Crystal structure of poly[bis­(μ-nicotinamide-κ2N1:O)bis­(μ-4-nitro­benzoato-κ2O1:O1′)zinc]

Aşkın, G. Ş.; Necefoğlu, H.; Tonbul, A.M.; Dilek, N.; Hökelek, T.

doi:10.1107/S2056989015006490

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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages 479-482

https://doi.org/10.1107/S2056989015006490

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Crystal structure of poly[bis(μ-nicotinamide-κ²N¹:O)bis(μ-4-nitrobenzoato-κ²O¹:O^1′)zinc]

Gülçin Şefiye Aşkın,^a Hacali Necefoğlu,^b Ali Murat Tonbul,^b Nefise Dilek ^c and Tuncer Hökelek ^a ^*

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, and ^cAksaray University, Department of Physics, 68100, Aksaray, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 21 March 2015; accepted 31 March 2015; online 11 April 2015)

The asymmetric unit of the title coordination polymer, [Zn(C₇H₄NO₄)₂(C₆H₆N₂O)₂]_n, contains two 4-nitrobenzoate (NB) anions and two nicotinamide (NA) ligands. The Zn^II atom has a slightly distorted octahedral coordination sphere. In the equatorial plane, it is coordinated by three carboxylate O atoms of the NB anions and one O atom of one of the two NA ligands. The axial positions are occupied by the pyridine N atoms of the two NA ligands. In the two NB anions, the carboxylate groups are twisted away from the attached benzene rings by 13.8 (2) and 13.4 (2)°, while the benzene rings are oriented at a dihedral angle of 11.5 (2)°. The dihedral angle between the NA rings is 10.3 (1)°. Only one of the two NB anions and one of the two NA ligands bridge adjacent Zn^II ions through eight- and twelve-membered rings, respectively, forming polymeric chains running along the a-axis direction. In the crystal, N—H ⋯ O hydrogen bonds link adjacent chains, enclosing R(16), R₂²(20) and R₆⁶(16) ring motifs, forming layers parallel to (01-1). The layers are linked via a number of C—H⋯O hydrogen bonds, forming a three-dimensional network.

Keywords: crystal structure; zinc(II) complex; benzoic acid; nicotinamide derivatives; hydrogen bonding.

CCDC reference: 1057121

1. Chemical context

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 change depending on the nature and position of the substituent 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 ; Nadzhafov 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 ).

2. Structural commentary

The asymmetric unit of the title polymeric compound contains two 4-nitrobenzoate (NB) anions and two nicotinamide (NA) ligands; the NB anions act as monodentate ligands (Fig. 1). Only one of the two NB anions and one of the two NA ligands bridge the adjacent Zn^II ions through eight- and twelve-membered rings, respectively, forming polymeric chains running along the a-axis direction (Fig. 2). In the eight- and twelve-membered rings, the distances between the symmetry related ions [Zn1⋯Zn1^a, N5⋯N5^a, O10⋯O10^a, and Zn1⋯Zn1^b, O5⋯O5^b, O6⋯O6^b are 7.3237 (6), 5.855 (4), 4.480 (3) Å and 4.67 (6), 3.668 (4), 4.256 (4) Å, respectively [symmetry codes (a) = −x + 1, − y, −z; (b) − x + 2, −y, − z]; see Fig. 3.

Figure 1
The asymmetric unit of the title molecule, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level [symmetry codes: (a) −x + 1, −y, −z; (b) −x + 2, −y, −z].

Figure 2
A partial view of the crystal packing of the title compound. H atoms have been omitted for clarity.

Figure 3
Part of the crystal packing of the title compound, showing the eight- and twelve-membered rings [symmetry codes (a) −x + 1, −y, −z; (b) −x + 2, −y, −z]. H atoms have been omitted for clarity.

The three carboxylate O atoms (O2, O5 and O6) of the three NB anions and one O atom (O10) of one of the two NA ligands in the equatorial plane around the Zn^II cation form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms (N3 and N5) of the two NA ligands in the axial positions (Table 1 and Fig. 3).

Table 1
Selected bond lengths (Å)

Zn1—O2	2.140 (2)	Zn1—O10ⁱⁱ	2.280 (2)
Zn1—O5ⁱ	2.142 (2)	Zn1—N3	2.288 (3)
Zn1—O6	2.160 (2)	Zn1—N5	2.282 (3)
Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y, -z.

The near equality of the C1—O1 [1.247 (4) Å], C1—O2 [1.261 (4) Å], C8—O5 [1.248 (4) Å] and C8—O6 [1.255 (4) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Zn—O_carboxylate and Zn—N distances are 2.147 (2) Å and 2.285 (3) Å, respectively, while Zn1—O10 distance is 2.280 (2) Å. The Zn1 atom lies 1.4330 (4) Å and 0.1897 (4) Å above the planar (O1/O2/C1) and (O5/O6/C8) carboxylate groups, respectively. The average O—Zn—O and O—Zn—N bond angles are 89.93 (10) and 89.99 (10)°, respectively.

The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O5/O6/C8)] and the adjacent benzene rings [A (C2—C7) and B (C9—C14)] are 13.8 (2) and 13.4 (2)°, respectively, while the benzene rings are oriented at a dihedral angle of 11.5 (2)°. The dihedral angle between the nicotinamide rings [C (N3/C15—C19) and D (N5/C21—C25)] is 10.3 (1)°, and they are oriented with respect to benzene rings A and B at dihedral angles of A/C = 17.3 (1), A/D = 7.7 (1), B/C = 28.8 (1) and B/D = 18.9 (1)°.

3. Supramolecular features

In the crystal, strong N—H⋯O_c (c = carboxylate) and N—H⋯O_n (n = nicotinamide) hydrogen bonds (Table 2) link adjacent chains through R(16), R₂²(20) and R₆⁶(16) ring motifs (Bernstein et al., 1995 ) into layers parallel to (01 $[\overline{1}]$ ) (Fig. 4). Weak intramolecular C—H_n⋯O_c and intermolecular C—H_n⋯O_nb (nb = nitrobenzoate) and C—H_n⋯O_n hydrogen bonds (Table 1) link the layers into a three-dimensional framework.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O1ⁱ	0.86	2.20	2.851 (4)	132
N6—H6A⋯O1ⁱⁱ	0.86	1.98	2.814 (4)	164
N6—H6B⋯O9ⁱⁱⁱ	0.86	2.09	2.880 (4)	153
C15—H15⋯O6	0.93	2.45	3.079 (4)	125
C19—H19⋯O3^iv	0.93	2.57	3.238 (7)	130
C21—H21⋯O10ⁱⁱ	0.93	2.38	3.058 (4)	130
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y, -z; (iii) -x+2, -y, -z; (iv) x-1, y-1, z.

Figure 4
Part of the crystal packing of the title compound with the N—H⋯O hydrogen bonds shown as dashed lines (see Table 1

for details; other H atoms have been omitted for clarity).

4. Synthesis and crystallization

The title compound was prepared by the reaction of ZnSO₄·H₂O (0.89 g, 5 mmol) in H₂O (25 ml) and nicotinamide (1.22 g, 10 mmol) in H₂O (25 ml) with sodium 4-nitrobenzoate (1.90 g, 10 mmol) in H₂O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving yellow block-like crystals.

5. Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 3. H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93 Å and N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(C,N). The highest residual electron density and the deepest hole were found 0.29 Å and 0.48 Å from atoms N6 and Zn1, respectively.

Table 3
Experimental details

Crystal data
Chemical formula	[Zn(C₆H₆N₂O)₂(C₇H₄NO₄)₂]
M_r	641.87
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.5118 (3), 10.5591 (3), 14.5326 (5)
α, β, γ (°)	109.846 (4), 93.618 (3), 104.815 (4)
V (Å³)	1309.11 (9)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.01
Crystal size (mm)	0.50 × 0.37 × 0.33

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.635, 0.705
No. of measured, independent and observed [I > 2σ(I)] reflections	34333, 6520, 5816
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.238, 1.09
No. of reflections	6520
No. of parameters	388
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.29, −0.60
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: 1057121

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015006490/su5099sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015006490/su5099Isup2.hkl

checkCIF report

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).

Poly[bis(µ-nicotinamide-κ²N¹:O)bis(µ-4-nitrobenzoato-κ²O¹:O^1')zinc] top

Crystal data top

[Zn(C₆H₆N₂O)₂(C₇H₄NO₄)₂]	Z = 2
M_r = 641.87	F(000) = 656
Triclinic, P1	D_x = 1.628 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5118 (3) Å	Cell parameters from 9922 reflections
b = 10.5591 (3) Å	θ = 2.5–28.4°
c = 14.5326 (5) Å	µ = 1.01 mm⁻¹
α = 109.846 (4)°	T = 296 K
β = 93.618 (3)°	Block, yellow
γ = 104.815 (4)°	0.50 × 0.37 × 0.33 mm
V = 1309.11 (9) Å³

Data collection top

Bruker SMART BREEZE CCD diffractometer	6520 independent reflections
Radiation source: fine-focus sealed tube	5816 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 28.4°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −12→12
T_min = 0.635, T_max = 0.705	k = −13→14
34333 measured reflections	l = −19→19

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.238	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.149P)² + 3.1586P] where P = (F_o² + 2F_c²)/3
6520 reflections	(Δ/σ)_max < 0.001
388 parameters	Δρ_max = 1.29 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

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	0.88909 (4)	0.14132 (4)	0.11465 (3)	0.02880 (19)
O1	0.8671 (3)	0.4391 (3)	0.3500 (2)	0.0410 (8)
O2	0.9117 (3)	0.3588 (3)	0.19518 (19)	0.0266 (5)
O3	1.5920 (5)	0.8555 (6)	0.3452 (4)	0.0923 (19)
O4	1.5777 (4)	0.8861 (4)	0.4965 (3)	0.0560 (10)
O5	1.1523 (3)	0.0826 (2)	−0.05180 (18)	0.0230 (5)
O6	1.1170 (3)	0.2086 (3)	0.09758 (19)	0.0266 (5)
O7	1.8536 (4)	0.5337 (5)	0.0411 (4)	0.0741 (14)
O8	1.8302 (4)	0.6372 (4)	0.1922 (4)	0.0651 (12)
O9	1.4003 (3)	0.3463 (3)	0.3975 (2)	0.0315 (6)
O10	0.3467 (2)	−0.0828 (3)	−0.14454 (17)	0.0235 (5)
N1	1.5271 (4)	0.8314 (4)	0.4092 (3)	0.0437 (9)
N2	1.7850 (4)	0.5475 (4)	0.1102 (4)	0.0464 (10)
N3	0.9685 (3)	0.1292 (3)	0.2625 (2)	0.0209 (5)
N4	1.3297 (3)	0.4235 (4)	0.5466 (2)	0.0301 (7)
H4A	1.4152	0.4830	0.5733	0.036*
H4B	1.2605	0.4171	0.5816	0.036*
N5	0.7923 (3)	0.1216 (3)	−0.0391 (2)	0.0192 (5)
N6	0.3979 (3)	−0.2171 (3)	−0.2888 (2)	0.0257 (6)
H6A	0.3090	−0.2722	−0.3076	0.031*
H6B	0.4633	−0.2315	−0.3263	0.031*
C1	0.9464 (4)	0.4401 (3)	0.2850 (3)	0.0231 (6)
C2	1.0981 (4)	0.5454 (3)	0.3168 (2)	0.0212 (6)
C3	1.1568 (4)	0.6153 (4)	0.4178 (3)	0.0337 (8)
H3	1.1008	0.5981	0.4648	0.040*
C4	1.2969 (5)	0.7097 (5)	0.4486 (3)	0.0377 (9)
H4	1.3356	0.7566	0.5157	0.045*
C5	1.3777 (4)	0.7324 (4)	0.3772 (3)	0.0295 (8)
C6	1.3225 (4)	0.6662 (5)	0.2774 (3)	0.0351 (8)
H6	1.3786	0.6851	0.2309	0.042*
C7	1.1821 (4)	0.5709 (4)	0.2470 (3)	0.0298 (8)
H7	1.1444	0.5241	0.1798	0.036*
C8	1.1944 (3)	0.1804 (3)	0.0309 (2)	0.0161 (5)
C9	1.3506 (3)	0.2755 (3)	0.0529 (2)	0.0170 (6)
C10	1.4151 (4)	0.3680 (4)	0.1489 (3)	0.0291 (7)
H10	1.3613	0.3707	0.2004	0.035*
C11	1.5580 (4)	0.4561 (5)	0.1691 (3)	0.0359 (9)
H11	1.6008	0.5176	0.2333	0.043*
C12	1.6357 (4)	0.4502 (4)	0.0910 (3)	0.0300 (8)
C13	1.5764 (4)	0.3579 (4)	−0.0052 (3)	0.0334 (8)
H13	1.6314	0.3547	−0.0562	0.040*
C14	1.4334 (4)	0.2706 (4)	−0.0237 (3)	0.0269 (7)
H14	1.3919	0.2079	−0.0879	0.032*
C15	1.1025 (3)	0.2154 (3)	0.3102 (2)	0.0198 (6)
H15	1.1637	0.2597	0.2758	0.024*
C16	1.1542 (3)	0.2416 (3)	0.4080 (2)	0.0188 (6)
C17	1.0644 (4)	0.1754 (4)	0.4601 (3)	0.0308 (8)
H17	1.0946	0.1935	0.5266	0.037*
C18	0.9282 (4)	0.0815 (5)	0.4100 (3)	0.0363 (9)
H18	0.8671	0.0319	0.4417	0.044*
C19	0.8841 (4)	0.0623 (4)	0.3123 (3)	0.0275 (7)
H19	0.7920	0.0002	0.2799	0.033*
C20	1.3046 (3)	0.3414 (3)	0.4512 (2)	0.0203 (6)
C21	0.6540 (3)	0.0355 (3)	−0.0750 (2)	0.0176 (6)
H21	0.5976	0.0097	−0.0307	0.021*
C22	0.5908 (3)	−0.0170 (3)	−0.1739 (2)	0.0154 (5)
C23	0.6756 (4)	0.0196 (4)	−0.2406 (3)	0.0247 (7)
H23	0.6386	−0.0170	−0.3081	0.030*
C24	0.8167 (4)	0.1120 (4)	−0.2041 (3)	0.0299 (8)
H24	0.8746	0.1411	−0.2466	0.036*
C25	0.8706 (3)	0.1609 (4)	−0.1032 (3)	0.0241 (7)
H25	0.9651	0.2234	−0.0794	0.029*
C26	0.4345 (3)	−0.1097 (3)	−0.2019 (2)	0.0156 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0193 (3)	0.0303 (3)	0.0256 (3)	0.00170 (18)	0.00168 (17)	0.00104 (19)
O1	0.0224 (13)	0.0400 (16)	0.0361 (16)	−0.0070 (11)	0.0135 (11)	−0.0058 (12)
O2	0.0249 (12)	0.0188 (11)	0.0245 (12)	0.0026 (9)	−0.0005 (9)	−0.0028 (9)
O3	0.045 (2)	0.110 (4)	0.081 (3)	−0.040 (3)	0.011 (2)	0.031 (3)
O4	0.0332 (17)	0.050 (2)	0.062 (2)	−0.0093 (15)	−0.0172 (16)	0.0128 (18)
O5	0.0187 (11)	0.0177 (11)	0.0223 (11)	0.0009 (9)	−0.0003 (9)	−0.0014 (9)
O6	0.0118 (11)	0.0315 (13)	0.0234 (12)	−0.0019 (9)	0.0054 (9)	−0.0002 (10)
O7	0.0295 (18)	0.081 (3)	0.101 (4)	−0.0137 (18)	0.022 (2)	0.040 (3)
O8	0.0286 (17)	0.046 (2)	0.096 (3)	−0.0137 (15)	−0.0084 (19)	0.018 (2)
O9	0.0135 (11)	0.0370 (14)	0.0249 (12)	−0.0004 (10)	0.0065 (9)	−0.0068 (10)
O10	0.0099 (10)	0.0289 (12)	0.0188 (11)	0.0011 (9)	0.0031 (8)	−0.0038 (9)
N1	0.0233 (16)	0.0369 (19)	0.059 (2)	−0.0085 (14)	−0.0031 (16)	0.0177 (18)
N2	0.0146 (15)	0.040 (2)	0.085 (3)	−0.0043 (14)	0.0024 (17)	0.033 (2)
N3	0.0121 (12)	0.0215 (13)	0.0204 (13)	−0.0026 (10)	−0.0018 (9)	0.0036 (10)
N4	0.0171 (13)	0.0356 (17)	0.0186 (14)	−0.0027 (12)	0.0024 (10)	−0.0055 (12)
N5	0.0084 (11)	0.0199 (12)	0.0218 (13)	−0.0016 (9)	−0.0011 (9)	0.0034 (10)
N6	0.0143 (12)	0.0277 (15)	0.0193 (13)	−0.0015 (10)	0.0047 (10)	−0.0054 (11)
C1	0.0163 (14)	0.0167 (14)	0.0266 (16)	0.0015 (11)	0.0037 (12)	−0.0015 (12)
C2	0.0168 (14)	0.0168 (14)	0.0223 (15)	0.0006 (11)	0.0027 (11)	0.0012 (11)
C3	0.0270 (18)	0.038 (2)	0.0215 (16)	−0.0058 (15)	0.0042 (13)	0.0036 (15)
C4	0.030 (2)	0.041 (2)	0.0248 (18)	−0.0070 (17)	−0.0043 (15)	0.0061 (16)
C5	0.0173 (15)	0.0241 (17)	0.039 (2)	−0.0046 (13)	−0.0007 (14)	0.0107 (15)
C6	0.0282 (19)	0.037 (2)	0.034 (2)	−0.0034 (15)	0.0099 (15)	0.0140 (16)
C7	0.0275 (18)	0.0305 (18)	0.0213 (16)	−0.0030 (14)	0.0043 (13)	0.0055 (14)
C8	0.0091 (12)	0.0141 (13)	0.0211 (14)	0.0007 (10)	0.0018 (10)	0.0037 (11)
C9	0.0098 (12)	0.0141 (13)	0.0237 (15)	0.0011 (10)	0.0036 (11)	0.0044 (11)
C10	0.0178 (15)	0.0339 (19)	0.0231 (16)	−0.0056 (13)	0.0014 (12)	0.0052 (14)
C11	0.0220 (17)	0.037 (2)	0.0325 (19)	−0.0087 (15)	−0.0044 (14)	0.0066 (16)
C12	0.0115 (14)	0.0246 (17)	0.053 (2)	−0.0024 (12)	0.0013 (14)	0.0205 (16)
C13	0.0211 (17)	0.036 (2)	0.047 (2)	0.0062 (15)	0.0187 (16)	0.0191 (18)
C14	0.0214 (16)	0.0251 (16)	0.0289 (17)	0.0023 (13)	0.0110 (13)	0.0056 (13)
C15	0.0125 (13)	0.0224 (15)	0.0176 (14)	−0.0010 (11)	0.0008 (10)	0.0035 (11)
C16	0.0115 (13)	0.0202 (14)	0.0176 (14)	0.0003 (11)	−0.0003 (10)	0.0020 (11)
C17	0.0218 (16)	0.041 (2)	0.0258 (17)	−0.0033 (15)	−0.0018 (13)	0.0171 (16)
C18	0.0227 (17)	0.045 (2)	0.037 (2)	−0.0087 (16)	−0.0014 (15)	0.0245 (18)
C19	0.0145 (14)	0.0291 (17)	0.0321 (18)	−0.0062 (12)	−0.0023 (12)	0.0133 (14)
C20	0.0119 (13)	0.0220 (15)	0.0178 (14)	0.0015 (11)	−0.0009 (10)	−0.0009 (12)
C21	0.0087 (12)	0.0214 (14)	0.0163 (13)	−0.0003 (10)	0.0006 (10)	0.0028 (11)
C22	0.0083 (12)	0.0182 (13)	0.0172 (13)	0.0027 (10)	0.0024 (10)	0.0041 (11)
C23	0.0169 (15)	0.0356 (18)	0.0205 (15)	0.0023 (13)	0.0042 (12)	0.0129 (14)
C24	0.0168 (15)	0.041 (2)	0.0340 (19)	−0.0005 (14)	0.0056 (13)	0.0225 (16)
C25	0.0106 (13)	0.0252 (16)	0.0347 (18)	−0.0020 (11)	0.0005 (12)	0.0150 (14)
C26	0.0085 (12)	0.0188 (13)	0.0142 (12)	0.0013 (10)	0.0008 (9)	0.0019 (11)

Geometric parameters (Å, º) top

Zn1—O2	2.140 (2)	C5—C6	1.377 (6)
Zn1—O5ⁱ	2.142 (2)	C6—H6	0.9300
Zn1—O6	2.160 (2)	C7—C6	1.389 (5)
Zn1—O10ⁱⁱ	2.280 (2)	C7—H7	0.9300
Zn1—N3	2.288 (3)	C8—C9	1.509 (4)
Zn1—N5	2.282 (3)	C9—C10	1.392 (5)
O1—C1	1.247 (4)	C9—C14	1.399 (4)
O2—C1	1.261 (4)	C10—C11	1.385 (5)
O4—N1	1.208 (6)	C10—H10	0.9300
O5—Zn1ⁱ	2.142 (2)	C11—H11	0.9300
O5—C8	1.248 (4)	C12—C11	1.384 (6)
O6—C8	1.255 (4)	C13—C12	1.384 (6)
O9—C20	1.239 (4)	C13—C14	1.384 (5)
O10—Zn1ⁱⁱ	2.280 (2)	C13—H13	0.9300
N1—O3	1.210 (6)	C14—H14	0.9300
N2—O7	1.220 (7)	C15—C16	1.383 (4)
N2—O8	1.210 (7)	C15—H15	0.9300
N2—C12	1.469 (4)	C16—C17	1.388 (5)
N3—C15	1.342 (4)	C16—C20	1.489 (4)
N3—C19	1.341 (4)	C17—H17	0.9300
N4—H4A	0.8600	C18—C17	1.388 (5)
N4—H4B	0.8600	C18—H18	0.9300
N5—C21	1.345 (4)	C19—C18	1.384 (5)
N5—C25	1.337 (4)	C19—H19	0.9300
N6—C26	1.332 (4)	C20—N4	1.329 (4)
N6—H6A	0.8600	C21—H21	0.9300
N6—H6B	0.8600	C22—C21	1.384 (4)
C1—C2	1.510 (4)	C22—C23	1.391 (4)
C2—C3	1.401 (5)	C23—C24	1.387 (5)
C2—C7	1.384 (5)	C23—H23	0.9300
C3—C4	1.383 (5)	C24—H24	0.9300
C3—H3	0.9300	C25—C24	1.391 (5)
C4—H4	0.9300	C25—H25	0.9300
C5—N1	1.468 (5)	C26—O10	1.233 (4)
C5—C4	1.379 (6)	C26—C22	1.497 (4)

O2—Zn1—O5ⁱ	170.95 (10)	O5—C8—O6	125.6 (3)
O2—Zn1—O6	86.90 (10)	O5—C8—C9	117.8 (3)
O2—Zn1—O10ⁱⁱ	89.70 (10)	O6—C8—C9	116.6 (3)
O2—Zn1—N3	87.21 (10)	C10—C9—C8	121.1 (3)
O2—Zn1—N5	99.61 (10)	C10—C9—C14	119.0 (3)
O5ⁱ—Zn1—O6	99.77 (10)	C14—C9—C8	119.9 (3)
O5ⁱ—Zn1—O10ⁱⁱ	83.34 (9)	C9—C10—H10	119.4
O5ⁱ—Zn1—N3	86.87 (10)	C11—C10—C9	121.1 (3)
O5ⁱ—Zn1—N5	85.89 (10)	C11—C10—H10	119.4
O6—Zn1—O10ⁱⁱ	175.66 (8)	C10—C11—H11	120.9
O6—Zn1—N3	88.43 (10)	C12—C11—C10	118.3 (4)
O6—Zn1—N5	95.75 (10)	C12—C11—H11	120.9
O10ⁱⁱ—Zn1—N3	88.71 (9)	C11—C12—N2	119.1 (4)
O10ⁱⁱ—Zn1—N5	87.48 (9)	C13—C12—N2	118.6 (4)
N5—Zn1—N3	172.16 (10)	C13—C12—C11	122.3 (3)
C1—O2—Zn1	135.7 (2)	C12—C13—H13	120.7
C8—O5—Zn1ⁱ	138.9 (2)	C14—C13—C12	118.5 (3)
C8—O6—Zn1	137.8 (2)	C14—C13—H13	120.7
C26—O10—Zn1ⁱⁱ	147.3 (2)	C9—C14—H14	119.6
O3—N1—C5	117.1 (4)	C13—C14—C9	120.8 (3)
O4—N1—O3	123.5 (4)	C13—C14—H14	119.6
O4—N1—C5	119.3 (4)	N3—C15—C16	123.3 (3)
O7—N2—C12	117.3 (4)	N3—C15—H15	118.3
O8—N2—O7	124.5 (4)	C16—C15—H15	118.3
O8—N2—C12	118.2 (4)	C15—C16—C17	119.0 (3)
C15—N3—Zn1	116.4 (2)	C15—C16—C20	117.1 (3)
C19—N3—Zn1	125.3 (2)	C17—C16—C20	123.9 (3)
C19—N3—C15	117.4 (3)	C16—C17—H17	121.0
C20—N4—H4A	120.0	C18—C17—C16	118.0 (3)
C20—N4—H4B	120.0	C18—C17—H17	121.0
H4A—N4—H4B	120.0	C17—C18—H18	120.3
C21—N5—Zn1	115.9 (2)	C19—C18—C17	119.3 (3)
C25—N5—Zn1	124.9 (2)	C19—C18—H18	120.3
C25—N5—C21	117.3 (3)	N3—C19—C18	122.9 (3)
C26—N6—H6A	120.0	N3—C19—H19	118.5
C26—N6—H6B	120.0	C18—C19—H19	118.5
H6A—N6—H6B	120.0	O9—C20—N4	122.6 (3)
O1—C1—O2	125.5 (3)	O9—C20—C16	119.4 (3)
O1—C1—C2	117.3 (3)	N4—C20—C16	118.0 (3)
O2—C1—C2	117.1 (3)	N5—C21—C22	123.9 (3)
C3—C2—C1	119.9 (3)	N5—C21—H21	118.0
C7—C2—C1	120.6 (3)	C22—C21—H21	118.0
C7—C2—C3	119.4 (3)	C21—C22—C23	118.2 (3)
C2—C3—H3	119.5	C21—C22—C26	117.5 (3)
C4—C3—C2	120.9 (3)	C23—C22—C26	124.3 (3)
C4—C3—H3	119.5	C22—C23—H23	120.8
C3—C4—H4	120.9	C24—C23—C22	118.4 (3)
C5—C4—C3	118.2 (4)	C24—C23—H23	120.8
C5—C4—H4	120.9	C23—C24—C25	119.4 (3)
C6—C5—C4	122.2 (3)	C23—C24—H24	120.3
C6—C5—N1	119.2 (4)	C25—C24—H24	120.3
C4—C5—N1	118.7 (4)	N5—C25—C24	122.7 (3)
C5—C6—C7	119.3 (3)	N5—C25—H25	118.7
C5—C6—H6	120.4	C24—C25—H25	118.7
C7—C6—H6	120.4	O10—C26—N6	123.5 (3)
C2—C7—C6	120.0 (3)	O10—C26—C22	119.1 (3)
C2—C7—H7	120.0	N6—C26—C22	117.4 (3)
C6—C7—H7	120.0

O6—Zn1—O2—C1	−91.7 (3)	C1—C2—C7—C6	−178.9 (4)
O10ⁱⁱ—Zn1—O2—C1	85.6 (3)	C3—C2—C7—C6	−0.7 (6)
N3—Zn1—O2—C1	−3.1 (3)	C2—C3—C4—C5	−0.4 (7)
N5—Zn1—O2—C1	173.0 (3)	C4—C5—N1—O3	−175.7 (5)
O2—Zn1—O6—C8	−138.6 (4)	C4—C5—N1—O4	2.9 (6)
O5ⁱ—Zn1—O6—C8	47.6 (4)	C6—C5—N1—O3	3.8 (7)
N3—Zn1—O6—C8	134.1 (4)	C6—C5—N1—O4	−177.6 (4)
N5—Zn1—O6—C8	−39.2 (4)	N1—C5—C4—C3	−179.4 (4)
O2—Zn1—N3—C15	−59.4 (2)	C6—C5—C4—C3	1.0 (7)
O2—Zn1—N3—C19	108.8 (3)	N1—C5—C6—C7	179.0 (4)
O5ⁱ—Zn1—N3—C15	127.5 (2)	C4—C5—C6—C7	−1.5 (7)
O5ⁱ—Zn1—N3—C19	−64.4 (3)	C2—C7—C6—C5	1.3 (6)
O6—Zn1—N3—C15	27.6 (2)	O5—C8—C9—C10	−167.0 (3)
O6—Zn1—N3—C19	−164.2 (3)	O5—C8—C9—C14	12.4 (4)
O10ⁱⁱ—Zn1—N3—C15	−149.2 (2)	O6—C8—C9—C10	14.2 (5)
O10ⁱⁱ—Zn1—N3—C19	19.0 (3)	O6—C8—C9—C14	−166.4 (3)
O2—Zn1—N5—C21	−115.0 (2)	C8—C9—C10—C11	−179.5 (4)
O2—Zn1—N5—C25	81.2 (3)	C14—C9—C10—C11	1.1 (6)
O5ⁱ—Zn1—N5—C21	57.8 (2)	C8—C9—C14—C13	179.4 (3)
O5ⁱ—Zn1—N5—C25	−106.0 (3)	C10—C9—C14—C13	−1.2 (5)
O6—Zn1—N5—C21	157.2 (2)	C9—C10—C11—C12	0.1 (6)
O6—Zn1—N5—C25	−6.6 (3)	N2—C12—C11—C10	177.2 (4)
O10ⁱⁱ—Zn1—N5—C21	−25.7 (2)	C13—C12—C11—C10	−1.3 (6)
O10ⁱⁱ—Zn1—N5—C25	170.5 (3)	C14—C13—C12—N2	−177.2 (4)
Zn1—O2—C1—O1	−73.4 (5)	C14—C13—C12—C11	1.2 (6)
Zn1—O2—C1—C2	105.2 (4)	C12—C13—C14—C9	0.1 (6)
Zn1ⁱ—O5—C8—O6	−77.3 (4)	N3—C15—C16—C17	0.4 (5)
Zn1ⁱ—O5—C8—C9	104.0 (3)	N3—C15—C16—C20	−179.1 (3)
Zn1—O6—C8—O5	−7.5 (6)	C15—C16—C17—C18	2.4 (6)
Zn1—O6—C8—C9	171.2 (2)	C20—C16—C17—C18	−178.1 (4)
O7—N2—C12—C11	175.7 (5)	C15—C16—C20—O9	−33.3 (5)
O7—N2—C12—C13	−5.9 (6)	C15—C16—C20—N4	145.8 (3)
O8—N2—C12—C11	−5.8 (6)	C17—C16—C20—O9	147.2 (4)
O8—N2—C12—C13	172.6 (4)	C17—C16—C20—N4	−33.7 (5)
Zn1—N3—C15—C16	166.7 (3)	C19—C18—C17—C16	−3.0 (7)
C19—N3—C15—C16	−2.4 (5)	N3—C19—C18—C17	1.0 (7)
C15—N3—C19—C18	1.7 (6)	C23—C22—C21—N5	0.9 (5)
Zn1—N3—C19—C18	−166.4 (3)	C26—C22—C21—N5	−178.9 (3)
Zn1—N5—C21—C22	−163.3 (2)	C21—C22—C23—C24	−3.0 (5)
C25—N5—C21—C22	1.8 (5)	C26—C22—C23—C24	176.8 (3)
Zn1—N5—C25—C24	161.1 (3)	C22—C23—C24—C25	2.3 (6)
C21—N5—C25—C24	−2.6 (5)	N5—C25—C24—C23	0.5 (6)
O1—C1—C2—C3	13.6 (5)	N6—C26—O10—Zn1ⁱⁱ	−1.0 (7)
O1—C1—C2—C7	−168.2 (4)	C22—C26—O10—Zn1ⁱⁱ	178.5 (3)
O2—C1—C2—C3	−165.0 (4)	O10—C26—C22—C21	36.8 (4)
O2—C1—C2—C7	13.1 (5)	O10—C26—C22—C23	−142.9 (3)
C1—C2—C3—C4	178.5 (4)	N6—C26—C22—C21	−143.6 (3)
C7—C2—C3—C4	0.3 (6)	N6—C26—C22—C23	36.6 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O1ⁱⁱⁱ	0.86	2.20	2.851 (4)	132
N6—H6A···O1ⁱⁱ	0.86	1.98	2.814 (4)	164
N6—H6B···O9ⁱ	0.86	2.09	2.880 (4)	153
C15—H15···O6	0.93	2.45	3.079 (4)	125
C19—H19···O3^iv	0.93	2.57	3.238 (7)	130
C21—H21···O10ⁱⁱ	0.93	2.38	3.058 (4)	130

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

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).

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