Crystal structure of tri­aqua­(4-cyano­benzoato-κ2O,O′)(nicotinamide-κN1)zinc 4-cyano­benzoate

Aşkın, G. Ş.; Necefoğlu, H.; Yılmaz Nayir, G.; Çatak Çelik, R.; Hökelek, T.

doi:10.1107/S2056989015009743

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 684-686

doi:10.1107/S2056989015009743

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Crystal structure of triaqua(4-cyanobenzoato-κ²O,O′)(nicotinamide-κN¹)zinc 4-cyanobenzoate

Gülçin Şefiye Aşkın,^a Hacali Necefoğlu,^b,^c Gamze Yılmaz Nayir,^b Raziye Çatak Çelik ^d and Tuncer Hökelek ^a ^*

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^cInternational Scientific Research Centre, Baku State University, 1148 Baku, Azerbaijan, and ^dScientific and Technological Application and Research Center, Aksaray University, 68100, Aksaray, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by M. Weil, Vienna University of Technology, Austria (Received 7 May 2015; accepted 20 May 2015; online 23 May 2015)

The asymmetric unit of the title salt, [Zn(C₈H₄NO₂)(C₆H₆N₂O)(H₂O)₃](C₈H₄NO₂), contains one complex cation and one 4-cyanobenzoate (CNB) counter-anion. The Zn^II atom in the cation is coordinated by one 4-cyanobenzoate ligand, one nicotinamide (NA) ligand and three water molecules, the CNB anion thereby coordinating in a bidentate O,O′-mode through the carboxylate group. The latter, together with one water O atom and the N atom of the NA ligand, form a distorted square-planar arrangement, while the considerably distorted octahedral coordination sphere of the Zn^II atom is completed by the two O atoms of additional water molecules in the axial positions. The dihedral angles between the planar carboxylate groups and the adjacent benzene rings in the two anions are 10.25 (10) and 5.89 (14)°. Intermolecular O—H⋯O hydrogen bonds link two of the coordinating water molecules to two free CNB anions. In the crystal, further hydrogen-bonding interactions are present, namely N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds that link the molecular components, enclosing R₂²(12), R₃³(8) and R₃³(9) ring motifs and forming layers parallel to (001). π–π contacts between benzene rings [centroid-to-centroid distances = 3.791 (1) and 3.882 (1) Å] may further stabilize the crystal structure.

Keywords: crystal structure; zinc; transition metal complexes; benzoic acid nicotinamide.

CCDC reference: 1401948

1. Chemical context

As parts 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.

2. Structural commentary

The asymmetric unit of the crystal structure of the title salt, [Zn(C₈H₄O₂N)(C₆H₆ON₂)(H₂O)₃](C₈H₄O₂N), is composed of one complex cation and one 4-cyanobenzoate (CNB) counter-anion. The Zn^II atom is coordinated by one 4-cyanobenzoate (CNB) anion, one nicotinamide (NA) ligand and three water molecules, the CNB anion and NA ligand coordinating in bidentate and monodentate modes, respectively (Fig. 1).

Figure 1
The molecular entities of the title salt, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intermolecular O—H⋯O hydrogen bonds are shown as dashed lines.

In the cation, the four coordinating atoms (O1, O2, O5 and N2) around the Zn1 atom show a distorted square-planar arrangement, while the considerably distorted octahedral coordination environment of Zn^II is completed by two additional water O atoms (O4 and O6) in the axial positions (Table 1, Fig. 1).

Table 1
Selected bond lengths (Å)

Zn1—O1	2.2724 (12)	Zn1—O5	2.0132 (11)
Zn1—O2	2.1163 (12)	Zn1—O6	2.1917 (14)
Zn1—O4	2.0917 (13)	Zn1—N2	2.0545 (12)

The near equality of the C1—O1 [1.2531 (18) Å], C1—O2 [1.2591 (19) Å] and C15—O7 [1.266 (2) Å], C15—O8 [1.237 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn—O bond lengths are 2.19 (11) Å for benzoate oxygen atoms and 2.10 (9) Å for water oxygen atoms; the Zn—N bond length is 2.0545 (12) Å, close to the values in related structures. The Zn1 atom lies 0.0093 (2) Å above the planar (O1/O2/C1) carboxylate group, with a bite angle of 59.48 (4)°. Corresponding O—Zn—O angles are 60.03 (6)° in [Zn(C₉H₁₀NO₂)(C₆H₆N₂O)·2H₂O] (Hökelek et al., 2009a ), 59.02 (8)° in [Zn(C₈H₈NO₂)(C₆H₆N₂O)]·H₂O (Hökelek et al., 2009b ) and 57.53 (5), 56.19 (5) and 59.04 (4)° in [Zn(C₈H₇O₃)₂(C₆H₆N₂O)] (Hökelek et al., 2010 ).

The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O7/O8/C15)] and the adjacent benzene rings [A (C2–C7) and C (C16–C21)] are 10.25 (10) and 5.89 (14)°, respectively, while the benzene rings and benzene and pyridine [B (N2/C9—13)] rings are oriented at dihedral angles of A/C = 77.84 (6), A/B = 8.97 (5) and B/C = 71.43 (5)°.

3. Supramolecular features

In the crystal, N—H⋯O_c (c = carboxylate), O—H_w⋯O_c (w = water), O—H_w⋯O_n (n = nicotinamide), O—H_w⋯N_n as well as C—H_n⋯O_c hydrogen bonds (Table 2) link the molecular components, enclosing $[R_{2}^{2}]$ (12), $[R_{3}^{3}]$ (8) and $[R_{3}^{3}]$ (9) ring motifs (Bernstein et al., 1995 ), forming layers parallel to (001) (Fig. 2). Additional π–π contacts between the benzene rings, Cg1⋯Cg1ⁱ and Cg1⋯Cg3ⁱⁱ [symmetry codes: (i) 1 − x, −y, −z; (ii) 1 − x, −y, 1 − z, where Cg1 and Cg3 are the centroids of rings A and C, respectively], may further stabilize the structure, with centroid-to-centroid distances of 3.791 (1) Å and 3.882 (1) Å, respectively.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31⋯O2ⁱ	0.82 (2)	2.13 (3)	2.914 (2)	162 (2)
N3—H32⋯O7ⁱ	0.92 (3)	2.35 (2)	3.261 (2)	171 (2)
O4—H41⋯O7ⁱⁱ	0.75 (2)	2.04 (2)	2.7890 (17)	173 (3)
O4—H42⋯O8	0.76 (3)	1.89 (3)	2.6547 (18)	175 (3)
O5—H51⋯O7	0.80 (2)	1.83 (2)	2.6264 (17)	171 (3)
O5—H52⋯O1ⁱⁱⁱ	0.74 (2)	2.05 (2)	2.7610 (17)	164 (2)
O6—H61⋯O3ⁱⁱⁱ	0.75 (3)	2.05 (3)	2.7993 (19)	170 (3)
O6—H62⋯N1^iv	0.76 (3)	2.17 (3)	2.918 (3)	170 (3)
C11—H11⋯O7ⁱ	0.93	2.49	3.415 (2)	177
Symmetry codes: (i) x-1, y+1, z; (ii) x-1, y, z; (iii) x+1, y, z; (iv) -x+1, -y, -z.

Figure 2
A partial packing diagram of the title complex. Intermolecular N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds are shown as dashed lines, enclosing $[R_{2}^{2}]$ (12), $[R_{3}^{3}]$ (8) and $[R_{3}^{3}]$ (9) ring motifs. Non-bonding H atoms have been omitted for clarity.

4. Synthesis and crystallization

The title compound was prepared by the reaction of ZnSO₄·7H₂O (1.44 g, 5 mmol) in H₂O (30 ml) and nicotinamide (1.22 g, 50 mmol) in H₂O (50 ml) with sodium 4-cyanobenzoate (1.69 g, 10 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.

5. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3. Atoms H31 and H32 (as part of the NH₂ group) and H41, H42, H51, H52, H61 and H62 (as part of the water molecules) were located in a difference Fourier map and were refined freely. The aromatic C-bound H atoms were positioned geometrically with C—H = 0.93 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	[Zn(C₈H₄NO₂)(C₆H₆N₂O)(H₂O)₃](C₈H₄NO₂)
M_r	533.81
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.0858 (2), 8.7031 (3), 22.2357 (6)
α, β, γ (°)	81.882 (2), 87.806 (3), 88.007 (3)
V (Å³)	1164.55 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.11
Crystal size (mm)	0.45 × 0.36 × 0.25

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.625, 0.758
No. of measured, independent and observed [I > 2σ(I)] reflections	27167, 5839, 5450
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.05
No. of reflections	5839
No. of parameters	348
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.33
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1401948

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015009743/wm5158sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009743/wm5158Isup2.hkl

checkCIF report

Chemical context top

As parts 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.

Structural commentary top

The near equality of the C1—O1 [1.2531 (18) Å], C1—O2 [1.2591 (19) Å] and C15—O7 [1.266 (2) Å], C15—O8 [1.237 (2) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn—O bond lengths are 2.19 (11) Å for benzoate oxygens atoms and 2.10 (9) Å for water oxygen atoms; the Zn—N bond length is 2.0545 (12) Å, close to the values in related structures. The Zn1 atom lies 0.0093 (2) Å above the planar (O1/O2/C1) carboxylate group, with a bite angle of 59.48 (4)°. Corresponding O—Zn—O angles are 60.03 (6)° in [Zn(C₉H₁₀NO₂)(C₆H₆N₂O)·2H₂O] (Hökelek et al., 2009a), 59.02 (8)° in [Zn(C₈H₈NO₂)(C₆H₆N₂O)]·H₂O (Hökelek et al., 2009b) and 57.53 (5), 56.19 (5) and 59.04 (4)° in [Zn(C₈H₇O₃)₂(C₆H₆N₂O)] (Hökelek et al., 2010).

Supramolecular features top

In the crystal, N—H···O_c (c = carboxylate), O—H_w···O_c (w = water), O—H_w···O_n (n = nicotinamide), O—H_w···N_n as well as C—H_n···O_c hydrogen bonds (Table 2) link the molecular components, enclosing R₂²(12), R₃³(8) and R₃³(9) ring motifs (Bernstein et al., 1995), forming layers parallel to (001) (Fig. 2). Additional π–π contacts between the benzene rings, Cg1···Cg1ⁱ and Cg1···Cg3ⁱⁱ [symmetry codes: (i) 1 - x, -y, -z; (ii) 1 - x, -y, 1 - z, where Cg1 and Cg3 are the centroids of rings A and C, respectively], may further stabilize the structure, with centroid-to-centroid distances of 3.791 (1) Å and 3.882 (1) Å, respectively.

Synthesis and crystallization top

Refinement top

Related literature top

Bernstein et al. (1995); Bigoli et al. (1972); Hökelek et al. (2009a, 2009b, 2010); Krishnamachari (1974).

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); 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 entities of the title salt, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Intermolecular O—H···O hydrogen bonds are shown as dashed lines.
	Fig. 2. A partial packing diagram of the title complex. Intermolecular N—H···O, O—H···O, O—H···N and C—H···O hydrogen bonds are shown as dashed lines, enclosing R₂²(12), R₃³(8) and R₃³(9) ring motifs. Non-bonding H atoms have been omitted for clarity.

Triaqua(4-cyanobenzoato-κ²O,O')(nicotinamide-κN¹)zinc 4-cyanobenzoate top

Crystal data top

[Zn(C₈H₄NO₂)(C₆H₆N₂O)(H₂O)₃](C₈H₄NO₂)	Z = 2
M_r = 533.81	F(000) = 548
Triclinic, P1	D_x = 1.522 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0858 (2) Å	Cell parameters from 9885 reflections
b = 8.7031 (3) Å	θ = 2.4–28.4°
c = 22.2357 (6) Å	µ = 1.11 mm⁻¹
α = 81.882 (2)°	T = 296 K
β = 87.806 (3)°	Prism, translucent light colourless
γ = 88.007 (3)°	0.45 × 0.36 × 0.25 mm
V = 1164.55 (6) Å³

Data collection top

Bruker SMART BREEZE CCD diffractometer	5839 independent reflections
Radiation source: fine-focus sealed tube	5450 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −7→8
T_min = 0.625, T_max = 0.758	k = −11→11
27167 measured reflections	l = −29→29

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0394P)² + 0.4376P] where P = (F_o² + 2F_c²)/3
5839 reflections	(Δ/σ)_max = 0.001
348 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Zn(C₈H₄NO₂)(C₆H₆N₂O)(H₂O)₃](C₈H₄NO₂)	γ = 88.007 (3)°
M_r = 533.81	V = 1164.55 (6) Å³
Triclinic, P1	Z = 2
a = 6.0858 (2) Å	Mo Kα radiation
b = 8.7031 (3) Å	µ = 1.11 mm⁻¹
c = 22.2357 (6) Å	T = 296 K
α = 81.882 (2)°	0.45 × 0.36 × 0.25 mm
β = 87.806 (3)°

Data collection top

Bruker SMART BREEZE CCD diffractometer	5839 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	5450 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.758	R_int = 0.034
27167 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.35 e Å⁻³
5839 reflections	Δρ_min = −0.33 e Å⁻³
348 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.90164 (3)	0.228852 (18)	0.220630 (8)	0.02931 (6)
O1	0.58663 (19)	0.18054 (14)	0.17586 (6)	0.0398 (3)
O2	0.89148 (19)	0.04418 (14)	0.16835 (6)	0.0386 (3)
O3	0.1991 (2)	0.64093 (14)	0.17635 (6)	0.0425 (3)
O4	0.8145 (2)	0.08998 (17)	0.30208 (6)	0.0456 (3)
H41	0.698 (4)	0.078 (3)	0.3136 (11)	0.051 (7)*
H42	0.887 (4)	0.079 (3)	0.3298 (12)	0.060 (7)*
O5	1.21393 (19)	0.21434 (14)	0.24815 (6)	0.0346 (2)
H51	1.258 (4)	0.162 (3)	0.2779 (11)	0.057 (7)*
H52	1.298 (4)	0.209 (2)	0.2238 (9)	0.035 (5)*
O6	1.0470 (3)	0.36922 (16)	0.14029 (6)	0.0442 (3)
H61	1.087 (4)	0.447 (3)	0.1457 (11)	0.052 (7)*
H62	0.983 (4)	0.379 (3)	0.1113 (12)	0.060 (8)*
O7	1.38028 (19)	0.02307 (15)	0.33815 (5)	0.0413 (3)
O8	1.0769 (2)	0.0341 (2)	0.39584 (6)	0.0620 (4)
N1	0.1949 (5)	−0.3612 (3)	−0.03004 (10)	0.0940 (9)
N2	0.7668 (2)	0.42834 (14)	0.24805 (6)	0.0315 (3)
N3	0.2052 (3)	0.83017 (18)	0.23482 (8)	0.0454 (4)
H31	0.101 (4)	0.872 (3)	0.2162 (11)	0.058 (7)*
H32	0.269 (4)	0.879 (3)	0.2633 (11)	0.057 (6)*
N4	1.7600 (4)	−0.5182 (3)	0.61042 (11)	0.0876 (8)
C1	0.6926 (2)	0.07134 (17)	0.15590 (7)	0.0292 (3)
C2	0.5848 (2)	−0.02630 (17)	0.11607 (6)	0.0294 (3)
C3	0.3787 (3)	0.0185 (2)	0.09399 (8)	0.0381 (3)
H3	0.3076	0.1079	0.1044	0.046*
C4	0.2796 (3)	−0.0701 (2)	0.05652 (8)	0.0469 (4)
H4	0.1420	−0.0405	0.0413	0.056*
C5	0.3867 (3)	−0.2038 (2)	0.04169 (8)	0.0470 (4)
C6	0.5917 (4)	−0.2502 (2)	0.06388 (9)	0.0473 (4)
H6	0.6618	−0.3402	0.0538	0.057*
C7	0.6911 (3)	−0.16065 (19)	0.10140 (8)	0.0371 (3)
H7	0.8286	−0.1905	0.1167	0.045*
C8	0.2809 (5)	−0.2932 (3)	0.00172 (10)	0.0665 (7)
C9	0.8671 (3)	0.4895 (2)	0.29107 (8)	0.0417 (4)
H9	0.9926	0.4393	0.3078	0.050*
C10	0.7913 (3)	0.6238 (3)	0.31145 (10)	0.0558 (5)
H10	0.8666	0.6654	0.3407	0.067*
C11	0.6017 (3)	0.6963 (2)	0.28798 (9)	0.0491 (5)
H11	0.5467	0.7867	0.3017	0.059*
C12	0.4942 (2)	0.63340 (16)	0.24389 (7)	0.0299 (3)
C13	0.5853 (3)	0.50013 (16)	0.22481 (7)	0.0303 (3)
H13	0.5169	0.4585	0.1943	0.036*
C14	0.2868 (3)	0.70160 (16)	0.21562 (7)	0.0317 (3)
C15	1.2702 (3)	−0.0089 (2)	0.38754 (7)	0.0346 (3)
C16	1.3816 (3)	−0.11192 (18)	0.43897 (7)	0.0318 (3)
C17	1.2673 (3)	−0.1557 (2)	0.49338 (8)	0.0423 (4)
H17	1.1254	−0.1161	0.4993	0.051*
C18	1.3630 (3)	−0.2582 (2)	0.53905 (8)	0.0503 (5)
H18	1.2857	−0.2876	0.5755	0.060*
C19	1.5746 (3)	−0.3167 (2)	0.53011 (8)	0.0446 (4)
C20	1.6928 (3)	−0.2701 (2)	0.47640 (9)	0.0445 (4)
H20	1.8358	−0.3079	0.4708	0.053*
C21	1.5961 (3)	−0.1669 (2)	0.43142 (8)	0.0379 (3)
H21	1.6757	−0.1340	0.3957	0.046*
C22	1.6768 (4)	−0.4285 (3)	0.57586 (10)	0.0600 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02640 (10)	0.02670 (9)	0.03590 (11)	0.00369 (6)	−0.00771 (7)	−0.00734 (7)
O1	0.0353 (6)	0.0404 (6)	0.0465 (7)	0.0023 (5)	−0.0002 (5)	−0.0171 (5)
O2	0.0304 (6)	0.0382 (6)	0.0498 (7)	0.0022 (5)	−0.0125 (5)	−0.0126 (5)
O3	0.0435 (7)	0.0344 (6)	0.0514 (7)	0.0022 (5)	−0.0162 (6)	−0.0087 (5)
O4	0.0294 (7)	0.0607 (8)	0.0418 (7)	−0.0051 (6)	−0.0061 (6)	0.0118 (6)
O5	0.0247 (5)	0.0420 (6)	0.0354 (6)	0.0037 (5)	−0.0037 (5)	0.0001 (5)
O6	0.0579 (8)	0.0391 (7)	0.0365 (7)	−0.0094 (6)	−0.0098 (6)	−0.0044 (5)
O7	0.0318 (6)	0.0549 (7)	0.0333 (6)	0.0080 (5)	−0.0017 (5)	0.0055 (5)
O8	0.0332 (7)	0.1071 (13)	0.0398 (7)	0.0214 (7)	−0.0021 (5)	0.0051 (7)
N1	0.135 (2)	0.0930 (17)	0.0616 (13)	−0.0520 (16)	−0.0348 (14)	−0.0149 (12)
N2	0.0299 (6)	0.0296 (6)	0.0357 (7)	0.0044 (5)	−0.0043 (5)	−0.0070 (5)
N3	0.0446 (9)	0.0346 (7)	0.0583 (10)	0.0146 (6)	−0.0166 (8)	−0.0113 (7)
N4	0.0892 (16)	0.0843 (15)	0.0815 (15)	−0.0089 (13)	−0.0451 (13)	0.0280 (12)
C1	0.0297 (7)	0.0299 (7)	0.0277 (7)	−0.0022 (5)	−0.0016 (5)	−0.0031 (5)
C2	0.0284 (7)	0.0334 (7)	0.0267 (7)	−0.0051 (6)	−0.0011 (5)	−0.0043 (5)
C3	0.0307 (8)	0.0458 (9)	0.0380 (8)	−0.0017 (7)	−0.0046 (6)	−0.0049 (7)
C4	0.0367 (9)	0.0646 (12)	0.0392 (9)	−0.0136 (8)	−0.0115 (7)	−0.0005 (8)
C5	0.0598 (12)	0.0532 (10)	0.0296 (8)	−0.0268 (9)	−0.0066 (8)	−0.0038 (7)
C6	0.0640 (12)	0.0378 (9)	0.0433 (9)	−0.0094 (8)	−0.0034 (8)	−0.0138 (7)
C7	0.0378 (9)	0.0358 (8)	0.0389 (8)	−0.0015 (6)	−0.0039 (7)	−0.0086 (6)
C8	0.0899 (17)	0.0679 (14)	0.0446 (11)	−0.0359 (13)	−0.0173 (11)	−0.0057 (10)
C9	0.0352 (9)	0.0491 (9)	0.0435 (9)	0.0117 (7)	−0.0118 (7)	−0.0156 (7)
C10	0.0502 (11)	0.0651 (12)	0.0609 (12)	0.0198 (9)	−0.0255 (9)	−0.0379 (10)
C11	0.0477 (10)	0.0479 (10)	0.0580 (11)	0.0169 (8)	−0.0167 (9)	−0.0292 (9)
C12	0.0306 (7)	0.0262 (6)	0.0324 (7)	0.0019 (5)	−0.0020 (6)	−0.0028 (5)
C13	0.0314 (7)	0.0262 (6)	0.0338 (7)	0.0008 (5)	−0.0052 (6)	−0.0056 (5)
C14	0.0323 (8)	0.0248 (6)	0.0369 (8)	0.0010 (5)	−0.0034 (6)	−0.0007 (5)
C15	0.0281 (7)	0.0446 (8)	0.0308 (7)	0.0026 (6)	−0.0058 (6)	−0.0048 (6)
C16	0.0306 (7)	0.0363 (7)	0.0292 (7)	−0.0011 (6)	−0.0064 (6)	−0.0055 (6)
C17	0.0365 (9)	0.0542 (10)	0.0354 (8)	0.0005 (7)	−0.0010 (7)	−0.0041 (7)
C18	0.0545 (11)	0.0608 (12)	0.0331 (9)	−0.0055 (9)	−0.0020 (8)	0.0031 (8)
C19	0.0488 (10)	0.0434 (9)	0.0407 (9)	−0.0062 (8)	−0.0185 (8)	0.0028 (7)
C20	0.0351 (9)	0.0472 (9)	0.0496 (10)	0.0035 (7)	−0.0121 (7)	0.0003 (8)
C21	0.0334 (8)	0.0428 (8)	0.0362 (8)	0.0003 (7)	−0.0040 (6)	−0.0007 (7)
C22	0.0617 (13)	0.0613 (13)	0.0544 (12)	−0.0092 (10)	−0.0247 (10)	0.0090 (10)

Geometric parameters (Å, º) top

Zn1—O1	2.2724 (12)	C5—C4	1.388 (3)
Zn1—O2	2.1163 (12)	C5—C6	1.385 (3)
Zn1—O4	2.0917 (13)	C5—C8	1.444 (3)
Zn1—O5	2.0132 (11)	C6—H6	0.9300
Zn1—O6	2.1917 (14)	C7—C6	1.387 (2)
Zn1—N2	2.0545 (12)	C7—H7	0.9300
Zn1—C1	2.5276 (15)	C9—C10	1.372 (2)
O1—C1	1.2531 (18)	C9—H9	0.9300
O2—C1	1.2591 (19)	C10—H10	0.9300
O3—C14	1.230 (2)	C11—C10	1.380 (3)
O4—H41	0.75 (3)	C11—H11	0.9300
O4—H42	0.77 (3)	C12—C11	1.384 (2)
O5—H51	0.80 (3)	C12—C13	1.382 (2)
O5—H52	0.74 (2)	C12—C14	1.498 (2)
O6—H61	0.75 (3)	C13—H13	0.9300
O6—H62	0.76 (3)	C14—N3	1.327 (2)
O7—C15	1.266 (2)	C15—O8	1.237 (2)
N1—C8	1.136 (3)	C15—C16	1.516 (2)
N2—C9	1.335 (2)	C16—C17	1.384 (2)
N2—C13	1.3351 (19)	C16—C21	1.387 (2)
N3—H31	0.82 (3)	C17—C18	1.385 (3)
N3—H32	0.91 (3)	C17—H17	0.9300
N4—C22	1.136 (3)	C18—H18	0.9300
C1—C2	1.494 (2)	C19—C18	1.386 (3)
C2—C3	1.388 (2)	C19—C22	1.447 (3)
C2—C7	1.390 (2)	C20—C19	1.388 (3)
C3—C4	1.380 (2)	C20—H20	0.9300
C3—H3	0.9300	C21—C20	1.381 (2)
C4—H4	0.9300	C21—H21	0.9300

O2—Zn1—O1	59.48 (4)	C5—C4—H4	120.2
O4—Zn1—O1	92.90 (5)	C4—C5—C8	118.5 (2)
O5—Zn1—O1	162.17 (5)	C6—C5—C4	121.15 (16)
O6—Zn1—O1	95.68 (5)	C6—C5—C8	120.4 (2)
N2—Zn1—O1	91.98 (5)	C5—C6—C7	119.12 (18)
O5—Zn1—O2	102.69 (5)	C5—C6—H6	120.4
O4—Zn1—O2	93.77 (6)	C7—C6—H6	120.4
N2—Zn1—O2	150.78 (5)	C2—C7—H7	120.1
O5—Zn1—O4	87.85 (6)	C6—C7—C2	119.86 (17)
N2—Zn1—O4	93.81 (6)	C6—C7—H7	120.1
O2—Zn1—O6	87.82 (5)	N1—C8—C5	178.7 (3)
O4—Zn1—O6	170.83 (6)	N2—C9—C10	122.20 (16)
O5—Zn1—O6	82.99 (6)	N2—C9—H9	118.9
N2—Zn1—O6	89.13 (5)	C10—C9—H9	118.9
O5—Zn1—N2	105.76 (5)	C9—C10—C11	119.10 (17)
O1—Zn1—C1	29.66 (4)	C9—C10—H10	120.5
O2—Zn1—C1	29.82 (5)	C11—C10—H10	120.5
O4—Zn1—C1	93.91 (5)	C10—C11—C12	119.40 (16)
O5—Zn1—C1	132.51 (5)	C10—C11—H11	120.3
O6—Zn1—C1	91.96 (5)	C12—C11—H11	120.3
N2—Zn1—C1	121.41 (5)	C11—C12—C14	123.93 (14)
C1—O1—Zn1	86.53 (9)	C13—C12—C11	117.67 (14)
C1—O2—Zn1	93.49 (9)	C13—C12—C14	118.40 (14)
Zn1—O4—H41	123.9 (18)	N2—C13—C12	123.08 (14)
Zn1—O4—H42	122.6 (19)	N2—C13—H13	118.5
H42—O4—H41	107 (3)	C12—C13—H13	118.5
Zn1—O5—H51	126.1 (17)	O3—C14—N3	122.30 (15)
Zn1—O5—H52	114.8 (16)	O3—C14—C12	121.07 (14)
H52—O5—H51	107 (2)	N3—C14—C12	116.63 (15)
Zn1—O6—H61	115.0 (18)	O7—C15—C16	117.31 (14)
Zn1—O6—H62	118 (2)	O8—C15—O7	124.46 (15)
H61—O6—H62	110 (3)	O8—C15—C16	118.19 (15)
C9—N2—Zn1	118.11 (11)	C17—C16—C15	120.11 (14)
C13—N2—Zn1	123.38 (10)	C17—C16—C21	119.38 (15)
C9—N2—C13	118.51 (13)	C21—C16—C15	120.49 (14)
C14—N3—H31	115.4 (17)	C16—C17—C18	120.40 (17)
C14—N3—H32	123.8 (15)	C16—C17—H17	119.8
H31—N3—H32	120 (2)	C18—C17—H17	119.8
O1—C1—Zn1	63.82 (8)	C17—C18—C19	119.64 (17)
O2—C1—Zn1	56.69 (8)	C17—C18—H18	120.2
C2—C1—Zn1	175.80 (11)	C19—C18—H18	120.2
O1—C1—O2	120.51 (14)	C18—C19—C20	120.37 (16)
O1—C1—C2	120.21 (14)	C18—C19—C22	121.19 (19)
O2—C1—C2	119.28 (13)	C20—C19—C22	118.43 (19)
C3—C2—C1	119.43 (14)	C19—C20—H20	120.3
C3—C2—C7	120.58 (15)	C21—C20—C19	119.37 (17)
C7—C2—C1	119.99 (14)	C21—C20—H20	120.3
C2—C3—H3	120.2	C16—C21—H21	119.6
C4—C3—C2	119.68 (17)	C20—C21—C16	120.76 (16)
C4—C3—H3	120.2	C20—C21—H21	119.6
C3—C4—C5	119.60 (17)	N4—C22—C19	178.0 (3)
C3—C4—H4	120.2

O2—Zn1—O1—C1	−0.14 (9)	C9—N2—C13—C12	−1.1 (2)
O4—Zn1—O1—C1	−92.81 (10)	O1—C1—C2—C3	9.5 (2)
O5—Zn1—O1—C1	−0.8 (2)	O1—C1—C2—C7	−170.49 (14)
O6—Zn1—O1—C1	83.95 (10)	O2—C1—C2—C3	−169.34 (14)
N2—Zn1—O1—C1	173.27 (9)	O2—C1—C2—C7	10.6 (2)
O1—Zn1—O2—C1	0.14 (8)	C1—C2—C3—C4	179.15 (15)
O4—Zn1—O2—C1	91.28 (10)	C7—C2—C3—C4	−0.8 (2)
O5—Zn1—O2—C1	179.92 (9)	C1—C2—C7—C6	−179.31 (15)
O6—Zn1—O2—C1	−97.77 (10)	C3—C2—C7—C6	0.7 (2)
N2—Zn1—O2—C1	−13.46 (16)	C2—C3—C4—C5	0.5 (3)
O1—Zn1—N2—C9	163.71 (13)	C6—C5—C4—C3	0.1 (3)
O1—Zn1—N2—C13	−16.72 (13)	C8—C5—C4—C3	−179.13 (17)
O2—Zn1—N2—C9	175.39 (12)	C4—C5—C6—C7	−0.2 (3)
O2—Zn1—N2—C13	−5.04 (19)	C8—C5—C6—C7	178.95 (17)
O4—Zn1—N2—C9	70.67 (14)	C2—C7—C6—C5	−0.1 (3)
O4—Zn1—N2—C13	−109.76 (13)	N2—C9—C10—C11	1.8 (4)
O5—Zn1—N2—C9	−18.17 (14)	C12—C11—C10—C9	−0.9 (4)
O5—Zn1—N2—C13	161.40 (12)	C13—C12—C11—C10	−0.8 (3)
O6—Zn1—N2—C9	−100.64 (14)	C14—C12—C11—C10	179.55 (19)
O6—Zn1—N2—C13	78.93 (13)	C11—C12—C13—N2	1.9 (2)
C1—Zn1—N2—C9	167.60 (12)	C14—C12—C13—N2	−178.46 (14)
C1—Zn1—N2—C13	−12.83 (15)	C11—C12—C14—O3	179.62 (17)
O1—Zn1—C1—O2	−179.76 (15)	C11—C12—C14—N3	0.1 (3)
O2—Zn1—C1—O1	179.76 (15)	C13—C12—C14—O3	0.0 (2)
O4—Zn1—C1—O1	88.99 (10)	C13—C12—C14—N3	−179.54 (15)
O4—Zn1—C1—O2	−90.77 (10)	O7—C15—C16—C17	−177.65 (16)
O5—Zn1—C1—O1	179.65 (9)	O7—C15—C16—C21	0.4 (2)
O5—Zn1—C1—O2	−0.11 (12)	O8—C15—C16—C17	0.1 (3)
O6—Zn1—C1—O1	−98.06 (10)	O8—C15—C16—C21	178.16 (18)
O6—Zn1—C1—O2	82.18 (10)	C15—C16—C17—C18	175.64 (17)
N2—Zn1—C1—O1	−7.89 (11)	C21—C16—C17—C18	−2.4 (3)
N2—Zn1—C1—O2	172.35 (9)	C15—C16—C21—C20	−175.12 (16)
Zn1—O1—C1—O2	0.23 (14)	C17—C16—C21—C20	3.0 (3)
Zn1—O1—C1—C2	−178.65 (12)	C16—C17—C18—C19	0.1 (3)
Zn1—O2—C1—O1	−0.25 (15)	C20—C19—C18—C17	1.7 (3)
Zn1—O2—C1—C2	178.64 (11)	C22—C19—C18—C17	−177.64 (19)
Zn1—N2—C9—C10	178.82 (17)	C21—C20—C19—C18	−1.2 (3)
C13—N2—C9—C10	−0.8 (3)	C21—C20—C19—C22	178.15 (18)
Zn1—N2—C13—C12	179.33 (11)	C16—C21—C20—C19	−1.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···O2ⁱ	0.82 (2)	2.13 (3)	2.914 (2)	162 (2)
N3—H32···O7ⁱ	0.92 (3)	2.35 (2)	3.261 (2)	171 (2)
O4—H41···O7ⁱⁱ	0.75 (2)	2.04 (2)	2.7890 (17)	173 (3)
O4—H42···O8	0.76 (3)	1.89 (3)	2.6547 (18)	175 (3)
O5—H51···O7	0.80 (2)	1.83 (2)	2.6264 (17)	171 (3)
O5—H52···O1ⁱⁱⁱ	0.74 (2)	2.05 (2)	2.7610 (17)	164 (2)
O6—H61···O3ⁱⁱⁱ	0.75 (3)	2.05 (3)	2.7993 (19)	170 (3)
O6—H62···N1^iv	0.76 (3)	2.17 (3)	2.918 (3)	170 (3)
C11—H11···O7ⁱ	0.93	2.49	3.415 (2)	177

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

Selected bond lengths (Å) top

Zn1—O1	2.2724 (12)	Zn1—O5	2.0132 (11)
Zn1—O2	2.1163 (12)	Zn1—O6	2.1917 (14)
Zn1—O4	2.0917 (13)	Zn1—N2	2.0545 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···O2ⁱ	0.82 (2)	2.13 (3)	2.914 (2)	162 (2)
N3—H32···O7ⁱ	0.92 (3)	2.35 (2)	3.261 (2)	171 (2)
O4—H41···O7ⁱⁱ	0.75 (2)	2.04 (2)	2.7890 (17)	173 (3)
O4—H42···O8	0.76 (3)	1.89 (3)	2.6547 (18)	175 (3)
O5—H51···O7	0.80 (2)	1.83 (2)	2.6264 (17)	171 (3)
O5—H52···O1ⁱⁱⁱ	0.74 (2)	2.05 (2)	2.7610 (17)	164 (2)
O6—H61···O3ⁱⁱⁱ	0.75 (3)	2.05 (3)	2.7993 (19)	170 (3)
O6—H62···N1^iv	0.76 (3)	2.17 (3)	2.918 (3)	170 (3)
C11—H11···O7ⁱ	0.93	2.49	3.415 (2)	177

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

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₄NO₂)(C₆H₆N₂O)(H₂O)₃](C₈H₄NO₂)
M_r	533.81
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.0858 (2), 8.7031 (3), 22.2357 (6)
α, β, γ (°)	81.882 (2), 87.806 (3), 88.007 (3)
V (Å³)	1164.55 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.11
Crystal size (mm)	0.45 × 0.36 × 0.25

Data collection
Diffractometer	Bruker SMART BREEZE CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.625, 0.758
No. of measured, independent and observed [I > 2σ(I)] reflections	27167, 5839, 5450
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.05
No. of reflections	5839
No. of parameters	348
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.33

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

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).

References

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Volume 71| Part 6| June 2015| Pages 684-686

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