Bis(4,4'-bi­pyridine-[kappa]N)­bis­(hydrogen phthalato)-[kappa]²O,O';[kappa]O-zinc(II)

The title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)₂], was obtained by the hydro­thermal reaction of ZnSO₄·7H₂O with phthalic acid (H₂pht) and 4,4'-bi­pyridine (4,4'-bipy). Crystallographic analysis shows that it has a one-dimensional double-chain structure via hydrogen-bonding interactions. Each Zn^II atom, adopting a distorted tetrahedral geometry, is coordinated by two N atoms from two 4,4'-bipy ligands, with Zn-N distances of 2.054 (4) and 2.104 (4) Å, and by two O atoms from symmetry-related Hpht^- ligands, with Zn-O distances of 1.921 (4) and 2.019 (4) Å.

S1. Comment

The design and construction of novel coordination polymers based on covalent interactions (Fujita et al., 1994) or supramolecular contacts, such as hydrogen bonds and/or π–π stacking interactions (Desiraju, 1995), is a rapidly developing research area, which is not only due to their fascinating structures (Blake et al., 1999; Batten & Robson, 1998) but also to their unexpected properties for potential applications (Matsumoto et al., 1999; Chui et al., 1999). The design of coordination polymers is greatly influenced by factors such as the coordination nature of the metal ion, the structural characteristics of the polydentate organic ligand, the metal-ligand ratio, and the possible counterion. Here, we report the title novel metal-organic coordination polymer, (I), obtained by the hydrothermal reaction of 4,4'-bipy, H₂pht and ZnSO₄·7H₂O. \sch

The present X-ray single-crystal diffraction study reveals that compound (I) consists of one Zn^II atom, two Hpht⁻ ligands and two 4,4'-bipy ligands. As shown in Fig.1, each Zn^II atom is a four-coordinated tetrahedrally, by two O atoms from two Hpht⁻ ligands, with Zn—O bond lengths of 1.921 (4) and 2.019 (4) Å, and two N atoms of two 4,4'-bipy ligands, with Zn—N bond distances of 2.054 (4) and 2.104 (4) Å. However, the Zn—O4 distance of 2.496 (4) Å suggests a non-negligible interaction with the uncoordinated O atom, which may be described as a semi-chelating coordination mode (Guilera & Steed, 1999). Hence, the Zn^II atom may also be regarded as having a trigonal-bipyramidal geometry. The aforementioned bond lengths agree with those observed in similar Zn complexes (Wu et al., 2002). Each 4,4'-bipy ligand acts as a terminal ligand to link to one Zn^II atom. Within each 4,4'-bipy molecule, the two pyridine rings are twisted by 33.61 and 44.88° relative to each other.

As each Hpht⁻ and 4,4'-bipy ligand acts as a terminal ligand, the uncoordinated carboxylic acid groups from the Hpht⁻ ligands link to the uncoordinated N atoms from the 4,4'-bipy ligands via hydrogen bonding. The O1···N3 and O8···N4 distances are 2.643 (5) and 2.665 (6) Å, respectively, indicating strong hydrogen bonds. The two C═O bonds, viz. C15—O2 and C8—O7, are 1.191 (6) and 1.218 (7) Å, respectively; these are much shorter than the other C—O bonds. It is interesting to note that two Zn^II atoms, two 4,4'-bipy molecules and two Hpht⁻ anions produce a 30-membered grid, with a Zn···Zn distance of 14.024 (7) Å, via coordination covalent bonds and hydrogen bonds. These grids, by sharing Zn^II atoms, extend to form double zigzag chains propagating along the c axis (Fig. 2). In contrast with other metal-organic frameworks constructed with 4,4'-bipy ligands and H₂pht (Ma et al., 2003; Lightfoot et al., 1999; Suresh et al., 2001), 4,4'-bipy acts as a terminal ligand in (I) instead of as a µ₂ bridging ligand and this results in a different structural topology. This also suggests that the combination of coordination covalent bonds and hydrogen bonds is an important tool for the construction of supramolecular architectures.

S2. Experimental

A mixture of ZnSO₄·7H₂O (0.144 g, 0.5 mmol), 4,4'-bipy (0.080 g, 0.5 mmol) and H₂pht (0.166 g, 0.5 mmol) in EtOH-H₂O (1:8 v/v, 18 ml) was sealed in a Teflon-lined stainless steel vessel and heated to 438 K for 36 h under autogeneous pressure. A large quantity of colourless crystals of (I) (yield 56%) was obtained after the solution had cooled to room temperature.

S3. Refinement

H atoms bonded to C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. H atoms bonded to O atoms were located from difference maps and refined isotropically, with O—H distances fixed at constrained to? 0.83 Å. Please clarify, as U_iso(H) for these atoms have no s.u. but the xyz values do.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL (Siemens, 1994); molecular graphics: SHELXTL (Bruker, 2???); software used to prepare material for publication: SHELXTL (Bruekr, 2???).

Figures

	Fig. 1. A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The double zigzag chains formed along the c axis of the crystal of (I), with hydrogen bonds shown as dotted lines.

Bis(4,4'-bipyridine-κN)bis(hydrogen phthlato)-κ²O,O';κO-zinc(II)

Crystal data

[Zn(C8H5O4)2(C10H8N2)2]	Z = 2
Mr = 708.00	F(000) = 728
Triclinic, P1	Dx = 1.507 Mg m^−3
a = 7.5100 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0003 (4) Å	Cell parameters from 3960 reflections
c = 22.0821 (6) Å	θ = 0.9–25.0°
α = 84.307 (1)°	µ = 0.85 mm^−1
β = 88.084 (1)°	T = 293 K
γ = 71.02°	Block, colourless
V = 1560.52 (10) Å^3	0.56 × 0.26 × 0.18 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5502 independent reflections
Radiation source: fine-focus sealed tube	4273 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ϕ and ω scans	θmax = 25.0°, θmin = 0.9°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −5→8
Tmin = 0.767, Tmax = 0.858	k = −11→11
8036 measured reflections	l = −23→26

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.177	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0795P)^2 + 3.685P] where P = (Fo^2 + 2Fc^2)/3
5390 reflections	(Δ/σ)max < 0.001
448 parameters	Δρmax = 0.75 e Å^−3
2 restraints	Δρmin = −0.64 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
Zn	−0.03938 (8)	0.02585 (6)	0.24332 (3)	0.0370 (2)
O1	−0.3487 (5)	0.2747 (4)	0.04990 (18)	0.0531 (10)
H1O	−0.252 (6)	0.256 (7)	0.029 (3)	0.080*
O2	−0.2576 (6)	0.4372 (4)	0.0898 (2)	0.0628 (11)
O3	−0.2063 (5)	0.1770 (4)	0.18365 (18)	0.0527 (10)
O4	−0.3228 (6)	0.2180 (5)	0.27532 (19)	0.0704 (13)
O5	−0.1663 (7)	−0.1117 (5)	0.2627 (2)	0.0776 (14)
O6	0.1031 (6)	−0.2595 (5)	0.2995 (2)	0.0719 (13)
O7	0.1530 (7)	−0.4698 (5)	0.4371 (3)	0.0869 (17)
O8	−0.0226 (6)	−0.2435 (4)	0.4306 (2)	0.0579 (11)
H8O	0.063 (7)	−0.235 (8)	0.451 (3)	0.087*
N1	0.1197 (5)	0.0692 (4)	0.30784 (18)	0.0380 (9)
N2	0.1847 (5)	−0.0401 (4)	0.18159 (18)	0.0360 (9)
N3	1.0287 (6)	−0.2187 (5)	0.01152 (19)	0.0439 (10)
N4	0.7700 (6)	0.1941 (5)	0.5006 (2)	0.0471 (11)
C1	−0.1755 (6)	−0.3210 (5)	0.3194 (2)	0.0359 (11)
C2	−0.3189 (8)	−0.3402 (6)	0.2875 (3)	0.0501 (14)
H2A	−0.3530	−0.2910	0.2495	0.060*
C3	−0.4119 (8)	−0.4315 (6)	0.3114 (3)	0.0559 (15)
H3B	−0.5074	−0.4442	0.2893	0.067*
C4	−0.3639 (8)	−0.5043 (6)	0.3682 (3)	0.0556 (15)
H4B	−0.4271	−0.5659	0.3842	0.067*
C5	−0.2221 (7)	−0.4854 (6)	0.4009 (3)	0.0461 (13)
H5A	−0.1891	−0.5344	0.4391	0.055*
C6	−0.1282 (6)	−0.3929 (5)	0.3767 (2)	0.0363 (11)
C7	−0.0692 (8)	−0.2228 (6)	0.2924 (2)	0.0485 (13)
C8	0.0191 (7)	−0.3727 (6)	0.4157 (3)	0.0448 (12)
C9	−0.5308 (6)	0.3906 (5)	0.1296 (2)	0.0345 (11)
C10	−0.7072 (7)	0.4714 (5)	0.1054 (2)	0.0427 (12)
H10A	−0.7178	0.5052	0.0645	0.051*
C11	−0.8652 (8)	0.5013 (6)	0.1419 (3)	0.0548 (15)
H11A	−0.9819	0.5546	0.1253	0.066*
C12	−0.8514 (8)	0.4529 (6)	0.2025 (3)	0.0539 (15)
H12A	−0.9582	0.4733	0.2270	0.065*
C13	−0.6774 (8)	0.3734 (6)	0.2269 (3)	0.0485 (13)
H13A	−0.6685	0.3422	0.2681	0.058*
C14	−0.5157 (7)	0.3391 (5)	0.1912 (2)	0.0365 (11)
C15	−0.3610 (6)	0.3690 (5)	0.0885 (2)	0.0372 (11)
C16	−0.3358 (7)	0.2394 (6)	0.2194 (2)	0.0432 (12)
C17	0.5858 (8)	0.2496 (6)	0.5103 (3)	0.0532 (14)
H17A	0.5461	0.3065	0.5422	0.064*
C18	0.4508 (7)	0.2272 (6)	0.4756 (2)	0.0455 (13)
H18A	0.3237	0.2674	0.4844	0.055*
C19	0.5071 (7)	0.1442 (5)	0.4276 (2)	0.0343 (10)
C20	0.6991 (7)	0.0864 (6)	0.4171 (2)	0.0415 (12)
H20A	0.7429	0.0298	0.3853	0.050*
C21	0.8233 (7)	0.1141 (6)	0.4543 (2)	0.0432 (12)
H21A	0.9515	0.0748	0.4468	0.052*
C22	0.2865 (7)	−0.0299 (6)	0.3229 (3)	0.0490 (14)
H22A	0.3175	−0.1166	0.3065	0.059*
C23	0.4125 (7)	−0.0091 (6)	0.3614 (3)	0.0466 (13)
H23A	0.5265	−0.0802	0.3702	0.056*
C24	0.3686 (7)	0.1185 (5)	0.3869 (2)	0.0366 (11)
C25	0.1957 (7)	0.2197 (5)	0.3728 (2)	0.0400 (11)
H25A	0.1598	0.3058	0.3899	0.048*
C26	0.0778 (7)	0.1918 (5)	0.3332 (2)	0.0392 (11)
H26A	−0.0368	0.2616	0.3236	0.047*
C27	0.9891 (7)	−0.1216 (6)	0.0519 (2)	0.0416 (12)
H27A	1.0782	−0.0781	0.0584	0.050*
C28	0.8236 (7)	−0.0829 (6)	0.0842 (2)	0.0421 (12)
H28A	0.8020	−0.0154	0.1121	0.051*
C29	0.6884 (7)	−0.1467 (5)	0.0746 (2)	0.0349 (11)
C30	0.7283 (7)	−0.2469 (5)	0.0325 (2)	0.0410 (12)
H30A	0.6419	−0.2918	0.0248	0.049*
C31	0.8999 (8)	−0.2785 (6)	0.0023 (2)	0.0451 (13)
H31A	0.9256	−0.3454	−0.0260	0.054*
C32	0.2494 (8)	0.0605 (6)	0.1542 (3)	0.0482 (13)
H32A	0.1826	0.1550	0.1591	0.058*
C33	0.4096 (7)	0.0309 (5)	0.1193 (2)	0.0438 (12)
H33A	0.4507	0.1043	0.1018	0.053*
C34	0.5102 (7)	−0.1091 (5)	0.1101 (2)	0.0365 (11)
C35	0.4399 (7)	−0.2137 (5)	0.1366 (2)	0.0394 (11)
H35A	0.5000	−0.3085	0.1305	0.047*
C36	0.2796 (6)	−0.1751 (5)	0.1723 (2)	0.0370 (11)
H36A	0.2357	−0.2462	0.1907	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0303 (3)	0.0421 (4)	0.0388 (3)	−0.0113 (2)	−0.0027 (2)	−0.0049 (2)
O1	0.044 (2)	0.068 (3)	0.055 (2)	−0.024 (2)	0.0167 (18)	−0.025 (2)
O2	0.054 (2)	0.058 (2)	0.088 (3)	−0.033 (2)	0.023 (2)	−0.018 (2)
O3	0.039 (2)	0.051 (2)	0.056 (2)	0.0016 (18)	−0.0045 (18)	−0.0002 (18)
O4	0.063 (3)	0.091 (3)	0.048 (3)	−0.013 (2)	−0.016 (2)	0.003 (2)
O5	0.067 (3)	0.070 (3)	0.100 (4)	−0.036 (3)	−0.011 (3)	0.023 (3)
O6	0.045 (3)	0.093 (3)	0.085 (3)	−0.037 (2)	−0.004 (2)	0.005 (3)
O7	0.071 (3)	0.055 (3)	0.124 (4)	0.000 (2)	−0.051 (3)	−0.015 (3)
O8	0.051 (2)	0.047 (2)	0.074 (3)	−0.0064 (19)	−0.026 (2)	−0.020 (2)
N1	0.030 (2)	0.040 (2)	0.041 (2)	−0.0066 (18)	−0.0020 (17)	−0.0068 (18)
N2	0.033 (2)	0.038 (2)	0.037 (2)	−0.0115 (18)	0.0013 (17)	−0.0046 (18)
N3	0.039 (2)	0.055 (3)	0.038 (2)	−0.015 (2)	0.0047 (19)	−0.004 (2)
N4	0.046 (3)	0.051 (3)	0.048 (3)	−0.021 (2)	−0.010 (2)	−0.004 (2)
C1	0.027 (2)	0.035 (3)	0.043 (3)	−0.005 (2)	0.003 (2)	−0.009 (2)
C2	0.044 (3)	0.052 (3)	0.049 (3)	−0.009 (3)	−0.012 (2)	−0.002 (3)
C3	0.037 (3)	0.054 (3)	0.082 (4)	−0.018 (3)	−0.008 (3)	−0.021 (3)
C4	0.047 (3)	0.039 (3)	0.087 (5)	−0.022 (3)	0.005 (3)	−0.007 (3)
C5	0.043 (3)	0.043 (3)	0.054 (3)	−0.018 (2)	0.004 (2)	−0.002 (2)
C6	0.030 (2)	0.034 (3)	0.046 (3)	−0.008 (2)	0.001 (2)	−0.012 (2)
C7	0.053 (4)	0.052 (3)	0.041 (3)	−0.018 (3)	0.004 (3)	0.000 (3)
C8	0.036 (3)	0.045 (3)	0.053 (3)	−0.011 (2)	−0.003 (2)	−0.010 (3)
C9	0.028 (2)	0.029 (2)	0.047 (3)	−0.009 (2)	0.000 (2)	−0.007 (2)
C10	0.035 (3)	0.039 (3)	0.048 (3)	−0.005 (2)	−0.004 (2)	−0.001 (2)
C11	0.035 (3)	0.044 (3)	0.078 (4)	−0.002 (2)	−0.007 (3)	−0.007 (3)
C12	0.033 (3)	0.052 (3)	0.075 (4)	−0.010 (3)	0.015 (3)	−0.022 (3)
C13	0.047 (3)	0.055 (3)	0.044 (3)	−0.016 (3)	0.005 (2)	−0.009 (3)
C14	0.030 (2)	0.038 (3)	0.043 (3)	−0.012 (2)	−0.001 (2)	−0.008 (2)
C15	0.026 (2)	0.035 (3)	0.050 (3)	−0.011 (2)	0.004 (2)	−0.001 (2)
C16	0.040 (3)	0.043 (3)	0.050 (3)	−0.017 (2)	−0.008 (2)	−0.003 (2)
C17	0.051 (3)	0.058 (4)	0.051 (3)	−0.013 (3)	−0.002 (3)	−0.023 (3)
C18	0.034 (3)	0.052 (3)	0.049 (3)	−0.008 (2)	0.000 (2)	−0.018 (3)
C19	0.036 (3)	0.032 (2)	0.035 (3)	−0.011 (2)	−0.001 (2)	−0.001 (2)
C20	0.038 (3)	0.050 (3)	0.037 (3)	−0.015 (2)	0.000 (2)	−0.011 (2)
C21	0.034 (3)	0.052 (3)	0.045 (3)	−0.016 (2)	−0.001 (2)	−0.002 (2)
C22	0.040 (3)	0.043 (3)	0.062 (4)	−0.005 (2)	−0.013 (3)	−0.020 (3)
C23	0.035 (3)	0.041 (3)	0.059 (3)	−0.002 (2)	−0.011 (2)	−0.013 (3)
C24	0.032 (3)	0.042 (3)	0.038 (3)	−0.016 (2)	0.000 (2)	−0.003 (2)
C25	0.032 (3)	0.039 (3)	0.047 (3)	−0.007 (2)	0.001 (2)	−0.012 (2)
C26	0.028 (2)	0.041 (3)	0.044 (3)	−0.005 (2)	0.000 (2)	−0.006 (2)
C27	0.038 (3)	0.052 (3)	0.039 (3)	−0.022 (2)	0.001 (2)	−0.002 (2)
C28	0.045 (3)	0.048 (3)	0.036 (3)	−0.018 (2)	0.002 (2)	−0.009 (2)
C29	0.033 (3)	0.037 (3)	0.034 (2)	−0.010 (2)	0.002 (2)	−0.002 (2)
C30	0.036 (3)	0.041 (3)	0.047 (3)	−0.012 (2)	0.002 (2)	−0.010 (2)
C31	0.047 (3)	0.042 (3)	0.042 (3)	−0.009 (2)	0.005 (2)	−0.011 (2)
C32	0.046 (3)	0.037 (3)	0.058 (3)	−0.007 (2)	0.009 (3)	−0.015 (2)
C33	0.044 (3)	0.035 (3)	0.054 (3)	−0.015 (2)	0.010 (2)	−0.006 (2)
C34	0.034 (3)	0.039 (3)	0.034 (3)	−0.009 (2)	−0.003 (2)	−0.003 (2)
C35	0.036 (3)	0.033 (3)	0.046 (3)	−0.005 (2)	0.002 (2)	−0.008 (2)
C36	0.031 (2)	0.034 (3)	0.046 (3)	−0.012 (2)	−0.002 (2)	−0.002 (2)

Geometric parameters (Å, º)

Zn—O5	1.921 (4)	C11—C12	1.373 (9)
Zn—O3	2.019 (4)	C11—H11A	0.9300
Zn—N1	2.054 (4)	C12—C13	1.384 (8)
Zn—N2	2.104 (4)	C12—H12A	0.9300
Zn—O4	2.496 (5)	C13—C14	1.390 (7)
Zn—C16	2.561 (5)	C13—H13A	0.9300
O1—C15	1.313 (6)	C14—C16	1.505 (7)
O1—H1O	0.83 (6)	C17—C18	1.377 (7)
O2—C15	1.191 (6)	C17—H17A	0.9300
O3—C16	1.269 (6)	C18—C19	1.381 (7)
O4—C16	1.234 (6)	C18—H18A	0.9300
O5—C7	1.248 (7)	C19—C20	1.389 (7)
O6—C7	1.236 (7)	C19—C24	1.496 (7)
O7—C8	1.218 (7)	C20—C21	1.373 (7)
O8—C8	1.301 (6)	C20—H20A	0.9300
O8—H8O	0.83 (6)	C21—H21A	0.9300
N1—C26	1.337 (6)	C22—C23	1.369 (7)
N1—C22	1.348 (6)	C22—H22A	0.9300
N2—C36	1.338 (6)	C23—C24	1.383 (7)
N2—C32	1.339 (7)	C23—H23A	0.9300
N3—C31	1.323 (7)	C24—C25	1.385 (7)
N3—C27	1.339 (7)	C25—C26	1.373 (7)
N4—C21	1.331 (7)	C25—H25A	0.9300
N4—C17	1.331 (7)	C26—H26A	0.9300
C1—C2	1.380 (7)	C27—C28	1.374 (7)
C1—C6	1.388 (7)	C27—H27A	0.9300
C1—C7	1.523 (7)	C28—C29	1.395 (7)
C2—C3	1.376 (8)	C28—H28A	0.9300
C2—H2A	0.9300	C29—C30	1.388 (7)
C3—C4	1.382 (9)	C29—C34	1.486 (6)
C3—H3B	0.9300	C30—C31	1.387 (7)
C4—C5	1.380 (8)	C30—H30A	0.9300
C4—H4B	0.9300	C31—H31A	0.9300
C5—C6	1.393 (7)	C32—C33	1.371 (7)
C5—H5A	0.9300	C32—H32A	0.9300
C6—C8	1.500 (7)	C33—C34	1.390 (7)
C9—C14	1.399 (7)	C33—H33A	0.9300
C9—C10	1.399 (7)	C34—C35	1.390 (7)
C9—C15	1.510 (6)	C35—C36	1.383 (7)
C10—C11	1.377 (8)	C35—H35A	0.9300
C10—H10A	0.9300	C36—H36A	0.9300
O5—Zn—O3	106.29 (19)	O2—C15—O1	124.9 (5)
O5—Zn—N1	120.43 (19)	O2—C15—C9	122.3 (5)
O3—Zn—N1	123.09 (16)	O1—C15—C9	112.6 (4)
O5—Zn—N2	113.3 (2)	O4—C16—O3	123.1 (5)
O3—Zn—N2	94.71 (15)	O4—C16—C14	119.4 (5)
N1—Zn—N2	94.83 (16)	O3—C16—C14	117.4 (5)
O5—Zn—O4	90.3 (2)	O4—C16—Zn	73.0 (3)
O3—Zn—O4	57.19 (14)	O3—C16—Zn	51.0 (2)
N1—Zn—O4	90.31 (15)	C14—C16—Zn	163.3 (4)
N2—Zn—O4	148.40 (16)	N4—C17—C18	123.5 (5)
O5—Zn—C16	96.55 (19)	N4—C17—H17A	118.2
O3—Zn—C16	29.22 (16)	C18—C17—H17A	118.2
N1—Zn—C16	110.22 (16)	C17—C18—C19	119.1 (5)
N2—Zn—C16	123.44 (17)	C17—C18—H18A	120.5
O4—Zn—C16	28.22 (15)	C19—C18—H18A	120.5
C15—O1—H1O	114 (5)	C18—C19—C20	117.7 (5)
C16—O3—Zn	99.8 (3)	C18—C19—C24	122.1 (4)
C16—O4—Zn	78.8 (3)	C20—C19—C24	120.2 (4)
C7—O5—Zn	114.3 (4)	C21—C20—C19	119.1 (5)
C8—O8—H8O	111 (5)	C21—C20—H20A	120.4
C26—N1—C22	116.9 (4)	C19—C20—H20A	120.4
C26—N1—Zn	125.4 (3)	N4—C21—C20	123.5 (5)
C22—N1—Zn	117.5 (3)	N4—C21—H21A	118.3
C36—N2—C32	117.4 (4)	C20—C21—H21A	118.3
C36—N2—Zn	125.4 (3)	N1—C22—C23	123.2 (5)
C32—N2—Zn	116.9 (3)	N1—C22—H22A	118.4
C31—N3—C27	117.7 (4)	C23—C22—H22A	118.4
C21—N4—C17	117.1 (4)	C22—C23—C24	119.4 (5)
C2—C1—C6	119.1 (5)	C22—C23—H23A	120.3
C2—C1—C7	120.8 (5)	C24—C23—H23A	120.3
C6—C1—C7	120.0 (4)	C23—C24—C25	117.7 (4)
C3—C2—C1	120.8 (5)	C23—C24—C19	120.0 (4)
C3—C2—H2A	119.6	C25—C24—C19	122.2 (4)
C1—C2—H2A	119.6	C26—C25—C24	119.5 (5)
C2—C3—C4	120.3 (5)	C26—C25—H25A	120.3
C2—C3—H3B	119.9	C24—C25—H25A	120.3
C4—C3—H3B	119.9	N1—C26—C25	123.2 (4)
C5—C4—C3	119.8 (5)	N1—C26—H26A	118.4
C5—C4—H4B	120.1	C25—C26—H26A	118.4
C3—C4—H4B	120.1	N3—C27—C28	123.3 (5)
C4—C5—C6	119.9 (5)	N3—C27—H27A	118.3
C4—C5—H5A	120.1	C28—C27—H27A	118.3
C6—C5—H5A	120.1	C27—C28—C29	118.9 (5)
C1—C6—C5	120.2 (5)	C27—C28—H28A	120.6
C1—C6—C8	122.7 (5)	C29—C28—H28A	120.6
C5—C6—C8	117.2 (5)	C30—C29—C28	118.0 (4)
O6—C7—O5	125.3 (6)	C30—C29—C34	122.1 (4)
O6—C7—C1	119.0 (5)	C28—C29—C34	119.8 (4)
O5—C7—C1	115.7 (5)	C31—C30—C29	118.6 (5)
O7—C8—O8	122.8 (5)	C31—C30—H30A	120.7
O7—C8—C6	123.7 (5)	C29—C30—H30A	120.7
O8—C8—C6	113.0 (4)	N3—C31—C30	123.5 (5)
C14—C9—C10	119.6 (4)	N3—C31—H31A	118.3
C14—C9—C15	122.3 (4)	C30—C31—H31A	118.3
C10—C9—C15	118.0 (4)	N2—C32—C33	123.2 (5)
C11—C10—C9	120.5 (5)	N2—C32—H32A	118.4
C11—C10—H10A	119.8	C33—C32—H32A	118.4
C9—C10—H10A	119.8	C32—C33—C34	119.7 (5)
C12—C11—C10	120.4 (5)	C32—C33—H33A	120.2
C12—C11—H11A	119.8	C34—C33—H33A	120.2
C10—C11—H11A	119.8	C35—C34—C33	117.4 (4)
C11—C12—C13	119.6 (5)	C35—C34—C29	121.0 (4)
C11—C12—H12A	120.2	C33—C34—C29	121.6 (4)
C13—C12—H12A	120.2	C36—C35—C34	119.3 (4)
C12—C13—C14	121.5 (5)	C36—C35—H35A	120.4
C12—C13—H13A	119.2	C34—C35—H35A	120.4
C14—C13—H13A	119.2	N2—C36—C35	123.0 (5)
C13—C14—C9	118.5 (5)	N2—C36—H36A	118.5
C13—C14—C16	118.4 (5)	C35—C36—H36A	118.5
C9—C14—C16	123.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N3^i	0.83 (6)	1.82 (6)	2.643 (5)	175 (7)
O8—H8O···N4^ii	0.83 (6)	1.84 (6)	2.665 (6)	172 (8)

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