Tetra­kis[μ-4-(methyl­amino)­benzoato-κ2O:O′]bis­[(N,N-diethyl­nicotinamide-N1)zinc(II)] dihydrate

Hökelek, T.; Yılmaz, F.; Tercan, B.; Aybirdi, Ö.; Necefoğlu, H.

doi:10.1107/S1600536809040409

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages m1328-m1329

https://doi.org/10.1107/S1600536809040409

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Tetrakis[μ-4-(methylamino)benzoato-κ²O:O′]bis[(N,N-diethylnicotinamide-N¹)zinc(II)] dihydrate

Tuncer Hökelek,^a ^* Filiz Yılmaz,^b Barış Tercan,^c Özgür Aybirdi ^d and Hacali Necefoğlu ^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Physics, Faculty of Science, Anadolu University, Department of Chemistry, 26470 Yenibağlar, Eskişehir, Turkey, ^cDepartment of Physics, Karabük University, 78050 Karabük, Turkey, and ^dDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 16 September 2009; accepted 4 October 2009; online 10 October 2009)

The title molecule, [Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]·2H₂O, is a centrosymmetric binuclear complex, with two Zn^II ions [Zn⋯Zn' = 2.9301 (4) Å] bridged by four methylaminobenzoate (MAB) ligands. The four nearest O atoms around each Zn^II ion form a distorted square-planar arrangement with the distorted square-pyramidal coordination completed by the pyridine N atom of the N,N-diethylnicotinamide (DENA) ligand. Each Zn^II ion is displaced by 0.3519 (2) Å from the plane of the four O atoms, with an average Zn—O distance of 2.030 Å. The dihedral angles between carboxylate groups and adjacent benzene rings are 10.57 (10) and 16.63 (12)°, while the benzene rings are oriented at a dihedral angle of 81.84 (5)°. The pyridine ring is oriented at dihedral angles of 40.49 (6) and 51.25 (6)° with respect to the benzene rings. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a three-dimensional network. The π–π contact between the inversion-related pyridine rings [centroid–centroid distance = 3.633 (1) Å] may further stabilize the crystal structure.

Related literature

For niacin, see: Krishnamachari (1974 ) and for the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (1995 , 2009 ); Speier & Fulop (1989 ); Usubaliev et al. (1980 ).

Experimental

Crystal data

[Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]·2H₂O
M_r = 1123.89
Monoclinic, P 2₁ /n
a = 10.1384 (2) Å
b = 25.6931 (3) Å
c = 10.5170 (4) Å
β = 103.061 (2)°
V = 2668.67 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 100 K
0.52 × 0.52 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.609, T_max = 0.905
23512 measured reflections
6638 independent reflections
5562 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.086
S = 1.02
6638 reflections
346 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.0224 (13)
Zn1—O2	2.0207 (13)
Zn1—O3	2.0819 (14)
Zn1—O4	2.0459 (13)
Zn1—N1	2.0516 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O6ⁱ	0.86	2.50	3.105 (3)	128
N4—H4A⋯O6ⁱⁱ	0.86	2.07	2.922 (3)	171
O6—H61⋯O4ⁱⁱⁱ	0.93 (4)	2.07 (4)	2.875 (2)	143 (3)
O6—H61⋯O2ⁱⁱⁱ	0.93 (4)	2.37 (4)	3.117 (2)	137 (3)
O6—H62⋯O5^iv	0.96 (4)	1.81 (4)	2.741 (2)	162 (3)
Symmetry codes: (i) x-2, y, z-1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) x+1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809040409/ci2912sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040409/ci2912Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

The title compound is a binuclear compound, consisting of two DENA and four methylaminobenzoate (MAB) ligands. The crystal structures of similar complexes of Cu²⁺ and Zn²⁺ ions, [Cu(C₆H₅COO)₂(C₅H₅N)]₂ (Usubaliev et al., 1980), [Cu(C₆H₅CO₂)₂(py)]₂ (Speier & Fulop, 1989), [Cu₂(C₆H₅COO)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 1995) and [Zn₂(C₁₁H₁₄NO₂)₄(C₁₀H₁₄N₂O)₂] (Hökelek et al., 2009) have also been reported. In these structures, the benzoate ion acts as a bidentate ligand.

The title dimeric complex, [Zn₂(MAB)₄(DENA)₂].H₂O, has a centre of symmetry and the two Zn^II ions are surrounded by four MAB groups and two DENA ligands. The DENA ligands are coordinated to Zn^II ions through pyridine N atoms only. The MAB groups act as bridging ligands. The Zn···Zn' distance is 2.9301 (4) Å. The average Zn—O distance is 2.0297 (13) Å (Table 1), and four O atoms of the bridging MAB ligands around each Zn^II ion form a distorted square plane. The Zn^II ion lies 0.3519 (2) Å below the least-squares plane. The average O—Zn—O bond angle is 88.30 (6)°. A distorted square-pyramidal arrangement around each Zn^II ion is completed by the pyridine N atom of DENA ligand at 2.0516 (14) Å (Table 1) from the Zn atom. The N1—Zn1···Zn1' angle is 159.67 (4)° and the dihedral angle between plane through atoms Zn1, O1, O2, C1, Zn1', O1', O2'and C1' and the plane through Zn1, O3, O4, C8, Zn1', O3', O4', and C8' atoms is 89.00 (7)°. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 10.57 (10)° and 16.63 (12)°, respectively, while that between rings A and B is A/B = 81.84 (5)°. Ring C (N1/C15-C19) is oriented with respect to rings A and B at dihedral angles A/C = 40.49 (6) and B/C = 51.25 (6) °.

In the crystal structure, intermolecular O—H···O and N—H···O interactions (Table 2) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. The π–π contact between the pyridine rings, Cg1—Cg1ⁱ, [symmetry code (i): 2 - x, -y, 1 - z, where Cg1 is centroid of the ring C (N1/C15—C19)] may further stabilize the structure, with centroid-centroid distance of 3.633 (1) Å.

Related literature top

For niacin, see: Krishnamachari (1974) and for the nicotinic acid derivative N,N-diethylnicotinamidegeneral background, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (1995, 2009); Speier & Fulop (1989); Usubaliev et al. (1980).

Experimental top

The title compound was prepared by the reaction of ZnSO₄.H₂O (0.9 g, 5 mmol) in H₂O (30 ml) and DENA (1.78 g, 10 mmol) in H₂O (20 ml) with sodium p-methylaminobenzoate (1.74 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colourless single crystals.

Structure description top

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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Primed atoms are generated by the symmetry operator: (') 1 - x, -y, -z.

Tetrakis[µ-4-(methylamino)benzoato- κ²O:O']bis[(N,N- diethylnicotinamide-N¹)zinc(II)] dihydrate top

Crystal data top

[Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]·2H₂O	F(000) = 1176
M_r = 1123.89	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8651 reflections
a = 10.1384 (2) Å	θ = 3.0–28.2°
b = 25.6931 (3) Å	µ = 0.97 mm⁻¹
c = 10.5170 (4) Å	T = 100 K
β = 103.061 (2)°	Plate, colorless
V = 2668.67 (12) Å³	0.52 × 0.52 × 0.10 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6638 independent reflections
Radiation source: fine-focus sealed tube	5562 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 28.3°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→10
T_min = 0.609, T_max = 0.905	k = −30→34
23512 measured reflections	l = −14→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0383P)² + 2.063P] where P = (F_o² + 2F_c²)/3
6638 reflections	(Δ/σ)_max = 0.001
346 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]·2H₂O	V = 2668.67 (12) Å³
M_r = 1123.89	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1384 (2) Å	µ = 0.97 mm⁻¹
b = 25.6931 (3) Å	T = 100 K
c = 10.5170 (4) Å	0.52 × 0.52 × 0.10 mm
β = 103.061 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6638 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5562 reflections with I > 2σ(I)
T_min = 0.609, T_max = 0.905	R_int = 0.029
23512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.74 e Å⁻³
6638 reflections	Δρ_min = −0.54 e Å⁻³
346 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
Zn1	−0.04338 (2)	−0.014479 (8)	0.118981 (18)	0.01584 (6)
O1	−0.20843 (14)	0.01538 (5)	−0.00434 (12)	0.0240 (3)
O2	0.14508 (13)	−0.04361 (5)	0.18309 (12)	0.0202 (3)
O3	0.03250 (15)	0.06111 (5)	0.13786 (14)	0.0268 (3)
O4	−0.09993 (14)	−0.08625 (5)	0.04128 (12)	0.0225 (3)
O5	−0.19322 (15)	0.13404 (5)	0.50417 (14)	0.0281 (3)
O6	0.95980 (18)	0.15202 (7)	0.75046 (18)	0.0397 (4)
H61	0.967 (4)	0.1239 (15)	0.808 (4)	0.087 (12)*
H62	0.904 (4)	0.1385 (15)	0.671 (4)	0.088 (13)*
N1	−0.12123 (15)	−0.00735 (6)	0.28204 (14)	0.0166 (3)
N2	−0.39214 (16)	0.12268 (6)	0.35808 (15)	0.0201 (3)
N3	−0.73560 (17)	0.14248 (7)	−0.25237 (16)	0.0279 (4)
H3A	−0.7889	0.1404	−0.1995	0.033*
N4	0.2505 (2)	0.28515 (7)	0.3274 (2)	0.0434 (5)
H4A	0.3067	0.3035	0.2962	0.052*
C1	−0.23030 (18)	0.03966 (7)	−0.11144 (16)	0.0168 (3)
C2	−0.36417 (18)	0.06493 (7)	−0.15463 (16)	0.0162 (3)
C3	−0.39620 (19)	0.09599 (7)	−0.26573 (17)	0.0194 (4)
H3	−0.3338	0.0997	−0.3178	0.023*
C4	−0.5190 (2)	0.12146 (7)	−0.29995 (17)	0.0217 (4)
H4	−0.5382	0.1421	−0.3744	0.026*
C5	−0.61546 (19)	0.11639 (7)	−0.22320 (17)	0.0204 (4)
C6	−0.58436 (19)	0.08385 (7)	−0.11255 (18)	0.0217 (4)
H6	−0.6477	0.0789	−0.0620	0.026*
C7	−0.46113 (19)	0.05944 (7)	−0.07914 (17)	0.0194 (4)
H7	−0.4413	0.0388	−0.0047	0.023*
C8	0.08144 (18)	0.09445 (7)	0.07307 (17)	0.0196 (4)
C9	0.1199 (2)	0.14569 (7)	0.13448 (17)	0.0212 (4)
C10	0.2042 (2)	0.17976 (7)	0.0866 (2)	0.0248 (4)
H10	0.2328	0.1713	0.0112	0.030*
C11	0.2458 (2)	0.22608 (8)	0.1502 (2)	0.0298 (4)
H11	0.3032	0.2481	0.1178	0.036*
C12	0.2017 (2)	0.24024 (8)	0.2638 (2)	0.0304 (5)
C13	0.1107 (2)	0.20754 (8)	0.3067 (2)	0.0321 (5)
H13	0.0755	0.2173	0.3776	0.038*
C14	0.0728 (2)	0.16080 (8)	0.24425 (19)	0.0274 (4)
H14	0.0147	0.1388	0.2758	0.033*
C15	−0.10860 (18)	−0.04226 (7)	0.37916 (16)	0.0170 (3)
H15	−0.0671	−0.0740	0.3710	0.020*
C16	−0.15508 (19)	−0.03269 (7)	0.49092 (17)	0.0195 (4)
H16	−0.1474	−0.0580	0.5555	0.023*
C17	−0.21321 (18)	0.01504 (7)	0.50527 (17)	0.0189 (3)
H17	−0.2428	0.0227	0.5807	0.023*
C18	−0.22681 (18)	0.05145 (7)	0.40509 (16)	0.0166 (3)
C19	−0.18061 (18)	0.03849 (7)	0.29495 (16)	0.0174 (3)
H19	−0.1911	0.0625	0.2272	0.021*
C20	−0.27156 (19)	0.10611 (7)	0.42525 (17)	0.0190 (4)
C21	−0.4910 (2)	0.09017 (8)	0.26852 (18)	0.0238 (4)
H21A	−0.4441	0.0615	0.2379	0.029*
H21B	−0.5342	0.1108	0.1933	0.029*
C22	−0.5985 (2)	0.06864 (9)	0.3335 (2)	0.0320 (5)
H22A	−0.6640	0.0495	0.2707	0.048*
H22B	−0.6426	0.0968	0.3672	0.048*
H22C	−0.5570	0.0460	0.4037	0.048*
C23	−0.4330 (2)	0.17653 (7)	0.3789 (2)	0.0264 (4)
H23A	−0.3975	0.1861	0.4695	0.032*
H23B	−0.5310	0.1784	0.3616	0.032*
C24	−0.3819 (3)	0.21482 (9)	0.2916 (3)	0.0398 (6)
H24A	−0.4139	0.2491	0.3050	0.060*
H24B	−0.4147	0.2049	0.2020	0.060*
H24C	−0.2847	0.2147	0.3124	0.060*
C25	−0.7761 (2)	0.17342 (9)	−0.3688 (2)	0.0345 (5)
H25A	−0.8664	0.1862	−0.3752	0.052*
H25B	−0.7740	0.1524	−0.4438	0.052*
H25C	−0.7151	0.2022	−0.3650	0.052*
C26	0.2125 (4)	0.30333 (9)	0.4443 (2)	0.0561 (8)
H26A	0.2589	0.3353	0.4726	0.084*
H26B	0.2368	0.2776	0.5118	0.084*
H26C	0.1165	0.3091	0.4261	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01825 (11)	0.01770 (11)	0.01276 (10)	0.00284 (8)	0.00601 (7)	0.00051 (7)
O1	0.0237 (7)	0.0314 (7)	0.0170 (6)	0.0086 (6)	0.0049 (5)	0.0050 (5)
O2	0.0183 (6)	0.0244 (7)	0.0186 (6)	0.0045 (5)	0.0054 (5)	0.0017 (5)
O3	0.0310 (8)	0.0206 (7)	0.0336 (7)	0.0001 (6)	0.0176 (6)	−0.0022 (6)
O4	0.0273 (7)	0.0194 (6)	0.0198 (6)	−0.0003 (5)	0.0036 (5)	−0.0022 (5)
O5	0.0265 (8)	0.0257 (7)	0.0314 (7)	−0.0034 (6)	0.0053 (6)	−0.0094 (6)
O6	0.0400 (10)	0.0393 (9)	0.0388 (9)	−0.0006 (8)	0.0065 (8)	0.0140 (8)
N1	0.0162 (7)	0.0194 (7)	0.0142 (6)	0.0017 (6)	0.0035 (5)	−0.0004 (5)
N2	0.0231 (8)	0.0165 (7)	0.0222 (7)	0.0021 (6)	0.0080 (6)	0.0000 (6)
N3	0.0219 (9)	0.0358 (10)	0.0256 (8)	0.0091 (7)	0.0048 (7)	−0.0014 (7)
N4	0.0683 (15)	0.0228 (9)	0.0382 (11)	−0.0077 (9)	0.0102 (10)	−0.0057 (8)
C1	0.0204 (9)	0.0164 (8)	0.0134 (7)	0.0007 (7)	0.0032 (6)	−0.0038 (6)
C2	0.0172 (8)	0.0170 (8)	0.0141 (7)	0.0002 (7)	0.0031 (6)	−0.0016 (6)
C3	0.0222 (9)	0.0218 (9)	0.0156 (8)	0.0010 (7)	0.0072 (7)	−0.0015 (7)
C4	0.0249 (10)	0.0235 (9)	0.0161 (8)	0.0043 (7)	0.0036 (7)	0.0021 (7)
C5	0.0176 (9)	0.0221 (9)	0.0203 (8)	0.0027 (7)	0.0017 (7)	−0.0051 (7)
C6	0.0189 (9)	0.0268 (9)	0.0207 (8)	−0.0022 (7)	0.0074 (7)	−0.0020 (7)
C7	0.0214 (9)	0.0203 (9)	0.0167 (8)	−0.0016 (7)	0.0048 (7)	0.0010 (6)
C8	0.0166 (9)	0.0202 (9)	0.0213 (8)	0.0039 (7)	0.0026 (7)	−0.0008 (7)
C9	0.0240 (10)	0.0180 (8)	0.0194 (8)	0.0033 (7)	0.0003 (7)	0.0000 (7)
C10	0.0232 (10)	0.0223 (9)	0.0278 (9)	0.0021 (8)	0.0033 (8)	−0.0008 (7)
C11	0.0294 (11)	0.0216 (10)	0.0373 (11)	−0.0022 (8)	0.0050 (9)	0.0027 (8)
C12	0.0376 (12)	0.0219 (10)	0.0272 (10)	0.0044 (9)	−0.0024 (9)	−0.0031 (8)
C13	0.0516 (14)	0.0230 (10)	0.0230 (10)	0.0044 (9)	0.0114 (9)	−0.0005 (8)
C14	0.0381 (12)	0.0209 (9)	0.0246 (9)	0.0031 (8)	0.0100 (8)	0.0016 (7)
C15	0.0177 (9)	0.0158 (8)	0.0177 (8)	0.0011 (7)	0.0045 (7)	−0.0003 (6)
C16	0.0219 (9)	0.0211 (8)	0.0163 (8)	−0.0013 (7)	0.0056 (7)	0.0021 (7)
C17	0.0200 (9)	0.0234 (9)	0.0147 (8)	−0.0027 (7)	0.0067 (7)	−0.0019 (7)
C18	0.0144 (8)	0.0189 (8)	0.0166 (8)	0.0002 (7)	0.0035 (6)	−0.0010 (6)
C19	0.0177 (9)	0.0196 (8)	0.0152 (8)	0.0023 (7)	0.0039 (6)	0.0017 (6)
C20	0.0215 (9)	0.0198 (8)	0.0181 (8)	−0.0012 (7)	0.0098 (7)	−0.0008 (7)
C21	0.0232 (10)	0.0249 (9)	0.0221 (9)	0.0059 (8)	0.0022 (7)	−0.0018 (7)
C22	0.0265 (11)	0.0347 (11)	0.0333 (11)	−0.0057 (9)	0.0036 (9)	−0.0037 (9)
C23	0.0299 (11)	0.0181 (9)	0.0340 (10)	0.0057 (8)	0.0134 (9)	0.0020 (8)
C24	0.0483 (15)	0.0235 (11)	0.0517 (14)	0.0038 (10)	0.0199 (12)	0.0103 (10)
C25	0.0324 (12)	0.0353 (12)	0.0332 (11)	0.0149 (10)	0.0019 (9)	−0.0003 (9)
C26	0.113 (3)	0.0223 (11)	0.0298 (12)	−0.0021 (14)	0.0087 (14)	−0.0038 (9)

Geometric parameters (Å, º) top

Zn1—Zn1ⁱ	2.9301 (4)	C10—C11	1.383 (3)
Zn1—O1	2.0224 (13)	C10—H10	0.93
Zn1—O2	2.0207 (13)	C11—H11	0.93
Zn1—O4	2.0459 (13)	C12—N4	1.369 (3)
Zn1—N1	2.0516 (14)	C12—C11	1.415 (3)
O1—C1	1.263 (2)	C12—C13	1.396 (3)
O2—C1ⁱ	1.272 (2)	C13—H13	0.93
O3—Zn1	2.0819 (14)	C14—C13	1.381 (3)
O3—C8	1.264 (2)	C14—H14	0.93
O4—C8ⁱ	1.276 (2)	C15—C16	1.384 (2)
O5—C20	1.240 (2)	C15—H15	0.93
O6—H61	0.94 (4)	C16—H16	0.93
O6—H62	0.96 (4)	C17—C16	1.384 (3)
N1—C15	1.344 (2)	C17—C18	1.392 (2)
N1—C19	1.343 (2)	C17—H17	0.93
N2—C20	1.336 (2)	C18—C19	1.385 (2)
N2—C21	1.471 (2)	C19—H19	0.93
N2—C23	1.475 (2)	C20—C18	1.505 (2)
N3—H3A	0.86	C21—C22	1.516 (3)
N4—C26	1.447 (3)	C21—H21A	0.97
N4—H4A	0.86	C21—H21B	0.97
C1—O2ⁱ	1.272 (2)	C22—H22A	0.96
C2—C1	1.480 (2)	C22—H22B	0.96
C2—C3	1.391 (2)	C22—H22C	0.96
C3—H3	0.93	C23—C24	1.515 (3)
C4—C3	1.381 (3)	C23—H23A	0.97
C4—C5	1.407 (3)	C23—H23B	0.97
C4—H4	0.93	C24—H24A	0.96
C5—N3	1.363 (2)	C24—H24B	0.96
C6—C5	1.410 (3)	C24—H24C	0.96
C6—H6	0.93	C25—N3	1.440 (3)
C7—C2	1.403 (2)	C25—H25A	0.96
C7—C6	1.371 (3)	C25—H25B	0.96
C7—H7	0.93	C25—H25C	0.96
C8—O4ⁱ	1.276 (2)	C26—H26A	0.96
C8—C9	1.479 (2)	C26—H26B	0.96
C9—C10	1.394 (3)	C26—H26C	0.96
C9—C14	1.400 (3)

O1—Zn1—Zn1ⁱ	73.77 (4)	C12—C11—H11	119.7
O1—Zn1—O3	86.65 (6)	N4—C12—C11	118.8 (2)
O1—Zn1—O4	88.23 (6)	N4—C12—C13	122.8 (2)
O1—Zn1—N1	94.78 (5)	C13—C12—C11	118.43 (19)
O2—Zn1—Zn1ⁱ	86.29 (4)	C12—C13—H13	119.9
O2—Zn1—O1	159.63 (5)	C14—C13—C12	120.18 (19)
O2—Zn1—O3	90.72 (6)	C14—C13—H13	119.9
O2—Zn1—O4	87.59 (5)	C9—C14—H14	119.2
O2—Zn1—N1	105.52 (5)	C13—C14—C9	121.57 (19)
O3—Zn1—Zn1ⁱ	70.66 (4)	C13—C14—H14	119.2
O4—Zn1—Zn1ⁱ	89.93 (4)	N1—C15—C16	122.34 (16)
O4—Zn1—O3	160.59 (5)	N1—C15—H15	118.8
O4—Zn1—N1	106.76 (6)	C16—C15—H15	118.8
N1—Zn1—Zn1ⁱ	159.67 (4)	C15—C16—H16	120.5
N1—Zn1—O3	92.33 (6)	C17—C16—C15	119.04 (16)
C1—O1—Zn1	135.44 (13)	C17—C16—H16	120.5
C1ⁱ—O2—Zn1	119.36 (11)	C16—C17—C18	119.00 (16)
C8—O3—Zn1	139.69 (12)	C16—C17—H17	120.5
C8ⁱ—O4—Zn1	115.95 (12)	C18—C17—H17	120.5
H62—O6—H61	103 (3)	C17—C18—C20	120.11 (15)
C15—N1—Zn1	125.96 (12)	C19—C18—C17	118.48 (16)
C19—N1—Zn1	115.38 (11)	C19—C18—C20	120.80 (15)
C19—N1—C15	118.45 (15)	N1—C19—C18	122.65 (16)
C20—N2—C21	124.58 (15)	N1—C19—H19	118.7
C20—N2—C23	118.32 (16)	C18—C19—H19	118.7
C21—N2—C23	117.04 (16)	O5—C20—N2	122.74 (17)
C5—N3—C25	122.12 (17)	O5—C20—C18	117.80 (17)
C5—N3—H3A	118.9	N2—C20—C18	119.45 (16)
C25—N3—H3A	118.9	N2—C21—C22	111.97 (16)
C12—N4—C26	123.4 (2)	N2—C21—H21A	109.2
C12—N4—H4A	118.3	N2—C21—H21B	109.2
C26—N4—H4A	118.3	C22—C21—H21A	109.2
O1—C1—O2ⁱ	124.19 (17)	C22—C21—H21B	109.2
O1—C1—C2	117.03 (15)	H21A—C21—H21B	107.9
O2ⁱ—C1—C2	118.78 (15)	C21—C22—H22A	109.5
C3—C2—C1	122.21 (16)	C21—C22—H22B	109.5
C3—C2—C7	118.19 (16)	C21—C22—H22C	109.5
C7—C2—C1	119.55 (15)	H22A—C22—H22B	109.5
C2—C3—H3	119.5	H22A—C22—H22C	109.5
C4—C3—C2	121.08 (17)	H22B—C22—H22C	109.5
C4—C3—H3	119.5	N2—C23—C24	111.91 (16)
C3—C4—C5	120.62 (17)	N2—C23—H23A	109.2
C3—C4—H4	119.7	N2—C23—H23B	109.2
C5—C4—H4	119.7	C24—C23—H23A	109.2
N3—C5—C4	121.78 (17)	C24—C23—H23B	109.2
N3—C5—C6	119.95 (17)	H23A—C23—H23B	107.9
C4—C5—C6	118.26 (17)	C23—C24—H24A	109.5
C5—C6—H6	119.9	C23—C24—H24B	109.5
C7—C6—C5	120.25 (17)	C23—C24—H24C	109.5
C7—C6—H6	119.9	H24A—C24—H24B	109.5
C2—C7—H7	119.2	H24A—C24—H24C	109.5
C6—C7—C2	121.56 (17)	H24B—C24—H24C	109.5
C6—C7—H7	119.2	N3—C25—H25A	109.5
O3—C8—O4ⁱ	123.76 (17)	N3—C25—H25B	109.5
O3—C8—C9	117.69 (16)	N3—C25—H25C	109.5
O4ⁱ—C8—C9	118.55 (16)	H25A—C25—H25B	109.5
C10—C9—C8	121.59 (17)	H25A—C25—H25C	109.5
C10—C9—C14	118.31 (18)	H25B—C25—H25C	109.5
C14—C9—C8	120.10 (17)	N4—C26—H26A	109.5
C9—C10—H10	119.6	N4—C26—H26B	109.5
C11—C10—C9	120.71 (19)	N4—C26—H26C	109.5
C11—C10—H10	119.6	H26A—C26—H26B	109.5
C10—C11—C12	120.6 (2)	H26A—C26—H26C	109.5
C10—C11—H11	119.7	H26B—C26—H26C	109.5

Zn1ⁱ—Zn1—O1—C1	−10.58 (16)	C20—N2—C23—C24	86.7 (2)
O2—Zn1—O1—C1	−22.8 (3)	C21—N2—C23—C24	−96.1 (2)
O3—Zn1—O1—C1	60.23 (17)	C3—C2—C1—O1	175.07 (16)
O4—Zn1—O1—C1	−101.03 (17)	C3—C2—C1—O2ⁱ	−4.9 (3)
N1—Zn1—O1—C1	152.30 (17)	C7—C2—C1—O1	−2.3 (2)
Zn1ⁱ—Zn1—O2—C1ⁱ	1.39 (12)	C7—C2—C1—O2ⁱ	177.77 (16)
O1—Zn1—O2—C1ⁱ	13.1 (2)	C1—C2—C3—C4	−176.37 (17)
O3—Zn1—O2—C1ⁱ	−69.17 (13)	C7—C2—C3—C4	1.0 (3)
O4—Zn1—O2—C1ⁱ	91.48 (13)	C3—C4—C5—N3	177.78 (18)
N1—Zn1—O2—C1ⁱ	−161.79 (12)	C5—C4—C3—C2	−0.3 (3)
Zn1ⁱ—Zn1—O4—C8ⁱ	−0.04 (12)	C3—C4—C5—C6	−1.3 (3)
O1—Zn1—O4—C8ⁱ	73.72 (13)	C4—C5—N3—C25	5.1 (3)
O2—Zn1—O4—C8ⁱ	−86.33 (13)	C6—C5—N3—C25	−175.77 (19)
O3—Zn1—O4—C8ⁱ	−1.0 (2)	C7—C6—C5—N3	−176.90 (18)
N1—Zn1—O4—C8ⁱ	168.18 (12)	C7—C6—C5—C4	2.2 (3)
Zn1ⁱ—Zn1—N1—C15	−165.91 (10)	C6—C7—C2—C1	177.35 (17)
Zn1ⁱ—Zn1—N1—C19	8.7 (2)	C6—C7—C2—C3	−0.1 (3)
O1—Zn1—N1—C15	139.65 (15)	C2—C7—C6—C5	−1.5 (3)
O1—Zn1—N1—C19	−45.76 (13)	O3—C8—C9—C10	163.73 (18)
O2—Zn1—N1—C15	−42.11 (16)	O3—C8—C9—C14	−15.5 (3)
O2—Zn1—N1—C19	132.48 (12)	O4ⁱ—C8—C9—C10	−15.9 (3)
O3—Zn1—N1—C15	−133.51 (15)	O4ⁱ—C8—C9—C14	164.81 (18)
O3—Zn1—N1—C19	41.08 (13)	C8—C9—C10—C11	−175.97 (18)
O4—Zn1—N1—C15	50.06 (15)	C14—C9—C10—C11	3.3 (3)
O4—Zn1—N1—C19	−135.35 (12)	C8—C9—C14—C13	177.63 (19)
Zn1—O1—C1—O2ⁱ	13.4 (3)	C10—C9—C14—C13	−1.6 (3)
Zn1—O1—C1—C2	−166.52 (12)	C9—C10—C11—C12	−1.1 (3)
C8—O3—Zn1—Zn1ⁱ	1.03 (19)	C13—C12—N4—C26	−0.3 (4)
C8—O3—Zn1—O1	−72.9 (2)	C11—C12—N4—C26	−180.0 (2)
C8—O3—Zn1—O2	86.8 (2)	N4—C12—C11—C10	176.8 (2)
C8—O3—Zn1—O4	2.1 (3)	C13—C12—C11—C10	−2.9 (3)
C8—O3—Zn1—N1	−167.6 (2)	N4—C12—C13—C14	−175.2 (2)
Zn1—O3—C8—O4ⁱ	−1.4 (3)	C11—C12—C13—C14	4.5 (3)
Zn1—O3—C8—C9	178.98 (14)	C9—C14—C13—C12	−2.3 (3)
Zn1—N1—C15—C16	174.78 (13)	N1—C15—C16—C17	−1.9 (3)
C19—N1—C15—C16	0.3 (3)	C18—C17—C16—C15	1.9 (3)
Zn1—N1—C19—C18	−173.78 (14)	C16—C17—C18—C19	−0.4 (3)
C15—N1—C19—C18	1.2 (3)	C16—C17—C18—C20	−171.52 (17)
C21—N2—C20—O5	−176.81 (17)	C17—C18—C19—N1	−1.2 (3)
C21—N2—C20—C18	3.5 (3)	C20—C18—C19—N1	169.86 (16)
C23—N2—C20—O5	0.2 (3)	O5—C20—C18—C17	67.7 (2)
C23—N2—C20—C18	−179.51 (15)	O5—C20—C18—C19	−103.2 (2)
C20—N2—C21—C22	97.4 (2)	N2—C20—C18—C17	−112.63 (19)
C23—N2—C21—C22	−79.6 (2)	N2—C20—C18—C19	76.5 (2)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O6ⁱⁱ	0.86	2.50	3.105 (3)	128
N4—H4A···O6ⁱⁱⁱ	0.86	2.07	2.922 (3)	171
O6—H61···O4^iv	0.93 (4)	2.07 (4)	2.875 (2)	143 (3)
O6—H61···O2^iv	0.93 (4)	2.37 (4)	3.117 (2)	137 (3)
O6—H62···O5^v	0.96 (4)	1.81 (4)	2.741 (2)	162 (3)

Symmetry codes: (ii) x−2, y, z−1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y, −z+1; (v) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₈H₈NO₂)₄(C₁₀H₁₄N₂O)₂]·2H₂O
M_r	1123.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.1384 (2), 25.6931 (3), 10.5170 (4)
β (°)	103.061 (2)
V (Å³)	2668.67 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.52 × 0.52 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.609, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	23512, 6638, 5562
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.086, 1.02
No. of reflections	6638
No. of parameters	346
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.54

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Zn1—O1	2.0224 (13)	Zn1—O4	2.0459 (13)
Zn1—O2	2.0207 (13)	Zn1—N1	2.0516 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O6ⁱ	0.86	2.50	3.105 (3)	128
N4—H4A···O6ⁱⁱ	0.86	2.07	2.922 (3)	171
O6—H61···O4ⁱⁱⁱ	0.93 (4)	2.07 (4)	2.875 (2)	143 (3)
O6—H61···O2ⁱⁱⁱ	0.93 (4)	2.37 (4)	3.117 (2)	137 (3)
O6—H62···O5^iv	0.96 (4)	1.81 (4)	2.741 (2)	162 (3)

Symmetry codes: (i) x−2, y, z−1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y, −z+1; (iv) x+1, y, z.

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.

References

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