Bis(μ-2-fluoro-benzoato-1:2κO:O')(2-fluoro-benzoato-1κO,O')(2-fluoro-benzoato-2κO)dinicotinamide-1κN,2κN-dizinc(II)-2-fluoro-benzoic acid (1/1).

The asymmetric unit of the title compound, [Zn(2)(C(7)H(4)FO(2))(4)(C(6)H(6)N(2)O)(2)]·C(7)H(5)FO(2), consists of a binuclear Zn(II) complex bridged by two carboxyl groups of 2-fluoro-benzoate (FB) anions and a 2-fluoro-benzoic acid mol-ecule. The two bridging FB anions, one chelating FB anion and one nicotinamide (NA) ligand coordinate to one Zn cation with a distorted square-pyramidal geometry, while the two bridging FB anions, one monodentate FB anion and one NA ligand coordinate to the other Zn cation with a distorted tetra-hedral geometry. Within the binuclear mol-ecule, the pyridine rings are oriented at a dihedral angle of 19.41 (14)°. In the crystal structure, the uncoordinated 2-fluorobenzoic acid mol-ecules are linked by O-H⋯O hydrogen bonding, forming centrosymmetric supra-molecular dimers. Inter-molecular N-H⋯O hydrogen bonds link the complex mol-ecules into a three-dimensional network. The π-π contacts between nearly parallel pyridine and benzene rings [dihedral angles of 19.41 (14) and 12.72 (16)°, respectively, centroid-centroid distances = 3.701 (2) and 3.857 (3) Å] may further stabilize the crystal structure. The fluorine atoms in two FB ligands are disordered over two positions, with occupancy ratios of 0.70:0.30.

Related literature

For general background to nicotinamide and the nicotinic acid derivative N,N-diethyl­nicotinamide, see: Bigoli et al. (1972 ▶); Krishnamachari (1974 ▶). For related structures, see: Hökelek & Necefoğlu (1996 ▶); Hökelek et al. (2009a ▶,b ▶,c ▶,d ▶); Greenaway et al. (1984 ▶).

Experimental

Crystal data

[Zn2(C7H4FO2)4(C6H6N2O)2]·C7H5FO2

M = 1071.55

Monoclinic,

a = 12.5143 (2) Å

b = 16.7106 (3) Å

c = 20.6673 (4) Å

β = 92.929 (2)°

V = 4316.33 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.21 mm−1

T = 100 K

0.29 × 0.25 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.710, T max = 0.840

37814 measured reflections

10696 independent reflections

7459 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.097

S = 1.01

10696 reflections

659 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.39 e Å−3

Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048089/xu2668sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048089/xu2668Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn2(C7H4FO2)4(C6H6N2O)2]·C7H5FO2	F(000) = 2176
Mr = 1071.55	Dx = 1.649 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9923 reflections
a = 12.5143 (2) Å	θ = 2.3–28.1°
b = 16.7106 (3) Å	µ = 1.21 mm−1
c = 20.6673 (4) Å	T = 100 K
β = 92.929 (2)°	Block, colorless
V = 4316.33 (13) Å3	0.29 × 0.25 × 0.14 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	10696 independent reflections
Radiation source: fine-focus sealed tube	7459 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 28.3°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→13
Tmin = 0.710, Tmax = 0.840	k = −22→22
37814 measured reflections	l = −26→27

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0383P)2 + 3.8099P] where P = (Fo2 + 2Fc2)/3
10696 reflections	(Δ/σ)max = 0.001
659 parameters	Δρmax = 1.39 e Å−3
10 restraints	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.17153 (4)	0.67257 (3)	0.24483 (2)	0.01406 (14)
Zn2	0.31257 (4)	0.51261 (3)	0.29078 (3)	0.01641 (14)
F1	−0.0139 (2)	0.6414 (2)	0.02860 (15)	0.0383 (8)
F2	0.1234 (3)	0.4736 (2)	0.09432 (18)	0.0236 (9)	0.70
F2'	0.4720 (5)	0.5834 (7)	0.0809 (5)	0.054 (3)*	0.30
F3	−0.0844 (2)	0.64099 (18)	0.36234 (15)	0.0362 (8)
F4	0.6020 (3)	0.6154 (2)	0.3631 (2)	0.0291 (10)	0.70
F4'	0.3673 (4)	0.8400 (4)	0.3434 (4)	0.0138 (17)*	0.30
F5	0.4883 (2)	0.73739 (19)	0.00733 (15)	0.0377 (8)
O1	0.0703 (3)	0.6540 (2)	0.15019 (15)	0.0240 (8)
O2	0.2346 (2)	0.6999 (2)	0.16036 (14)	0.0199 (7)
O3	0.2399 (2)	0.5160 (2)	0.20262 (16)	0.0270 (8)
O4	0.4067 (2)	0.5492 (2)	0.19029 (16)	0.0242 (8)
O5	0.0874 (2)	0.60130 (18)	0.29767 (14)	0.0163 (7)
O6	0.1828 (2)	0.49874 (19)	0.34017 (15)	0.0199 (7)
O7	0.3061 (2)	0.6981 (2)	0.29769 (14)	0.0182 (7)
O8	0.4007 (2)	0.59306 (19)	0.33526 (16)	0.0211 (7)
O9	0.2568 (3)	0.9875 (2)	0.26713 (19)	0.0319 (9)
O10	0.2451 (2)	0.2018 (2)	0.27913 (16)	0.0228 (8)
O11	0.6174 (3)	0.9659 (2)	0.0211 (2)	0.0380 (10)
O12	0.4706 (3)	0.8936 (2)	0.00208 (19)	0.0331 (9)
H121	0.443 (5)	0.943 (5)	−0.008 (3)	0.07 (2)*
N1	0.0910 (3)	0.7776 (2)	0.26319 (17)	0.0148 (8)
N2	0.1202 (4)	1.0617 (3)	0.3008 (2)	0.0235 (10)
H2A	0.058 (4)	1.063 (3)	0.310 (2)	0.022 (14)*
H2B	0.158 (4)	1.102 (3)	0.296 (3)	0.030 (16)*
N3	0.4006 (3)	0.4123 (2)	0.30545 (17)	0.0142 (8)
N4	0.3912 (4)	0.1241 (3)	0.2944 (2)	0.0209 (9)
H4A	0.454 (4)	0.120 (3)	0.304 (2)	0.024 (15)*
H4B	0.347 (5)	0.082 (4)	0.284 (3)	0.06 (2)*
C1	0.1502 (4)	0.6839 (3)	0.1255 (2)	0.0172 (10)
C2	0.1499 (3)	0.7054 (3)	0.0554 (2)	0.0163 (10)
C3	0.0668 (4)	0.6878 (3)	0.0113 (2)	0.0203 (10)
C4	0.0640 (4)	0.7140 (3)	−0.0521 (2)	0.0273 (12)
H4	0.0060	0.7019	−0.0803	0.033*
C5	0.1486 (4)	0.7584 (3)	−0.0729 (2)	0.0290 (12)
H5	0.1472	0.7774	−0.1152	0.035*
C6	0.2351 (4)	0.7745 (3)	−0.0310 (2)	0.0255 (12)
H6	0.2931	0.8030	−0.0455	0.031*
C7	0.2356 (4)	0.7483 (3)	0.0323 (2)	0.0196 (10)
H7	0.2944	0.7595	0.0602	0.023*
C8	0.3164 (3)	0.5334 (3)	0.1666 (2)	0.0179 (10)
C9	0.2958 (3)	0.5326 (3)	0.0950 (2)	0.0169 (10)
C10	0.2015 (4)	0.5058 (3)	0.0629 (2)	0.0230 (11)
H14'	0.1473	0.4853	0.0872	0.028*	0.30
C11	0.1859 (4)	0.5086 (3)	−0.0046 (3)	0.0282 (12)
H11	0.1222	0.4903	−0.0246	0.034*
C12	0.2649 (4)	0.5383 (3)	−0.0407 (3)	0.0312 (13)
H12	0.2543	0.5405	−0.0855	0.037*
C13	0.3598 (4)	0.5651 (3)	−0.0124 (2)	0.0306 (13)
H13	0.4132	0.5850	−0.0377	0.037*
C14	0.3749 (4)	0.5620 (3)	0.0552 (2)	0.0234 (11)
H14	0.4394	0.5799	0.0744	0.028*	0.70
C15	0.0994 (3)	0.5414 (3)	0.3341 (2)	0.0145 (9)
C16	0.0079 (3)	0.5168 (3)	0.3735 (2)	0.0164 (10)
C17	−0.0787 (4)	0.5654 (3)	0.3857 (2)	0.0218 (11)
C18	−0.1606 (4)	0.5413 (3)	0.4231 (2)	0.0286 (12)
H18	−0.2176	0.5754	0.4301	0.034*
C19	−0.1571 (4)	0.4659 (4)	0.4501 (3)	0.0362 (14)
H19	−0.2119	0.4489	0.4756	0.043*
C20	−0.0727 (4)	0.4155 (3)	0.4393 (3)	0.0367 (14)
H20	−0.0700	0.3647	0.4576	0.044*
C21	0.0082 (4)	0.4410 (3)	0.4010 (2)	0.0258 (12)
H21	0.0644	0.4064	0.3934	0.031*
C22	0.3881 (3)	0.6668 (3)	0.3252 (2)	0.0158 (10)
C23	0.4772 (3)	0.7209 (3)	0.3453 (2)	0.0141 (9)
C24	0.5816 (3)	0.6927 (3)	0.3596 (2)	0.0174 (10)
H28'	0.5940	0.6378	0.3605	0.021*	0.30
C25	0.6675 (4)	0.7452 (3)	0.3726 (2)	0.0216 (11)
H25	0.7362	0.7253	0.3811	0.026*
C26	0.6492 (4)	0.8258 (3)	0.3728 (2)	0.0216 (11)
H26	0.7064	0.8605	0.3812	0.026*
C27	0.5482 (4)	0.8570 (3)	0.3608 (2)	0.0214 (11)
H27	0.5364	0.9119	0.3621	0.026*
C28	0.4637 (3)	0.8040 (3)	0.3467 (2)	0.0186 (10)
H28	0.3957	0.8248	0.3378	0.022*	0.70
C29	0.1429 (3)	0.8473 (3)	0.2675 (2)	0.0146 (9)
H29	0.2162	0.8472	0.2620	0.018*
C30	0.0941 (3)	0.9198 (3)	0.2797 (2)	0.0150 (10)
C31	−0.0155 (3)	0.9193 (3)	0.2884 (2)	0.0168 (10)
H31	−0.0515	0.9665	0.2972	0.020*
C32	−0.0698 (3)	0.8475 (3)	0.2837 (2)	0.0181 (10)
H32	−0.1430	0.8459	0.2895	0.022*
C33	−0.0157 (3)	0.7782 (3)	0.2707 (2)	0.0168 (10)
H33	−0.0536	0.7304	0.2668	0.020*
C34	0.1630 (3)	0.9929 (3)	0.2819 (2)	0.0187 (10)
C35	0.3537 (3)	0.3409 (3)	0.2987 (2)	0.0142 (9)
H35	0.2799	0.3393	0.2906	0.017*
C36	0.4082 (3)	0.2690 (3)	0.3032 (2)	0.0133 (9)
C37	0.5183 (3)	0.2716 (3)	0.3166 (2)	0.0170 (10)
H37	0.5579	0.2246	0.3204	0.020*
C38	0.5676 (3)	0.3453 (3)	0.3241 (2)	0.0184 (10)
H38	0.6409	0.3483	0.3336	0.022*
C39	0.5075 (3)	0.4143 (3)	0.3175 (2)	0.0174 (10)
H39	0.5418	0.4636	0.3214	0.021*
C40	0.3426 (3)	0.1945 (3)	0.2915 (2)	0.0169 (10)
C41	0.7570 (4)	0.6917 (3)	0.0614 (3)	0.0303 (12)
H41	0.7990	0.6469	0.0709	0.036*
C42	0.6512 (4)	0.6824 (3)	0.0410 (2)	0.0269 (12)
H42	0.6215	0.6316	0.0367	0.032*
C43	0.5899 (4)	0.7494 (3)	0.0272 (2)	0.0225 (11)
C44	0.6319 (4)	0.8263 (3)	0.0324 (2)	0.0195 (10)
C45	0.7393 (4)	0.8332 (3)	0.0534 (2)	0.0268 (12)
H45	0.7699	0.8838	0.0578	0.032*
C46	0.8006 (4)	0.7669 (3)	0.0677 (3)	0.0329 (13)
H46	0.8719	0.7729	0.0817	0.039*
C47	0.5720 (4)	0.9010 (3)	0.0178 (2)	0.0214 (11)

	U11	U22	U33	U12	U13	U23
Zn1	0.0128 (2)	0.0158 (3)	0.0136 (3)	−0.0009 (2)	0.00059 (19)	0.0017 (2)
Zn2	0.0136 (2)	0.0104 (3)	0.0248 (3)	0.0005 (2)	−0.0018 (2)	0.0001 (2)
F1	0.0310 (16)	0.042 (2)	0.0416 (19)	−0.0084 (15)	−0.0021 (14)	−0.0026 (16)
F2	0.0158 (18)	0.029 (2)	0.026 (2)	−0.0116 (17)	0.0042 (16)	0.0000 (18)
F3	0.0401 (17)	0.0233 (17)	0.0473 (19)	0.0134 (14)	0.0224 (15)	0.0138 (15)
F4	0.025 (2)	0.018 (2)	0.044 (3)	0.0016 (18)	−0.0054 (18)	0.003 (2)
F5	0.0316 (16)	0.0317 (19)	0.049 (2)	−0.0060 (14)	−0.0037 (14)	0.0023 (16)
O1	0.0318 (18)	0.021 (2)	0.0194 (17)	−0.0047 (16)	0.0082 (14)	0.0002 (15)
O2	0.0195 (15)	0.0255 (19)	0.0146 (16)	0.0056 (15)	−0.0014 (13)	0.0000 (15)
O3	0.0132 (15)	0.044 (2)	0.0240 (18)	0.0029 (16)	0.0032 (13)	0.0131 (17)
O4	0.0199 (16)	0.024 (2)	0.0287 (19)	−0.0058 (15)	−0.0002 (14)	−0.0004 (16)
O5	0.0183 (15)	0.0118 (17)	0.0189 (16)	−0.0005 (13)	0.0019 (13)	0.0034 (14)
O6	0.0169 (15)	0.0185 (19)	0.0246 (18)	0.0032 (14)	0.0033 (13)	0.0032 (14)
O7	0.0148 (15)	0.0205 (18)	0.0189 (17)	−0.0008 (14)	−0.0040 (13)	−0.0011 (14)
O8	0.0203 (16)	0.0134 (18)	0.0292 (19)	−0.0025 (14)	−0.0035 (14)	−0.0016 (15)
O9	0.0190 (16)	0.0164 (19)	0.061 (3)	−0.0025 (15)	0.0111 (17)	−0.0072 (18)
O10	0.0151 (15)	0.0142 (18)	0.039 (2)	0.0004 (14)	−0.0032 (14)	0.0005 (16)
O11	0.0239 (18)	0.022 (2)	0.068 (3)	−0.0010 (17)	0.0012 (18)	0.005 (2)
O12	0.0241 (18)	0.025 (2)	0.050 (3)	0.0028 (17)	−0.0048 (17)	0.0043 (19)
N1	0.0137 (17)	0.017 (2)	0.0136 (19)	−0.0028 (16)	−0.0004 (14)	0.0001 (16)
N2	0.015 (2)	0.015 (2)	0.040 (3)	0.001 (2)	−0.0005 (19)	0.000 (2)
N3	0.0141 (17)	0.013 (2)	0.0158 (19)	0.0004 (16)	0.0007 (14)	−0.0001 (16)
N4	0.017 (2)	0.013 (2)	0.032 (2)	0.0016 (19)	−0.0005 (18)	−0.0005 (19)
C1	0.024 (2)	0.012 (2)	0.016 (2)	0.005 (2)	0.0054 (19)	−0.001 (2)
C2	0.018 (2)	0.015 (2)	0.016 (2)	0.003 (2)	0.0017 (18)	−0.002 (2)
C3	0.022 (2)	0.018 (3)	0.021 (2)	−0.003 (2)	0.0013 (19)	−0.001 (2)
C4	0.035 (3)	0.027 (3)	0.019 (3)	0.003 (2)	−0.010 (2)	−0.004 (2)
C5	0.048 (3)	0.026 (3)	0.013 (2)	0.006 (3)	0.004 (2)	0.001 (2)
C6	0.029 (3)	0.026 (3)	0.022 (3)	0.000 (2)	0.010 (2)	0.002 (2)
C7	0.021 (2)	0.019 (3)	0.019 (2)	0.003 (2)	0.0038 (19)	−0.001 (2)
C8	0.018 (2)	0.011 (2)	0.024 (3)	0.0041 (19)	0.0036 (19)	0.003 (2)
C9	0.017 (2)	0.011 (2)	0.023 (2)	0.0040 (19)	0.0033 (18)	0.003 (2)
C10	0.023 (2)	0.013 (3)	0.033 (3)	0.001 (2)	0.003 (2)	0.001 (2)
C11	0.031 (3)	0.016 (3)	0.036 (3)	−0.001 (2)	−0.011 (2)	−0.006 (2)
C12	0.047 (3)	0.024 (3)	0.022 (3)	0.000 (3)	−0.001 (2)	−0.003 (2)
C13	0.038 (3)	0.031 (3)	0.024 (3)	−0.004 (3)	0.012 (2)	0.002 (2)
C14	0.021 (2)	0.023 (3)	0.027 (3)	−0.001 (2)	0.006 (2)	0.000 (2)
C15	0.016 (2)	0.013 (2)	0.015 (2)	−0.0024 (19)	−0.0026 (17)	−0.003 (2)
C16	0.016 (2)	0.015 (2)	0.017 (2)	0.000 (2)	−0.0012 (17)	0.001 (2)
C17	0.025 (2)	0.017 (3)	0.024 (3)	0.003 (2)	0.003 (2)	0.005 (2)
C18	0.023 (2)	0.030 (3)	0.033 (3)	0.009 (2)	0.010 (2)	0.009 (3)
C19	0.025 (3)	0.035 (3)	0.049 (4)	0.001 (3)	0.015 (2)	0.018 (3)
C20	0.030 (3)	0.024 (3)	0.058 (4)	0.000 (2)	0.014 (3)	0.021 (3)
C21	0.019 (2)	0.017 (3)	0.041 (3)	0.002 (2)	0.003 (2)	0.006 (2)
C22	0.018 (2)	0.017 (3)	0.012 (2)	−0.002 (2)	0.0047 (17)	−0.003 (2)
C23	0.019 (2)	0.013 (2)	0.010 (2)	−0.0023 (19)	0.0013 (17)	−0.0009 (19)
C24	0.019 (2)	0.015 (3)	0.018 (2)	−0.002 (2)	−0.0016 (18)	0.002 (2)
C25	0.018 (2)	0.025 (3)	0.022 (3)	−0.002 (2)	−0.0028 (19)	0.003 (2)
C26	0.021 (2)	0.021 (3)	0.023 (2)	−0.011 (2)	0.0035 (19)	−0.003 (2)
C27	0.028 (2)	0.014 (3)	0.023 (3)	−0.004 (2)	0.009 (2)	−0.003 (2)
C28	0.019 (2)	0.019 (3)	0.018 (2)	0.000 (2)	0.0037 (18)	−0.001 (2)
C29	0.0118 (19)	0.016 (3)	0.015 (2)	−0.0012 (19)	−0.0009 (17)	0.0019 (19)
C30	0.014 (2)	0.015 (2)	0.016 (2)	0.0012 (19)	−0.0018 (17)	0.0013 (19)
C31	0.017 (2)	0.019 (3)	0.015 (2)	0.004 (2)	0.0007 (18)	0.002 (2)
C32	0.0097 (19)	0.027 (3)	0.018 (2)	0.001 (2)	0.0000 (17)	0.005 (2)
C33	0.015 (2)	0.019 (3)	0.016 (2)	−0.004 (2)	−0.0022 (17)	0.004 (2)
C34	0.018 (2)	0.015 (3)	0.022 (2)	0.003 (2)	−0.0029 (19)	0.000 (2)
C35	0.0138 (19)	0.014 (2)	0.015 (2)	0.0004 (19)	−0.0006 (17)	0.0002 (19)
C36	0.016 (2)	0.012 (2)	0.012 (2)	0.0012 (19)	0.0012 (17)	−0.0001 (18)
C37	0.017 (2)	0.017 (3)	0.016 (2)	0.005 (2)	0.0019 (18)	0.002 (2)
C38	0.013 (2)	0.021 (3)	0.021 (2)	0.000 (2)	−0.0008 (18)	0.001 (2)
C39	0.017 (2)	0.016 (3)	0.019 (2)	−0.004 (2)	−0.0001 (18)	−0.001 (2)
C40	0.018 (2)	0.015 (3)	0.018 (2)	0.002 (2)	0.0024 (18)	0.000 (2)
C41	0.033 (3)	0.027 (3)	0.032 (3)	0.007 (2)	0.006 (2)	0.001 (2)
C42	0.040 (3)	0.018 (3)	0.024 (3)	−0.004 (2)	0.010 (2)	−0.001 (2)
C43	0.022 (2)	0.028 (3)	0.018 (2)	−0.004 (2)	0.0018 (19)	−0.001 (2)
C44	0.021 (2)	0.022 (3)	0.016 (2)	0.001 (2)	0.0037 (18)	−0.001 (2)
C45	0.025 (2)	0.023 (3)	0.033 (3)	0.000 (2)	0.002 (2)	0.000 (2)
C46	0.027 (3)	0.029 (3)	0.042 (3)	0.003 (3)	0.000 (2)	−0.001 (3)
C47	0.023 (2)	0.023 (3)	0.018 (2)	0.000 (2)	0.0057 (19)	0.000 (2)

Zn1—O1	2.296 (3)	C13—H13	0.9300
Zn1—O2	2.006 (3)	C14—C13	1.402 (7)
Zn1—O5	1.958 (3)	C14—H14	0.9300
Zn1—O7	2.005 (3)	C16—C15	1.496 (6)
Zn1—N1	2.068 (4)	C16—C17	1.389 (6)
Zn2—O3	1.995 (3)	C16—C21	1.387 (7)
Zn2—O6	1.975 (3)	C18—C17	1.375 (6)
Zn2—O8	1.940 (3)	C18—C19	1.378 (7)
Zn2—N3	2.021 (4)	C18—H18	0.9300
F1—C3	1.338 (5)	C19—C20	1.378 (7)
F3—C17	1.353 (6)	C19—H19	0.9300
F5—C43	1.331 (5)	C20—H20	0.9300
O1—C1	1.250 (5)	C21—C20	1.384 (7)
O2—C1	1.276 (5)	C21—H21	0.9300
O3—C8	1.276 (5)	C22—C23	1.479 (6)
O4—C8	1.237 (5)	C24—C23	1.406 (6)
O5—C15	1.256 (5)	C24—H28'	0.9300
O6—C15	1.266 (5)	C25—C24	1.403 (6)
O7—C22	1.261 (5)	C25—H25	0.9300
O8—C22	1.259 (5)	C26—C25	1.367 (7)
O9—C34	1.231 (5)	C26—C27	1.378 (7)
O10—C40	1.240 (5)	C26—H26	0.9300
O11—C47	1.225 (6)	C27—C28	1.398 (6)
O12—C47	1.301 (6)	C27—H27	0.9300
O12—H121	0.92 (8)	C28—C23	1.398 (6)
N1—C29	1.335 (6)	C28—H28	0.9300
N1—C33	1.353 (5)	C29—C30	1.387 (6)
N2—C34	1.335 (6)	C29—H29	0.9300
N2—H2A	0.82 (5)	C31—C30	1.392 (6)
N2—H2B	0.84 (6)	C31—C32	1.380 (7)
N3—C35	1.335 (6)	C31—H31	0.9300
N3—C39	1.349 (5)	C32—H32	0.9300
N4—C40	1.324 (6)	C33—C32	1.374 (6)
N4—H4A	0.81 (5)	C33—H33	0.9300
N4—H4B	0.92 (7)	C34—C30	1.494 (6)
C2—C1	1.494 (6)	C35—H35	0.9300
C2—C3	1.379 (6)	C36—C35	1.382 (6)
C2—C7	1.394 (6)	C36—C37	1.391 (6)
C3—C4	1.379 (7)	C36—C40	1.504 (6)
C4—H4	0.9300	C37—C38	1.382 (6)
C5—C4	1.379 (7)	C37—H37	0.9300
C5—H5	0.9300	C38—H38	0.9300
C6—C5	1.378 (7)	C39—C38	1.380 (6)
C6—H6	0.9300	C39—H39	0.9300
C7—C6	1.380 (6)	C41—C46	1.374 (8)
C7—H7	0.9300	C41—H41	0.9300
C8—C9	1.490 (6)	C42—C41	1.377 (7)
C9—C14	1.407 (6)	C42—H42	0.9300
C10—C9	1.398 (6)	C43—C42	1.379 (7)
C10—C11	1.398 (7)	C44—C43	1.391 (7)
C10—H14'	0.9300	C44—C47	1.479 (7)
C11—H11	0.9300	C45—C44	1.395 (6)
C12—C11	1.363 (7)	C45—C46	1.371 (7)
C12—H12	0.9300	C45—H45	0.9300
C13—C12	1.372 (7)	C46—H46	0.9300
O2—Zn1—O1	60.92 (12)	C19—C18—H18	120.4
O2—Zn1—N1	100.57 (14)	C18—C19—C20	120.1 (5)
O5—Zn1—O1	95.98 (12)	C18—C19—H19	120.0
O5—Zn1—O2	150.56 (13)	C20—C19—H19	120.0
O5—Zn1—O7	106.60 (12)	C19—C20—C21	119.6 (5)
O5—Zn1—N1	97.64 (13)	C19—C20—H20	120.2
O7—Zn1—O1	154.68 (12)	C21—C20—H20	120.2
O7—Zn1—O2	93.94 (12)	C16—C21—H21	119.0
O7—Zn1—N1	97.05 (13)	C20—C21—C16	121.9 (5)
N1—Zn1—O1	91.04 (13)	C20—C21—H21	119.0
O3—Zn2—N3	112.33 (15)	O7—C22—C23	117.3 (4)
O6—Zn2—O3	97.28 (12)	O8—C22—O7	124.9 (4)
O6—Zn2—N3	106.36 (14)	O8—C22—C23	117.7 (4)
O8—Zn2—O3	129.40 (14)	C24—C23—C22	122.2 (4)
O8—Zn2—O6	107.39 (13)	C28—C23—C22	121.5 (4)
O8—Zn2—N3	102.19 (14)	C28—C23—C24	116.2 (4)
C1—O1—Zn1	82.8 (3)	C23—C24—H28'	119.2
C1—O2—Zn1	95.3 (3)	C25—C24—C23	121.6 (4)
C8—O3—Zn2	102.6 (3)	C25—C24—H28'	119.2
C15—O5—Zn1	140.1 (3)	C24—C25—H25	120.3
C15—O6—Zn2	125.3 (3)	C26—C25—C24	119.4 (4)
C22—O7—Zn1	143.0 (3)	C26—C25—H25	120.3
C22—O8—Zn2	122.4 (3)	C25—C26—C27	121.6 (4)
C47—O12—H121	109 (4)	C25—C26—H26	119.2
C29—N1—Zn1	120.9 (3)	C27—C26—H26	119.2
C29—N1—C33	117.7 (4)	C26—C27—C28	118.4 (4)
C33—N1—Zn1	121.4 (3)	C26—C27—H27	120.8
C34—N2—H2A	120 (4)	C28—C27—H27	120.8
C34—N2—H2B	115 (4)	C23—C28—C27	122.8 (4)
H2A—N2—H2B	124 (5)	C23—C28—H28	118.6
C35—N3—Zn2	119.5 (3)	C27—C28—H28	118.6
C35—N3—C39	118.0 (4)	N1—C29—C30	123.9 (4)
C39—N3—Zn2	122.4 (3)	N1—C29—H29	118.0
C40—N4—H4A	122 (4)	C30—C29—H29	118.0
C40—N4—H4B	114 (4)	C29—C30—C31	117.7 (4)
H4A—N4—H4B	124 (5)	C29—C30—C34	117.4 (4)
O1—C1—O2	120.7 (4)	C31—C30—C34	124.9 (4)
O1—C1—C2	122.0 (4)	C30—C31—H31	120.6
O2—C1—C2	117.3 (4)	C32—C31—C30	118.7 (4)
C3—C2—C1	123.7 (4)	C32—C31—H31	120.6
C3—C2—C7	116.8 (4)	C31—C32—H32	120.0
C7—C2—C1	119.5 (4)	C33—C32—C31	120.1 (4)
F1—C3—C2	120.1 (4)	C33—C32—H32	120.0
F1—C3—C4	117.1 (4)	N1—C33—C32	121.9 (4)
C4—C3—C2	122.8 (4)	N1—C33—H33	119.1
C3—C4—H4	120.5	C32—C33—H33	119.1
C5—C4—C3	118.9 (5)	O9—C34—N2	122.5 (4)
C5—C4—H4	120.5	O9—C34—C30	119.3 (4)
C4—C5—H5	120.0	N2—C34—C30	118.3 (4)
C6—C5—C4	120.1 (5)	N3—C35—C36	123.8 (4)
C6—C5—H5	120.0	N3—C35—H35	118.1
C5—C6—C7	119.9 (5)	C36—C35—H35	118.1
C5—C6—H6	120.1	C35—C36—C37	117.9 (4)
C7—C6—H6	120.1	C35—C36—C40	116.4 (4)
C2—C7—H7	119.3	C37—C36—C40	125.7 (4)
C6—C7—C2	121.4 (4)	C36—C37—H37	120.6
C6—C7—H7	119.3	C38—C37—C36	118.8 (4)
O3—C8—C9	118.7 (4)	C38—C37—H37	120.6
O4—C8—O3	121.1 (4)	C37—C38—H38	120.1
O4—C8—C9	120.2 (4)	C39—C38—C37	119.8 (4)
C10—C9—C8	125.0 (4)	C39—C38—H38	120.1
C14—C9—C10	115.9 (4)	N3—C39—C38	121.8 (4)
C14—C9—C8	119.1 (4)	N3—C39—H39	119.1
C9—C10—H14'	118.9	C38—C39—H39	119.1
C11—C10—C9	122.3 (4)	O10—C40—N4	122.8 (4)
C11—C10—H14'	118.9	O10—C40—C36	118.3 (4)
C10—C11—H11	120.3	N4—C40—C36	118.9 (4)
C12—C11—C10	119.4 (5)	C42—C41—H41	119.9
C12—C11—H11	120.3	C46—C41—C42	120.2 (5)
C11—C12—C13	121.5 (5)	C46—C41—H41	119.9
C11—C12—H12	119.3	C41—C42—C43	119.2 (5)
C13—C12—H12	119.3	C41—C42—H42	120.4
C12—C13—C14	118.9 (5)	C43—C42—H42	120.4
C12—C13—H13	120.6	F5—C43—C42	117.0 (5)
C14—C13—H13	120.6	F5—C43—C44	121.0 (4)
C9—C14—C13	122.2 (4)	C42—C43—C44	122.0 (4)
C9—C14—H14	118.9	C43—C44—C45	117.1 (5)
C13—C14—H14	118.9	C43—C44—C47	125.3 (4)
O5—C15—O6	125.5 (4)	C45—C44—C47	117.6 (4)
O5—C15—C16	118.4 (4)	C44—C45—H45	119.4
O6—C15—C16	116.1 (4)	C46—C45—C44	121.3 (5)
C17—C16—C15	124.3 (4)	C46—C45—H45	119.4
C21—C16—C15	119.2 (4)	C41—C46—H46	119.9
C21—C16—C17	116.4 (4)	C45—C46—C41	120.3 (5)
F3—C17—C16	120.6 (4)	C45—C46—H46	119.9
F3—C17—C18	116.6 (4)	O11—C47—O12	122.8 (5)
C18—C17—C16	122.8 (5)	O11—C47—C44	120.5 (4)
C17—C18—C19	119.1 (5)	O12—C47—C44	116.7 (5)
C17—C18—H18	120.4
O2—Zn1—O1—C1	−3.1 (3)	C2—C7—C6—C5	0.0 (7)
O5—Zn1—O1—C1	−163.8 (3)	O3—C8—C9—C10	−7.4 (7)
O7—Zn1—O1—C1	−10.6 (4)	O3—C8—C9—C14	171.5 (4)
N1—Zn1—O1—C1	98.4 (3)	O4—C8—C9—C10	171.3 (4)
O1—Zn1—O2—C1	3.0 (2)	O4—C8—C9—C14	−9.7 (7)
O5—Zn1—O2—C1	45.1 (4)	C10—C9—C14—C13	0.8 (7)
O7—Zn1—O2—C1	179.9 (3)	C8—C9—C14—C13	−178.3 (5)
N1—Zn1—O2—C1	−82.2 (3)	C11—C10—C9—C14	−0.7 (7)
O1—Zn1—O5—C15	125.1 (5)	C11—C10—C9—C8	178.3 (5)
O2—Zn1—O5—C15	89.0 (5)	C9—C10—C11—C12	0.1 (8)
O7—Zn1—O5—C15	−43.3 (5)	C13—C12—C11—C10	0.4 (8)
N1—Zn1—O5—C15	−143.1 (5)	C14—C13—C12—C11	−0.4 (8)
O1—Zn1—O7—C22	−91.5 (5)	C9—C14—C13—C12	−0.3 (8)
O2—Zn1—O7—C22	−98.0 (5)	C17—C16—C15—O5	−17.1 (7)
O5—Zn1—O7—C22	60.6 (5)	C17—C16—C15—O6	163.6 (4)
N1—Zn1—O7—C22	160.8 (5)	C21—C16—C15—O5	163.9 (4)
O1—Zn1—N1—C29	−118.6 (3)	C21—C16—C15—O6	−15.4 (6)
O1—Zn1—N1—C33	60.8 (3)	C15—C16—C17—F3	−0.8 (7)
O2—Zn1—N1—C29	−58.0 (3)	C15—C16—C17—C18	−178.8 (5)
O2—Zn1—N1—C33	121.4 (3)	C21—C16—C17—F3	178.2 (4)
O5—Zn1—N1—C29	145.2 (3)	C21—C16—C17—C18	0.2 (7)
O5—Zn1—N1—C33	−35.4 (3)	C17—C16—C21—C20	−0.8 (7)
O7—Zn1—N1—C29	37.3 (3)	C15—C16—C21—C20	178.3 (5)
O7—Zn1—N1—C33	−143.2 (3)	C19—C18—C17—F3	−177.8 (5)
O8—Zn2—O3—C8	53.8 (3)	C19—C18—C17—C16	0.3 (8)
O6—Zn2—O3—C8	173.4 (3)	C17—C18—C19—C20	−0.3 (9)
N3—Zn2—O3—C8	−75.5 (3)	C18—C19—C20—C21	−0.3 (9)
O3—Zn2—O6—C15	−50.5 (4)	C16—C21—C20—C19	0.9 (9)
O8—Zn2—O6—C15	84.8 (4)	O7—C22—C23—C24	−162.1 (4)
N3—Zn2—O6—C15	−166.4 (3)	O7—C22—C23—C28	13.1 (6)
O3—Zn2—O8—C22	29.6 (4)	O8—C22—C23—C24	16.2 (6)
O6—Zn2—O8—C22	−85.8 (3)	O8—C22—C23—C28	−168.5 (4)
N3—Zn2—O8—C22	162.5 (3)	C25—C24—C23—C28	−1.8 (6)
O3—Zn2—N3—C35	−57.3 (3)	C25—C24—C23—C22	173.8 (4)
O3—Zn2—N3—C39	117.9 (3)	C26—C25—C24—C23	1.4 (7)
O6—Zn2—N3—C35	48.0 (3)	C27—C26—C25—C24	0.3 (7)
O6—Zn2—N3—C39	−136.8 (3)	C25—C26—C27—C28	−1.6 (7)
O8—Zn2—N3—C35	160.4 (3)	C26—C27—C28—C23	1.1 (7)
O8—Zn2—N3—C39	−24.3 (4)	C27—C28—C23—C24	0.5 (6)
Zn1—O1—C1—O2	5.0 (4)	C27—C28—C23—C22	−175.1 (4)
Zn1—O1—C1—C2	−172.5 (4)	N1—C29—C30—C31	0.5 (7)
Zn1—O2—C1—O1	−5.7 (5)	N1—C29—C30—C34	−178.9 (4)
Zn1—O2—C1—C2	171.9 (3)	C32—C31—C30—C29	−0.8 (6)
Zn2—O3—C8—O4	−5.4 (5)	C32—C31—C30—C34	178.7 (4)
Zn2—O3—C8—C9	173.4 (3)	C30—C31—C32—C33	−0.1 (6)
Zn1—O5—C15—O6	−11.4 (8)	N1—C33—C32—C31	1.3 (7)
Zn1—O5—C15—C16	169.4 (3)	N2—C34—C30—C29	−172.6 (4)
Zn2—O6—C15—O5	−3.1 (6)	N2—C34—C30—C31	8.0 (7)
Zn2—O6—C15—C16	176.2 (3)	O9—C34—C30—C29	6.7 (7)
Zn1—O7—C22—O8	−12.9 (7)	O9—C34—C30—C31	−172.8 (4)
Zn1—O7—C22—C23	165.3 (3)	C37—C36—C35—N3	1.1 (6)
Zn2—O8—C22—O7	16.4 (6)	C40—C36—C35—N3	−177.4 (4)
Zn2—O8—C22—C23	−161.8 (3)	C35—C36—C37—C38	−0.6 (6)
Zn1—N1—C29—C30	−180.0 (3)	C40—C36—C37—C38	177.9 (4)
C33—N1—C29—C30	0.6 (6)	C35—C36—C40—O10	−0.5 (6)
Zn1—N1—C33—C32	179.1 (3)	C37—C36—C40—O10	−179.0 (4)
C29—N1—C33—C32	−1.5 (6)	C35—C36—C40—N4	179.2 (4)
Zn2—N3—C35—C36	175.3 (3)	C37—C36—C40—N4	0.7 (7)
C39—N3—C35—C36	−0.2 (6)	C36—C37—C38—C39	−0.8 (6)
Zn2—N3—C39—C38	−176.6 (3)	N3—C39—C38—C37	1.8 (7)
C35—N3—C39—C38	−1.3 (6)	C42—C41—C46—C45	−0.4 (8)
C3—C2—C1—O1	−6.1 (7)	C43—C42—C41—C46	−0.1 (8)
C3—C2—C1—O2	176.3 (4)	F5—C43—C42—C41	179.6 (4)
C7—C2—C1—O1	171.4 (4)	C44—C43—C42—C41	0.8 (7)
C7—C2—C1—O2	−6.2 (6)	C45—C44—C43—F5	−179.7 (4)
C1—C2—C3—F1	−7.9 (7)	C45—C44—C43—C42	−0.9 (7)
C1—C2—C3—C4	174.4 (5)	C47—C44—C43—F5	0.5 (7)
C7—C2—C3—F1	174.6 (4)	C47—C44—C43—C42	179.2 (4)
C7—C2—C3—C4	−3.2 (7)	C43—C44—C47—O11	−176.7 (5)
C1—C2—C7—C6	−175.2 (4)	C43—C44—C47—O12	3.8 (7)
C3—C2—C7—C6	2.5 (7)	C45—C44—C47—O11	3.5 (7)
F1—C3—C4—C5	−176.5 (4)	C45—C44—C47—O12	−176.0 (4)
C2—C3—C4—C5	1.3 (8)	C46—C45—C44—C43	0.5 (7)
C6—C5—C4—C3	1.4 (8)	C46—C45—C44—C47	−179.7 (5)
C7—C6—C5—C4	−2.0 (8)	C44—C45—C46—C41	0.2 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1i	0.82 (5)	2.39 (5)	3.056 (6)	140 (5)
N2—H2B···O10ii	0.84 (6)	2.03 (5)	2.863 (6)	176.4 (5)
N4—H4A···O4iii	0.81 (5)	2.11 (5)	2.825 (5)	149 (5)
N4—H4B···O9iv	0.92 (7)	1.96 (7)	2.874 (6)	176 (7)
O12—H121···O11v	0.92 (8)	1.71 (8)	2.626 (5)	174 (6)

Table 1

Selected bond lengths (Å)

Zn1—O1	2.296 (3)
Zn1—O2	2.006 (3)
Zn1—O5	1.958 (3)
Zn1—O7	2.005 (3)
Zn1—N1	2.068 (4)
Zn2—O3	1.995 (3)
Zn2—O6	1.975 (3)
Zn2—O8	1.940 (3)
Zn2—N3	2.021 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1i	0.82 (5)	2.39 (5)	3.056 (6)	140 (5)
N2—H2B⋯O10ii	0.84 (6)	2.03 (5)	2.863 (6)	176.4 (5)
N4—H4A⋯O4iii	0.81 (5)	2.11 (5)	2.825 (5)	149 (5)
N4—H4B⋯O9iv	0.92 (7)	1.96 (7)	2.874 (6)	176 (7)
O12—H121⋯O11v	0.92 (8)	1.71 (8)	2.626 (5)	174 (6)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .