Crystal structure of trans-di-aqua-bis-(4-cyano-benzoato-κO)bis-(N,N-di-ethyl-nicotinamide-κN)zinc(II).

In the title complex, [Zn(C8H4NO2)2(C10H14N2O)2(H2O)2], the ZnII cation, located on an inversion centre, is coordinated by two water mol-ecules, two 4-cyano-benzoate (CB) anions and two di-ethyl-nicotinamide (DENA) ligands in a distorted N2O4 octa-hedral geometry. In the mol-ecule, the dihedral angle between the planar carboxyl-ate group and the adjacent benzene ring is 9.50 (14)°, while the benzene and pyridine rings are oriented at a dihedral angle of 56.99 (5)°. The water mol-ecules exhibit both an intra-molecular hydrogen bond [to the non-coordinating carboxyl-ate O atom, enclosing an S(6) hydrogen-bonding motif, where O⋯O = 2.6419 (19) Å] and an inter-molecular hydrogen bond [to the amide carbonyl O atom, enclosing an R22(16) ring motif, where O⋯O = 2.827 (2) Å]; the latter lead to the formation of supra-molecular chains propagating along the [110] direction.

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 ▸). The structures of some complexes obtained from the reactions of transition metal(II) ions with NA and DENA as ligands, e.g. [Ni(NA)2(C7H4ClO2)2(H2O)2] (Hökelek et al., 2009a ▸) and [Ni(C7H4ClO2)2(C10H14N2O)2(H2O)2] (Hökelek et al., 2009b ▸), have been the subject of much inter­est in our laboratory.

The structure-function–coordination relationships of the aryl­carboxyl­ate ion in ZnII complexes of benzoic acid deriv­atives may change depending on the nature and position of the substituted groups on the benzene ring, the nature of the additional ligand mol­ecule or solvent, and the pH and temperature of synthesis (Shnulin et al., 1981 ▸; 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 ▸). In this context, we synthesized a ZnII-containing compound with 4-cyano­benzoate (CB) and DENA ligands, namely trans-di­aqua­bis­(4-cyano­benzoato-κO)bis­(N,N-di­ethyl­nicotinamide-κN)zinc(II), [Zn(DENA)2(CB)2(H2O)2], and report herein its crystal structure.

Structural commentary

The asymmetric unit of the crystal structure of the title complex contains one ZnII atom located on an inversion centre, one 4-cyano­benzoate (CB) ligand, one N,N-di­ethyl­nicotinamide (DENA) ligand and one water mol­ecule, all ligands coordinating to the ZnII atom in a monodentate manner (Fig. 1 ▸).

Figure 1

The mol­ecular structure of the title complex, showing the atom-numbering scheme for the asymmetric unit. Unlabelled atoms are generated by the symmetry operation −x, −y, −z. Displacement ellipsoids are drawn at the 40% probability level. Intra­molecular O—Hw⋯Oc (w = water and c = non-coordinating carboxyl­ate O atom) hydrogen bonds, enclosing S(6) hydrogen-bonding motifs, are shown as dashed lines.

The two carboxyl­ate O atoms (O2 and O2i) of the two symmetry-related monodentate CB anions and the two symmetry-related water O atoms (O4 and O4i) around the Zn1 atom form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination sphere is completed by the two pyridine N atoms (N2 and N2i) of the two symmetry-related monodentate DENA ligands in the axial positions [symmetry code: (i) −x, −y, −z] (Fig. 1 ▸).

In the carboxyl­ate groups, the C—O bonds for coordinating O atoms are 0.0148 (19) Å longer than those of the non-coordinating ones [C1—O1 = 1.2436 (19) Å and C1—O2 = 1.2584 (18) Å], indicating delocalized bonding arrangements rather than localized single and double bonds. The Zn—O bond lengths are 2.1503 (11) Å (for water O atoms) and 2.0842 (10) Å (for benzoate O atoms) and the Zn—N bond length is 2.1501 (11) Å, the Zn—O bond lengths for water oxygen atoms are ca 0.07 Å longer than those involving the benzoate oxygen atoms. The Zn1 atom lies 0.7093 (1) Å below the planar (O1/O2/C1) carboxyl­ate group. The O—Zn—O and O–Zn—N bond angles range from 87.64 (5) to 92.36 (5)°.

The dihedral angle between the planar carboxyl­ate group (O1/O2/C1) and the adjacent benzene ring (C2–C7) is 9.50 (14)°, while the benzene and pyridine (N2/C9–C14) rings are oriented at a dihedral angle of 56.99 (5)°.

Supra­molecular features

Intra­molecular O—Hw⋯Oc (w = water, c = non-coordinating carboxyl­ate O atom) hydrogen bonds (Table 1 ▸) link two of the water ligands to the CB anions, enclosing S(6) hydrogen-bonding motifs (Fig. 1 ▸). The other water H atom is involved in inter­molecular O—Hw⋯ODENA (ODENA = carbonyl O atom of N,N-di­ethyl­nicotinamide) hydrogen bonds (Table 1 ▸), enclosing (16) ring motifs and leading to the formation of infinite chains (Fig. 2 ▸) propagating along the [110] direction (Fig. 3 ▸).

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O1i	0.83 (2)	1.84 (2)	2.6419 (19)	161 (2)
O4—H42⋯O3ii	0.82 (2)	2.03 (2)	2.827 (2)	163 (2)

Symmetry codes: (i) ; (ii) .

Figure 2

Part of the supra­molecular chain of the title compound. Inter­molecular O—Hw⋯ODENA (ODENA = carbonyl O atom of N,N-di­ethyl­nicotin­amide) hydrogen bonds, enclosing (16) ring motifs, are shown as dashed lines. The non-bonding H atoms have been omitted for clarity.

Figure 3

Part of the crystal structure. Intra- and inter­molecular (O—Hw⋯Oc and O—Hw⋯ODENA, respectively) hydrogen bonds are shown as dashed lines (see Table 1 ▸). The non-bonding H atoms have been omitted for clarity.

Synthesis and crystallization

The title compound was prepared by the reaction of ZnSO4·7H2O (1.44 g, 5 mmol) in H2O (50 ml) and di­ethyl­nicotinamide (1.78 g, 10 mmol) in H2O (10 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 translucent intense colourless single crystals.

Refinement

The experimental details including the crystal data, data collection and refinement are summarized in Table 2 ▸. Atoms H41 and H42 (for H2O) were located in a difference Fourier map and were refined freely. The C-bound H atoms were positioned geometrically with C—H = 0.93, 0.97 and 0.96 Å, for aromatic, methyl­ene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with U iso(H) = k × U eq(C), where k = 1.5 for methyl H atoms and k = 1.2 for aromatic and methyl­ene H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	[Zn(C8H4NO2)2(C10H14N2O)2(H2O)2]
M r	750.13
Crystal system, space group	Triclinic, P
Temperature (K)	296
a, b, c (Å)	7.4916 (3), 8.5915 (3), 15.0343 (6)
α, β, γ (°)	86.363 (3), 75.894 (2), 74.390 (2)
V (Å3)	903.87 (6)
Z	1
Radiation type	Mo Kα
μ (mm−1)	0.74
Crystal size (mm)	0.45 × 0.30 × 0.24
Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.74, 0.84
No. of measured, independent and observed [I > 2σ(I)] reflections	19149, 4366, 4029
R int	0.020
(sin θ/λ)max (Å−1)	0.666
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.032, 0.084, 1.06
No. of reflections	4366
No. of parameters	242
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.56, −0.23

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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013815/xu5890sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016013815/xu5890Isup2.hkl

CCDC reference: 1501337

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn(C8H4NO2)2(C10H14N2O)2(H2O)2]	Z = 1
Mr = 750.13	F(000) = 392
Triclinic, P1	Dx = 1.378 Mg m−3
a = 7.4916 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5915 (3) Å	Cell parameters from 9994 reflections
c = 15.0343 (6) Å	θ = 2.8–28.2°
α = 86.363 (3)°	µ = 0.74 mm−1
β = 75.894 (2)°	T = 296 K
γ = 74.390 (2)°	Prism, translucent intense colourless
V = 903.87 (6) Å3	0.45 × 0.30 × 0.24 mm

Bruker SMART BREEZE CCD diffractometer	4366 independent reflections
Radiation source: fine-focus sealed tube	4029 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 28.3°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→9
Tmin = 0.74, Tmax = 0.84	k = −11→11
19149 measured reflections	l = −19→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0458P)2 + 0.2769P] where P = (Fo2 + 2Fc2)/3
4366 reflections	(Δ/σ)max < 0.001
242 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn1	0.0000	0.0000	0.0000	0.02730 (8)
O1	0.10666 (18)	0.0679 (2)	−0.22778 (9)	0.0585 (4)
O2	0.23197 (15)	0.01976 (13)	−0.10544 (7)	0.0340 (2)
O3	0.51295 (19)	−0.62718 (18)	−0.11834 (9)	0.0571 (4)
O4	0.19075 (17)	−0.10842 (16)	0.08623 (9)	0.0414 (3)
H41	0.115 (3)	−0.110 (3)	0.1366 (17)	0.056 (7)*
H42	0.277 (3)	−0.191 (3)	0.0848 (16)	0.059 (7)*
N1	1.1465 (3)	−0.2028 (3)	−0.46622 (14)	0.0755 (6)
N2	0.02013 (16)	−0.22996 (14)	−0.05596 (8)	0.0288 (2)
N3	0.4843 (2)	−0.58488 (17)	−0.26504 (9)	0.0402 (3)
C1	0.2428 (2)	0.02304 (18)	−0.19037 (10)	0.0324 (3)
C2	0.4408 (2)	−0.03327 (17)	−0.25173 (10)	0.0304 (3)
C3	0.4653 (2)	−0.0552 (2)	−0.34513 (11)	0.0423 (4)
H3	0.3593	−0.0388	−0.3698	0.051*
C4	0.6461 (3)	−0.1012 (2)	−0.40159 (11)	0.0466 (4)
H4	0.6621	−0.1157	−0.4641	0.056*
C5	0.8044 (2)	−0.12572 (19)	−0.36423 (11)	0.0383 (3)
C6	0.7815 (2)	−0.1071 (2)	−0.27117 (12)	0.0415 (4)
H6	0.8876	−0.1252	−0.2463	0.050*
C7	0.5995 (2)	−0.0614 (2)	−0.21525 (11)	0.0368 (3)
H7	0.5836	−0.0493	−0.1525	0.044*
C8	0.9951 (3)	−0.1689 (2)	−0.42235 (13)	0.0507 (4)
C9	−0.1333 (2)	−0.28196 (18)	−0.05414 (10)	0.0323 (3)
H9	−0.2528	−0.2183	−0.0253	0.039*
C10	−0.1218 (2)	−0.4269 (2)	−0.09346 (12)	0.0379 (3)
H10	−0.2314	−0.4600	−0.0909	0.045*
C11	0.0555 (2)	−0.52178 (18)	−0.13656 (11)	0.0386 (3)
H11	0.0669	−0.6187	−0.1644	0.046*
C12	0.2158 (2)	−0.47000 (17)	−0.13758 (10)	0.0317 (3)
C13	0.1916 (2)	−0.32445 (17)	−0.09573 (10)	0.0302 (3)
H13	0.2994	−0.2907	−0.0952	0.036*
C14	0.4178 (2)	−0.56899 (17)	−0.17441 (11)	0.0354 (3)
C15	0.3800 (3)	−0.5002 (2)	−0.33283 (12)	0.0488 (4)
H15A	0.4514	−0.4299	−0.3693	0.059*
H15B	0.2577	−0.4329	−0.3008	0.059*
C16	0.3474 (3)	−0.6144 (3)	−0.39581 (16)	0.0663 (6)
H16A	0.2720	−0.5537	−0.4359	0.099*
H16B	0.2815	−0.6874	−0.3600	0.099*
H16C	0.4680	−0.6748	−0.4317	0.099*
C17	0.6830 (3)	−0.6752 (2)	−0.30132 (13)	0.0481 (4)
H17A	0.6893	−0.7410	−0.3527	0.058*
H17B	0.7267	−0.7473	−0.2542	0.058*
C18	0.8137 (4)	−0.5660 (4)	−0.3324 (2)	0.0831 (8)
H18A	0.9426	−0.6304	−0.3527	0.125*
H18B	0.8053	−0.4984	−0.2823	0.125*
H18C	0.7766	−0.4997	−0.3821	0.125*

	U11	U22	U33	U12	U13	U23
Zn1	0.02409 (12)	0.02632 (12)	0.02797 (13)	−0.00158 (8)	−0.00370 (8)	−0.00585 (8)
O1	0.0317 (6)	0.0954 (11)	0.0390 (7)	−0.0015 (6)	−0.0080 (5)	0.0024 (7)
O2	0.0289 (5)	0.0415 (6)	0.0297 (5)	−0.0098 (4)	−0.0014 (4)	−0.0061 (4)
O3	0.0501 (7)	0.0621 (8)	0.0419 (7)	0.0212 (6)	−0.0165 (6)	−0.0093 (6)
O4	0.0310 (6)	0.0488 (7)	0.0375 (6)	0.0048 (5)	−0.0113 (5)	−0.0020 (5)
N1	0.0492 (10)	0.0958 (16)	0.0549 (11)	0.0045 (10)	0.0111 (9)	−0.0003 (10)
N2	0.0268 (6)	0.0263 (5)	0.0297 (6)	−0.0019 (4)	−0.0049 (5)	−0.0032 (4)
N3	0.0392 (7)	0.0349 (7)	0.0353 (7)	0.0061 (5)	−0.0050 (6)	−0.0021 (5)
C1	0.0295 (7)	0.0314 (7)	0.0343 (7)	−0.0074 (5)	−0.0040 (6)	−0.0017 (6)
C2	0.0314 (7)	0.0303 (7)	0.0284 (7)	−0.0094 (5)	−0.0033 (6)	−0.0001 (5)
C3	0.0372 (8)	0.0564 (10)	0.0321 (8)	−0.0091 (7)	−0.0094 (6)	−0.0015 (7)
C4	0.0471 (10)	0.0597 (11)	0.0266 (7)	−0.0070 (8)	−0.0034 (7)	−0.0035 (7)
C5	0.0343 (8)	0.0374 (8)	0.0349 (8)	−0.0048 (6)	0.0025 (6)	−0.0014 (6)
C6	0.0318 (8)	0.0527 (10)	0.0379 (8)	−0.0086 (7)	−0.0059 (6)	−0.0035 (7)
C7	0.0334 (8)	0.0469 (9)	0.0287 (7)	−0.0099 (6)	−0.0040 (6)	−0.0046 (6)
C8	0.0421 (10)	0.0553 (11)	0.0406 (9)	−0.0013 (8)	0.0036 (8)	0.0016 (8)
C9	0.0281 (7)	0.0340 (7)	0.0323 (7)	−0.0042 (5)	−0.0067 (6)	−0.0002 (6)
C10	0.0364 (8)	0.0381 (8)	0.0436 (9)	−0.0124 (6)	−0.0148 (7)	0.0002 (7)
C11	0.0466 (9)	0.0285 (7)	0.0422 (8)	−0.0065 (6)	−0.0158 (7)	−0.0061 (6)
C12	0.0349 (7)	0.0258 (6)	0.0296 (7)	0.0007 (5)	−0.0077 (6)	−0.0015 (5)
C13	0.0276 (7)	0.0275 (6)	0.0323 (7)	−0.0032 (5)	−0.0052 (5)	−0.0024 (5)
C14	0.0373 (8)	0.0257 (6)	0.0367 (8)	0.0032 (6)	−0.0080 (6)	−0.0054 (6)
C15	0.0511 (10)	0.0477 (10)	0.0367 (9)	0.0030 (8)	−0.0089 (8)	0.0050 (7)
C16	0.0596 (13)	0.0810 (16)	0.0555 (12)	−0.0073 (11)	−0.0190 (10)	−0.0058 (11)
C17	0.0395 (9)	0.0476 (9)	0.0434 (9)	0.0054 (7)	−0.0015 (7)	−0.0057 (8)
C18	0.0576 (14)	0.099 (2)	0.093 (2)	−0.0287 (14)	−0.0102 (13)	0.0008 (16)

Zn1—O2	2.0842 (10)	C6—H6	0.9300
Zn1—O2i	2.0842 (10)	C7—C6	1.384 (2)
Zn1—O4	2.1503 (11)	C7—H7	0.9300
Zn1—O4i	2.1503 (11)	C8—N1	1.135 (3)
Zn1—N2	2.1501 (11)	C9—C10	1.385 (2)
Zn1—N2i	2.1501 (11)	C9—H9	0.9300
O1—C1	1.2436 (19)	C10—H10	0.9300
O2—C1	1.2584 (18)	C11—C10	1.383 (2)
O3—C14	1.231 (2)	C11—H11	0.9300
O4—H41	0.83 (2)	C12—C11	1.385 (2)
O4—H42	0.82 (2)	C12—C14	1.509 (2)
N2—C9	1.3348 (19)	C13—C12	1.384 (2)
N2—C13	1.3389 (17)	C13—H13	0.9300
N3—C14	1.334 (2)	C15—C16	1.510 (3)
N3—C15	1.472 (2)	C15—H15A	0.9700
N3—C17	1.467 (2)	C15—H15B	0.9700
C1—C2	1.513 (2)	C16—H16A	0.9600
C2—C3	1.389 (2)	C16—H16B	0.9600
C2—C7	1.386 (2)	C16—H16C	0.9600
C3—C4	1.380 (2)	C17—C18	1.508 (3)
C3—H3	0.9300	C17—H17A	0.9700
C4—H4	0.9300	C17—H17B	0.9700
C5—C4	1.393 (2)	C18—H18A	0.9600
C5—C6	1.382 (2)	C18—H18B	0.9600
C5—C8	1.446 (2)	C18—H18C	0.9600
O2—Zn1—O2i	180.00 (7)	C6—C7—H7	119.7
O2—Zn1—O4	89.94 (5)	N1—C8—C5	178.4 (2)
O2i—Zn1—O4	90.06 (5)	N2—C9—C10	122.61 (14)
O2—Zn1—O4i	90.06 (5)	N2—C9—H9	118.7
O2i—Zn1—O4i	89.94 (5)	C10—C9—H9	118.7
O2—Zn1—N2	88.48 (4)	C9—C10—H10	120.6
O2i—Zn1—N2	91.52 (4)	C11—C10—C9	118.88 (14)
O2—Zn1—N2i	91.52 (4)	C11—C10—H10	120.6
O2i—Zn1—N2i	88.48 (4)	C10—C11—C12	118.92 (14)
O4i—Zn1—O4	180.00 (10)	C10—C11—H11	120.5
N2—Zn1—O4	92.36 (5)	C12—C11—H11	120.5
N2i—Zn1—O4	87.64 (5)	C11—C12—C14	124.06 (13)
N2—Zn1—O4i	87.64 (5)	C13—C12—C11	118.44 (13)
N2i—Zn1—O4i	92.36 (5)	C13—C12—C14	117.28 (13)
N2i—Zn1—N2	180.00 (6)	N2—C13—C12	122.99 (13)
C1—O2—Zn1	127.55 (9)	N2—C13—H13	118.5
Zn1—O4—H41	101.6 (16)	C12—C13—H13	118.5
Zn1—O4—H42	135.9 (16)	O3—C14—N3	123.94 (14)
H41—O4—H42	106 (2)	O3—C14—C12	117.46 (14)
C9—N2—Zn1	122.37 (9)	N3—C14—C12	118.58 (13)
C9—N2—C13	118.12 (12)	N3—C15—C16	112.80 (17)
C13—N2—Zn1	119.50 (9)	N3—C15—H15A	109.0
C14—N3—C15	124.36 (14)	N3—C15—H15B	109.0
C14—N3—C17	118.81 (14)	C16—C15—H15A	109.0
C17—N3—C15	116.34 (14)	C16—C15—H15B	109.0
O1—C1—O2	126.05 (14)	H15A—C15—H15B	107.8
O1—C1—C2	117.65 (14)	C15—C16—H16A	109.5
O2—C1—C2	116.30 (13)	C15—C16—H16B	109.5
C3—C2—C1	120.47 (14)	C15—C16—H16C	109.5
C7—C2—C3	119.42 (14)	H16A—C16—H16B	109.5
C7—C2—C1	120.10 (13)	H16A—C16—H16C	109.5
C2—C3—H3	119.8	H16B—C16—H16C	109.5
C4—C3—C2	120.43 (15)	N3—C17—C18	112.50 (18)
C4—C3—H3	119.8	N3—C17—H17A	109.1
C3—C4—C5	119.49 (15)	N3—C17—H17B	109.1
C3—C4—H4	120.3	C18—C17—H17A	109.1
C5—C4—H4	120.3	C18—C17—H17B	109.1
C4—C5—C8	120.56 (16)	H17A—C17—H17B	107.8
C6—C5—C4	120.54 (15)	C17—C18—H18A	109.5
C6—C5—C8	118.90 (16)	C17—C18—H18B	109.5
C5—C6—C7	119.41 (15)	C17—C18—H18C	109.5
C5—C6—H6	120.3	H18A—C18—H18B	109.5
C7—C6—H6	120.3	H18A—C18—H18C	109.5
C2—C7—H7	119.7	H18B—C18—H18C	109.5
C6—C7—C2	120.68 (15)
O4—Zn1—O2—C1	153.35 (13)	C15—N3—C17—C18	73.3 (2)
O4i—Zn1—O2—C1	−26.65 (13)	O1—C1—C2—C3	−8.8 (2)
N2—Zn1—O2—C1	60.99 (12)	O1—C1—C2—C7	170.29 (16)
N2i—Zn1—O2—C1	−119.01 (12)	O2—C1—C2—C3	171.11 (15)
O2—Zn1—N2—C9	−144.71 (12)	O2—C1—C2—C7	−9.8 (2)
O2i—Zn1—N2—C9	35.29 (12)	C1—C2—C3—C4	177.77 (16)
O2—Zn1—N2—C13	34.08 (11)	C7—C2—C3—C4	−1.4 (3)
O2i—Zn1—N2—C13	−145.92 (11)	C1—C2—C7—C6	−177.60 (15)
O4—Zn1—N2—C9	125.41 (12)	C3—C2—C7—C6	1.5 (2)
O4i—Zn1—N2—C9	−54.59 (12)	C2—C3—C4—C5	0.0 (3)
O4—Zn1—N2—C13	−55.80 (11)	C6—C5—C4—C3	1.2 (3)
O4i—Zn1—N2—C13	124.20 (11)	C8—C5—C4—C3	−178.01 (18)
Zn1—O2—C1—O1	25.4 (2)	C4—C5—C6—C7	−1.0 (3)
Zn1—O2—C1—C2	−154.52 (10)	C8—C5—C6—C7	178.20 (17)
Zn1—N2—C9—C10	177.24 (12)	C2—C7—C6—C5	−0.4 (3)
C13—N2—C9—C10	−1.6 (2)	N2—C9—C10—C11	−0.1 (2)
Zn1—N2—C13—C12	−176.49 (11)	C12—C11—C10—C9	1.1 (2)
C9—N2—C13—C12	2.3 (2)	C13—C12—C11—C10	−0.4 (2)
C15—N3—C14—O3	−172.38 (18)	C14—C12—C11—C10	174.11 (15)
C15—N3—C14—C12	5.8 (2)	C11—C12—C14—O3	−107.28 (19)
C17—N3—C14—O3	−0.7 (3)	C11—C12—C14—N3	74.5 (2)
C17—N3—C14—C12	177.46 (14)	C13—C12—C14—O3	67.3 (2)
C14—N3—C15—C16	−121.41 (19)	C13—C12—C14—N3	−111.00 (17)
C17—N3—C15—C16	66.7 (2)	N2—C13—C12—C11	−1.4 (2)
C14—N3—C17—C18	−99.1 (2)	N2—C13—C12—C14	−176.26 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O1i	0.83 (2)	1.84 (2)	2.6419 (19)	161 (2)
O4—H42···O3ii	0.82 (2)	2.03 (2)	2.827 (2)	163 (2)