catena-Poly[[di-aqua-bis-(4-formyl-benzo-ato-κO (1))nickel(II)]-μ-pyrazine-κ(2) N:N'].

In the title polymeric compound, [Ni(C8H5O3)2(C4H4N2)(H2O)2] n , the Ni(II) atom is located on a twofold rotation axis and has a slightly distorted octa-hedral coordination sphere. In the equatorial plane, it is coordinated by two carboxyl-ate O atoms of two symmetry-related monodentate formyl-benzoate anions and by two N atoms of the bridging pyrazine ligand, which is bis-ected by the twofold rotation axis. The axial positions are occupied by two O atoms of the coordinating water mol-ecules. In the formyl-benzoate anion, the carboxyl-ate group is twisted away from the attached benzene ring by 7.0 (6)°, while the benzene and pyrazine rings are oriented at a dihedral angle of 66.2 (3)°. The pyrazine ligands bridge the Ni(II) cations, forming polymeric chains running along the b-axis direction. Intra-molecular O-H⋯O hydrogen bonds link the water ligands to the carboxyl-ate O atoms. In the crystal, water-water O-H⋯O hydrogen bonds link adjacent chains into layers parallel to the bc plane. Pyrazine-formyl C-H⋯O hydrogen bonds link the layers, forming a three-dimensional network. There are also weak C-H⋯π inter-actions present. The title compound is isotypic with the copper(II) complex [Çelik et al. (2014a). Acta Cryst. E70, m4-m5].

Related literature

For the structural functions and coordination relationships of the aryl­carboxyl­ate ion in transition-metal complexes of benzoic acid derivatives, see: Nadzhafov et al. (1981 ▶); Shnulin et al. (1981 ▶). For applications of transition-metal complexes with biochemical mol­ecules in biological systems, see: Antolini et al. (1982 ▶). Some benzoic acid derivatives, such as 4-amino­benzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes, see: Chen & Chen (2002 ▶); Amiraslanov et al. (1979 ▶); Hauptmann et al. (2000 ▶). For the isotypic copper(II) complex, see: Çelik et al. (2014a ▶). For other related structures involving 4-formyl­benzoate, see: Çelik et al. (2014b ▶); Hökelek et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(C8H5O3)2(C4H4N2)(H2O)2]

M = 473.07

Monoclinic,

a = 22.1032 (5) Å

b = 6.9925 (2) Å

c = 12.3366 (3) Å

β = 94.160 (3)°

V = 1901.68 (8) Å3

Z = 4

Mo Kα radiation

μ = 1.08 mm−1

T = 296 K

0.48 × 0.23 × 0.14 mm

Data collection

Bruker SMART BREEZE CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T min = 0.743, T max = 0.860

9913 measured reflections

1717 independent reflections

1554 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.079

wR(F 2) = 0.209

S = 1.16

1717 reflections

150 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 2.49 e Å−3

Δρmin = −1.05 e Å−3

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681400155X/su2690sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400155X/su2690Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(C8H5O3)2(C4H4N2)(H2O)2]	F(000) = 976
Mr = 473.07	Dx = 1.652 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5837 reflections
a = 22.1032 (5) Å	θ = 3.1–28.3°
b = 6.9925 (2) Å	µ = 1.08 mm−1
c = 12.3366 (3) Å	T = 296 K
β = 94.160 (3)°	Prism, blue
V = 1901.68 (8) Å3	0.48 × 0.23 × 0.14 mm
Z = 4

Bruker SMART BREEZE CCD diffractometer	1717 independent reflections
Radiation source: fine-focus sealed tube	1554 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
φ and ω scans	θmax = 25.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −26→26
Tmin = 0.743, Tmax = 0.860	k = −8→8
9913 measured reflections	l = −14→12

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ2(Fo2) + (0.1238P)2 + 9.9995P] where P = (Fo2 + 2Fc2)/3
1717 reflections	(Δ/σ)max < 0.001
150 parameters	Δρmax = 2.49 e Å−3
2 restraints	Δρmin = −1.05 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
Ni1	0.00000	0.44790 (12)	0.25000	0.0222 (3)
O1	0.13672 (19)	0.3246 (7)	0.3338 (3)	0.0435 (14)
O2	0.08397 (17)	0.4511 (5)	0.1900 (3)	0.0294 (11)
O3	0.3999 (2)	0.3724 (9)	0.0460 (4)	0.0614 (19)
O4	0.0372 (2)	0.4332 (6)	0.4119 (3)	0.0342 (12)
N1	0.00000	0.1464 (8)	0.25000	0.0242 (17)
N2	0.00000	0.7500 (8)	0.25000	0.0260 (19)
C1	0.1321 (2)	0.3907 (7)	0.2394 (5)	0.0277 (16)
C2	0.1890 (2)	0.3983 (7)	0.1787 (5)	0.0284 (16)
C3	0.1889 (3)	0.4908 (8)	0.0787 (5)	0.0300 (17)
C4	0.2420 (3)	0.5042 (9)	0.0271 (5)	0.0320 (17)
C5	0.2955 (3)	0.4294 (8)	0.0736 (5)	0.0339 (17)
C6	0.2958 (3)	0.3342 (8)	0.1733 (5)	0.0338 (17)
C7	0.2424 (2)	0.3196 (8)	0.2243 (5)	0.0290 (17)
C8	0.3520 (3)	0.4471 (10)	0.0178 (6)	0.045 (2)
C9	0.0252 (3)	0.0463 (7)	0.1723 (5)	0.0290 (17)
C10	0.0250 (2)	0.8494 (7)	0.1733 (4)	0.0280 (17)
H3	0.15320	0.54320	0.04700	0.0360*
H4	0.24170	0.56450	−0.04010	0.0380*
H6	0.33140	0.28130	0.20480	0.0410*
H7	0.24240	0.25590	0.29040	0.0350*
H8	0.35070	0.52240	−0.04450	0.0540*
H9	0.04310	0.11080	0.11700	0.0350*
H10	0.04300	0.78400	0.11840	0.0340*
H41	0.040 (4)	0.545 (5)	0.430 (7)	0.06 (3)*
H42	0.0721 (18)	0.396 (13)	0.407 (7)	0.07 (3)*

	U11	U22	U33	U12	U13	U23
Ni1	0.0321 (6)	0.0093 (5)	0.0253 (6)	0.0000	0.0022 (4)	0.0000
O1	0.046 (2)	0.049 (3)	0.036 (2)	0.008 (2)	0.0059 (18)	0.012 (2)
O2	0.032 (2)	0.0188 (19)	0.038 (2)	0.0020 (14)	0.0065 (16)	0.0009 (16)
O3	0.045 (3)	0.085 (4)	0.055 (3)	0.001 (3)	0.010 (2)	−0.006 (3)
O4	0.047 (2)	0.031 (2)	0.024 (2)	0.0063 (19)	−0.0012 (17)	−0.0034 (17)
N1	0.036 (3)	0.011 (3)	0.026 (3)	0.0000	0.005 (2)	0.0000
N2	0.034 (3)	0.006 (3)	0.038 (4)	0.0000	0.003 (3)	0.0000
C1	0.039 (3)	0.012 (2)	0.032 (3)	−0.002 (2)	0.002 (2)	0.000 (2)
C2	0.040 (3)	0.013 (2)	0.032 (3)	−0.002 (2)	0.002 (2)	−0.004 (2)
C3	0.036 (3)	0.022 (3)	0.031 (3)	0.000 (2)	−0.004 (2)	−0.002 (2)
C4	0.047 (3)	0.023 (3)	0.026 (3)	−0.006 (2)	0.003 (2)	0.000 (2)
C5	0.040 (3)	0.026 (3)	0.036 (3)	−0.005 (2)	0.004 (2)	−0.007 (2)
C6	0.036 (3)	0.027 (3)	0.038 (3)	0.005 (2)	0.001 (2)	−0.002 (2)
C7	0.039 (3)	0.021 (3)	0.027 (3)	0.005 (2)	0.003 (2)	0.002 (2)
C8	0.050 (4)	0.044 (4)	0.043 (4)	−0.007 (3)	0.008 (3)	−0.002 (3)
C9	0.045 (3)	0.017 (3)	0.026 (3)	−0.002 (2)	0.009 (2)	0.002 (2)
C10	0.041 (3)	0.016 (3)	0.028 (3)	0.000 (2)	0.010 (2)	−0.004 (2)

Ni1—O2	2.048 (4)	C2—C3	1.393 (8)
Ni1—O4	2.107 (4)	C2—C7	1.384 (7)
Ni1—N1	2.108 (6)	C3—C4	1.378 (9)
Ni1—N2	2.112 (6)	C4—C5	1.379 (9)
Ni1—O2i	2.048 (4)	C5—C6	1.398 (9)
Ni1—O4i	2.107 (4)	C5—C8	1.474 (9)
O1—C1	1.250 (7)	C6—C7	1.381 (8)
O2—C1	1.260 (6)	C9—C10ii	1.377 (7)
O3—C8	1.209 (8)	C3—H3	0.9300
O4—H42	0.82 (5)	C4—H4	0.9300
O4—H41	0.81 (4)	C6—H6	0.9300
N1—C9i	1.340 (7)	C7—H7	0.9300
N1—C9	1.340 (7)	C8—H8	0.9300
N2—C10	1.327 (6)	C9—H9	0.9300
N2—C10i	1.327 (6)	C10—H10	0.9300
C1—C2	1.511 (7)
O2—Ni1—O4	92.38 (16)	C3—C2—C7	119.4 (5)
O2—Ni1—N1	90.63 (10)	C1—C2—C7	120.0 (5)
O2—Ni1—N2	89.37 (10)	C1—C2—C3	120.5 (5)
O2—Ni1—O2i	178.75 (15)	C2—C3—C4	119.6 (6)
O2—Ni1—O4i	87.68 (16)	C3—C4—C5	121.0 (6)
O4—Ni1—N1	87.20 (12)	C4—C5—C6	119.7 (6)
O4—Ni1—N2	92.80 (12)	C4—C5—C8	120.2 (6)
O2i—Ni1—O4	87.68 (16)	C6—C5—C8	120.0 (6)
O4—Ni1—O4i	174.41 (17)	C5—C6—C7	119.1 (6)
N1—Ni1—N2	180.00 (1)	C2—C7—C6	121.2 (6)
O2i—Ni1—N1	90.63 (10)	O3—C8—C5	125.7 (7)
O4i—Ni1—N1	87.20 (12)	N1—C9—C10ii	120.9 (5)
O2i—Ni1—N2	89.37 (10)	N2—C10—C9iii	122.2 (5)
O4i—Ni1—N2	92.80 (12)	C2—C3—H3	120.00
O2i—Ni1—O4i	92.38 (16)	C4—C3—H3	120.00
Ni1—O2—C1	125.3 (4)	C3—C4—H4	119.00
Ni1—O4—H41	103 (6)	C5—C4—H4	120.00
Ni1—O4—H42	105 (6)	C5—C6—H6	120.00
H41—O4—H42	106 (9)	C7—C6—H6	120.00
C9—N1—C9i	117.0 (5)	C2—C7—H7	120.00
Ni1—N1—C9	121.5 (3)	C6—C7—H7	119.00
Ni1—N1—C9i	121.5 (3)	O3—C8—H8	117.00
Ni1—N2—C10	121.6 (3)	C5—C8—H8	117.00
Ni1—N2—C10i	121.6 (3)	N1—C9—H9	120.00
C10—N2—C10i	116.8 (5)	C10ii—C9—H9	120.00
O1—C1—O2	125.7 (5)	N2—C10—H10	119.00
O2—C1—C2	116.9 (5)	C9iii—C10—H10	119.00
O1—C1—C2	117.4 (4)
O4—Ni1—O2—C1	22.0 (4)	Ni1—N1—C9—C10ii	179.9 (4)
N1—Ni1—O2—C1	−65.3 (4)	Ni1—N2—C10—C9iii	179.9 (4)
N2—Ni1—O2—C1	114.7 (4)	O1—C1—C2—C3	−172.2 (5)
O4i—Ni1—O2—C1	−152.5 (4)	O1—C1—C2—C7	5.2 (8)
O2—Ni1—N1—C9	−35.6 (3)	O2—C1—C2—C3	8.0 (7)
O2—Ni1—N1—C9i	144.4 (3)	O2—C1—C2—C7	−174.5 (5)
O4—Ni1—N1—C9	−128.0 (3)	C1—C2—C3—C4	176.9 (5)
O4—Ni1—N1—C9i	52.0 (3)	C7—C2—C3—C4	−0.6 (8)
O2i—Ni1—N1—C9	144.4 (3)	C1—C2—C7—C6	−176.3 (5)
O4i—Ni1—N1—C9	52.0 (3)	C3—C2—C7—C6	1.2 (8)
O2—Ni1—N2—C10	35.5 (3)	C2—C3—C4—C5	−0.8 (9)
O2—Ni1—N2—C10i	−144.5 (3)	C3—C4—C5—C6	1.6 (9)
O4—Ni1—N2—C10	127.9 (3)	C3—C4—C5—C8	−179.3 (6)
O4—Ni1—N2—C10i	−52.1 (3)	C4—C5—C6—C7	−1.0 (9)
O2i—Ni1—N2—C10	−144.5 (3)	C8—C5—C6—C7	179.9 (6)
O4i—Ni1—N2—C10	−52.1 (3)	C4—C5—C8—O3	−172.9 (7)
Ni1—O2—C1—O1	−2.3 (8)	C6—C5—C8—O3	6.3 (10)
Ni1—O2—C1—C2	177.5 (3)	C5—C6—C7—C2	−0.4 (9)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H42···O1	0.82 (5)	1.81 (6)	2.579 (6)	155 (8)
O4—H41···O3iv	0.82 (2)	2.65 (5)	3.395 (8)	152 (8)
C9—H9···O3v	0.93	2.45	3.311 (8)	154
C7—H7···Cg1vi	0.93	2.62	3.395 (6)	141

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H42⋯O1	0.82 (5)	1.81 (6)	2.579 (6)	155 (8)
O4—H41⋯O3i	0.82 (2)	2.65 (5)	3.395 (8)	152 (8)
C9—H9⋯O3ii	0.93	2.45	3.311 (8)	154
C7—H7⋯Cg1iii	0.93	2.62	3.395 (6)	141

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