Diaqua­bis[4-(dimethyl­amino)benzoato](isonicotinamide)zinc(II)

Hökelek, T.; Dal, H.; Tercan, B.; Aybirdi, Ö.; Necefoğlu, H.

doi:10.1107/S1600536809017620

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m651-m652

doi:10.1107/S1600536809017620

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Diaquabis[4-(dimethylamino)benzoato](isonicotinamide)zinc(II)

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

^aHacettepe University, Department of Physics, 06800 Beytepe, Ankara, Turkey, ^bAnadolu University, Faculty of Science, Department of Chemistry, 26470 Yenibağlar, Eskişehir, Turkey, ^cKarabük University, Department of Physics, 78050, Karabük, Turkey, and ^dKafkas University, Department of Chemistry, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 7 May 2009; accepted 11 May 2009; online 14 May 2009)

The molecule of the title Zn^II complex, [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂], contains two 4-(dimethylamino)benzoate (DMAB) ligands, one isonicotinamide (INA) ligand and two water molecules; one of the DMAB ions acts as a bidentate ligand while the other and INA are monodentate ligands. The four O atoms in the equatorial plane around the Zn atom form a distorted square-planar arrangement, while the distorted octahedral coordination is completed by the N atom of the INA ligand and the O atom of the water molecule in the axial positions. Intramolecular C—H⋯O hydrogen bonding results in the formation of a six-membered ring adopting an envelope conformation. The dihedral angle between the carboxyl groups and the adjacent benzene rings are 4.87 (16) and 2.2 (2)°, while the two benzene rings are oriented at a dihedral angle of 65.13 (8)°. The dihedral angle between the benzene and pyridine rings are 11.47 (7) and 74.83 (8)°, respectively. In the crystal structure, intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure. π–π contacts between the pyridine and benzene rings and between the benzene rings [centroid–centroid distances = 3.695 (1) and 3.841 (1) Å, respectively] further stabilize the structure. Weak intermolecular C—H⋯π interactions are also present.

Related literature

For general backgroud, see: Antolini et al. (1982 ); Chen & Chen (2002 ); Amiraslanov et al. (1979 ); Bigoli et al. (1972 ); Hauptmann et al. (2000 ); Shnulin et al. (1981 ); Antsyshkina et al. (1980 ); Adiwidjaja et al. (1978 ); Catterick et al. (1974 ); Krishnamachari (1974 ). For related structures, see: Greenaway et al. (1984 ); Hökelek et al. (1995 , 1997 , 2007 , 2008 ); Hökelek & Necefoğlu (1996 , 1997 , 2007 ).

Experimental

Crystal data

[Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]
M_r = 551.91
Triclinic, $[P \overline 1]$
a = 6.8616 (2) Å
b = 8.0947 (3) Å
c = 22.4953 (4) Å
α = 90.683 (2)°
β = 92.838 (2)°
γ = 93.313 (3)°
V = 1245.69 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 100 K
0.57 × 0.27 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.720, T_max = 0.810
21315 measured reflections
6053 independent reflections
5647 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.078
S = 1.29
6053 reflections
353 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.0353 (17)
Zn1—O3	2.1328 (17)
Zn1—O4	2.2584 (17)
Zn1—O6	2.1393 (17)
Zn1—O7	2.0647 (17)
Zn1—N1	2.1307 (19)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O4ⁱ	0.89 (3)	2.15 (3)	3.034 (3)	174 (3)
N2—H22⋯O3ⁱⁱ	0.89 (3)	1.95 (3)	2.820 (3)	164 (3)
O6—H61⋯O2	0.89 (3)	1.79 (3)	2.646 (2)	161 (3)
O6—H62⋯O5ⁱⁱⁱ	0.88 (3)	1.88 (3)	2.749 (2)	169 (3)
O7—H71⋯N3^iv	0.89 (3)	2.01 (3)	2.863 (3)	162 (3)
O7—H72⋯O2^v	0.87 (3)	1.80 (3)	2.667 (2)	171 (3)
C22—H22A⋯Cg3^vi	0.96	2.74	3.567 (3)	145
C23—H23C⋯Cg2^vii	0.96	2.86	3.644 (3)	140
Symmetry codes: (i) x-1, y+1, z; (ii) x, y+1, z; (iii) x+1, y-1, z; (iv) x-1, y-1, z; (v) x-1, y, z; (vi) -x+1, -y+1, -z; (vii) -x+1, -y, -z. Cg2 and Cg3 are the centroids of the C9–C14 and N1/C15–C19 rings, respectively.

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: 10.1107/S1600536809017620/xu2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017620/xu2522Isup2.hkl

checkCIF report

Comment top

Nicotinamide (NA) is one form of niacin. A deficiency of this vitamin leads to loss of copper from the body, known as pellagra disease. Victims of pellagra show unusually high serum and urinary copper levels (Krishnamachari, 1974). The nicotinic acid derivative N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant (Bigoli et al., 1972). Transition metal complexes with biochemical molecules show interesting physical and/or chemical properties, through which they may find applications in biological systems (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 (Chen & Chen, 2002; Amiraslanov et al., 1979; Hauptmann et al., 2000).

The structure-function-coordination relationships of the arylcarboxylate ion in Zn^II complexes of benzoic acid derivatives may also change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the pH and temperature of synthesis (Shnulin et al., 1981; Antsyshkina et al., 1980; Adiwidjaja et al., 1978). When pyridine and its derivatives are used instead of water molecules, the structure is completely different (Catterick et al., 1974).

The structure determination of the title compound, (I), a zinc complex with two 4-dimethylaminobenzoate (DMAB) and one isonicotinamide (INA) ligands and two water molecules, was undertaken in order to determine the properties of the ligands and also to compare the results obtained with those reported previously.

In the monomeric title complex, (I), the Zn atom is surrounded by two DMAB and INA ligands and two water molecules. One of the DMAB ions acts as a bidentate ligand, while the other and INA are monodentate ligands (Fig. 1). The four O atoms (O1, O3, O4 and O7 atoms) in the equatorial plane around the Zn atom form a highly distorted square-planar arrangement, while the distorted octahedral coordination is completed by the N atom of the INA ligand (N1) and the O atom of the water molecule (O6) in the axial positions (Table 1 and Fig. 1).

The near equality of the C1—O1 [1.265 (3) Å], C1—O2 [1.265 (3) Å], C8—O3 [1.278 (3) Å] and C8—O4 [1.271 (3) Å], bonds in the carboxylate group indicates a delocalized bonding arrangement, rather than localized single and double bonds, and may be compared with the corresponding distances: 1.256 (6) and 1.245 (6) Å in [Mn(DENA)₂(C₇H₄ClO₂)₂(H₂O)₂], (II) (Hökelek et al., 2008), 1.265 (6) and 1.275 (6) Å in [Mn(C₉H₁₀NO₂)₂(H₂O)₄]. 2(H₂O), (III) (Hökelek & Necefoğlu, 2007), 1.260 (4) and 1.252 (4) Å in [Zn(DENA)₂(C₇H₄FO₂)₂(H₂O)₂],(IV) (Hökelek et al., 2007), 1.259 (9) and 1.273 (9) Å in Cu₂(DENA)₂(C₆H₅COO)₄, (V) (Hökelek et al., 1995), 1.279 (4) and 1.246 (4) Å in [Zn₂(DENA)₂(C₇H₅O₃)₄]. 2H₂O, (VI) (Hökelek & Necefoğlu, 1996), 1.251 (6) and 1.254 (7) Å in [Co(DENA)₂(C₇H₅O₃)₂(H₂O)₂], (VII) (Hökelek & Necefoğlu, 1997) and 1.278 (3) and 1.246 (3) Å in [Cu(DENA)₂(C₇H₄NO₄)₂(H₂O)₂], (VIII) (Hökelek et al., 1997). In (I), the average Zn—O bond length is 2.1261 (17) Å and the Zn atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C8/O4) by -0.531 (1) Å and 0.023 (3) Å, respectively. The dihedral angle between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and B (C9—C14) are 4.87 (16)° and 2.23 (21)°, respectively, while those between rings A, B and C (N1/C15—C19) are A/B = 65.13 (8), A/C = 11.47 (7) and B/C = 74.83 (8) °. Intramolecular C—H···O hydrogen bond (Table 2) results in the formation of a six-membered ring D (Zn1/O1/O2/O6/C1/H61) adopting envelope conformation, with atom Zn1 displaced by 0.610 (1) Å from the plane of the other ring atoms. In (I), the O3—Zn1—O4 angle is 60.03 (6)°. The corresponding O—M—O (where M is a metal) angles are 58.3 (3)° in (VI) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(IX); Greenaway et al., 1984].

In the crystal structure, strong intermolecular O—H···O, O—H···N and N—H···O hydrogen bonds (Table 2) link the molecules into a supramolecular structure, in which they may be effective in the stabilization of the structure. The π–π contacts between the pyridine and the benzene rings and the benzene rings, Cg1—Cg3ⁱ and Cg2···Cg2ⁱⁱ [symmetry codes: (i) x - 1, y, z, (ii) 1 - x, 1 - y, -z, where Cg1, Cg2 and Cg3 are centroids of the rings A (C2—C7), B (C9—C14) and C (N1/C15—C19), respectively] may further stabilize the structure, with centroid-centroid distances of 3.695 (1) and 3.841 (1) Å, respectively. There also exist two weak C—H···π interactions (Table 1).

Related literature top

For general backgroud, see: Antolini et al. (1982); Chen & Chen (2002); Amiraslanov et al. (1979); Bigoli et al. (1972); Hauptmann et al. (2000); Shnulin et al. (1981); Antsyshkina et al. (1980); Adiwidjaja et al. (1978); Catterick et al. (1974); Krishnamachari (1974). For related structures, see: Greenaway et al. (1984); Hökelek et al. (1995, 1997, 2007, 2008); Hökelek & Necefoğlu (1996, 1997, 2007).

Experimental top

The title compound was prepared by the reaction of ZnSO₄.H₂O (0.90 g, 5 mmol) in H₂O (30 ml) and INA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium p-dimethylaminobenzoate (1.88 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, 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, 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 molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.

Diaquabis[4-(dimethylamino)benzoato](isonicotinamide)zinc(II) top

Crystal data top

[Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]	Z = 2
M_r = 551.91	F(000) = 576
Triclinic, P1	D_x = 1.471 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8616 (2) Å	Cell parameters from 9908 reflections
b = 8.0947 (3) Å	θ = 2.7–28.4°
c = 22.4953 (4) Å	µ = 1.04 mm⁻¹
α = 90.683 (2)°	T = 100 K
β = 92.838 (2)°	Block, colorless
γ = 93.313 (3)°	0.57 × 0.27 × 0.20 mm
V = 1245.69 (6) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6053 independent reflections
Radiation source: fine-focus sealed tube	5647 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.720, T_max = 0.810	k = −10→10
21315 measured reflections	l = −30→30

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.29	w = 1/[σ²(F_o²) + 1.9543P] where P = (F_o² + 2F_c²)/3
6053 reflections	(Δ/σ)_max = 0.001
353 parameters	Δρ_max = 0.43 e Å⁻³
6 restraints	Δρ_min = −0.99 e Å⁻³

Crystal data top

[Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]	γ = 93.313 (3)°
M_r = 551.91	V = 1245.69 (6) Å³
Triclinic, P1	Z = 2
a = 6.8616 (2) Å	Mo Kα radiation
b = 8.0947 (3) Å	µ = 1.04 mm⁻¹
c = 22.4953 (4) Å	T = 100 K
α = 90.683 (2)°	0.57 × 0.27 × 0.20 mm
β = 92.838 (2)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	6053 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5647 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.810	R_int = 0.021
21315 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.29	Δρ_max = 0.43 e Å⁻³
6053 reflections	Δρ_min = −0.99 e Å⁻³
353 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	0.43308 (4)	0.52665 (3)	0.277312 (12)	0.00968 (7)
O1	0.6072 (2)	0.6802 (2)	0.33222 (7)	0.0139 (3)
O2	0.8588 (2)	0.5241 (2)	0.35273 (8)	0.0151 (3)
O3	0.3267 (2)	0.4011 (2)	0.19727 (7)	0.0136 (3)
O4	0.6263 (2)	0.5140 (2)	0.19916 (7)	0.0140 (3)
O5	−0.3021 (2)	1.0876 (2)	0.23256 (8)	0.0152 (3)
O6	0.5716 (2)	0.3151 (2)	0.31154 (8)	0.0137 (3)
H61	0.683 (3)	0.366 (4)	0.3259 (14)	0.034 (9)*
H62	0.605 (5)	0.250 (4)	0.2826 (13)	0.043 (11)*
O7	0.2121 (2)	0.4297 (2)	0.32786 (8)	0.0156 (4)
H71	0.241 (5)	0.362 (4)	0.3573 (12)	0.041 (10)*
H72	0.102 (4)	0.471 (4)	0.3366 (15)	0.040 (10)*
N1	0.2604 (3)	0.7288 (2)	0.25405 (8)	0.0111 (4)
N2	−0.0589 (3)	1.2657 (3)	0.20535 (10)	0.0150 (4)
H21	−0.144 (5)	1.345 (4)	0.2033 (14)	0.028 (9)*
H22	0.065 (5)	1.293 (4)	0.1978 (14)	0.026 (8)*
N3	1.2354 (3)	1.2427 (2)	0.43495 (9)	0.0134 (4)
N4	0.5670 (4)	0.1902 (3)	−0.06335 (10)	0.0295 (6)
C1	0.7806 (3)	0.6619 (3)	0.35163 (10)	0.0118 (4)
C2	0.8980 (3)	0.8119 (3)	0.37526 (10)	0.0116 (4)
C3	1.0944 (3)	0.8040 (3)	0.39285 (10)	0.0133 (4)
H3	1.1525	0.7032	0.3907	0.016*
C4	1.2056 (3)	0.9437 (3)	0.41358 (10)	0.0137 (4)
H4	1.3366	0.9350	0.4251	0.016*
C5	1.1230 (3)	1.0971 (3)	0.41741 (10)	0.0116 (4)
C6	0.9246 (3)	1.1047 (3)	0.39978 (11)	0.0148 (5)
H6	0.8656	1.2049	0.4023	0.018*
C7	0.8157 (3)	0.9653 (3)	0.37883 (10)	0.0138 (5)
H7	0.6850	0.9738	0.3669	0.017*
C8	0.4856 (3)	0.4329 (3)	0.17119 (10)	0.0118 (4)
C9	0.5045 (4)	0.3732 (3)	0.10964 (10)	0.0138 (5)
C10	0.3518 (4)	0.2825 (3)	0.07888 (11)	0.0186 (5)
H10	0.2349	0.2609	0.0974	0.022*
C11	0.3696 (4)	0.2240 (3)	0.02182 (12)	0.0223 (5)
H11	0.2643	0.1656	0.0022	0.027*
C12	0.5457 (4)	0.2517 (3)	−0.00729 (11)	0.0223 (6)
C13	0.6994 (4)	0.3448 (3)	0.02368 (12)	0.0227 (6)
H13	0.8169	0.3664	0.0056	0.027*
C14	0.6774 (4)	0.4042 (3)	0.08049 (11)	0.0181 (5)
H14	0.7802	0.4665	0.0999	0.022*
C15	0.3272 (3)	0.8873 (3)	0.25996 (10)	0.0134 (5)
H15	0.4576	0.9101	0.2721	0.016*
C16	0.2101 (3)	1.0188 (3)	0.24869 (11)	0.0138 (5)
H16	0.2620	1.1274	0.2524	0.017*
C17	0.0147 (3)	0.9856 (3)	0.23173 (10)	0.0103 (4)
C18	−0.0561 (3)	0.8214 (3)	0.22551 (10)	0.0117 (4)
H18	−0.1868	0.7952	0.2145	0.014*
C19	0.0719 (3)	0.6980 (3)	0.23603 (10)	0.0120 (4)
H19	0.0254	0.5884	0.2304	0.014*
C20	1.1361 (4)	1.3649 (3)	0.46894 (11)	0.0172 (5)
H20A	1.2236	1.4601	0.4773	0.026*
H20B	1.0964	1.3173	0.5056	0.026*
H20C	1.0230	1.3975	0.4462	0.026*
C21	1.4337 (4)	1.2219 (3)	0.45885 (13)	0.0240 (6)
H21A	1.4981	1.3285	0.4675	0.036*
H21B	1.5046	1.1645	0.4301	0.036*
H21C	1.4290	1.1589	0.4947	0.036*
C22	0.7510 (5)	0.2163 (4)	−0.09166 (13)	0.0376 (8)
H22A	0.7477	0.1513	−0.1277	0.056*
H22B	0.8556	0.1835	−0.0652	0.056*
H22C	0.7719	0.3313	−0.1008	0.056*
C23	0.4016 (5)	0.1097 (4)	−0.09693 (13)	0.0358 (8)
H23A	0.4403	0.0798	−0.1359	0.054*
H23B	0.2978	0.1841	−0.1005	0.054*
H23C	0.3572	0.0119	−0.0767	0.054*
C24	−0.1275 (3)	1.1191 (3)	0.22302 (10)	0.0117 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.00962 (12)	0.00784 (13)	0.01170 (12)	0.00169 (9)	0.00048 (9)	−0.00011 (9)
O1	0.0114 (8)	0.0130 (8)	0.0170 (8)	0.0028 (6)	−0.0028 (6)	−0.0015 (6)
O2	0.0125 (8)	0.0096 (8)	0.0232 (9)	0.0023 (6)	−0.0006 (7)	−0.0010 (7)
O3	0.0134 (8)	0.0131 (8)	0.0145 (8)	−0.0001 (6)	0.0033 (6)	−0.0011 (6)
O4	0.0138 (8)	0.0123 (8)	0.0156 (8)	−0.0018 (6)	−0.0003 (6)	−0.0008 (6)
O5	0.0109 (8)	0.0115 (8)	0.0232 (9)	0.0010 (6)	0.0018 (7)	−0.0018 (7)
O6	0.0108 (8)	0.0128 (9)	0.0177 (8)	0.0020 (6)	0.0005 (6)	0.0000 (7)
O7	0.0133 (8)	0.0166 (9)	0.0180 (8)	0.0055 (7)	0.0050 (7)	0.0059 (7)
N1	0.0113 (9)	0.0118 (10)	0.0102 (9)	−0.0001 (7)	0.0011 (7)	0.0004 (7)
N2	0.0107 (10)	0.0095 (10)	0.0249 (11)	0.0017 (8)	−0.0012 (8)	0.0026 (8)
N3	0.0125 (9)	0.0118 (10)	0.0155 (9)	0.0011 (7)	−0.0012 (7)	−0.0021 (8)
N4	0.0458 (16)	0.0308 (14)	0.0131 (11)	0.0092 (12)	0.0045 (10)	−0.0039 (9)
C1	0.0141 (11)	0.0119 (11)	0.0096 (10)	0.0010 (8)	0.0016 (8)	−0.0002 (8)
C2	0.0127 (11)	0.0122 (11)	0.0100 (10)	0.0003 (8)	0.0011 (8)	−0.0001 (8)
C3	0.0140 (11)	0.0104 (11)	0.0157 (11)	0.0027 (8)	0.0004 (9)	0.0006 (9)
C4	0.0115 (11)	0.0148 (12)	0.0148 (11)	0.0022 (9)	−0.0014 (8)	0.0011 (9)
C5	0.0140 (11)	0.0111 (11)	0.0097 (10)	0.0005 (8)	0.0004 (8)	0.0007 (8)
C6	0.0143 (11)	0.0114 (11)	0.0189 (11)	0.0044 (9)	−0.0005 (9)	−0.0010 (9)
C7	0.0114 (11)	0.0143 (12)	0.0156 (11)	0.0024 (9)	−0.0009 (8)	−0.0008 (9)
C8	0.0120 (11)	0.0088 (11)	0.0151 (11)	0.0027 (8)	0.0007 (8)	0.0017 (8)
C9	0.0170 (11)	0.0120 (11)	0.0126 (11)	0.0027 (9)	0.0009 (9)	0.0007 (8)
C10	0.0202 (13)	0.0200 (13)	0.0154 (12)	0.0008 (10)	0.0003 (9)	−0.0016 (10)
C11	0.0285 (14)	0.0203 (14)	0.0176 (12)	0.0024 (11)	−0.0044 (10)	−0.0039 (10)
C12	0.0370 (16)	0.0181 (13)	0.0128 (11)	0.0090 (11)	0.0020 (10)	0.0007 (10)
C13	0.0274 (14)	0.0234 (14)	0.0186 (12)	0.0053 (11)	0.0093 (10)	0.0029 (10)
C14	0.0213 (13)	0.0170 (13)	0.0162 (11)	0.0013 (10)	0.0035 (9)	0.0008 (9)
C15	0.0113 (11)	0.0123 (11)	0.0166 (11)	−0.0003 (8)	−0.0003 (8)	0.0031 (9)
C16	0.0128 (11)	0.0094 (11)	0.0190 (11)	−0.0002 (8)	0.0004 (9)	0.0009 (9)
C17	0.0113 (10)	0.0097 (11)	0.0103 (10)	0.0021 (8)	0.0018 (8)	0.0004 (8)
C18	0.0102 (10)	0.0116 (11)	0.0131 (10)	0.0008 (8)	0.0006 (8)	−0.0004 (8)
C19	0.0141 (11)	0.0079 (11)	0.0136 (10)	−0.0015 (8)	−0.0001 (8)	−0.0009 (8)
C20	0.0220 (13)	0.0149 (12)	0.0148 (11)	0.0026 (9)	0.0013 (9)	−0.0029 (9)
C21	0.0171 (13)	0.0168 (13)	0.0372 (16)	0.0029 (10)	−0.0089 (11)	−0.0057 (11)
C22	0.056 (2)	0.043 (2)	0.0170 (14)	0.0158 (16)	0.0132 (14)	−0.0017 (13)
C23	0.057 (2)	0.0350 (18)	0.0164 (13)	0.0177 (16)	−0.0076 (13)	−0.0072 (12)
C24	0.0120 (11)	0.0103 (11)	0.0127 (10)	0.0013 (8)	−0.0004 (8)	−0.0023 (8)

Geometric parameters (Å, º) top

Zn1—O1	2.0353 (17)	C7—C6	1.381 (3)
Zn1—O3	2.1328 (17)	C7—H7	0.9300
Zn1—O4	2.2584 (17)	C9—C8	1.475 (3)
Zn1—O6	2.1393 (17)	C9—C10	1.394 (3)
Zn1—O7	2.0647 (17)	C9—C14	1.395 (3)
Zn1—N1	2.1307 (19)	C10—C11	1.376 (4)
Zn1—C8	2.545 (2)	C10—H10	0.9300
O1—C1	1.265 (3)	C11—H11	0.9300
O2—C1	1.265 (3)	C12—C11	1.410 (4)
O3—C8	1.278 (3)	C13—C12	1.410 (4)
O4—C8	1.271 (3)	C13—H13	0.9300
O5—C24	1.240 (3)	C14—C13	1.378 (4)
O6—H61	0.891 (17)	C14—H14	0.9300
O6—H62	0.879 (19)	C15—C16	1.389 (3)
O7—H71	0.89 (3)	C15—H15	0.9300
O7—H72	0.875 (18)	C16—C17	1.386 (3)
N1—C15	1.340 (3)	C16—H16	0.9300
N1—C19	1.345 (3)	C18—C17	1.392 (3)
N2—H21	0.89 (3)	C18—C19	1.382 (3)
N2—H22	0.89 (3)	C18—H18	0.9300
N3—C5	1.412 (3)	C19—H19	0.9300
N3—C20	1.463 (3)	C20—H20A	0.9600
N3—C21	1.458 (3)	C20—H20B	0.9600
N4—C12	1.368 (3)	C20—H20C	0.9600
N4—C22	1.448 (4)	C21—H21A	0.9600
N4—C23	1.449 (4)	C21—H21B	0.9600
C1—C2	1.495 (3)	C21—H21C	0.9600
C3—C2	1.391 (3)	C22—H22A	0.9600
C3—C4	1.389 (3)	C22—H22B	0.9600
C3—H3	0.9300	C22—H22C	0.9600
C4—C5	1.398 (3)	C23—H23A	0.9600
C4—H4	0.9300	C23—H23B	0.9600
C5—C6	1.404 (3)	C23—H23C	0.9600
C6—H6	0.9300	C24—N2	1.325 (3)
C7—C2	1.396 (3)	C24—C17	1.505 (3)

O1—Zn1—O3	158.68 (7)	C10—C9—C8	121.4 (2)
O1—Zn1—O4	99.43 (6)	C10—C9—C14	117.7 (2)
O1—Zn1—O6	91.08 (7)	C14—C9—C8	120.9 (2)
O1—Zn1—O7	106.57 (7)	C9—C10—H10	119.2
O1—Zn1—N1	89.59 (7)	C11—C10—C9	121.6 (2)
O3—Zn1—O4	60.03 (6)	C11—C10—H10	119.2
O3—Zn1—O6	93.40 (7)	C10—C11—C12	120.8 (3)
O6—Zn1—O4	87.44 (6)	C10—C11—H11	119.6
O7—Zn1—O3	94.72 (7)	C12—C11—H11	119.6
O7—Zn1—O4	151.55 (7)	N4—C12—C11	121.4 (3)
O7—Zn1—O6	80.80 (7)	N4—C12—C13	121.2 (3)
O7—Zn1—N1	89.90 (7)	C11—C12—C13	117.4 (2)
N1—Zn1—O3	89.40 (7)	C12—C13—H13	119.6
N1—Zn1—O4	101.82 (7)	C14—C13—C12	120.8 (2)
N1—Zn1—O6	170.47 (7)	C14—C13—H13	119.6
C1—O1—Zn1	128.40 (15)	C9—C14—H14	119.2
C8—O3—Zn1	93.10 (14)	C13—C14—C9	121.6 (3)
C8—O4—Zn1	87.63 (13)	C13—C14—H14	119.2
Zn1—O6—H61	98 (2)	N1—C15—C16	122.8 (2)
Zn1—O6—H62	111 (2)	N1—C15—H15	118.6
H61—O6—H62	106 (3)	C16—C15—H15	118.6
Zn1—O7—H71	119 (2)	C15—C16—H16	120.6
Zn1—O7—H72	130 (2)	C17—C16—C15	118.9 (2)
H72—O7—H71	106 (2)	C17—C16—H16	120.6
C15—N1—Zn1	123.02 (16)	C16—C17—C18	118.7 (2)
C15—N1—C19	117.8 (2)	C16—C17—C24	122.9 (2)
C19—N1—Zn1	119.03 (16)	C18—C17—C24	118.3 (2)
C24—N2—H21	116 (2)	C17—C18—H18	120.7
C24—N2—H22	126 (2)	C19—C18—C17	118.6 (2)
H22—N2—H21	118 (3)	C19—C18—H18	120.7
C5—N3—C21	116.7 (2)	N1—C19—C18	123.1 (2)
C5—N3—C20	116.3 (2)	N1—C19—H19	118.4
C21—N3—C20	112.2 (2)	C18—C19—H19	118.4
C12—N4—C22	120.3 (3)	N3—C20—H20A	109.5
C12—N4—C23	120.4 (3)	N3—C20—H20B	109.5
C22—N4—C23	119.1 (2)	N3—C20—H20C	109.5
O1—C1—O2	123.7 (2)	H20A—C20—H20B	109.5
O1—C1—C2	117.7 (2)	H20A—C20—H20C	109.5
O2—C1—C2	118.5 (2)	H20B—C20—H20C	109.5
C3—C2—C1	121.0 (2)	N3—C21—H21A	109.5
C3—C2—C7	117.9 (2)	N3—C21—H21B	109.5
C7—C2—C1	121.2 (2)	N3—C21—H21C	109.5
C2—C3—H3	119.4	H21A—C21—H21B	109.5
C4—C3—C2	121.3 (2)	H21A—C21—H21C	109.5
C4—C3—H3	119.4	H21B—C21—H21C	109.5
C3—C4—C5	120.9 (2)	N4—C22—H22A	109.5
C3—C4—H4	119.6	N4—C22—H22B	109.5
C5—C4—H4	119.6	N4—C22—H22C	109.5
C4—C5—N3	122.0 (2)	H22A—C22—H22B	109.5
C4—C5—C6	117.7 (2)	H22A—C22—H22C	109.5
C6—C5—N3	120.2 (2)	H22B—C22—H22C	109.5
C5—C6—H6	119.5	N4—C23—H23A	109.5
C7—C6—C5	121.0 (2)	N4—C23—H23B	109.5
C7—C6—H6	119.5	N4—C23—H23C	109.5
C2—C7—H7	119.3	H23A—C23—H23B	109.5
C6—C7—C2	121.3 (2)	H23A—C23—H23C	109.5
C6—C7—H7	119.3	H23B—C23—H23C	109.5
O3—C8—C9	119.8 (2)	O5—C24—N2	123.0 (2)
O4—C8—O3	119.2 (2)	O5—C24—C17	119.1 (2)
O4—C8—C9	121.0 (2)	N2—C24—C17	117.9 (2)

O3—Zn1—O1—C1	−71.5 (3)	C23—N4—C12—C13	−173.5 (3)
O4—Zn1—O1—C1	−56.9 (2)	O1—C1—C2—C3	−174.7 (2)
O6—Zn1—O1—C1	30.69 (19)	O1—C1—C2—C7	3.5 (3)
O7—Zn1—O1—C1	111.42 (19)	O2—C1—C2—C3	6.0 (3)
N1—Zn1—O1—C1	−158.81 (19)	O2—C1—C2—C7	−175.8 (2)
O1—Zn1—O3—C8	16.4 (2)	C4—C3—C2—C1	178.5 (2)
O4—Zn1—O3—C8	−0.36 (12)	C4—C3—C2—C7	0.3 (3)
O6—Zn1—O3—C8	−85.43 (13)	C2—C3—C4—C5	0.0 (4)
O7—Zn1—O3—C8	−166.47 (13)	C3—C4—C5—N3	−176.2 (2)
N1—Zn1—O3—C8	103.68 (13)	C3—C4—C5—C6	0.2 (3)
O1—Zn1—O4—C8	−173.56 (13)	N3—C5—C6—C7	175.8 (2)
O3—Zn1—O4—C8	0.36 (12)	C4—C5—C6—C7	−0.7 (3)
O6—Zn1—O4—C8	95.77 (13)	C6—C7—C2—C1	−179.0 (2)
O7—Zn1—O4—C8	30.5 (2)	C6—C7—C2—C3	−0.8 (3)
N1—Zn1—O4—C8	−81.99 (13)	C2—C7—C6—C5	1.0 (4)
O1—Zn1—N1—C15	22.18 (18)	C10—C9—C8—O3	0.2 (3)
O1—Zn1—N1—C19	−153.57 (17)	C10—C9—C8—O4	179.2 (2)
O3—Zn1—N1—C15	−136.52 (18)	C14—C9—C8—O3	−179.1 (2)
O3—Zn1—N1—C19	47.73 (17)	C14—C9—C8—O4	−0.1 (3)
O4—Zn1—N1—C19	106.89 (17)	C8—C9—C10—C11	−178.9 (2)
O4—Zn1—N1—C15	−77.36 (18)	C14—C9—C10—C11	0.4 (4)
O7—Zn1—N1—C15	128.76 (18)	C8—C9—C14—C13	178.0 (2)
O7—Zn1—N1—C19	−46.99 (17)	C10—C9—C14—C13	−1.3 (4)
Zn1—O1—C1—O2	−19.5 (3)	C9—C10—C11—C12	1.1 (4)
Zn1—O1—C1—C2	161.36 (15)	N4—C12—C11—C10	178.1 (3)
Zn1—O3—C8—O4	0.6 (2)	C13—C12—C11—C10	−1.7 (4)
Zn1—O3—C8—C9	179.65 (18)	C14—C13—C12—N4	−179.0 (2)
Zn1—O4—C8—O3	−0.6 (2)	C14—C13—C12—C11	0.8 (4)
Zn1—O4—C8—C9	−179.61 (19)	C9—C14—C13—C12	0.8 (4)
Zn1—N1—C15—C16	−175.38 (17)	N1—C15—C16—C17	1.3 (4)
C19—N1—C15—C16	0.4 (3)	C15—C16—C17—C18	−1.2 (3)
Zn1—N1—C19—C18	173.64 (17)	C15—C16—C17—C24	175.2 (2)
C15—N1—C19—C18	−2.3 (3)	C19—C18—C17—C16	−0.5 (3)
C20—N3—C5—C4	−146.3 (2)	C19—C18—C17—C24	−177.2 (2)
C20—N3—C5—C6	37.4 (3)	C17—C18—C19—N1	2.4 (3)
C21—N3—C5—C4	−10.4 (3)	O5—C24—C17—C16	−150.0 (2)
C21—N3—C5—C6	173.4 (2)	O5—C24—C17—C18	26.5 (3)
C22—N4—C12—C11	−178.3 (3)	N2—C24—C17—C16	30.0 (3)
C22—N4—C12—C13	1.5 (4)	N2—C24—C17—C18	−153.5 (2)
C23—N4—C12—C11	6.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O4ⁱ	0.89 (3)	2.15 (3)	3.034 (3)	174 (3)
N2—H22···O3ⁱⁱ	0.89 (3)	1.95 (3)	2.820 (3)	164 (3)
O6—H61···O2	0.89 (3)	1.79 (3)	2.646 (2)	161 (3)
O6—H62···O5ⁱⁱⁱ	0.88 (3)	1.88 (3)	2.749 (2)	169 (3)
O7—H71···N3^iv	0.89 (3)	2.01 (3)	2.863 (3)	162 (3)
O7—H72···O2^v	0.87 (3)	1.80 (3)	2.667 (2)	171 (3)
C22—H22A···Cg3^vi	0.96	2.74	3.567 (3)	145
C23—H23C···Cg2^vii	0.96	2.86	3.644 (3)	140

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)(H₂O)₂]
M_r	551.91
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.8616 (2), 8.0947 (3), 22.4953 (4)
α, β, γ (°)	90.683 (2), 92.838 (2), 93.313 (3)
V (Å³)	1245.69 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.57 × 0.27 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.720, 0.810
No. of measured, independent and observed [I > 2σ(I)] reflections	21315, 6053, 5647
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.078, 1.29
No. of reflections	6053
No. of parameters	353
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.99

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	2.0353 (17)	Zn1—O6	2.1393 (17)
Zn1—O3	2.1328 (17)	Zn1—O7	2.0647 (17)
Zn1—O4	2.2584 (17)	Zn1—N1	2.1307 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O4ⁱ	0.89 (3)	2.15 (3)	3.034 (3)	174 (3)
N2—H22···O3ⁱⁱ	0.89 (3)	1.95 (3)	2.820 (3)	164 (3)
O6—H61···O2	0.89 (3)	1.79 (3)	2.646 (2)	161 (3)
O6—H62···O5ⁱⁱⁱ	0.88 (3)	1.88 (3)	2.749 (2)	169 (3)
O7—H71···N3^iv	0.89 (3)	2.01 (3)	2.863 (3)	162 (3)
O7—H72···O2^v	0.87 (3)	1.80 (3)	2.667 (2)	171 (3)
C22—H22A···Cg3^vi	0.96	2.74	3.567 (3)	145
C23—H23C···Cg2^vii	0.96	2.86	3.644 (3)	140

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

Acknowledgements

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

References

Adiwidjaja, G., Rossmanith, E. & Küppers, H. (1978). Acta Cryst. B34, 3079–3083. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Amiraslanov, I. R., Mamedov, Kh. S., Movsumov, E. M., Musaev, F. N. & Nadzhafov, G. N. (1979). Zh. Strukt. Khim. 20, 1075–1080. CAS Google Scholar
Antolini, L., Battaglia, L. P., Corradi, A. B., Marcotrigiano, G., Menabue, L., Pellacani, G. C. & Saladini, M. (1982). Inorg. Chem. 21, 1391–1395. CSD CrossRef CAS Web of Science Google Scholar
Antsyshkina, A. S., Chiragov, F. M. & Poray-Koshits, M. A. (1980). Koord. Khim. 15, 1098–1103. Google Scholar
Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc. Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Catterick, J., Hursthouse, M. B., New, D. B. & Thorhton, P. (1974). J. Chem. Soc. Chem. Commun. pp. 843–844. CrossRef Web of Science Google Scholar
Chen, H. J. & Chen, X. M. (2002). Inorg. Chim. Acta, 329, 13–21. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Greenaway, F. T., Pezeshk, A., Cordes, A. W., Noble, M. C. & Sorenson, J. R. J. (1984). Inorg. Chim. Acta, 93, 67–71. CSD CrossRef CAS Web of Science Google Scholar
Hauptmann, R., Kondo, M. & Kitagawa, S. (2000). Z. Kristallogr. New Cryst. Struct. 215, 169–172. CAS Google Scholar
Hökelek, T., Budak, K. & Necefoğlu, H. (1997). Acta Cryst. C53, 1049–1051. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T., Çaylak, N. & Necefoğlu, H. (2007). Acta Cryst. E63, m2561–m2562. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Çaylak, N. & Necefoğlu, H. (2008). Acta Cryst. E64, m505–m506. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (1996). Acta Cryst. C52, 1128–1131. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (1997). Acta Cryst. C53, 187–189. CSD CrossRef Web of Science IUCr Journals Google Scholar
Hökelek, T. & Necefoğlu, H. (2007). Acta Cryst. E63, m821–m823. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Necefoğlu, H. & Balcı, M. (1995). Acta Cryst. C51, 2020–2023. CSD CrossRef Web of Science IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shnulin, A. N., Nadzhafov, G. N., Amiraslanov, I. R., Usubaliev, B. T. & Mamedov, Kh. S. (1981). Koord. Khim. 7, 1409–1416. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar