trans-Tetra­aqua­bis­(isonicotinamide-κN1)zinc bis­(3-hy­droxy­benzoate) tetra­hydrate

Zaman, İ.G.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536813006466

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Pages m198-m199

doi:10.1107/S1600536813006466

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trans-Tetraaquabis(isonicotinamide-κN¹)zinc bis(3-hydroxybenzoate) tetrahydrate

Ibrahim Göker Zaman,^a Nagihan Çaylak Delibaş,^b Hacali Necefoğlu ^a and Tuncer Hökelek ^c ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^cDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 4 March 2013; accepted 6 March 2013; online 13 March 2013)

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-hydroxybenzoate counter-anion and two uncoordinating water molecules. 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 octahedral geometry is completed by the two N atoms [Zn—N = 2.117 (2) Å] from two isonicotinamide ligands. In the anion, the carboxylate 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 molecule 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. (2009a ,b ). For isostructural Ni and Co complexes, see: Zaman et al. (2012a ,b ).

Experimental

Crystal data

[Zn(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M_r = 727.99
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.047
wR(F²) = 0.114
S = 1.27
3808 reflections
264 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.41 e Å⁻³
Δρ_min = −0.47 e Å⁻³

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⋯O2^iv	0.83 (5)	1.89 (5)	2.689 (3)	161 (5)
O6—H62⋯O4^v	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⋯O8^vi	0.76 (9)	2.08 (9)	2.814 (4)	163 (8)
O7—H72B⋯O7^vii	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⋯O7^viii	0.69 (8)	2.13 (8)	2.814 (4)	167 (6)
O8—H82B⋯O8^ix	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) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) -x, -y, -z+1; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) x-1, y, z; (vii) -x, -y, -z+2; (viii) x+1, y, z; (ix) -x+1, -y, -z+2.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813006466/xu5683sup1.cif

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

checkCIF report

Comment top

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA) and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA) (Hökelek et al., 2009a; Hökelek et al., 2009b; Hökelek et al., 2009c; Hökelek et al., 2009d; Hökelek et al., 2009e; Sertçelik et al., 2009a,b), the title compound was synthesized and its crystal structure is reported herein.

The title compound (I) is isostructural with the related Ni (Zaman et al., 2012a) and Co (Zaman et al., 2012b) complexes. In (I) (Fig. 1), four O atoms (O5, O6, and the symmetry-related atoms, O5', O6') in the equatorial plane around the Zn atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N1, N1') of the INA ligands at 2.117 (2) Å from the Zn atom in the axial positions (Fig. 1). The average Zn—O bond length is 2.108 (2) Å. The intramolecular O—H···O hydrogen bonds (Table 1)link the uncoordinated water molecules to the HB anion. The dihedral angle between the planar carboxylate group (O1/O2/C1) and the benzene ring A (C2—C7) is 9.0 (2)°, while that between rings A and B (N1/C8—C12) is 1.26 (8)°.

In the crystal structure, intermolecular O—H···O, N—H···O and weak C—H···O hydrogen bonds (Table 1) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. π···π Contacts between the benzene and phenyl rings, Cg1—Cg2 and Cg2—Cg1ⁱ, [symmetry code: (i) 1 + x, y, z, where Cg1 and Cg2 are centroids of the rings A (C2—C7) and B (N1/C8—C12), respectively] may further stabilize the structure, with centroid-centroid distances of 3.609 (2) and 3.458 (2) Å, respectively.

Related literature top

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

Experimental top

The title compound was prepared by the reaction of ZnSO₄.H₂O (0.89 g, 5 mmol) in H₂O (100 ml) and INA (1.220 g, 10 mmol) in H₂O (50 ml) with sodium 3-hydroxybenzoate (1.601 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for four weeks, giving colorless single crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Primed atoms are generated by the symmetry operator: (') - x, - y, - z. Only one of the disordered hydrogen atoms for each of the two uncoordinated water molecules is shown for clarity. Hydrogen bonds are shown as dashed lines.

trans-Tetraaquabis(isonicotinamide-κN¹)zinc bis(3-hydroxybenzoate) tetrahydrate top

Crystal data top

[Zn(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	F(000) = 760
M_r = 727.99	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0244P)² + 3.4855P] where P = (F_o² + 2F_c²)/3
3808 reflections	(Δ/σ)_max < 0.001
264 parameters	Δρ_max = 1.41 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Zn(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O	V = 1525.63 (7) Å³
M_r = 727.99	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.7002 (2) Å	µ = 0.89 mm⁻¹
b = 17.0005 (4) Å	T = 100 K
c = 13.6000 (3) Å	0.38 × 0.38 × 0.32 mm
β = 99.993 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	3808 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3497 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.752	R_int = 0.033
14180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.27	Δρ_max = 1.41 e Å⁻³
3808 reflections	Δρ_min = −0.47 e Å⁻³
264 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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.83 (5)	1.89 (5)	2.689 (3)	161 (5)
O6—H62···O4^v	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···O8^vi	0.76 (9)	2.08 (9)	2.814 (4)	163 (8)
O7—H72B···O7^vii	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···O7^viii	0.69 (8)	2.13 (8)	2.814 (4)	167 (6)
O8—H82B···O8^ix	0.82 (9)	1.96 (9)	2.787 (3)	178 (6)
C11—H11···O7ⁱⁱⁱ	0.93	2.54	3.455 (3)	168

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x+1/2, −y+1/2, z−1/2; (iv) −x, −y, −z+1; (v) x−1/2, −y+1/2, z−1/2; (vi) x−1, y, z; (vii) −x, −y, −z+2; (viii) x+1, y, z; (ix) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Zn(C₆H₆N₂O)₂(H₂O)₄](C₇H₅O₃)₂·4H₂O
M_r	727.99
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.7002 (2), 17.0005 (4), 13.6000 (3)
β (°)	99.993 (3)
V (Å³)	1525.63 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.38 × 0.38 × 0.32

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.720, 0.752
No. of measured, independent and observed [I > 2σ(I)] reflections	14180, 3808, 3497
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.114, 1.27
No. of reflections	3808
No. of parameters	264
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.41, −0.47

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···O2^iv	0.83 (5)	1.89 (5)	2.689 (3)	161 (5)
O6—H62···O4^v	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···O8^vi	0.76 (9)	2.08 (9)	2.814 (4)	163 (8)
O7—H72B···O7^vii	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···O7^viii	0.69 (8)	2.13 (8)	2.814 (4)	167 (6)
O8—H82B···O8^ix	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) −x+1/2, y+1/2, −z+3/2; (ii) x+1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z+1; (v) x−1/2, −y+1/2, z−1/2; (vi) x−1, y, z; (vii) −x, −y, −z+2; (viii) x+1, y, z; (ix) −x+1, −y, −z+2.

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer.

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