trans-Tetra-aqua-bis-(isonicotinamide-κN (1))zinc bis-(3-hy-droxy-benzoate) tetra-hydrate.

The asymmetric unit of the title compound, [Zn(C6H6N2O)2(H2O)4](C7H5O3)2·4H2O, contains half of the complex cation with the Zn(II) ion located on an inversion center, a 3-hy-droxy-benzoate counter-anion and two uncoordinating water mol-ecules. Four water O atoms in the equatorial plane around the Zn(II) ion [Zn-O = 2.089 (2) and 2.128 (2) Å] form a slightly distorted square-planar arrangement and the distorted octa-hedral geometry is completed by the two N atoms [Zn-N = 2.117 (2) Å] from two isonicotinamide ligands. In the anion, the carboxyl-ate group is twisted from the attached benzene ring at 9.0 (2)°. In the crystal, a three-dimensional hydrogen-bonding network, formed by classical O-H⋯O and N-H⋯O and weak C-H⋯O hydrogen bonds, consolidates the crystal packing, which exhibits π-π stacking between the benzene and pyridine rings, with centroid-centroid distances of 3.458 (2) and 3.609 (2) Å. One of the two H atoms of each uncoordinating water mol-ecule is disordered over two orientations with an occupancy ratio of 0.60:0.40.

Related literature

For related structures, see: Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶,e ▶); Sertçelik et al. (2009 ▶). For isostructural Ni and Co complexes, see: Zaman et al. (2012 ▶).

Experimental

Crystal data

[Zn(C6H6N2O)2(H2O)4](C7H5O3)2·4H2O

M = 727.99

Monoclinic,

a = 6.7002 (2) Å

b = 17.0005 (4) Å

c = 13.6000 (3) Å

β = 99.993 (3)°

V = 1525.63 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.89 mm−1

T = 100 K

0.38 × 0.38 × 0.32 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.720, T max = 0.752

14180 measured reflections

3808 independent reflections

3497 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.114

S = 1.27

3808 reflections

264 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.41 e Å−3

Δρmin = −0.47 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, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006466/xu5683sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006466/xu5683Isup2.hkl

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

[Zn(C6H6N2O)2(H2O)4](C7H5O3)2·4H2O	F(000) = 760
Mr = 727.99	Dx = 1.585 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7045 reflections
a = 6.7002 (2) Å	θ = 2.4–28.4°
b = 17.0005 (4) Å	µ = 0.89 mm−1
c = 13.6000 (3) Å	T = 100 K
β = 99.993 (3)°	Block, colorless
V = 1525.63 (7) Å3	0.38 × 0.38 × 0.32 mm
Z = 2

Bruker Kappa APEXII CCD area-detector diffractometer	3808 independent reflections
Radiation source: fine-focus sealed tube	3497 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 28.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.720, Tmax = 0.752	k = −22→22
14180 measured reflections	l = −18→18

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	w = 1/[σ2(Fo2) + (0.0244P)2 + 3.4855P] where P = (Fo2 + 2Fc2)/3
3808 reflections	(Δ/σ)max < 0.001
264 parameters	Δρmax = 1.41 e Å−3
0 restraints	Δρmin = −0.47 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	Occ. (<1)
Zn1	0.5000	0.0000	0.5000	0.00963 (12)
O1	0.1790 (3)	0.11717 (11)	0.83803 (14)	0.0153 (4)
O2	0.0781 (3)	0.04165 (11)	0.70518 (14)	0.0141 (4)
O3	0.0140 (3)	0.39187 (11)	0.71927 (15)	0.0172 (4)
H3A	0.004 (7)	0.428 (3)	0.678 (4)	0.051 (14)*
O4	0.6024 (3)	0.33081 (11)	0.81904 (14)	0.0168 (4)
O5	0.6799 (3)	0.04833 (12)	0.40047 (15)	0.0144 (4)
H51	0.763 (7)	0.017 (3)	0.381 (3)	0.041 (12)*
H52	0.636 (6)	0.070 (2)	0.353 (3)	0.028 (11)*
O6	0.2262 (3)	0.03391 (12)	0.41227 (15)	0.0166 (4)
H61	0.140 (8)	0.002 (3)	0.385 (4)	0.052 (14)*
H62	0.192 (6)	0.073 (3)	0.386 (3)	0.037 (12)*
O7	−0.0930 (4)	0.06755 (13)	0.95598 (17)	0.0201 (4)
H71	−0.009 (7)	0.084 (3)	0.920 (3)	0.040 (12)*
H72A	−0.201 (14)	0.059 (5)	0.930 (6)	0.05 (2)*	0.60
H72B	−0.05 (2)	0.026 (8)	0.967 (9)	0.059*	0.40
O8	0.5012 (4)	0.01950 (12)	0.90057 (16)	0.0171 (4)
H81	0.398 (7)	0.052 (3)	0.882 (3)	0.045 (13)*
H82A	0.596 (12)	0.037 (4)	0.910 (5)	0.03 (2)*	0.60
H82B	0.497 (16)	0.008 (6)	0.959 (7)	0.030*	0.40
N1	0.5135 (3)	0.10959 (12)	0.57473 (16)	0.0104 (4)
N2	0.4845 (4)	0.39638 (14)	0.67657 (18)	0.0148 (5)
H21	0.440 (6)	0.395 (2)	0.616 (3)	0.037 (11)*
H22	0.474 (5)	0.438 (2)	0.705 (3)	0.019 (9)*
C1	0.1097 (4)	0.10822 (15)	0.74642 (19)	0.0111 (5)
C2	0.0586 (4)	0.18077 (15)	0.68340 (19)	0.0109 (5)
C3	0.0647 (4)	0.25421 (15)	0.72947 (19)	0.0117 (5)
H3	0.1021	0.2584	0.7984	0.014*
C4	0.0147 (4)	0.32091 (15)	0.67183 (19)	0.0124 (5)
C5	−0.0367 (4)	0.31508 (15)	0.5682 (2)	0.0144 (5)
H5	−0.0688	0.3600	0.5298	0.017*
C6	−0.0395 (4)	0.24190 (16)	0.5227 (2)	0.0149 (5)
H6	−0.0723	0.2380	0.4536	0.018*
C7	0.0063 (4)	0.17457 (15)	0.57989 (19)	0.0132 (5)
H7	0.0022	0.1255	0.5493	0.016*
C8	0.5621 (4)	0.11492 (15)	0.67488 (19)	0.0120 (5)
H8	0.5891	0.0689	0.7118	0.014*
C9	0.5736 (4)	0.18572 (15)	0.72495 (19)	0.0120 (5)
H9	0.6091	0.1871	0.7941	0.014*
C10	0.5317 (4)	0.25512 (14)	0.67106 (19)	0.0101 (5)
C11	0.4793 (4)	0.24979 (15)	0.56786 (19)	0.0122 (5)
H11	0.4491	0.2948	0.5293	0.015*
C12	0.4728 (4)	0.17650 (15)	0.52330 (19)	0.0127 (5)
H12	0.4385	0.1736	0.4541	0.015*
C13	0.5426 (4)	0.33143 (15)	0.72775 (19)	0.0118 (5)

	U11	U22	U33	U12	U13	U23
Zn1	0.0128 (2)	0.00708 (19)	0.00863 (19)	0.00011 (15)	0.00070 (14)	−0.00048 (15)
O1	0.0184 (10)	0.0151 (9)	0.0118 (9)	0.0005 (7)	0.0012 (7)	0.0016 (7)
O2	0.0166 (9)	0.0098 (8)	0.0150 (9)	−0.0010 (7)	0.0003 (7)	−0.0002 (7)
O3	0.0250 (11)	0.0099 (9)	0.0162 (9)	0.0003 (8)	0.0025 (8)	−0.0012 (7)
O4	0.0261 (11)	0.0121 (9)	0.0112 (9)	−0.0017 (8)	0.0006 (8)	−0.0013 (7)
O5	0.0175 (10)	0.0138 (9)	0.0125 (9)	0.0015 (8)	0.0048 (8)	0.0016 (7)
O6	0.0172 (10)	0.0104 (9)	0.0187 (10)	0.0010 (8)	−0.0061 (8)	0.0019 (8)
O7	0.0234 (12)	0.0196 (10)	0.0189 (10)	−0.0029 (9)	0.0078 (9)	−0.0003 (8)
O8	0.0185 (11)	0.0133 (9)	0.0183 (10)	0.0019 (8)	0.0000 (8)	−0.0001 (8)
N1	0.0094 (10)	0.0106 (10)	0.0110 (10)	−0.0018 (8)	0.0010 (8)	−0.0011 (8)
N2	0.0215 (12)	0.0100 (10)	0.0124 (11)	0.0012 (9)	0.0015 (9)	−0.0027 (8)
C1	0.0079 (11)	0.0122 (11)	0.0135 (12)	−0.0005 (9)	0.0028 (9)	0.0007 (9)
C2	0.0106 (11)	0.0105 (11)	0.0117 (11)	0.0000 (9)	0.0023 (9)	0.0023 (9)
C3	0.0095 (11)	0.0142 (12)	0.0107 (11)	−0.0013 (9)	0.0001 (9)	−0.0001 (9)
C4	0.0114 (11)	0.0098 (11)	0.0158 (12)	−0.0014 (9)	0.0016 (9)	−0.0018 (9)
C5	0.0150 (12)	0.0123 (12)	0.0152 (12)	−0.0013 (10)	0.0008 (10)	0.0038 (9)
C6	0.0162 (13)	0.0169 (13)	0.0110 (12)	−0.0017 (10)	0.0008 (9)	0.0004 (9)
C7	0.0144 (12)	0.0124 (11)	0.0130 (12)	−0.0016 (9)	0.0030 (9)	−0.0012 (9)
C8	0.0131 (12)	0.0101 (11)	0.0129 (12)	0.0004 (9)	0.0025 (9)	0.0014 (9)
C9	0.0127 (12)	0.0130 (12)	0.0102 (11)	0.0005 (9)	0.0015 (9)	−0.0002 (9)
C10	0.0081 (11)	0.0103 (11)	0.0122 (11)	−0.0006 (9)	0.0021 (9)	−0.0021 (9)
C11	0.0141 (12)	0.0095 (11)	0.0126 (12)	0.0014 (9)	0.0010 (9)	0.0009 (9)
C13	0.0117 (12)	0.0110 (11)	0.0131 (12)	−0.0018 (9)	0.0034 (9)	−0.0020 (9)
C12	0.0149 (12)	0.0125 (12)	0.0105 (11)	−0.0008 (9)	0.0020 (9)	−0.0009 (9)

Zn1—O5	2.1276 (19)	N2—C13	1.327 (3)
Zn1—O5i	2.1276 (19)	N2—H21	0.83 (4)
Zn1—O6	2.089 (2)	N2—H22	0.81 (4)
Zn1—O6i	2.089 (2)	C2—C1	1.507 (3)
Zn1—N1	2.117 (2)	C2—C3	1.394 (3)
Zn1—N1i	2.117 (2)	C2—C7	1.394 (3)
O1—C1	1.261 (3)	C3—H3	0.9300
O2—C1	1.264 (3)	C4—C3	1.386 (4)
O3—C4	1.369 (3)	C5—C4	1.395 (4)
O3—H3A	0.83 (5)	C5—C6	1.388 (4)
O4—C13	1.237 (3)	C5—H5	0.9300
O5—H51	0.85 (5)	C6—H6	0.9300
O5—H52	0.76 (4)	C7—C6	1.388 (4)
O6—H61	0.83 (5)	C7—H7	0.9300
O6—H62	0.77 (5)	C8—C9	1.379 (3)
O7—H71	0.85 (5)	C8—H8	0.9300
O7—H72A	0.76 (9)	C9—C10	1.392 (3)
O7—H72B	0.78 (13)	C9—H9	0.9300
O8—H81	0.88 (5)	C10—C11	1.389 (3)
O8—H82A	0.69 (8)	C10—C13	1.504 (3)
O8—H82B	0.82 (9)	C11—C12	1.383 (3)
N1—C8	1.347 (3)	C11—H11	0.9300
N1—C12	1.338 (3)	C12—H12	0.9300
O5—Zn1—O5i	180.0	C3—C2—C1	119.4 (2)
O6—Zn1—O5	93.93 (8)	C3—C2—C7	120.3 (2)
O6i—Zn1—O5	86.07 (8)	C7—C2—C1	120.3 (2)
O6—Zn1—O5i	86.07 (8)	C2—C3—H3	120.2
O6i—Zn1—O5i	93.93 (8)	C4—C3—C2	119.5 (2)
O6—Zn1—O6i	180.00 (10)	C4—C3—H3	120.2
O6—Zn1—N1	89.51 (8)	O3—C4—C3	118.4 (2)
O6i—Zn1—N1	90.49 (8)	O3—C4—C5	121.2 (2)
O6—Zn1—N1i	90.49 (8)	C3—C4—C5	120.4 (2)
O6i—Zn1—N1i	89.51 (8)	C4—C5—H5	120.1
N1—Zn1—O5	89.07 (8)	C6—C5—C4	119.7 (2)
N1i—Zn1—O5	90.93 (8)	C6—C5—H5	120.1
N1—Zn1—O5i	90.93 (8)	C5—C6—H6	119.8
N1i—Zn1—O5i	89.07 (8)	C7—C6—C5	120.3 (2)
N1—Zn1—N1i	180.00 (5)	C7—C6—H6	119.8
C4—O3—H3A	110 (3)	C2—C7—H7	120.1
Zn1—O5—H51	116 (3)	C6—C7—C2	119.7 (2)
Zn1—O5—H52	123 (3)	C6—C7—H7	120.1
H52—O5—H51	102 (4)	N1—C8—C9	122.7 (2)
Zn1—O6—H61	123 (3)	N1—C8—H8	118.6
Zn1—O6—H62	131 (3)	C9—C8—H8	118.6
H61—O6—H62	103 (4)	C8—C9—C10	119.4 (2)
H71—O7—H72B	96 (10)	C8—C9—H9	120.3
H72A—O7—H71	118 (7)	C10—C9—H9	120.3
H72A—O7—H72B	104 (10)	C9—C10—C13	118.3 (2)
H81—O8—H82A	116 (6)	C11—C10—C9	118.0 (2)
H81—O8—H82B	106 (8)	C11—C10—C13	123.7 (2)
H82A—O8—H82B	96 (9)	C10—C11—H11	120.5
C8—N1—Zn1	121.81 (17)	C12—C11—C10	119.0 (2)
C12—N1—Zn1	120.62 (17)	C12—C11—H11	120.5
C12—N1—C8	117.6 (2)	N1—C12—C11	123.3 (2)
C13—N2—H21	122 (3)	N1—C12—H12	118.4
C13—N2—H22	121 (2)	C11—C12—H12	118.4
H22—N2—H21	117 (4)	O4—C13—N2	123.2 (2)
O1—C1—O2	123.4 (2)	O4—C13—C10	119.1 (2)
O1—C1—C2	118.1 (2)	N2—C13—C10	117.7 (2)
O2—C1—C2	118.4 (2)
O5—Zn1—N1—C8	−131.4 (2)	C1—C2—C7—C6	−179.7 (2)
O5i—Zn1—N1—C8	48.6 (2)	C3—C2—C7—C6	0.1 (4)
O5—Zn1—N1—C12	48.9 (2)	O3—C4—C3—C2	177.4 (2)
O5i—Zn1—N1—C12	−131.1 (2)	C5—C4—C3—C2	−1.6 (4)
O6—Zn1—N1—C8	134.7 (2)	C6—C5—C4—O3	−178.3 (2)
O6i—Zn1—N1—C8	−45.3 (2)	C6—C5—C4—C3	0.6 (4)
O6—Zn1—N1—C12	−45.1 (2)	C4—C5—C6—C7	0.7 (4)
O6i—Zn1—N1—C12	134.9 (2)	C2—C7—C6—C5	−1.0 (4)
Zn1—N1—C8—C9	179.39 (19)	N1—C8—C9—C10	0.7 (4)
C12—N1—C8—C9	−0.8 (4)	C8—C9—C10—C11	0.1 (4)
Zn1—N1—C12—C11	−179.9 (2)	C8—C9—C10—C13	179.2 (2)
C8—N1—C12—C11	0.3 (4)	C9—C10—C11—C12	−0.6 (4)
C3—C2—C1—O1	−8.0 (4)	C13—C10—C11—C12	−179.6 (2)
C3—C2—C1—O2	170.9 (2)	C9—C10—C13—O4	5.2 (4)
C7—C2—C1—O1	171.8 (2)	C9—C10—C13—N2	−174.0 (2)
C7—C2—C1—O2	−9.3 (4)	C11—C10—C13—O4	−175.7 (2)
C1—C2—C3—C4	−179.0 (2)	C11—C10—C13—N2	5.1 (4)
C7—C2—C3—C4	1.2 (4)	C10—C11—C12—N1	0.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O8ii	0.83 (5)	1.88 (5)	2.705 (3)	172 (5)
N2—H21···O7iii	0.83 (4)	2.24 (4)	3.017 (3)	157 (3)
N2—H22···O2ii	0.82 (4)	2.21 (4)	3.016 (3)	172 (3)
O5—H51···O2i	0.85 (5)	1.98 (5)	2.800 (3)	162 (4)
O5—H52···O3iii	0.76 (4)	1.97 (4)	2.719 (3)	170 (4)
O6—H61···O2iv	0.83 (5)	1.89 (5)	2.689 (3)	161 (5)
O6—H62···O4v	0.77 (5)	1.92 (5)	2.687 (3)	179 (5)
O7—H71···O1	0.85 (5)	1.91 (5)	2.761 (3)	178 (3)
O7—H72A···O8vi	0.76 (9)	2.08 (9)	2.814 (4)	163 (8)
O7—H72B···O7vii	0.78 (9)	2.03 (9)	2.783 (3)	160 (8)
O8—H81···O1	0.89 (5)	1.85 (5)	2.739 (3)	177 (4)
O8—H82A···O7viii	0.69 (8)	2.13 (8)	2.814 (4)	167 (6)
O8—H82B···O8ix	0.82 (9)	1.96 (9)	2.787 (3)	178 (6)
C11—H11···O7iii	0.93	2.54	3.455 (3)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O8i	0.83 (5)	1.88 (5)	2.705 (3)	172 (5)
N2—H21⋯O7ii	0.83 (4)	2.24 (4)	3.017 (3)	157 (3)
N2—H22⋯O2i	0.82 (4)	2.21 (4)	3.016 (3)	172 (3)
O5—H51⋯O2iii	0.85 (5)	1.98 (5)	2.800 (3)	162 (4)
O5—H52⋯O3ii	0.76 (4)	1.97 (4)	2.719 (3)	170 (4)
O6—H61⋯O2iv	0.83 (5)	1.89 (5)	2.689 (3)	161 (5)
O6—H62⋯O4v	0.77 (5)	1.92 (5)	2.687 (3)	179 (5)
O7—H71⋯O1	0.85 (5)	1.91 (5)	2.761 (3)	178 (3)
O7—H72A⋯O8vi	0.76 (9)	2.08 (9)	2.814 (4)	163 (8)
O7—H72B⋯O7vii	0.78 (9)	2.03 (9)	2.783 (3)	160 (8)
O8—H81⋯O1	0.89 (5)	1.85 (5)	2.739 (3)	177 (4)
O8—H82A⋯O7viii	0.69 (8)	2.13 (8)	2.814 (4)	167 (6)
O8—H82B⋯O8ix	0.82 (9)	1.96 (9)	2.787 (3)	178 (6)
C11—H11⋯O7ii	0.93	2.54	3.455 (3)	168

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