N-(3-tert-Butyl-1-phenyl-1H-pyrazol-5-yl)-N-(4-methoxy­benz­yl)acetamide: a hydrogen-bonded chain of centrosymmetric rings

The mol­ecule of the title compound, C₂₃H₂₇N₃O₂, adopts a conformation having no inter­nal symmetry so that the compound exhibits conformational chirality. The mol­ecules are linked by a combination of C-H...O and C-H...[pi](arene) hydrogen bonds into a chain of rings in which two types of centrosymmetric ring alternate.

S1. Comment

We report here the structure and supramolecular aggregation of the title compound, (I) (Fig. 1); this compound was prepared by acetylation of the amine, (II), whose structure was reported several years ago (Abonía et al., 2007). Compound (I) was originally prepared as a possible intermediate for the synthesis of new, fused pyrazolobenzazepine derivatives with potential biological applications (Lucács et al., 2001; Wikström et al., 2002; Crecente-Campo et al., 2009), and here we compare its structure with those of the precursor, (II), and some analogues of (II) (Castillo et al., 2009).

The molecular conformation of compound (I) can conveniently be considered in terms of the orientations of the three substituents bonded to the pyrazole ring relative to the plane of the pyrazole ring itself, as indicated by the leading torsion angles (Table 1). The unsubstituted ring makes a dihedral angle of 50.3 (2)° with the pyrazole ring; coplanarity of these two rings would lead to some short non-bonded contacts, in particular between the H atom bonded to atom C12 (Fig. 1) and the atoms of the amide group. As often found in systems of this type (Abonía et al., 2007; Castillo et al., 2009) the tert-butyl group adopts an orientation in which one of the methyl C atoms, here C32, is close to, but no precisely in, the plane of the adjacent pyrazole ring: in (I), atom C32 is displaced by only 0.111 (2) Å from the plane of the pyrazole ring. Although the amide unit based on atoms N51 and C58 is planar, this plane is almost orthogonal to that of the pyrazole ring, as the torsion angles N1—C5—N51—C57 and N1—C5—N51—C58 show (Table 1). On the other hand, the methoxy group is almost coplanar with the adjacent phenyl ring and the methyl atom C541 is displaced from the plane of this ring by only 0.100 (2) Å. Accordingly, the exocyclic bond angles at atom C54 differ by almost 10° (Table 1). The remaining bond distances and angles present no unusual values.

The conformation means that the molecules of compound (I) exhibit no internal symmetry and hence they are conformationally chiral; however, the centrosymmetric space group accommodates equal numbers of the two conformational enantiomers. The non-acylated precursor, (II), adopts a rather similar conformation to that of (I) but it crystallizes in the enantiomeric pair of space groups P4₁2₁2 and P4₃2₁2, so that each crystal contains only a single conformational enantiomer (Abonía et al., 2007). While it was not possible to determine the correct space group for the crystal selected for data collection, because of the absence of significant resonant scattering, it was concluded that the distribution of the crystalline products between the two space groups was essentially statistical. Despite their very close similarities in constitution and conformation, the series of compounds (II)–(VII) (Abonía et al., 2007; Castillo et al., 2009) exhibit a wide range of crystallization behaviour and some unexpected isomorphisms. Thus, compounds (II) (X = OMe) and (IV) (X = Me) are isomorphous in the enantiomeric space groups P4₁2₁2 and P4₃2₁2, and compounds (III) X = H), (V) X = CF₃) and (VII) X = Br) are isomorphous in space group C2/c, but compound (VI) X = Cl) is isomorphous with neither (IV) nor (VII).

The molecules of compound (I) are linked into a chain of centrosymmetric edge-fused rings by a combination of one C—H···O hydrogen bond and one C—H···π(arene) hydrogen bond (Table 2), in which the unsubstituted phenyl ring (C11–C16) provides the donor in the C—H···O hydrogen bond as well as acting as the acceptor in the C—H···π(arene) hydrogen bond. This latter interaction may be an important influence on the orientation of the phenyl ring relative to the pyrazole core of the molecule.

In the first of these interactions, the aryl atom C14 in the molecule at (x, y, z) acts as hydrogen-bond donor to the carbonyl atom O58 in the molecule at (-x, 1 - y, 1 - z), so forming a centrosymmetric R²₂(20) (Bernstein et al., 1995) ring, centred at (0, 1/2, 1/2). In the second interaction, the aryl atom C52 at (x, y, z) acts as hydrogen-bond donor to the aryl ring (C11–C16) in the molecule at (1 - x, 1 - y, 1 - z), so forming a second centrosymmetric ring, this time centred at (1/2, 1/2, 1/2). Propagation by inversion of these two motifs thus generates a chain of edge-fused rings running parallel to the [100] direction, with the rings built from paired C—H···O hydrogen bonds centred at (n, 1/2, 1/2), where n represents an integer, and those built from paired C—H···π(arene) hydrogen bonds centred at (n + 1/2, 1/2, 1/2), where n again represents an integer (Fig. 2).

The supramolecular aggregation in compound (I) may be briefly contrasted with that in compounds (II)–(VII). (Abonía et al., 2007; Castillo et al., 2009). In each of compounds (III)–(VII) the crystal structures are dominated by N—H···π hydrogen bonds, often accompanied by C—H···π hydrogen bonds, leading to the formation of a finite dimer in compound (IV), a simple chain in (III), a chain of rings in (VI), and sheets in both (V) and (VII). In compound (II), however, the N—H bond plays no role in the intermolecular aggregation, which instead is determined by a single C—H···N hydrogen bond, which forms a simple C(9) chain.

Related literature

For related literature, see: Abonía et al. (2007); Bernstein et al. (1995); Castillo et al. (2009); Crecente-Campo, Vázquez-Tato & Seijas (2009); Lucács et al. (2001); Wikström et al. (2002).

S2. Experimental

Sodium borohydride (3.8 mmol) was added portion-wise during the course of 1 h to a solution of 5-amino-(E)-3-tert-butyl-N-(4-methoxybenzylidene)-1-phenyl-1H-pyrazole (1.50 mmol) in methanol (10 cm³). After the reduction was complete, the volume of the solution was reduced to around 3 cm³ under reduced pressure, and water (5 cm³) was then added. The resulting mixture was extracted with ethyl acetate (2 x 5 cm³) and the combined extracts were dried with anhydrous sodium sulfate; then the solvent was removed to give the pure amine intermediate, (II) (see scheme), in 98% isolated yield. A mixture of the amine intermediate, (II), obtained above (0.89 mmol) and acetic anhydride (0.18 g, 2.0 mmol) was heated to 373 K in an oil bath for 10 min. After the reaction was completed, the mixture was cooled to ambient temperature and water (3 cm³) was added. The resulting solid product, (I), was collected by filtration in quantitative yield. Colourless crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in methanol: m.p. 390 K; MS (IE 70 eV) m/z (%) 377 (7 [M⁺]), 121 (100), 77 (6). Analysis found C,73.1, H 7.4, N 11.12%; C₂₃H₂₇N ₃O₂ requires C 73.2, H 7.2, N 11.1%.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H distances 0.95 Å (aromatic and pyrazole), 0.98 Å (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of compound (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of compound (I) showing the formation of a chain of hydrogen-bonded rings running parallel to the [100] direction. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

N-(3-tert-Butyl-1-phenyl-1H-pyrazol-5-yl)-N- (4-methoxybenzyl)acetamide

Crystal data

C23H27N3O2	Z = 2
Mr = 377.48	F(000) = 404
Triclinic, P1	Dx = 1.208 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.8325 (3) Å	Cell parameters from 4079 reflections
b = 9.8649 (4) Å	θ = 3.0–26.1°
c = 12.0365 (3) Å	µ = 0.08 mm^−1
α = 97.468 (2)°	T = 120 K
β = 95.512 (2)°	Block, colourless
γ = 114.643 (1)°	0.18 × 0.12 × 0.10 mm
V = 1037.44 (5) Å^3

Data collection

Bruker Nonius KappaCCD diffractometer	4079 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3269 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 3.0°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.986, Tmax = 0.992	l = −14→14
18936 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.359P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4079 reflections	Δρmax = 0.20 e Å^−3
259 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (4)

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

	x	y	z	Uiso*/Ueq
N1	0.44674 (13)	0.62459 (13)	0.37549 (9)	0.0201 (3)
N2	0.59005 (13)	0.73012 (13)	0.37241 (10)	0.0218 (3)
C3	0.63534 (16)	0.66918 (16)	0.28598 (12)	0.0214 (3)
C4	0.52111 (16)	0.52545 (16)	0.23298 (12)	0.0225 (3)
H4	0.5257	0.4592	0.1702	0.027*
C5	0.40220 (15)	0.50091 (15)	0.29046 (12)	0.0197 (3)
C11	0.35766 (16)	0.66222 (16)	0.45032 (11)	0.0206 (3)
C12	0.27899 (19)	0.56247 (17)	0.51741 (13)	0.0307 (4)
H12	0.2837	0.4679	0.5154	0.037*
C13	0.1929 (2)	0.60322 (19)	0.58795 (15)	0.0384 (4)
H13	0.1367	0.5348	0.6333	0.046*
C14	0.18784 (18)	0.74143 (18)	0.59302 (13)	0.0316 (4)
H14	0.1291	0.7681	0.6420	0.038*
C15	0.26851 (17)	0.84108 (18)	0.52666 (13)	0.0267 (3)
H15	0.2660	0.9368	0.5305	0.032*
C16	0.35299 (16)	0.80138 (16)	0.45454 (12)	0.0240 (3)
H16	0.4075	0.8692	0.4081	0.029*
C31	0.78820 (16)	0.76085 (16)	0.25340 (13)	0.0243 (3)
C32	0.8253 (2)	0.66268 (19)	0.16361 (16)	0.0397 (4)
H32A	0.8268	0.5755	0.1936	0.059*
H32B	0.9249	0.7230	0.1444	0.059*
H32C	0.7478	0.6266	0.0953	0.059*
C33	0.91334 (17)	0.82470 (19)	0.35810 (15)	0.0353 (4)
H33A	0.8903	0.8894	0.4147	0.053*
H33B	1.0109	0.8847	0.3358	0.053*
H33C	0.9188	0.7408	0.3907	0.053*
C34	0.77956 (18)	0.89327 (18)	0.20399 (14)	0.0311 (4)
H34A	0.6991	0.8534	0.1374	0.047*
H34B	0.8769	0.9536	0.1816	0.047*
H34C	0.7571	0.9574	0.2615	0.047*
N51	0.25424 (13)	0.38195 (12)	0.27122 (10)	0.0204 (3)
C51	0.27037 (16)	0.13326 (15)	0.23943 (11)	0.0201 (3)
C52	0.38457 (17)	0.09610 (17)	0.28144 (12)	0.0261 (3)
H52	0.4376	0.1409	0.3568	0.031*
C53	0.42250 (17)	−0.00439 (18)	0.21611 (13)	0.0281 (4)
H53	0.5010	−0.0280	0.2467	0.034*
C54	0.34618 (16)	−0.07127 (16)	0.10558 (12)	0.0218 (3)
C55	0.23038 (16)	−0.03786 (16)	0.06177 (12)	0.0219 (3)
H55	0.1762	−0.0844	−0.0131	0.026*
C56	0.19448 (16)	0.06479 (16)	0.12890 (12)	0.0219 (3)
H56	0.1161	0.0887	0.0984	0.026*
C57	0.22972 (17)	0.24092 (15)	0.31406 (12)	0.0225 (3)
H57A	0.1216	0.1878	0.3218	0.027*
H57B	0.2910	0.2684	0.3907	0.027*
O54	0.39547 (12)	−0.16561 (12)	0.04702 (9)	0.0281 (3)
C58	0.13542 (16)	0.39108 (17)	0.20805 (12)	0.0230 (3)
O58	0.00863 (11)	0.28455 (12)	0.18798 (9)	0.0316 (3)
C59	0.16800 (18)	0.53697 (18)	0.16580 (14)	0.0309 (4)
H59A	0.0836	0.5214	0.1073	0.046*
H59B	0.2617	0.5681	0.1334	0.046*
H59C	0.1798	0.6163	0.2292	0.046*
C541	0.32253 (19)	−0.23165 (19)	−0.06787 (13)	0.0327 (4)
H54A	0.2162	−0.3015	−0.0693	0.049*
H54B	0.3741	−0.2875	−0.1037	0.049*
H54C	0.3271	−0.1513	−0.1096	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0193 (6)	0.0164 (6)	0.0210 (6)	0.0049 (5)	0.0032 (5)	0.0015 (5)
N2	0.0179 (6)	0.0173 (6)	0.0264 (6)	0.0042 (5)	0.0038 (5)	0.0032 (5)
C3	0.0204 (7)	0.0191 (7)	0.0264 (7)	0.0098 (6)	0.0040 (6)	0.0055 (6)
C4	0.0226 (7)	0.0186 (7)	0.0262 (8)	0.0096 (6)	0.0052 (6)	0.0015 (6)
C5	0.0195 (7)	0.0154 (7)	0.0226 (7)	0.0069 (6)	0.0018 (5)	0.0024 (5)
C11	0.0191 (7)	0.0209 (7)	0.0186 (7)	0.0069 (6)	0.0016 (5)	0.0003 (5)
C12	0.0414 (10)	0.0201 (8)	0.0309 (8)	0.0121 (7)	0.0138 (7)	0.0047 (6)
C13	0.0476 (11)	0.0263 (9)	0.0395 (10)	0.0103 (8)	0.0247 (8)	0.0079 (7)
C14	0.0288 (8)	0.0304 (9)	0.0329 (9)	0.0110 (7)	0.0111 (7)	−0.0007 (7)
C15	0.0266 (8)	0.0254 (8)	0.0295 (8)	0.0142 (7)	0.0019 (6)	0.0017 (6)
C16	0.0244 (8)	0.0230 (8)	0.0241 (7)	0.0095 (6)	0.0038 (6)	0.0055 (6)
C31	0.0201 (7)	0.0182 (7)	0.0343 (8)	0.0076 (6)	0.0071 (6)	0.0048 (6)
C32	0.0308 (9)	0.0288 (9)	0.0583 (11)	0.0103 (8)	0.0223 (8)	0.0026 (8)
C33	0.0202 (8)	0.0323 (9)	0.0476 (10)	0.0051 (7)	0.0022 (7)	0.0130 (8)
C34	0.0281 (8)	0.0269 (8)	0.0407 (9)	0.0109 (7)	0.0117 (7)	0.0137 (7)
N51	0.0187 (6)	0.0148 (6)	0.0247 (6)	0.0049 (5)	0.0028 (5)	0.0021 (5)
C57	0.0255 (8)	0.0169 (7)	0.0218 (7)	0.0061 (6)	0.0049 (6)	0.0036 (6)
C51	0.0199 (7)	0.0149 (7)	0.0216 (7)	0.0034 (6)	0.0047 (5)	0.0042 (5)
C52	0.0279 (8)	0.0269 (8)	0.0208 (7)	0.0111 (7)	−0.0011 (6)	0.0022 (6)
C53	0.0279 (8)	0.0323 (9)	0.0272 (8)	0.0171 (7)	−0.0007 (6)	0.0064 (6)
C54	0.0232 (7)	0.0183 (7)	0.0258 (7)	0.0096 (6)	0.0073 (6)	0.0058 (6)
C55	0.0218 (7)	0.0205 (7)	0.0202 (7)	0.0071 (6)	0.0013 (6)	0.0018 (6)
C56	0.0198 (7)	0.0210 (7)	0.0244 (7)	0.0087 (6)	0.0023 (6)	0.0041 (6)
O54	0.0302 (6)	0.0290 (6)	0.0293 (6)	0.0187 (5)	0.0033 (4)	0.0003 (4)
C541	0.0344 (9)	0.0309 (9)	0.0331 (9)	0.0179 (8)	0.0044 (7)	−0.0050 (7)
C58	0.0216 (8)	0.0238 (8)	0.0212 (7)	0.0085 (6)	0.0042 (6)	−0.0001 (6)
O58	0.0200 (6)	0.0307 (6)	0.0361 (6)	0.0053 (5)	0.0009 (5)	0.0026 (5)
C59	0.0285 (8)	0.0288 (9)	0.0344 (9)	0.0123 (7)	−0.0002 (7)	0.0070 (7)

Geometric parameters (Å, º)

N1—N2	1.3666 (16)	C34—H34A	0.9800
N1—C5	1.3680 (18)	C34—H34B	0.9800
N1—C11	1.4325 (18)	C34—H34C	0.9800
N2—C3	1.3385 (18)	N51—C58	1.3733 (18)
C3—C4	1.406 (2)	N51—C57	1.4799 (17)
C3—C31	1.517 (2)	C57—C51	1.507 (2)
C4—C5	1.367 (2)	C57—H57A	0.9900
C4—H4	0.9500	C57—H57B	0.9900
C5—N51	1.4101 (17)	C51—C52	1.390 (2)
C11—C12	1.382 (2)	C51—C56	1.3922 (19)
C11—C16	1.387 (2)	C52—C53	1.379 (2)
C12—C13	1.390 (2)	C52—H52	0.9500
C12—H12	0.9500	C53—C54	1.391 (2)
C13—C14	1.379 (2)	C53—H53	0.9500
C13—H13	0.9500	C54—O54	1.3672 (17)
C14—C15	1.382 (2)	C54—C55	1.388 (2)
C14—H14	0.9500	C55—C56	1.394 (2)
C15—C16	1.385 (2)	C55—H55	0.9500
C15—H15	0.9500	C56—H56	0.9500
C16—H16	0.9500	O54—C541	1.4272 (18)
C31—C32	1.529 (2)	C541—H54A	0.9800
C31—C33	1.532 (2)	C541—H54B	0.9800
C31—C34	1.534 (2)	C541—H54C	0.9800
C32—H32A	0.9800	C58—O58	1.2250 (17)
C32—H32B	0.9800	C58—C59	1.507 (2)
C32—H32C	0.9800	C59—H59A	0.9800
C33—H33A	0.9800	C59—H59B	0.9800
C33—H33B	0.9800	C59—H59C	0.9800
C33—H33C	0.9800
N2—N1—C5	111.09 (11)	C31—C34—H34A	109.5
N2—N1—C11	119.51 (11)	C31—C34—H34B	109.5
C5—N1—C11	128.69 (12)	H34A—C34—H34B	109.5
C3—N2—N1	105.23 (11)	C31—C34—H34C	109.5
N2—C3—C4	110.88 (12)	H34A—C34—H34C	109.5
N2—C3—C31	119.53 (12)	H34B—C34—H34C	109.5
C4—C3—C31	129.44 (13)	C58—N51—C5	121.35 (11)
C5—C4—C3	105.73 (13)	C58—N51—C57	119.72 (11)
C5—C4—H4	127.1	C5—N51—C57	118.81 (11)
C3—C4—H4	127.1	N51—C57—C51	114.13 (11)
C4—C5—N1	107.05 (12)	N51—C57—H57A	108.7
C4—C5—N51	131.42 (13)	C51—C57—H57A	108.7
N1—C5—N51	121.43 (12)	N51—C57—H57B	108.7
C12—C11—C16	120.77 (13)	C51—C57—H57B	108.7
C12—C11—N1	120.70 (13)	H57A—C57—H57B	107.6
C16—C11—N1	118.53 (12)	C52—C51—C56	117.71 (13)
C11—C12—C13	118.69 (15)	C52—C51—C57	119.98 (13)
C11—C12—H12	120.7	C56—C51—C57	122.29 (13)
C13—C12—H12	120.7	C53—C52—C51	121.43 (13)
C14—C13—C12	120.99 (15)	C53—C52—H52	119.3
C14—C13—H13	119.5	C51—C52—H52	119.3
C12—C13—H13	119.5	C52—C53—C54	120.19 (14)
C13—C14—C15	119.82 (15)	C52—C53—H53	119.9
C13—C14—H14	120.1	C54—C53—H53	119.9
C15—C14—H14	120.1	O54—C54—C53	115.54 (13)
C14—C15—C16	119.98 (14)	O54—C54—C55	124.75 (13)
C14—C15—H15	120.0	C55—C54—C53	119.70 (13)
C16—C15—H15	120.0	C54—C55—C56	119.22 (13)
C15—C16—C11	119.75 (14)	C54—C55—H55	120.4
C15—C16—H16	120.1	C56—C55—H55	120.4
C11—C16—H16	120.1	C51—C56—C55	121.74 (13)
C3—C31—C32	110.51 (12)	C51—C56—H56	119.1
C3—C31—C33	110.51 (12)	C55—C56—H56	119.1
C32—C31—C33	109.76 (13)	C54—O54—C541	116.67 (11)
C3—C31—C34	108.01 (12)	O54—C541—H54A	109.5
C32—C31—C34	109.05 (13)	O54—C541—H54B	109.5
C33—C31—C34	108.96 (12)	H54A—C541—H54B	109.5
C31—C32—H32A	109.5	O54—C541—H54C	109.5
C31—C32—H32B	109.5	H54A—C541—H54C	109.5
H32A—C32—H32B	109.5	H54B—C541—H54C	109.5
C31—C32—H32C	109.5	O58—C58—N51	120.79 (13)
H32A—C32—H32C	109.5	O58—C58—C59	122.01 (13)
H32B—C32—H32C	109.5	N51—C58—C59	117.20 (12)
C31—C33—H33A	109.5	C58—C59—H59A	109.5
C31—C33—H33B	109.5	C58—C59—H59B	109.5
H33A—C33—H33B	109.5	H59A—C59—H59B	109.5
C31—C33—H33C	109.5	C58—C59—H59C	109.5
H33A—C33—H33C	109.5	H59A—C59—H59C	109.5
H33B—C33—H33C	109.5	H59B—C59—H59C	109.5
C5—N1—N2—C3	−1.29 (15)	C4—C3—C31—C33	−133.91 (16)
C11—N1—N2—C3	−172.45 (12)	N2—C3—C31—C34	−68.09 (17)
N1—N2—C3—C4	0.49 (15)	C4—C3—C31—C34	106.99 (17)
N1—N2—C3—C31	176.43 (12)	C53—C54—O54—C541	−177.94 (13)
N2—C3—C4—C5	0.46 (16)	C4—C5—N51—C58	−92.78 (19)
C31—C3—C4—C5	−174.97 (14)	N1—C5—N51—C57	−100.84 (15)
C3—C4—C5—N1	−1.21 (15)	N1—C5—N51—C58	83.16 (17)
C3—C4—C5—N51	175.17 (14)	C4—C5—N51—C57	83.22 (19)
N2—N1—C5—C4	1.60 (16)	C58—N51—C57—C51	95.56 (15)
C11—N1—C5—C4	171.73 (13)	C5—N51—C57—C51	−80.52 (15)
N2—N1—C5—N51	−175.22 (11)	N51—C57—C51—C52	118.10 (14)
C11—N1—C5—N51	−5.1 (2)	N51—C57—C51—C56	−63.63 (17)
N2—N1—C11—C12	−133.97 (14)	C56—C51—C52—C53	0.4 (2)
C5—N1—C11—C12	56.6 (2)	C57—C51—C52—C53	178.70 (13)
N2—N1—C11—C16	45.58 (17)	C51—C52—C53—C54	0.0 (2)
C5—N1—C11—C16	−123.84 (15)	C52—C53—C54—O54	178.14 (13)
C16—C11—C12—C13	1.1 (2)	C52—C53—C54—C55	−0.8 (2)
N1—C11—C12—C13	−179.40 (14)	O54—C54—C55—C56	−177.61 (13)
C11—C12—C13—C14	−1.3 (3)	C53—C54—C55—C56	1.2 (2)
C12—C13—C14—C15	0.4 (3)	C52—C51—C56—C55	0.1 (2)
C13—C14—C15—C16	0.6 (2)	C57—C51—C56—C55	−178.21 (13)
C14—C15—C16—C11	−0.8 (2)	C54—C55—C56—C51	−0.9 (2)
C12—C11—C16—C15	−0.1 (2)	C55—C54—O54—C541	0.9 (2)
N1—C11—C16—C15	−179.61 (12)	C5—N51—C58—O58	176.99 (13)
N2—C3—C31—C32	172.69 (13)	C57—N51—C58—O58	1.0 (2)
C4—C3—C31—C32	−12.2 (2)	C5—N51—C58—C59	−3.36 (19)
N2—C3—C31—C33	51.01 (18)	C57—N51—C58—C59	−179.33 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O58^i	0.95	2.55	3.389 (2)	147
C52—H52···Cg^ii	0.95	2.75	3.544 (2)	142

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.