Bis(5-methyl­pyrazine-2-carboxyl­ato-κ2N,O)nickel(II)

Shi, Q.-Y.; Zhang, G.-C.; Zhou, C.-S.; Yang, Q.

doi:10.1107/S1600536812024749

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m919

https://doi.org/10.1107/S1600536812024749

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Bis(5-methylpyrazine-2-carboxylato-κ²N,O)nickel(II)

Qi-Ying Shi,^a Guo-Chun Zhang,^a,^b Chun-Sheng Zhou ^a and Qi Yang ^b ^*

^aDepartment of Chemistry and Chemical Engineering, Shangluo University, Shangluo 726000, Shaanxi, People's Republic of China, and ^bCollege of Chemistry and Materials Science, Northwest University, Xi'an 710069, Shaanxi, People's Republic of China
^*Correspondence e-mail: ken730@126.com

(Received 23 May 2012; accepted 30 May 2012; online 16 June 2012)

In the title complex, [Ni(C₆H₅O₂N₂)₂], the Ni^II atom is situated on an inversion centre and is coordinated in a square-planar geometry by four O atoms and two N atoms of the chelating ligands.

Related literature

For applications of complexes derived from 2-methylpyrazine-5-carboxylic acid, see: Chapman et al. (2002 ); Ptasiewicz-Bak & Leciejewicz (2000 ); Tanase et al. (2006 ); Wang et al. (2008 ) For a related structure, see: Liu et al. (2007 ).

Experimental

Crystal data

[Ni(C₆H₅N₂O₂)₂]
M_r = 332.95
Monoclinic, P 2₁ /c
a = 11.3098 (19) Å
b = 7.6721 (11) Å
c = 7.5467 (10) Å
β = 105.647 (2)°
V = 630.56 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.56 mm⁻¹
T = 298 K
0.42 × 0.31 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.560, T_max = 0.756
2875 measured reflections
1105 independent reflections
827 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.176
S = 1.03
1105 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −1.37 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: https://doi.org/10.1107/S1600536812024749/ru2036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024749/ru2036Isup2.hkl

checkCIF report

Comment top

Since the mononuclear complex [Cu(mpca)₂(H₂O)3H₂O](Hmpca = 2-methylpyrazine-5-carboxylic acid) was reported by Leciejewicz, many complexes based on the Hmpca have been prepared. The complex of Hmpca have been extensively investigated and have often been considered for practical use as a class of functional materials. In this paper, we report on the synthesis and characterization of [Ni(mpca)₂]_n.

Single-crystal analysis shows the complex crystallizes in monoclinic space group P2₁/c and exists as a two-dimensional geometry. As shown in Figure 1, Ni1 is four-coordinated by two oxygen atoms and two nitrogen atoms from two mpca^- ligands, displaying a square planar coordination geometry with Ni1—O1 = 1.947 (3) Å and Ni1—N1 = 1.977 (4) Å. The weak coordiantion between Ni1 and O2, which from the adjacent mpca^- igand, result in the formation of a distorted octahedral geometry for nickle atom (Ni1—O2=2.509 (2) Å). Then the complex is further extend into a two-dimensional layer structure, see Figure 2.

Related literature top

For applications of 2-methylpyrazine-5-carboxylic acid complexes, see: Chapman et al. (2002); Ptasiewicz-Bak & Leciejewicz (2000); Tanase et al. (2006); Wang et al. (2008) For a related structure, see: Liu et al. (2007).

Experimental top

A mixture of NiCl₂.6H₂O (0.238 g, 1 mmol), Hmpca (0.304 g, 1 mmol) and distilled H₂O (6 ml) was sealed in a 15 ml Teflon-lined stainless steel vessel, which was heated at 120°C for 3 days and then cooled to room temperature at a rate of 5°C/h. Red crystals were obtained, washed with ethanol (yield 43% based on Ni).

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 the molecular structure of (I) with the atom-labling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Two dimensional layer sructure of (I)

Bis(5-methylpyrazine-2-carboxylato-κ²N,O)nickel(II) top

Crystal data top

[Ni(C₆H₅N₂O₂)₂]	F(000) = 340
M_r = 332.95	D_x = 1.754 Mg m⁻³ D_m = 1.754 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2220 reflections
a = 11.3098 (19) Å	θ = 1.3–24.1°
b = 7.6721 (11) Å	µ = 1.56 mm⁻¹
c = 7.5467 (10) Å	T = 298 K
β = 105.647 (2)°	Block, green
V = 630.56 (16) Å³	0.42 × 0.31 × 0.19 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1105 independent reflections
Radiation source: fine-focus sealed tube	827 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
φ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→10
T_min = 0.560, T_max = 0.756	k = −9→6
2875 measured reflections	l = −8→8

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.121P)² + 0.167P] where P = (F_o² + 2F_c²)/3
1105 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 1.34 e Å⁻³
0 restraints	Δρ_min = −1.37 e Å⁻³

Crystal data top

[Ni(C₆H₅N₂O₂)₂]	V = 630.56 (16) Å³
M_r = 332.95	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.3098 (19) Å	µ = 1.56 mm⁻¹
b = 7.6721 (11) Å	T = 298 K
c = 7.5467 (10) Å	0.42 × 0.31 × 0.19 mm
β = 105.647 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1105 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	827 reflections with I > 2σ(I)
T_min = 0.560, T_max = 0.756	R_int = 0.057
2875 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.03	Δρ_max = 1.34 e Å⁻³
1105 reflections	Δρ_min = −1.37 e Å⁻³
97 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	0.5000	0.5000	0.5000	0.0317 (4)
N1	0.3510 (4)	0.4618 (5)	0.5844 (6)	0.0312 (10)
N2	0.1370 (5)	0.4682 (6)	0.6946 (7)	0.0475 (13)
O1	0.4846 (3)	0.7385 (4)	0.5791 (5)	0.0412 (9)
O2	0.3624 (4)	0.9088 (5)	0.6943 (5)	0.0485 (10)
C1	0.3918 (5)	0.7680 (7)	0.6395 (7)	0.0355 (12)
C2	0.3114 (5)	0.6106 (6)	0.6398 (6)	0.0342 (12)
C3	0.2062 (5)	0.6111 (7)	0.6967 (8)	0.0463 (14)
H3	0.1814	0.7151	0.7389	0.056*
C4	0.2869 (4)	0.3151 (7)	0.5865 (7)	0.0360 (12)
H4	0.3148	0.2096	0.5523	0.043*
C5	0.1780 (5)	0.3214 (7)	0.6401 (7)	0.0404 (13)
C6	0.1017 (5)	0.1600 (8)	0.6309 (8)	0.0529 (15)
H6A	0.0434	0.1771	0.7011	0.079*
H6B	0.1541	0.0633	0.6806	0.079*
H6C	0.0588	0.1362	0.5051	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0421 (6)	0.0079 (5)	0.0502 (7)	−0.0023 (3)	0.0210 (4)	−0.0035 (3)
N1	0.039 (2)	0.016 (2)	0.040 (2)	−0.0016 (17)	0.0133 (18)	0.0004 (16)
N2	0.052 (3)	0.033 (3)	0.062 (3)	−0.003 (2)	0.023 (2)	−0.005 (2)
O1	0.053 (2)	0.0154 (18)	0.059 (2)	−0.0040 (16)	0.0209 (18)	−0.0051 (17)
O2	0.067 (2)	0.014 (2)	0.068 (3)	0.0046 (18)	0.0242 (19)	−0.0060 (17)
C1	0.048 (3)	0.016 (3)	0.041 (3)	0.000 (2)	0.010 (2)	−0.001 (2)
C2	0.046 (3)	0.019 (3)	0.039 (3)	0.001 (2)	0.013 (2)	−0.004 (2)
C3	0.059 (4)	0.026 (3)	0.061 (3)	0.004 (2)	0.027 (3)	−0.007 (2)
C4	0.044 (3)	0.016 (3)	0.048 (3)	−0.001 (2)	0.012 (2)	−0.002 (2)
C5	0.050 (3)	0.030 (3)	0.044 (3)	−0.007 (2)	0.018 (2)	0.001 (2)
C6	0.058 (3)	0.037 (3)	0.067 (4)	−0.015 (3)	0.022 (3)	−0.003 (3)

Geometric parameters (Å, º) top

Ni1—O1	1.947 (3)	C1—C2	1.512 (7)
Ni1—O1ⁱ	1.947 (3)	C2—C3	1.370 (7)
Ni1—N1	1.977 (4)	C3—H3	0.9300
Ni1—N1ⁱ	1.977 (4)	C4—C5	1.397 (7)
N1—C2	1.335 (6)	C4—H4	0.9300
N1—C4	1.341 (6)	C5—C6	1.501 (7)
N2—C5	1.325 (7)	C6—H6A	0.9600
N2—C3	1.345 (7)	C6—H6B	0.9600
O1—C1	1.272 (6)	C6—H6C	0.9600
O2—C1	1.233 (6)

O1—Ni1—O1ⁱ	180.000 (1)	C3—C2—C1	124.9 (5)
O1—Ni1—N1	83.45 (16)	N2—C3—C2	123.1 (5)
O1ⁱ—Ni1—N1	96.55 (16)	N2—C3—H3	118.5
O1—Ni1—N1ⁱ	96.55 (16)	C2—C3—H3	118.5
O1ⁱ—Ni1—N1ⁱ	83.45 (16)	N1—C4—C5	119.7 (5)
N1—Ni1—N1ⁱ	180.0	N1—C4—H4	120.1
C2—N1—C4	119.1 (4)	C5—C4—H4	120.1
C2—N1—Ni1	111.2 (3)	N2—C5—C4	122.0 (5)
C4—N1—Ni1	129.7 (4)	N2—C5—C6	118.1 (5)
C5—N2—C3	116.4 (5)	C4—C5—C6	119.9 (5)
C1—O1—Ni1	115.3 (3)	C5—C6—H6A	109.5
O2—C1—O1	126.8 (5)	C5—C6—H6B	109.5
O2—C1—C2	118.9 (4)	H6A—C6—H6B	109.5
O1—C1—C2	114.4 (4)	C5—C6—H6C	109.5
N1—C2—C3	119.6 (5)	H6A—C6—H6C	109.5
N1—C2—C1	115.5 (4)	H6B—C6—H6C	109.5

O1—Ni1—N1—C2	3.6 (3)	Ni1—N1—C2—C1	−4.3 (5)
O1ⁱ—Ni1—N1—C2	−176.4 (3)	O2—C1—C2—N1	−177.9 (4)
N1ⁱ—Ni1—N1—C2	−75 (100)	O1—C1—C2—N1	2.7 (6)
O1—Ni1—N1—C4	−178.8 (5)	O2—C1—C2—C3	0.1 (8)
O1ⁱ—Ni1—N1—C4	1.2 (5)	O1—C1—C2—C3	−179.3 (5)
N1ⁱ—Ni1—N1—C4	102 (100)	C5—N2—C3—C2	2.5 (9)
O1ⁱ—Ni1—O1—C1	−153 (100)	N1—C2—C3—N2	−2.2 (9)
N1—Ni1—O1—C1	−2.3 (3)	C1—C2—C3—N2	179.9 (5)
N1ⁱ—Ni1—O1—C1	177.7 (3)	C2—N1—C4—C5	2.2 (7)
Ni1—O1—C1—O2	−178.9 (4)	Ni1—N1—C4—C5	−175.2 (3)
Ni1—O1—C1—C2	0.5 (5)	C3—N2—C5—C4	−0.4 (8)
C4—N1—C2—C3	−0.3 (7)	C3—N2—C5—C6	−178.4 (5)
Ni1—N1—C2—C3	177.6 (4)	N1—C4—C5—N2	−1.9 (8)
C4—N1—C2—C1	177.8 (4)	N1—C4—C5—C6	176.0 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₅N₂O₂)₂]
M_r	332.95
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.3098 (19), 7.6721 (11), 7.5467 (10)
β (°)	105.647 (2)
V (Å³)	630.56 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.56
Crystal size (mm)	0.42 × 0.31 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.560, 0.756
No. of measured, independent and observed [I > 2σ(I)] reflections	2875, 1105, 827
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.176, 1.03
No. of reflections	1105
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.34, −1.37

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

We gratefully acknowledge the Scientific Research Program Funded by Shaanxi Provincial Education Department (Nos. 11 J K0578 and 2010 J K882), the Natural Science Foundation of Shaanxi Province (No. 2010JQ2007) and the Open Foundation of the Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education.

References

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