	0.074*
C13	0.2960 (3)	0.4340 (4)	−0.0856 (4)	0.0504 (14)
H13	0.2707	0.4695	−0.0345	0.060*
Cl1	0.39581 (12)	−0.21688 (11)	0.23773 (13)	0.1081 (7)
N1	0.3352 (3)	0.1319 (3)	−0.0552 (3)	0.0487 (11)
N2	0.2844 (3)	0.3389 (3)	−0.0971 (3)	0.0480 (11)
N3	0.3486 (3)	0.4739 (3)	−0.1563 (3)	0.0584 (12)
H3A	0.3641	0.5349	−0.1622	0.070*
O1	0.1862 (2)	0.1302 (2)	0.0935 (2)	0.0494 (9)
O2	0.0962 (3)	0.0119 (3)	0.3416 (3)	0.1061 (15)

	U11	U22	U33	U12	U13	U23
Ni1	0.0453 (3)	0.0453 (3)	0.0393 (5)	0.0010 (4)	0.0040 (3)	−0.0040 (3)
C1	0.038 (3)	0.050 (3)	0.040 (3)	−0.012 (3)	−0.004 (3)	0.003 (3)
C2	0.057 (4)	0.056 (4)	0.056 (4)	−0.014 (3)	−0.008 (3)	0.009 (3)
C3	0.067 (4)	0.064 (4)	0.066 (4)	−0.024 (3)	−0.020 (5)	0.016 (4)
C4	0.059 (4)	0.055 (4)	0.079 (5)	0.001 (3)	−0.026 (4)	0.017 (4)
C5	0.041 (3)	0.060 (4)	0.077 (5)	−0.003 (3)	−0.011 (3)	−0.002 (3)
C6	0.043 (3)	0.043 (3)	0.050 (4)	−0.003 (3)	−0.006 (3)	0.001 (3)
C7	0.080 (5)	0.115 (5)	0.045 (5)	−0.021 (4)	0.001 (4)	0.030 (4)
C8	0.048 (3)	0.044 (3)	0.064 (4)	0.007 (3)	0.004 (3)	−0.013 (3)
C9	0.094 (4)	0.056 (4)	0.060 (4)	0.015 (3)	0.028 (4)	0.004 (3)
C10	0.082 (4)	0.069 (4)	0.040 (4)	0.011 (3)	0.020 (3)	−0.006 (3)
C11	0.060 (4)	0.053 (4)	0.038 (4)	0.003 (3)	0.002 (3)	0.002 (3)
C12	0.070 (4)	0.068 (4)	0.048 (4)	0.015 (3)	0.018 (3)	0.000 (3)
C13	0.052 (4)	0.054 (4)	0.045 (4)	0.004 (3)	0.009 (3)	0.006 (3)
Cl1	0.1068 (12)	0.0770 (11)	0.1405 (16)	0.0095 (10)	−0.0362 (12)	0.0368 (12)
N1	0.052 (3)	0.054 (3)	0.041 (3)	−0.001 (2)	0.009 (2)	−0.003 (2)
N2	0.063 (3)	0.042 (3)	0.039 (3)	−0.003 (2)	0.003 (2)	0.000 (2)
N3	0.063 (3)	0.053 (3)	0.059 (3)	−0.009 (2)	0.006 (3)	0.018 (3)
O1	0.043 (2)	0.059 (2)	0.046 (2)	0.0090 (17)	0.0044 (17)	0.0083 (18)
O2	0.116 (4)	0.135 (4)	0.068 (4)	−0.013 (3)	0.017 (3)	0.026 (3)

Ni1—O1	2.054 (3)	C7—H7	0.9300
Ni1—O1i	2.054 (3)	C8—N1	1.296 (5)
Ni1—N2i	2.068 (4)	C8—H8	0.9300
Ni1—N2	2.068 (4)	C9—N1	1.474 (5)
Ni1—N1	2.102 (4)	C9—C10	1.519 (6)
Ni1—N1i	2.102 (4)	C9—H9A	0.9700
C1—O1	1.301 (5)	C9—H9B	0.9700
C1—C2	1.412 (6)	C10—C11	1.477 (6)
C1—C6	1.431 (6)	C10—H10A	0.9700
C2—C3	1.401 (6)	C10—H10B	0.9700
C2—C7	1.474 (7)	C11—C12	1.355 (6)
C3—C4	1.362 (7)	C11—N2	1.382 (5)
C3—H3	0.9300	C12—N3	1.356 (5)
C4—C5	1.376 (7)	C12—H12	0.9300
C4—Cl1	1.752 (5)	C13—N2	1.312 (5)
C5—C6	1.380 (6)	C13—N3	1.337 (5)
C5—H5	0.9300	C13—H13	0.9300
C6—C8	1.429 (6)	N3—H3A	0.8600
C7—O2	1.208 (5)
O1—Ni1—O1i	87.37 (17)	C2—C7—H7	117.9
O1—Ni1—N2i	91.40 (14)	N1—C8—C6	128.9 (5)
O1i—Ni1—N2i	178.49 (14)	N1—C8—H8	115.5
O1—Ni1—N2	178.49 (14)	C6—C8—H8	115.5
O1i—Ni1—N2	91.40 (14)	N1—C9—C10	112.8 (4)
N2i—Ni1—N2	89.8 (2)	N1—C9—H9A	109.0
O1—Ni1—N1	88.84 (14)	C10—C9—H9A	109.0
O1i—Ni1—N1	89.72 (13)	N1—C9—H9B	109.0
N2i—Ni1—N1	91.14 (15)	C10—C9—H9B	109.0
N2—Ni1—N1	90.27 (15)	H9A—C9—H9B	107.8
O1—Ni1—N1i	89.72 (13)	C11—C10—C9	112.2 (4)
O1i—Ni1—N1i	88.84 (14)	C11—C10—H10A	109.2
N2i—Ni1—N1i	90.27 (15)	C9—C10—H10A	109.2
N2—Ni1—N1i	91.14 (15)	C11—C10—H10B	109.2
N1—Ni1—N1i	178.0 (2)	C9—C10—H10B	109.2
O1—C1—C2	120.9 (5)	H10A—C10—H10B	107.9
O1—C1—C6	122.8 (4)	C12—C11—N2	108.9 (5)
C2—C1—C6	116.2 (5)	C12—C11—C10	131.3 (5)
C3—C2—C1	122.2 (5)	N2—C11—C10	119.7 (5)
C3—C2—C7	117.6 (5)	C11—C12—N3	106.8 (5)
C1—C2—C7	120.2 (5)	C11—C12—H12	126.6
C4—C3—C2	119.4 (5)	N3—C12—H12	126.6
C4—C3—H3	120.3	N2—C13—N3	111.9 (5)
C2—C3—H3	120.3	N2—C13—H13	124.1
C3—C4—C5	120.3 (5)	N3—C13—H13	124.1
C3—C4—Cl1	120.3 (5)	C8—N1—C9	114.6 (4)
C5—C4—Cl1	119.4 (5)	C8—N1—Ni1	122.1 (3)
C4—C5—C6	121.9 (5)	C9—N1—Ni1	123.2 (3)
C4—C5—H5	119.0	C13—N2—C11	105.3 (4)
C6—C5—H5	119.0	C13—N2—Ni1	128.9 (4)
C5—C6—C8	115.6 (5)	C11—N2—Ni1	124.4 (3)
C5—C6—C1	119.9 (5)	C13—N3—C12	107.2 (4)
C8—C6—C1	124.4 (4)	C13—N3—H3A	126.4
O2—C7—C2	124.1 (6)	C12—N3—H3A	126.4
O2—C7—H7	117.9	C1—O1—Ni1	126.1 (3)
O1—C1—C2—C3	173.9 (4)	C10—C9—N1—Ni1	−28.0 (6)
C6—C1—C2—C3	−3.1 (6)	O1—Ni1—N1—C8	−17.2 (4)
O1—C1—C2—C7	−7.0 (7)	O1i—Ni1—N1—C8	−104.6 (4)
C6—C1—C2—C7	176.0 (4)	N2i—Ni1—N1—C8	74.1 (4)
C1—C2—C3—C4	1.5 (7)	N2—Ni1—N1—C8	164.0 (4)
C7—C2—C3—C4	−177.6 (5)	O1—Ni1—N1—C9	167.8 (4)
C2—C3—C4—C5	0.8 (8)	O1i—Ni1—N1—C9	80.4 (4)
C2—C3—C4—Cl1	−179.0 (3)	N2i—Ni1—N1—C9	−100.8 (4)
C3—C4—C5—C6	−1.3 (8)	N2—Ni1—N1—C9	−11.0 (4)
Cl1—C4—C5—C6	178.5 (4)	N3—C13—N2—C11	−0.2 (5)
C4—C5—C6—C8	−177.3 (5)	N3—C13—N2—Ni1	166.5 (3)
C4—C5—C6—C1	−0.4 (7)	C12—C11—N2—C13	0.6 (6)
O1—C1—C6—C5	−174.4 (4)	C10—C11—N2—C13	178.1 (5)
C2—C1—C6—C5	2.5 (6)	C12—C11—N2—Ni1	−166.8 (3)
O1—C1—C6—C8	2.2 (7)	C10—C11—N2—Ni1	10.7 (6)
C2—C1—C6—C8	179.2 (4)	N2i—Ni1—N2—C13	−52.1 (4)
C3—C2—C7—O2	−8.3 (8)	N1—Ni1—N2—C13	−143.3 (4)
C1—C2—C7—O2	172.5 (5)	N2i—Ni1—N2—C11	112.2 (4)
C5—C6—C8—N1	−173.5 (5)	N1—Ni1—N2—C11	21.0 (4)
C1—C6—C8—N1	9.8 (8)	N1i—Ni1—N2—C11	−157.6 (4)
N1—C9—C10—C11	69.3 (6)	N2—C13—N3—C12	−0.3 (6)
C9—C10—C11—C12	115.1 (6)	C11—C12—N3—C13	0.6 (6)
C9—C10—C11—N2	−61.8 (6)	C2—C1—O1—Ni1	157.3 (3)
N2—C11—C12—N3	−0.7 (6)	C6—C1—O1—Ni1	−25.9 (6)
C10—C11—C12—N3	−177.9 (5)	O1i—Ni1—O1—C1	118.8 (4)
C6—C8—N1—C9	178.7 (5)	N1—Ni1—O1—C1	29.0 (4)
C6—C8—N1—Ni1	3.3 (7)	N1i—Ni1—O1—C1	−152.4 (3)
C10—C9—N1—C8	156.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Cl1ii	0.97	2.82	3.475 (5)	125
C12—H12···O2iii	0.93	2.36	3.287 (7)	174
N3—H3A···O1iv	0.86	2.06	2.899 (5)	166

Ni1—O1	2.054 (3)
Ni1—N2	2.068 (4)
Ni1—N1	2.102 (4)

O1—Ni1—O1i	87.37 (17)
O1—Ni1—N2i	91.40 (14)
O1—Ni1—N2	178.49 (14)
N2i—Ni1—N2	89.8 (2)
O1—Ni1—N1	88.84 (14)
N2—Ni1—N1	90.27 (15)
O1—Ni1—N1i	89.72 (13)
N2—Ni1—N1i	91.14 (15)
N1—Ni1—N1i	178.0 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯Cl1ii	0.97	2.82	3.475 (5)	125
C12—H12⋯O2iii	0.93	2.36	3.287 (7)	174
N3—H3A⋯O1iv	0.86	2.06	2.899 (5)	166

Symmetry codes: (ii) ; (iii) ; (iv) .