Bis[2-(benzyl-amino)-pyridine-κN]bis-(2-formyl-phenolato-κO,O')nickel(II).

In the title complex, [Ni(C(7)H(5)O(2))(2)(C(12)H(12)N(2))(2)], the Ni(II) atom lies on a center of inversion and is coordinated in an octa-hedral geometry by two 2-(benzyl-amino)-pyridine (2-BAP) and two 2-formyl-phenolate ligands with the O-atom donors in the equatorial plane and the pyridine N atoms in axial positions. There are hydrogen-bonding inter-actions between the secondary amine H atom and the phenolate O atom, as well as C-H⋯O inter-actions, which result in the dihedral angle between the aromatic phenyl ring of the 2-formyl-phenolate moiety and the pyridine ring being 80.23 (4)°. In the packing, there are both C-H⋯π inter-actions, which link the mol-ecules into chains along the b axis, and offset π-π inter-actions involving both the pyridine and phenyl rings of the 2-BAP ligands [centroid-centroid distances = 4.0100 (8) Å for the pyridine rings and 3.6601 (8) and 4.8561 (8) Å for the phenyl rings].

Related literature

For the structures of similar octa­hedral nickel complexes, see: Assey et al. (2010a ▶,b ▶); Butcher et al. (2009 ▶); Gultneh et al. (2008 ▶). For bond-length data, Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(C7H5O2)2(C12H12N2)2]

M = 669.40

Triclinic,

a = 8.1747 (5) Å

b = 9.3365 (5) Å

c = 10.9183 (6) Å

α = 73.926 (5)°

β = 84.766 (5)°

γ = 77.247 (5)°

V = 780.58 (8) Å3

Z = 1

Mo Kα radiation

μ = 0.67 mm−1

T = 110 K

0.47 × 0.41 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby detector

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.932, T max = 1.000

9822 measured reflections

5136 independent reflections

4216 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.086

S = 1.05

5136 reflections

218 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 I, global. DOI: 10.1107/S1600536811001425/zl2338sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001425/zl2338Isup2.hkl

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

[Ni(C7H5O2)2(C12H12N2)2]	Z = 1
Mr = 669.40	F(000) = 350
Triclinic, P1	Dx = 1.424 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1747 (5) Å	Cell parameters from 5541 reflections
b = 9.3365 (5) Å	θ = 4.8–32.6°
c = 10.9183 (6) Å	µ = 0.67 mm−1
α = 73.926 (5)°	T = 110 K
β = 84.766 (5)°	Block, pale green
γ = 77.247 (5)°	0.47 × 0.41 × 0.35 mm
V = 780.58 (8) Å3

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Mo) detector	5136 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4216 reflections with I > 2σ(I)
graphite	Rint = 0.025
Detector resolution: 10.5081 pixels mm-1	θmax = 32.6°, θmin = 4.8°
ω scans	h = −12→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −14→13
Tmin = 0.932, Tmax = 1.000	l = −16→15
9822 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0457P)2] where P = (Fo2 + 2Fc2)/3
5136 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.27 e Å−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. 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.

	x	y	z	Uiso*/Ueq
Ni	0.5000	1.0000	0.5000	0.01289 (7)
O1A	0.27528 (11)	1.00213 (9)	0.43885 (9)	0.01507 (18)
O2A	0.61193 (11)	0.98245 (10)	0.32627 (9)	0.01674 (18)
C1A	0.24508 (15)	0.97081 (12)	0.33607 (12)	0.0140 (2)
C2A	0.07923 (16)	0.95941 (13)	0.31617 (13)	0.0172 (2)
H2AA	−0.0068	0.9765	0.3782	0.021*
C3A	0.04021 (17)	0.92416 (14)	0.20916 (14)	0.0213 (3)
H3AA	−0.0721	0.9184	0.1990	0.026*
C4A	0.16279 (18)	0.89655 (14)	0.11473 (14)	0.0221 (3)
H4AA	0.1346	0.8713	0.0419	0.026*
C5A	0.32436 (17)	0.90699 (14)	0.13020 (13)	0.0190 (3)
H5AA	0.4081	0.8885	0.0670	0.023*
C6A	0.36945 (16)	0.94477 (13)	0.23829 (12)	0.0150 (2)
C7A	0.54127 (16)	0.95393 (13)	0.24225 (12)	0.0172 (2)
H7A	0.6106	0.9358	0.1712	0.021*
N1B	0.55584 (13)	0.75527 (11)	0.56185 (10)	0.0146 (2)
N2B	0.28723 (13)	0.72549 (12)	0.63564 (11)	0.0173 (2)
H2BN	0.262 (2)	0.8111 (19)	0.6004 (18)	0.026 (4)*
C1B	0.71914 (16)	0.69158 (14)	0.54563 (13)	0.0166 (2)
H1BA	0.7937	0.7570	0.5059	0.020*
C2B	0.78339 (16)	0.53754 (14)	0.58336 (13)	0.0168 (2)
H2BA	0.8998	0.4981	0.5729	0.020*
C3B	0.67321 (16)	0.44103 (13)	0.63735 (12)	0.0165 (2)
H3BA	0.7134	0.3339	0.6621	0.020*
C4B	0.50697 (16)	0.50075 (13)	0.65462 (12)	0.0150 (2)
H4BA	0.4310	0.4356	0.6915	0.018*
C5B	0.44918 (15)	0.66092 (13)	0.61691 (12)	0.0139 (2)
C6B	0.16081 (15)	0.63865 (14)	0.69494 (13)	0.0172 (2)
H6BA	0.1547	0.5660	0.6453	0.021*
H6BB	0.0503	0.7091	0.6912	0.021*
C7B	0.19397 (15)	0.55083 (14)	0.83287 (13)	0.0167 (2)
C8B	0.26795 (17)	0.60818 (16)	0.91340 (14)	0.0221 (3)
H8BA	0.2980	0.7048	0.8822	0.027*
C9B	0.29842 (19)	0.52611 (18)	1.03870 (15)	0.0295 (3)
H9BA	0.3482	0.5672	1.0929	0.035*
C10B	0.25672 (19)	0.38432 (18)	1.08552 (15)	0.0313 (3)
H10A	0.2794	0.3275	1.1711	0.038*
C11B	0.1819 (2)	0.32658 (16)	1.00657 (16)	0.0294 (3)
H11A	0.1515	0.2302	1.0383	0.035*
C12B	0.15109 (17)	0.40869 (15)	0.88107 (14)	0.0222 (3)
H12A	0.1002	0.3677	0.8274	0.027*

	U11	U22	U33	U12	U13	U23
Ni	0.01303 (11)	0.01272 (11)	0.01305 (12)	−0.00388 (8)	−0.00051 (8)	−0.00262 (8)
O1A	0.0149 (4)	0.0147 (4)	0.0160 (4)	−0.0035 (3)	−0.0011 (3)	−0.0040 (3)
O2A	0.0159 (4)	0.0184 (4)	0.0162 (5)	−0.0050 (3)	−0.0002 (3)	−0.0040 (3)
C1A	0.0162 (6)	0.0083 (5)	0.0158 (6)	−0.0020 (4)	−0.0039 (5)	0.0001 (4)
C2A	0.0148 (6)	0.0146 (5)	0.0212 (6)	−0.0012 (5)	−0.0035 (5)	−0.0036 (5)
C3A	0.0193 (6)	0.0186 (6)	0.0268 (7)	−0.0031 (5)	−0.0088 (5)	−0.0055 (5)
C4A	0.0286 (7)	0.0193 (6)	0.0191 (7)	−0.0036 (5)	−0.0097 (6)	−0.0043 (5)
C5A	0.0246 (7)	0.0174 (5)	0.0139 (6)	−0.0046 (5)	−0.0023 (5)	−0.0017 (5)
C6A	0.0177 (6)	0.0123 (5)	0.0144 (6)	−0.0040 (5)	−0.0018 (5)	−0.0011 (4)
C7A	0.0193 (6)	0.0172 (5)	0.0137 (6)	−0.0048 (5)	0.0009 (5)	−0.0012 (5)
N1B	0.0143 (5)	0.0147 (4)	0.0150 (5)	−0.0045 (4)	0.0000 (4)	−0.0032 (4)
N2B	0.0144 (5)	0.0126 (5)	0.0219 (6)	−0.0035 (4)	0.0008 (4)	0.0005 (4)
C1B	0.0155 (6)	0.0175 (5)	0.0179 (6)	−0.0059 (5)	0.0017 (5)	−0.0050 (5)
C2B	0.0139 (6)	0.0184 (5)	0.0174 (6)	−0.0010 (5)	0.0014 (5)	−0.0060 (5)
C3B	0.0207 (6)	0.0136 (5)	0.0143 (6)	−0.0016 (5)	−0.0009 (5)	−0.0036 (4)
C4B	0.0177 (6)	0.0128 (5)	0.0140 (6)	−0.0047 (5)	0.0002 (5)	−0.0016 (4)
C5B	0.0148 (5)	0.0146 (5)	0.0127 (6)	−0.0042 (4)	−0.0009 (4)	−0.0032 (4)
C6B	0.0141 (6)	0.0182 (5)	0.0197 (6)	−0.0066 (5)	0.0000 (5)	−0.0032 (5)
C7B	0.0132 (5)	0.0170 (5)	0.0188 (6)	−0.0024 (5)	0.0024 (5)	−0.0043 (5)
C8B	0.0208 (6)	0.0264 (6)	0.0209 (7)	−0.0069 (5)	0.0020 (5)	−0.0086 (5)
C9B	0.0260 (7)	0.0431 (8)	0.0207 (7)	−0.0039 (7)	−0.0005 (6)	−0.0129 (7)
C10B	0.0258 (7)	0.0380 (8)	0.0187 (7)	0.0049 (6)	0.0035 (6)	0.0006 (6)
C11B	0.0301 (8)	0.0211 (6)	0.0287 (8)	−0.0029 (6)	0.0079 (7)	0.0023 (6)
C12B	0.0216 (6)	0.0186 (6)	0.0253 (7)	−0.0058 (5)	0.0031 (6)	−0.0040 (5)

Ni—O1A	2.0052 (9)	N2B—H2BN	0.775 (17)
Ni—O1Ai	2.0052 (9)	C1B—C2B	1.3755 (17)
Ni—O2A	2.0618 (9)	C1B—H1BA	0.9500
Ni—O2Ai	2.0618 (9)	C2B—C3B	1.3920 (17)
Ni—N1Bi	2.1509 (10)	C2B—H2BA	0.9500
Ni—N1B	2.1509 (10)	C3B—C4B	1.3676 (18)
O1A—C1A	1.2923 (15)	C3B—H3BA	0.9500
O2A—C7A	1.2434 (15)	C4B—C5B	1.4184 (16)
C1A—C2A	1.4237 (17)	C4B—H4BA	0.9500
C1A—C6A	1.4384 (18)	C6B—C7B	1.5187 (19)
C2A—C3A	1.3793 (18)	C6B—H6BA	0.9900
C2A—H2AA	0.9500	C6B—H6BB	0.9900
C3A—C4A	1.406 (2)	C7B—C8B	1.3878 (18)
C3A—H3AA	0.9500	C7B—C12B	1.3950 (17)
C4A—C5A	1.3745 (19)	C8B—C9B	1.385 (2)
C4A—H4AA	0.9500	C8B—H8BA	0.9500
C5A—C6A	1.4214 (17)	C9B—C10B	1.387 (2)
C5A—H5AA	0.9500	C9B—H9BA	0.9500
C6A—C7A	1.4311 (18)	C10B—C11B	1.381 (2)
C7A—H7A	0.9500	C10B—H10A	0.9500
N1B—C1B	1.3534 (16)	C11B—C12B	1.387 (2)
N1B—C5B	1.3594 (15)	C11B—H11A	0.9500
N2B—C5B	1.3507 (16)	C12B—H12A	0.9500
N2B—C6B	1.4497 (15)
O1A—Ni—O1Ai	180.000 (1)	C5B—N2B—H2BN	114.7 (13)
O1A—Ni—O2A	90.90 (4)	C6B—N2B—H2BN	120.9 (13)
O1Ai—Ni—O2A	89.10 (4)	N1B—C1B—C2B	123.78 (11)
O1A—Ni—O2Ai	89.10 (4)	N1B—C1B—H1BA	118.1
O1Ai—Ni—O2Ai	90.90 (4)	C2B—C1B—H1BA	118.1
O2A—Ni—O2Ai	180.000 (1)	C1B—C2B—C3B	118.18 (11)
O1A—Ni—N1Bi	88.39 (4)	C1B—C2B—H2BA	120.9
O1Ai—Ni—N1Bi	91.61 (4)	C3B—C2B—H2BA	120.9
O2A—Ni—N1Bi	92.32 (4)	C4B—C3B—C2B	119.85 (11)
O2Ai—Ni—N1Bi	87.68 (4)	C4B—C3B—H3BA	120.1
O1A—Ni—N1B	91.61 (4)	C2B—C3B—H3BA	120.1
O1Ai—Ni—N1B	88.39 (4)	C3B—C4B—C5B	119.29 (11)
O2A—Ni—N1B	87.68 (4)	C3B—C4B—H4BA	120.4
O2Ai—Ni—N1B	92.32 (4)	C5B—C4B—H4BA	120.4
N1Bi—Ni—N1B	180.00 (6)	N2B—C5B—N1B	117.55 (10)
C1A—O1A—Ni	127.16 (8)	N2B—C5B—C4B	121.45 (11)
C7A—O2A—Ni	123.83 (8)	N1B—C5B—C4B	120.99 (11)
O1A—C1A—C2A	119.19 (11)	N2B—C6B—C7B	113.76 (10)
O1A—C1A—C6A	124.31 (11)	N2B—C6B—H6BA	108.8
C2A—C1A—C6A	116.50 (11)	C7B—C6B—H6BA	108.8
C3A—C2A—C1A	121.71 (12)	N2B—C6B—H6BB	108.8
C3A—C2A—H2AA	119.1	C7B—C6B—H6BB	108.8
C1A—C2A—H2AA	119.1	H6BA—C6B—H6BB	107.7
C2A—C3A—C4A	121.58 (12)	C8B—C7B—C12B	118.46 (13)
C2A—C3A—H3AA	119.2	C8B—C7B—C6B	121.46 (11)
C4A—C3A—H3AA	119.2	C12B—C7B—C6B	120.08 (12)
C5A—C4A—C3A	118.48 (12)	C9B—C8B—C7B	120.72 (13)
C5A—C4A—H4AA	120.8	C9B—C8B—H8BA	119.6
C3A—C4A—H4AA	120.8	C7B—C8B—H8BA	119.6
C4A—C5A—C6A	121.73 (12)	C8B—C9B—C10B	120.44 (14)
C4A—C5A—H5AA	119.1	C8B—C9B—H9BA	119.8
C6A—C5A—H5AA	119.1	C10B—C9B—H9BA	119.8
C5A—C6A—C7A	116.26 (12)	C11B—C10B—C9B	119.35 (15)
C5A—C6A—C1A	119.98 (11)	C11B—C10B—H10A	120.3
C7A—C6A—C1A	123.76 (12)	C9B—C10B—H10A	120.3
O2A—C7A—C6A	128.67 (12)	C10B—C11B—C12B	120.30 (13)
O2A—C7A—H7A	115.7	C10B—C11B—H11A	119.9
C6A—C7A—H7A	115.7	C12B—C11B—H11A	119.9
C1B—N1B—C5B	117.88 (10)	C11B—C12B—C7B	120.72 (13)
C1B—N1B—Ni	114.15 (8)	C11B—C12B—H12A	119.6
C5B—N1B—Ni	127.95 (8)	C7B—C12B—H12A	119.6
C5B—N2B—C6B	123.33 (10)
O2A—Ni—O1A—C1A	11.63 (9)	O1A—Ni—N1B—C5B	−37.62 (10)
O2Ai—Ni—O1A—C1A	−168.37 (9)	O1Ai—Ni—N1B—C5B	142.38 (10)
N1Bi—Ni—O1A—C1A	103.93 (9)	O2A—Ni—N1B—C5B	−128.46 (10)
N1B—Ni—O1A—C1A	−76.07 (9)	O2Ai—Ni—N1B—C5B	51.54 (10)
O1A—Ni—O2A—C7A	−11.59 (10)	C5B—N1B—C1B—C2B	−1.03 (19)
O1Ai—Ni—O2A—C7A	168.41 (10)	Ni—N1B—C1B—C2B	177.25 (10)
N1Bi—Ni—O2A—C7A	−100.02 (10)	N1B—C1B—C2B—C3B	2.3 (2)
N1B—Ni—O2A—C7A	79.98 (10)	C1B—C2B—C3B—C4B	−1.76 (19)
Ni—O1A—C1A—C2A	172.05 (8)	C2B—C3B—C4B—C5B	0.07 (19)
Ni—O1A—C1A—C6A	−7.43 (16)	C6B—N2B—C5B—N1B	−179.07 (11)
O1A—C1A—C2A—C3A	−179.07 (11)	C6B—N2B—C5B—C4B	0.13 (19)
C6A—C1A—C2A—C3A	0.45 (18)	C1B—N1B—C5B—N2B	178.42 (12)
C1A—C2A—C3A—C4A	0.5 (2)	Ni—N1B—C5B—N2B	0.40 (16)
C2A—C3A—C4A—C5A	−0.71 (19)	C1B—N1B—C5B—C4B	−0.78 (17)
C3A—C4A—C5A—C6A	−0.05 (19)	Ni—N1B—C5B—C4B	−178.80 (9)
C4A—C5A—C6A—C7A	−179.21 (12)	C3B—C4B—C5B—N2B	−177.92 (12)
C4A—C5A—C6A—C1A	1.01 (19)	C3B—C4B—C5B—N1B	1.25 (18)
O1A—C1A—C6A—C5A	178.32 (10)	C5B—N2B—C6B—C7B	63.67 (16)
C2A—C1A—C6A—C5A	−1.18 (17)	N2B—C6B—C7B—C8B	34.66 (16)
O1A—C1A—C6A—C7A	−1.45 (19)	N2B—C6B—C7B—C12B	−144.86 (12)
C2A—C1A—C6A—C7A	179.06 (11)	C12B—C7B—C8B—C9B	0.0 (2)
Ni—O2A—C7A—C6A	7.87 (18)	C6B—C7B—C8B—C9B	−179.53 (12)
C5A—C6A—C7A—O2A	−178.85 (12)	C7B—C8B—C9B—C10B	0.6 (2)
C1A—C6A—C7A—O2A	0.9 (2)	C8B—C9B—C10B—C11B	−1.0 (2)
O1A—Ni—N1B—C1B	144.30 (9)	C9B—C10B—C11B—C12B	0.9 (2)
O1Ai—Ni—N1B—C1B	−35.70 (9)	C10B—C11B—C12B—C7B	−0.4 (2)
O2A—Ni—N1B—C1B	53.46 (9)	C8B—C7B—C12B—C11B	−0.1 (2)
O2Ai—Ni—N1B—C1B	−126.54 (9)	C6B—C7B—C12B—C11B	179.45 (12)

Cg4 is the centroid of the C1A–C6A ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2B—H2BN···O1A	0.775 (17)	2.147 (18)	2.8550 (14)	152.0 (17)
C1B—H1BA···O1Ai	0.95	2.42	2.9216 (14)	113
C3B—H3BA···Cg4ii	0.95	2.44	3.3674 (14)	166
C11B—H11A···Cg4iii	0.95	2.91	3.7535 (17)	148

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C1A–C6A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2B—H2BN⋯O1A	0.775 (17)	2.147 (18)	2.8550 (14)	152.0 (17)
C1B—H1BA⋯O1Ai	0.95	2.42	2.9216 (14)	113
C3B—H3BA⋯Cg4ii	0.95	2.44	3.3674 (14)	166
C11B—H11A⋯Cg4iii	0.95	2.91	3.7535 (17)	148

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