Crystal structure of (E)-N'-(3,4-di-hydroxy-benzyl-idene)-4-hy-droxy-benzohydrazide.

In the title benzohydrazide derivative, C14H12N2O4, the azomethine C=N double bond has an E configuration. The hydrazide connecting bridge, (C=O)-(NH)-N=(CH), is nearly planar with C-C-N-N and C-N-N=C torsion angles of -177.33 (10) and -174.98 (12)°, respectively. The 4-hy-droxy-phenyl and 3,4-di-hydroxy-phenyl rings are slightly twisted, making a dihedral angle of 9.18 (6)°. In the crystal, mol-ecules are connected by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network, while further consolidated via π-π inter-actions [centroid-centroid distances = 3.6480 (8) and 3.7607 (8) Å]. The conformation is compared to those of related benzyl-idene-4-hy-droxy-benzohydrazide derivatives.

Chemical context

Hydrazides and n class="Chemical">hydrazones are important synthons for several transformations and have gained importance because of their various biological and clinical applications (Narasimhan et al., 2010 ▸). Benzohydrazide derivatives containing an azomethine (–NHN=CH–) group have been reported to possess diverse biological activities such as anti­tumor (Xia et al., 2007 ▸; Kumari & Bansal, 2018 ▸), anti­oxidant (Aziz et al., 2014 ▸), anti­tubercular and anti­microbial (Maheswari & Manjula, 2015 ▸) and α-glucosidase inhibition (Taha et al., 2015 ▸) activities. The inter­esting biological activities of benzohydrazides led us to synthesize several benzohydrazides to study their bioactivities (Fun et al., 2011 ▸; Horkaew et al., 2011 ▸; Chantrapromma et al., 2016 ▸), including the title compound (I), which was found to exhibit anti­oxidant activity with an IC50 value of 0.035 ± 0.004 mM (ascorbic acid used as the reference standard; Thaipong et al., 2006 ▸) and α-glucosidase inhibitory activity with an IC50 value of 0.014 ± 0.001 mM (acarbose as the reference standard; Bachhawat et al., 2011 ▸).

Structural commentary

The title hydrazide derivative, (I), consists of a 4-hy­droxy­phenyl ring, a 3,4-di­hydroxyphenyl ring and a n class="Chemical">hydrazide (C=O)—(NH)—N=(CH) connecting bridge (Fig. 1 ▸). The C6—C7, C7—N1 and C8—C9 bond lengths of 1.4861 (15), 1.3385 (17) and 1.4584 (16) Å, respectively, confirm their single-bond character, whereas the C7=O2 and N2=C8 bond lengths of 1.2403 (15) and 1.2738 (17) Å, respectively, confirm the presence of the double bonds. The sp 2-hybridized character of atoms C7 and C8 is further supported by the bond angles C6—C7—N1 [116.49 (11)°] and N2—C8—C9 [120.86 (12)°]. The bond lengths and angles of the central hydrazide connecting bridge are consistent with those in related structures (Fun et al., 2011 ▸; Chantrapromma et al., 2016 ▸). The mol­ecule exhibits an E configuration with respect to the azomethine C=N double bond. As the torsion angle C6—C7—N1—N2 [−177.33 (10)°] and C7—N1—N2—C8 [−174.98 (12)°] are both in an anti-periplanar conformation, the overall conformation for the hydrazide connecting bridge is almost planar. Furthermore, the 4-hy­droxy­phenyl and 3,4-di­hydroxy­phenyl rings are also coplanar to the corresponding azomethine and carbonyl double bonds, with torsion angles N2—C8—C9—C10 [−0.76 (19)°] and C5—C6—C7—O2 [−1.18 (19)°] both in a syn-periplanar conformation. Those torsion angles result in an overall flat shape of the title compound with the dihedral angle between the terminal benzene rings being 9.18 (6)°.

Figure 1

The mol­ecular structure of the title compound with the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Supra­molecular features

In the crystal, mol­ecules are linked by N—H⋯O and O—H⋯O hydrogen bonds (Table 1 ▸) into a three-dimensional network. Mol­ecules are connected into infinite chains along [101] through an O4—H1O4⋯O1iii n class="Chemical">hydrogen bond and those chains are further connected into two-dimensional plates parallel to the ac plane via N1—H1N1⋯O3i and O1—H1O1⋯O2i hydrogen bonds with an (18) ring motif (Fig. 2a ▸ and 3a ▸; symmetry codes as in Table 1 ▸). Those plate are inter­connected via an O3—H1O3⋯O2ii hydrogen bond with an (20) ring motif, forming a three-dimensional network (Fig. 2b ▸ and 3b ▸; symmetry code as in Table 1 ▸). In addition, the mol­ecules are further stabilized by π–π inter­actions involving both aromatic rings with Cg1⋯Cg2iv = 3.6480 (8) Å and Cg1⋯Cg2v = 3.7607 (8) Å [symmetry codes: (iv) 1 − x, − + y,  − z; (v) 1 − x,  + y,  − z; Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 aromatic rings, respectively.]

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2i	0.80 (2)	1.92 (2)	2.7203 (15)	171 (2)
O3—H1O3⋯O2ii	0.88 (2)	2.17 (2)	3.0276 (13)	163 (2)
O4—H1O4⋯O1iii	0.82 (2)	1.93 (2)	2.7379 (16)	166 (2)
N1—H1N1⋯O3i	0.87 (2)	2.24 (2)	3.0017 (16)	146.1 (19)

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

Figure 2

(a) A partial packing diagram of the title compound, showing a two-dimensional plate formed by O—H⋯O and N—H⋯O hydrogen bonds (cyan dotted lines). [Symmetry codes: (i) x, −y + , z + ; (iii) x − 1, y, z − 1.] (b) A partial packing diagram of the title compound with additional O—H⋯O hydrogen bonds (magenta dotted lines). [Symmetry code: (ii) −x + 1, −y + 1, −z.] Hydrogen atoms not involved in with these inter­actions are omitted for clarity.

Figure 3

A view of dimers with (a) (18) and (b) (20) ring motifs. [Symmetry codes: (i) x, −y + , z + ; (ii) −x + 1, −y + 1, −z.]

Database survey

A search of the Cambridge Structural Database (CSD version 5.40, last update May 2019; Groom et al., 2016 ▸) using (E)-N′-benzenyl­idene-4-hy­droxy­benzohydrazide as the reference moiety resulted in 31 structures with different substituents at the benzyl­idenyl ring. The different substituent () together with selected torsion angles, τ 1 (C5—C6—C7—O2), τ 2 (C6—C7—N1—N2), τ 3 (C7—N1—N2—C8) and τ 4 (N2—C8—C9—C10) as shown in Fig. 4 ▸, and the dihedral angle between the terminal aromatic rings are summarized in Table 2 ▸. The torsion angles τ 2 and τ 3 are anti-periplanar (151.7–179.8°), showing that the n class="Chemical">hydrazide connecting bridges are nearly planar. As for the torsion angle τ 4, all structures adopt a syn-periplanar conformation (0.6–19.6°). Similar to the title compound, the τ 1 torsion angles for most of the structures are syn-periplanar (2.0–29.1°). However, there are three outliers (CEDBAQ, HUCWOS and PAQJID) whose τ 1 torsion angles are syn-clinal (34.9–50.9°). By comparing the dihedral angles, the structures can be divided into planar compounds (dihedral angle = 2.5–29.3°) and non-planar compounds (dihedral angle = 30.5–77.3°). In general, as the hydrazide-connecting bridges are nearly planar, relatively flat τ 1 and τ 4 torsion angles are observed in the former compounds, while relatively twisted τ 1 and τ 4 torsion angles are observed in the latter.

Figure 4

General chemical diagram, showing torsion angles τ 1, τ 2, τ 3 and τ 4 in the benzyl­idene-4-hy­droxy­benzohydrazide derivative.

Table 2

Selected torsion angles (°) and the dihedral angle (°) between the terminal benzene rings

Compound	R	τ 1	τ 2	τ 3	τ 4	Dihedral angle
Planar
(I)	3,4-di­hydroxy­phen­yl	−1.2	−177.3	−175.0	−0.8	9.2
ABALIA (Fun et al., 2011 ▸)	3-hy­droxy-4-meth­oxy­phen­yl	3.2	178.4	170.1	−14.2	24.2
CECZOB (Subashini et al., 2012 ▸)	4-chloro­phen­yl	26.1	−174.4	166.6	−8.9	5.8
CECZUH (Subashini et al., 2012 ▸)	4-bromo­phen­yl	25.6	−174.9	169.0	−7.2	9.8
ESOTUD (Chantrapromma et al., 2016 ▸)	3-meth­oxy­phen­yl	−19.4, 20.7	−173.5, −177.8	−175.7, −173.0	1.2, 0.6	24.0, 29.3
HOZBII (Li & Ban, 2009 ▸)	4-nitro­phen­yl	2.0	177.7	178.3	−0.6	2.5
IJUKEE (Zhang, 2011 ▸)	4-hy­droxy-3-nitro­phen­yl	−7.2	−177.0	−179.3	6.0	5.5
IRAXEF (Sánchez-Lozano et al., 2011 ▸)	2,4-di­hydroxy­phen­yl	−7.7	−177.8	−177.2	−4.1	6.9
MOZPEX (Ren, 2009 ▸)	3,5-di­chloro-2-hy­droxy­phen­yl	12.3	178.7	−179.4	−7.3	5.1
ROFMOP (Xue et al., 2008 ▸)	3-bromo-5-chloro-2-hy­droxy­phen­yl	−2.3	175.9	−176.5	−1.3	3.0
TEWLAL (Ayyannan et al., 2016 ▸)	5-bromo-2-hy­droxy­phen­yl	−15.7	−173.6	168.9	3.1	27.0
WACVON (Shalash et al., 2010 ▸)	4-hy­droxy-3-meth­oxy­phen­yl	−34.2	−175.5	174.7	15.4	28.6
WACXOP (Huang, 2010 ▸)	2,4-di­chloro­phen­yl	−14.3	−179.8	−175.0	3.0	7.0
YAGYAI (Horkaew et al., 2011 ▸)	3,4,5-tri­meth­oxy­phen­yl	−10.6	172.2	175.8	2.8	19.4
YIFPAF (Salhin et al., 2007 ▸)	2-hy­droxy­phen­yl	18.8	179.5	178.7	3.3	21.7
ZAPKOS (Hou, 2012 ▸)	3-nitro­phen­yl	−14.6	169.4	177.4	13.8	9.2
ZIPLAO (Prachumrat et al., 2018 ▸)	2,3-di­meth­oxy­phen­yl	9.6	−175.3	172.9	−1.3	9.3
Non-planar
CABWUA (Meng et al., 2014 ▸)	2-hy­droxy-5-methyl­phen­yl	18.4	−178.5	−169.8	8.0	40.8
CEDBAQ (Subashini et al., 2012 ▸)	4-(di­ethyl­amino)­phen­yl	34.9	−178.5	−151.7	8.75	77.3
HUCVIL (Hao, 2009 ▸)	2-chloro­phen­yl	−22.5	−179.2	177.4	−4.2	30.5
HUCWOS (Shi, 2009 ▸)	4-meth­oxy­phen­yl	−50.9	−177.5	174.8	9.2	46.6
MOSPEQ (Qiu, 2009 ▸)	5-chloro-2-hy­droxy­phen­yl	19.0	−178.5	−170.9	7.59	40.2
PAQJID (Gopal Reddy et al., 2017 ▸)	4-ethyl­phen­yl	−39.9	171.1	173.9	7.4	49.9
PAWVUG (Rassem et al., 2012a ▸)	2-meth­oxy­phen­yl	29.1	−166.8	−175.1	19.2	66.6
PEDGOW (Saad et al., 2012 ▸)	3-chloro­phen­yl	−21.1	179.5	175.3	−9.3	39.0
XEBYUA (Rassem et al., 2012b ▸)	2-hy­droxy-4-meth­oxy­phen­yl	28.7	178.1	−169.8	1.3	40.6

Synthesis and crystallization

The title compound (I) was prepared by dissolving 4-hy­droxy­benzohydrazide (2 mmol, 0.30 g) in n class="Chemical">ethanol (10 ml). A solution of 3,4-di­hydroxy­benzaldehyde (2 mmol, 0.28 g) in ethanol (10 ml) was then added to the reaction. The mixture was refluxed for 6 h and the white solid of the product that appeared was collected by filtration, washed with ethanol and dried in air. Colourless single crystals of (I) were obtained after recrystallization from methanol at room temperature for several days.

M.p. 572–573 K. UV–Vis (MeOH) λmax 213, 327 nm; FT–IR (KBr) ν (cm−1): 3121 (O—H stretching), 2800 (C—H aromatic stretching), 1615 (amide C=O stretching), 1570 (C=N stretching), 1506 (C=C stretching of aromatic compound) cm−1; 1H NMR (300 MHz, d 6-DMSO) δ 11.39 (s, 1H, NH), 10.10 (s, 1H, Ar—OH), 8.23 (s, 1H, N=CH), 7.77 (d, J = 8.4 Hz, 2H, Ar—H), 6.84 (d, J = 8.4, 2H, Ar—H), 9.33 (s, 2H, Ar—OH), 7.22 (s, 1H, Ar—H), 6.90 (d, J = 7.8 Hz, 1H, Ar—H), 6.77 (d, J = 8.1 Hz, 1H, Ar—H).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸ . C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined using a riding model with U iso(H) = 1.2U eq(C). All O- and N-bound n class="Disease">H atoms were located in a difference-Fourier map and refined freely [O—H = 0.80 (2)–0.88 (2) Å and N—H = 0.87 (2) Å].

Table 3

Experimental details

Crystal data
Chemical formula	C14H12N2O4
M r	272.26
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	11.5352 (8), 7.1711 (5), 15.0606 (10)
β (°)	108.548 (2)
V (Å3)	1181.10 (14)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.11
Crystal size (mm)	0.80 × 0.21 × 0.07
Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2012 ▸)
T min, T max	0.924, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	22559, 3200, 2453
R int	0.024
(sin θ/λ)max (Å−1)	0.686
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.050, 0.161, 1.05
No. of reflections	3200
No. of parameters	197
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.35, −0.19

Computer programs: APEX2 and SAINT (Bruker, 2012 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2013 (Sheldrick, 2015 ▸), Mercury (Macrae et al., 2006 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019010442/is5518sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019010442/is5518Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019010442/is5518Isup3.cml

CCDC reference: 1942396

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

C14H12N2O4	F(000) = 568
Mr = 272.26	Dx = 1.531 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.5352 (8) Å	Cell parameters from 6293 reflections
b = 7.1711 (5) Å	θ = 2.9–29.2°
c = 15.0606 (10) Å	µ = 0.11 mm−1
β = 108.548 (2)°	T = 296 K
V = 1181.10 (14) Å3	Plate, colourless
Z = 4	0.80 × 0.21 × 0.07 mm

Bruker APEXII DUO CCD area-detector diffractometer	3200 independent reflections
Radiation source: fine-focus sealed tube	2453 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 29.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −15→15
Tmin = 0.924, Tmax = 0.954	k = −9→9
22559 measured reflections	l = −20→20

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161	w = 1/[σ2(Fo2) + (0.0999P)2 + 0.1317P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3200 reflections	Δρmax = 0.35 e Å−3
197 parameters	Δρmin = −0.18 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
O1	0.87093 (9)	0.31797 (18)	0.75119 (6)	0.0493 (3)
O2	0.72990 (8)	0.42338 (15)	0.31133 (6)	0.0439 (3)
O3	0.36583 (9)	0.37514 (15)	−0.12560 (6)	0.0432 (3)
O4	0.11997 (10)	0.35694 (18)	−0.18715 (7)	0.0547 (3)
N1	0.54178 (10)	0.37659 (17)	0.32223 (7)	0.0392 (3)
N2	0.48862 (10)	0.38068 (17)	0.22612 (7)	0.0387 (3)
C1	0.64041 (11)	0.3493 (2)	0.52044 (8)	0.0360 (3)
H1A	0.555998	0.341901	0.493279	0.043*
C2	0.69125 (11)	0.32969 (19)	0.61626 (8)	0.0370 (3)
H2A	0.641478	0.308993	0.653221	0.044*
C3	0.81673 (12)	0.34105 (19)	0.65681 (8)	0.0359 (3)
C4	0.89049 (12)	0.3773 (2)	0.60204 (9)	0.0429 (3)
H4A	0.974622	0.389056	0.629625	0.051*
C5	0.83860 (12)	0.3960 (2)	0.50639 (9)	0.0398 (3)
H5A	0.888474	0.419686	0.469812	0.048*
C6	0.71320 (11)	0.38002 (16)	0.46381 (8)	0.0312 (3)
C7	0.66306 (11)	0.39454 (18)	0.36014 (8)	0.0334 (3)
C8	0.37218 (12)	0.37651 (18)	0.19709 (8)	0.0357 (3)
H8A	0.329660	0.374477	0.240199	0.043*
C9	0.30468 (12)	0.37489 (17)	0.09713 (8)	0.0332 (3)
C10	0.36617 (11)	0.38007 (18)	0.03124 (8)	0.0339 (3)
H10A	0.451058	0.387612	0.051040	0.041*
C11	0.30251 (11)	0.37414 (17)	−0.06263 (8)	0.0332 (3)
C12	0.17505 (12)	0.36368 (19)	−0.09316 (9)	0.0377 (3)
C13	0.11375 (12)	0.3624 (2)	−0.02790 (9)	0.0434 (3)
H13A	0.028756	0.358471	−0.047790	0.052*
C14	0.17809 (12)	0.3669 (2)	0.06705 (9)	0.0400 (3)
H14A	0.136252	0.364586	0.110600	0.048*
H1O1	0.8288 (18)	0.256 (3)	0.7732 (15)	0.074 (6)*
H1O3	0.324 (2)	0.421 (3)	−0.1808 (16)	0.092 (7)*
H1O4	0.046 (2)	0.345 (3)	−0.1964 (16)	0.085 (7)*
H1N1	0.4954 (19)	0.342 (3)	0.3546 (14)	0.069 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0364 (5)	0.0836 (8)	0.0215 (4)	−0.0105 (5)	0.0004 (4)	0.0057 (4)
O2	0.0376 (5)	0.0700 (7)	0.0267 (4)	−0.0036 (4)	0.0139 (4)	−0.0016 (4)
O3	0.0344 (5)	0.0719 (7)	0.0236 (4)	0.0037 (4)	0.0095 (4)	0.0026 (4)
O4	0.0352 (6)	0.0991 (9)	0.0227 (5)	−0.0083 (5)	−0.0009 (4)	0.0033 (5)
N1	0.0326 (6)	0.0651 (7)	0.0185 (5)	−0.0038 (5)	0.0060 (4)	0.0023 (4)
N2	0.0380 (6)	0.0576 (7)	0.0182 (5)	−0.0033 (5)	0.0056 (4)	0.0010 (4)
C1	0.0254 (6)	0.0554 (7)	0.0248 (6)	−0.0019 (5)	0.0046 (4)	−0.0004 (5)
C2	0.0319 (6)	0.0558 (8)	0.0232 (6)	−0.0014 (5)	0.0086 (5)	0.0005 (5)
C3	0.0335 (6)	0.0485 (7)	0.0220 (5)	−0.0024 (5)	0.0037 (5)	−0.0001 (5)
C4	0.0272 (6)	0.0688 (9)	0.0289 (6)	−0.0039 (6)	0.0037 (5)	0.0022 (6)
C5	0.0307 (6)	0.0611 (8)	0.0284 (6)	−0.0029 (5)	0.0105 (5)	0.0014 (5)
C6	0.0300 (6)	0.0411 (6)	0.0213 (5)	0.0007 (4)	0.0063 (4)	−0.0010 (4)
C7	0.0337 (6)	0.0440 (7)	0.0222 (6)	−0.0001 (5)	0.0086 (5)	−0.0019 (4)
C8	0.0352 (7)	0.0481 (7)	0.0231 (6)	0.0003 (5)	0.0081 (5)	0.0012 (5)
C9	0.0332 (6)	0.0416 (6)	0.0219 (5)	0.0005 (5)	0.0046 (5)	0.0009 (4)
C10	0.0261 (5)	0.0492 (7)	0.0234 (6)	0.0004 (5)	0.0038 (4)	−0.0001 (5)
C11	0.0311 (6)	0.0443 (7)	0.0234 (5)	0.0008 (5)	0.0073 (4)	0.0010 (4)
C12	0.0313 (6)	0.0521 (7)	0.0243 (6)	−0.0013 (5)	0.0012 (5)	0.0026 (5)
C13	0.0255 (6)	0.0686 (9)	0.0321 (7)	−0.0003 (5)	0.0038 (5)	0.0046 (6)
C14	0.0329 (6)	0.0582 (8)	0.0298 (6)	0.0015 (5)	0.0110 (5)	0.0037 (5)

O1—C3	1.3688 (14)	C4—C5	1.3794 (18)
O1—H1O1	0.80 (2)	C4—H4A	0.9300
O2—C7	1.2403 (15)	C5—C6	1.3880 (18)
O3—C11	1.3688 (15)	C5—H5A	0.9300
O3—H1O3	0.88 (2)	C6—C7	1.4861 (15)
O4—C12	1.3556 (15)	C8—C9	1.4584 (16)
O4—H1O4	0.83 (3)	C8—H8A	0.9300
N1—C7	1.3385 (17)	C9—C14	1.3856 (18)
N1—N2	1.3811 (14)	C9—C10	1.3918 (17)
N1—H1N1	0.87 (2)	C10—C11	1.3709 (16)
N2—C8	1.2738 (17)	C10—H10A	0.9300
C1—C2	1.3812 (16)	C11—C12	1.3959 (18)
C1—C6	1.3916 (17)	C12—C13	1.3815 (19)
C1—H1A	0.9300	C13—C14	1.3861 (17)
C2—C3	1.3828 (18)	C13—H13A	0.9300
C2—H2A	0.9300	C14—H14A	0.9300
C3—C4	1.3852 (19)
C3—O1—H1O1	111.0 (15)	O2—C7—N1	121.71 (11)
C11—O3—H1O3	113.5 (15)	O2—C7—C6	121.79 (11)
C12—O4—H1O4	107.2 (16)	N1—C7—C6	116.49 (11)
C7—N1—N2	120.02 (11)	N2—C8—C9	120.86 (12)
C7—N1—H1N1	122.4 (13)	N2—C8—H8A	119.6
N2—N1—H1N1	116.6 (13)	C9—C8—H8A	119.6
C8—N2—N1	115.30 (11)	C14—C9—C10	119.41 (11)
C2—C1—C6	121.20 (11)	C14—C9—C8	119.93 (12)
C2—C1—H1A	119.4	C10—C9—C8	120.66 (11)
C6—C1—H1A	119.4	C11—C10—C9	120.47 (11)
C1—C2—C3	119.49 (11)	C11—C10—H10A	119.8
C1—C2—H2A	120.3	C9—C10—H10A	119.8
C3—C2—H2A	120.3	O3—C11—C10	119.04 (11)
O1—C3—C2	121.31 (12)	O3—C11—C12	120.68 (11)
O1—C3—C4	118.49 (11)	C10—C11—C12	120.26 (11)
C2—C3—C4	120.20 (11)	O4—C12—C13	124.53 (12)
C5—C4—C3	119.69 (12)	O4—C12—C11	116.14 (12)
C5—C4—H4A	120.2	C13—C12—C11	119.33 (11)
C3—C4—H4A	120.2	C12—C13—C14	120.43 (12)
C4—C5—C6	121.12 (12)	C12—C13—H13A	119.8
C4—C5—H5A	119.4	C14—C13—H13A	119.8
C6—C5—H5A	119.4	C9—C14—C13	120.07 (12)
C5—C6—C1	118.24 (11)	C9—C14—H14A	120.0
C5—C6—C7	118.67 (11)	C13—C14—H14A	120.0
C1—C6—C7	123.09 (11)
C7—N1—N2—C8	−174.98 (12)	N1—N2—C8—C9	−178.29 (10)
C6—C1—C2—C3	0.1 (2)	N2—C8—C9—C14	178.83 (12)
C1—C2—C3—O1	−178.44 (12)	N2—C8—C9—C10	−0.76 (19)
C1—C2—C3—C4	1.9 (2)	C14—C9—C10—C11	−1.11 (18)
O1—C3—C4—C5	178.19 (13)	C8—C9—C10—C11	178.47 (11)
C2—C3—C4—C5	−2.1 (2)	C9—C10—C11—O3	−178.51 (12)
C3—C4—C5—C6	0.3 (2)	C9—C10—C11—C12	0.29 (19)
C4—C5—C6—C1	1.6 (2)	O3—C11—C12—O4	−0.71 (19)
C4—C5—C6—C7	−177.78 (12)	C10—C11—C12—O4	−179.50 (12)
C2—C1—C6—C5	−1.9 (2)	O3—C11—C12—C13	179.81 (13)
C2—C1—C6—C7	177.51 (12)	C10—C11—C12—C13	1.03 (19)
N2—N1—C7—O2	3.3 (2)	O4—C12—C13—C14	179.03 (13)
N2—N1—C7—C6	−177.33 (10)	C11—C12—C13—C14	−1.5 (2)
C5—C6—C7—O2	−1.18 (19)	C10—C9—C14—C13	0.60 (19)
C1—C6—C7—O2	179.44 (13)	C8—C9—C14—C13	−178.99 (12)
C5—C6—C7—N1	179.42 (12)	C12—C13—C14—C9	0.7 (2)
C1—C6—C7—N1	0.04 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2i	0.80 (2)	1.92 (2)	2.7203 (15)	171 (2)
O3—H1O3···O2ii	0.88 (2)	2.17 (2)	3.0276 (13)	163 (2)
O4—H1O4···O1iii	0.82 (2)	1.93 (2)	2.7379 (16)	166 (2)
N1—H1N1···O3i	0.87 (2)	2.24 (2)	3.0017 (16)	146.1 (19)