Bis(5-methyl­pyrazine-2-carboxyl­ato-κ² N,O)nickel(II)

Abstract

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,

• a = 11.3098 (19) Å

• b = 7.6721 (11) Å

• c = 7.5467 (10) Å

• β = 105.647 (2)°

• V = 630.56 (16) ų

• 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[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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.

Experimental

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

The H atoms of C atoms were positioned geometrically and refined with a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(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.

Figures

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)

Crystal data

[Ni(C6H5N2O2)2]	F(000) = 340
Mr = 332.95	Dx = 1.754 Mg m−3Dm = 1.754 Mg m−3Dm 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

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

Refinement

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(Fo2) + (0.121P)2 + 0.167P] where P = (Fo2 + 2Fc2)/3
1105 reflections	(Δ/σ)max < 0.001
97 parameters	Δρmax = 1.34 e Å−3
0 restraints	Δρmin = −1.37 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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.