Bis(4-hydroxy­benzoato-κO)­bis­(nicotin­amide-κN)­zinc(II)

The title compound, [Zn(C₆H₆N₂O)₂(C₇H₅O₃)₂], crystallizes as mononuclear mol­ecules with distorted trigonal–bipyram­idal zinc coordination. One of the 4-hydroxy­benzoate ions is coordinated to zinc as a bidentate ligand, while the other is monodentate. Intermolecular hydrogen bonds between nicotin­amide N and carboxyl O atoms, as well as between the nicotin­amide O and hydroxy­benzoate O atoms, support the molecular packing. Hydro­gen bonding of the carboxyl­ate O atoms has an effect on the delocalization in the carboxyl­ate groups.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.033
• wR factor = 0.095
• Data-to-parameter ratio = 11.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

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 structures of some complexes obtained from the reactions of transition metal(II) ions with different benzoic and/or nicotinic acid derivatives as ligands have been the subject of much interest in our laboratory; examples are [Zn(C₇H₅O₃)(OH₂)₃(NA)]·C₇O₃H₅ [(II); Hökelek & Necefoğlu, 2001], [Co(C₇H₆NO₂)₂(H₂O)₂(NA)₂] [(III); Hökelek & Necefoğlu, 1999a], [Co(C₇H₅O₂)₂(NA)₂(H₂O)₂] [(IV); Hökelek & Necefoğlu, 1999b], [Co(C₇H₅O₃)₂(NA)₂(H₂O)₂] [(V); Hökelek & Necefoğlu, 1999c], [Cu(C₇H₅O₃)₂(NA)₂(H₂O)₂] [(VI); Hökelek, Budak et al., 1998], [Cu₃{(NO₂)₂C₆H₃COO}₆(CH₃OH)₂]_n [(VII); Hökelek, Mert & Ünaleroğlu, 1998], [Co(C₇H₄NO₄)₂(NA)₂(H₂O)₂] [(VIII); Hökelek & Necefoğlu, 1998], [Cu(C₇H₄NO₄)₂(DENA)₂(H₂O)₂] [(IX); Hökelek et al., 1997], [Co(C₇H₅O₃)₂(DENA)₂(H₂O)₂] [(X); Hökelek & Necefoğlu, 1997], [Zn₂(C₇H₅O₃)₄(DENA)₂(H₂O)₂] [(XI); Hökelek & Necefoğlu, 1996], [Cu(C₇H₅O₂)₂(DENA)₂] [(XII); Hökelek et al., 1996] and [Cu₂(C₆H₅COO)₄(DENA)₂] [(XIII); Hökelek et al., 1995]. In (XIII), the benzoate ion acts as a bidentate ligand, but in (XI) two of the benzoate ions acts as monodentate ligands, while the other two are bidentate, bridging the two Zn atoms.

The solid-state structures of anhydrous zinc(II) carboxylates include one-dimensional (Guseinov et al., 1984; Clegg et al., 1986a), two-dimensional (Clegg et al., 1986b, 1987) and three-dimensional (Capilla & Aranda, 1979) polymeric motifs of different types, while discrete monomeric complexes with octahedral and tetrahedral coordination geometry are found if water or other donor molecules are coordinated to Zn (van Niekerk et al., 1953; Usubaliev et al., 1992). In hexaaquazinc(II) bis(4-hydroxybenzoate) dihydrate, [Zn(H₂O)₆](4-HOC₆H₄COO)₂·2H₂O, which is isostructural with the corresponding Mg^II, Co^II, Ni^II and Mn^II compounds, the carboxylate ion lies outside the coordination sphere of the Zn atom (Musaev et al., 1983), while [Zn(4-HOC₆H₄COO)₂]·4C₅H₅N forms a clathrate, consisting of [Zn(4-HOC₆H₄COO)₂(C₅H₅N)₂] units with tetrahedral coordination geometry and free pyridine molecules (Nadzhafov et al., 1981).

The structure determination of the title compound, (I), a zinc complex with two NA and two 4-hydroxybenzoate ligands, was undertaken in order to determine the ligand properties of (NA) and 4-hydroxybenzoate ligands and also to compare the results obtained with those reported previously. In the monomeric title complex, [Zn(C₇O₃H₅)₂(NA)₂], the Zn atom is surrounded by two NA and two 4-hydroxybenzoate ligands. One of the 4-hydroxybenzoate ions acts as a bidentate ligand, while the other and two NA are monodentate ligands. A view of the molecule with the atomic numbering scheme is shown in Fig. 1.

Although the Zn atom has four-coordination, close contact of the O4 atom [Zn1···O4 = 2.404 (2) Å] may be considered to give five-coordination; 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 et al., 1981) and 2.494 (8) Å in [Zn(p—H₂NC₆H₄COO)₂]_n.1.5nH₂O (Amiraslanov et al., 1980). The five-coordination around Zn^II can be described as a distorted trigonal bipyramid or a distorted square pyramid. Further information can be obtained by estimating the structural index τ (Uhlenbrock et al., 1996), which represents the relative amount of trigonality [square pyramid, τ = 0; trigonal bipyramid, τ = 1; τ = (β-α)/60°, α and β being the two largest angles around the central atom]. The value of τ is 0.36 for (I) [α = 138.00 (7) and β = 159.61 (6) °]. The coordination of the Zn^II atom is therefore best described as a distorted trigonal bipyramid.

In the binuclear complex (XI), the average Zn—O bond length [1.953 (2) Å] is shorter than the corresponding value in (I) [2.107 (2) Å], but Zn is four-coordinate. The average Zn—N bond length [2.075 (2) Å] in (I) is in good agreement with the values reported for tetrahedrally coordinated Zn complexes [2.006 (5) Å in Zn₂(DENA)₂(NCS)₄ (Bigoli et al., 1973a), 2.054 (6) and 2.055 (6) Å in ZnCl₂(DENA)₂ (Khodashova et al., 1978), and 2.068 (7) Å in ZnI₂(DENA)₂ (Sergienko et al., 1978)], while it is shorter than the corresponding value in the octahedrally coordinated zinc complex [Zn(DENA)₂(NCS)₂]·2H₂O [2.171 (4) Å; Bigoli et al., 1973b]. The aromatic bonds C5—O5 [1.365 (3) Å] and C12—O6 [1.359 (3) Å] are in agreement with the corresponding values for 4-hydroxybenzoic acid monohydrate (Colapietro et al., 1979).

The N1—Zn1···O4 and O3—Zn1···O4 angles are 88.86 (7) and 58.79 (6)°, respectively. The corresponding N—M···O and O—M···O (where M is metal atom) angles are 90.4 (4) and 58.3 (3)° in (XI) (Hökelek et al., 1996), and 89.6 (1), 89.0 (1) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) (Greenaway et al., 1984). The Zn1 atom lies −0.1931 (2) and 0.2208 (2) 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 [1.281 (3) and 1.274 (3) Å] are a little larger than the C1—O2 and C8—O4 [1.240 (3) and 1.245 (3) Å] bond lengths and may be compared with the corresponding distances in the monomeric and dimeric carboxylate pyridine complexes: 1.266 (5) and 1.248 (6) Å in (III), 1.255 (1) and 1.253 (2) Å in (IV), 1.263 (5) and 1.258 (6) Å in (V), 1.278 (3) and 1.246 (3) Å in (VI), 1.254 (2) and 1.251 (2) Å in (VIII), 1.267 (6) and 1.237 (4) Å in (IX), 1.251 (6) and 1.254 (7) Å in (X), 1.279 (4) and 1.246 (4) Å in (XI), and 1.277 (4) and 1.239 (4) Å in (XII).

One of the carboxylates is bidentate, while the other is monodentate, but the near equality of the two C—O bond lengths in each carboxylate groups (Table 1) indicates a delocalized bonding arrangement, rather than localized single and double bonds. This may be due to the intermolecular hydrogen bonds of the carboxyl O atoms (Table 2).

The dihedral angles between the mean planes of the carboxyl groups (O1/C1/O2 and O3/C8/O4) and the phenyl rings [A (C2—C7) and B (C9—C14)] in the hydroxybenzoate anions are 12.2 (2) and 10.0 (2)°, respectively; these may be compared with the corresponding values of 24.1 (4)° in (III), 13.0 (2)° in (IV), 14.2 (3)° in (V), 23.7 (3)° in (VIII), 10.2 (7)° in (IX), 2.2 (6)° in (X), 17.9 (7) and 136.1 (2)° in (XI), and 6.7 (9)° in (XII). The configuration around the Zn1 atom is given by the torsion angles listed in Table 1.

There are intermolecular hydrogen bonds between nicotinamide N atoms and carboxyl O atoms, as well as between the nicotinamide O atoms and hydroxybenzoate O atoms of neighbouring molecules (Table 2). These intermolecular hydrogen bonds, together with dipole-dipole and van der Waals interactions, support the molecular packing.

All rings are essentially planar, with maximum deviations of 0.011 (2) Å for C7 and 0.011 (2) Å for C21. The rings are twisted with respect to each other; dihedral angles between least-squares planes are A/B = 79.36 (7), A/C = 84.50 (8), A/D = 12.62 (8), B/C = 20.39 (7), B/D = 77.28 (6) and C/D = 89.57 (7)°.

S2. Experimental

The title compound, (I), was prepared by the reaction of 0.02 mol of NA, in H₂O (50 ml), 0.01 mol of ZnSO₄ in H₂O (100 ml), and 0.02 mol of sodium p-hydroxybenzoate in H₂O (100 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving colourless single crystals.

S3. Refinement

H atoms were located in a difference map and refined isotropically.

Computing details

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.

(I)

Crystal data

[Zn(C6H6N2O)2(C7H5O3)2]	F(000) = 1200
Mr = 583.85	Dx = 1.533 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.3159 (10) Å	θ = 10–18°
b = 22.606 (3) Å	µ = 1.03 mm^−1
c = 10.8926 (10) Å	T = 293 K
β = 95.375 (6)°	Rod-shaped, colourless
V = 2529.0 (5) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Enraf Nonius TurboCAD4 diffractometer	4089 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
Graphite monochromator	θmax = 26.3°, θmin = 2.1°
non–profiled ω scans	h = −12→0
Absorption correction: ψ scan (North et al., 1968)	k = −28→0
Tmin = 0.748, Tmax = 0.861	l = −13→13
5409 measured reflections	3 standard reflections every 120 min
5124 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 0.716P] where P = (Fo^2 + 2Fc^2)/3
5124 reflections	(Δ/σ)max = 0.003
440 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.75623 (2)	0.883728 (11)	0.86158 (2)	0.03518 (10)
O1	0.76143 (17)	0.84265 (8)	1.01724 (15)	0.0508 (4)
O2	0.88676 (19)	0.91508 (7)	1.09916 (17)	0.0558 (5)
O3	0.87220 (15)	0.93536 (7)	0.77245 (16)	0.0459 (4)
O4	0.96989 (17)	0.85151 (7)	0.82001 (16)	0.0490 (4)
O5	0.91427 (18)	0.72931 (9)	1.54104 (15)	0.0508 (4)
O6	1.3646 (2)	0.96147 (12)	0.4693 (2)	0.0731 (7)
O7	0.27913 (17)	0.87490 (7)	1.03315 (18)	0.0515 (4)
O8	0.5124 (2)	0.86786 (8)	0.39748 (16)	0.0564 (5)
N1	0.67746 (17)	0.82025 (8)	0.73917 (17)	0.0373 (4)
N2	0.59081 (16)	0.93635 (8)	0.85935 (15)	0.0335 (4)
N3	0.5000 (2)	0.77479 (12)	0.3258 (2)	0.0517 (5)
N4	0.1655 (2)	0.95877 (10)	1.0012 (2)	0.0449 (5)
C1	0.8329 (2)	0.86633 (10)	1.1065 (2)	0.0397 (5)
C2	0.8500 (2)	0.83090 (10)	1.22303 (19)	0.0361 (5)
C3	0.9082 (3)	0.85423 (11)	1.3320 (2)	0.0519 (6)
C4	0.9281 (3)	0.82086 (12)	1.4371 (2)	0.0546 (7)
C5	0.8922 (2)	0.76198 (10)	1.4358 (2)	0.0394 (5)
C6	0.8348 (2)	0.73762 (11)	1.3280 (2)	0.0452 (5)
C7	0.8124 (2)	0.77220 (11)	1.2237 (2)	0.0436 (5)
C8	0.9676 (2)	0.90006 (10)	0.7659 (2)	0.0372 (5)
C9	1.07416 (19)	0.91741 (9)	0.69028 (19)	0.0341 (4)
C10	1.0820 (2)	0.97336 (11)	0.6404 (2)	0.0466 (6)
C11	1.1794 (3)	0.98740 (13)	0.5666 (3)	0.0572 (7)
C12	1.2707 (2)	0.94520 (12)	0.5421 (2)	0.0476 (6)
C13	1.2636 (2)	0.88913 (12)	0.5909 (2)	0.0482 (6)
C14	1.1659 (2)	0.87582 (11)	0.6644 (2)	0.0419 (5)
C15	0.5763 (2)	0.98543 (10)	0.7896 (2)	0.0399 (5)
C16	0.4627 (2)	1.01752 (11)	0.7803 (2)	0.0458 (6)
C17	0.3605 (2)	0.99941 (10)	0.8439 (2)	0.0404 (5)
C18	0.37350 (19)	0.94894 (9)	0.91583 (18)	0.0315 (4)
C19	0.4912 (2)	0.91906 (9)	0.92089 (19)	0.0339 (4)
C20	0.2681 (2)	0.92475 (9)	0.9878 (2)	0.0357 (5)
C21	0.6834 (2)	0.76251 (10)	0.7703 (2)	0.0389 (5)
C22	0.6438 (2)	0.71868 (10)	0.6889 (2)	0.0413 (5)
C23	0.5934 (2)	0.73319 (10)	0.5712 (2)	0.0384 (5)
C24	0.58346 (19)	0.79243 (9)	0.53787 (19)	0.0341 (4)
C25	0.6282 (2)	0.83412 (10)	0.6248 (2)	0.0374 (5)
C26	0.5294 (2)	0.81442 (10)	0.4142 (2)	0.0395 (5)
H3A	0.467 (3)	0.7854 (14)	0.255 (3)	0.066 (9)*
H3B	0.512 (3)	0.7365 (14)	0.340 (3)	0.061 (9)*
H4A	0.160 (3)	0.9934 (15)	0.975 (3)	0.064 (9)*
H4B	0.106 (3)	0.9433 (12)	1.037 (2)	0.051 (8)*
H5A	0.873 (4)	0.6979 (17)	1.534 (3)	0.094 (13)*
H6A	1.407 (5)	0.937 (2)	0.454 (5)	0.13 (2)*
H31	0.932 (3)	0.8927 (14)	1.332 (3)	0.070 (10)*
H41	0.962 (3)	0.8356 (12)	1.510 (3)	0.055 (7)*
H61	0.814 (3)	0.6949 (14)	1.323 (3)	0.066 (8)*
H71	0.778 (3)	0.7547 (13)	1.150 (2)	0.059 (8)*
H101	1.024 (3)	1.0018 (13)	0.661 (3)	0.063 (8)*
H111	1.183 (3)	1.0263 (15)	0.533 (3)	0.075 (9)*
H131	1.324 (3)	0.8588 (13)	0.572 (3)	0.060 (8)*
H141	1.154 (2)	0.8388 (12)	0.700 (2)	0.052 (7)*
H151	0.648 (2)	1.0001 (10)	0.749 (2)	0.037 (6)*
H161	0.459 (3)	1.0502 (13)	0.732 (3)	0.061 (8)*
H171	0.281 (2)	1.0187 (12)	0.838 (2)	0.046 (7)*
H191	0.503 (2)	0.8867 (11)	0.972 (2)	0.044 (7)*
H211	0.715 (2)	0.7538 (11)	0.852 (2)	0.042 (6)*
H221	0.649 (2)	0.6810 (12)	0.715 (2)	0.046 (7)*
H231	0.568 (2)	0.7063 (10)	0.520 (2)	0.032 (6)*
H251	0.625 (2)	0.8752 (10)	0.603 (2)	0.030 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03253 (14)	0.03641 (15)	0.03653 (15)	−0.00278 (10)	0.00285 (10)	0.00115 (10)
O1	0.0511 (10)	0.0595 (11)	0.0409 (9)	−0.0047 (8)	−0.0003 (7)	0.0140 (8)
O2	0.0715 (12)	0.0347 (9)	0.0632 (11)	0.0019 (8)	0.0164 (9)	0.0081 (8)
O3	0.0371 (8)	0.0428 (9)	0.0601 (10)	0.0010 (7)	0.0157 (7)	0.0033 (8)
O4	0.0479 (9)	0.0448 (9)	0.0551 (10)	−0.0018 (7)	0.0100 (8)	0.0127 (8)
O5	0.0558 (11)	0.0586 (11)	0.0360 (9)	−0.0091 (9)	−0.0057 (7)	0.0053 (8)
O6	0.0657 (13)	0.0806 (16)	0.0790 (15)	0.0114 (12)	0.0382 (11)	0.0275 (12)
O7	0.0523 (10)	0.0359 (9)	0.0695 (11)	0.0007 (7)	0.0224 (9)	0.0111 (8)
O8	0.0768 (13)	0.0454 (10)	0.0475 (10)	0.0066 (9)	0.0079 (9)	0.0084 (8)
N1	0.0346 (9)	0.0355 (9)	0.0416 (10)	−0.0017 (7)	0.0023 (8)	−0.0032 (8)
N2	0.0326 (9)	0.0336 (9)	0.0345 (9)	−0.0014 (7)	0.0038 (7)	0.0021 (7)
N3	0.0571 (13)	0.0534 (14)	0.0424 (12)	−0.0031 (11)	−0.0079 (10)	−0.0042 (10)
N4	0.0380 (11)	0.0397 (12)	0.0590 (13)	0.0012 (9)	0.0160 (9)	0.0024 (10)
C1	0.0381 (12)	0.0390 (12)	0.0433 (12)	0.0089 (9)	0.0113 (10)	0.0033 (10)
C2	0.0329 (11)	0.0378 (11)	0.0382 (11)	0.0010 (9)	0.0062 (8)	−0.0011 (9)
C3	0.0699 (17)	0.0354 (13)	0.0505 (14)	−0.0094 (12)	0.0062 (12)	−0.0092 (11)
C4	0.0749 (18)	0.0527 (15)	0.0344 (12)	−0.0132 (13)	−0.0041 (12)	−0.0126 (11)
C5	0.0361 (11)	0.0479 (13)	0.0340 (11)	−0.0034 (10)	0.0018 (9)	−0.0017 (9)
C6	0.0541 (14)	0.0408 (13)	0.0390 (12)	−0.0152 (11)	−0.0052 (10)	0.0010 (10)
C7	0.0476 (13)	0.0456 (13)	0.0360 (12)	−0.0129 (11)	−0.0052 (10)	−0.0001 (10)
C8	0.0347 (11)	0.0387 (11)	0.0373 (11)	−0.0050 (9)	−0.0008 (9)	−0.0039 (9)
C9	0.0312 (11)	0.0372 (11)	0.0331 (10)	−0.0001 (8)	−0.0018 (8)	−0.0005 (8)
C10	0.0421 (13)	0.0377 (12)	0.0617 (15)	0.0043 (10)	0.0140 (11)	0.0030 (11)
C11	0.0568 (16)	0.0448 (14)	0.0728 (18)	0.0010 (12)	0.0204 (14)	0.0160 (13)
C12	0.0412 (13)	0.0597 (15)	0.0434 (13)	0.0003 (11)	0.0110 (10)	0.0077 (11)
C13	0.403 (13)	0.0538 (15)	0.0513 (14)	0.0106 (11)	0.0092 (11)	0.0062 (11)
C14	0.0368 (12)	0.0425 (13)	0.0459 (13)	0.0048 (10)	0.0018 (10)	0.0087 (10)
C15	0.0418 (12)	0.0420 (12)	0.0366 (11)	−0.0039 (10)	0.0082 (9)	0.0051 (9)
C16	0.0538 (14)	0.0405 (13)	0.0439 (13)	0.0043 (11)	0.0085 (11)	0.0137 (10)
C17	0.0399 (13)	0.0389 (12)	0.0422 (12)	0.0062 (10)	0.0031 (10)	0.0020 (10)
C18	0.0325 (10)	0.0302 (10)	0.0314 (10)	−0.0032 (8)	0.0019 (8)	−0.0050 (8)
C19	0.0353 (11)	0.0313 (11)	0.0352 (11)	−0.0024 (8)	0.0034 (8)	0.0026 (9)
C20	0.0346 (11)	0.0326 (11)	0.0403 (11)	−0.0039 (9)	0.0059 (9)	−0.0046 (9)
C21	0.0344 (11)	0.0405 (12)	0.0421 (12)	0.0046 (9)	0.0040 (9)	0.0022 (10)
C22	0.0407 (12)	0.0327 (11)	0.0514 (13)	0.0042 (9)	0.0088 (10)	0.0023 (10)
C23	0.0371 (11)	0.0342 (12)	0.0444 (12)	−0.0027 (9)	0.0064 (9)	−0.0068 (10)
C24	0.0302 (10)	0.0361 (11)	0.0371 (11)	−0.0011 (8)	0.0084 (8)	−0.0024 (9)
C25	0.0379 (12)	0.0315 (11)	0.0432 (12)	−0.0015 (9)	0.0057 (9)	−0.0002 (9)
C26	0.0331 (11)	0.0439 (13)	0.0422 (12)	−0.0015 (9)	0.0080 (9)	0.0016 (10)

Geometric parameters (Å, º)

Zn1—O1	1.9295 (16)	C18—C20	1.501 (3)
Zn1—O3	1.9883 (16)	C5—O5	1.365 (3)
Zn1—N1	2.0723 (18)	C5—C6	1.379 (3)
Zn1—N2	2.0784 (17)	C5—C4	1.381 (4)
Zn1—O4	2.4042 (18)	N3—C26	1.329 (3)
Zn1—C8	2.530 (2)	N3—H3B	0.89 (3)
O3—C8	1.274 (3)	N3—H3A	0.85 (3)
O2—C1	1.240 (3)	C9—C10	1.382 (3)
N2—C19	1.337 (3)	C6—C7	1.381 (3)
N2—C15	1.345 (3)	C6—H61	0.99 (3)
O1—C1	1.281 (3)	C21—C22	1.367 (3)
C1—C2	1.498 (3)	C21—H211	0.94 (2)
N1—C25	1.338 (3)	C7—H71	0.93 (3)
N1—C21	1.349 (3)	C22—H221	0.90 (3)
C24—C25	1.384 (3)	C17—C16	1.376 (3)
C24—C23	1.389 (3)	C17—H171	0.92 (3)
C24—C26	1.494 (3)	O7—C20	1.232 (3)
C25—H251	0.96 (2)	O5—H5A	0.83 (4)
C19—C18	1.386 (3)	N4—C20	1.328 (3)
C19—H191	0.92 (3)	N4—H4A	0.83 (3)
C2—C3	1.383 (3)	N4—H4B	0.83 (3)
C2—C7	1.383 (3)	C10—C11	1.381 (4)
C15—C16	1.374 (3)	C10—H101	0.92 (3)
C15—H151	0.96 (2)	C12—O6	1.359 (3)
O8—C26	1.232 (3)	C12—C13	1.379 (4)
C8—O4	1.245 (3)	C12—C11	1.384 (4)
C8—C9	1.487 (3)	C13—H131	0.97 (3)
C14—C13	1.377 (4)	C11—H111	0.95 (3)
C14—C9	1.382 (3)	C16—H161	0.91 (3)
C14—H141	0.94 (3)	C4—C3	1.371 (4)
C23—C22	1.377 (3)	C4—H41	0.90 (3)
C23—H231	0.85 (2)	C3—H31	0.90 (3)
C18—C17	1.384 (3)	O6—H6A	0.74 (5)
O1—Zn1—O3	138.00 (7)	O5—C5—C4	119.3 (2)
O1—Zn1—N1	102.07 (8)	C6—C5—C4	119.1 (2)
O3—Zn1—N1	108.05 (7)	C26—N3—H3B	120.9 (19)
O1—Zn1—N2	103.94 (7)	C26—N3—H3A	121 (2)
O3—Zn1—N2	100.91 (7)	H3B—N3—H3A	118 (3)
N1—Zn1—N2	96.70 (7)	C14—C9—C10	118.4 (2)
O1—Zn1—O4	93.97 (7)	C14—C9—C8	119.3 (2)
O3—Zn1—O4	58.79 (6)	C10—C9—C8	122.2 (2)
N1—Zn1—O4	88.86 (7)	C5—C6—C7	120.0 (2)
N2—Zn1—O4	159.61 (6)	C5—C6—H61	120.5 (17)
O1—Zn1—C8	118.55 (7)	C7—C6—H61	119.5 (17)
O3—Zn1—C8	29.79 (7)	O8—C26—N3	122.3 (2)
N1—Zn1—C8	97.89 (7)	O8—C26—C24	119.7 (2)
N2—Zn1—C8	130.54 (7)	N3—C26—C24	118.0 (2)
O4—Zn1—C8	29.08 (6)	N1—C21—C22	122.3 (2)
C8—O3—Zn1	99.37 (14)	N1—C21—H211	116.4 (15)
C19—N2—C15	118.32 (19)	C22—C21—H211	121.2 (15)
C19—N2—Zn1	119.71 (14)	C6—C7—C2	121.5 (2)
C15—N2—Zn1	121.76 (14)	C6—C7—H71	119.0 (18)
C1—O1—Zn1	115.62 (15)	C2—C7—H71	119.2 (18)
O2—C1—O1	123.5 (2)	C21—C22—C23	119.7 (2)
O2—C1—C2	120.8 (2)	C21—C22—H221	118.2 (16)
O1—C1—C2	115.7 (2)	C23—C22—H221	122.1 (16)
C25—N1—C21	117.75 (19)	C16—C17—C18	119.5 (2)
C25—N1—Zn1	121.91 (15)	C16—C17—H171	122.6 (16)
C21—N1—Zn1	120.16 (15)	C18—C17—H171	117.9 (16)
C25—C24—C23	117.8 (2)	C5—O5—H5A	110 (3)
C25—C24—C26	117.56 (19)	C8—O4—Zn1	81.08 (13)
C23—C24—C26	124.7 (2)	C20—N4—H4A	122 (2)
N1—C25—C24	123.4 (2)	C20—N4—H4B	116.0 (19)
N1—C25—H251	117.2 (13)	H4A—N4—H4B	122 (3)
C24—C25—H251	119.4 (13)	O7—C20—N4	122.0 (2)
N2—C19—C18	123.32 (19)	O7—C20—C18	119.93 (19)
N2—C19—H191	118.3 (17)	N4—C20—C18	118.1 (2)
C18—C19—H191	118.3 (17)	C11—C10—C9	120.8 (2)
C3—C2—C7	117.4 (2)	C11—C10—H101	120.4 (18)
C3—C2—C1	122.1 (2)	C9—C10—H101	118.7 (18)
C7—C2—C1	120.5 (2)	O6—C12—C13	122.7 (2)
N2—C15—C16	121.7 (2)	O6—C12—C11	117.5 (2)
N2—C15—H151	119.8 (14)	C13—C12—C11	119.8 (2)
C16—C15—H151	118.4 (14)	C14—C13—C12	119.5 (2)
O4—C8—O3	120.4 (2)	C14—C13—H131	119.8 (17)
O4—C8—C9	120.8 (2)	C12—C13—H131	120.6 (17)
O3—C8—C9	118.7 (2)	C10—C11—C12	119.9 (2)
O4—C8—Zn1	69.84 (12)	C10—C11—H111	119.3 (19)
O3—C8—Zn1	50.84 (11)	C12—C11—H111	120.7 (19)
C9—C8—Zn1	167.70 (16)	C15—C16—C17	119.6 (2)
C13—C14—C9	121.5 (2)	C15—C16—H161	117.2 (18)
C13—C14—H141	124.8 (16)	C17—C16—H161	123.2 (18)
C9—C14—H141	113.7 (16)	C3—C4—C5	120.2 (2)
C22—C23—C24	119.0 (2)	C3—C4—H41	123.3 (18)
C22—C23—H231	120.4 (15)	C5—C4—H41	116.5 (17)
C24—C23—H231	120.6 (15)	C4—C3—C2	121.7 (2)
C17—C18—C19	117.56 (19)	C4—C3—H31	120 (2)
C17—C18—C20	124.01 (19)	C2—C3—H31	118 (2)
C19—C18—C20	118.44 (19)	C12—O6—H6A	113 (4)
O5—C5—C6	121.6 (2)
O1—Zn1—O3—C8	59.86 (18)	N1—Zn1—C8—C9	78.4 (7)
N1—Zn1—O3—C8	−73.82 (15)	N2—Zn1—C8—C9	−27.5 (8)
N2—Zn1—O3—C8	−174.65 (13)	O4—Zn1—C8—C9	151.5 (8)
O4—Zn1—O3—C8	3.36 (12)	C25—C24—C23—C22	1.6 (3)
O1—Zn1—N2—C19	−28.41 (17)	C26—C24—C23—C22	−179.2 (2)
O3—Zn1—N2—C19	−174.26 (15)	N2—C19—C18—C17	−0.6 (3)
N1—Zn1—N2—C19	75.84 (16)	N2—C19—C18—C20	179.18 (18)
O4—Zn1—N2—C19	−179.15 (16)	C13—C14—C9—C10	0.1 (4)
C8—Zn1—N2—C19	−177.76 (14)	C13—C14—C9—C8	177.5 (2)
O1—Zn1—N2—C15	156.90 (16)	O4—C8—C9—C14	9.9 (3)
O3—Zn1—N2—C15	11.05 (18)	O3—C8—C9—C14	−168.6 (2)
N1—Zn1—N2—C15	−98.85 (17)	Zn1—C8—C9—C14	−138.6 (7)
O4—Zn1—N2—C15	6.2 (3)	O4—C8—C9—C10	−172.7 (2)
C8—Zn1—N2—C15	7.6 (2)	O3—C8—C9—C10	8.8 (3)
O3—Zn1—O1—C1	29.4 (2)	Zn1—C8—C9—C10	38.7 (8)
N1—Zn1—O1—C1	164.68 (16)	O5—C5—C6—C7	179.2 (2)
N2—Zn1—O1—C1	−95.18 (16)	C4—C5—C6—C7	−0.9 (4)
O4—Zn1—O1—C1	74.99 (17)	C25—C24—C26—O8	−8.2 (3)
C8—Zn1—O1—C1	58.65 (18)	C23—C24—C26—O8	172.6 (2)
Zn1—O1—C1—O2	6.4 (3)	C25—C24—C26—N3	172.4 (2)
Zn1—O1—C1—C2	−172.88 (14)	C23—C24—C26—N3	−6.7 (3)
O1—Zn1—N1—C25	163.89 (16)	C25—N1—C21—C22	1.4 (3)
O3—Zn1—N1—C25	−45.78 (18)	Zn1—N1—C21—C22	−173.84 (17)
N2—Zn1—N1—C25	58.03 (17)	C5—C6—C7—C2	2.1 (4)
O4—Zn1—N1—C25	−102.30 (17)	C3—C2—C7—C6	−1.6 (4)
C8—Zn1—N1—C25	−74.58 (17)	C1—C2—C7—C6	175.8 (2)
O1—Zn1—N1—C21	−21.09 (18)	N1—C21—C22—C23	−1.3 (3)
O3—Zn1—N1—C21	129.25 (16)	C24—C23—C22—C21	−0.3 (3)
N2—Zn1—N1—C21	−126.94 (16)	C19—C18—C17—C16	0.5 (3)
O4—Zn1—N1—C21	72.73 (16)	C20—C18—C17—C16	−179.3 (2)
C8—Zn1—N1—C21	100.45 (17)	O3—C8—O4—Zn1	5.3 (2)
C21—N1—C25—C24	0.1 (3)	C9—C8—O4—Zn1	−173.20 (19)
Zn1—N1—C25—C24	175.21 (16)	O1—Zn1—O4—C8	−149.43 (14)
C23—C24—C25—N1	−1.6 (3)	O3—Zn1—O4—C8	−3.44 (13)
C26—C24—C25—N1	179.22 (19)	N1—Zn1—O4—C8	108.55 (14)
C15—N2—C19—C18	0.4 (3)	N2—Zn1—O4—C8	2.2 (3)
Zn1—N2—C19—C18	−174.45 (15)	C17—C18—C20—O7	168.2 (2)
O2—C1—C2—C3	10.4 (3)	C19—C18—C20—O7	−11.5 (3)
O1—C1—C2—C3	−170.3 (2)	C17—C18—C20—N4	−12.4 (3)
O2—C1—C2—C7	−166.9 (2)	C19—C18—C20—N4	167.8 (2)
O1—C1—C2—C7	12.4 (3)	C14—C9—C10—C11	−0.1 (4)
C19—N2—C15—C16	−0.2 (3)	C8—C9—C10—C11	−177.5 (2)
Zn1—N2—C15—C16	174.61 (18)	C9—C14—C13—C12	0.2 (4)
Zn1—O3—C8—O4	−6.5 (2)	O6—C12—C13—C14	179.8 (3)
Zn1—O3—C8—C9	172.11 (16)	C11—C12—C13—C14	−0.5 (4)
O1—Zn1—C8—O4	35.29 (15)	C9—C10—C11—C12	−0.2 (4)
O3—Zn1—C8—O4	174.1 (2)	O6—C12—C11—C10	−179.8 (3)
N1—Zn1—C8—O4	−73.12 (14)	C13—C12—C11—C10	0.5 (4)
N2—Zn1—C8—O4	−179.00 (12)	N2—C15—C16—C17	0.1 (4)
O1—Zn1—C8—O3	−138.79 (14)	C18—C17—C16—C15	−0.3 (4)
N1—Zn1—C8—O3	112.81 (14)	O5—C5—C4—C3	179.2 (2)
N2—Zn1—C8—O3	6.93 (17)	C6—C5—C4—C3	−0.8 (4)
O4—Zn1—C8—O3	−174.1 (2)	C5—C4—C3—C2	1.3 (4)
O1—Zn1—C8—C9	−173.2 (7)	C7—C2—C3—C4	−0.1 (4)
O3—Zn1—C8—C9	−34.4 (7)	C1—C2—C3—C4	−177.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O8^i	0.74 (5)	2.03 (5)	2.764 (3)	175 (6)
O5—H5A···O7^ii	0.83 (4)	1.91 (4)	2.735 (3)	175 (4)
N3—H3B···O4^iii	0.89 (3)	2.04 (3)	2.872 (3)	155 (3)
N4—H4A···O2^iv	0.83 (3)	2.26 (3)	3.084 (3)	171 (3)

Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z−1/2; (iv) −x+1, −y+2, −z+2.