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ISSN: 2056-9890

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

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 NiII 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[Chapman, C. T., Ciurtin, D. M., Smith, M. D. & Loye zur, H. C. (2002). Solid State Sci. 4, 1187-1189.]); Ptasiewicz-Bak & Leciejewicz (2000[Ptasiewicz-Bak, H. & Leciejewicz, J. (2000). Pol. J. Chem. 74, 877-883.]); Tanase et al. (2006[Tanase, S., Martin, V. S., Van Albada, G. A., DeGelder, R., Bouwman, E. & Reedijk, J. (2006). Polyhedron, 25, 2967-2975.]); Wang et al. (2008[Wang, F. Q., Mu, W. H., Zheng, X. J., Li, L. C., Fang, D. C. & Jin, L. P. (2008). Inorg. Chem. 47, 5225-5233.]) For a related structure, see: Liu et al. (2007[Liu, F.-Y., Shang, R.-L., Du, L., Zhao, Q.-H. & Fang, R.-B. (2007). Acta Cryst. E63, m120-m122.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni(C6H5N2O2)2]

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.560, Tmax = 0.756

  • 2875 measured reflections

  • 1105 independent reflections

  • 827 reflections with I > 2σ(I)

  • Rint = 0.057

Refinement
  • R[F2 > 2σ(F2)] = 0.062

  • wR(F2) = 0.176

  • S = 1.03

  • 1105 reflections

  • 97 parameters

  • H-atom parameters constrained

  • Δρmax = 1.34 e Å−3

  • Δρmin = −1.37 e Å−3

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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).

Refinement top

The H atoms of C atoms were positioned geometrically and refined with a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The water H atoms were located in difference Fourier maps, and were refined with distance restraints of O—H = 0.85±0.02 Å and H···H = 1.39±0.02 Å.

Structure description 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.

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).

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
[Figure 1] 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.
[Figure 2] 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
Mr = 332.95Dx = 1.754 Mg m3
Dm = 1.754 Mg m3
Dm measured by not measured
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2220 reflections
a = 11.3098 (19) Åθ = 1.3–24.1°
b = 7.6721 (11) ŵ = 1.56 mm1
c = 7.5467 (10) ÅT = 298 K
β = 105.647 (2)°Block, green
V = 630.56 (16) Å30.42 × 0.31 × 0.19 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
1105 independent reflections
Radiation source: fine-focus sealed tube827 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1310
Tmin = 0.560, Tmax = 0.756k = 96
2875 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.121P)2 + 0.167P]
where P = (Fo2 + 2Fc2)/3
1105 reflections(Δ/σ)max < 0.001
97 parametersΔρmax = 1.34 e Å3
0 restraintsΔρmin = 1.37 e Å3
Crystal data top
[Ni(C6H5N2O2)2]V = 630.56 (16) Å3
Mr = 332.95Z = 2
Monoclinic, P21/cMo Kα radiation
a = 11.3098 (19) ŵ = 1.56 mm1
b = 7.6721 (11) ÅT = 298 K
c = 7.5467 (10) Å0.42 × 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)
Tmin = 0.560, Tmax = 0.756Rint = 0.057
2875 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0620 restraints
wR(F2) = 0.176H-atom parameters constrained
S = 1.03Δρmax = 1.34 e Å3
1105 reflectionsΔρmin = 1.37 e Å3
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
xyzUiso*/Ueq
Ni10.50000.50000.50000.0317 (4)
N10.3510 (4)0.4618 (5)0.5844 (6)0.0312 (10)
N20.1370 (5)0.4682 (6)0.6946 (7)0.0475 (13)
O10.4846 (3)0.7385 (4)0.5791 (5)0.0412 (9)
O20.3624 (4)0.9088 (5)0.6943 (5)0.0485 (10)
C10.3918 (5)0.7680 (7)0.6395 (7)0.0355 (12)
C20.3114 (5)0.6106 (6)0.6398 (6)0.0342 (12)
C30.2062 (5)0.6111 (7)0.6967 (8)0.0463 (14)
H30.18140.71510.73890.056*
C40.2869 (4)0.3151 (7)0.5865 (7)0.0360 (12)
H40.31480.20960.55230.043*
C50.1780 (5)0.3214 (7)0.6401 (7)0.0404 (13)
C60.1017 (5)0.1600 (8)0.6309 (8)0.0529 (15)
H6A0.04340.17710.70110.079*
H6B0.15410.06330.68060.079*
H6C0.05880.13620.50510.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0421 (6)0.0079 (5)0.0502 (7)0.0023 (3)0.0210 (4)0.0035 (3)
N10.039 (2)0.016 (2)0.040 (2)0.0016 (17)0.0133 (18)0.0004 (16)
N20.052 (3)0.033 (3)0.062 (3)0.003 (2)0.023 (2)0.005 (2)
O10.053 (2)0.0154 (18)0.059 (2)0.0040 (16)0.0209 (18)0.0051 (17)
O20.067 (2)0.014 (2)0.068 (3)0.0046 (18)0.0242 (19)0.0060 (17)
C10.048 (3)0.016 (3)0.041 (3)0.000 (2)0.010 (2)0.001 (2)
C20.046 (3)0.019 (3)0.039 (3)0.001 (2)0.013 (2)0.004 (2)
C30.059 (4)0.026 (3)0.061 (3)0.004 (2)0.027 (3)0.007 (2)
C40.044 (3)0.016 (3)0.048 (3)0.001 (2)0.012 (2)0.002 (2)
C50.050 (3)0.030 (3)0.044 (3)0.007 (2)0.018 (2)0.001 (2)
C60.058 (3)0.037 (3)0.067 (4)0.015 (3)0.022 (3)0.003 (3)
Geometric parameters (Å, º) top
Ni1—O11.947 (3)C1—C21.512 (7)
Ni1—O1i1.947 (3)C2—C31.370 (7)
Ni1—N11.977 (4)C3—H30.9300
Ni1—N1i1.977 (4)C4—C51.397 (7)
N1—C21.335 (6)C4—H40.9300
N1—C41.341 (6)C5—C61.501 (7)
N2—C51.325 (7)C6—H6A0.9600
N2—C31.345 (7)C6—H6B0.9600
O1—C11.272 (6)C6—H6C0.9600
O2—C11.233 (6)
O1—Ni1—O1i180.000 (1)C3—C2—C1124.9 (5)
O1—Ni1—N183.45 (16)N2—C3—C2123.1 (5)
O1i—Ni1—N196.55 (16)N2—C3—H3118.5
O1—Ni1—N1i96.55 (16)C2—C3—H3118.5
O1i—Ni1—N1i83.45 (16)N1—C4—C5119.7 (5)
N1—Ni1—N1i180.0N1—C4—H4120.1
C2—N1—C4119.1 (4)C5—C4—H4120.1
C2—N1—Ni1111.2 (3)N2—C5—C4122.0 (5)
C4—N1—Ni1129.7 (4)N2—C5—C6118.1 (5)
C5—N2—C3116.4 (5)C4—C5—C6119.9 (5)
C1—O1—Ni1115.3 (3)C5—C6—H6A109.5
O2—C1—O1126.8 (5)C5—C6—H6B109.5
O2—C1—C2118.9 (4)H6A—C6—H6B109.5
O1—C1—C2114.4 (4)C5—C6—H6C109.5
N1—C2—C3119.6 (5)H6A—C6—H6C109.5
N1—C2—C1115.5 (4)H6B—C6—H6C109.5
O1—Ni1—N1—C23.6 (3)Ni1—N1—C2—C14.3 (5)
O1i—Ni1—N1—C2176.4 (3)O2—C1—C2—N1177.9 (4)
N1i—Ni1—N1—C275 (100)O1—C1—C2—N12.7 (6)
O1—Ni1—N1—C4178.8 (5)O2—C1—C2—C30.1 (8)
O1i—Ni1—N1—C41.2 (5)O1—C1—C2—C3179.3 (5)
N1i—Ni1—N1—C4102 (100)C5—N2—C3—C22.5 (9)
O1i—Ni1—O1—C1153 (100)N1—C2—C3—N22.2 (9)
N1—Ni1—O1—C12.3 (3)C1—C2—C3—N2179.9 (5)
N1i—Ni1—O1—C1177.7 (3)C2—N1—C4—C52.2 (7)
Ni1—O1—C1—O2178.9 (4)Ni1—N1—C4—C5175.2 (3)
Ni1—O1—C1—C20.5 (5)C3—N2—C5—C40.4 (8)
C4—N1—C2—C30.3 (7)C3—N2—C5—C6178.4 (5)
Ni1—N1—C2—C3177.6 (4)N1—C4—C5—N21.9 (8)
C4—N1—C2—C1177.8 (4)N1—C4—C5—C6176.0 (5)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C6H5N2O2)2]
Mr332.95
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)11.3098 (19), 7.6721 (11), 7.5467 (10)
β (°) 105.647 (2)
V3)630.56 (16)
Z2
Radiation typeMo Kα
µ (mm1)1.56
Crystal size (mm)0.42 × 0.31 × 0.19
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.560, 0.756
No. of measured, independent and
observed [I > 2σ(I)] reflections
2875, 1105, 827
Rint0.057
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.062, 0.176, 1.03
No. of reflections1105
No. of parameters97
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChapman, C. T., Ciurtin, D. M., Smith, M. D. & Loye zur, H. C. (2002). Solid State Sci. 4, 1187–1189.  Web of Science CSD CrossRef CAS Google Scholar
First citationLiu, F.-Y., Shang, R.-L., Du, L., Zhao, Q.-H. & Fang, R.-B. (2007). Acta Cryst. E63, m120–m122.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPtasiewicz-Bak, H. & Leciejewicz, J. (2000). Pol. J. Chem. 74, 877–883.  CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTanase, S., Martin, V. S., Van Albada, G. A., DeGelder, R., Bouwman, E. & Reedijk, J. (2006). Polyhedron, 25, 2967–2975.  Web of Science CSD CrossRef CAS Google Scholar
First citationWang, F. Q., Mu, W. H., Zheng, X. J., Li, L. C., Fang, D. C. & Jin, L. P. (2008). Inorg. Chem. 47, 5225–5233.  Web of Science CSD CrossRef PubMed CAS Google Scholar

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