The honeycomb network structure of poly[[[μ₂-1,3-bis­(1H-benzimidazol-2-yl)benzene-κ²N³:N^3′](μ₂-terephthalato-κ²O:O′)zinc(II)] ethanol solvate]

The terephthalate dianion and the bis­(imidazol­yl)benzene ligand of the title compound, {[Zn(C₈H₄O₄)(C₂₀H₁₄N₄)]·C₂H₆O}_n, each bridges two adjacent zinc centers, resulting in a layer-type coordination polymer; the zinc center shows tetra­hedral coordination. The disordered ethanol solvent mol­ecules occupy the spaces between the layers and are hydrogen bonded to the layers. The two symmetry-independent dianions lie on different inversion sites.

S1. Comment

Zinc terephthalate forms a number of 1:1 adducts with bidentate N-heterocyclic ligands; crystallographic studies have focused on rigid heterocycles such as, for example, 4,4'-bipyridine (Tao et al., 2000) and 1,10-phenanthroline (Sun et al., 2001). As the terephthalate entity itself is rigid, the adducts adopt architectures that reflect such rigidity, i.e. the 4,4'-bipyridine adduct is a three-dimensional network and the 1,10-phenanthroline adduct is a linear chain. With a flexible ligand such as 1,3,4-bis(triazol-1-yl)ethane, a two-dimensional rhombic network is formed (Li et al., 2004). 1,3,4-Bis(triazol-1-yl)butane affords a threefold, interpenetrating diamondoid network based on a zinc center (Wang et al., 2006)

1,3-Bis(benzimidazol-2-yl)benzene, an N-heterocycle that can be conveniently synthesized by condensing m-phenylenediamine and phthalic acid under the influence of microwaves (Song et al., 2000), is a ligand that can bind to two metal centers through its two tertiary nitrogen-donor sites. Spectroscopic measurements are available for a small number of adducts with transition metals, and among the zinc complexes that have been characterized spectroscopically are the halide and perchlorate complexes (Chawla & Gill, 1997; Shivakumaraiah & Nanje Gowda, 2003), but to date, no example of an adduct is found in the structural literature (CSD Version 5.28, November 2006 release; Allen, 2002).

The 1:1 zinc terephthalate–bis(benzimidazolyl)benzene adduct {[Zn(C₈H₄O₄)(C₂₀H₁₄N₄)]·C₂H₆O}_n, (I), which exists as an ethanol solvate, is a coordination polymer in which the carboxylate group and ligand both engage in bridging two tetrahedral zinc centers (Fig. 1), this bridging mode giving rise to a layer motif. The two symmetry-independent dianions lie on different inversion sites. The two benzimidazolyl arms are bent with respect to the phenylene ring, one (with the N1 atom) being twisted by 31.6 (1)° and the other (with the N3 atom) being twisted by 15.7 (1)°. The twist angles parallel the deviation of the metal atom from the plane of the arms, the atom being displaced by 0.807 (3) Å from the first and by 0.507 (3) Å from the second. The topology of the layer is a (6,3) honeycomb (Fig. 2) that is somewhat buckled as the two bridging components are of different sizes. The atoms comprising the layer framework constitute only about 79% of the volume, as calculated by PLATON (Spek, 2003). The layers are consolidated by N—H···O hydrogen bonds (Table 2) but the space between layers is large enough to accommodate ethanol molecules.

Related literature

For related literature, see: Allen (2002); Chawla & Gill (1997); Li et al. (2004); Shivakumaraiah & Nanje Gowda (2003); Song et al. (2000); Spek (2003); Sun et al. (2001); Tao et al. (2000); Wang et al. (2006).

S2. Experimental

The N-heterocycle was prepared using a reported procedure (Chawla & Gill, 1997). Zinc nitrate hexahydrate (0.074 g, 0.25 mmol), 1,4-benzenedicarboxylic acid (0.021 g, 0.125 mmol), 1,3-bis-(benzimidazol-2-ylmethyl)benzene (0.039 g, 0.125 mmol), ethanol (2 ml) and water (15 ml) were placed in a 23 ml, Teflon-lined, stainless steel Parr bomb. (Neither sodium nor potassium hydroxide was added.) The bomb was heated at 433 K for 5 days and cooled to room temperature at Kh^-1. Colorless block crystals were obtained in 20% yield.

S3. Refinement

The ethanol molecule is disordered in the carbon atoms, and was refined with two ethyl components in a 0.72:0.28 ratio. The O—C distance was restrained to 1.45 (0.01) Å and the C—C distance to 1.50 (0.01) Å. The temperature factors of the four C atoms were restrained to be nearly isotropic.

Carbon-bound H atoms were positioned geometrically (C—H 0.93 and 0.97 Å), and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). The water and amino H atoms were located in a difference Fourier map, and were refined with a distance restraint of O—H = N—H = 0.85 (1) Å.

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. Tetrahedral geometry of Zn in the layer structure of (I). Displacement ellipsoids are drawn at the 70% probability level. The disordered ethanol molecule is not shown. [Symmetry code (i): -x, 1 - y, 1 - z.]
	Fig. 2. OLEX (Dolomanov et al., 2003) depiction of the (6,3) honeycomb topology, shown projected against the unit cell.

poly[[[µ₂-1,3-bis(1H-benzimidazol-2-yl)benzene- κ²N³:N^3'](µ₂-terephthalato- κ²O:O')zinc(II)] ethanol solvate]

Crystal data

[Zn(C8H4O4)(C20H14N4)]·C2H6O	Z = 2
Mr = 585.90	F(000) = 604
Triclinic, P1	Dx = 1.462 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0660 (8) Å	Cell parameters from 3996 reflections
b = 9.3077 (9) Å	θ = 2.5–27.3°
c = 15.921 (2) Å	µ = 0.97 mm^−1
α = 86.731 (1)°	T = 291 K
β = 83.140 (1)°	Block, colorless
γ = 87.931 (1)°	0.28 × 0.21 × 0.18 mm
V = 1331.1 (2) Å^3

Data collection

Bruker APEX area-detector diffractometer	5834 independent reflections
Radiation source: fine-focus sealed tube	4918 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ϕ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.712, Tmax = 0.845	k = −12→12
10765 measured reflections	l = −20→20

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.3524P] where P = (Fo^2 + 2Fc^2)/3
5834 reflections	(Δ/σ)max = 0.001
389 parameters	Δρmax = 0.38 e Å^−3
31 restraints	Δρmin = −0.41 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.12048 (3)	0.34731 (2)	0.704774 (14)	0.02477 (9)
O1	0.27282 (19)	0.22493 (18)	0.64807 (10)	0.0378 (4)
O2	0.3880 (2)	0.37354 (18)	0.54777 (11)	0.0448 (4)
O3	0.07302 (19)	0.25817 (16)	0.81934 (9)	0.0322 (4)
O4	0.0327 (2)	0.04796 (17)	0.76770 (10)	0.0400 (4)
O5	0.4019 (5)	0.0591 (6)	0.7905 (3)	0.1492 (16)
H5O	0.360 (7)	0.105 (7)	0.751 (3)	0.179*
N1	0.1885 (2)	0.54158 (19)	0.73633 (11)	0.0259 (4)
N2	0.1515 (2)	0.7688 (2)	0.77254 (12)	0.0306 (4)
H2N	0.120 (3)	0.8550 (13)	0.7709 (16)	0.037*
N3	0.0816 (2)	0.60449 (19)	0.33495 (10)	0.0253 (4)
N4	0.2672 (2)	0.5222 (2)	0.40534 (12)	0.0363 (5)
H4N	0.322 (3)	0.503 (3)	0.4450 (13)	0.044*
C1	0.2394 (2)	0.5550 (2)	0.81518 (13)	0.0283 (5)
C2	0.3053 (3)	0.4532 (3)	0.86742 (16)	0.0376 (6)
H2	0.3234	0.3587	0.8521	0.045*
C3	0.3426 (3)	0.4982 (3)	0.94286 (17)	0.0464 (7)
H3	0.3863	0.4323	0.9792	0.056*
C4	0.3166 (3)	0.6408 (3)	0.96628 (16)	0.0477 (7)
H4	0.3421	0.6666	1.0181	0.057*
C5	0.2543 (3)	0.7436 (3)	0.91446 (16)	0.0421 (6)
H5	0.2388	0.8386	0.9294	0.050*
C6	0.2158 (3)	0.6976 (2)	0.83843 (14)	0.0305 (5)
C7	0.1375 (2)	0.6726 (2)	0.71378 (13)	0.0256 (4)
C8	0.0765 (2)	0.7121 (2)	0.63368 (13)	0.0254 (4)
C9	−0.0331 (3)	0.8208 (2)	0.62899 (14)	0.0319 (5)
H9	−0.0721	0.8669	0.6774	0.038*
C10	−0.0832 (3)	0.8593 (2)	0.55174 (15)	0.0359 (5)
H10	−0.1567	0.9312	0.5486	0.043*
C11	−0.0251 (3)	0.7919 (2)	0.47898 (14)	0.0331 (5)
H11	−0.0564	0.8213	0.4270	0.040*
C12	0.0805 (2)	0.6799 (2)	0.48389 (13)	0.0264 (4)
C13	0.1310 (2)	0.6407 (2)	0.56145 (13)	0.0258 (4)
H13	0.2017	0.5663	0.5650	0.031*
C14	0.1406 (2)	0.6044 (2)	0.40773 (13)	0.0268 (4)
C15	0.2920 (3)	0.4619 (3)	0.32729 (15)	0.0341 (5)
C16	0.4012 (3)	0.3648 (3)	0.29415 (18)	0.0500 (7)
H16	0.4786	0.3316	0.3242	0.060*
C17	0.3879 (3)	0.3205 (3)	0.21419 (18)	0.0543 (8)
H17	0.4563	0.2533	0.1902	0.065*
C18	0.2742 (3)	0.3743 (3)	0.16875 (16)	0.0459 (7)
H18	0.2697	0.3425	0.1148	0.055*
C19	0.1676 (3)	0.4731 (3)	0.20060 (14)	0.0362 (5)
H19	0.0934	0.5095	0.1691	0.043*
C20	0.1769 (2)	0.5158 (2)	0.28273 (13)	0.0288 (5)
C21	0.3622 (3)	0.2532 (2)	0.58054 (14)	0.0304 (5)
C22	0.4353 (2)	0.1211 (2)	0.53972 (14)	0.0286 (5)
C23	0.3858 (3)	−0.0166 (3)	0.56556 (15)	0.0345 (5)
H23	0.3092	−0.0284	0.6096	0.041*
C24	0.4508 (3)	−0.1365 (2)	0.52561 (15)	0.0330 (5)
H24	0.4170	−0.2278	0.5431	0.049*
C25	0.0422 (2)	0.1256 (2)	0.82785 (13)	0.0266 (4)
C26	0.0178 (3)	0.0624 (2)	0.91749 (13)	0.0268 (4)
C27	0.0834 (3)	0.1223 (2)	0.98164 (14)	0.0323 (5)
H27	0.1389	0.2046	0.9697	0.039*
C28	0.0663 (3)	0.0596 (2)	1.06329 (14)	0.0324 (5)
H28	0.1116	0.0997	1.1055	0.049*
C29	0.5448 (12)	0.0873 (18)	0.8193 (9)	0.215 (7)	0.721 (14)
H29A	0.5788	0.0062	0.8536	0.258*	0.721 (14)
H29B	0.5381	0.1727	0.8519	0.258*	0.721 (14)
C30	0.6464 (16)	0.1092 (15)	0.7384 (8)	0.214 (6)	0.721 (14)
H30A	0.7456	0.1230	0.7512	0.322*	0.721 (14)
H30B	0.6131	0.1925	0.7067	0.322*	0.721 (14)
H30C	0.6457	0.0260	0.7054	0.322*	0.721 (14)
C29'	0.5483 (14)	0.118 (3)	0.7679 (13)	0.113 (8)	0.279 (14)
H29C	0.5364	0.2070	0.7345	0.135*	0.279 (14)
H29D	0.6059	0.0514	0.7312	0.135*	0.279 (14)
C30'	0.638 (3)	0.148 (3)	0.8359 (15)	0.147 (11)	0.279 (14)
H30D	0.7280	0.1926	0.8117	0.221*	0.279 (14)
H30E	0.6617	0.0590	0.8659	0.221*	0.279 (14)
H30F	0.5823	0.2108	0.8744	0.221*	0.279 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.03333 (15)	0.02150 (13)	0.01889 (13)	0.00217 (10)	−0.00162 (10)	−0.00096 (9)
O1	0.0420 (10)	0.0350 (9)	0.0333 (9)	0.0086 (8)	0.0071 (7)	−0.0043 (7)
O2	0.0613 (12)	0.0293 (9)	0.0406 (10)	0.0102 (8)	0.0022 (9)	0.0008 (7)
O3	0.0530 (10)	0.0217 (7)	0.0212 (7)	−0.0045 (7)	−0.0021 (7)	0.0027 (6)
O4	0.0704 (13)	0.0283 (8)	0.0221 (8)	−0.0031 (8)	−0.0079 (8)	−0.0025 (6)
O5	0.114 (3)	0.191 (5)	0.138 (4)	0.003 (3)	−0.026 (3)	0.051 (3)
N1	0.0325 (10)	0.0246 (9)	0.0214 (9)	−0.0003 (8)	−0.0067 (7)	−0.0012 (7)
N2	0.0444 (11)	0.0241 (9)	0.0245 (9)	0.0055 (8)	−0.0097 (8)	−0.0050 (7)
N3	0.0313 (10)	0.0262 (9)	0.0180 (8)	−0.0012 (8)	−0.0013 (7)	−0.0010 (7)
N4	0.0352 (11)	0.0485 (12)	0.0255 (10)	0.0078 (9)	−0.0076 (8)	−0.0025 (9)
C1	0.0304 (11)	0.0311 (11)	0.0240 (10)	−0.0016 (9)	−0.0068 (9)	−0.0005 (9)
C2	0.0400 (13)	0.0347 (13)	0.0397 (13)	0.0000 (11)	−0.0136 (11)	0.0040 (10)
C3	0.0486 (16)	0.0569 (17)	0.0359 (14)	0.0019 (13)	−0.0205 (12)	0.0086 (12)
C4	0.0498 (16)	0.0676 (19)	0.0292 (13)	0.0019 (14)	−0.0177 (12)	−0.0086 (12)
C5	0.0491 (15)	0.0471 (15)	0.0329 (13)	0.0066 (12)	−0.0132 (11)	−0.0145 (11)
C6	0.0341 (12)	0.0332 (12)	0.0251 (11)	0.0011 (10)	−0.0073 (9)	−0.0032 (9)
C7	0.0319 (11)	0.0238 (10)	0.0210 (10)	−0.0014 (9)	−0.0026 (9)	−0.0011 (8)
C8	0.0339 (11)	0.0204 (10)	0.0222 (10)	−0.0034 (9)	−0.0051 (9)	0.0010 (8)
C9	0.0430 (13)	0.0274 (11)	0.0258 (11)	0.0040 (10)	−0.0056 (10)	−0.0050 (9)
C10	0.0457 (14)	0.0265 (11)	0.0374 (13)	0.0093 (10)	−0.0144 (11)	−0.0035 (10)
C11	0.0478 (14)	0.0281 (11)	0.0253 (11)	0.0012 (10)	−0.0142 (10)	0.0005 (9)
C12	0.0347 (12)	0.0231 (10)	0.0215 (10)	−0.0036 (9)	−0.0035 (9)	0.0002 (8)
C13	0.0330 (11)	0.0211 (10)	0.0233 (10)	0.0002 (9)	−0.0044 (9)	0.0010 (8)
C14	0.0333 (12)	0.0242 (10)	0.0226 (10)	−0.0032 (9)	−0.0030 (9)	0.0018 (8)
C15	0.0342 (12)	0.0391 (13)	0.0278 (11)	0.0025 (10)	0.0001 (10)	−0.0019 (10)
C16	0.0392 (15)	0.0648 (19)	0.0441 (15)	0.0155 (13)	−0.0002 (12)	−0.0062 (14)
C17	0.0501 (17)	0.0630 (19)	0.0457 (16)	0.0160 (15)	0.0110 (13)	−0.0136 (14)
C18	0.0483 (16)	0.0572 (17)	0.0304 (13)	−0.0023 (13)	0.0088 (11)	−0.0140 (12)
C19	0.0380 (13)	0.0447 (14)	0.0252 (11)	−0.0014 (11)	0.0004 (10)	−0.0049 (10)
C20	0.0315 (11)	0.0290 (11)	0.0245 (11)	−0.0037 (9)	0.0028 (9)	−0.0001 (9)
C21	0.0304 (11)	0.0323 (12)	0.0287 (11)	0.0056 (10)	−0.0050 (9)	−0.0030 (9)
C22	0.0295 (11)	0.0284 (11)	0.0275 (11)	0.0042 (9)	−0.0029 (9)	−0.0018 (9)
C23	0.0322 (12)	0.0364 (13)	0.0320 (12)	0.0006 (10)	0.0078 (10)	−0.0002 (10)
C24	0.0337 (12)	0.0275 (11)	0.0356 (12)	−0.0007 (10)	0.0034 (10)	0.0005 (9)
C25	0.0328 (11)	0.0238 (10)	0.0227 (10)	0.0001 (9)	−0.0031 (9)	0.0017 (8)
C26	0.0370 (12)	0.0216 (10)	0.0210 (10)	0.0017 (9)	−0.0022 (9)	0.0007 (8)
C27	0.0450 (13)	0.0262 (11)	0.0255 (11)	−0.0100 (10)	−0.0027 (10)	0.0021 (9)
C28	0.0448 (14)	0.0292 (11)	0.0246 (11)	−0.0071 (10)	−0.0085 (10)	−0.0009 (9)
C29	0.190 (10)	0.220 (10)	0.239 (10)	0.022 (8)	−0.045 (9)	−0.028 (9)
C30	0.193 (10)	0.236 (10)	0.221 (10)	−0.035 (8)	−0.069 (8)	0.039 (8)
C29'	0.071 (9)	0.154 (12)	0.111 (11)	0.031 (8)	−0.012 (8)	0.000 (9)
C30'	0.125 (13)	0.158 (14)	0.165 (14)	−0.014 (9)	−0.021 (9)	−0.043 (9)

Geometric parameters (Å, º)

Zn1—O1	1.930 (2)	C11—H11	0.9300
Zn1—O3	1.966 (2)	C12—C13	1.392 (3)
Zn1—N1	2.040 (2)	C12—C14	1.474 (3)
Zn1—N3^i	2.036 (2)	C13—H13	0.9300
O1—C21	1.287 (3)	C15—C16	1.393 (3)
O2—C21	1.227 (3)	C15—C20	1.394 (3)
O3—C25	1.271 (3)	C16—C17	1.380 (4)
O4—C25	1.245 (3)	C16—H16	0.9300
O5—C29'	1.452 (10)	C17—C18	1.392 (4)
O5—C29	1.462 (9)	C17—H17	0.9300
O5—H5O	0.86 (4)	C18—C19	1.381 (3)
N1—C7	1.333 (3)	C18—H18	0.9300
N1—C1	1.402 (3)	C19—C20	1.401 (3)
N2—C7	1.351 (3)	C19—H19	0.9300
N2—C6	1.385 (3)	C21—C22	1.517 (3)
N2—H2N	0.842 (10)	C22—C24^ii	1.381 (3)
N3—C14	1.333 (3)	C22—C23	1.397 (3)
N3—C20	1.405 (3)	C23—C24	1.393 (3)
N3—Zn1^i	2.0357 (18)	C23—H23	0.9300
N4—C14	1.354 (3)	C24—C22^ii	1.381 (3)
N4—C15	1.383 (3)	C24—H24	0.9300
N4—H4N	0.856 (10)	C25—C26	1.507 (3)
C1—C2	1.391 (3)	C26—C28^iii	1.390 (3)
C1—C6	1.400 (3)	C26—C27	1.394 (3)
C2—C3	1.377 (3)	C27—C28	1.388 (3)
C2—H2	0.9300	C27—H27	0.9300
C3—C4	1.403 (4)	C28—C26^iii	1.390 (3)
C3—H3	0.9300	C28—H28	0.9300
C4—C5	1.377 (4)	C29—C30	1.500 (9)
C4—H4	0.9300	C29—H29A	0.9700
C5—C6	1.393 (3)	C29—H29B	0.9700
C5—H5	0.9300	C30—H30A	0.9600
C7—C8	1.472 (3)	C30—H30B	0.9600
C8—C13	1.391 (3)	C30—H30C	0.9600
C8—C9	1.398 (3)	C29'—C30'	1.473 (10)
C9—C10	1.385 (3)	C29'—H29C	0.9700
C9—H9	0.9300	C29'—H29D	0.9700
C10—C11	1.388 (3)	C30'—H30D	0.9600
C10—H10	0.9300	C30'—H30E	0.9600
C11—C12	1.395 (3)	C30'—H30F	0.9600
O1—Zn1—O3	106.0 (1)	N4—C15—C20	105.44 (19)
O1—Zn1—N3^i	125.1 (1)	C16—C15—C20	123.0 (2)
O1—Zn1—N1	115.7 (1)	C17—C16—C15	116.2 (3)
O3—Zn1—N1	98.9 (1)	C17—C16—H16	121.9
O3—Zn1—N3^i	104.2 (1)	C15—C16—H16	121.9
N1—Zn1—N3^i	103.30 (7)	C16—C17—C18	121.4 (2)
C21—O1—Zn1	128.94 (15)	C16—C17—H17	119.3
C25—O3—Zn1	119.12 (13)	C18—C17—H17	119.3
C29'—O5—H5O	97 (5)	C19—C18—C17	122.6 (2)
C29—O5—H5O	128 (5)	C19—C18—H18	118.7
C7—N1—C1	105.44 (17)	C17—C18—H18	118.7
C7—N1—Zn1	128.14 (14)	C18—C19—C20	116.7 (2)
C1—N1—Zn1	119.96 (14)	C18—C19—H19	121.6
C7—N2—C6	107.96 (18)	C20—C19—H19	121.6
C7—N2—H2N	125.6 (18)	C15—C20—C19	120.1 (2)
C6—N2—H2N	126.3 (18)	C15—C20—N3	109.03 (19)
C14—N3—C20	105.67 (18)	C19—C20—N3	130.8 (2)
C14—N3—Zn1^i	136.49 (15)	O2—C21—O1	125.8 (2)
C20—N3—Zn1^i	115.54 (14)	O2—C21—C22	120.0 (2)
C14—N4—C15	108.35 (19)	O1—C21—C22	114.2 (2)
C14—N4—H4N	128.2 (19)	C24^ii—C22—C23	119.1 (2)
C15—N4—H4N	123.3 (19)	C24^ii—C22—C21	120.0 (2)
C2—C1—C6	120.7 (2)	C23—C22—C21	120.8 (2)
C2—C1—N1	130.3 (2)	C24—C23—C22	120.2 (2)
C6—C1—N1	109.00 (18)	C24—C23—H23	119.9
C3—C2—C1	117.2 (2)	C22—C23—H23	119.9
C3—C2—H2	121.4	C22^ii—C24—C23	120.7 (2)
C1—C2—H2	121.4	C22^ii—C24—H24	119.7
C2—C3—C4	121.8 (2)	C23—C24—H24	119.7
C2—C3—H3	119.1	O4—C25—O3	124.2 (2)
C4—C3—H3	119.1	O4—C25—C26	119.76 (19)
C5—C4—C3	121.7 (2)	O3—C25—C26	116.04 (18)
C5—C4—H4	119.1	C28^iii—C26—C27	119.1 (2)
C3—C4—H4	119.1	C28^iii—C26—C25	120.35 (19)
C4—C5—C6	116.4 (2)	C27—C26—C25	120.5 (2)
C4—C5—H5	121.8	C28—C27—C26	120.3 (2)
C6—C5—H5	121.8	C28—C27—H27	119.9
N2—C6—C5	132.3 (2)	C26—C27—H27	119.9
N2—C6—C1	105.50 (18)	C27—C28—C26^iii	120.6 (2)
C5—C6—C1	122.2 (2)	C27—C28—H28	119.7
N1—C7—N2	112.09 (18)	C26^iii—C28—H28	119.7
N1—C7—C8	125.11 (18)	O5—C29—C30	103.5 (10)
N2—C7—C8	122.77 (19)	O5—C29—H29A	111.1
C13—C8—C9	119.81 (19)	C30—C29—H29A	111.1
C13—C8—C7	119.04 (19)	O5—C29—H29B	111.1
C9—C8—C7	121.15 (19)	C30—C29—H29B	111.1
C10—C9—C8	119.5 (2)	H29A—C29—H29B	109.0
C10—C9—H9	120.2	C29—C30—H30A	109.5
C8—C9—H9	120.2	C29—C30—H30B	109.5
C9—C10—C11	120.7 (2)	H30A—C30—H30B	109.5
C9—C10—H10	119.6	C29—C30—H30C	109.5
C11—C10—H10	119.6	H30A—C30—H30C	109.5
C10—C11—C12	119.9 (2)	H30B—C30—H30C	109.5
C10—C11—H11	120.0	O5—C29'—C30'	118.9 (17)
C12—C11—H11	120.0	O5—C29'—H29C	107.6
C13—C12—C11	119.5 (2)	C30'—C29'—H29C	107.6
C13—C12—C14	119.84 (19)	O5—C29'—H29D	107.6
C11—C12—C14	120.69 (19)	C30'—C29'—H29D	107.6
C8—C13—C12	120.5 (2)	H29C—C29'—H29D	107.0
C8—C13—H13	119.8	C29'—C30'—H30D	109.5
C12—C13—H13	119.8	C29'—C30'—H30E	109.5
N3—C14—N4	111.47 (19)	H30D—C30'—H30E	109.5
N3—C14—C12	126.8 (2)	C29'—C30'—H30F	109.5
N4—C14—C12	121.75 (19)	H30D—C30'—H30F	109.5
N4—C15—C16	131.6 (2)	H30E—C30'—H30F	109.5
O3—Zn1—O1—C21	−162.78 (19)	C11—C12—C13—C8	0.2 (3)
N3^i—Zn1—O1—C21	76.3 (2)	C14—C12—C13—C8	179.3 (2)
N1—Zn1—O1—C21	−54.3 (2)	C20—N3—C14—N4	0.2 (2)
O1—Zn1—O3—C25	−51.46 (18)	Zn1^i—N3—C14—N4	161.33 (17)
N3^i—Zn1—O3—C25	82.19 (17)	C20—N3—C14—C12	−178.9 (2)
N1—Zn1—O3—C25	−171.56 (17)	Zn1^i—N3—C14—C12	−17.8 (3)
O1—Zn1—N1—C7	122.62 (18)	C15—N4—C14—N3	−1.3 (3)
O3—Zn1—N1—C7	−124.70 (18)	C15—N4—C14—C12	177.9 (2)
N3^i—Zn1—N1—C7	−17.7 (2)	C13—C12—C14—N3	163.1 (2)
O1—Zn1—N1—C1	−89.91 (17)	C11—C12—C14—N3	−17.8 (3)
O3—Zn1—N1—C1	22.78 (17)	C13—C12—C14—N4	−15.9 (3)
N3^i—Zn1—N1—C1	129.74 (16)	C11—C12—C14—N4	163.1 (2)
C7—N1—C1—C2	−179.0 (2)	C14—N4—C15—C16	−176.5 (3)
Zn1—N1—C1—C2	27.0 (3)	C14—N4—C15—C20	1.8 (3)
C7—N1—C1—C6	0.4 (2)	N4—C15—C16—C17	176.5 (3)
Zn1—N1—C1—C6	−153.58 (16)	C20—C15—C16—C17	−1.6 (4)
C6—C1—C2—C3	1.3 (4)	C15—C16—C17—C18	2.1 (5)
N1—C1—C2—C3	−179.3 (2)	C16—C17—C18—C19	−0.7 (5)
C1—C2—C3—C4	−0.4 (4)	C17—C18—C19—C20	−1.3 (4)
C2—C3—C4—C5	−0.9 (5)	N4—C15—C20—C19	−178.9 (2)
C3—C4—C5—C6	1.3 (4)	C16—C15—C20—C19	−0.3 (4)
C7—N2—C6—C5	−179.6 (3)	N4—C15—C20—N3	−1.7 (3)
C7—N2—C6—C1	0.3 (3)	C16—C15—C20—N3	176.9 (2)
C4—C5—C6—N2	179.5 (3)	C18—C19—C20—C15	1.7 (4)
C4—C5—C6—C1	−0.4 (4)	C18—C19—C20—N3	−174.7 (2)
C2—C1—C6—N2	179.1 (2)	C14—N3—C20—C15	0.9 (2)
N1—C1—C6—N2	−0.4 (3)	Zn1^i—N3—C20—C15	−164.75 (16)
C2—C1—C6—C5	−1.0 (4)	C14—N3—C20—C19	177.7 (2)
N1—C1—C6—C5	179.5 (2)	Zn1^i—N3—C20—C19	12.0 (3)
C1—N1—C7—N2	−0.2 (3)	Zn1—O1—C21—O2	15.4 (4)
Zn1—N1—C7—N2	150.87 (16)	Zn1—O1—C21—C22	−162.91 (15)
C1—N1—C7—C8	178.1 (2)	O2—C21—C22—C24^ii	11.0 (3)
Zn1—N1—C7—C8	−30.8 (3)	O1—C21—C22—C24^ii	−170.6 (2)
C6—N2—C7—N1	0.0 (3)	O2—C21—C22—C23	−167.0 (2)
C6—N2—C7—C8	−178.4 (2)	O1—C21—C22—C23	11.4 (3)
N1—C7—C8—C13	−31.2 (3)	C24^ii—C22—C23—C24	−0.1 (4)
N2—C7—C8—C13	146.9 (2)	C21—C22—C23—C24	177.9 (2)
N1—C7—C8—C9	149.6 (2)	C22—C23—C24—C22^ii	0.1 (4)
N2—C7—C8—C9	−32.2 (3)	Zn1—O3—C25—O4	−3.6 (3)
C13—C8—C9—C10	−1.9 (3)	Zn1—O3—C25—C26	175.78 (14)
C7—C8—C9—C10	177.2 (2)	O4—C25—C26—C28^iii	−24.0 (3)
C8—C9—C10—C11	−0.4 (4)	O3—C25—C26—C28^iii	156.5 (2)
C9—C10—C11—C12	2.7 (4)	O4—C25—C26—C27	153.7 (2)
C10—C11—C12—C13	−2.6 (4)	O3—C25—C26—C27	−25.7 (3)
C10—C11—C12—C14	178.4 (2)	C28^iii—C26—C27—C28	0.8 (4)
C9—C8—C13—C12	2.0 (3)	C25—C26—C27—C28	−177.0 (2)
C7—C8—C13—C12	−177.1 (2)	C26—C27—C28—C26^iii	−0.8 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O4^iv	0.84 (2)	1.94 (2)	2.777 (2)	176 (3)
N4—H4N···O2	0.86 (2)	2.11 (2)	2.895 (3)	152 (3)
O5—H5O···O1	0.86 (4)	2.14 (4)	2.999 (4)	176 (7)

Symmetry code: (iv) x, y+1, z.