Crystal structure and Hirshfeld surface analysis of 2-oxo-2-phenyl-ethyl 3-nitroso-2-phenyl-imidazo[1,2-a]pyridine-8-carboxyl-ate.

The title compound, C22H15N3O4, is built up from a central imidazo[1,2-a]pyridine ring system connected to a nitroso group, a phenyl ring and a 2-oxo-2-phenyl-ethyl acetate group. The imidazo[1,2-a] pyridine ring system is almost planar (r.m.s. deviation = 0.017 Å) and forms dihedral angles of 22.74 (5) and 45.37 (5)°, respectively, with the phenyl ring and the 2-oxo-2-phenyl-ethyl acetate group. In the crystal, the mol-ecules are linked into chains parallel to the b axis by C-H⋯O hydrogen bonds, generating R 2 1 (5) and R 4 4 (28) graph-set motifs. The chains are further linked into a three-dimensional network by C-H⋯π and π-stacking inter-actions. The inter-molecular inter-actions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most important contributions for the crystal packing are from H⋯H (36.2%), H⋯C/C⋯H (20.5%), H⋯O/O⋯H (20.0%), C⋯O/O⋯C (6.5%), C⋯N/N⋯C (6.2%), H⋯N/N⋯H (4.5%) and C⋯C (4.3%) inter-actions. © El Kalai et al. 2022.

Chemical context

Numerous drugs contain N-heterocycles as the core structure, including imidazo[1,2-a]pyridine and its derivatives, which are used in medicinal chemistry (Swainston Harrison & Keating, 2005 ▸; Deep et al., 2017 ▸) or that exhibit diverse biological properties, such as anti­bacterial (Mishra et al., 2021 ▸), anti­tubercular (Wang et al., 2019 ▸), tyrosinase inhibitory (Damghani et al., 2020 ▸), HIV inhibitory (Bode et al., 2011 ▸), anti­diabetic (Saeedi et al., 2021 ▸), anti-inflammatory (Gundlewad et al., 2020 ▸) or anti­cancer activities (Yu et al., 2020 ▸; Sigalapalli et al., 2021 ▸). Encouraged by these features and in a continuation of our exploration of the synthesis, mol­ecular structures and Hirshfeld surface analysis of new N-heterocyclic compounds (Daoui et al., 2021 ▸, 2022 ▸; El Kalai et al., 2021a ▸,b ▸), we report herein the crystal structure and Hirshfeld surface analysis of 2-oxo-2-phenyl­ethyl 3-nitroso-2-phenyl­imidazo[1,2-a]pyridine-8-carboxyl­ate, C22H15N3O4 (I).

Structural commentary

The mol­ecular structure of (I) is shown in Fig. 1 ▸. The imidazo[1,2-a] pyridine ring system is planar with an r.m.s deviation of 0.017 Å and a maximum deviation of 0.028 (1) Å for atom C11. The mean plane through the fused ring system makes dihedral angles of 22.74 (5) and 45.37 (5)° with the phenyl ring (C1–C6) and the 2-oxo-2-phenyl­ethyl acetate group (C14–C22), respectively. The dihedral angle between the two aromatic rings (C1–C6 and C17–C22) is 59.63 (5)°. The mol­ecular conformation is stabilized by two weak intra­molecular C9—H9⋯O1 and C1—H1⋯N1 hydrogen bonds, generating S(6) ring motifs (Table 1 ▸, Fig. 1 ▸).

Figure 1

The mol­ecular structure of (I), with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Intra­molecular hydrogen bonds are indicated by dashed lines.

Table 1

Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C17–C22 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯O4i	0.97	2.54	3.1257 (19)	119
C15—H15B⋯O1ii	0.97	2.61	3.4841 (18)	150
C9—H9⋯O2iii	0.93	2.46	3.1176 (16)	128
C10—H10⋯O2iii	0.93	2.67	3.2243 (17)	119
C9—H9⋯O1	0.93	2.35	2.8736 (18)	116
C1—H1⋯N1	0.93	2.51	3.081 (2)	120
C22—H22⋯Cg4iv	0.93	2.80	3.657 (2)	153

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

Supra­molecular features

In the crystal, mol­ecules are linked by C9—H9⋯O2iii and C10—H10⋯O2iii hydrogen bonds, forming chains that propagate parallel to the b axis and enclose (5) ring motifs (Table 1 ▸, Fig. 2 ▸). Additionally, inter­molecular C15—H15A⋯O4i and C15—H15B⋯O1ii hydrogen bonds with (28) ring motifs are also present, generating a three-dimensional supra­molecular network that also comprises a weak C22—H22⋯Cg4iv inter­action (Cg4 is the centroid of the C17–C22 phenyl ring) as well as π–π stacking inter­actions involving the centroids (Cg1 and Cg2) of the N2/C13/N3/C7–C8 and N2/C9–C13 rings with a centroid-to-centroid distance Cg1⋯Cg2 (x, 1/2 − y, −1/2 + z) of 3.5750 (9) Å and a slippage of 0.685 Å (Fig. 2 ▸).

Figure 2

A view along the a axis of the crystal structure of (I). Blue, black, purple and orange dashed lines symbolize inter­molecular C15—H15A⋯O4i, C15—H15B⋯O1ii, C9—H9⋯O2iii and C10—H10⋯O2iii hydrogen bonds, respectively; π–π and C—H⋯π inter­actions are shown as green dashed lines.

Database survey

A search of the Cambridge Structural Database (CSD, version 5.40, update of August 2019; Groom et al., 2016 ▸) using 2-phenyl­imidazo[1,2-a]pyridin-3-amine as the main skeleton revealed the presence of 54 structures with different substit­uents on the imidazo[1,2-a]pyridine ring. The two structures most similar to (I) are N-(2-phenyl­imidazo[1,2-a]pyridin-3-yl)acetamide (MIXZOJ; Anaflous et al., 2008 ▸) and 4-[(7-methyl-2-phenyl­imidazo[1,2-a]pyridin-3-yl)carbonoimido­yl]phenol (TUQCEP; Elaatiaoui et al., 2015 ▸). In MIXZOJ, C15H13N3O, the crystal structure consists of mol­ecular columns that are inter­connected by N—H⋯N hydrogen bonds along the b-axis direction. The torsion angle between the imidazo[1,2-a]pyridine ring system and the phenyl ring is 9.04 (5)°. In TUQCEP, C21H17N3O, the fused ring system is almost planar (r.m.s. deviation = 0.031 Å) and forms dihedral angles of 64.97 (7) and 18.52 (6)° with the phenyl ring and the (imino­meth­yl)phenol group, respectively. In its crystal, mol­ecules are linked by pairs of C—H⋯π inter­actions into centrosymmetric dimeric units, which are further connected by O—H⋯N hydrogen bonds, forming layers parallel to (101).

Hirshfeld surface analysis

Hirshfeld surface analysis was used to qu­antify the inter­molecular contacts of the title compound, using Crystal Explorer (Turner et al., 2017 ▸). The Hirshfeld surface was generated with a standard (high) surface resolution and with the three-dimensional d norm surface plotted over a fixed colour scale of −0.1706 (red) to 1.2371 (blue) a.u. (Fig. 3 ▸ a). The shape-index map of the title mol­ecule was generated in the range −1 to 1 Å (Fig. 3 ▸ b), revealing the presence of red and blue triangles that are indicative of the presence of π–π stacking inter­actions. The curvedness map of the title complex was generated in the range −4.0 to 4.0 Å (Fig. 3 ▸ c) and shows flat surface patches characteristic of planar stacking. The Hirshfeld surface representations with the function d norm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, C⋯O/O⋯C, C⋯N/N⋯C, H⋯N/N⋯H and C⋯C inter­actions in Fig. 4 ▸ a–g, respectively. The overall two-dimensional fingerprint plot is illustrated in Fig. 5 ▸ a, with those delineated into H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, C⋯O/O⋯C, C⋯N/N⋯C, H⋯N/N⋯H and C⋯C contacts associated with their relative contributions to the Hirshfeld surface in Fig. 5 ▸ b–h, respectively. The most important inter­molecular inter­action is H⋯H, contributing 36.2% to the overall crystal packing (Fig. 5 ▸ b). H⋯C/C⋯H contacts, with a 20.5% contribution to the Hirshfeld surface, indicate the presence of the weak C—H⋯π inter­action (Table 1 ▸). Two pairs of characteristic wings in the fingerprint plot with pairs of tips at d e + d i ∼2.74 Å are present (Fig. 5 ▸ c). H⋯O/O⋯H contacts arising from inter­molecular C—H⋯O hydrogen bonding make a 20.0% contribution to the Hirshfeld surface and are represented by a pair of sharp spikes in the region d e + d i ∼2.34 Å (Fig. 5 ▸ d). The C⋯C contacts are a measure of π–π stacking inter­actions and contribute 4.3% of the Hirshfeld surface (Fig. 5 ▸ h). The contributions of the other contacts to the Hirshfeld surface are C⋯O/O⋯C of 6.5%, C⋯N/N⋯C of 6.2% and H⋯N/N⋯H of 4.5%.

Figure 3

(a) d norm mapped on the Hirshfeld surface to visualize the inter­molecular inter­actions, (b) shape-index map of the title compound and (c) curvedness map of the title compound using a range from −4 to 4 Å.

Figure 4

The Hirshfeld surface representations of (I) with the function d norm plotted onto the surface for (a) H⋯H, (b) H⋯C/C⋯H, (c) H⋯O/O⋯H, (d) C⋯O/O⋯C, (e) C⋯N/N⋯C, (f) H⋯N/N⋯H and (g) C⋯C inter­actions.

Figure 5

The full two-dimensional fingerprint plots for the title compound, showing (a) all inter­actions, and delineated into (b) H⋯H, (c) H⋯C/C⋯H, (d) H⋯O/ O⋯H, (e) C⋯O/O⋯C, (f) C⋯N/N⋯C, (g) H⋯N/N⋯H and (h) C⋯C inter­actions, together with their relative contributions.

Synthesis and crystallization

To a solution of 2-oxo-2-phenyl­ethyl 2-phenyl­imidazo[1,2-a]pyridine-8-carboxyl­ate (0.71 g, 2 mmol) in acetic acid (50 ml), sodium nitrite (1.4 g, 2 mmol) was added at room temperature. The resulting precipitate was washed with water and extracted with di­chloro­methane (3 × 20 ml). The combined di­chloro­methane extracts were dried over anhydrous sodium sulfate and filtered. The remaining solution was concentrated under reduced pressure. The residue was purified chromatographically on a neutral alumina gel column using di­chloro­methane as eluent. Single crystals were obtained by slow evaporation of a di­chloro­methane solution at room temperature (yield 80%).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Hydrogen atoms were fixed geometrically and treated as riding, with C—H = 0.97 Å for methyl­ene [U iso(H) = 1.5U eq(C)], C—H = 0.93 Å for aromatic [U iso(H) = 1.2U eq(C)] and C—H = 0.98 Å for methine [U iso(H) = 1.2U eq(C)] H atoms.

Table 2

Experimental details

Crystal data
Chemical formula	C22H15N3O4
M r	385.37
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	296
a, b, c (Å)	15.9256 (14), 14.8256 (14), 7.6787 (6)
β (°)	90.566 (7)
V (Å3)	1812.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.10
Crystal size (mm)	0.56 × 0.38 × 0.15
Data collection
Diffractometer	Stoe IPDS 2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2012 ▸)
T min, T max	0.946, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	27945, 6703, 3040
R int	0.070
(sin θ/λ)max (Å−1)	0.765
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.046, 0.118, 0.92
No. of reflections	6703
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.15, −0.16

Computer programs: X-AREA and X-RED (Stoe & Cie, 2012 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), Mercury (Macrae et al., 2020 ▸), WinGX (Farrugia, 2012 ▸), PLATON (Spek, 2020 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001517/wm5632sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001517/wm5632Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989022001517/wm5632Isup3.cml

CCDC reference: 2106558

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

C22H15N3O4	F(000) = 800
Mr = 385.37	Dx = 1.412 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.9256 (14) Å	Cell parameters from 18578 reflections
b = 14.8256 (14) Å	θ = 1.9–32.8°
c = 7.6787 (6) Å	µ = 0.10 mm−1
β = 90.566 (7)°	T = 296 K
V = 1812.9 (3) Å3	Rod, green
Z = 4	0.56 × 0.38 × 0.15 mm

Stoe IPDS 2 diffractometer	6703 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3040 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.070
Detector resolution: 6.67 pixels mm-1	θmax = 32.9°, θmin = 2.6°
rotation method scans	h = −24→24
Absorption correction: integration (X-RED32; Stoe & Cie, 2012)	k = −22→22
Tmin = 0.946, Tmax = 0.969	l = −10→11
27945 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-atom parameters constrained
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.0506P)2] where P = (Fo2 + 2Fc2)/3
S = 0.92	(Δ/σ)max < 0.001
6703 reflections	Δρmax = 0.15 e Å−3
262 parameters	Δρmin = −0.16 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
O3	0.63005 (6)	0.31601 (7)	0.48667 (14)	0.0542 (3)
O2	0.58609 (6)	0.39797 (6)	0.25605 (15)	0.0595 (3)
N3	0.40012 (7)	0.34790 (7)	0.20621 (16)	0.0441 (3)
N2	0.39287 (6)	0.19477 (7)	0.20006 (16)	0.0435 (3)
O4	0.75836 (8)	0.26469 (8)	0.30406 (19)	0.0788 (4)
O1	0.25639 (7)	0.09653 (7)	0.0672 (2)	0.0780 (4)
N1	0.25076 (8)	0.18024 (9)	0.06361 (19)	0.0599 (4)
C14	0.58089 (8)	0.33230 (9)	0.34708 (19)	0.0416 (3)
C12	0.52135 (8)	0.25563 (8)	0.31845 (18)	0.0414 (3)
C13	0.44102 (8)	0.27009 (8)	0.24261 (18)	0.0404 (3)
C7	0.32472 (8)	0.32353 (9)	0.13986 (19)	0.0441 (3)
C17	0.86457 (9)	0.34187 (9)	0.46238 (19)	0.0464 (3)
C8	0.31681 (8)	0.22879 (9)	0.1315 (2)	0.0465 (3)
C6	0.26278 (8)	0.39215 (9)	0.08286 (19)	0.0459 (3)
C11	0.54667 (9)	0.16813 (9)	0.3493 (2)	0.0483 (3)
H11	0.598339	0.157821	0.403177	0.058*
C16	0.77582 (9)	0.32058 (9)	0.4145 (2)	0.0495 (3)
C15	0.70537 (8)	0.36842 (9)	0.5070 (2)	0.0498 (3)
H15A	0.719202	0.375040	0.629688	0.060*
H15B	0.697194	0.428055	0.457752	0.060*
C18	0.88553 (9)	0.40814 (10)	0.5833 (2)	0.0524 (4)
H18	0.843669	0.443252	0.632786	0.063*
C9	0.42025 (9)	0.10793 (9)	0.2257 (2)	0.0508 (4)
H9	0.387103	0.059250	0.191712	0.061*
C10	0.49660 (9)	0.09435 (9)	0.3016 (2)	0.0529 (4)
H10	0.515667	0.035964	0.321857	0.063*
C5	0.28989 (9)	0.47829 (10)	0.0411 (2)	0.0537 (4)
H5	0.346539	0.492649	0.052027	0.064*
C4	0.23357 (10)	0.54324 (11)	−0.0168 (2)	0.0618 (4)
H4	0.252468	0.600751	−0.044788	0.074*
C19	0.96856 (10)	0.42184 (11)	0.6299 (3)	0.0645 (4)
H19	0.982383	0.465939	0.711376	0.077*
C3	0.14938 (11)	0.52236 (12)	−0.0328 (2)	0.0669 (5)
H3	0.111528	0.565477	−0.073272	0.080*
C1	0.17725 (9)	0.37247 (11)	0.0689 (3)	0.0633 (4)
H1	0.157736	0.315422	0.098519	0.076*
C22	0.92826 (10)	0.29109 (11)	0.3880 (2)	0.0639 (4)
H22	0.914895	0.247016	0.306093	0.077*
C20	1.03132 (10)	0.37028 (13)	0.5559 (3)	0.0719 (5)
H20	1.087105	0.379435	0.588214	0.086*
C2	0.12162 (10)	0.43762 (13)	0.0113 (3)	0.0727 (5)
H2	0.064726	0.424057	0.002223	0.087*
C21	1.01088 (11)	0.30541 (13)	0.4343 (3)	0.0736 (5)
H21	1.053005	0.271212	0.383457	0.088*

	U11	U22	U33	U12	U13	U23
O3	0.0450 (5)	0.0615 (6)	0.0559 (7)	−0.0123 (4)	−0.0143 (5)	0.0119 (5)
O2	0.0558 (6)	0.0431 (5)	0.0792 (8)	−0.0076 (4)	−0.0223 (5)	0.0138 (5)
N3	0.0351 (5)	0.0412 (5)	0.0558 (7)	−0.0003 (4)	−0.0046 (5)	0.0017 (5)
N2	0.0354 (5)	0.0418 (6)	0.0534 (7)	−0.0037 (4)	−0.0030 (5)	0.0028 (5)
O4	0.0687 (7)	0.0791 (8)	0.0882 (9)	0.0000 (6)	−0.0168 (7)	−0.0363 (7)
O1	0.0631 (7)	0.0515 (6)	0.1188 (11)	−0.0111 (5)	−0.0220 (7)	−0.0053 (6)
N1	0.0451 (7)	0.0562 (7)	0.0783 (10)	−0.0071 (6)	−0.0122 (6)	−0.0018 (7)
C14	0.0327 (6)	0.0428 (7)	0.0492 (8)	0.0027 (5)	−0.0041 (6)	0.0002 (6)
C12	0.0360 (6)	0.0430 (7)	0.0451 (8)	−0.0008 (5)	−0.0008 (6)	0.0031 (6)
C13	0.0362 (6)	0.0389 (6)	0.0461 (8)	−0.0031 (5)	0.0003 (6)	0.0024 (6)
C7	0.0348 (6)	0.0467 (7)	0.0508 (8)	−0.0018 (5)	−0.0025 (6)	0.0013 (6)
C17	0.0450 (7)	0.0460 (7)	0.0481 (8)	−0.0002 (5)	−0.0044 (6)	0.0044 (6)
C8	0.0352 (6)	0.0478 (7)	0.0565 (9)	−0.0034 (5)	−0.0068 (6)	0.0020 (6)
C6	0.0382 (7)	0.0485 (7)	0.0511 (9)	0.0024 (5)	−0.0056 (6)	−0.0015 (6)
C11	0.0391 (7)	0.0487 (7)	0.0569 (9)	0.0006 (6)	−0.0046 (6)	0.0084 (6)
C16	0.0525 (8)	0.0448 (7)	0.0511 (9)	−0.0020 (6)	−0.0115 (7)	0.0009 (6)
C15	0.0424 (7)	0.0488 (7)	0.0579 (9)	−0.0040 (6)	−0.0137 (6)	0.0008 (7)
C18	0.0424 (7)	0.0526 (8)	0.0621 (10)	−0.0019 (6)	−0.0039 (7)	−0.0011 (7)
C9	0.0479 (8)	0.0384 (7)	0.0659 (10)	−0.0038 (6)	−0.0058 (7)	0.0021 (6)
C10	0.0482 (8)	0.0385 (7)	0.0719 (11)	0.0012 (6)	−0.0054 (7)	0.0077 (7)
C5	0.0432 (7)	0.0497 (8)	0.0680 (11)	0.0025 (6)	−0.0064 (7)	0.0001 (7)
C4	0.0622 (10)	0.0507 (8)	0.0727 (12)	0.0089 (7)	−0.0027 (8)	0.0057 (8)
C19	0.0520 (9)	0.0631 (9)	0.0780 (12)	−0.0102 (7)	−0.0117 (8)	−0.0004 (9)
C3	0.0594 (10)	0.0706 (10)	0.0704 (12)	0.0231 (8)	−0.0138 (8)	0.0037 (9)
C1	0.0421 (8)	0.0605 (9)	0.0871 (13)	−0.0009 (7)	−0.0118 (8)	0.0028 (8)
C22	0.0569 (9)	0.0647 (10)	0.0702 (12)	0.0109 (7)	−0.0026 (8)	−0.0061 (8)
C20	0.0408 (8)	0.0788 (11)	0.0959 (15)	−0.0031 (8)	−0.0076 (8)	0.0195 (11)
C2	0.0422 (8)	0.0765 (11)	0.0990 (15)	0.0076 (8)	−0.0172 (8)	−0.0003 (10)
C21	0.0534 (9)	0.0793 (12)	0.0880 (15)	0.0150 (9)	0.0052 (9)	0.0043 (10)

O3—C14	1.3431 (16)	C15—H15A	0.9700
O3—C15	1.4365 (16)	C15—H15B	0.9700
O2—C14	1.2018 (16)	C18—C19	1.381 (2)
N3—C7	1.3491 (16)	C18—H18	0.9300
N3—C13	1.3526 (16)	C9—C10	1.3581 (19)
N2—C9	1.3729 (17)	C9—H9	0.9300
N2—C13	1.3918 (16)	C10—H10	0.9300
N2—C8	1.4092 (16)	C5—C4	1.386 (2)
O4—C16	1.2157 (17)	C5—H5	0.9300
O1—N1	1.2446 (16)	C4—C3	1.380 (2)
N1—C8	1.3732 (17)	C4—H4	0.9300
C14—C12	1.4951 (18)	C19—C20	1.385 (3)
C12—C11	1.3783 (18)	C19—H19	0.9300
C12—C13	1.4166 (18)	C3—C2	1.375 (3)
C7—C8	1.4115 (19)	C3—H3	0.9300
C7—C6	1.4803 (18)	C1—C2	1.381 (2)
C17—C18	1.390 (2)	C1—H1	0.9300
C17—C22	1.391 (2)	C22—C21	1.376 (2)
C17—C16	1.4907 (19)	C22—H22	0.9300
C6—C5	1.387 (2)	C20—C21	1.377 (3)
C6—C1	1.396 (2)	C20—H20	0.9300
C11—C10	1.4002 (19)	C2—H2	0.9300
C11—H11	0.9300	C21—H21	0.9300
C16—C15	1.511 (2)
C14—O3—C15	117.98 (11)	H15A—C15—H15B	108.4
C7—N3—C13	105.94 (10)	C19—C18—C17	119.98 (15)
C9—N2—C13	123.04 (11)	C19—C18—H18	120.0
C9—N2—C8	131.29 (11)	C17—C18—H18	120.0
C13—N2—C8	105.67 (10)	C10—C9—N2	118.84 (12)
O1—N1—C8	117.36 (12)	C10—C9—H9	120.6
O2—C14—O3	124.53 (12)	N2—C9—H9	120.6
O2—C14—C12	125.28 (12)	C9—C10—C11	120.11 (13)
O3—C14—C12	110.15 (11)	C9—C10—H10	119.9
C11—C12—C13	118.33 (11)	C11—C10—H10	119.9
C11—C12—C14	120.41 (11)	C4—C5—C6	120.80 (14)
C13—C12—C14	120.94 (11)	C4—C5—H5	119.6
N3—C13—N2	111.88 (10)	C6—C5—H5	119.6
N3—C13—C12	130.17 (11)	C3—C4—C5	119.83 (15)
N2—C13—C12	117.93 (11)	C3—C4—H4	120.1
N3—C7—C8	111.24 (11)	C5—C4—H4	120.1
N3—C7—C6	121.04 (11)	C18—C19—C20	120.37 (16)
C8—C7—C6	127.70 (11)	C18—C19—H19	119.8
C18—C17—C22	119.06 (13)	C20—C19—H19	119.8
C18—C17—C16	122.36 (13)	C2—C3—C4	119.82 (14)
C22—C17—C16	118.53 (13)	C2—C3—H3	120.1
N1—C8—N2	127.33 (12)	C4—C3—H3	120.1
N1—C8—C7	127.34 (12)	C2—C1—C6	120.06 (16)
N2—C8—C7	105.26 (10)	C2—C1—H1	120.0
C5—C6—C1	118.72 (13)	C6—C1—H1	120.0
C5—C6—C7	119.55 (12)	C21—C22—C17	120.64 (16)
C1—C6—C7	121.73 (13)	C21—C22—H22	119.7
C12—C11—C10	121.69 (12)	C17—C22—H22	119.7
C12—C11—H11	119.2	C21—C20—C19	119.80 (15)
C10—C11—H11	119.2	C21—C20—H20	120.1
O4—C16—C17	121.74 (14)	C19—C20—H20	120.1
O4—C16—C15	118.84 (13)	C3—C2—C1	120.74 (15)
C17—C16—C15	119.41 (12)	C3—C2—H2	119.6
O3—C15—C16	108.54 (11)	C1—C2—H2	119.6
O3—C15—H15A	110.0	C22—C21—C20	120.14 (17)
C16—C15—H15A	110.0	C22—C21—H21	119.9
O3—C15—H15B	110.0	C20—C21—H21	119.9
C16—C15—H15B	110.0
C15—O3—C14—O2	−14.9 (2)	C8—C7—C6—C1	23.0 (3)
C15—O3—C14—C12	163.13 (11)	C13—C12—C11—C10	2.5 (2)
O2—C14—C12—C11	141.14 (16)	C14—C12—C11—C10	−171.16 (15)
O3—C14—C12—C11	−36.82 (19)	C18—C17—C16—O4	177.35 (15)
O2—C14—C12—C13	−32.3 (2)	C22—C17—C16—O4	−5.1 (2)
O3—C14—C12—C13	149.69 (13)	C18—C17—C16—C15	−3.6 (2)
C7—N3—C13—N2	0.14 (16)	C22—C17—C16—C15	173.89 (14)
C7—N3—C13—C12	−178.13 (15)	C14—O3—C15—C16	−89.28 (14)
C9—N2—C13—N3	−179.58 (13)	O4—C16—C15—O3	19.49 (19)
C8—N2—C13—N3	0.31 (16)	C17—C16—C15—O3	−159.56 (12)
C9—N2—C13—C12	−1.1 (2)	C22—C17—C18—C19	−1.0 (2)
C8—N2—C13—C12	178.82 (12)	C16—C17—C18—C19	176.52 (14)
C11—C12—C13—N3	176.84 (15)	C13—N2—C9—C10	2.4 (2)
C14—C12—C13—N3	−9.5 (2)	C8—N2—C9—C10	−177.50 (15)
C11—C12—C13—N2	−1.3 (2)	N2—C9—C10—C11	−1.2 (2)
C14—C12—C13—N2	172.27 (13)	C12—C11—C10—C9	−1.2 (3)
C13—N3—C7—C8	−0.56 (17)	C1—C6—C5—C4	−1.3 (2)
C13—N3—C7—C6	−179.33 (13)	C7—C6—C5—C4	178.39 (15)
O1—N1—C8—N2	2.6 (2)	C6—C5—C4—C3	0.2 (3)
O1—N1—C8—C7	179.29 (16)	C17—C18—C19—C20	0.4 (2)
C9—N2—C8—N1	−3.5 (3)	C5—C4—C3—C2	1.0 (3)
C13—N2—C8—N1	176.62 (15)	C5—C6—C1—C2	1.2 (3)
C9—N2—C8—C7	179.26 (15)	C7—C6—C1—C2	−178.44 (16)
C13—N2—C8—C7	−0.61 (15)	C18—C17—C22—C21	0.7 (2)
N3—C7—C8—N1	−176.49 (15)	C16—C17—C22—C21	−176.95 (16)
C6—C7—C8—N1	2.2 (3)	C18—C19—C20—C21	0.4 (3)
N3—C7—C8—N2	0.74 (17)	C4—C3—C2—C1	−1.0 (3)
C6—C7—C8—N2	179.42 (14)	C6—C1—C2—C3	−0.1 (3)
N3—C7—C6—C5	21.9 (2)	C17—C22—C21—C20	0.2 (3)
C8—C7—C6—C5	−156.69 (16)	C19—C20—C21—C22	−0.8 (3)
N3—C7—C6—C1	−158.46 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15A···O4i	0.97	2.54	3.1257 (19)	119
C15—H15B···O1ii	0.97	2.61	3.4841 (18)	150
C9—H9···O2iii	0.93	2.46	3.1176 (16)	128
C10—H10···O2iii	0.93	2.67	3.2243 (17)	119
C9—H9···O1	0.93	2.35	2.8736 (18)	116
C1—H1···N1	0.93	2.51	3.081 (2)	120
C22—H22···Cg4iv	0.93	2.80	3.657 (2)	153