1-[(1-Eth­oxy­propyl­idene)amino]-2-ethyl-4-(4-hy­droxy­benz­yl)imidazol-5(4H)-one

The racemic title compound, C₁₇H₂₃N₃O₃, isolated from the reaction of L-(-)-tyrosine hydrazide with triethyl ortho­propionate in the presence of a catalytic quantity of p-toluene­sulfonic acid (p-TsOH), crystallizes with Z' = 1 in a centrosymmetric monoclinic unit cell. The mol­ecule contains two planar fragments, viz. the benzene and imidazole rings, linked by two C-C single bonds. The dihedral angle between the two planes is 59.54 (5)° and the mol­ecule adopts a synclinal conformation. The HOMA (harmonic oscillator model of aromaticity) index, calculated for the benzene ring, demonstrates no substantial inter­action between the two [pi]-electron delocalization regions in the mol­ecule. In the crystal structure, there is an O-H...N hydrogen bond that links the mol­ecules along the c axis.

S1. Comment

Carboxylic acid hydrazides constitute useful precursors for the synthesis of nitrogen- and nitrogen/oxygen-containing heterocycles. Numerous transformations of this class of compounds are known to lead to four-membered azetidines (Amr et al., 2008), five-membered pyrroles (Alawandi & Kulkarni, 2006), 1,3,4-oxadiazoles (Dabiri et al., 2006; Leiby, 1984) or1,2,4-triazoles (Francis et al., 1991; Taha & El-Badry, 2007) and to six-membered systems such as substituted pyrimidines (Elgemeie et al., 2001), oxadiazines (Dubey et al., 2005) or triazines (Neunhoeffer & Klein-Cullmann, 1992; Lobanov et al., 1991). One subgroup of the hydrazide family is the class of α-aminocarboxylic acid hydrazides, which are compounds containing at least two potential reaction sites. They react with equimolar quantities of triethyl orthoesters to yield 2-(1-amino-1-phenylmethyl)-1,3,4-oxadiazoles and 1,2,4-triazin-6-ones (Kudelko et al., 2011). We found that the product formed depended strongly on the basicity of the amino group, which was influenced by the electronic nature and steric hindrance of substituents adjacent to the α C atom. In contrast, transformations conducted with excess orthoester may follow a different path due to the fact that both nitrogen nucleophilic centres may react fully with the ethoxymethylene synthon. Thus, heating of L-(-)-tyrosine hydrazide in an excess of the orthoester resulted in the formation of another five-membered heterocycle, (I), 1-[(1-ethoxypropylidene)amino]-4-(4-hydroxybenzyl)imidazol-5(4H)-one. Imidazole derivatives have attracted interest in medicinal chemistry mainly for their antifungal, antiprotozoal and antihypertensive activities (Shargel et al., 2010). They have also been utilized as corrosion inhibitors, as ionic liquids, and for the production of thermally stable polymers (Grimmet, 1984; Lin, 1988). Here, we report the synthesis and the crystal structure of the title compound, (Ib), which resulted from the reaction of L-(-)-tyrosine hydrazide with triethyl orthopropionate in the presence of catalytic quantities of p-toluenesulfonic acid (p-TsOH).

Compound (Ib) is racemic and crystallizes in a centrosymmetric monoclinic space group with one molecule (isomer) in the asymmetric unit. The molecular structure of (Ib) (isomer 4R) is depicted in Fig. 1, and selected geometric data are given in Table 1. In the studied molecule, two planar fragments may be distinguished, viz. the benzene and the imidazole rings, linked by two C—C single bonds. These rings are not coplanar, the dihedral angle between them being 59.54 (5)°. An intramolecular C9—H9B···N1 hydrogen bond (Table 2) forms a five-membered quasi-ring which makes a dihedral angle of 73.82 (6)° with the imidazole ring. The molecule of (Ib) adopts a synclinal conformation with respect to rotation around the C4—C16 bond. A density functional theory (DFT) study also predicts this conformation as the preferential one for an isolated molecule of (Ib). The remaining rotamers resulting from the former rotation of 60° along the C4—C16 bond are less stable in the following order: synclinal by 0.40–0.82 kcal mol^-1, antiperiplanar by 2.12–2.23 kcal mol^-1, anticlinal by 2.51–3.24 kcal mol^-1, synperiplanar by 5.42–5.97 kcal mol^-1 and anticlinal by 6.14–6.42 kcal mol^-1 (1 kcal mol^-1 = 4.184 kJ mol^-1). Amide atom N1 lies only 0.118 (1) Å out of the plane defined by the three neighbouring atoms (C2, C5 and C7). Therefore, the sum of the valence angles around atom N1 of 357.85° demonstrates sp² hybridization (360° for sp² and 328° for sp³). The N1—N7 bond length is typical of the N—N distance between two trigonal N atoms (Allen et al., 1987). The imidazolone moiety contains two localized double bonds [O6═C5 = 1.201 (4) Å and N3—C2 = 1.275 (4) Å], the lengths of which are in good agreement with the literature data (Nalepa et al., 1999; Zhang & Jiao, 2006; Sun et al., 2007) and similar ring systems found in the Cambridge Structural Database (CSD, Version?; Allen, 2002). Two C—N bonds located between them (N1—C2 and N1—C5) exhibit intermediate values due to π-electron delocalization between the C═N and C═O groups. The other two bonds within the imidazole ring (N3—C4 and C4—C5) are common single bonds. In the studied molecule, the remaining bond lengths and angles are not unusual. There are no significant differences between the geometry of (Ib) in the crystalline state and the calculated structure; the differences do not exceed 0.02 Å for bond lengths, 2° for bond angles and 10° for torsion angles.

To estimate the influence of π-electron delocalization in the imidazolone group on the aromaticity of the benzene ring, the HOMA (harmonic oscillator model of aromaticity) index (Kruszewski & Krygowski, 1973; Krygowski, 1993) was calculated. This descriptor of aromaticity is a leading method for the quantitative determination of cyclic π-electron delocalization in chemical compounds. It is based on the geometric criterion of aromaticity, which stipulates that bond lengths in aromatic systems are between values that are typical for single and double bonds (Kruszewski & Krygowski, 1973; Krygowski, 1993). Therefore, HOMA = 0 for a model non-aromatic system, e.g. the Kekulé structure of benzene, and HOMA = 1 for the system with all bonds equal to the optimal value, assumed to be realised for full aromatic systems. The HOMA value [based on B3LYP/6-311++G(d,p) optimized geometries] for the benzene ring of (Ib) (0.983) is almost identical to the value calculated for the 4-methylphenol ring (0.984). This result is evidence that both π-electron delocalization regions in the molecule of (Ib) are separated from each other and do not interact significantly.

The crystal structure of (Ib) is presented in Fig. 2. The –OH substituent on the benzene ring forms an intermolecular hydrogen bond with atom N3 of the imidazole ring of a neighbouring molecule. These interactions form zigzag chains extending along the c axis.

Related literature

For related literature, see: Alawandi & Kulkarni (2006); Allen (2002); Allen et al. (1987); Amr et al. (2008); Becke (1988, 1993); Dabiri et al. (2006); Dubey et al. (2005); Elgemeie et al. (2001); Francis et al. (1991); Frisch (2010); Grimmet (1984); Kruszewski & Krygowski (1973); Krygowski (1993); Kudelko et al. (2011); Lee et al. (1988); Leiby (1984); Lin (1988); Lobanov et al. (1991); Nalepa et al. (1999); Neunhoeffer & Klein-Cullmann (1992); Shargel et al. (2010); Sun et al. (2007); Taha & El-Badry (2007); Zhang & Jiao (2006).

S2. Experimental

L-(-)-Tyrosine hydrazide (1.95 g, 10 mmol) was added to a mixture of triethyl orthopropionate (8.88 g, 50 mmol, 10 ml) and p-TsOH (0.1 g) and kept under reflux for 20 h (thin-layer chromatography). After cooling, the mixture was washed with water (30 ml), dried over MgSO₄ and then concentrated under reduced pressure. The crude solid was crystallized from ethyl acetate to give colourless crystals of (Ib) (2.47 g, 78%; m.p. 446–448 K). [α]_D²⁰ 0.0 (MeOH, c 1). Analysis, calculated for C₁₇H₂₃N₃O₃: C 64.32, H 7.32, N 13.23%; found: C 64.19, H 7.27, N 13.29%. ¹H NMR (300 MHz, DMSO-d₆, δ, p.p.m.): 0.78 (3H, t, J = 7.5 Hz, C2—R: CH₂CH₃), 1.02 (3H, t, J = 7.5 Hz, N1—R: CH₂CH₃), 1.22 (3H, t, J = 7.2 Hz, OCH₂CH₃), 1.47–1.67 (2H, m, R: CH₂CH₃), 2.21 (2H, q, J = 7.5 Hz, R: CH₂CH₃), 2.80–2.87 (1H, dd, J = 6.0 and 13.8 Hz, Ph—CH₂–), 3.02–3.09 (1H, dd, J = 6.0 and 13.8 Hz, Ph—CH₂–), 4.18 (2H, q, J = 7.2 Hz, OCH₂CH₃), 4.29 (1H, br s, C4: H), 6.59 (2H, d, J = 7.8 Hz, Ar: H3', H5'), 6.92 (2H, d, J = 7.8 Hz, Ar: H2', H6'), 9.17 (1H, s, OH). ¹³C NMR (DMSO-d₆, δ, p.p.m.): 9.2, 9.4, 13.8, 21.3, 22.0, 35.0, 63.1, 66.5, 114.4, 126.1, 130.5, 156.1, 164.0, 175.5, 176.2.

S3. Refinement

The molecular geometries of the (Ib) isomers were optimized using standard density functional theory (DFT) and employed the B3LYP hybrid functional (Becke, 1988, 1993; Lee et al., 1988) with the 6-311++G** level of theory. All species corresponded to the minima at the B3LYP/6-311++G** level with no imaginary frequencies. The conformational energy was calculated at the 6-311++G** level. In each rotamer, the geometric parameters were fully relaxed, except for the constrained C17—C16—C4—N3 torsion angle. The values of this angle were chosen using a step size of 10° within the range -180 to 180°. All calculations were performed using the GAUSSIAN09 program package (Frisch et al., 2010).

All H atoms were generated in idealized positions and treated as riding, with aromatic C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C), Csp³—H = 0.98 Å and U_iso(H) = 1.2U_eq(C), methylene C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C), and methyl C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C), and with O—H = 0.82 Å and U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (Ib) (isomer 4R), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. A packing diagram for (Ib), showing the O23—H23···N3^i hydrogen bonds as dashed lines. [Symmetry code (i) x, -y + 1/2, z + 1/2.]

1-[(1-Ethoxypropylidene)amino]-2-ethyl-4-(4-hydroxybenzyl)imidazol- 5(4H)-one

Crystal data

C17H23N3O3	F(000) = 680
Mr = 317.38	Dx = 1.270 Mg m^−3
Monoclinic, P21/c	Melting point < 447 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9622 (2) Å	Cell parameters from 10140 reflections
b = 14.3492 (4) Å	θ = 2.8–25.0°
c = 14.6469 (4) Å	µ = 0.09 mm^−1
β = 97.210 (2)°	T = 100 K
V = 1660.19 (8) Å^3	Plate, colourless
Z = 4	0.22 × 0.18 × 0.15 mm

Data collection

Oxford Xcalibur CCD area-detector diffractometer	2771 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ω scans	h = −10→9
12349 measured reflections	k = −18→13
3799 independent reflections	l = −18→18

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0524P)^2] where P = (Fo^2 + 2Fc^2)/3
3799 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
N1	0.38117 (11)	0.44037 (6)	0.11372 (6)	0.0166 (2)
C2	0.36439 (14)	0.34599 (8)	0.09057 (7)	0.0168 (2)
N3	0.50095 (11)	0.30916 (6)	0.06994 (6)	0.0182 (2)
C4	0.63060 (14)	0.38256 (8)	0.07730 (8)	0.0187 (2)
H4	0.6696	0.3914	0.0171	0.022*
C5	0.54151 (14)	0.47026 (8)	0.10292 (7)	0.0177 (2)
O6	0.59424 (10)	0.54957 (5)	0.11310 (5)	0.02224 (19)
N7	0.24214 (11)	0.49972 (6)	0.12151 (6)	0.0173 (2)
C8	0.23909 (13)	0.53122 (7)	0.20361 (7)	0.0162 (2)
C9	0.35258 (14)	0.51017 (8)	0.29025 (7)	0.0204 (3)
H9A	0.3975	0.5681	0.3174	0.025*
H9B	0.4472	0.4729	0.2756	0.025*
C10	0.26185 (17)	0.45828 (9)	0.35996 (9)	0.0311 (3)
H10A	0.3394	0.4466	0.4144	0.047*
H10B	0.2196	0.4001	0.3340	0.047*
H10C	0.1692	0.4953	0.3755	0.047*
O11	0.11561 (9)	0.59036 (5)	0.21772 (5)	0.01852 (18)
C12	0.00326 (14)	0.62247 (8)	0.13803 (8)	0.0195 (3)
H12A	−0.0616	0.5708	0.1091	0.023*
H12B	0.0680	0.6504	0.0932	0.023*
C13	−0.11232 (15)	0.69319 (8)	0.17237 (9)	0.0247 (3)
H13A	−0.1889	0.7165	0.1217	0.037*
H13B	−0.0465	0.7438	0.2009	0.037*
H13C	−0.1756	0.6646	0.2165	0.037*
C14	0.19997 (14)	0.29842 (8)	0.09544 (8)	0.0205 (3)
H14A	0.1143	0.3275	0.0517	0.025*
H14B	0.1673	0.3076	0.1564	0.025*
C15	0.20288 (17)	0.19463 (9)	0.07556 (9)	0.0300 (3)
H15A	0.0932	0.1686	0.0801	0.045*
H15B	0.2855	0.1649	0.1194	0.045*
H15C	0.2318	0.1848	0.0146	0.045*
C16	0.78280 (14)	0.35753 (8)	0.14815 (8)	0.0201 (3)
H16A	0.8253	0.2969	0.1328	0.024*
H16B	0.8721	0.4027	0.1437	0.024*
C17	0.74311 (13)	0.35520 (8)	0.24614 (8)	0.0178 (2)
C18	0.65116 (14)	0.28209 (8)	0.27849 (8)	0.0189 (2)
H18	0.6145	0.2336	0.2388	0.023*
C19	0.61311 (14)	0.28002 (8)	0.36816 (8)	0.0198 (3)
H19	0.5506	0.2309	0.3880	0.024*
C20	0.66871 (15)	0.35175 (8)	0.42864 (8)	0.0208 (3)
C21	0.76147 (15)	0.42469 (8)	0.39765 (8)	0.0231 (3)
H21	0.7997	0.4727	0.4375	0.028*
C22	0.79714 (14)	0.42603 (8)	0.30756 (8)	0.0213 (3)
H22	0.8587	0.4755	0.2877	0.026*
O23	0.63477 (12)	0.35437 (6)	0.51734 (6)	0.0288 (2)
H23	0.5797 (18)	0.3038 (11)	0.5304 (10)	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0163 (5)	0.0166 (5)	0.0173 (5)	0.0032 (4)	0.0038 (4)	−0.0007 (4)
C2	0.0220 (6)	0.0179 (6)	0.0105 (5)	0.0023 (4)	0.0017 (4)	0.0004 (4)
N3	0.0210 (5)	0.0201 (5)	0.0141 (5)	0.0024 (4)	0.0043 (4)	0.0003 (4)
C4	0.0206 (6)	0.0209 (6)	0.0157 (6)	0.0024 (5)	0.0073 (4)	0.0015 (5)
C5	0.0201 (6)	0.0222 (6)	0.0109 (5)	0.0026 (5)	0.0025 (4)	0.0031 (4)
O6	0.0235 (4)	0.0191 (4)	0.0244 (4)	−0.0007 (3)	0.0037 (3)	0.0023 (3)
N7	0.0167 (5)	0.0173 (5)	0.0184 (5)	0.0040 (4)	0.0040 (4)	−0.0007 (4)
C8	0.0165 (6)	0.0149 (5)	0.0179 (6)	−0.0004 (4)	0.0051 (4)	0.0018 (4)
C9	0.0209 (6)	0.0242 (6)	0.0165 (6)	0.0035 (5)	0.0035 (4)	−0.0008 (5)
C10	0.0389 (8)	0.0317 (7)	0.0216 (7)	−0.0075 (6)	−0.0003 (5)	0.0078 (6)
O11	0.0193 (4)	0.0198 (4)	0.0167 (4)	0.0055 (3)	0.0035 (3)	−0.0008 (3)
C12	0.0195 (6)	0.0193 (6)	0.0196 (6)	0.0023 (5)	0.0020 (5)	0.0013 (5)
C13	0.0218 (6)	0.0215 (6)	0.0302 (7)	0.0041 (5)	0.0011 (5)	−0.0038 (5)
C14	0.0216 (6)	0.0218 (6)	0.0186 (6)	0.0006 (5)	0.0043 (4)	−0.0014 (5)
C15	0.0341 (7)	0.0232 (7)	0.0337 (7)	−0.0056 (5)	0.0091 (6)	−0.0056 (5)
C16	0.0158 (6)	0.0224 (6)	0.0230 (6)	0.0035 (5)	0.0062 (4)	0.0031 (5)
C17	0.0150 (5)	0.0198 (6)	0.0186 (6)	0.0045 (4)	0.0021 (4)	0.0040 (5)
C18	0.0205 (6)	0.0164 (6)	0.0193 (6)	0.0019 (4)	0.0007 (4)	−0.0001 (5)
C19	0.0225 (6)	0.0160 (6)	0.0209 (6)	−0.0028 (4)	0.0022 (5)	0.0043 (5)
C20	0.0261 (6)	0.0201 (6)	0.0160 (6)	−0.0006 (5)	0.0023 (5)	0.0032 (5)
C21	0.0299 (7)	0.0193 (6)	0.0195 (6)	−0.0058 (5)	0.0007 (5)	−0.0002 (5)
C22	0.0188 (6)	0.0208 (6)	0.0239 (6)	−0.0033 (5)	0.0020 (4)	0.0062 (5)
O23	0.0474 (6)	0.0233 (5)	0.0170 (4)	−0.0124 (4)	0.0088 (4)	−0.0006 (4)

Geometric parameters (Å, º)

N1—C5	1.3746 (14)	C13—H13B	0.9600
N1—C2	1.3984 (14)	C13—H13C	0.9600
N1—N7	1.4127 (12)	C14—C15	1.5181 (17)
C2—N3	1.2788 (13)	C14—H14A	0.9700
C2—C14	1.4860 (16)	C14—H14B	0.9700
N3—C4	1.4692 (14)	C15—H15A	0.9600
C4—C5	1.5147 (15)	C15—H15B	0.9600
C4—C16	1.5358 (15)	C15—H15C	0.9600
C4—H4	0.9800	C16—C17	1.5082 (15)
C5—O6	1.2158 (13)	C16—H16A	0.9700
N7—C8	1.2878 (14)	C16—H16B	0.9700
C8—O11	1.3343 (13)	C17—C22	1.3893 (16)
C8—C9	1.4935 (15)	C17—C18	1.3957 (15)
C9—C10	1.5179 (16)	C18—C19	1.3848 (15)
C9—H9A	0.9700	C18—H18	0.9300
C9—H9B	0.9700	C19—C20	1.3934 (16)
C10—H10A	0.9600	C19—H19	0.9300
C10—H10B	0.9600	C20—O23	1.3603 (14)
C10—H10C	0.9600	C20—C21	1.3897 (16)
O11—C12	1.4536 (13)	C21—C22	1.3842 (16)
C12—C13	1.4986 (15)	C21—H21	0.9300
C12—H12A	0.9700	C22—H22	0.9300
C12—H12B	0.9700	O23—H23	0.881 (16)
C13—H13A	0.9600
C5—N1—C2	109.64 (9)	H13A—C13—H13B	109.5
C5—N1—N7	124.73 (9)	C12—C13—H13C	109.5
C2—N1—N7	123.47 (9)	H13A—C13—H13C	109.5
N3—C2—N1	113.54 (10)	H13B—C13—H13C	109.5
N3—C2—C14	127.00 (10)	C2—C14—C15	113.99 (10)
N1—C2—C14	119.42 (9)	C2—C14—H14A	108.8
C2—N3—C4	107.27 (9)	C15—C14—H14A	108.8
N3—C4—C5	105.50 (9)	C2—C14—H14B	108.8
N3—C4—C16	111.69 (9)	C15—C14—H14B	108.8
C5—C4—C16	112.41 (9)	H14A—C14—H14B	107.6
N3—C4—H4	109.0	C14—C15—H15A	109.5
C5—C4—H4	109.0	C14—C15—H15B	109.5
C16—C4—H4	109.0	H15A—C15—H15B	109.5
O6—C5—N1	126.11 (10)	C14—C15—H15C	109.5
O6—C5—C4	130.00 (10)	H15A—C15—H15C	109.5
N1—C5—C4	103.88 (9)	H15B—C15—H15C	109.5
C8—N7—N1	113.19 (9)	C17—C16—C4	113.98 (9)
N7—C8—O11	117.94 (10)	C17—C16—H16A	108.8
N7—C8—C9	129.96 (10)	C4—C16—H16A	108.8
O11—C8—C9	112.09 (9)	C17—C16—H16B	108.8
C8—C9—C10	112.49 (10)	C4—C16—H16B	108.8
C8—C9—H9A	109.1	H16A—C16—H16B	107.7
C10—C9—H9A	109.1	C22—C17—C18	117.58 (10)
C8—C9—H9B	109.1	C22—C17—C16	121.01 (10)
C10—C9—H9B	109.1	C18—C17—C16	121.41 (10)
H9A—C9—H9B	107.8	C19—C18—C17	121.64 (11)
C9—C10—H10A	109.5	C19—C18—H18	119.2
C9—C10—H10B	109.5	C17—C18—H18	119.2
H10A—C10—H10B	109.5	C18—C19—C20	119.82 (10)
C9—C10—H10C	109.5	C18—C19—H19	120.1
H10A—C10—H10C	109.5	C20—C19—H19	120.1
H10B—C10—H10C	109.5	O23—C20—C21	117.94 (10)
C8—O11—C12	117.93 (8)	O23—C20—C19	122.84 (10)
O11—C12—C13	106.68 (9)	C21—C20—C19	119.22 (10)
O11—C12—H12A	110.4	C22—C21—C20	120.18 (11)
C13—C12—H12A	110.4	C22—C21—H21	119.9
O11—C12—H12B	110.4	C20—C21—H21	119.9
C13—C12—H12B	110.4	C21—C22—C17	121.55 (11)
H12A—C12—H12B	108.6	C21—C22—H22	119.2
C12—C13—H13A	109.5	C17—C22—H22	119.2
C12—C13—H13B	109.5	C20—O23—H23	110.4 (10)
C5—N1—C2—N3	3.38 (13)	O11—C8—C9—C10	65.27 (13)
N7—N1—C2—N3	167.34 (9)	N7—C8—O11—C12	−6.07 (14)
C5—N1—C2—C14	−178.99 (9)	C9—C8—O11—C12	175.44 (9)
N7—N1—C2—C14	−15.04 (15)	C8—O11—C12—C13	−175.40 (9)
N1—C2—N3—C4	−0.68 (12)	N3—C2—C14—C15	1.66 (17)
C14—C2—N3—C4	−178.09 (10)	N1—C2—C14—C15	−175.62 (10)
C2—N3—C4—C5	−1.97 (11)	N3—C4—C16—C17	−67.46 (12)
C2—N3—C4—C16	120.44 (10)	C5—C4—C16—C17	50.90 (13)
C2—N1—C5—O6	176.28 (11)	C4—C16—C17—C22	−105.64 (12)
N7—N1—C5—O6	12.57 (17)	C4—C16—C17—C18	74.40 (13)
C2—N1—C5—C4	−4.26 (11)	C22—C17—C18—C19	0.61 (16)
N7—N1—C5—C4	−167.97 (9)	C16—C17—C18—C19	−179.42 (10)
N3—C4—C5—O6	−176.77 (11)	C17—C18—C19—C20	−0.70 (17)
C16—C4—C5—O6	61.29 (15)	C18—C19—C20—O23	179.51 (10)
N3—C4—C5—N1	3.80 (11)	C18—C19—C20—C21	0.21 (17)
C16—C4—C5—N1	−118.14 (10)	O23—C20—C21—C22	−179.01 (11)
C5—N1—N7—C8	−82.41 (13)	C19—C20—C21—C22	0.33 (18)
C2—N1—N7—C8	116.06 (11)	C20—C21—C22—C17	−0.41 (18)
N1—N7—C8—O11	177.93 (9)	C18—C17—C22—C21	−0.06 (16)
N1—N7—C8—C9	−3.89 (16)	C16—C17—C22—C21	179.98 (10)
N7—C8—C9—C10	−112.99 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O23—H23···N3^i	0.881 (16)	1.857 (16)	2.7279 (13)	169.5 (14)
C9—H9B···N1	0.97	2.41	2.8086 (14)	104

Symmetry code: (i) x, −y+1/2, z+1/2.