Methyl 4-[(1-acetyl-3-tert-butyl-1H-pyrazol-5-yl)amino]-3-nitro­benzoate

In the mol­ecule of the title compound, C₁₇H₂₀N₄O₅, there are two intra­molecular N-H...O hydrogen bonds having amidic and nitro-group O atoms as the acceptors and together forming a three-centre N-H...(O)₂ system. These inter­actions appear to play an important role in controlling the relative orientation of the pyrazole and aryl rings. The bond distances provide evidence for some polarization of the electronic structure. Mol­ecules are linked into simple chains by a single C-H...O hydrogen bond.

S1. Comment

We report here the structure of the title compound, (I) (Fig. 1), which we compare with those of some aryl analogues (Quiroga et al., 2008, 2010) containing unsubstituted amino groups, compounds (II)–(IV) (see Scheme). Compound (I) was prepared as an intermediate within a current programme for the synthesis of novel benzimidazole derivatives of antitumoral interest (Abonía et al., 2010).

The intramolecular dimensions in compound (I) show some interesting features, involving both the molecular conformation and the intramolecular distances and angles. Firstly, the dihedral angle between the two rings is only 22.3 (2)° despite the rather short non-bonded distance, 1.97 Å, between the two H atoms bonded to atoms C4 and C56. Associated with this short distance is a large C—N—C angle (Table 1) at the amino atom N51 which links the two rings, whose magnitude is reminiscent of the large C—C—C angle at the bridging methine atom in each of a series of seven (Z)-5-arylmethylene-2-thioxothiazolidin-4-ones, (V) (Delgado et al., 2005, 2006), where it was concluded that the short intramolecular C—H···S contact between the two independent rings was strongly repulsive. A similarly wide angle at the bridging methine C atom was also observed in the dimethylamino derivative, (VI), obtained by aminolysis of the corresponding derivative of type (V) (Low et al., 2007). In addition, the two exocyclic bond angles at atom C5 differ by more than 15° (Table 1) in a sense consistent with the occurrence of a strong repulsive interaction between the H atoms bonded to C4 and C56: on the other hand, the two exocyclic angles at atom C51 are the same within experimental uncertainty, although the C51—N51 distance is longer than expected (cf. the discussion of the intramolecular distances, below).

The question thus arises why the dihedral angle between the ring is not larger, since rotation about the C—N bonds, particularly about the C5—N51 bond, seems at first sight to provide a means of avoiding the short intramolecular H···H contact which involves a lower energy cost than the substantial distortion of the bond angles at C5 and N51. A possible answer lies in the observation that atom N51 acts as the hydrogen-bond donor to atoms O11 and O522 in a planar three-centre N—H···.(O)₂ system. While both the acetyl and the nitro substituents are slightly twisted out of the plane of their adjacent rings, with dihedral angles of 10.8 (2) and 8.1 (2)° respectively, it is notable that in each case the sense of the rotation about the exocyclic bonds, N1—C11 and C52—N521, respectively, is such as to bring the atoms O11 and O522 closer to atom H51 than they would be if the acetyl and nitro substituents were coplanar with their adjacent rings. Accordingly, it can be concluded that the N—H···O interactions are strongly attractive, and probably charge-assisted (Gilli et al., 1994) (cf. the discussion of the intramolecular distances, below) and that they are probably one of the key factors controlling the molecular conformation, in particular the relative orientations of the two rings.

Secondly, there is evidence for some quinonoid-type bond fixation within the aryl ring. Thus, the C53—C54 and C55—C56 distances (Table 1) are the shortest within this ring, while C51—C52 is the longest. In addition, the C52—N521 distance is short for its type [mean value (Allen et al., 1987) 1.468 Å, lower quartile value 1.460 Å], while the two associated N—O distances are both slightly long for their type. However, the N51—C51 distance does not differ significantly from the mean value for bonds of this type, possibly for reasons connected with the steric demands in the vicinity of atom N51, as discussed above. Overall, however, the bond distances provide some support for a contribution to the electronic structure from the polarized form (Ia) (see Scheme). However, there is no evidence for any participation by the ester function.

As noted above, the N—H bond participates in a three-centre intramolecular hydrogen bond (Table 2), giving rise to two edge-fused S(6) (Bernstein et al., 1995) motifs, but it plays no role in the intermolecular hydrogen bonding. This is determined solely by a C—H···O hydrogen bond in which, despite the presence of two independent carbonyl groups in the molecule, one in an amide group and the other in an ester group, the hydrogen-bond acceptor is one of the nitro-group O atoms, O522, which is also a participant in the intramolecular three-centre system. By contrast, where amidic carbonyl groups and nitro groups are present in the same molecules, the amidic O atoms usually appear [to?] act as the better hydrogen-bond acceptors (Garden et al., 2005; Wardell et al., 2005, 2006). The acceptor behaviour in compound (I) is thus consistent with the development of significant negative charge on the O atoms of the nitro group as a consequence of the electronic polarization discussed above. The effect of the C—H···O hydrogen bond is to link molecules related by the 2₁ screw axis along (1/2, y, 3/4) into a C(7) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 2).

It is of interest briefly to compare the supramolecular aggregation in compound (I), where there is an excess of conventional hydrogen-bond acceptors over donors with that in the closely related series of compounds in (II)–(IV) (see Scheme). In compound (II) (Quiroga et al., 2010) there is an excess of conventional hydrogen-bond donors over acceptors; compound (III) (Quiroga et al., 2008) contains equal numbers of conventional hydrogen-bond donors and acceptors; and in compound (IV) (Quiroga et al., 2008) the conventional hydrogen-bond acceptors are in excess over the donors, as in compound (I). In each of the structures of compounds (II)–(IV) there is an intramolecular N—H···O hydrogen bond. The molecules of compound (II) are linked into sheets by a combination of N—H···N, C—H···O and C—H···π(arene) hydrogen bonds, so that the single O atom present acts as a double acceptor of hydrogen bonds, while the aryl ring and the two-connected N atom of the pyrazole ring both also act as acceptors. In the 4-methoxy derivative, compound (III), the molecules are linked into a chain of rings by a combination of N—H···N and N—H···π(arene) hydrogen bonds, while in the 2-nitro derivative, compound (IV), a combination of one N—H···N hydrogen bond and three C—H···O hydrogen bonds, all of which utilize nitro O atoms as the acceptors, links the molecules into a three-dimensional framework structure. Thus, in each of the crystal structures of compounds (I)–(IV), a different range of hydrogen bonds is utilized in the aggregation and the resulting hydrogen-bonded structures are all different: a simple chain in (I), a chain of rings in (III), a sheet in (II) and a three-dimensional framework structure in (IV).

Related literature

For related literature, see: Abonía et al. (2010); Allen et al. (1987); Bernstein et al. (1995); Delgado et al. (2005, 2006); Garden et al. (2005); Gilli et al. (1994); Low et al. (2007); Quiroga et al. (2008, 2010); Wardell et al. (2005, 2006).

S2. Experimental

A mixture of methyl 4-(3-tert-butyl-1H-pyrazol-5-ylamino)-3-nitrobenzoate (1.0 mmol) and acetic anhydride (0.5 cm³) was heated at 323 K for 5 min. When the starting ester had been completely acetylated, as indicated by thin-layer chromatography, the reaction mixture was cooled to ambient temperature and the excess of solvent was removed under reduced pressure. The resulting solid was washed twice with ethanol (0.5 cm³) to give the title compound, (I), as an orange solid; yield 96%, m. p. 429 K. MS (70 eV) m/z (%): 360 (34) [M⁺], 318 (100) [(M-43)⁺], 303 (21), 272 (27), 216 (29). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, of a solution in ethanol.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms. The H atom bonded to atom N51 was permitted to ride at the position deduced from the difference map, with U_iso(H) = 1.2U_eq(N), giving an N—H distance of 0.88 Å. The H atoms bonded to C atoms were treated as riding atoms in geometrically idealized positions, with distances 0.95 Å (aromatic and pyrazole) or 0.98 Å (methyl) 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 bonded to C 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 edge-fused S(6) rings and a C(7) hydrogen-bonded chain parallel to [010]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Methyl 4-[(1-acetyl-3-tert-butyl-1H-pyrazol-5-yl)amino]-3-nitrobenzoate

Crystal data

C17H20N4O5	F(000) = 760
Mr = 360.37	Dx = 1.389 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3200 reflections
a = 11.9079 (15) Å	θ = 3.0–25.5°
b = 15.6452 (13) Å	µ = 0.10 mm^−1
c = 9.255 (1) Å	T = 120 K
β = 91.727 (11)°	Plate, orange
V = 1723.4 (3) Å^3	0.44 × 0.28 × 0.10 mm
Z = 4

Data collection

Bruker Nonius KappaCCD diffractometer	3200 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2743 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.0°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
Tmin = 0.965, Tmax = 0.990	l = −11→11
19894 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.8903P] where P = (Fo^2 + 2Fc^2)/3
3200 reflections	(Δ/σ)max = 0.001
240 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.24201 (13)	0.41106 (10)	0.39672 (17)	0.0189 (4)
N2	0.17858 (13)	0.47680 (10)	0.33613 (18)	0.0207 (4)
C3	0.19966 (16)	0.54255 (12)	0.4195 (2)	0.0191 (4)
C4	0.27613 (16)	0.52293 (12)	0.5338 (2)	0.0209 (4)
H4	0.3035	0.5605	0.6074	0.025*
C5	0.30256 (16)	0.43934 (12)	0.5171 (2)	0.0194 (4)
C11	0.22648 (16)	0.32802 (12)	0.3461 (2)	0.0205 (4)
O11	0.26893 (12)	0.26889 (8)	0.41225 (15)	0.0256 (3)
C12	0.15868 (18)	0.31848 (13)	0.2111 (2)	0.0257 (5)
H12A	0.1471	0.2576	0.1906	0.039*
H12B	0.1981	0.3450	0.1313	0.039*
H12C	0.0858	0.3464	0.2218	0.039*
C31	0.14041 (16)	0.62649 (12)	0.3951 (2)	0.0225 (5)
C32	0.2194 (2)	0.69988 (14)	0.4319 (3)	0.0403 (6)
H32A	0.2855	0.6964	0.3716	0.060*
H32B	0.2431	0.6964	0.5341	0.060*
H32C	0.1806	0.7543	0.4139	0.060*
C33	0.0413 (2)	0.62931 (16)	0.4936 (3)	0.0520 (8)
H33A	0.0677	0.6205	0.5938	0.078*
H33B	−0.0121	0.5841	0.4658	0.078*
H33C	0.0043	0.6851	0.4848	0.078*
C34	0.1002 (2)	0.63483 (15)	0.2388 (3)	0.0407 (6)
H34A	0.0526	0.5858	0.2125	0.061*
H34B	0.1652	0.6363	0.1763	0.061*
H34C	0.0569	0.6877	0.2266	0.061*
N51	0.37010 (14)	0.38238 (10)	0.59221 (17)	0.0211 (4)
H51	0.3609	0.3281	0.5701	0.025*
C51	0.45152 (16)	0.40100 (12)	0.6940 (2)	0.0187 (4)
C52	0.50298 (16)	0.33741 (11)	0.7819 (2)	0.0190 (4)
C53	0.57975 (16)	0.35787 (12)	0.8904 (2)	0.0201 (4)
H53	0.6104	0.3139	0.9502	0.024*
C54	0.61272 (16)	0.44094 (12)	0.9135 (2)	0.0195 (4)
C55	0.56732 (16)	0.50417 (12)	0.8235 (2)	0.0195 (4)
H55	0.5912	0.5617	0.8358	0.023*
C56	0.48952 (16)	0.48483 (12)	0.7185 (2)	0.0203 (4)
H56	0.4597	0.5296	0.6594	0.024*
N521	0.48079 (14)	0.24731 (10)	0.76104 (18)	0.0218 (4)
O521	0.52136 (12)	0.19654 (9)	0.84859 (16)	0.0302 (4)
O522	0.42288 (12)	0.22442 (8)	0.65621 (15)	0.0257 (4)
C57	0.69856 (17)	0.45835 (12)	1.0271 (2)	0.0218 (5)
O57	0.73884 (13)	0.40563 (9)	1.10730 (16)	0.0337 (4)
O58	0.72868 (12)	0.54046 (8)	1.02999 (15)	0.0253 (3)
C58	0.82269 (19)	0.56068 (14)	1.1244 (2)	0.0308 (5)
H58A	0.8912	0.5360	1.0856	0.046*
H58B	0.8103	0.5370	1.2206	0.046*
H58C	0.8309	0.6229	1.1314	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0209 (8)	0.0140 (8)	0.0218 (9)	−0.0001 (6)	0.0000 (7)	−0.0002 (7)
N2	0.0209 (9)	0.0165 (8)	0.0248 (9)	0.0002 (7)	0.0013 (7)	0.0007 (7)
C3	0.0175 (10)	0.0166 (10)	0.0233 (10)	−0.0033 (8)	0.0041 (8)	−0.0009 (8)
C4	0.0248 (11)	0.0158 (10)	0.0221 (10)	−0.0013 (8)	−0.0002 (9)	−0.0025 (8)
C5	0.0211 (10)	0.0179 (10)	0.0193 (10)	−0.0014 (8)	0.0023 (8)	0.0004 (8)
C11	0.0219 (10)	0.0160 (10)	0.0239 (10)	−0.0038 (8)	0.0074 (9)	−0.0014 (9)
O11	0.0354 (9)	0.0154 (7)	0.0259 (8)	−0.0030 (6)	0.0001 (7)	0.0008 (6)
C12	0.0308 (12)	0.0201 (10)	0.0261 (11)	−0.0043 (9)	−0.0008 (9)	−0.0037 (9)
C31	0.0212 (11)	0.0165 (10)	0.0297 (11)	0.0014 (8)	0.0009 (9)	0.0011 (9)
C32	0.0403 (14)	0.0153 (11)	0.0643 (17)	0.0012 (10)	−0.0118 (13)	0.0008 (11)
C33	0.0492 (16)	0.0355 (14)	0.073 (2)	0.0189 (12)	0.0323 (15)	0.0175 (14)
C34	0.0477 (15)	0.0303 (13)	0.0433 (15)	0.0144 (11)	−0.0129 (12)	−0.0004 (11)
N51	0.0280 (9)	0.0108 (8)	0.0242 (9)	0.0001 (7)	−0.0022 (8)	−0.0004 (7)
C51	0.0217 (10)	0.0154 (10)	0.0191 (10)	0.0010 (8)	0.0044 (8)	−0.0013 (8)
C52	0.0224 (10)	0.0117 (9)	0.0230 (10)	−0.0005 (8)	0.0051 (8)	−0.0002 (8)
C53	0.0216 (10)	0.0164 (9)	0.0227 (10)	0.0042 (8)	0.0039 (9)	0.0029 (8)
C54	0.0208 (10)	0.0166 (10)	0.0214 (10)	0.0006 (8)	0.0041 (8)	0.0003 (8)
C55	0.0214 (10)	0.0137 (9)	0.0236 (10)	−0.0007 (8)	0.0057 (9)	0.0008 (8)
C56	0.0234 (10)	0.0147 (10)	0.0228 (11)	0.0023 (8)	0.0014 (9)	0.0031 (8)
N521	0.0236 (9)	0.0146 (8)	0.0272 (9)	0.0007 (7)	0.0023 (8)	0.0010 (7)
O521	0.0358 (9)	0.0144 (7)	0.0398 (9)	0.0018 (6)	−0.0078 (7)	0.0063 (7)
O522	0.0354 (9)	0.0143 (7)	0.0272 (8)	−0.0017 (6)	−0.0050 (7)	−0.0018 (6)
C57	0.0254 (11)	0.0171 (10)	0.0231 (11)	0.0025 (8)	0.0041 (9)	−0.0012 (9)
O57	0.0468 (10)	0.0183 (8)	0.0349 (9)	0.0033 (7)	−0.0147 (8)	0.0003 (7)
O58	0.0300 (8)	0.0173 (7)	0.0280 (8)	−0.0043 (6)	−0.0064 (6)	0.0004 (6)
C58	0.0339 (13)	0.0282 (12)	0.0298 (12)	−0.0074 (9)	−0.0078 (10)	−0.0001 (10)

Geometric parameters (Å, º)

N1—C5	1.382 (2)	C34—H34B	0.9800
N1—N2	1.385 (2)	C34—H34C	0.9800
N1—C11	1.391 (2)	N51—H51	0.8801
N2—C3	1.306 (2)	C51—C52	1.413 (3)
C3—C4	1.409 (3)	C52—C53	1.375 (3)
C3—C31	1.505 (3)	C53—C54	1.372 (3)
C4—C5	1.355 (3)	C53—H53	0.9500
C4—H4	0.9500	C54—C55	1.392 (3)
C5—N51	1.375 (2)	C56—C51	1.404 (3)
C11—O11	1.211 (2)	C55—C56	1.357 (3)
C11—C12	1.475 (3)	C55—H55	0.9500
C12—H12A	0.9800	C56—H56	0.9500
C12—H12B	0.9800	N51—C51	1.363 (3)
C12—H12C	0.9800	C52—N521	1.446 (2)
C31—C33	1.513 (3)	N521—O521	1.224 (2)
C31—C34	1.515 (3)	N521—O522	1.227 (2)
C31—C32	1.516 (3)	C54—C57	1.470 (3)
C32—H32A	0.9800	C57—O57	1.200 (2)
C32—H32B	0.9800	C57—O58	1.334 (2)
C32—H32C	0.9800	O58—C58	1.434 (2)
C33—H33A	0.9800	C58—H58A	0.9800
C33—H33B	0.9800	C58—H58B	0.9800
C33—H33C	0.9800	C58—H58C	0.9800
C34—H34A	0.9800
C5—N1—N2	110.72 (15)	C31—C34—H34A	109.5
C5—N1—C11	129.15 (16)	C31—C34—H34B	109.5
N2—N1—C11	119.46 (15)	H34A—C34—H34B	109.5
C3—N2—N1	104.66 (15)	C31—C34—H34C	109.5
N2—C3—C4	112.37 (17)	H34A—C34—H34C	109.5
N2—C3—C31	121.20 (17)	H34B—C34—H34C	109.5
C4—C3—C31	126.32 (17)	C5—N51—C51	127.15 (16)
C5—C4—C3	105.77 (17)	C51—N51—H51	116.6
C5—C4—H4	127.1	C5—N51—H51	116.2
C3—C4—H4	127.1	N51—C51—C56	122.03 (17)
C4—C5—N51	134.62 (18)	N51—C51—C52	122.32 (17)
C4—C5—N1	106.48 (17)	C56—C51—C52	115.66 (18)
N1—C5—N51	118.89 (16)	C53—C52—C51	121.58 (17)
O11—C11—N1	119.59 (18)	C53—C52—N521	116.06 (17)
O11—C11—C12	124.07 (18)	C51—C52—N521	122.34 (17)
N1—C11—C12	116.33 (17)	C54—C53—C52	120.98 (18)
C11—C12—H12A	109.5	C54—C53—H53	119.5
C11—C12—H12B	109.5	C52—C53—H53	119.5
H12A—C12—H12B	109.5	C53—C54—C55	118.42 (18)
C11—C12—H12C	109.5	C53—C54—C57	118.44 (18)
H12A—C12—H12C	109.5	C55—C54—C57	123.06 (17)
H12B—C12—H12C	109.5	C56—C55—C54	120.98 (18)
C3—C31—C33	107.81 (17)	C56—C55—H55	119.5
C3—C31—C34	110.57 (17)	C54—C55—H55	119.5
C33—C31—C34	110.0 (2)	C55—C56—C51	122.26 (18)
C3—C31—C32	110.02 (16)	C55—C56—H56	118.9
C33—C31—C32	109.4 (2)	C51—C56—H56	118.9
C34—C31—C32	108.97 (19)	O521—N521—O522	122.38 (16)
C31—C32—H32A	109.5	O521—N521—C52	118.51 (16)
C31—C32—H32B	109.5	O522—N521—C52	119.10 (16)
H32A—C32—H32B	109.5	O57—C57—O58	123.18 (19)
C31—C32—H32C	109.5	O57—C57—C54	124.86 (18)
H32A—C32—H32C	109.5	O58—C57—C54	111.95 (17)
H32B—C32—H32C	109.5	C57—O58—C58	115.42 (16)
C31—C33—H33A	109.5	O58—C58—H58A	109.5
C31—C33—H33B	109.5	O58—C58—H58B	109.5
H33A—C33—H33B	109.5	H58A—C58—H58B	109.5
C31—C33—H33C	109.5	O58—C58—H58C	109.5
H33A—C33—H33C	109.5	H58A—C58—H58C	109.5
H33B—C33—H33C	109.5	H58B—C58—H58C	109.5
C5—N1—N2—C3	−0.8 (2)	C5—N51—C51—C52	169.05 (18)
C11—N1—N2—C3	170.69 (17)	N51—C51—C52—C53	−175.75 (18)
N1—N2—C3—C4	0.4 (2)	C56—C51—C52—C53	4.1 (3)
N1—N2—C3—C31	−176.11 (16)	N51—C51—C52—N521	6.0 (3)
N2—C3—C4—C5	0.0 (2)	C56—C51—C52—N521	−174.10 (17)
C31—C3—C4—C5	176.38 (18)	C51—C52—C53—C54	−2.7 (3)
C3—C4—C5—N51	−179.0 (2)	N521—C52—C53—C54	175.66 (17)
C3—C4—C5—N1	−0.5 (2)	C52—C53—C54—C55	−0.6 (3)
N2—N1—C5—C4	0.8 (2)	C52—C53—C54—C57	−177.48 (18)
C11—N1—C5—C4	−169.58 (18)	C53—C54—C55—C56	2.2 (3)
N2—N1—C5—N51	179.59 (16)	C57—C54—C55—C56	178.92 (19)
C11—N1—C5—N51	9.2 (3)	C54—C55—C56—C51	−0.5 (3)
C5—N1—C11—O11	0.6 (3)	N51—C51—C56—C55	177.33 (18)
N2—N1—C11—O11	−169.03 (17)	C52—C51—C56—C55	−2.6 (3)
C5—N1—C11—C12	−178.64 (18)	C51—C52—N521—O521	−174.16 (17)
N2—N1—C11—C12	11.7 (3)	C51—C52—N521—O522	6.3 (3)
N2—C3—C31—C33	95.7 (2)	C53—C52—N521—O521	7.5 (3)
C4—C3—C31—C33	−80.3 (3)	C53—C52—N521—O522	−171.99 (17)
N2—C3—C31—C34	−24.6 (3)	C53—C54—C57—O57	−3.9 (3)
C4—C3—C31—C34	159.3 (2)	C55—C54—C57—O57	179.4 (2)
N2—C3—C31—C32	−145.1 (2)	C53—C54—C57—O58	175.12 (17)
C4—C3—C31—C32	38.9 (3)	C55—C54—C57—O58	−1.6 (3)
C4—C5—N51—C51	−15.6 (4)	O57—C57—O58—C58	7.1 (3)
N1—C5—N51—C51	166.06 (18)	C54—C57—O58—C58	−171.90 (17)
C5—N51—C51—C56	−10.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51···O11	0.88	2.02	2.694 (2)	132
N51—H51···O522	0.88	1.94	2.614 (2)	132
C55—H55···O522^i	0.95	2.55	3.452 (2)	158

Symmetry code: (i) −x+1, y+1/2, −z+3/2.