Bis(1H-imidazole-κN3)bis­(2-oxidopyridinium-3-carboxyl­ato-κ2O2,O3)nickel(II)

Zhang, B.-Y.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536809028347

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m977

doi:10.1107/S1600536809028347

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Bis(1H-imidazole-κN³)bis(2-oxidopyridinium-3-carboxylato-κ²O²,O³)nickel(II)

Bing-Yu Zhang,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 14 July 2009; accepted 17 July 2009; online 22 July 2009)

In the crystal structure of the title Ni^II complex, [Ni(C₆H₄NO₃)₂(C₃H₄N₂)₂], the Ni^II atom is located on a twofold rotation axis and is chelated by two oxidopyridiniumcarboxylate anions and further cis-coordinated by two imidazole ligands in a distorted cis-N₂O₄ octahedral geometry. The C—O bond distance of 1.2573 (19) Å found for the non-coordinating O atom of the carboxylate 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 hydroxy group and the pyridinium ring. The uncoordinated carboxylate O atom links with the imidazole and pyridinium rings of adjacent molecules 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_r = 471.08
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.067
S = 1.09
1934 reflections
141 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x, -y, z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

As π-π stacking between aromatic rings is correlated with electron transfer process in some biological systems (Deisenhofer & Michel, 1989), metal complexes incorporating aromatic ligands have attracted much attention. As a part of an on-going investigation of π-π stacking (Xu et al., 2007a, b; Li et al., 2005), the title complex, (I), has been prepared and its crystal structure reported herein.

The analysis of (I) shows the Ni atom to be located on a 2-fold axis and to be chelated by two oxidopyridinium-carboxylate anions and two cis-orientated imidazole ligands to complete a distorted octahedral coordination geometry (Fig. 1). The carboxylate group is twisted with respect to the benzene ring with a dihedral angle of 22.09 (11)°. The C1—O3 bond distance of 1.260 (2) Å is much shorter than a normal single C—O bond, indicating delocalization of π-electron density over the deprotonated hydroxy group and the pyridinium ring, an observation which agrees with similiar features found in the other transition metal complexes of oxidopyridinium-carboxylate (Yao et al., 2004; Yan & Hu, 2007a,b; Wen & Liu, 2007).

The uncoordinated carboxyl-O atom simutaneously links the imidazole and pyridinium rings via N—H···O hydrogen bonding leading to a 2-D array (Table 2). Weak C—H···O hydrogen bonding is also present in the crystal structure but no π-π stacking is evident.

Related literature top

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 top

2-Hydroxy-pyridine-3-carboxylic acid (0.13 g, 1 mmol), NaOH (0.04 g, 1 mmol), imidazole (0.14 g, 2 mmol) and NiCl₂.6H₂O (0.24 g, 1 mmol) were dissolved in water (15 ml). The solution was refluxed for 4.5 h. After cooling to room temperature, the solution was filtered. Single crystals of (I) were obtained from the filtrate after one week.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); 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).

Figures top

Fig. 1. The molecular structure of (I) showing 40% probability displacement ellipsoids (arbitrary spheres for H atoms) [symmetry code: (i) 1 - x, y, 1/2 - z].

Bis(1H-imidazole-κN³)bis(2-oxidopyridinium-3-carboxylato- κ²O²,O³)nickel(II) top

Crystal data top

[Ni(C₆H₄NO₃)₂(C₃H₄N₂)₂]	F(000) = 968
M_r = 471.08	D_x = 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

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1934 independent reflections
Radiation source: fine-focus sealed tube	1690 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.00 pixels mm^-1	θ_max = 26.0°, θ_min = 2.4°
ω scans	h = −20→20
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→12
T_min = 0.730, T_max = 0.830	l = −15→15
10787 measured reflections

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0299P)² + 1.5451P] where P = (F_o² + 2F_c²)/3
1934 reflections	(Δ/σ)_max = 0.001
141 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Ni(C₆H₄NO₃)₂(C₃H₄N₂)₂]	V = 1969.7 (2) Å³
M_r = 471.08	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.5603 (12) Å	µ = 1.04 mm⁻¹
b = 9.9687 (7) Å	T = 294 K
c = 12.7981 (9) Å	0.28 × 0.22 × 0.18 mm
β = 111.203 (2)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1934 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1690 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.830	R_int = 0.026
10787 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.09	Δρ_max = 0.26 e Å⁻³
1934 reflections	Δρ_min = −0.23 e Å⁻³
141 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
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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···O3^iv	0.93	2.41	3.323 (2)	167

Symmetry codes: (ii) x, −y, z−1/2; (iii) x, −y+1, z−1/2; (iv) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₄NO₃)₂(C₃H₄N₂)₂]
M_r	471.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	16.5603 (12), 9.9687 (7), 12.7981 (9)
β (°)	111.203 (2)
V (Å³)	1969.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.28 × 0.22 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.730, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	10787, 1934, 1690
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.067, 1.09
No. of reflections	1934
No. of parameters	141
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) x, −y, z−1/2; (ii) x, −y+1, z−1/2; (iii) x, −y, z+1/2.

Acknowledgements

The project was supported by the ZIJIN project of Zhejiang University, China.

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