trans-Tetra-aqua-bis-(isonicotinamide-κN)nickel(II) bis-(3-hy-droxy-benzoate) tetra-hydrate.

The asymmetric unit of the title compound, [Ni(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(7)H(5)O(3))(2)·4H(2)O, contains one-half of the complex cation with the Ni(II) ion located on an inversion center, a 3-hy-droxy-benzoate counter-anion and two uncoordinated water mol-ecules. Four water O atoms in the equatorial plane around the Ni(II) ion [Ni-O = 2.052 (2) and 2.079 (2) Å] form a slightly distorted square-planar arrangement, which is completed up to a distorted octa-hedron by the two N atoms [Ni-N = 2.075 (3) Å] from two isonicotinamide ligands. In the anion, the carboxyl-ate group is twisted from the attached benzene ring by 8.8 (3)°. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O-H⋯O and N-H⋯O hydrogen bonds, consolidates the crystal packing, which also exhibits π-π inter-actions between the benzene and pyridine rings, with centroid-centroid distances of 3.455 (2) and 3.621 (2) Å, respectively.

Related literature

For general background, see: Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶,e ▶); Sertçelik et al. (2009a ▶,b ▶).

Experimental

Crystal data

[Ni(C6H6N2O)2(H2O)4](C7H5O3)2·4H2O

M = 721.29

Monoclinic,

a = 6.6884 (3) Å

b = 16.9271 (5) Å

c = 13.5543 (4) Å

β = 100.186 (3)°

V = 1510.37 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.73 mm−1

T = 100 K

0.46 × 0.33 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.750, T max = 0.877

13495 measured reflections

3723 independent reflections

3365 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.157

S = 1.26

3723 reflections

256 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.86 e Å−3

Δρmin = −0.69 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812002218/cv5237sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002218/cv5237Isup2.hkl

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

[Ni(C6H6N2O)2(H2O)4](C7H5O3)2·4H2O	F(000) = 756
Mr = 721.29	Dx = 1.586 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7580 reflections
a = 6.6884 (3) Å	θ = 2.4–28.4°
b = 16.9271 (5) Å	µ = 0.73 mm−1
c = 13.5543 (4) Å	T = 100 K
β = 100.186 (3)°	Rod-shaped, blue
V = 1510.37 (9) Å3	0.46 × 0.33 × 0.18 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	3723 independent reflections
Radiation source: fine-focus sealed tube	3365 reflections with I > 2σ(I)
graphite	Rint = 0.029
φ and ω scans	θmax = 28.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.750, Tmax = 0.877	k = −22→21
13495 measured reflections	l = −17→15

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ2(Fo2) + (0.0492P)2 + 5.1781P] where P = (Fo2 + 2Fc2)/3
3723 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.86 e Å−3
12 restraints	Δρmin = −0.69 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.0000	0.5000	0.00840 (16)
O1	−0.0786 (4)	0.04089 (13)	0.29703 (18)	0.0135 (5)
O2	−0.1778 (4)	0.11616 (14)	0.16276 (17)	0.0145 (5)
O3	−0.0150 (4)	0.39248 (14)	0.27901 (19)	0.0151 (5)
H31	−0.011 (8)	0.428 (3)	0.317 (4)	0.027 (13)*
O4	0.3941 (4)	0.32984 (14)	0.18014 (18)	0.0160 (5)
O5	0.3225 (4)	0.04752 (14)	0.59662 (18)	0.0128 (5)
H51	0.372 (9)	0.068 (3)	0.653 (3)	0.051 (17)*
H52	0.245 (8)	0.014 (3)	0.616 (5)	0.054 (18)*
O6	0.7696 (4)	0.03386 (14)	0.58654 (19)	0.0148 (5)
H61	0.803 (7)	0.0796 (16)	0.609 (3)	0.026 (12)*
H62	0.851 (7)	0.000 (3)	0.618 (4)	0.041 (16)*
O7	0.0025 (4)	0.51961 (15)	0.40009 (19)	0.0168 (5)
H71	−0.018 (9)	0.508 (4)	0.453 (2)	0.050*
H72	−0.101 (6)	0.548 (3)	0.380 (4)	0.047 (17)*
O8	0.0926 (4)	0.06780 (16)	0.04380 (19)	0.0192 (5)
H81	0.196 (5)	0.060 (4)	0.077 (4)	0.050*
H82	0.021 (7)	0.082 (3)	0.085 (3)	0.047 (17)*
N1	0.4858 (4)	0.10763 (15)	0.4259 (2)	0.0098 (5)
N2	0.5148 (5)	0.39569 (17)	0.3228 (2)	0.0140 (6)
H21	0.525 (7)	0.439 (3)	0.296 (3)	0.017 (11)*
H22	0.559 (8)	0.396 (3)	0.385 (4)	0.030 (13)*
C1	−0.1092 (5)	0.10742 (18)	0.2549 (2)	0.0112 (6)
C2	−0.0587 (5)	0.18065 (18)	0.3173 (2)	0.0106 (6)
C3	−0.0642 (5)	0.25416 (18)	0.2706 (2)	0.0110 (6)
H3	−0.1005	0.2580	0.2013	0.013*
C4	−0.0156 (5)	0.32139 (18)	0.3277 (3)	0.0120 (6)
C5	0.0358 (5)	0.31639 (19)	0.4314 (3)	0.0130 (6)
H5	0.0684	0.3619	0.4694	0.016*
C6	0.0386 (5)	0.2433 (2)	0.4783 (3)	0.0137 (6)
H6	0.0707	0.2399	0.5478	0.016*
C7	−0.0068 (5)	0.17514 (19)	0.4214 (2)	0.0121 (6)
H7	−0.0026	0.1261	0.4526	0.015*
C8	0.4370 (5)	0.11290 (18)	0.3253 (2)	0.0113 (6)
H8	0.4102	0.0666	0.2884	0.014*
C9	0.4250 (5)	0.18391 (18)	0.2748 (2)	0.0119 (6)
H9	0.3897	0.1851	0.2053	0.014*
C10	0.4660 (5)	0.25372 (18)	0.3287 (2)	0.0106 (6)
C11	0.5176 (5)	0.24858 (18)	0.4322 (2)	0.0124 (6)
H11	0.5467	0.2940	0.4706	0.015*
C12	0.5253 (5)	0.17508 (19)	0.4776 (2)	0.0118 (6)
H12	0.5594	0.1724	0.5471	0.014*
C13	0.4552 (5)	0.33050 (18)	0.2717 (2)	0.0115 (6)

	U11	U22	U33	U12	U13	U23
Ni1	0.0102 (3)	0.0075 (3)	0.0072 (3)	−0.00025 (19)	0.00071 (19)	0.00018 (19)
O1	0.0146 (11)	0.0103 (10)	0.0151 (12)	0.0006 (8)	0.0015 (9)	0.0001 (8)
O2	0.0171 (12)	0.0151 (11)	0.0105 (11)	−0.0004 (9)	0.0007 (9)	−0.0006 (9)
O3	0.0218 (13)	0.0101 (11)	0.0132 (12)	0.0002 (9)	0.0022 (10)	0.0006 (9)
O4	0.0246 (13)	0.0122 (11)	0.0107 (11)	0.0019 (9)	0.0016 (10)	0.0017 (8)
O5	0.0145 (12)	0.0136 (11)	0.0113 (11)	−0.0003 (8)	0.0049 (9)	−0.0006 (9)
O6	0.0155 (12)	0.0098 (11)	0.0162 (12)	0.0000 (9)	−0.0052 (9)	−0.0013 (9)
O7	0.0199 (13)	0.0139 (11)	0.0155 (12)	0.0031 (9)	0.0004 (10)	0.0000 (9)
O8	0.0202 (13)	0.0214 (13)	0.0173 (13)	0.0031 (10)	0.0064 (10)	0.0001 (10)
N1	0.0084 (12)	0.0117 (12)	0.0096 (12)	0.0005 (9)	0.0025 (10)	0.0005 (9)
N2	0.0199 (15)	0.0109 (13)	0.0105 (14)	−0.0009 (10)	0.0007 (11)	0.0027 (10)
C1	0.0072 (13)	0.0127 (14)	0.0142 (15)	0.0003 (10)	0.0030 (11)	−0.0011 (11)
C2	0.0079 (14)	0.0115 (14)	0.0126 (15)	0.0008 (10)	0.0022 (11)	−0.0012 (11)
C3	0.0095 (14)	0.0147 (14)	0.0088 (14)	0.0014 (11)	0.0015 (11)	0.0008 (11)
C4	0.0094 (14)	0.0108 (14)	0.0160 (16)	0.0009 (11)	0.0027 (12)	0.0020 (12)
C5	0.0117 (14)	0.0129 (14)	0.0141 (16)	0.0003 (11)	0.0019 (12)	−0.0030 (11)
C6	0.0133 (15)	0.0172 (15)	0.0101 (15)	0.0010 (11)	0.0010 (12)	0.0001 (12)
C7	0.0129 (15)	0.0116 (14)	0.0124 (15)	0.0017 (11)	0.0034 (12)	0.0020 (11)
C8	0.0107 (14)	0.0113 (14)	0.0118 (15)	−0.0002 (11)	0.0019 (11)	−0.0009 (11)
C9	0.0120 (14)	0.0132 (14)	0.0105 (15)	0.0002 (11)	0.0016 (12)	0.0006 (11)
C10	0.0092 (14)	0.0102 (13)	0.0125 (15)	0.0011 (10)	0.0024 (11)	0.0018 (11)
C11	0.0143 (15)	0.0100 (14)	0.0129 (15)	0.0003 (11)	0.0026 (12)	−0.0011 (11)
C12	0.0107 (14)	0.0135 (14)	0.0115 (15)	0.0007 (11)	0.0028 (11)	−0.0003 (11)
C13	0.0100 (14)	0.0119 (14)	0.0133 (15)	0.0022 (11)	0.0038 (12)	0.0020 (11)

Ni1—O5	2.079 (2)	N2—H21	0.83 (5)
Ni1—O5i	2.079 (2)	N2—H22	0.84 (5)
Ni1—O6	2.052 (2)	C2—C1	1.505 (4)
Ni1—O6i	2.052 (2)	C2—C3	1.394 (4)
Ni1—N1	2.075 (3)	C2—C7	1.395 (4)
Ni1—N1i	2.075 (3)	C3—H3	0.9300
O1—C1	1.263 (4)	C4—C3	1.383 (4)
O2—C1	1.260 (4)	C5—C4	1.389 (5)
O3—C4	1.373 (4)	C5—C6	1.390 (5)
O3—H31	0.79 (5)	C5—H5	0.9300
O4—C13	1.236 (4)	C6—H6	0.9300
O5—H51	0.85 (2)	C7—C6	1.391 (5)
O5—H52	0.85 (2)	C7—H7	0.9300
O6—H61	0.85 (2)	C8—H8	0.9300
O6—H62	0.85 (2)	C9—C8	1.378 (4)
O7—H71	0.784 (18)	C9—C10	1.391 (4)
O7—H72	0.85 (2)	C9—H9	0.9300
O8—H81	0.769 (18)	C10—C11	1.386 (5)
O8—H82	0.83 (2)	C10—C13	1.507 (4)
N1—C8	1.347 (4)	C11—H11	0.9300
N1—C12	1.341 (4)	C12—C11	1.385 (4)
N2—C13	1.326 (4)	C12—H12	0.9300
O5—Ni1—O5i	180.00 (9)	C7—C2—C1	120.3 (3)
O6—Ni1—O5	94.23 (10)	C2—C3—H3	120.1
O6i—Ni1—O5	85.77 (10)	C4—C3—C2	119.7 (3)
O6—Ni1—O5i	85.77 (10)	C4—C3—H3	120.1
O6i—Ni1—O5i	94.23 (10)	O3—C4—C3	118.2 (3)
O6i—Ni1—O6	180.0	O3—C4—C5	121.2 (3)
O6—Ni1—N1	89.53 (10)	C3—C4—C5	120.5 (3)
O6i—Ni1—N1	90.47 (10)	C4—C5—C6	119.9 (3)
O6—Ni1—N1i	90.47 (10)	C4—C5—H5	120.1
O6i—Ni1—N1i	89.53 (10)	C6—C5—H5	120.1
N1—Ni1—O5	89.02 (10)	C5—C6—C7	120.1 (3)
N1i—Ni1—O5	90.98 (10)	C5—C6—H6	120.0
N1—Ni1—O5i	90.98 (10)	C7—C6—H6	120.0
N1i—Ni1—O5i	89.02 (10)	C2—C7—H7	120.1
N1i—Ni1—N1	180.0	C6—C7—C2	119.8 (3)
C4—O3—H31	111 (4)	C6—C7—H7	120.1
Ni1—O5—H51	123 (4)	N1—C8—C9	122.8 (3)
Ni1—O5—H52	113 (4)	N1—C8—H8	118.6
H52—O5—H51	99 (6)	C9—C8—H8	118.6
Ni1—O6—H61	128 (3)	C8—C9—C10	119.4 (3)
Ni1—O6—H62	121 (4)	C8—C9—H9	120.3
H61—O6—H62	110 (5)	C10—C9—H9	120.3
H72—O7—H71	100 (4)	C9—C10—C13	118.5 (3)
H81—O8—H82	103 (4)	C11—C10—C9	117.9 (3)
C8—N1—Ni1	122.0 (2)	C11—C10—C13	123.6 (3)
C12—N1—Ni1	120.4 (2)	C10—C11—H11	120.4
C12—N1—C8	117.6 (3)	C12—C11—C10	119.3 (3)
C13—N2—H21	123 (3)	C12—C11—H11	120.4
C13—N2—H22	123 (3)	N1—C12—C11	122.9 (3)
H21—N2—H22	113 (4)	N1—C12—H12	118.5
O1—C1—C2	118.5 (3)	C11—C12—H12	118.5
O2—C1—O1	123.7 (3)	O4—C13—N2	123.2 (3)
O2—C1—C2	117.8 (3)	O4—C13—C10	119.0 (3)
C3—C2—C1	119.6 (3)	N2—C13—C10	117.9 (3)
C3—C2—C7	120.1 (3)
O5—Ni1—N1—C8	−131.1 (3)	C1—C2—C7—C6	−179.7 (3)
O5i—Ni1—N1—C8	48.9 (3)	C3—C2—C7—C6	0.2 (5)
O5—Ni1—N1—C12	48.7 (2)	O3—C4—C3—C2	177.5 (3)
O5i—Ni1—N1—C12	−131.3 (2)	C5—C4—C3—C2	−0.9 (5)
O6—Ni1—N1—C8	134.6 (3)	C6—C5—C4—O3	−178.4 (3)
O6i—Ni1—N1—C8	−45.4 (3)	C6—C5—C4—C3	0.0 (5)
O6—Ni1—N1—C12	−45.5 (2)	C4—C5—C6—C7	1.1 (5)
O6i—Ni1—N1—C12	134.5 (2)	C2—C7—C6—C5	−1.2 (5)
Ni1—N1—C8—C9	179.4 (2)	C10—C9—C8—N1	0.5 (5)
C12—N1—C8—C9	−0.5 (5)	C8—C9—C10—C11	−0.1 (5)
Ni1—N1—C12—C11	−179.8 (2)	C8—C9—C10—C13	179.0 (3)
C8—N1—C12—C11	0.1 (5)	C9—C10—C11—C12	−0.3 (5)
C3—C2—C1—O1	171.2 (3)	C13—C10—C11—C12	−179.4 (3)
C3—C2—C1—O2	−8.0 (4)	C9—C10—C13—O4	6.0 (5)
C7—C2—C1—O1	−8.9 (5)	C9—C10—C13—N2	−173.2 (3)
C7—C2—C1—O2	171.9 (3)	C11—C10—C13—O4	−175.0 (3)
C1—C2—C3—C4	−179.3 (3)	C11—C10—C13—N2	5.8 (5)
C7—C2—C3—C4	0.8 (5)	N1—C12—C11—C10	0.3 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ii	0.83 (5)	2.20 (5)	3.018 (4)	169 (4)
N2—H22···O8iii	0.84 (5)	2.21 (5)	3.012 (4)	159 (5)
O3—H31···O7	0.79 (5)	1.91 (5)	2.696 (4)	175 (5)
O5—H51···O3iii	0.85 (4)	1.87 (4)	2.716 (3)	177 (5)
O5—H52···O1iv	0.84 (5)	1.99 (6)	2.795 (4)	160 (6)
O6—H61···O4iii	0.85 (3)	1.86 (3)	2.693 (3)	169 (4)
O6—H62···O1i	0.85 (5)	1.87 (5)	2.685 (4)	159 (5)
O7—H71···O7v	0.78 (4)	2.03 (3)	2.795 (4)	167 (6)
O7—H72···O2vi	0.85 (5)	1.88 (5)	2.731 (4)	177 (5)
O8—H81···O7vii	0.77 (4)	2.10 (4)	2.802 (4)	152 (6)
O8—H82···O2	0.83 (4)	1.93 (5)	2.752 (4)	171 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1i	0.83 (5)	2.20 (5)	3.018 (4)	169 (4)
N2—H22⋯O8ii	0.84 (5)	2.21 (5)	3.012 (4)	159 (5)
O3—H31⋯O7	0.79 (5)	1.91 (5)	2.696 (4)	175 (5)
O5—H51⋯O3ii	0.85 (4)	1.87 (4)	2.716 (3)	177 (5)
O5—H52⋯O1iii	0.84 (5)	1.99 (6)	2.795 (4)	160 (6)
O6—H61⋯O4ii	0.85 (3)	1.86 (3)	2.693 (3)	169 (4)
O6—H62⋯O1iv	0.85 (5)	1.87 (5)	2.685 (4)	159 (5)
O7—H71⋯O7v	0.78 (4)	2.03 (3)	2.795 (4)	167 (6)
O7—H72⋯O2vi	0.85 (5)	1.88 (5)	2.731 (4)	177 (5)
O8—H81⋯O7vii	0.77 (4)	2.10 (4)	2.802 (4)	152 (6)
O8—H82⋯O2	0.83 (4)	1.93 (5)	2.752 (4)	171 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .