Bis(4-fluoro­benzoato-κ2O,O′)bis­(nicotinamide-κN1)zinc(II) monohydrate

Hökelek, T.; Çaylak, N.; Necefoğlu, H.

doi:10.1107/S1600536808003747

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Pages m460-m461

doi:10.1107/S1600536808003747

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Bis(4-fluorobenzoato-κ²O,O′)bis(nicotinamide-κN¹)zinc(II) monohydrate

Tuncer Hökelek,^a Nagihan Çaylak ^b and Hacali Necefoğlu ^c ^*

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Physics, Faculty of Arts and Science, Sakarya University, 54187 Esentepe, Adapazarı, Turkey, and ^cDepartment of Chemistry, Kafkas University, 63100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 22 January 2008; accepted 4 February 2008; online 6 February 2008)

The title compound, [Zn(C₇H₄FO₂)₂(C₆H₆N₂O)₂]·H₂O, is a monomeric complex. It contains two 4-fluorobenzoate and two nicotinamide ligands and one uncoordinated water molecule. The 4-fluorobenzoates act as bidentate chelating ligands, while the nicotinamides are monodentate. The six-coordinate geometry around the Zn^II atom may be described as highly distorted octahedral, with the two nicotinamide ligands arranged cis. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure.

Related literature

For general background, see: Adiwidjaja et al. (1978 ); Amiraslanov et al. (1979 ); Antsyshkina et al. (1980 ); Bigoli et al. (1972 ); Day & Selbin (1969 ); Krishnamachari (1974 ); Nadzhafov, Shnulin & Mamedov (1981 ); Shnulin et al. (1981 ). For related structures, see: Amiraslanov et al. (1980 ); Capilla & Aranda (1979 ); Clegg et al. (1986a ,b , 1987 ); Guseinov et al. (1984 ); Hökelek et al. (2007 ); Hökelek & Necefoğlu (1996 , 2001 ); Nadzhafov, Usubaliev et al. (1981 ); Necefoğlu et al. (2002 ); Niekerk et al. (1953 ); Usubaliev et al. (1992 ).

Experimental

Crystal data

[Zn(C₇H₄FO₂)₂(C₆H₆N₂O)₂]·H₂O
M_r = 605.87
Triclinic, $[P \overline 1]$
a = 8.2363 (2) Å
b = 12.3711 (2) Å
c = 14.8971 (3) Å
α = 113.178 (14)°
β = 99.015 (17)°
γ = 99.465 (16)°
V = 1334.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 294 (2) K
0.30 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.735, T_max = 0.816
5794 measured reflections
5401 independent reflections
4454 reflections with I > 2σ(I)
R_int = 0.058
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.152
S = 1.14
5401 reflections
368 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn—O1	1.978 (2)
Zn—O2	2.564 (3)
Zn—O3	2.010 (3)
Zn—O4	2.458 (3)
Zn—N1	2.079 (2)
Zn—N3	2.095 (3)

O1—Zn—O2	55.96 (12)
O1—Zn—O3	142.65 (12)
O1—Zn—O4	97.49 (10)
O1—Zn—N1	102.97 (9)
O1—Zn—N3	106.17 (10)
O2—Zn—O3	93.35 (10)
O2—Zn—O4	88.13 (10)
O2—Zn—N1	158.51 (9)
O2—Zn—N3	90.70 (9)
O3—Zn—O4	57.04 (10)
O3—Zn—N1	104.14 (10)
O3—Zn—N3	93.66 (11)
O4—Zn—N1	90.96 (10)
O4—Zn—N3	150.53 (10)
N1—Zn—N3	100.39 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H71⋯O1	0.97 (7)	2.08 (7)	2.910 (8)	144 (6)
O7—H72⋯O4ⁱ	0.92 (8)	1.81 (8)	2.713 (10)	167 (8)
N2—H2A⋯O5ⁱⁱ	0.86	2.07	2.905 (4)	165
N2—H2B⋯O6ⁱⁱⁱ	0.86	2.15	2.977 (4)	161
N4—H4A⋯O2^iv	0.86	2.14	2.961 (4)	159
N4—H4B⋯O2^v	0.86	2.11	2.920 (4)	157
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y, -z+1; (iii) x, y-1, z; (iv) -x, -y+1, -z; (v) x-1, y, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003747/hy2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808003747/hy2118Isup2.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). The structural functions and coordination relationships of the arylcarboxylate ion in zinc(II) complexes of benzoic acid derivatives may be changed, 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 medium of the synthesis (Adiwidjaja et al., 1978; Antsyshkina et al., 1980; Amiraslanov et al., 1979; Nadzhafov, Shnulin & Mamedov, 1981; Shnulin et al., 1981).

The solid-state structures of anhydrous zinc(II) carboxylates include one-dimensional (Clegg et al., 1986a; Guseinov et al., 1984), two-dimensional (Clegg et al., 1986b, 1987) and three-dimensional (Capilla & Aranda, 1979) polymeric motifs of different types, while discerete monomeric complexes with octahedral or tetrahedral coordination geometry are found if water or other donor molecules are coordinated to Zn (Niekerk et al., 1953; Usubaliev et al., 1992). The structures of several complexes obtained by reacting Zn^II with NA and DENA have been determined in our laboratory, including those of [Zn(C₇H₄FO₂)₂(DENA)₂(H₂O)₂], (II), (Hökelek et al., 2007), [Zn(C₇H₅O₃)₂(NA)₂], (III), (Necefoğlu et al., 2002), [Zn(C₇H₅O₃)(OH₂)₃(NA)].C₇O₃H₅, (IV), (Hökelek & Necefoğlu, 2001), [Zn₂(C₇H₅O₃)₄(DENA)₂(H₂O)₂], (V), (Hökelek & Necefoğlu, 1996). In (III), one of the 4-hydroxybenzoate ions acts as bidentate ligand, while the other one is monodentate, but in (V), two of the benzoate ions act as monodentate ligands, while the other two are bidentate, bridging two Zn atoms. The structure determination of the title compound, (I), a zinc(II) complex with two fluorobenzoate (FB), two NA ligands and one uncoordinated water molecule, was undertaken in order to determine the properties of the FB and NA ligands and also to compare the results obtained with those reported previously.

In the monomeric title complex, the Zn^II atom is coordinated by two NA and two FB ligands. Two FB ions act as bidentate ligands, while two NA molecules are monodentate ligands (Fig. 1). Besides four short coordination bonds, the close contact of the O4 atom with the Zn atom [Zn···O4 = 2.458 (3) Å] may be considered to give the fifth coordination bond, as in (III) [Zn···O4 = 2.404 (2) Å]; this distance is much greater than the sum of the corresponding ionic radii (2.14 Å; Day & Selbin, 1969). Similar reported Zn···O contacts are 2.50 (1) Å in [Zn(n-HOC₆H₄COO)₂(C₅H₅N)₂].2C₅H₅N (Nadzhafov, Usubaliev et al., 1981) and 2.494 (8) Å in [Zn(p-H₂NC₆H₄COO)₂]_n.1.5nH₂O (Amiraslanov et al., 1980). On the other hand, the Zn···O2 distance [2.564 (3) Å] in (I) may also be considered as a coordination bond, although it is weak. Thus, the six-coordination geometry around the Zn^II atom may be described as highly distorted octahedral (Table 1), with the two nicotinamide ligands arranged cis.

In the binuclear complex (V), the average Zn—O bond length [1.953 (2) Å] is shorter than the corresponding value in (I) [2.253 (3) Å], but Zn is four-coordinate. In complexes (II), (III) and (IV), where Zn atoms are six-, five- and five-coordinate, the average Zn—O bond lengths are 2.117 (2) Å, 2.107 (2) Å and 2.047 (5) Å, respectively. The average Zn—N bond length [2.087 (3) Å] in (I) is in good agreement with the values reported in (III) [2.075 (2) Å], (IV) [2.089 (5) Å] and (V) [2.049 (2) Å], while it is shorter than the corresponding value in (II) [2.169 (3) Å]. The Zn atom lies -0.0682 (5) and -0.0030 (4) Å out of the O1/C1/O2 and O3/C8/O4 carboxyl planes, respectively.

In the carboxylate group, the C1—O1 and C8—O3 bond lengths [1.266 (4) and 1.264 (4) Å] are a little larger than the C1—O2 and C8—O4 [1.246 (4) and 1.229 (4) Å] bond lengths and may be compared with the corresponding distances: 1.260 (4) and 1.252 (4) Å in (II), 1.281 (3), 1.274 (3) and 1.240 (3), 1.245 (3) Å in (III) and 1.279 (4) and 1.246 (4) Å in (V). The dihedral angles between the mean planes of the carboxyl groups (O1/C1/O2 and O3/C8/O4) and the benzene rings [A (C2 to C7) and B (C9 to C14)] in the FB ligands are 8.2 (2) and 7.5 (2)°, respectively; these may be compared with the corresponding values of 2.8 (3)° in (II), 12.2 (2) and 10.0 (2)° in (III). The configuration around the Zn atom is given by the torsion angles. Rings A, B, C (N1/C15 to C19) and D (N3/C21 to C25) are, of course, planar and they are oriented with respect to each other at dihedral angles of A/B = 81.33 (13), A/C = 25.48 (13), A/D = 85.10 (12), B/C = 79.78 (12), B/D = 3.78 (11) and C/D = 83.06 (12)°.

As can be seen from the packing diagram (Fig. 2), the molecules of (I) are linked by intermolecular O—H···O and N—H···O hydrogen bonds (Table 2), forming a supramolecular structure.

Related literature top

For general background, see: Adiwidjaja et al. (1978); Amiraslanov et al. (1979); Antsyshkina et al. (1980); Bigoli et al. (1972); Day & Selbin (1969); Krishnamachari (1974); Nadzhafov, Shnulin & Mamedov (1981); Shnulin et al. (1981). For related structures, see: Amiraslanov et al. (1980); Capilla & Aranda (1979); Clegg et al. (1986a,b, 1987); Guseinov et al. (1984); Hökelek et al. (2007); Hökelek & Necefoğlu (1996, 2001); Nadzhafov, Usubaliev et al. (1981); Necefoğlu et al. (2002); Niekerk et al. (1953); Usubaliev et al. (1992).

Experimental top

The title compound was prepared by the reaction of Zn(NO₃)₂ (1.89 g, 10 mmol) in H₂O (25 ml) and nicotinamide (2.16 g, 20 mmol) in H₂O (25 ml) with sodium p-fluorobenzoate (3.24 g, 20 mmol) in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colorless single crystals.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 10% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. A packing diagram of the title compound, viewed down the a axis, showing hydrogen bonds (dashed lines) linking the molecules. H atoms have been omitted for clarity.

Bis(4-fluorobenzoato-κ²O,O')bis(nicotinamide-κN¹)zinc(II) monohydrate top

Crystal data top

[Zn(C₇H₄FO₂)₂(C₆H₆N₂O)₂]·H₂O	Z = 2
M_r = 605.87	F(000) = 620
Triclinic, P1	D_x = 1.508 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2363 (2) Å	Cell parameters from 25 reflections
b = 12.3711 (2) Å	θ = 6.3–15.8°
c = 14.8971 (3) Å	µ = 0.99 mm⁻¹
α = 113.178 (14)°	T = 294 K
β = 99.015 (17)°	Block, colorless
γ = 99.465 (16)°	0.30 × 0.25 × 0.20 mm
V = 1334.7 (2) Å³

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	4454 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.058
Graphite monochromator	θ_max = 26.3°, θ_min = 2.6°
ω scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −15→15
T_min = 0.735, T_max = 0.816	l = −18→18
5794 measured reflections	3 standard reflections every 120 min
5401 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.1013P)² + 0.1012P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
5401 reflections	Δρ_max = 0.70 e Å⁻³
368 parameters	Δρ_min = −0.90 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.052 (4)

Crystal data top

[Zn(C₇H₄FO₂)₂(C₆H₆N₂O)₂]·H₂O	γ = 99.465 (16)°
M_r = 605.87	V = 1334.7 (2) Å³
Triclinic, P1	Z = 2
a = 8.2363 (2) Å	Mo Kα radiation
b = 12.3711 (2) Å	µ = 0.99 mm⁻¹
c = 14.8971 (3) Å	T = 294 K
α = 113.178 (14)°	0.30 × 0.25 × 0.20 mm
β = 99.015 (17)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	4454 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.058
T_min = 0.735, T_max = 0.816	3 standard reflections every 120 min
5794 measured reflections	intensity decay: 1%
5401 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	4 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	Δρ_max = 0.70 e Å⁻³
5401 reflections	Δρ_min = −0.90 e Å⁻³
368 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn	0.39886 (4)	0.27400 (3)	0.12795 (2)	0.04482 (17)
F1	0.3683 (5)	−0.0772 (3)	−0.46673 (18)	0.1135 (10)
F2	1.3183 (4)	0.6557 (3)	0.5118 (2)	0.1174 (11)
O1	0.3504 (3)	0.14478 (19)	−0.01064 (16)	0.0548 (5)
O2	0.4950 (3)	0.30575 (19)	−0.01740 (17)	0.0551 (5)
O3	0.5801 (3)	0.4167 (3)	0.2340 (2)	0.0702 (7)
O4	0.6874 (4)	0.2602 (2)	0.1867 (2)	0.0769 (8)
O5	0.1224 (4)	0.1149 (2)	0.48350 (18)	0.0745 (8)
O6	−0.0625 (3)	0.71261 (19)	0.16243 (18)	0.0596 (6)
O7	0.2133 (11)	−0.0996 (5)	−0.0339 (6)	0.230 (4)
H71	0.295 (9)	−0.022 (4)	−0.005 (7)	0.237*
H72	0.260 (10)	−0.154 (6)	−0.078 (6)	0.237*
N1	0.3033 (3)	0.1816 (2)	0.20611 (18)	0.0459 (6)
N2	0.0163 (4)	−0.0739 (3)	0.3616 (2)	0.0637 (8)
H2A	−0.0266	−0.0998	0.4007	0.076*
H2B	0.0043	−0.1228	0.2996	0.076*
N3	0.2216 (3)	0.3771 (2)	0.12605 (18)	0.0447 (5)
N4	−0.2859 (4)	0.5519 (3)	0.0811 (2)	0.0590 (7)
H4A	−0.3543	0.5964	0.0773	0.071*
H4B	−0.3235	0.4743	0.0560	0.071*
C1	0.4207 (4)	0.1958 (3)	−0.0584 (2)	0.0456 (6)
C2	0.4091 (4)	0.1219 (3)	−0.1675 (2)	0.0468 (7)
C3	0.4631 (5)	0.1776 (3)	−0.2257 (3)	0.0686 (10)
H3	0.5087	0.2611	−0.1964	0.082*
C4	0.4501 (6)	0.1109 (4)	−0.3262 (3)	0.0845 (13)
H4	0.4858	0.1482	−0.3655	0.101*
C5	0.3844 (6)	−0.0099 (4)	−0.3665 (3)	0.0733 (10)
C6	0.3290 (6)	−0.0687 (3)	−0.3127 (3)	0.0720 (10)
H6	0.2827	−0.1522	−0.3432	0.086*
C7	0.3433 (5)	−0.0015 (3)	−0.2115 (3)	0.0616 (9)
H7	0.3081	−0.0400	−0.1729	0.074*
C8	0.7031 (4)	0.3684 (3)	0.2396 (2)	0.0561 (8)
C9	0.8671 (4)	0.4466 (3)	0.3131 (2)	0.0471 (7)
C10	0.8903 (5)	0.5711 (3)	0.3645 (3)	0.0576 (8)
H10	0.8025	0.6065	0.3537	0.069*
C11	1.0424 (5)	0.6425 (4)	0.4315 (3)	0.0723 (11)
H11	1.0592	0.7261	0.4657	0.087*
C12	1.1677 (5)	0.5872 (4)	0.4462 (3)	0.0720 (10)
C13	1.1497 (5)	0.4663 (4)	0.3980 (3)	0.0731 (11)
H13	1.2379	0.4319	0.4103	0.088*
C14	0.9975 (5)	0.3947 (3)	0.3299 (3)	0.0601 (8)
H14	0.9831	0.3114	0.2954	0.072*
C15	0.3619 (4)	0.2332 (3)	0.3051 (2)	0.0552 (8)
H15	0.4493	0.3037	0.3344	0.066*
C16	0.2988 (4)	0.1868 (3)	0.3668 (2)	0.0563 (8)
H16	0.3419	0.2268	0.4362	0.068*
C17	0.1730 (4)	0.0820 (3)	0.3253 (2)	0.0468 (7)
C18	0.1122 (5)	0.0265 (3)	0.2222 (3)	0.0710 (11)
H18	0.0274	−0.0455	0.1911	0.085*
C19	0.1796 (5)	0.0799 (4)	0.1658 (3)	0.0714 (11)
H19	0.1364	0.0430	0.0963	0.086*
C20	0.0998 (5)	0.0398 (3)	0.3964 (2)	0.0536 (8)
C21	0.0622 (4)	0.3283 (3)	0.0705 (2)	0.0474 (7)
H21	0.0288	0.2448	0.0311	0.057*
C22	−0.0549 (4)	0.3948 (3)	0.0684 (2)	0.0460 (6)
H22	−0.1649	0.3563	0.0288	0.055*
C23	−0.0092 (4)	0.5193 (2)	0.1254 (2)	0.0415 (6)
C24	0.1563 (4)	0.5696 (3)	0.1836 (2)	0.0535 (7)
H24	0.1932	0.6528	0.2237	0.064*
C25	0.2657 (4)	0.4967 (3)	0.1819 (3)	0.0539 (7)
H25	0.3760	0.5326	0.2217	0.065*
C26	−0.1227 (4)	0.6028 (3)	0.1256 (2)	0.0451 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0522 (2)	0.0428 (2)	0.0383 (2)	0.00425 (15)	0.01085 (15)	0.01931 (16)
F1	0.165 (3)	0.109 (2)	0.0478 (13)	0.020 (2)	0.0416 (16)	0.0141 (14)
F2	0.0804 (17)	0.103 (2)	0.097 (2)	−0.0022 (15)	−0.0312 (15)	0.0000 (17)
O1	0.0764 (15)	0.0430 (11)	0.0404 (11)	0.0061 (10)	0.0155 (10)	0.0162 (9)
O2	0.0579 (13)	0.0396 (11)	0.0532 (13)	0.0014 (9)	0.0015 (10)	0.0138 (10)
O3	0.0574 (14)	0.0737 (17)	0.0754 (17)	0.0012 (12)	−0.0024 (12)	0.0409 (14)
O4	0.0813 (18)	0.0568 (15)	0.0639 (16)	−0.0109 (13)	0.0102 (14)	0.0110 (13)
O5	0.118 (2)	0.0515 (13)	0.0494 (14)	−0.0009 (14)	0.0378 (14)	0.0188 (11)
O6	0.0685 (14)	0.0359 (11)	0.0611 (14)	0.0063 (10)	0.0086 (11)	0.0128 (10)
O7	0.314 (9)	0.100 (4)	0.263 (8)	0.007 (5)	0.209 (7)	0.032 (4)
N1	0.0529 (14)	0.0467 (13)	0.0400 (12)	0.0058 (11)	0.0124 (11)	0.0229 (11)
N2	0.094 (2)	0.0480 (15)	0.0496 (16)	0.0031 (15)	0.0304 (15)	0.0221 (13)
N3	0.0516 (13)	0.0441 (13)	0.0379 (12)	0.0068 (11)	0.0113 (10)	0.0190 (10)
N4	0.0539 (15)	0.0421 (13)	0.078 (2)	0.0074 (12)	0.0060 (14)	0.0285 (14)
C1	0.0475 (15)	0.0436 (15)	0.0431 (15)	0.0108 (12)	0.0083 (12)	0.0172 (12)
C2	0.0505 (16)	0.0437 (15)	0.0422 (15)	0.0080 (12)	0.0104 (12)	0.0164 (12)
C3	0.087 (3)	0.055 (2)	0.059 (2)	−0.0021 (18)	0.0273 (19)	0.0243 (17)
C4	0.110 (3)	0.086 (3)	0.063 (2)	0.008 (3)	0.039 (2)	0.037 (2)
C5	0.088 (3)	0.082 (3)	0.0430 (18)	0.020 (2)	0.0239 (18)	0.0166 (18)
C6	0.103 (3)	0.0466 (18)	0.0481 (19)	0.0094 (19)	0.0173 (19)	0.0058 (15)
C7	0.086 (2)	0.0482 (17)	0.0474 (18)	0.0106 (17)	0.0178 (17)	0.0196 (14)
C8	0.0600 (19)	0.065 (2)	0.0458 (17)	−0.0015 (16)	0.0115 (14)	0.0338 (16)
C9	0.0522 (16)	0.0520 (16)	0.0373 (14)	0.0053 (13)	0.0119 (12)	0.0219 (13)
C10	0.0627 (19)	0.0558 (18)	0.0514 (18)	0.0169 (15)	0.0130 (15)	0.0196 (15)
C11	0.082 (3)	0.051 (2)	0.056 (2)	0.0103 (18)	0.0054 (19)	0.0022 (16)
C12	0.059 (2)	0.074 (2)	0.051 (2)	0.0022 (18)	−0.0064 (16)	0.0081 (18)
C13	0.062 (2)	0.077 (3)	0.071 (2)	0.0246 (19)	0.0039 (19)	0.024 (2)
C14	0.069 (2)	0.0504 (18)	0.0531 (19)	0.0128 (16)	0.0121 (16)	0.0161 (15)
C15	0.0567 (18)	0.0554 (18)	0.0450 (16)	−0.0059 (15)	0.0072 (14)	0.0228 (14)
C16	0.0651 (19)	0.0599 (19)	0.0378 (15)	−0.0006 (15)	0.0093 (14)	0.0225 (14)
C17	0.0584 (17)	0.0448 (15)	0.0439 (15)	0.0130 (13)	0.0184 (13)	0.0235 (13)
C18	0.092 (3)	0.058 (2)	0.0443 (18)	−0.0178 (19)	0.0138 (18)	0.0188 (16)
C19	0.088 (3)	0.072 (2)	0.0381 (16)	−0.016 (2)	0.0103 (17)	0.0226 (16)
C20	0.072 (2)	0.0472 (16)	0.0471 (17)	0.0085 (15)	0.0245 (15)	0.0242 (14)
C21	0.0565 (17)	0.0362 (14)	0.0408 (14)	0.0014 (12)	0.0078 (13)	0.0133 (12)
C22	0.0476 (15)	0.0407 (14)	0.0402 (14)	−0.0001 (12)	0.0045 (12)	0.0145 (12)
C23	0.0504 (15)	0.0396 (14)	0.0349 (13)	0.0036 (12)	0.0121 (11)	0.0188 (11)
C24	0.0565 (18)	0.0373 (14)	0.0522 (17)	−0.0011 (13)	0.0031 (14)	0.0134 (13)
C25	0.0503 (17)	0.0437 (16)	0.0545 (18)	0.0015 (13)	0.0016 (14)	0.0159 (14)
C26	0.0553 (17)	0.0424 (15)	0.0373 (14)	0.0059 (13)	0.0117 (12)	0.0191 (12)

Geometric parameters (Å, º) top

Zn—O1	1.978 (2)	C6—H6	0.9300
Zn—O2	2.564 (3)	C7—C6	1.379 (5)
Zn—O3	2.010 (3)	C7—H7	0.9300
Zn—O4	2.458 (3)	C9—C14	1.377 (5)
Zn—N1	2.079 (2)	C9—C10	1.386 (4)
Zn—N3	2.095 (3)	C9—C8	1.494 (4)
F1—C5	1.365 (4)	C10—H10	0.9300
F2—C12	1.354 (4)	C11—C10	1.376 (5)
O2—C1	1.246 (4)	C11—C12	1.364 (6)
O3—C8	1.264 (4)	C11—H11	0.9300
O4—C8	1.229 (4)	C12—C13	1.350 (6)
O5—C20	1.225 (4)	C13—H13	0.9300
O6—C26	1.224 (4)	C14—C13	1.384 (5)
O7—H71	0.97 (8)	C14—H14	0.9300
O7—H72	0.92 (8)	C15—C16	1.383 (4)
N1—C15	1.322 (4)	C15—H15	0.9300
N1—C19	1.332 (4)	C16—H16	0.9300
N2—C20	1.310 (4)	C17—C16	1.365 (4)
N2—H2A	0.8600	C17—C18	1.377 (4)
N2—H2B	0.8600	C17—C20	1.514 (4)
N3—C25	1.332 (4)	C18—H18	0.9300
N3—C21	1.333 (4)	C19—C18	1.382 (5)
N4—H4A	0.8600	C19—H19	0.9300
N4—H4B	0.8600	C21—H21	0.9300
C1—O1	1.266 (4)	C22—C21	1.372 (4)
C1—C2	1.497 (4)	C22—H22	0.9300
C2—C3	1.384 (4)	C23—C22	1.384 (4)
C2—C7	1.372 (4)	C23—C24	1.387 (4)
C3—C4	1.371 (6)	C23—C26	1.502 (4)
C3—H3	0.9300	C24—C25	1.371 (5)
C4—H4	0.9300	C24—H24	0.9300
C5—C4	1.346 (6)	C25—H25	0.9300
C5—C6	1.359 (6)	C26—N4	1.326 (4)

O1—Zn—O2	55.96 (12)	O4—C8—Zn	70.8 (2)
O1—Zn—O3	142.65 (12)	C9—C8—Zn	168.1 (3)
O1—Zn—O4	97.49 (10)	C10—C9—C8	120.9 (3)
O1—Zn—N1	102.97 (9)	C14—C9—C10	119.4 (3)
O1—Zn—N3	106.17 (10)	C14—C9—C8	119.7 (3)
O2—Zn—O3	93.35 (10)	C9—C10—H10	119.8
O2—Zn—O4	88.13 (10)	C11—C10—C9	120.4 (3)
O2—Zn—N1	158.51 (9)	C11—C10—H10	119.8
O2—Zn—N3	90.70 (9)	C10—C11—H11	120.9
O3—Zn—O4	57.04 (10)	C12—C11—C10	118.2 (3)
O3—Zn—N1	104.14 (10)	C12—C11—H11	120.9
O3—Zn—N3	93.66 (11)	F2—C12—C11	119.1 (4)
O4—Zn—N1	90.96 (10)	C13—C12—F2	117.7 (4)
O4—Zn—N3	150.53 (10)	C13—C12—C11	123.1 (3)
N1—Zn—N3	100.39 (10)	C12—C13—C14	118.7 (4)
C1—O1—Zn	104.58 (18)	C12—C13—H13	120.7
C8—O3—Zn	101.0 (2)	C14—C13—H13	120.7
C8—O4—Zn	81.0 (2)	C9—C14—C13	120.1 (3)
H72—O7—H71	107 (4)	C9—C14—H14	119.9
C15—N1—C19	117.5 (3)	C13—C14—H14	119.9
C15—N1—Zn	116.9 (2)	N1—C15—C16	122.8 (3)
C19—N1—Zn	125.4 (2)	N1—C15—H15	118.6
C20—N2—H2A	120.0	C16—C15—H15	118.6
C20—N2—H2B	120.0	C15—C16—H16	120.2
H2A—N2—H2B	120.0	C17—C16—C15	119.6 (3)
C21—N3—Zn	122.8 (2)	C17—C16—H16	120.2
C25—N3—C21	117.0 (3)	C16—C17—C18	118.1 (3)
C25—N3—Zn	120.2 (2)	C16—C17—C20	117.5 (3)
C26—N4—H4A	120.0	C18—C17—C20	124.2 (3)
C26—N4—H4B	120.0	C17—C18—C19	118.8 (3)
H4A—N4—H4B	120.0	C17—C18—H18	120.6
O1—C1—C2	118.5 (3)	C19—C18—H18	120.6
O2—C1—O1	121.6 (3)	N1—C19—C18	123.2 (3)
O2—C1—C2	119.8 (3)	N1—C19—H19	118.4
C3—C2—C1	120.2 (3)	C18—C19—H19	118.4
C7—C2—C3	119.1 (3)	O5—C20—N2	124.0 (3)
C7—C2—C1	120.7 (3)	O5—C20—C17	117.5 (3)
C2—C3—H3	119.7	N2—C20—C17	118.5 (3)
C4—C3—C2	120.7 (3)	N3—C21—C22	123.4 (3)
C4—C3—H3	119.7	N3—C21—H21	118.3
C3—C4—H4	120.8	C22—C21—H21	118.3
C5—C4—C3	118.4 (4)	C21—C22—C23	119.9 (3)
C5—C4—H4	120.8	C21—C22—H22	120.0
C4—C5—C6	123.2 (3)	C23—C22—H22	120.0
C4—C5—F1	119.1 (4)	C22—C23—C24	116.5 (3)
C6—C5—F1	117.8 (4)	C22—C23—C26	125.0 (3)
C5—C6—C7	118.3 (3)	C24—C23—C26	118.5 (3)
C5—C6—H6	120.9	C23—C24—H24	120.0
C7—C6—H6	120.9	C25—C24—C23	120.1 (3)
C2—C7—C6	120.4 (3)	C25—C24—H24	120.0
C2—C7—H7	119.8	N3—C25—C24	123.2 (3)
C6—C7—H7	119.8	N3—C25—H25	118.4
O3—C8—Zn	50.10 (17)	C24—C25—H25	118.4
O3—C8—C9	118.0 (3)	O6—C26—N4	122.7 (3)
O4—C8—O3	120.9 (3)	O6—C26—C23	120.1 (3)
O4—C8—C9	121.1 (3)	N4—C26—C23	117.2 (3)

O1—Zn—N1—C15	159.4 (2)	C3—C2—C7—C6	−0.9 (6)
O1—Zn—N1—C19	−25.8 (3)	C1—C2—C7—C6	178.4 (4)
O3—Zn—N1—C15	5.4 (3)	C7—C2—C3—C4	0.5 (6)
O3—Zn—N1—C19	−179.9 (3)	C1—C2—C3—C4	−178.8 (4)
O4—Zn—N1—C15	61.5 (3)	C6—C5—C4—C3	0.6 (8)
O4—Zn—N1—C19	−123.7 (3)	F1—C5—C4—C3	179.0 (4)
N3—Zn—N1—C15	−91.1 (3)	C2—C3—C4—C5	−0.3 (7)
N3—Zn—N1—C19	83.6 (3)	C4—C5—C6—C7	−1.0 (7)
O1—Zn—N3—C21	35.9 (2)	F1—C5—C6—C7	−179.4 (4)
O1—Zn—N3—C25	−144.1 (2)	C2—C7—C6—C5	1.1 (6)
O3—Zn—N3—C21	−176.1 (2)	C14—C9—C8—O4	−6.9 (4)
O3—Zn—N3—C25	3.9 (2)	C10—C9—C8—O4	172.9 (3)
O4—Zn—N3—C21	178.0 (2)	C14—C9—C8—O3	172.5 (3)
O4—Zn—N3—C25	−2.0 (3)	C10—C9—C8—O3	−7.7 (4)
N1—Zn—N3—C21	−71.0 (2)	C14—C9—C8—Zn	170.6 (8)
N1—Zn—N3—C25	109.0 (2)	C10—C9—C8—Zn	−9.6 (12)
O3—Zn—O1—C1	−38.7 (3)	C14—C9—C10—C11	0.3 (5)
O4—Zn—O1—C1	−81.6 (2)	C8—C9—C10—C11	−179.5 (3)
N1—Zn—O1—C1	−174.32 (19)	C10—C9—C14—C13	0.4 (5)
N3—Zn—O1—C1	80.6 (2)	C8—C9—C14—C13	−179.8 (3)
O1—Zn—O3—C8	−53.5 (3)	C12—C11—C10—C9	−0.7 (6)
N1—Zn—O3—C8	81.8 (2)	C10—C11—C12—C13	0.4 (7)
N3—Zn—O3—C8	−176.5 (2)	C10—C11—C12—F2	180.0 (4)
O4—Zn—O3—C8	0.04 (18)	F2—C12—C13—C14	−179.3 (4)
O1—Zn—O4—C8	150.46 (19)	C11—C12—C13—C14	0.3 (7)
O3—Zn—O4—C8	−0.04 (19)	C9—C14—C13—C12	−0.7 (6)
N1—Zn—O4—C8	−106.3 (2)	N1—C15—C16—C17	1.3 (6)
N3—Zn—O4—C8	7.0 (3)	C18—C17—C16—C15	−0.5 (5)
Zn—O3—C8—O4	−0.1 (4)	C20—C17—C16—C15	−175.8 (3)
Zn—O3—C8—C9	−179.5 (2)	C16—C17—C18—C19	−0.7 (6)
Zn—O4—C8—O3	0.1 (3)	C20—C17—C18—C19	174.2 (4)
Zn—O4—C8—C9	179.5 (3)	C16—C17—C20—O5	19.1 (5)
C19—N1—C15—C16	−0.8 (6)	C18—C17—C20—O5	−155.9 (4)
Zn—N1—C15—C16	174.4 (3)	C16—C17—C20—N2	−161.1 (3)
C15—N1—C19—C18	−0.5 (6)	C18—C17—C20—N2	23.9 (5)
Zn—N1—C19—C18	−175.2 (3)	N1—C19—C18—C17	1.3 (7)
C25—N3—C21—C22	0.2 (4)	C23—C22—C21—N3	0.6 (5)
Zn—N3—C21—C22	−179.8 (2)	C24—C23—C22—C21	−0.9 (4)
C21—N3—C25—C24	−0.5 (5)	C26—C23—C22—C21	176.7 (3)
Zn—N3—C25—C24	179.5 (3)	C22—C23—C24—C25	0.6 (5)
O2—C1—O1—Zn	−2.1 (3)	C26—C23—C24—C25	−177.2 (3)
C2—C1—O1—Zn	179.6 (2)	C23—C24—C25—N3	0.1 (5)
O2—C1—C2—C7	173.3 (3)	C22—C23—C26—O6	−165.7 (3)
O1—C1—C2—C7	−8.3 (5)	C24—C23—C26—O6	11.9 (4)
O2—C1—C2—C3	−7.4 (5)	C22—C23—C26—N4	11.7 (4)
O1—C1—C2—C3	171.0 (3)	C24—C23—C26—N4	−170.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O1	0.97 (7)	2.08 (7)	2.910 (8)	144 (6)
O7—H72···O4ⁱ	0.92 (8)	1.81 (8)	2.713 (10)	167 (8)
N2—H2A···O5ⁱⁱ	0.86	2.07	2.905 (4)	165
N2—H2B···O6ⁱⁱⁱ	0.86	2.15	2.977 (4)	161
N4—H4A···O2^iv	0.86	2.14	2.961 (4)	159
N4—H4B···O2^v	0.86	2.11	2.920 (4)	157

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₄FO₂)₂(C₆H₆N₂O)₂]·H₂O
M_r	605.87
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	8.2363 (2), 12.3711 (2), 14.8971 (3)
α, β, γ (°)	113.178 (14), 99.015 (17), 99.465 (16)
V (Å³)	1334.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.99
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.735, 0.816
No. of measured, independent and observed [I > 2σ(I)] reflections	5794, 5401, 4454
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.623

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.152, 1.14
No. of reflections	5401
No. of parameters	368
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.90

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Zn—O1	1.978 (2)	Zn—O4	2.458 (3)
Zn—O2	2.564 (3)	Zn—N1	2.079 (2)
Zn—O3	2.010 (3)	Zn—N3	2.095 (3)

O1—Zn—O2	55.96 (12)	O2—Zn—N3	90.70 (9)
O1—Zn—O3	142.65 (12)	O3—Zn—O4	57.04 (10)
O1—Zn—O4	97.49 (10)	O3—Zn—N1	104.14 (10)
O1—Zn—N1	102.97 (9)	O3—Zn—N3	93.66 (11)
O1—Zn—N3	106.17 (10)	O4—Zn—N1	90.96 (10)
O2—Zn—O3	93.35 (10)	O4—Zn—N3	150.53 (10)
O2—Zn—O4	88.13 (10)	N1—Zn—N3	100.39 (10)
O2—Zn—N1	158.51 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O1	0.97 (7)	2.08 (7)	2.910 (8)	144 (6)
O7—H72···O4ⁱ	0.92 (8)	1.81 (8)	2.713 (10)	167 (8)
N2—H2A···O5ⁱⁱ	0.86	2.07	2.905 (4)	165
N2—H2B···O6ⁱⁱⁱ	0.86	2.15	2.977 (4)	161
N4—H4A···O2^iv	0.86	2.14	2.961 (4)	159
N4—H4B···O2^v	0.86	2.11	2.920 (4)	157

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

Acknowledgements

The authors acknowledge the purchase of a CAD-4 diffractometer under grant DPT/TBAG1 of the Scientific and Technical Research Council of Turkey.

References

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