Synthesis, structural analysis, and docking studies with SARS-CoV-2 of a trinuclear zinc com­plex with N-phenyl­anthranilic acid ligands

The structure of a trinuclear zinc com­plex, hexa­kis­(μ₂-2-anilinobenzoato)di­aqua­trizinc(II), [Zn₂(C₁₃H₁₀NO₂)₆(H₂O)₂] or (NPA)₆Zn₃(H₂O)₂ (NPA is 2-anil­inobenzoate or N-phenyl­anthranilate), is reported. The com­plex crystallizes in the triclinic space group P and the central Zn^II atom is located on an inversion center. The NPA ligand is found to coordinate via the car­box­yl­ate O atoms with unique C—O bond lengths that support an unequal distribution of resonance over the car­box­yl­ate fragment. The axial H₂O ligands form hydrogen bonds with neighboring mol­ecules that stabilize the supra­molecular system in rigid straight chains, with an angle of 180° along the c axis. π stacking is the primary stabilization along the a and b axes, resulting in a highly ordered supra­molecular structure. Docking studies show that this unique supra­molecular structure of a trinuclear zinc com­plex has potential for binding to the main protease (M^pro) in SARS-CoV-2 in a different location from Remdesivir, but with a similar binding strength.

Computing details

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Hexakis(µ₂-2-anilinobenzoato)diaquatrizinc(II)

Crystal data

[Zn3(C13H10NO2)6(H2O)2]	Z = 1
Mr = 1505.46	F(000) = 776
Triclinic, P1	Dx = 1.521 Mg m^−3
a = 11.0968 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.8319 (6) Å	Cell parameters from 9800 reflections
c = 13.3134 (6) Å	θ = 2.5–38.9°
α = 111.703 (2)°	µ = 1.16 mm^−1
β = 108.028 (2)°	T = 100 K
γ = 93.125 (2)°	Prism, clear colourless
V = 1643.97 (13) Å^3	0.3 × 0.1 × 0.03 mm

Data collection

Bruker Kappa Venture D8 diffractometer	10025 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	8556 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.044
Detector resolution: 7.9 pixels mm^-1	θmax = 30.5°, θmin = 2.9°
ω and φ scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2017)	k = −18→18
Tmin = 0.664, Tmax = 0.748	l = −19→19
86106 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0319P)^2 + 1.352P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
10025 reflections	Δρmax = 0.65 e Å^−3
477 parameters	Δρmin = −0.84 e Å^−3
0 restraints

Special details

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. (NPA)₆Zn₃(H₂O)₂ was mounted on a Bruker Kappa Venture D8 instrument on a Kapton sample holder that was then placed in a liquid nitrogen stream to cool the sample down to 100 K. The sample was run with a molybdenum micro source (Mo Kα, λ= 0.71073 Å) using a Photon II detector. The unit cell of was determined prior to full data collection, and data were integrated using the Bruker SAINT program using SADABS for absorption correction. Structural refinement was conducted using APEX3 and OLEX2 software that interfaced with the SHELXL PC Suite (Dolomanov et al., 2009; Sheldrick, Sheldrick, 2015b). All non-H atoms were refined using anisotropic thermal parameters.

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

	x	y	z	Uiso*/Ueq
Zn1	0.21623 (2)	0.57673 (2)	0.53262 (2)	0.01224 (4)
Zn2	0.500000	0.500000	0.500000	0.01101 (5)
O3	0.18796 (10)	0.46312 (9)	0.59622 (9)	0.01493 (19)
O5	0.33767 (10)	0.71566 (9)	0.63184 (9)	0.0163 (2)
O6	0.50591 (10)	0.67473 (9)	0.57499 (9)	0.0156 (2)
O4	0.38584 (10)	0.46623 (9)	0.59513 (10)	0.0169 (2)
O7	0.05686 (11)	0.64469 (11)	0.54001 (12)	0.0257 (3)
O2	0.34886 (11)	0.47459 (10)	0.35584 (9)	0.0199 (2)
O1	0.15384 (11)	0.48147 (10)	0.36899 (9)	0.0207 (2)
N2	0.52659 (12)	0.32556 (11)	0.66916 (12)	0.0165 (2)
N3	0.70966 (13)	0.84458 (12)	0.65803 (12)	0.0209 (3)
N1	−0.05046 (13)	0.40036 (14)	0.17526 (12)	0.0248 (3)
C29	0.47282 (14)	0.91895 (12)	0.80522 (13)	0.0152 (3)
H29	0.392254	0.886158	0.802241	0.018*
C28	0.52736 (13)	0.85540 (11)	0.72560 (12)	0.0128 (2)
C16	0.41632 (13)	0.28630 (12)	0.68010 (12)	0.0137 (2)
C33	0.64919 (14)	0.90238 (12)	0.73231 (12)	0.0154 (3)
C2	0.16772 (14)	0.37100 (13)	0.18719 (12)	0.0165 (3)
C26	0.75406 (14)	0.31903 (13)	0.72482 (13)	0.0169 (3)
H26	0.771698	0.394102	0.783266	0.020*
C3	0.03344 (14)	0.35001 (13)	0.12401 (12)	0.0169 (3)
C21	0.62687 (14)	0.26427 (13)	0.65586 (13)	0.0153 (3)
C30	0.53243 (15)	1.02765 (12)	0.88784 (13)	0.0175 (3)
H30	0.494528	1.068533	0.941905	0.021*
C32	0.70667 (15)	1.01528 (13)	0.81453 (14)	0.0203 (3)
H32	0.786401	1.049860	0.817622	0.024*
C7	0.24937 (16)	0.31571 (15)	0.13244 (14)	0.0225 (3)
H7	0.339316	0.331356	0.175194	0.027*
C17	0.41055 (15)	0.19384 (13)	0.71268 (14)	0.0183 (3)
H17	0.481000	0.154891	0.720440	0.022*
C22	0.60164 (15)	0.15393 (14)	0.57133 (14)	0.0201 (3)
H22	0.515144	0.116452	0.523614	0.024*
C19	0.19940 (15)	0.21460 (15)	0.72331 (15)	0.0228 (3)
H19	0.127418	0.191002	0.739352	0.027*
C18	0.30479 (16)	0.15924 (15)	0.73335 (15)	0.0218 (3)
H18	0.303180	0.096516	0.754887	0.026*
C20	0.20171 (14)	0.30396 (14)	0.68974 (13)	0.0182 (3)
H20	0.130606	0.342222	0.683176	0.022*
C15	0.30715 (13)	0.33982 (12)	0.66494 (12)	0.0138 (2)
C25	0.85502 (15)	0.26398 (14)	0.70820 (15)	0.0215 (3)
H25	0.941724	0.302140	0.754172	0.026*
C34	0.84477 (15)	0.86983 (13)	0.68544 (15)	0.0193 (3)
C14	0.29532 (13)	0.42742 (12)	0.61725 (12)	0.0129 (2)
C31	0.64947 (15)	1.07621 (13)	0.89027 (14)	0.0201 (3)
H31	0.690087	1.151989	0.944656	0.024*
C4	−0.01196 (15)	0.27355 (14)	0.00644 (13)	0.0195 (3)
H4	−0.101030	0.259682	−0.038487	0.023*
C27	0.45353 (13)	0.74034 (12)	0.63763 (12)	0.0129 (2)
C24	0.82974 (16)	0.15365 (15)	0.62484 (16)	0.0247 (3)
H24	0.898868	0.115683	0.614252	0.030*
C1	0.22793 (14)	0.44702 (12)	0.31205 (12)	0.0161 (3)
C23	0.70285 (17)	0.09865 (15)	0.55673 (16)	0.0248 (3)
H23	0.685355	0.022754	0.499856	0.030*
C5	0.07081 (16)	0.21858 (15)	−0.04435 (13)	0.0224 (3)
H5	0.037349	0.165888	−0.123144	0.027*
C35	0.93108 (17)	0.88179 (14)	0.79226 (17)	0.0273 (4)
H35	0.899654	0.873909	0.848340	0.033*
C9	−0.27061 (16)	0.33864 (14)	0.15414 (14)	0.0224 (3)
H9	−0.238626	0.311924	0.213239	0.027*
C8	−0.18516 (15)	0.38650 (14)	0.11840 (13)	0.0207 (3)
C6	0.20304 (17)	0.23893 (16)	0.01791 (15)	0.0268 (3)
H6	0.259623	0.200922	−0.017628	0.032*
C10	−0.40284 (17)	0.32986 (15)	0.10340 (16)	0.0274 (4)
H10	−0.460956	0.299287	0.129504	0.033*
C39	0.89097 (18)	0.88128 (14)	0.60371 (17)	0.0258 (3)
H39	0.832464	0.873032	0.530741	0.031*
C13	−0.23263 (17)	0.42410 (16)	0.03090 (15)	0.0265 (3)
H13	−0.174607	0.457781	0.006907	0.032*
C11	−0.44982 (17)	0.36558 (17)	0.01499 (16)	0.0312 (4)
H11	−0.540240	0.358033	−0.020802	0.037*
C12	−0.36467 (18)	0.41245 (18)	−0.02135 (16)	0.0309 (4)
H12	−0.396992	0.436662	−0.082321	0.037*
C36	1.06257 (19)	0.90516 (17)	0.8164 (2)	0.0407 (5)
H36	1.121435	0.913366	0.889251	0.049*
C38	1.0236 (2)	0.90494 (16)	0.6292 (2)	0.0392 (5)
H38	1.055534	0.913039	0.573478	0.047*
C37	1.10874 (19)	0.91665 (17)	0.7347 (3)	0.0463 (6)
H37	1.199117	0.932597	0.751558	0.056*
H3	0.671 (2)	0.7818 (19)	0.6117 (19)	0.022 (5)*
H2	0.533 (2)	0.386 (2)	0.6618 (19)	0.028 (6)*
H1	−0.023 (2)	0.436 (2)	0.247 (2)	0.030 (6)*
H7A	−0.026 (3)	0.615 (2)	0.494 (3)	0.055 (8)*
H7B	0.059 (3)	0.714 (3)	0.578 (2)	0.050 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00879 (7)	0.01233 (8)	0.01258 (8)	−0.00010 (5)	0.00274 (6)	0.00297 (6)
Zn2	0.00780 (10)	0.01103 (10)	0.01193 (10)	0.00122 (7)	0.00275 (8)	0.00293 (8)
O3	0.0114 (4)	0.0154 (5)	0.0185 (5)	0.0039 (4)	0.0047 (4)	0.0077 (4)
O5	0.0103 (4)	0.0150 (5)	0.0184 (5)	−0.0016 (4)	0.0047 (4)	0.0020 (4)
O6	0.0153 (5)	0.0124 (4)	0.0168 (5)	−0.0005 (4)	0.0075 (4)	0.0025 (4)
O4	0.0158 (5)	0.0182 (5)	0.0230 (5)	0.0051 (4)	0.0110 (4)	0.0115 (4)
O7	0.0115 (5)	0.0166 (5)	0.0392 (7)	0.0030 (4)	0.0039 (5)	0.0049 (5)
O2	0.0152 (5)	0.0220 (5)	0.0175 (5)	−0.0016 (4)	−0.0004 (4)	0.0084 (4)
O1	0.0172 (5)	0.0243 (6)	0.0132 (5)	−0.0028 (4)	0.0022 (4)	0.0032 (4)
N2	0.0115 (5)	0.0190 (6)	0.0252 (6)	0.0053 (5)	0.0086 (5)	0.0135 (5)
N3	0.0144 (6)	0.0165 (6)	0.0230 (6)	−0.0039 (5)	0.0095 (5)	−0.0027 (5)
N1	0.0155 (6)	0.0360 (8)	0.0114 (6)	0.0019 (6)	0.0021 (5)	0.0001 (6)
C29	0.0127 (6)	0.0144 (6)	0.0173 (6)	0.0016 (5)	0.0061 (5)	0.0047 (5)
C28	0.0108 (6)	0.0115 (6)	0.0136 (6)	0.0007 (5)	0.0027 (5)	0.0039 (5)
C16	0.0107 (6)	0.0174 (6)	0.0140 (6)	0.0024 (5)	0.0044 (5)	0.0076 (5)
C33	0.0118 (6)	0.0147 (6)	0.0162 (6)	−0.0003 (5)	0.0048 (5)	0.0029 (5)
C2	0.0149 (6)	0.0177 (6)	0.0136 (6)	−0.0009 (5)	0.0028 (5)	0.0054 (5)
C26	0.0138 (6)	0.0192 (7)	0.0198 (7)	0.0035 (5)	0.0055 (5)	0.0107 (6)
C3	0.0145 (6)	0.0192 (7)	0.0137 (6)	−0.0004 (5)	0.0036 (5)	0.0049 (5)
C21	0.0120 (6)	0.0200 (7)	0.0202 (7)	0.0062 (5)	0.0078 (5)	0.0126 (6)
C30	0.0179 (7)	0.0146 (6)	0.0170 (6)	0.0030 (5)	0.0069 (5)	0.0025 (5)
C32	0.0150 (7)	0.0159 (7)	0.0227 (7)	−0.0037 (5)	0.0065 (6)	0.0012 (6)
C7	0.0152 (7)	0.0283 (8)	0.0194 (7)	0.0011 (6)	0.0036 (6)	0.0074 (6)
C17	0.0150 (6)	0.0216 (7)	0.0225 (7)	0.0048 (5)	0.0064 (5)	0.0137 (6)
C22	0.0141 (6)	0.0226 (7)	0.0221 (7)	0.0035 (6)	0.0045 (6)	0.0092 (6)
C19	0.0158 (7)	0.0331 (9)	0.0286 (8)	0.0032 (6)	0.0106 (6)	0.0203 (7)
C18	0.0192 (7)	0.0263 (8)	0.0273 (8)	0.0036 (6)	0.0082 (6)	0.0190 (7)
C20	0.0135 (6)	0.0250 (7)	0.0213 (7)	0.0047 (5)	0.0083 (5)	0.0132 (6)
C15	0.0117 (6)	0.0161 (6)	0.0151 (6)	0.0023 (5)	0.0055 (5)	0.0074 (5)
C25	0.0120 (6)	0.0263 (8)	0.0285 (8)	0.0047 (6)	0.0057 (6)	0.0148 (7)
C34	0.0147 (7)	0.0127 (6)	0.0292 (8)	0.0004 (5)	0.0109 (6)	0.0048 (6)
C14	0.0115 (6)	0.0139 (6)	0.0118 (6)	0.0025 (5)	0.0044 (5)	0.0035 (5)
C31	0.0190 (7)	0.0144 (6)	0.0192 (7)	−0.0009 (5)	0.0047 (6)	0.0008 (5)
C4	0.0152 (7)	0.0232 (7)	0.0136 (6)	−0.0021 (6)	0.0028 (5)	0.0033 (6)
C27	0.0112 (6)	0.0130 (6)	0.0128 (6)	0.0006 (5)	0.0029 (5)	0.0048 (5)
C24	0.0183 (7)	0.0272 (8)	0.0349 (9)	0.0108 (6)	0.0135 (7)	0.0151 (7)
C1	0.0168 (7)	0.0149 (6)	0.0145 (6)	−0.0004 (5)	0.0021 (5)	0.0069 (5)
C23	0.0225 (8)	0.0220 (7)	0.0297 (8)	0.0072 (6)	0.0112 (7)	0.0084 (7)
C5	0.0206 (7)	0.0264 (8)	0.0135 (6)	−0.0002 (6)	0.0048 (6)	0.0025 (6)
C35	0.0219 (8)	0.0187 (7)	0.0367 (9)	0.0010 (6)	0.0053 (7)	0.0110 (7)
C9	0.0220 (7)	0.0215 (7)	0.0176 (7)	0.0034 (6)	0.0087 (6)	0.0003 (6)
C8	0.0146 (7)	0.0243 (7)	0.0136 (6)	0.0016 (6)	0.0038 (5)	−0.0011 (6)
C6	0.0212 (8)	0.0337 (9)	0.0211 (8)	0.0064 (7)	0.0088 (6)	0.0052 (7)
C10	0.0193 (8)	0.0256 (8)	0.0283 (8)	0.0018 (6)	0.0116 (7)	−0.0009 (7)
C39	0.0270 (8)	0.0187 (7)	0.0393 (10)	0.0077 (6)	0.0219 (8)	0.0112 (7)
C13	0.0227 (8)	0.0318 (9)	0.0191 (7)	0.0023 (7)	0.0061 (6)	0.0056 (7)
C11	0.0163 (7)	0.0332 (9)	0.0279 (9)	0.0066 (7)	0.0037 (6)	−0.0018 (7)
C12	0.0258 (9)	0.0375 (10)	0.0207 (8)	0.0102 (7)	0.0028 (7)	0.0065 (7)
C36	0.0194 (8)	0.0237 (9)	0.0672 (15)	0.0031 (7)	−0.0011 (9)	0.0195 (9)
C38	0.0336 (10)	0.0251 (9)	0.0799 (16)	0.0133 (8)	0.0415 (11)	0.0253 (10)
C37	0.0161 (8)	0.0241 (9)	0.105 (2)	0.0072 (7)	0.0233 (11)	0.0304 (11)

Geometric parameters (Å, º)

Zn1—O3	1.9920 (10)	C7—H7	0.9500
Zn1—O5	1.9063 (10)	C7—C6	1.381 (2)
Zn1—O7	2.0274 (12)	C17—H17	0.9500
Zn1—O1	1.9298 (11)	C17—C18	1.372 (2)
Zn2—O6^i	2.0775 (10)	C22—H22	0.9500
Zn2—O6	2.0775 (10)	C22—C23	1.386 (2)
Zn2—O4^i	2.1762 (10)	C19—H19	0.9500
Zn2—O4	2.1762 (10)	C19—C18	1.398 (2)
Zn2—O2	2.0219 (11)	C19—C20	1.378 (2)
Zn2—O2^i	2.0219 (11)	C18—H18	0.9500
O3—C14	1.2866 (17)	C20—H20	0.9500
O5—C27	1.2788 (17)	C20—C15	1.4080 (19)
O6—C27	1.2555 (17)	C15—C14	1.4752 (19)
O4—C14	1.2572 (17)	C25—H25	0.9500
O7—H7A	0.90 (3)	C25—C24	1.384 (2)
O7—H7B	0.84 (3)	C34—C35	1.394 (3)
O2—C1	1.2559 (18)	C34—C39	1.387 (2)
O1—C1	1.2742 (19)	C31—H31	0.9500
N2—C16	1.3674 (18)	C4—H4	0.9500
N2—C21	1.4151 (18)	C4—C5	1.379 (2)
N2—H2	0.81 (2)	C24—H24	0.9500
N3—C33	1.3787 (19)	C24—C23	1.390 (2)
N3—C34	1.4166 (19)	C23—H23	0.9500
N3—H3	0.80 (2)	C5—H5	0.9500
N1—C3	1.372 (2)	C5—C6	1.398 (2)
N1—C8	1.418 (2)	C35—H35	0.9500
N1—H1	0.83 (2)	C35—C36	1.383 (3)
C29—H29	0.9500	C9—H9	0.9500
C29—C28	1.4024 (19)	C9—C8	1.391 (2)
C29—C30	1.381 (2)	C9—C10	1.391 (2)
C28—C33	1.4126 (19)	C8—C13	1.389 (2)
C28—C27	1.4893 (19)	C6—H6	0.9500
C16—C17	1.410 (2)	C10—H10	0.9500
C16—C15	1.4220 (19)	C10—C11	1.383 (3)
C33—C32	1.414 (2)	C39—H39	0.9500
C2—C3	1.419 (2)	C39—C38	1.393 (3)
C2—C7	1.397 (2)	C13—H13	0.9500
C2—C1	1.484 (2)	C13—C12	1.386 (2)
C26—H26	0.9500	C11—H11	0.9500
C26—C21	1.393 (2)	C11—C12	1.387 (3)
C26—C25	1.388 (2)	C12—H12	0.9500
C3—C4	1.410 (2)	C36—H36	0.9500
C21—C22	1.390 (2)	C36—C37	1.387 (4)
C30—H30	0.9500	C38—H38	0.9500
C30—C31	1.395 (2)	C38—C37	1.377 (4)
C32—H32	0.9500	C37—H37	0.9500
C32—C31	1.378 (2)
O3—Zn1—O7	97.20 (5)	C18—C19—H19	120.6
O5—Zn1—O3	118.92 (5)	C20—C19—H19	120.6
O5—Zn1—O7	95.94 (5)	C20—C19—C18	118.87 (14)
O5—Zn1—O1	135.15 (5)	C17—C18—C19	121.21 (14)
O1—Zn1—O3	101.15 (5)	C17—C18—H18	119.4
O1—Zn1—O7	98.30 (5)	C19—C18—H18	119.4
O6^i—Zn2—O6	180.0	C19—C20—H20	119.3
O6^i—Zn2—O4	87.99 (4)	C19—C20—C15	121.44 (14)
O6—Zn2—O4	92.00 (4)	C15—C20—H20	119.3
O6—Zn2—O4^i	88.00 (4)	C16—C15—C14	122.83 (12)
O6^i—Zn2—O4^i	92.00 (4)	C20—C15—C16	119.33 (13)
O4^i—Zn2—O4	180.00 (4)	C20—C15—C14	117.73 (13)
O2^i—Zn2—O6^i	93.86 (4)	C26—C25—H25	119.9
O2—Zn2—O6^i	86.14 (4)	C24—C25—C26	120.20 (15)
O2^i—Zn2—O6	86.14 (4)	C24—C25—H25	119.9
O2—Zn2—O6	93.85 (4)	C35—C34—N3	120.97 (15)
O2—Zn2—O4	96.22 (4)	C39—C34—N3	119.10 (16)
O2^i—Zn2—O4	83.78 (4)	C39—C34—C35	119.92 (16)
O2^i—Zn2—O4^i	96.22 (4)	O3—C14—C15	118.44 (12)
O2—Zn2—O4^i	83.78 (4)	O4—C14—O3	119.60 (13)
O2^i—Zn2—O2	180.0	O4—C14—C15	121.96 (12)
C14—O3—Zn1	104.17 (9)	C30—C31—H31	119.7
C27—O5—Zn1	127.60 (9)	C32—C31—C30	120.62 (14)
C27—O6—Zn2	137.10 (9)	C32—C31—H31	119.7
C14—O4—Zn2	161.37 (10)	C3—C4—H4	119.5
Zn1—O7—H7A	129.0 (18)	C5—C4—C3	121.07 (14)
Zn1—O7—H7B	123.9 (19)	C5—C4—H4	119.5
H7A—O7—H7B	106 (3)	O5—C27—C28	115.79 (12)
C1—O2—Zn2	142.24 (10)	O6—C27—O5	124.31 (13)
C1—O1—Zn1	123.40 (10)	O6—C27—C28	119.89 (12)
C16—N2—C21	125.40 (13)	C25—C24—H24	120.1
C16—N2—H2	118.8 (16)	C25—C24—C23	119.74 (15)
C21—N2—H2	115.4 (16)	C23—C24—H24	120.1
C33—N3—C34	122.70 (13)	O2—C1—O1	123.47 (14)
C33—N3—H3	114.7 (15)	O2—C1—C2	118.44 (14)
C34—N3—H3	118.4 (15)	O1—C1—C2	118.09 (13)
C3—N1—C8	125.41 (13)	C22—C23—C24	120.36 (16)
C3—N1—H1	118.4 (16)	C22—C23—H23	119.8
C8—N1—H1	115.7 (16)	C24—C23—H23	119.8
C28—C29—H29	118.9	C4—C5—H5	119.4
C30—C29—H29	118.9	C4—C5—C6	121.24 (15)
C30—C29—C28	122.13 (13)	C6—C5—H5	119.4
C29—C28—C33	119.06 (13)	C34—C35—H35	120.1
C29—C28—C27	118.00 (12)	C36—C35—C34	119.87 (19)
C33—C28—C27	122.94 (12)	C36—C35—H35	120.1
N2—C16—C17	120.21 (13)	C8—C9—H9	120.0
N2—C16—C15	121.75 (13)	C10—C9—H9	120.0
C17—C16—C15	117.98 (13)	C10—C9—C8	120.04 (17)
N3—C33—C28	122.43 (13)	C9—C8—N1	119.28 (15)
N3—C33—C32	119.45 (13)	C13—C8—N1	120.97 (15)
C28—C33—C32	118.03 (13)	C13—C8—C9	119.70 (15)
C3—C2—C1	123.36 (14)	C7—C6—C5	118.31 (15)
C7—C2—C3	119.75 (14)	C7—C6—H6	120.8
C7—C2—C1	116.86 (13)	C5—C6—H6	120.8
C21—C26—H26	120.0	C9—C10—H10	120.0
C25—C26—H26	120.0	C11—C10—C9	120.07 (17)
C25—C26—C21	120.06 (15)	C11—C10—H10	120.0
N1—C3—C2	121.58 (13)	C34—C39—H39	120.2
N1—C3—C4	120.70 (14)	C34—C39—C38	119.63 (19)
C4—C3—C2	117.71 (14)	C38—C39—H39	120.2
C26—C21—N2	118.72 (14)	C8—C13—H13	120.0
C22—C21—N2	121.48 (13)	C12—C13—C8	119.98 (17)
C22—C21—C26	119.69 (13)	C12—C13—H13	120.0
C29—C30—H30	120.7	C10—C11—H11	120.1
C29—C30—C31	118.65 (14)	C10—C11—C12	119.88 (16)
C31—C30—H30	120.7	C12—C11—H11	120.1
C33—C32—H32	119.3	C13—C12—C11	120.29 (18)
C31—C32—C33	121.37 (14)	C13—C12—H12	119.9
C31—C32—H32	119.3	C11—C12—H12	119.9
C2—C7—H7	119.1	C35—C36—H36	119.9
C6—C7—C2	121.88 (15)	C35—C36—C37	120.2 (2)
C6—C7—H7	119.1	C37—C36—H36	119.9
C16—C17—H17	119.5	C39—C38—H38	119.8
C18—C17—C16	121.07 (14)	C37—C38—C39	120.4 (2)
C18—C17—H17	119.5	C37—C38—H38	119.8
C21—C22—H22	120.0	C36—C37—H37	120.0
C23—C22—C21	119.94 (15)	C38—C37—C36	120.01 (18)
C23—C22—H22	120.0	C38—C37—H37	120.0
Zn1—O3—C14—O4	−0.51 (15)	C3—C4—C5—C6	−1.7 (3)
Zn1—O3—C14—C15	−179.36 (10)	C21—N2—C16—C17	18.7 (2)
Zn1—O5—C27—O6	1.2 (2)	C21—N2—C16—C15	−164.39 (14)
Zn1—O5—C27—C28	−178.84 (9)	C21—C26—C25—C24	−1.4 (2)
Zn1—O1—C1—O2	−2.4 (2)	C21—C22—C23—C24	−1.1 (3)
Zn1—O1—C1—C2	178.08 (10)	C30—C29—C28—C33	2.1 (2)
Zn2—O6—C27—O5	−34.5 (2)	C30—C29—C28—C27	−178.18 (14)
Zn2—O6—C27—C28	145.52 (11)	C7—C2—C3—N1	178.35 (16)
Zn2—O4—C14—O3	−71.0 (3)	C7—C2—C3—C4	−0.5 (2)
Zn2—O4—C14—C15	107.8 (3)	C7—C2—C1—O2	13.3 (2)
Zn2—O2—C1—O1	40.1 (3)	C7—C2—C1—O1	−167.15 (14)
Zn2—O2—C1—C2	−140.43 (14)	C17—C16—C15—C20	4.0 (2)
N2—C16—C17—C18	174.60 (15)	C17—C16—C15—C14	−172.21 (13)
N2—C16—C15—C20	−172.99 (14)	C19—C20—C15—C16	−3.0 (2)
N2—C16—C15—C14	10.8 (2)	C19—C20—C15—C14	173.35 (15)
N2—C21—C22—C23	176.60 (14)	C18—C19—C20—C15	0.4 (3)
N3—C33—C32—C31	179.89 (16)	C20—C19—C18—C17	1.3 (3)
N3—C34—C35—C36	179.26 (16)	C20—C15—C14—O3	−2.8 (2)
N3—C34—C39—C38	−179.35 (15)	C20—C15—C14—O4	178.34 (14)
N1—C3—C4—C5	−177.00 (16)	C15—C16—C17—C18	−2.4 (2)
N1—C8—C13—C12	−178.26 (16)	C25—C26—C21—N2	−175.45 (14)
C29—C28—C33—N3	179.21 (14)	C25—C26—C21—C22	0.7 (2)
C29—C28—C33—C32	−4.3 (2)	C25—C24—C23—C22	0.4 (3)
C29—C28—C27—O5	9.52 (19)	C34—N3—C33—C28	−157.76 (15)
C29—C28—C27—O6	−170.54 (13)	C34—N3—C33—C32	25.8 (2)
C29—C30—C31—C32	−2.4 (2)	C34—C35—C36—C37	0.0 (3)
C28—C29—C30—C31	1.3 (2)	C34—C39—C38—C37	0.2 (3)
C28—C33—C32—C31	3.3 (2)	C4—C5—C6—C7	0.2 (3)
C16—N2—C21—C26	−132.15 (16)	C27—C28—C33—N3	−0.5 (2)
C16—N2—C21—C22	51.8 (2)	C27—C28—C33—C32	175.99 (14)
C16—C17—C18—C19	−0.2 (3)	C1—C2—C3—N1	0.5 (2)
C16—C15—C14—O3	173.38 (13)	C1—C2—C3—C4	−178.34 (14)
C16—C15—C14—O4	−5.4 (2)	C1—C2—C7—C6	176.93 (16)
C33—N3—C34—C35	47.6 (2)	C35—C34—C39—C38	−0.1 (2)
C33—N3—C34—C39	−133.18 (17)	C35—C36—C37—C38	0.1 (3)
C33—C28—C27—O5	−170.79 (13)	C9—C8—C13—C12	−0.8 (3)
C33—C28—C27—O6	9.2 (2)	C9—C10—C11—C12	−1.4 (3)
C33—C32—C31—C30	0.0 (3)	C8—N1—C3—C2	178.42 (16)
C2—C3—C4—C5	1.9 (2)	C8—N1—C3—C4	−2.8 (3)
C2—C7—C6—C5	1.2 (3)	C8—C9—C10—C11	1.9 (2)
C26—C21—C22—C23	0.5 (2)	C8—C13—C12—C11	1.4 (3)
C26—C25—C24—C23	0.8 (3)	C10—C9—C8—N1	176.66 (15)
C3—N1—C8—C9	118.66 (18)	C10—C9—C8—C13	−0.8 (2)
C3—N1—C8—C13	−63.9 (2)	C10—C11—C12—C13	−0.3 (3)
C3—C2—C7—C6	−1.0 (3)	C39—C34—C35—C36	0.1 (2)
C3—C2—C1—O2	−168.80 (14)	C39—C38—C37—C36	−0.2 (3)
C3—C2—C1—O1	10.7 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.