4-(4-Acetyl-5-methyl-1H-1,2,3-triazol-1-yl)benzo-nitrile: crystal structure and Hirshfeld surface analysis.

The title compound, C12H10N4O, comprises a central 1,2,3-triazole ring (r.m.s. deviation = 0.0030 Å) flanked by N-bound 4-cyano-phenyl and C-bound acetyl groups, which make dihedral angles of 54.64 (5) and 6.8 (3)° with the five-membered ring, indicating a twisted mol-ecule. In the crystal, the three-dimensional architecture is sustained by carbonyl-C=O⋯π(triazo-yl), cyano-C≡N⋯π(triazo-yl) (these inter-actions are shown to be attractive based on non-covalent inter-action plots) and π-π stacking inter-actions [inter-centroid separation = 3.9242 (9) Å]. An analysis of the Hirshfeld surface shows the important contributions made by H⋯H (35.9%) and N⋯H (26.2%) contacts to the overall surface, as well as notable contributions by O⋯H (9.9%), C⋯H (8.7%), C⋯C (7.3%) and C⋯N (7.2%) contacts.

Chemical context

The 1,2,3-triazoles comprise an inter­esting class of heterocyclic compounds, with diverse applications in biological and material chemistry (Struthers et al., 2010 ▸; Bonandi et al., 2017 ▸; Dheer et al., 2017 ▸). In particular, 1,2,3-triazoles containing a carbonyl or carboxyl group in their structures have received considerable attention as they are found in a great number of biologically and pharmaceutically active mol­ecules that exhibit a broad spectrum of properties (Shu et al., 2009 ▸; Morzherin et al., 2011 ▸; Cheng et al., 2012 ▸; Gilchrist et al., 2014 ▸). In this context, the organocatalytic cyclo­addition reaction of organic azides with β-ketoesters, β-keto­amides, enones and allyl ketones has proven to be a powerful strategy for the synthesis of such class of compounds (John et al., 2015 ▸; Lima et al., 2015 ▸). Although much progress has been achieved, most of the available methodologies usually employ a homogenous catalyst, which can be difficult to recover. In view of environmental concerns, very recently, we reported for the first time, a heterogeneous strategy for the synthesis of 1,4,5-tris-substituted-1,2,3-triazoles through the 1,3-dipolar cyclo­addition between aryl azides and active methyl­ene compounds using CuO nanoparticles as catalyst in DMSO under microwave irradiation (Dias et al., 2018 ▸). The title compound, (I), was prepared in this study and despite having been prepared by another route in a different study (Kamalraj et al., 2008 ▸), no crystal structure is available. The availability of crystals in the latter study prompted the present structural analysis.

Structural commentary

The mol­ecular structure of (I), Fig. 1 ▸, comprises an essentially planar 1,2,3-triazolyl ring with a r.m.s. deviation of the fitted atoms of 0.0030 Å; the maximum deviation of 0.0037 (9) Å is found for the N2 atom. A 4-cyano­phenyl residue is connected to the 1,2,3-triazolyl ring at the N1-position and forms a dihedral angle of 54.64 (5)° with it, indicating a significant twist between the rings. By contrast, the acetyl group connected at the C2-position is approximately co-planar with the central ring, forming a dihedral angle of 6.8 (3)°. The dihedral angle between the phenyl and acetyl groups is 60.82 (13)°, indicating a dis-rotatory relationship. The acetyl-carbonyl group occupies a position approximately syn to the ring-bound methyl substituent with the C1—C2—C3—O1 and C4—C1—C2—C3 torsion angles being 6.2 (3) and −1.5 (3)°, respectively.

Figure 1

The mol­ecular structure of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Supra­molecular features

The mol­ecular packing of (I) features inter­actions involving both the five- and six-membered rings. Centrosymmetrically related mol­ecules are connected via carbonyl-C=O⋯π(triazo­yl) inter­actions, Table 1 ▸. Further connections between mol­ecules are of the type cyano-C≡N⋯π(triazo­yl) to the opposite face of the five-membered ring (Fig. 2 ▸, Table 1 ▸), which together lead to a supra­molecular layer parallel to (01). The O⋯π or N⋯π separations for these inter­actions are significantly longer that the van der Waals’ separations for these species (3.32 and 3.35 Å, respectively) but the non-covalent inter­actions plots (see below) indicate that they are weakly attractive in nature. Connections between the layers giving rise to a three-dimensional architecture are weak π–π stacking inter­actions between centrosymmetrically related phenyl rings, with the inter-centroid separation being 3.9242 (9) Å; symmetry operation (i): 2 − x, 2 − y, 1 − z. A view of the unit cell contents is shown in Fig. 2 ▸. The specified and other weak inter­molecular inter­actions are discussed in more detail below in Hirshfeld surface analysis.

Table 1

π(Triazol­yl) inter­action geometry (Å, °)

Cg1 is the centroid of the N1–N3/C1/C2 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—O1⋯Cg1i	1.21 (1)	3.69 (1)	3.7359 (17)	83 (1)
C12—N4⋯Cg1ii	1.14 (1)	3.68 (1)	3.8468 (19)	90 (1)

Symmetry codes: (i) ; (ii) .

Figure 2

A view of the unit-cell contents shown in projection down the b axis. The C= O⋯π(triazo­yl), C≡N⋯π(triazo­yl) and π(tol­yl)–π(tol­yl) contacts are shown as orange, blue and purple dashed lines, respectively.

Hirshfeld surface analysis

The Hirshfeld surface calculations for (I) were performed in accord with related studies (Caracelli et al., 2018 ▸) and provide information on the influence of other weak inter­molecular inter­actions instrumental in the mol­ecular packing. In addition to the presence of carbonyl-C=O⋯π(triazol­yl) and cyano-C≡N⋯π(triazol­yl) inter­actions (Table 1 ▸) in the formation of three-dimensional architecture as discussed above, the mol­ecular packing also features weak C—H⋯N inter­actions. On the Hirshfeld surface mapped over d norm in Fig. 3 ▸, these inter­actions are characterized as the bright-red spots near the triazolyl-N3, cyano-N4 (Fig. 3 ▸ a), phenyl-H8 and H10 atoms (Fig. 3 ▸ b), and the diminutive-red spots near cyano-N4 (Fig. 3 ▸ b) and phenyl-H7 (Fig. 3 ▸ a) atoms. The influence of short inter­atomic C⋯O/O⋯C contacts involving methyl-C4 and carbonyl-O1 atoms (Table 2 ▸) is also observed as the faint-red spots near these atoms in Fig. 3 ▸ b. The donors and acceptors of inter­molecular C—H⋯N inter­actions are also evident as the blue and red regions corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential shown in Fig. 4 ▸. Views of the immediate environment about a reference mol­ecule within the Hirshfeld surface mapped over the shape-index property, highlighting inter­molecular C=O⋯π, C≡N⋯π and π–π stacking inter­actions, are illustrated in Fig. 5 ▸.

Figure 3

Two views of the Hirshfeld surface for (I) mapped over d norm in the range −0.065 to +1.215 a.u.

Table 2

Summary of short inter­atomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
H4C⋯H4C	2.39	1 − x, 1 − y, 1 − z
H10⋯N3	2.48	+ x,  − y,  + z
H7⋯N4	2.58	− + x,  − y, − + z
H8⋯N4	2.53	− x, − + y,  − z
C4⋯O1	3.208 (2)	1 − x, 1 − y, 1 − z

Figure 4

Two views of the Hirshfeld surface mapped over the electrostatic potential in the range −0.092 to +0.055 a.u. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 5

Views of the Hirshfeld surface mapped the shape-index property showing (a) π–π and C≡N⋯π inter­actions with black and sky-blue dotted lines, respectively and (b) C=O⋯π contacts with red-dotted lines.

The overall two-dimensional fingerprint plot for (I) (Fig. 6 ▸ a) and those delineated into H⋯H, N⋯H/H⋯N, O⋯H/H⋯O, C⋯H/H⋯C, C⋯C, C⋯N/N⋯C and N⋯N contacts (McKinnon et al., 2007 ▸) are illustrated in Fig. 6 ▸ b–i, respectively; the percentage contributions from identified inter­atomic contacts to the Hirshfeld surface are summarized in Table 3 ▸. The short inter­atomic H⋯H contact involving symmetry-related methyl-H4C atoms (Table 2 ▸) is viewed as the cone-shaped tip at d e + d i ∼ 2.3 Å in the fingerprint plot delineated into H⋯H contacts (Fig. 6 ▸ b). The second largest contribution to the Hirshfeld surface, i.e. 26.2%, is from N⋯H/H⋯N contacts (Fig. 6 ▸ c) and arise from the inter­molecular C—H⋯N contacts involving cyano-N4 and triazolyl-N3 atoms (Table 2 ▸) and are viewed as the pair of overlapping green and blue spikes with their tips at d e + d i ∼2.5 Å. Although the carbonyl-O1 atom makes a significant contribution of 9.9% to the overall surface owing to inter­atomic O⋯H/H⋯O contacts, it is evident from the respective delineated fingerprint plot (Fig. 6 ▸ d) that these are beyond van der Waals separations. The relatively small contribution from C⋯H/H⋯C contacts to the Hirshfeld surface (Table 3 ▸) is indicative of the absence of C—H⋯π contacts in the mol­ecular packing, Fig. 6 ▸ e. The weak π–π stacking inter­actions between symmetry related phenyl-(C6–C11) rings are evident from the fingerprint delineated into C⋯C contacts (Fig. 6 ▸ f) as the rocket-like tip at d e + d i ∼ 3.6 Å. The involvement of the triazolyl ring in inter­molecular triazolyl-C≡N⋯π and carbonyl C=O⋯π contacts in the crystal is reflected from the percentage contributions due to C⋯N/N⋯C, C⋯O/O⋯C, N⋯N and N⋯O/O⋯N contacts to the Hirshfeld surface (Table 3 ▸). These inter­molecular inter­actions are also evident from the fingerprint plots delineated into C⋯N/N⋯C, C⋯O/O⋯C and N⋯N contacts in Fig. 6 ▸ f–h, respectively.

Figure 6

(a) The full two-dimensional fingerprint plot for (I) and (b)-(h) those delineated into H⋯H, N⋯H/H⋯N, O⋯H/H⋯O, C⋯H/H⋯C, C⋯C, C⋯N/N⋯C and N⋯N contacts, respectively.

Table 3

Percentage contributions of inter­atomic contacts to the Hirshfeld surface for (I)

Contact	Percentage contribution
H⋯H	35.9
N⋯H/H⋯N	26.2
O⋯H/H⋯O	9.9
C⋯H/H⋯C	8.7
C⋯C	7.3
C⋯N/N⋯C	7.2
N⋯N	2.1
C⋯O/O⋯C	1.4
N⋯O/O⋯N	1.4

Non-covalent inter­action plots

Non-covalent inter­action (NCI) plots are a convenient means by which the nature of an inter­action between residues may be assessed in terms of being attractive or otherwise (Johnson et al., 2010 ▸; Contreras-García et al., 2011 ▸). In NCI plots, a weakly attractive inter­action will appear green on the isosurface, whereas attractive and repulsive inter­actions will result in blue and red isosurfaces, respectively. The NCI plots for the inter­acting entities of the carbonyl-C=O⋯π(triazol­yl) and cyano-C≡N⋯π(triazol­yl) inter­actions are shown in Fig. 7 ▸ a,b, indicating the weakly attractive nature of these inter­actions. The arrows in Fig. 7 ▸ b, highlight a weak phenyl-C—H⋯N(cyano) inter­action (Table 2 ▸).

Figure 7

Non-covalent inter­action plots for the (a) carbonyl-C= O⋯π(triazol­yl) and (b) cyano-C≡N⋯π(triazol­yl) inter­actions. The arrows in (b) indicate attractive phenyl-C—H⋯N(cyano) inter­actions (see text).

Database survey

There are four closely related compounds in the literature whereby the cyano group of (I) is replaced by chloride and bromide, which are isostructural (Zeghada et al., 2011 ▸), methyl (El-Hiti et al., 2017 ▸) and nitro (Vinutha et al. (2013 ▸); two independent mol­ecules comprise the asymmetric unit of the nitro compound. Key dihedral angle data are included in Table 4 ▸. This shows that the greatest variations in dihedral angles between the phenyl and acetyl residues is found for the two independent mol­ecules of the nitro compound. The different relative conformations in the aforementioned mol­ecules is highlighted in the overlay diagram of Fig. 8 ▸.

Table 4

Dihedral angle data (°) for (I) and 4-X-phenyl derivatives

X	triazol­yl/phen­yl	triazol­yl/acet­yl	phen­yl/acet­yl	Ref.
Me	50.11 (7)	6.12 (18)	50.14 (12)	El-Hiti et al. (2017 ▸)
Cl	45.60 (4)	6.97 (9)	45.19 (6)	Zeghada et al. (2011 ▸)
Br	47.03 (5)	7.08 (12)	46.5 (7)	Zeghada et al. (2011 ▸)
NO2 a	38.26 (15)	13.4 (4)	27.9 (3)	Vinutha et al. (2013 ▸)
	87.11 (18)	15.2 (3)	74.4 (2)
C≡N	54.64 (5)	6.8 (3)	60.82 (13)	This work

Note: (a) Two independent mol­ecules comprise the asymmetric unit.

Figure 8

Overlay diagram for (I) and 4-X-phenyl derivatives: (I) (red image), X = Cl (green), X = Br (blue), X = Me (pink), X = NO2 (first independent mol­ecule; aqua) and X = NO2 (second mol­ecule; yellow). The mol­ecules have been overlapped so that the triazolyl rings are coincident.

Synthesis and crystallization

Compound (I) was prepared as described in the literature (Dias et al., 2018 ▸) and crystals were obtained by the slow evaporation from its ethyl acetate/hexane (v/v) solution. M.p. 426–428 K. 1H NMR (400 MHz, CDCl3) δ = 7.91 (d, J = 8.7 Hz, 2H), 7.65 (d, J = 8.7 Hz, 2H), 2.76 (s, 3H), 2.66 (s, 3H). 13C NMR (100 MHz,CDCl3) δ = 194.30, 144.20, 138.89, 137.42, 133.85, 125.84, 117.51, 114.23, 28.10, 10.43 ppm.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U iso(H) set to 1.2–1.5U eq(C).

Table 5

Experimental details

Crystal data
Chemical formula	C12H10N4O
M r	226.24
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	293
a, b, c (Å)	11.8533 (5), 6.8299 (3), 14.7329 (6)
β (°)	107.477 (1)
V (Å3)	1137.67 (8)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.09
Crystal size (mm)	0.44 × 0.27 × 0.12
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 ▸)
T min, T max	0.726, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	30812, 2333, 2083
R int	0.023
(sin θ/λ)max (Å−1)	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.044, 0.126, 1.10
No. of reflections	2333
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.21, −0.20

Computer programs: APEX2 and SAINT (Bruker, 2009 ▸), SIR2014 (Burla et al., 2015 ▸), SHELXL2014 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸), DIAMOND (Brandenburg, 2006 ▸), MarvinSketch (ChemAxon, 2010 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018010885/hb7764sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018010885/hb7764Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018010885/hb7764Isup3.cml

CCDC reference: 1859008

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

C12H10N4O	F(000) = 472
Mr = 226.24	Dx = 1.321 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.8533 (5) Å	Cell parameters from 9978 reflections
b = 6.8299 (3) Å	θ = 2.6–26.3°
c = 14.7329 (6) Å	µ = 0.09 mm−1
β = 107.477 (1)°	T = 293 K
V = 1137.67 (8) Å3	Irregular, colourless
Z = 4	0.44 × 0.27 × 0.12 mm

Bruker APEXII CCD diffractometer	2083 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.023
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 26.4°, θmin = 1.9°
Tmin = 0.726, Tmax = 0.745	h = −14→14
30812 measured reflections	k = −8→8
2333 independent reflections	l = −18→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044	H-atom parameters constrained
wR(F2) = 0.126	w = 1/[σ2(Fo2) + (0.0573P)2 + 0.3916P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max < 0.001
2333 reflections	Δρmax = 0.21 e Å−3
156 parameters	Δρmin = −0.20 e Å−3
0 restraints

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	0.39515 (11)	0.7197 (2)	0.36712 (11)	0.0785 (5)
N1	0.73587 (10)	0.95924 (17)	0.48424 (8)	0.0357 (3)
N2	0.70535 (11)	1.13354 (19)	0.43684 (10)	0.0476 (3)
N3	0.59641 (11)	1.11608 (19)	0.38456 (10)	0.0462 (3)
N4	1.27442 (13)	0.8725 (3)	0.80947 (11)	0.0623 (4)
C1	0.64418 (11)	0.8326 (2)	0.46207 (10)	0.0364 (3)
C2	0.55549 (12)	0.9350 (2)	0.39775 (10)	0.0364 (3)
C3	0.43345 (13)	0.8728 (2)	0.34833 (11)	0.0451 (4)
C4	0.64687 (15)	0.6346 (3)	0.50374 (14)	0.0614 (5)
H4A	0.7168	0.6210	0.5570	0.092*
H4B	0.6473	0.5378	0.4566	0.092*
H4C	0.5782	0.6168	0.5246	0.092*
C5	0.35961 (15)	1.0069 (3)	0.27426 (14)	0.0668 (6)
H5A	0.3902	1.0108	0.2209	0.100*
H5B	0.3615	1.1361	0.3004	0.100*
H5C	0.2795	0.9602	0.2538	0.100*
C6	0.85161 (11)	0.9389 (2)	0.55064 (9)	0.0354 (3)
C7	0.92321 (13)	0.7849 (2)	0.54291 (11)	0.0454 (4)
H7	0.8976	0.6944	0.4938	0.054*
C8	1.03376 (14)	0.7662 (2)	0.60904 (11)	0.0482 (4)
H8	1.0827	0.6622	0.6050	0.058*
C9	1.07120 (12)	0.9032 (2)	0.68124 (10)	0.0403 (3)
C10	0.99970 (13)	1.0600 (3)	0.68695 (11)	0.0494 (4)
H10	1.0261	1.1532	0.7347	0.059*
C11	0.88901 (13)	1.0776 (2)	0.62138 (11)	0.0472 (4)
H11	0.8401	1.1820	0.6249	0.057*
C12	1.18561 (13)	0.8846 (3)	0.75178 (11)	0.0470 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0477 (7)	0.0734 (9)	0.0927 (10)	−0.0232 (7)	−0.0117 (7)	0.0290 (8)
N1	0.0288 (6)	0.0351 (6)	0.0380 (6)	−0.0012 (4)	0.0023 (5)	0.0037 (5)
N2	0.0366 (6)	0.0393 (7)	0.0589 (8)	−0.0023 (5)	0.0022 (6)	0.0124 (6)
N3	0.0334 (6)	0.0443 (7)	0.0534 (7)	0.0003 (5)	0.0020 (5)	0.0125 (6)
N4	0.0443 (8)	0.0714 (11)	0.0552 (9)	0.0006 (7)	−0.0094 (7)	−0.0012 (7)
C1	0.0307 (6)	0.0376 (7)	0.0364 (7)	−0.0032 (5)	0.0036 (5)	0.0021 (6)
C2	0.0302 (7)	0.0401 (7)	0.0361 (7)	−0.0003 (5)	0.0054 (5)	0.0049 (6)
C3	0.0317 (7)	0.0553 (9)	0.0424 (8)	−0.0039 (6)	0.0024 (6)	0.0068 (7)
C4	0.0469 (9)	0.0476 (10)	0.0732 (12)	−0.0105 (7)	−0.0071 (8)	0.0224 (8)
C5	0.0377 (8)	0.0836 (14)	0.0641 (11)	−0.0017 (9)	−0.0074 (8)	0.0234 (10)
C6	0.0273 (6)	0.0391 (7)	0.0358 (7)	−0.0026 (5)	0.0033 (5)	0.0015 (6)
C7	0.0376 (8)	0.0462 (8)	0.0436 (8)	0.0026 (6)	−0.0009 (6)	−0.0114 (6)
C8	0.0383 (8)	0.0475 (9)	0.0512 (9)	0.0077 (6)	0.0019 (7)	−0.0067 (7)
C9	0.0301 (7)	0.0493 (8)	0.0365 (7)	−0.0029 (6)	0.0025 (5)	0.0008 (6)
C10	0.0388 (8)	0.0544 (9)	0.0477 (8)	−0.0026 (7)	0.0018 (7)	−0.0157 (7)
C11	0.0356 (8)	0.0460 (8)	0.0538 (9)	0.0032 (6)	0.0038 (7)	−0.0120 (7)
C12	0.0385 (8)	0.0526 (9)	0.0434 (8)	−0.0017 (7)	0.0025 (7)	−0.0012 (7)

O1—C3	1.205 (2)	C5—H5A	0.9600
N1—C1	1.3500 (17)	C5—H5B	0.9600
N1—N2	1.3726 (17)	C5—H5C	0.9600
N1—C6	1.4326 (16)	C6—C7	1.378 (2)
N2—N3	1.2952 (17)	C6—C11	1.379 (2)
N3—C2	1.3634 (19)	C7—C8	1.384 (2)
N4—C12	1.140 (2)	C7—H7	0.9300
C1—C2	1.3762 (19)	C8—C9	1.385 (2)
C1—C4	1.482 (2)	C8—H8	0.9300
C2—C3	1.4734 (19)	C9—C10	1.384 (2)
C3—C5	1.491 (2)	C9—C12	1.4452 (19)
C4—H4A	0.9600	C10—C11	1.381 (2)
C4—H4B	0.9600	C10—H10	0.9300
C4—H4C	0.9600	C11—H11	0.9300
C1—N1—N2	111.26 (11)	C3—C5—H5C	109.5
C1—N1—C6	129.75 (12)	H5A—C5—H5C	109.5
N2—N1—C6	118.91 (11)	H5B—C5—H5C	109.5
N3—N2—N1	106.62 (11)	C7—C6—C11	121.37 (13)
N2—N3—C2	109.42 (12)	C7—C6—N1	120.33 (12)
N1—C1—C2	103.53 (12)	C11—C6—N1	118.29 (13)
N1—C1—C4	124.68 (12)	C6—C7—C8	119.25 (14)
C2—C1—C4	131.77 (13)	C6—C7—H7	120.4
N3—C2—C1	109.16 (12)	C8—C7—H7	120.4
N3—C2—C3	121.99 (13)	C7—C8—C9	119.71 (14)
C1—C2—C3	128.84 (14)	C7—C8—H8	120.1
O1—C3—C2	121.25 (14)	C9—C8—H8	120.1
O1—C3—C5	121.51 (15)	C10—C9—C8	120.56 (13)
C2—C3—C5	117.25 (14)	C10—C9—C12	118.92 (14)
C1—C4—H4A	109.5	C8—C9—C12	120.52 (14)
C1—C4—H4B	109.5	C11—C10—C9	119.66 (14)
H4A—C4—H4B	109.5	C11—C10—H10	120.2
C1—C4—H4C	109.5	C9—C10—H10	120.2
H4A—C4—H4C	109.5	C6—C11—C10	119.42 (14)
H4B—C4—H4C	109.5	C6—C11—H11	120.3
C3—C5—H5A	109.5	C10—C11—H11	120.3
C3—C5—H5B	109.5	N4—C12—C9	177.85 (18)
H5A—C5—H5B	109.5
C1—N1—N2—N3	−0.81 (17)	C1—C2—C3—C5	−173.75 (16)
C6—N1—N2—N3	−177.77 (12)	C1—N1—C6—C7	57.1 (2)
N1—N2—N3—C2	0.54 (17)	N2—N1—C6—C7	−126.64 (15)
N2—N1—C1—C2	0.72 (16)	C1—N1—C6—C11	−123.36 (17)
C6—N1—C1—C2	177.26 (13)	N2—N1—C6—C11	52.95 (19)
N2—N1—C1—C4	−177.72 (16)	C11—C6—C7—C8	1.7 (2)
C6—N1—C1—C4	−1.2 (2)	N1—C6—C7—C8	−178.73 (14)
N2—N3—C2—C1	−0.10 (18)	C6—C7—C8—C9	−0.6 (3)
N2—N3—C2—C3	179.34 (14)	C7—C8—C9—C10	−1.0 (3)
N1—C1—C2—N3	−0.38 (16)	C7—C8—C9—C12	179.08 (15)
C4—C1—C2—N3	177.90 (17)	C8—C9—C10—C11	1.5 (3)
N1—C1—C2—C3	−179.78 (14)	C12—C9—C10—C11	−178.55 (15)
C4—C1—C2—C3	−1.5 (3)	C7—C6—C11—C10	−1.2 (2)
N3—C2—C3—O1	−173.09 (17)	N1—C6—C11—C10	179.25 (14)
C1—C2—C3—O1	6.2 (3)	C9—C10—C11—C6	−0.4 (3)
N3—C2—C3—C5	6.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C3—O1···Cg1i	1.21 (1)	3.69 (1)	3.7359 (17)	83 (1)
C12—N4···Cg1ii	1.14 (1)	3.68 (1)	3.8468 (19)	90 (1)