Bis(1H-imidazole-κN)bis-(2-oxidopyridinium-3-carboxyl-ato-κO,O)nickel(II).

In the crystal structure of the title Ni(II) complex, [Ni(C(6)H(4)NO(3))(2)(C(3)H(4)N(2))(2)], the Ni(II) atom is located on a twofold rotation axis and is chelated by two oxidopyridiniumcarboxyl-ate anions and further cis-coordinated by two imidazole ligands in a distorted cis-N(2)O(4) octa-hedral geometry. The C-O bond distance of 1.2573 (19) Å found for the non-coordinating O atom of the carboxyl-ate group indicates significant delocalization of π-electron density over this residue. Similarly, the C-O bond distance of 1.260 (2) Å in the heteroaromatic ring indicates delocalization between the deprotonated hydr-oxy group and the pyridinium ring. The uncoordinated carboxyl-ate O atom links with the imidazole and pyridinium rings of adjacent mol-ecules via N-H⋯O and C-H⋯O hydrogen bonding, leading to a two-dimensional array parallel to (100).

Related literature

For the nature of π-π stacking, see: Deisenhofer & Michel (1989 ▶); Xu et al. (2007 ▶); Li et al. (2005 ▶). For the short C—O bond distance between a pyridine ring and hydr­oxy-O atom in metal complexes of 2-oxidopyridinium-3-carboxyl­ate, see: Yao et al. (2004 ▶); Yan & Hu (2007a ▶,b ▶); Wen & Liu (2007 ▶).

Experimental

Crystal data

[Ni(C6H4NO3)2(C3H4N2)2]

M = 471.08

Monoclinic,

a = 16.5603 (12) Å

b = 9.9687 (7) Å

c = 12.7981 (9) Å

β = 111.203 (2)°

V = 1969.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 1.04 mm−1

T = 294 K

0.28 × 0.22 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.730, T max = 0.830

10787 measured reflections

1934 independent reflections

1690 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.067

S = 1.09

1934 reflections

141 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.23 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028347/tk2499sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028347/tk2499Isup2.hkl

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

[Ni(C6H4NO3)2(C3H4N2)2]	F(000) = 968
Mr = 471.08	Dx = 1.589 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3268 reflections
a = 16.5603 (12) Å	θ = 2.5–25.0°
b = 9.9687 (7) Å	µ = 1.04 mm−1
c = 12.7981 (9) Å	T = 294 K
β = 111.203 (2)°	Block, green
V = 1969.7 (2) Å3	0.28 × 0.22 × 0.18 mm
Z = 4

Rigaku R-AXIS RAPID IP diffractometer	1934 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 10.00 pixels mm-1	θmax = 26.0°, θmin = 2.4°
ω scans	h = −20→20
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→12
Tmin = 0.730, Tmax = 0.830	l = −15→15
10787 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0299P)2 + 1.5451P] where P = (Fo2 + 2Fc2)/3
1934 reflections	(Δ/σ)max = 0.001
141 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.23 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	0.24819 (3)	0.2500	0.02609 (11)
N1	0.61183 (10)	−0.12600 (15)	0.30054 (12)	0.0340 (4)
H1	0.6130	−0.1389	0.2346	0.041*
N2	0.58315 (9)	0.39012 (14)	0.22850 (12)	0.0307 (3)
N3	0.62487 (11)	0.55962 (16)	0.15138 (14)	0.0413 (4)
H3	0.6224	0.6275	0.1088	0.050*
O1	0.55981 (9)	0.25034 (11)	0.42031 (10)	0.0345 (3)
O2	0.62229 (8)	0.17047 (12)	0.59099 (9)	0.0370 (3)
O3	0.58766 (8)	0.09254 (12)	0.25646 (9)	0.0320 (3)
C1	0.59865 (11)	0.00219 (17)	0.32922 (13)	0.0269 (4)
C2	0.60022 (10)	0.01871 (17)	0.44182 (13)	0.0270 (4)
C3	0.61083 (12)	−0.09161 (18)	0.50917 (14)	0.0347 (4)
H3A	0.6108	−0.0806	0.5813	0.042*
C4	0.62173 (15)	−0.22061 (19)	0.47285 (16)	0.0429 (5)
H4	0.6278	−0.2947	0.5192	0.051*
C5	0.62318 (15)	−0.23420 (18)	0.36860 (17)	0.0418 (5)
H5	0.6320	−0.3184	0.3433	0.050*
C6	0.59302 (11)	0.15609 (17)	0.48631 (13)	0.0273 (4)
C7	0.55757 (13)	0.48832 (18)	0.15514 (15)	0.0362 (4)
H7	0.5001	0.5059	0.1115	0.043*
C8	0.67175 (12)	0.4006 (2)	0.27398 (16)	0.0404 (4)
H8	0.7082	0.3442	0.3287	0.049*
C9	0.69804 (13)	0.5053 (2)	0.22712 (18)	0.0456 (5)
H9	0.7547	0.5343	0.2434	0.055*

	U11	U22	U33	U12	U13	U23
Ni	0.03550 (19)	0.02420 (17)	0.01909 (17)	0.000	0.01048 (13)	0.000
N1	0.0520 (9)	0.0317 (8)	0.0228 (7)	0.0040 (7)	0.0192 (7)	−0.0015 (6)
N2	0.0348 (8)	0.0290 (8)	0.0276 (7)	−0.0003 (6)	0.0106 (6)	0.0026 (6)
N3	0.0577 (11)	0.0309 (8)	0.0428 (9)	−0.0040 (7)	0.0272 (8)	0.0049 (7)
O1	0.0514 (8)	0.0281 (6)	0.0213 (6)	0.0057 (5)	0.0098 (6)	0.0002 (5)
O2	0.0551 (8)	0.0371 (7)	0.0175 (6)	0.0040 (6)	0.0117 (5)	−0.0025 (5)
O3	0.0475 (7)	0.0306 (6)	0.0229 (6)	0.0056 (5)	0.0190 (5)	0.0040 (5)
C1	0.0297 (8)	0.0290 (9)	0.0234 (8)	0.0004 (7)	0.0114 (7)	−0.0011 (7)
C2	0.0313 (9)	0.0301 (9)	0.0207 (8)	0.0008 (7)	0.0109 (7)	−0.0010 (7)
C3	0.0479 (11)	0.0357 (10)	0.0230 (9)	0.0020 (8)	0.0156 (8)	0.0016 (7)
C4	0.0682 (14)	0.0303 (10)	0.0339 (10)	0.0057 (9)	0.0229 (10)	0.0069 (8)
C5	0.0647 (14)	0.0268 (10)	0.0370 (11)	0.0057 (9)	0.0222 (10)	−0.0012 (8)
C6	0.0309 (9)	0.0317 (9)	0.0220 (8)	−0.0007 (7)	0.0127 (7)	−0.0021 (7)
C7	0.0415 (10)	0.0335 (10)	0.0335 (10)	−0.0003 (8)	0.0134 (8)	0.0034 (8)
C8	0.0371 (10)	0.0394 (11)	0.0419 (11)	0.0031 (8)	0.0108 (8)	0.0026 (8)
C9	0.0393 (11)	0.0432 (11)	0.0589 (13)	−0.0039 (9)	0.0233 (10)	−0.0059 (10)

Ni—O1i	2.0422 (12)	O2—C6	1.2573 (19)
Ni—O1	2.0422 (12)	O3—C1	1.260 (2)
Ni—O3i	2.1059 (12)	C1—C2	1.441 (2)
Ni—O3	2.1058 (12)	C2—C3	1.369 (2)
Ni—N2	2.0610 (14)	C2—C6	1.504 (2)
Ni—N2i	2.0610 (14)	C3—C4	1.401 (3)
N1—C5	1.356 (2)	C3—H3A	0.9300
N1—C1	1.369 (2)	C4—C5	1.350 (3)
N1—H1	0.8600	C4—H4	0.9300
N2—C7	1.316 (2)	C5—H5	0.9300
N2—C8	1.373 (2)	C7—H7	0.9300
N3—C7	1.337 (2)	C8—C9	1.352 (3)
N3—C9	1.361 (3)	C8—H8	0.9300
N3—H3	0.8600	C9—H9	0.9300
O1—C6	1.250 (2)
O1i—Ni—O1	178.80 (6)	O3—C1—C2	127.05 (15)
O1i—Ni—N2	86.55 (5)	N1—C1—C2	115.33 (14)
O1—Ni—N2	92.62 (5)	C3—C2—C1	119.31 (15)
O1i—Ni—N2i	92.62 (5)	C3—C2—C6	120.19 (14)
O1—Ni—N2i	86.55 (5)	C1—C2—C6	120.47 (14)
N2—Ni—N2i	93.29 (8)	C2—C3—C4	122.08 (16)
O1i—Ni—O3i	84.52 (5)	C2—C3—H3A	119.0
O1—Ni—O3i	96.37 (5)	C4—C3—H3A	119.0
N2—Ni—O3i	170.03 (5)	C5—C4—C3	118.07 (17)
N2i—Ni—O3i	91.53 (5)	C5—C4—H4	121.0
O1i—Ni—O3	96.37 (5)	C3—C4—H4	121.0
O1—Ni—O3	84.52 (5)	C4—C5—N1	120.47 (17)
N2—Ni—O3	91.53 (5)	C4—C5—H5	119.8
N2i—Ni—O3	170.03 (5)	N1—C5—H5	119.8
O3i—Ni—O3	85.08 (7)	O1—C6—O2	122.70 (15)
C5—N1—C1	124.68 (15)	O1—C6—C2	120.28 (14)
C5—N1—H1	117.7	O2—C6—C2	117.02 (15)
C1—N1—H1	117.7	N2—C7—N3	111.32 (17)
C7—N2—C8	105.36 (15)	N2—C7—H7	124.3
C7—N2—Ni	123.21 (12)	N3—C7—H7	124.3
C8—N2—Ni	131.20 (12)	C9—C8—N2	109.68 (17)
C7—N3—C9	107.57 (16)	C9—C8—H8	125.2
C7—N3—H3	126.2	N2—C8—H8	125.2
C9—N3—H3	126.2	C8—C9—N3	106.06 (17)
C6—O1—Ni	129.67 (11)	C8—C9—H9	127.0
C1—O3—Ni	117.96 (10)	N3—C9—H9	127.0
O3—C1—N1	117.62 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ii	0.86	1.93	2.7848 (19)	177
N3—H3···O2iii	0.86	2.03	2.796 (2)	148
C3—H3A···O3iv	0.93	2.41	3.323 (2)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	1.93	2.7848 (19)	177
N3—H3⋯O2ii	0.86	2.03	2.796 (2)	148
C3—H3A⋯O3iii	0.93	2.41	3.323 (2)	167

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