A two-dimensional Zn coordination polymer with a three-dimensional supra-molecular architecture.

The title compound, poly[bis-{μ2-4,4'-bis-[(1,2,4-triazol-1-yl)meth-yl]biphenyl-κ2N4:N4'}bis-(nitrato-κO)zinc(II)], [Zn(NO3)2(C18H16N6)2] n , is a two-dimensional zinc coordination polymer constructed from 4,4'-bis-[(1H-1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl units. It was synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The ZnII cation is located on an inversion centre and is coordinated by two O atoms from two symmetry-related nitrate groups and four N atoms from four symmetry-related 4,4'-bis-[(1H-1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl ligands, forming a distorted octa-hedral {ZnN4O2} coordination geometry. The linear 4,4'-bis-[(1H-1,2,4-triazol-1-yl)meth-yl]-1,1'-biphenyl ligand links two ZnII cations, generating two-dimensional layers parallel to the crystallographic (132) plane. The parallel layers are connected by C-H⋯O, C-H⋯N, C-H⋯π and π-π stacking inter-actions, resulting in a three-dimensional supra-molecular architecture.

Chemical context

Over the past few decades, the self-assembly of coordination polymers (CPs) or metal–organic frameworks (MOFs) based on metal ions or clusters and organic ligands has attracted much attention, owing to their intriguing mol­ecular topologies and potential applications. Multidentate ligands derived from 1,2,4-triazole that contain an aromatic core have been used for this purpose, examples being 1,4-bis­(1H-1,2,4-triazol-1-ylmeth­yl)benzene (Wang et al., 2007 ▸; Ding & Zou, 2010 ▸; Zhu et al., 2010 ▸), 1,3-bis­(1H-1,2,4-triazol-1-ylmeth­yl)benzene (Zhang et al., 2012 ▸; Ge et al., 2008 ▸; Zhu et al., 2015 ▸), 1,2-bis­(1H-1,2,4-triazol-1-ylmeth­yl)benzene (Yang et al., 2009 ▸; Zhao et al., 2017 ▸; Zhang et al., 2013 ▸), 1,3,5-tris­(1H-1,2,4-triazol-1-ylmeth­yl)benzene (Li et al., 2012 ▸; Yin et al., 2009 ▸; Shi et al., 2011 ▸), 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl (Mu et al., 2011 ▸; Ren et al., 2010 ▸; Ni et al., 2010 ▸). Hydro­thermal synthesis has been proved to be an effective method for the construction of these new coordination polymers. In this study, a new two-dimensional CP, viz. poly[bis­{μ2-4,4′-bis­[(1,2,4-triazol-1-yl)meth­yl]biphenyl-κ2 N 4:N 4′}bis­(nitrato-κO)zinc], [Zn(NO3)2(C18H16N6)2], was synthesized under hydro­thermal conditions by the reaction of Zn(NO3)2·6H2O and 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl at 313 K for 48 h. We report here its crystal structure and its elemental analysis.

Structural commentary

The title complex crystallizes in the triclinic space group P ; the asymmetric unit of the structure consists of one ZnII cation (site symmetry ), one nitrate anion and one 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl ligand.

As shown in Fig. 1 ▸, each ZnII cation exhibits a slightly distorted octa­hedral {ZnN4O2} coordination geometry and is coordinated by four N atoms (N1, N4, N1i and N4i) from four symmetry-related organic ligands and two O atoms (O3 and O3i) from two symmetry-related nitrate groups (see Fig. 1 ▸ for symmetry code). The Zn—O [2.191 (2) Å] and Zn—N bond lengths [2.124 (3)–2.168 (2) Å] are in agreement with corresponding bond lengths found in previously reported ZnII coordination polymers. For the title coordination polymer, the ZnII cation is coordinated by four 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl ligands and two nitrate anions, and each organic ligand in turn connects two ZnII cations to generate a two-dimensional layer parallel to the crystallographic (132) plane. The organic ligand adopts a cis,cis substituent conformation. The two distinct Zn⋯Zn distances are 18.397 (3) and 18.964 (3) Å (see Fig. 2 ▸). The two benzene rings of the 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl ligand lie nearly in one plane [dihedral angle = 0.00 (2)°]. The two triazole groups of the 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl ligand are inclined to the plane of the central biphenyl groups, with dihedral angles of 80.050 (2) (C1/C2/N1/N2/N3) and 85.511 (2)° (C10/C11/N4/N5/N6). Four adjacent ZnII cations are connected by four linear organic ligands and form a 72-membered macrocyclic ring in the above-mentioned two-dimensional layer (see Fig. 2 ▸).

Figure 1

The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids drawn at the 25% probability level. [Symmetry code: (i) −x, 2 − y, −z.]

Figure 2

The two-dimensional layer parallel to the crystallographic (132) plane.

Supra­molecular features

Neighbouring layers are linked to each other by by weak interactions (Table 1 ▸), including C—H⋯O, C—H⋯N, C—H⋯π [C11—H11⋯Cg1ii = 3.6756 (8) Å and C12—H12⋯Cg2iii = 3.5252 (7) Å; Cg1 and Cg2 are the centroids of the triazole (C1/C2/N1/N2/N3) and phenyl (C4–C9) rings, respectively; symmetry codes: (ii) 2 − x, −y, −z; (iii) 1 − x, 1 − y, −z] contacts and π–π stacking inter­actions [Cg1⋯Cg1ii = 3.6296 (10) Å]. These interactions, together with the covalent inter­actions in the infinite two-dimensional polymeric-like layer, make up a three-dimensional supra­molecular structure.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O1i	0.97	2.31	3.2728 (7)	170
C3—H3B⋯O1A i	0.97	2.33	3.2765 (7)	165
C10—H10⋯O2A ii	0.93	2.53	3.0888 (6)	115
C14—H14⋯O2ii	0.93	2.46	3.5454 (7)	158
C15—H15⋯N6iii	0.93	2.58	3.482 (16)	162

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

Database survey

A search in the Cambridge Structural Database (Groom et al., 2016 ▸) for zinc and the 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl moiety gave eight hits. Seven of them are con­structed by 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl units and different carboxyl­ate ligands. One example is a chain structure based on Zn and 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-biphenyl (PUQWAA; Ni et al., 2010 ▸).

Synthesis and crystallization

Zn(NO3)2·6H2O (0.1 mmol), 4,4′-bis­[(1H-1,2,4-triazol-1-yl)meth­yl]-1,1′-n class="Chemical">biphenyl (0.1 mmol) and water (6 ml) were mixed and placed in a thick Pyrex tube, which was sealed and heated to 413 K for 72 h. After cooling to room temperature, colourless block-shaped crystals (53% yield, based on Zn) suitable for X-ray analysis were obtained. Elemental analysis calculated for C36H32N14O6Zn: C 52.59, H 3.92, N 23.85%; found: C 52.23, H 3.74, N 23.49%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms bonded to C atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å with U iso(H) = 1.2U eq(C) for other H atoms. Atoms O1 and O2 of the nitrate group are disordered over two orientations, with occupancies of 0.511 (11) and 0.489 (11), and were refined through the use of SADI, RIGU and SIMU commands.

Table 2

Experimental details

Crystal data
Chemical formula	[Zn(NO3)2(C18H16N6)2]
M r	822.12
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c (Å)	7.3257 (15), 9.0188 (18), 15.578 (3)
α, β, γ (°)	81.70 (3), 77.64 (3), 68.90 (3)
V (Å3)	935.4 (4)
Z	1
Radiation type	Mo Kα
μ (mm−1)	0.72
Crystal size (mm)	0.24 × 0.22 × 0.20
Data collection
Diffractometer	Bruker APEXII Quazar
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.84, 0.86
No. of measured, independent and observed [I > 2σ(I)] reflections	7292, 3271, 2589
R int	0.042
(sin θ/λ)max (Å−1)	0.595
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.051, 0.143, 1.05
No. of reflections	3271
No. of parameters	278
No. of restraints	85
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.34, −0.54

Computer programs: APEX3 (Bruker, 2016 ▸), SAINT-Plus (Bruker, 2016 ▸), SHELXT (Sheldrick, 2008 ▸), SHELXTL-Plus (Sheldrick, 2008 ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017012452/vn2130sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017012452/vn2130Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017012452/vn2130Isup3.mol

CCDC reference: 1564369

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

[Zn(NO3)2(C18H16N6)2]	Z = 1
Mr = 822.12	F(000) = 424
Triclinic, P1	Dx = 1.459 Mg m−3
a = 7.3257 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0188 (18) Å	Cell parameters from 7292 reflections
c = 15.578 (3) Å	θ = 1.6–25.1°
α = 81.70 (3)°	µ = 0.72 mm−1
β = 77.64 (3)°	T = 293 K
γ = 68.90 (3)°	Block, colorless
V = 935.4 (4) Å3	0.24 × 0.22 × 0.2 mm

Bruker APEXII Quazar diffractometer	3271 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2589 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.042
Detector resolution: 7.9 pixels mm-1	θmax = 25.0°, θmin = 3.0°
0.5° ω and 0.5° φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −10→9
Tmin = 0.84, Tmax = 0.86	l = −18→18
7292 measured reflections

Refinement on F2	85 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.143	w = 1/[σ2(Fo2) + (0.079P)2 + 0.2956P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3271 reflections	Δρmax = 0.34 e Å−3
278 parameters	Δρmin = −0.54 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.000000	1.000000	0.000000	0.0406 (2)
O3	0.1631 (4)	1.1607 (3)	0.00189 (17)	0.0574 (7)
N1	0.2322 (4)	0.8123 (3)	0.05733 (18)	0.0441 (7)
N2	0.4790 (5)	0.6937 (4)	0.1274 (2)	0.0482 (7)
N3	0.4061 (6)	0.5766 (4)	0.1198 (2)	0.0602 (9)
N4	0.1701 (4)	0.9540 (4)	−0.12813 (18)	0.0457 (7)
N5	0.3961 (5)	0.8456 (4)	−0.23645 (19)	0.0466 (7)
N6	0.2787 (6)	0.9865 (5)	−0.2713 (2)	0.0729 (11)
N7	0.1398 (5)	1.2530 (4)	0.0601 (2)	0.0570 (8)
C1	0.2590 (6)	0.6550 (5)	0.0771 (3)	0.0554 (10)
H1	0.179295	0.606514	0.061538	0.066*
C2	0.3743 (6)	0.8301 (4)	0.0904 (2)	0.0474 (8)
H2	0.397217	0.925660	0.087958	0.057*
C3	0.6466 (6)	0.6585 (5)	0.1731 (3)	0.0601 (10)
H3A	0.687840	0.751186	0.165279	0.072*
H3B	0.757323	0.571442	0.146296	0.072*
C4	0.5997 (6)	0.6146 (4)	0.2700 (3)	0.0513 (9)
C5	0.7455 (7)	0.5120 (7)	0.3132 (4)	0.0902 (17)
H5	0.873179	0.468413	0.281685	0.108*
C6	0.7082 (8)	0.4711 (8)	0.4028 (4)	0.0927 (17)
H6	0.812884	0.404978	0.430318	0.111*
C7	0.5224 (6)	0.5251 (4)	0.4518 (3)	0.0532 (9)
C8	0.3756 (8)	0.6273 (6)	0.4079 (3)	0.0813 (16)
H8	0.246945	0.667746	0.439147	0.098*
C9	0.4126 (8)	0.6717 (6)	0.3195 (3)	0.0823 (16)
H9	0.309014	0.741721	0.292602	0.099*
C10	0.3284 (6)	0.8298 (5)	−0.1520 (2)	0.0515 (9)
H10	0.384162	0.743198	−0.114162	0.062*
C11	0.1465 (6)	1.0486 (5)	−0.2035 (2)	0.0588 (10)
H11	0.046686	1.147437	−0.206804	0.071*
C12	0.5625 (7)	0.7311 (5)	−0.2909 (3)	0.0658 (13)
H12A	0.509806	0.678916	−0.324861	0.079*
H12B	0.641231	0.649898	−0.252615	0.079*
C13	0.6941 (6)	0.8103 (4)	−0.3527 (3)	0.0530 (10)
C14	0.8175 (7)	0.8650 (6)	−0.3228 (3)	0.0722 (13)
H14	0.821652	0.853057	−0.262825	0.087*
C15	0.9375 (7)	0.9384 (6)	−0.3803 (3)	0.0684 (13)
H15	1.021917	0.973475	−0.358088	0.082*
C16	0.9348 (5)	0.9608 (4)	−0.4696 (2)	0.0431 (8)
C17	0.8101 (7)	0.9040 (6)	−0.4990 (3)	0.0738 (14)
H17	0.804965	0.915631	−0.558860	0.089*
C18	0.6915 (8)	0.8296 (6)	−0.4409 (3)	0.0750 (14)
H18	0.608813	0.792084	−0.462688	0.090*
O1	−0.0075 (14)	1.3759 (11)	0.0613 (8)	0.0890 (19)	0.500 (12)
O2	0.2754 (14)	1.2075 (12)	0.1048 (6)	0.0792 (17)	0.500 (12)
O1A	−0.0249 (12)	1.3242 (11)	0.1028 (7)	0.0807 (18)	0.500 (12)
O2A	0.2775 (13)	1.2743 (14)	0.0828 (7)	0.0812 (17)	0.500 (12)

	U11	U22	U33	U12	U13	U23
Zn1	0.0365 (3)	0.0492 (4)	0.0287 (3)	−0.0098 (2)	−0.0025 (2)	0.0033 (2)
O3	0.0658 (17)	0.0635 (16)	0.0492 (15)	−0.0325 (14)	−0.0020 (13)	−0.0084 (13)
N1	0.0444 (16)	0.0499 (17)	0.0331 (15)	−0.0123 (13)	−0.0074 (13)	0.0027 (13)
N2	0.0514 (18)	0.0509 (17)	0.0384 (16)	−0.0136 (14)	−0.0123 (14)	0.0052 (13)
N3	0.077 (2)	0.0481 (18)	0.060 (2)	−0.0216 (17)	−0.0251 (19)	0.0036 (16)
N4	0.0463 (17)	0.0559 (18)	0.0310 (15)	−0.0158 (14)	−0.0048 (13)	0.0013 (13)
N5	0.0506 (17)	0.0545 (17)	0.0347 (16)	−0.0245 (15)	0.0054 (14)	−0.0049 (14)
N6	0.072 (3)	0.088 (3)	0.042 (2)	−0.019 (2)	0.0022 (19)	0.0074 (19)
N7	0.0616 (17)	0.0610 (18)	0.0580 (19)	−0.0299 (14)	−0.0085 (15)	−0.0136 (15)
C1	0.065 (3)	0.052 (2)	0.052 (2)	−0.0185 (19)	−0.022 (2)	−0.0003 (18)
C2	0.052 (2)	0.0469 (19)	0.0385 (19)	−0.0165 (17)	−0.0040 (17)	0.0047 (15)
C3	0.052 (2)	0.071 (3)	0.057 (3)	−0.020 (2)	−0.020 (2)	0.009 (2)
C4	0.059 (2)	0.048 (2)	0.046 (2)	−0.0146 (17)	−0.0201 (18)	0.0056 (17)
C5	0.044 (3)	0.133 (5)	0.070 (3)	−0.017 (3)	−0.018 (2)	0.044 (3)
C6	0.057 (3)	0.133 (5)	0.070 (3)	−0.021 (3)	−0.028 (3)	0.047 (3)
C7	0.071 (3)	0.043 (2)	0.047 (2)	−0.0121 (18)	−0.027 (2)	0.0009 (16)
C8	0.083 (3)	0.077 (3)	0.041 (2)	0.025 (2)	−0.010 (2)	−0.006 (2)
C9	0.091 (4)	0.075 (3)	0.045 (2)	0.021 (3)	−0.027 (2)	0.002 (2)
C10	0.052 (2)	0.055 (2)	0.0356 (19)	−0.0112 (17)	0.0015 (17)	0.0035 (16)
C11	0.049 (2)	0.068 (2)	0.036 (2)	−0.0013 (19)	0.0002 (17)	0.0047 (18)
C12	0.079 (3)	0.055 (2)	0.057 (3)	−0.033 (2)	0.028 (2)	−0.017 (2)
C13	0.058 (2)	0.047 (2)	0.045 (2)	−0.0194 (18)	0.0153 (18)	−0.0088 (17)
C14	0.087 (3)	0.100 (3)	0.034 (2)	−0.048 (3)	0.002 (2)	0.000 (2)
C15	0.075 (3)	0.108 (4)	0.039 (2)	−0.054 (3)	−0.004 (2)	−0.002 (2)
C16	0.0386 (18)	0.0427 (18)	0.0388 (18)	−0.0073 (14)	0.0024 (15)	−0.0055 (15)
C17	0.087 (3)	0.114 (4)	0.038 (2)	−0.060 (3)	−0.007 (2)	0.003 (2)
C18	0.085 (3)	0.111 (4)	0.051 (3)	−0.066 (3)	−0.002 (2)	−0.005 (2)
O1	0.091 (3)	0.077 (3)	0.080 (4)	−0.006 (3)	−0.008 (3)	−0.016 (3)
O2	0.094 (3)	0.080 (4)	0.075 (3)	−0.035 (3)	−0.032 (3)	−0.003 (3)
O1A	0.080 (3)	0.075 (3)	0.074 (4)	−0.020 (3)	0.009 (3)	−0.016 (3)
O2A	0.085 (3)	0.088 (4)	0.087 (4)	−0.041 (3)	−0.030 (3)	−0.008 (3)

Zn1—O3	2.191 (2)	C4—C5	1.367 (6)
Zn1—O3i	2.191 (2)	C4—C9	1.376 (6)
Zn1—N1i	2.167 (3)	C5—H5	0.9300
Zn1—N1	2.167 (3)	C5—C6	1.385 (7)
Zn1—N4i	2.124 (3)	C6—H6	0.9300
Zn1—N4	2.124 (3)	C6—C7	1.363 (7)
O3—N7	1.263 (4)	C7—C7ii	1.505 (8)
N1—C1	1.359 (5)	C7—C8	1.376 (6)
N1—C2	1.322 (5)	C8—H8	0.9300
N2—N3	1.372 (4)	C8—C9	1.375 (7)
N2—C2	1.318 (5)	C9—H9	0.9300
N2—C3	1.465 (5)	C10—H10	0.9300
N3—C1	1.314 (5)	C11—H11	0.9300
N4—C10	1.318 (5)	C12—H12A	0.9700
N4—C11	1.353 (5)	C12—H12B	0.9700
N5—N6	1.365 (5)	C12—C13	1.506 (5)
N5—C10	1.310 (5)	C13—C14	1.359 (6)
N5—C12	1.475 (5)	C13—C18	1.364 (6)
N6—C11	1.307 (5)	C14—H14	0.9300
N7—O1	1.237 (8)	C14—C15	1.387 (6)
N7—O2	1.249 (8)	C15—H15	0.9300
N7—O1A	1.237 (7)	C15—C16	1.381 (5)
N7—O2A	1.221 (8)	C16—C16iii	1.487 (7)
C1—H1	0.9300	C16—C17	1.375 (5)
C2—H2	0.9300	C17—H17	0.9300
C3—H3A	0.9700	C17—C18	1.390 (6)
C3—H3B	0.9700	C18—H18	0.9300
C3—C4	1.501 (6)
O3—Zn1—O3i	180.0	C5—C4—C3	120.3 (4)
N1—Zn1—O3i	92.22 (11)	C5—C4—C9	116.5 (4)
N1i—Zn1—O3	92.22 (11)	C9—C4—C3	123.2 (4)
N1i—Zn1—O3i	87.78 (11)	C4—C5—H5	119.1
N1—Zn1—O3	87.78 (11)	C4—C5—C6	121.8 (5)
N1i—Zn1—N1	180.0	C6—C5—H5	119.1
N4—Zn1—O3i	94.65 (10)	C5—C6—H6	119.1
N4i—Zn1—O3	94.65 (10)	C7—C6—C5	121.9 (5)
N4—Zn1—O3	85.35 (10)	C7—C6—H6	119.1
N4i—Zn1—O3i	85.35 (10)	C6—C7—C7ii	122.4 (5)
N4i—Zn1—N1i	90.36 (12)	C6—C7—C8	116.2 (4)
N4i—Zn1—N1	89.64 (12)	C8—C7—C7ii	121.4 (5)
N4—Zn1—N1	90.36 (12)	C7—C8—H8	118.9
N4—Zn1—N1i	89.64 (12)	C9—C8—C7	122.2 (4)
N4i—Zn1—N4	180.0	C9—C8—H8	118.9
N7—O3—Zn1	128.5 (2)	C4—C9—H9	119.3
C1—N1—Zn1	130.5 (3)	C8—C9—C4	121.4 (4)
C2—N1—Zn1	126.5 (2)	C8—C9—H9	119.3
C2—N1—C1	102.7 (3)	N4—C10—H10	124.8
N3—N2—C3	120.7 (3)	N5—C10—N4	110.5 (4)
C2—N2—N3	109.9 (3)	N5—C10—H10	124.8
C2—N2—C3	129.4 (3)	N4—C11—H11	123.6
C1—N3—N2	102.0 (3)	N6—C11—N4	112.9 (4)
C10—N4—Zn1	128.1 (3)	N6—C11—H11	123.6
C10—N4—C11	103.9 (3)	N5—C12—H12A	109.2
C11—N4—Zn1	128.0 (3)	N5—C12—H12B	109.2
N6—N5—C12	122.6 (3)	N5—C12—C13	112.2 (3)
C10—N5—N6	109.0 (3)	H12A—C12—H12B	107.9
C10—N5—C12	128.3 (4)	C13—C12—H12A	109.2
C11—N6—N5	103.8 (3)	C13—C12—H12B	109.2
O1—N7—O3	115.4 (6)	C14—C13—C12	121.5 (4)
O1—N7—O2	130.6 (7)	C14—C13—C18	118.1 (4)
O2—N7—O3	114.0 (5)	C18—C13—C12	120.4 (4)
O1A—N7—O3	122.8 (5)	C13—C14—H14	119.5
O2A—N7—O3	123.5 (6)	C13—C14—C15	121.0 (4)
O2A—N7—O1A	113.6 (7)	C15—C14—H14	119.5
N1—C1—H1	122.6	C14—C15—H15	119.2
N3—C1—N1	114.8 (3)	C16—C15—C14	121.7 (4)
N3—C1—H1	122.6	C16—C15—H15	119.2
N1—C2—H2	124.7	C15—C16—C16iii	120.9 (4)
N2—C2—N1	110.7 (3)	C17—C16—C15	116.7 (3)
N2—C2—H2	124.7	C17—C16—C16iii	122.4 (4)
N2—C3—H3A	108.9	C16—C17—H17	119.4
N2—C3—H3B	108.9	C16—C17—C18	121.2 (4)
N2—C3—C4	113.5 (3)	C18—C17—H17	119.4
H3A—C3—H3B	107.7	C13—C18—C17	121.4 (4)
C4—C3—H3A	108.9	C13—C18—H18	119.3
C4—C3—H3B	108.9	C17—C18—H18	119.3

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1iv	0.97	2.31	3.2728 (7)	170
C3—H3B···O1Aiv	0.97	2.33	3.2765 (7)	165
C10—H10···O2Av	0.93	2.53	3.0888 (6)	115
C14—H14···O2v	0.93	2.46	3.5454 (7)	158
C15—H15···N6vi	0.93	2.58	3.482 (16)	162