A hydrogen-bonded chain of rings in 5-amino-1-(4-methoxy­benzo­yl)-3-methyl­pyrazole and a three-dimensional hydrogen-bonded framework in 5-amino-3-methyl-1-(2-nitro­benzo­yl)­pyrazole

The mol­ecules of 5-amino-1-(4-methoxy­benzo­yl)-3-methyl­pyrazole, C₁₂H₁₃N₃O₂, (I), and 5-amino-3-methyl-1-(2-nitro­benzo­yl)pyrazole, C₁₁H₁₀N₄O₃, (II), both contain intra­molecular N—H...O hydrogen bonds. The mol­ecules of (I) are linked into a chain of rings by a combination of N—H...N and N—H...π(arene) hydrogen bonds, while those of (II) are linked into a three-dimensional framework structure by N—H...N and C—H...O hydrogen bonds.

S1. Comment

5-Aminopyrazoles containing two or more functionalized substituent groups are versatile intermediates for the synthesis of polyheterocyclic systems (Bauer & Mahajanshetti, 1967; Tominaga et al., 1995), which are themselves of interest because of their potential bioactivity. We describe here the structures of two new 5-amino-1-aroylpyrazoles, 5-amino-1-(4-methoxybenzoyl)-3-methylpyrazole, (I) (Fig. 1), and 5-amino-3-methyl-1-(2-nitrobenzoyl)pyrazole, (II) (Fig. 2), which were both initially prepared for synthetic purposes using reactions between 3-aminocrotononitrile and an appropriately-substituted aroylhydrazide in the presence of sodium acetate.

The molecules of compounds (I) and (II) both contain an intramolecular N—H···O hydrogen bond (Tables 1 and 2), generating in each case an S(6) motif (Bernstein et al., 1995). These interactions may have some influence in controlling the molecular conformations, where the carbonyl groups are nearly coplanar with the adjacent pyrazole rings, as shown by the key torsion angles (Table 1). On the other hand the phenyl rings are twisted out of this plane; while the methoxy C atom C141 in (I) is effectively coplanar with the phenyl ring, the nitro group in (II) makes a dihedral angle of 23.8 (2)° with the adjacent phenyl ring.

Two factors may contribute to the difference between the phenyl ring conformations in (I) and (II). First, there is a short intramolecular C—H···N contact in (I) which, although probably not appropriately described as a hydrogen bond, may nonetheless be a weakly attractive interaction. Secondly, detailed comparison of the bond distances in the phenyl rings of (I) and (II) (Table 3) shows that in (I) the C12—C13 and C15—C16 distances are slightly, but significantly, shorter than the remainder, indicative of a modest degree of quinonoid character; the C1—C11 bond is significantly shorter in (I) than in (II), while C1—O1 is possibly longer in (I); and the C14—O14 bond is slightly short for its type [mean value (Allen et al., 1987) 1.370 Å, lower quartile value 1.363 Å]. The resulting polarized form, (Ia), would enhance the barrier to rotation about the C1—C11 bond in compound (I). The remaining bond distances and inter-bond angles show no unusual features.

The molecules of compound (I) are linked by a combination of N—H···N and N—H···π(arene) hydrogen bonds into a chain of rings generated by translation along the [100] direction (Fig. 3): within this chain, the N—H···N interaction generates a C(5) motif. The only direction-specific interaction of possible structural significance between adjacent chains is a rather long C—H···O contact, between molecules in pairs of chains related by inversion.

By contrast, the molecules of (II) are linked by one N—H···N and three C—H···O hydrogen bonds all involving nitro O atoms as the acceptors. It is sufficient to consider the framework formation in terms of just two hydrogen bonds, the N—H···N interaction and the shortest of the C—H···O interactions. Each of these two hydrogen bonds, acting independently, forms a simple chain, while the combination of the two interactions generates a third chain motif.

Amino atom N5 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H5B, to the ring atom N2 in the molecule at (1/2 + x, 3/2 - y, z), so forming a C(5) chain running parallel to the [100] direction and consisting of molecules related by the a-glide plane at y = 0.75 (Fig. 4). In the second chain motif, atom C16 at (x, y, z) acts as hydrogen-bond donor to nitro atom O122 in the molecule at (1 - x, 1 - y, -1/2 + z), so forming a C(6) chain running parallel to the [001] direction and consisting of molecules related by the 2₁ screw axis along (1/2, 1/2, z) (Fig. 5). Finally, the combination of these two hydrogen bonds, acting alternately, generates a C²₂(15) chain running parallel to the [011] direction (Fig. 6). The combination of the chains along [100], [011] and [001] is sufficient to generate a continuous three-dimensional framework structure. This framework may be modestly reinforced by the two hydrogen bonds involving C13 and C15, which generate, respectively, a C(5) chain parallel to [100] and a C(7) chain parallel to [011].

Hence, in each of (I) and (II), an N—H···N hydrogen bond forms a C(5) chain parallel to [100]. However, the hydrogen-bonded structure of (II) is much more complex than that of (I) by virtue of the presence of the nitro group with its two quite polar hydrogen-bond acceptors. It is noteworthy that the carbonyl O atom plays no significant role in the intermolecular hydrogen bonding in either compound, and that the resulting deficiency of hydrogen-bond acceptors in (I) leads to the formation of an N—H···π(arene) interaction.

Related literature

For related literature, see: Allen et al. (1987).

S2. Experimental

Mixtures containing equimolar quantities (2 mmol of each component) of 3-aminocrotononitrile, an aroylhydrazide, 4-methoxybenzlhydrazide for (I) and 2-nitrobenzhydrazide for (II), and sodium acetate trihydrate in ethanol (50 ml) were heated under reflux for 2 h. The reaction mixtures were allowed to cool to ambient temperature, and then they were poured into water (50 ml) with vigorous stirring; stirring was then continued for 20 min. The resulting solid products were collected by filtration and recrystallized from ethanol to provide crystals of (I) and (II) suitable for single-crystal X-ray diffraction. For (I), colourless crystals, m.p. 354–355 K, yield 90%; MS (30 eV) m/z (%) 231 (16, M⁺), 135 (100), 107 (13), 77 (20). For (II), yellow crystals, m.p. 490–491 K, yield 97%; MS (70 eV) m/z (%) 246 (34, M⁺), 151 (66), 121 (70), 76 (85), 51 (91), 41 (100).

S3. Refinement

Crystals of (I) are triclinic; the space group P1 was selected and confirmed by the structure analysis. For (II), the systematic absences permitted Pna2₁ or Pnam (= Pnma) as possible space groups: Pna2₁ was selected and confirmed by the structure analysis. All H atoms were located in difference maps. H atoms bonded to C atoms were then treated as riding atoms in geometrically idealized positions with distances C—H 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 and 1.2 for all other H atoms. The H atoms bonded to N atoms were permitted to ride at the positions deduced from the difference maps with U_iso(H) = 1.2U_eq(N), giving N—H distances in the range 0.94–0.97 Å. In the absence of significant resonant scattering, it was not possible to determine the correct orientation of the structure of (II) relative to the polar axis direction: accordingly, the Friedel-equivalent reflections were merged prior to the final cycles of refinement.

Computing details

For both compounds, 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: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a chain of rings along [100] built from N—H···O, N—H···N and N—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 + x, y, z) and (-1 + x, y, z), respectively.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a chain of rings along [100] containing N—H···O and N—H···N hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 3/2 - y, z) and (-1/2 + x, 3/2 - y, z), respectively.
	Fig. 5. Part of the crystal structure of (II), showing the formation of a chain along [001] containing N—H···O and C—H···O hydrogen bonds only. For the sake of clarity, H atoms bonded to C atoms and not involved in the hydrogen bonding have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1 - x, 1 - y, -1/2 + z) and (1 - x, 1 - y, 1/2 + z), respectively.
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a chain along [011] containing N—H···O, N—H···N and C—H···O hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms and not involved in the hydrogen bonding have been omitted.

(I) 5-Amino-1-(4-methoxybenzoyl)-3-methylpyrazole

Crystal data

C12H13N3O2	Z = 2
Mr = 231.25	F(000) = 244
Triclinic, P1	Dx = 1.345 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1920 (15) Å	Cell parameters from 2614 reflections
b = 9.192 (2) Å	θ = 3.3–27.5°
c = 10.546 (2) Å	µ = 0.10 mm^−1
α = 73.69 (2)°	T = 120 K
β = 85.634 (17)°	Block, colourless
γ = 82.83 (3)°	0.50 × 0.35 × 0.27 mm
V = 571.1 (2) Å^3

Data collection

Bruker–Nonius KappaCCD diffractometer	2614 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1936 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ϕ & ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.958, Tmax = 0.975	l = −13→13
13948 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0703P)^2 + 0.2759P] where P = (Fo^2 + 2Fc^2)/3
2614 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.67655 (19)	0.41134 (14)	0.18740 (12)	0.0279 (3)
O14	−0.1286 (2)	0.08983 (14)	0.10792 (13)	0.0313 (3)
N1	0.5772 (2)	0.32071 (16)	0.40425 (13)	0.0216 (3)
N2	0.4089 (2)	0.27730 (16)	0.49827 (13)	0.0230 (3)
N5	0.9386 (2)	0.39991 (17)	0.39145 (15)	0.0266 (3)
C1	0.5515 (3)	0.33904 (18)	0.26987 (16)	0.0222 (4)
C3	0.4870 (3)	0.27986 (18)	0.61073 (16)	0.0229 (4)
C4	0.6997 (3)	0.32419 (19)	0.59450 (17)	0.0238 (4)
C5	0.7549 (3)	0.35168 (19)	0.46240 (17)	0.0224 (4)
C11	0.3717 (3)	0.26982 (19)	0.23174 (16)	0.0227 (4)
C12	0.2977 (3)	0.13189 (19)	0.30579 (17)	0.0252 (4)
C13	0.1331 (3)	0.07495 (19)	0.26012 (18)	0.0279 (4)
C14	0.0375 (3)	0.15420 (19)	0.14054 (17)	0.0238 (4)
C15	0.1137 (3)	0.28931 (19)	0.06448 (16)	0.0241 (4)
C16	0.2804 (3)	0.34537 (19)	0.11027 (16)	0.0228 (4)
C31	0.3521 (3)	0.2367 (2)	0.73602 (17)	0.0292 (4)
C141	−0.2301 (3)	0.1654 (2)	−0.01429 (18)	0.0326 (4)
H4	0.7869	0.3331	0.6617	0.029*
H5A	0.9434	0.4026	0.2992	0.032*
H5B	1.0720	0.3622	0.4381	0.032*
H12	0.3609	0.0778	0.3873	0.030*
H13	0.0839	−0.0190	0.3102	0.033*
H15	0.0520	0.3423	−0.0178	0.029*
H16	0.3339	0.4370	0.0582	0.027*
H14A	−0.2912	0.2686	−0.0130	0.049*
H14B	−0.3470	0.1081	−0.0258	0.049*
H14C	−0.1216	0.1712	−0.0877	0.049*
H31A	0.2009	0.2350	0.7154	0.044*
H31B	0.3577	0.3114	0.7859	0.044*
H31C	0.4090	0.1354	0.7891	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0253 (6)	0.0350 (7)	0.0229 (6)	−0.0061 (5)	0.0021 (5)	−0.0067 (5)
O14	0.0336 (7)	0.0306 (7)	0.0318 (7)	−0.0089 (5)	−0.0097 (5)	−0.0072 (5)
N1	0.0180 (7)	0.0260 (7)	0.0206 (7)	−0.0030 (5)	−0.0005 (5)	−0.0058 (5)
N2	0.0204 (7)	0.0268 (7)	0.0207 (7)	−0.0035 (6)	0.0011 (5)	−0.0048 (6)
N5	0.0187 (7)	0.0333 (8)	0.0275 (8)	−0.0040 (6)	−0.0007 (6)	−0.0075 (6)
C1	0.0210 (8)	0.0222 (8)	0.0224 (8)	0.0004 (6)	−0.0009 (6)	−0.0059 (6)
C3	0.0233 (8)	0.0214 (8)	0.0234 (8)	−0.0018 (6)	−0.0024 (7)	−0.0051 (6)
C4	0.0237 (8)	0.0238 (8)	0.0243 (8)	−0.0024 (7)	−0.0037 (7)	−0.0066 (7)
C5	0.0192 (8)	0.0220 (8)	0.0262 (8)	−0.0016 (6)	−0.0026 (6)	−0.0069 (6)
C11	0.0211 (8)	0.0265 (8)	0.0215 (8)	−0.0012 (6)	0.0003 (6)	−0.0090 (7)
C12	0.0302 (9)	0.0222 (8)	0.0231 (8)	0.0000 (7)	−0.0067 (7)	−0.0058 (7)
C13	0.0360 (10)	0.0206 (8)	0.0275 (9)	−0.0045 (7)	−0.0060 (7)	−0.0054 (7)
C14	0.0230 (8)	0.0241 (8)	0.0270 (9)	−0.0016 (7)	−0.0024 (7)	−0.0116 (7)
C15	0.0225 (8)	0.0283 (9)	0.0207 (8)	0.0011 (7)	−0.0009 (6)	−0.0071 (7)
C16	0.0211 (8)	0.0252 (8)	0.0210 (8)	−0.0016 (6)	0.0016 (6)	−0.0057 (6)
C31	0.0288 (9)	0.0360 (10)	0.0222 (9)	−0.0059 (7)	−0.0009 (7)	−0.0058 (7)
C141	0.0324 (10)	0.0360 (10)	0.0319 (10)	−0.0024 (8)	−0.0124 (8)	−0.0111 (8)

Geometric parameters (Å, º)

O1—C1	1.224 (2)	N5—H5B	0.9693
N2—C3	1.322 (2)	C15—C16	1.383 (2)
N2—N1	1.3973 (19)	C15—C14	1.392 (2)
C4—C5	1.368 (2)	C15—H15	0.95
C4—C3	1.411 (2)	C14—C13	1.401 (2)
C4—H4	0.95	C31—C3	1.490 (2)
C12—C13	1.376 (2)	C31—H31A	0.98
C12—C11	1.401 (2)	C31—H31B	0.98
C12—H12	0.95	C31—H31C	0.98
N1—C5	1.395 (2)	C11—C16	1.398 (2)
N1—C1	1.398 (2)	C16—H16	0.95
C1—C11	1.481 (2)	C13—H13	0.95
O14—C14	1.359 (2)	C141—H14A	0.98
O14—C141	1.432 (2)	C141—H14B	0.98
N5—C5	1.364 (2)	C141—H14C	0.98
N5—H5A	0.9639
C3—N2—N1	104.15 (13)	C15—C14—C13	120.01 (15)
C5—C4—C3	106.09 (15)	C3—C31—H31A	109.5
C5—C4—H4	127.0	C3—C31—H31B	109.5
C3—C4—H4	127.0	H31A—C31—H31B	109.5
C13—C12—C11	119.83 (16)	C3—C31—H31C	109.5
C13—C12—H12	120.1	H31A—C31—H31C	109.5
C11—C12—H12	120.1	H31B—C31—H31C	109.5
C5—N1—N2	111.02 (13)	N2—C3—C4	112.68 (15)
C5—N1—C1	127.54 (14)	N2—C3—C31	119.75 (15)
N2—N1—C1	121.28 (13)	C4—C3—C31	127.56 (15)
O1—C1—N1	119.61 (15)	C16—C11—C12	119.09 (15)
O1—C1—C11	121.90 (15)	C16—C11—C1	116.60 (15)
N1—C1—C11	118.48 (14)	C12—C11—C1	124.22 (15)
C14—O14—C141	117.57 (14)	C15—C16—C11	121.27 (16)
C5—N5—H5A	115.5	C15—C16—H16	119.4
C5—N5—H5B	114.3	C11—C16—H16	119.4
H5A—N5—H5B	117.0	C12—C13—C14	120.62 (16)
C16—C15—C14	119.11 (15)	C12—C13—H13	119.7
C16—C15—H15	120.4	C14—C13—H13	119.7
C14—C15—H15	120.4	O14—C141—H14A	109.5
N5—C5—C4	131.29 (16)	O14—C141—H14B	109.5
N5—C5—N1	122.67 (15)	H14A—C141—H14B	109.5
C4—C5—N1	106.04 (14)	O14—C141—H14C	109.5
O14—C14—C15	124.61 (15)	H14A—C141—H14C	109.5
O14—C14—C13	115.37 (15)	H14B—C141—H14C	109.5
C3—N2—N1—C5	−1.05 (17)	N1—N2—C3—C4	0.37 (18)
C3—N2—N1—C1	−176.71 (14)	N1—N2—C3—C31	−178.99 (14)
C5—N1—C1—O1	−12.6 (3)	C5—C4—C3—N2	0.4 (2)
N2—N1—C1—O1	162.24 (14)	C5—C4—C3—C31	179.73 (16)
C5—N1—C1—C11	167.48 (15)	C13—C12—C11—C16	−1.7 (2)
N2—N1—C1—C11	−17.6 (2)	C13—C12—C11—C1	−178.26 (15)
C3—C4—C5—N5	178.67 (17)	O1—C1—C11—C16	−30.8 (2)
C3—C4—C5—N1	−1.03 (18)	N1—C1—C11—C16	149.09 (15)
N2—N1—C5—N5	−178.40 (15)	O1—C1—C11—C12	145.82 (17)
C1—N1—C5—N5	−3.1 (3)	N1—C1—C11—C12	−34.3 (2)
N2—N1—C5—C4	1.33 (18)	C14—C15—C16—C11	−0.7 (2)
C1—N1—C5—C4	176.65 (15)	C12—C11—C16—C15	2.3 (2)
C141—O14—C14—C15	1.0 (2)	C1—C11—C16—C15	179.13 (14)
C141—O14—C14—C13	−179.22 (15)	C11—C12—C13—C14	−0.5 (3)
C16—C15—C14—O14	178.27 (15)	O14—C14—C13—C12	−177.68 (15)
C16—C15—C14—C13	−1.6 (2)	C15—C14—C13—C12	2.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1	0.96	2.08	2.763 (2)	126
N5—H5A···Cg^i	0.96	2.71	3.365 (2)	126
N5—H5B···N2^i	0.97	2.21	3.160 (2)	167
C12—H12···N2	0.95	2.49	2.889 (2)	105
C16—H16···O1^ii	0.95	2.58	3.317 (2)	135

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

(II) 5-Amino-3-methyl-1-(2-nitrobenzoyl)pyrazole

Crystal data

C11H10N4O3	F(000) = 512
Mr = 246.23	Dx = 1.504 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1309 reflections
a = 11.4212 (15) Å	θ = 3.2–27.5°
b = 7.1787 (14) Å	µ = 0.11 mm^−1
c = 13.2595 (10) Å	T = 120 K
V = 1087.1 (3) Å^3	Block, yellow
Z = 4	0.55 × 0.51 × 0.45 mm

Data collection

Bruker–Nonius KappaCCD diffractometer	1309 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	1197 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.943, Tmax = 0.950	l = −16→17
23596 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 0.5442P] where P = (Fo^2 + 2Fc^2)/3
1309 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.20 e Å^−3
1 restraint	Δρmin = −0.21 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.67677 (17)	0.4541 (3)	0.50590 (15)	0.0258 (4)
O121	0.53764 (16)	0.2764 (3)	0.70553 (16)	0.0266 (4)
O122	0.36585 (18)	0.3140 (3)	0.77307 (17)	0.0299 (5)
N1	0.64417 (19)	0.6216 (3)	0.64926 (17)	0.0193 (4)
N2	0.56231 (18)	0.7122 (3)	0.71101 (17)	0.0203 (4)
N5	0.85228 (19)	0.5661 (3)	0.63892 (19)	0.0246 (5)
N12	0.43602 (19)	0.3340 (3)	0.70350 (17)	0.0218 (5)
C1	0.6075 (2)	0.5218 (4)	0.56546 (18)	0.0191 (5)
C3	0.6277 (2)	0.7868 (3)	0.7831 (2)	0.0205 (5)
C4	0.7478 (2)	0.7483 (4)	0.7716 (2)	0.0209 (5)
C5	0.7576 (2)	0.6442 (3)	0.6856 (2)	0.0202 (5)
C11	0.4777 (2)	0.5132 (3)	0.5484 (2)	0.0187 (5)
C12	0.3959 (2)	0.4307 (3)	0.6120 (2)	0.0202 (5)
C13	0.2772 (2)	0.4291 (4)	0.5914 (2)	0.0248 (6)
C14	0.2381 (2)	0.5128 (4)	0.5034 (2)	0.0286 (6)
C15	0.3172 (3)	0.5943 (4)	0.4377 (2)	0.0272 (6)
C16	0.4369 (2)	0.5941 (4)	0.4596 (2)	0.0229 (5)
C31	0.5710 (3)	0.8975 (4)	0.8653 (2)	0.0276 (6)
H5A	0.8393	0.5262	0.5725	0.030*
H5B	0.9232	0.6285	0.6537	0.030*
H4	0.8095	0.7868	0.8149	0.025*
H13	0.2235	0.3719	0.6366	0.030*
H14	0.1569	0.5143	0.4882	0.034*
H15	0.2899	0.6508	0.3773	0.033*
H16	0.4906	0.6493	0.4137	0.027*
H31A	0.4915	0.9320	0.8448	0.041*
H31B	0.6168	1.0105	0.8780	0.041*
H31C	0.5675	0.8224	0.9270	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0246 (10)	0.0291 (10)	0.0237 (10)	0.0021 (8)	0.0031 (9)	−0.0039 (8)
O121	0.0229 (9)	0.0267 (9)	0.0303 (10)	0.0023 (8)	0.0002 (9)	0.0057 (9)
O122	0.0329 (10)	0.0329 (11)	0.0240 (9)	−0.0048 (9)	0.0085 (9)	0.0004 (9)
N1	0.0165 (9)	0.0211 (10)	0.0203 (10)	0.0001 (8)	0.0011 (8)	−0.0026 (9)
N2	0.0196 (9)	0.0212 (10)	0.0201 (10)	0.0021 (8)	0.0020 (9)	−0.0047 (9)
N5	0.0194 (10)	0.0259 (11)	0.0286 (12)	−0.0009 (9)	0.0018 (9)	0.0008 (10)
N12	0.0246 (10)	0.0198 (10)	0.0210 (10)	−0.0034 (8)	0.0011 (9)	−0.0025 (10)
C1	0.0204 (12)	0.0182 (11)	0.0186 (12)	−0.0021 (10)	0.0011 (10)	0.0005 (10)
C3	0.0247 (12)	0.0175 (11)	0.0193 (11)	−0.0002 (10)	−0.0033 (11)	0.0039 (10)
C4	0.0211 (11)	0.0230 (12)	0.0185 (12)	−0.0024 (10)	−0.0029 (10)	0.0041 (11)
C5	0.0170 (11)	0.0187 (11)	0.0250 (12)	−0.0020 (9)	−0.0019 (10)	0.0049 (10)
C11	0.0208 (12)	0.0159 (11)	0.0195 (11)	0.0002 (10)	−0.0003 (9)	−0.0033 (10)
C12	0.0216 (12)	0.0180 (11)	0.0210 (12)	−0.0001 (10)	−0.0031 (10)	−0.0013 (9)
C13	0.0205 (12)	0.0245 (13)	0.0293 (14)	−0.0033 (10)	0.0016 (11)	−0.0066 (12)
C14	0.0234 (13)	0.0295 (15)	0.0329 (15)	0.0031 (11)	−0.0082 (13)	−0.0113 (12)
C15	0.0319 (15)	0.0265 (13)	0.0232 (13)	0.0046 (12)	−0.0090 (12)	−0.0042 (11)
C16	0.0272 (12)	0.0221 (13)	0.0194 (12)	0.0015 (10)	−0.0026 (11)	−0.0028 (11)
C31	0.0334 (15)	0.0262 (13)	0.0233 (14)	0.0010 (11)	0.0000 (11)	−0.0050 (12)

Geometric parameters (Å, º)

O1—C1	1.219 (3)	C4—H4	0.95
O121—N12	1.232 (3)	C11—C12	1.392 (4)
O122—N12	1.231 (3)	C11—C16	1.393 (4)
N1—C1	1.387 (3)	C12—C13	1.383 (4)
N1—C5	1.392 (3)	C13—C14	1.386 (4)
N1—N2	1.403 (3)	C13—H13	0.95
N2—C3	1.326 (3)	C14—C15	1.385 (4)
N5—C5	1.366 (3)	C14—H14	0.95
N5—H5A	0.9383	C15—C16	1.397 (4)
N5—H5B	0.9457	C15—H15	0.95
N12—C12	1.471 (3)	C16—H16	0.95
C1—C11	1.501 (4)	C31—H31A	0.98
C3—C4	1.408 (4)	C31—H31B	0.98
C3—C31	1.496 (4)	C31—H31C	0.98
C4—C5	1.369 (4)
C1—N1—C5	128.2 (2)	C12—C11—C1	126.1 (2)
C1—N1—N2	120.4 (2)	C16—C11—C1	116.2 (2)
C5—N1—N2	111.4 (2)	C13—C12—C11	122.9 (2)
C3—N2—N1	103.5 (2)	C13—C12—N12	117.7 (2)
C5—N5—H5A	115.2	C11—C12—N12	119.4 (2)
C5—N5—H5B	112.9	C12—C13—C14	118.5 (3)
H5A—N5—H5B	118.3	C12—C13—H13	120.7
O122—N12—O121	123.9 (2)	C14—C13—H13	120.7
O122—N12—C12	118.1 (2)	C15—C14—C13	120.2 (3)
O121—N12—C12	118.0 (2)	C15—C14—H14	119.9
O1—C1—N1	122.0 (2)	C13—C14—H14	119.9
O1—C1—C11	121.8 (2)	C14—C15—C16	120.4 (3)
N1—C1—C11	116.1 (2)	C14—C15—H15	119.8
N2—C3—C4	113.0 (2)	C16—C15—H15	119.8
N2—C3—C31	119.7 (2)	C11—C16—C15	120.2 (3)
C4—C3—C31	127.2 (3)	C11—C16—H16	119.9
C5—C4—C3	106.1 (2)	C15—C16—H16	119.9
C5—C4—H4	126.9	C3—C31—H31A	109.5
C3—C4—H4	126.9	C3—C31—H31B	109.5
N5—C5—C4	131.8 (2)	H31A—C31—H31B	109.5
N5—C5—N1	122.1 (2)	C3—C31—H31C	109.5
C4—C5—N1	106.0 (2)	H31A—C31—H31C	109.5
C12—C11—C16	117.7 (2)	H31B—C31—H31C	109.5
C1—N1—N2—C3	178.4 (2)	O1—C1—C11—C16	−58.7 (3)
C5—N1—N2—C3	−0.1 (3)	N1—C1—C11—C16	117.2 (3)
C5—N1—C1—O1	−7.7 (4)	C16—C11—C12—C13	−1.2 (4)
N2—N1—C1—O1	174.0 (2)	C1—C11—C12—C13	179.6 (2)
C5—N1—C1—C11	176.4 (2)	C16—C11—C12—N12	176.4 (2)
N2—N1—C1—C11	−1.9 (3)	C1—C11—C12—N12	−2.8 (4)
N1—N2—C3—C4	−0.4 (3)	O122—N12—C12—C13	−24.6 (3)
N1—N2—C3—C31	180.0 (2)	O121—N12—C12—C13	154.7 (2)
N2—C3—C4—C5	0.7 (3)	O122—N12—C12—C11	157.6 (2)
C31—C3—C4—C5	−179.6 (2)	O121—N12—C12—C11	−23.1 (3)
C3—C4—C5—N5	−179.0 (3)	C11—C12—C13—C14	0.3 (4)
C3—C4—C5—N1	−0.7 (3)	N12—C12—C13—C14	−177.4 (2)
C1—N1—C5—N5	0.6 (4)	C12—C13—C14—C15	0.6 (4)
N2—N1—C5—N5	179.0 (2)	C13—C14—C15—C16	−0.4 (4)
C1—N1—C5—C4	−177.9 (2)	C12—C11—C16—C15	1.3 (4)
N2—N1—C5—C4	0.6 (3)	C1—C11—C16—C15	−179.4 (2)
O1—C1—C11—C12	120.5 (3)	C14—C15—C16—C11	−0.6 (4)
N1—C1—C11—C12	−63.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1	0.94	2.12	2.788 (3)	127
N5—H5B···N2^i	0.95	2.10	3.033 (3)	169
C13—H13···O121^ii	0.95	2.54	3.457 (3)	161
C15—H15···O122^iii	0.95	2.54	3.409 (4)	152
C16—H16···O122^iv	0.95	2.50	3.410 (3)	161

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z; (iii) −x+1/2, y+1/2, z−1/2; (iv) −x+1, −y+1, z−1/2.