Hydro­gen bonding in N,N′-bis­[(1S)-2-azido-1-(2-methyl­propyl)­ethyl]­oxal­amide: twofold symmetry of R(10) hydrogen-bonded dimers connected into an α-network

The title compound, C₁₄H₂₆N₈O₂, belongs to a class of retropeptides with an oxal­amide unit (–NH–CO–CO–NH–), and is a precursor for the synthesis of an amine-terminal gelator. The compound is a good synthon for one-dimensional hydrogen bonding. The crystal structure reveals a hydrogen-bonded cyclic dimer with unusual twofold rotation symmetry.

S1. Comment

The present structure determination is part of a systematic study related to hydrogen bonding and gelation properties of bis(amino acid) and bis(amino alcohol) oxalamide derivatives (Makaravić et al., 2001, 2003). A number of compounds of this class have been designed and synthesized to introduce the proton donor/acceptor functionalities required for one-dimensional or two-dimensional hydrogen-bonded assemblies in order to investigate the delicate interplay of structure, noncovalent interactions and gelating properties (Jokić et al., 1995; Perić, Makarević et al., 2001; Perić, Kojić-Prodić et al., 2001). The oxalamide moiety was selected as a good structural unit for the design of molecular solids (Coe et al., 1997; Nguyen et al., 1998). Coe et al. (1997) studied centrosymmetric oxalamide with terminal substituted carboxyl groups. In this group of compounds there are two distinctive hydrogen-bonding patterns, both generating two-dimensional β-network: (i) N—H···O hydrogen bonds between oxalamide units and O—H···O hydrogen bonds between terminal carboxyl groups (forming polymorph A) and (ii) O—H···O hydrogen bonds between oxalamide and carboxyl groups (forming polymorph B). Pattern (i) is composed of an α-network generated by hydrogen bonding within oxalamide groups that are self assembled into a β-network via hydrogen bonds between carboxyl groups, including centrosymmetric cyclic carboxylic acid dimers. The title compound, (I), served as a precursor of a novel aminoterminal oxalamide gelator; substitution of azide groups precludes hydrogen bonding at the terminal sides of the molecule. However, the oxalamide groups are available for intermolecular N—H···O hydrogen bonds generating the α-network.

In this paper the structure of (I) is presented. The ORTEP-3 (Burnett, 1996) drawing (Fig. 1) reveals two molecules, viz. A and B, in an asymmetric unit. The overall conformational differences of A and B are illustrated in Fig. 2. The (S)-leucyl residues are positioned on the same side of the central oxalamide unit with the similar conformations (Fig. 2 and Table 1). Torsion angles ω, ω', ϕ, ϕ', ψ, ψ', χ and χ' are labelled according to the literature (IUPAC-IUB Commission on Biochemical Nomenclature, http://www.chem.qmul.ac.uk/iupac/misc/ppep1.html Karle et al. 1994). The significantly different conformation is associated with ψ' of molecule A because of the unique conformation of the N21—N31—N41 azide group. Among the four azide groups, three are perpendicular to the plane of oxalamide units, whereas the N21—N31—N41 group is parallel to this plane (Table 2). The average values of bond lengths and angles of azide groups are ??1.146 (4) and 1.173 (5) Å for N—N bonds and 1.517 (4) Å for N—C bonds, with a bonding angle of 173.0 (4) °. This observation is based on the analysis of bond-geometry parameters that exceed differences larger than 3σ. The crystal packing is defined as the α-network (Coe et al., 1997) realised by the N—H···O hydrogen bonds between oxalamide groups (Table 2, Fig. 3) forming three crystallographically different dimers. Two crystallographically independent molecules, A and B, are connected by a pair of N—H···O hydrogen bonds to form a dimer of approximately digonal symmetry. The crystallographic twofold axes generate hydrogen-bonded dimers of types A···A and B···B, defined by graph-set notation as R₂²(10) (Bernstein et al., 1995). An inspection of the Cambridge Structural Database (version 5.24 of November 2002; Allen, 2002) using the oxalamide fragment revealed 33 structures, among which a single example of a hydrogen bonded dimer with digonal symmetry was found. The structure of N-hydroxyoxamide (Larsen, 1980) crystallizes in the space group C2/c. However, the three-dimensional hydrogen-bonded network of N-hydroxyoxamide cannot be compared with the one-dimensional network of (I). Dimers of sequence B···B···A···A···B···B··· are connected in the direction of the c axes. A ladder pattern (Fig. 3 and Table 2) formed in this way is based on intramolecular N—H···O hydrogen bonds of a pseudo-C₅ arrangement typical of retropeptides and intermolecular hydrogen bonds involving chemically identical but crystallographically different amide groups. Each amide H atom acts as a double donor (three-centred or bifurcated hydrogen bond).

S2. Experimental

To a solution of the diol (b, R is iso-butyl) (1.12 g, 3.88 mmol) in dry pyridine (20 ml), p-TsCl (1.77 g, 9.28 mmol) was added, and the reaction mixture was stirred for 2 d at room temperature. When the reaction was complete (TLC), the solvent was evaporated under reduced pressure, and the residue was dissolved in CH₂Cl₂ (20 ml) and washed with H₂O, HOAc (5%), and H₂O. The organic phase was dried (Na₂SO₄) and evaporated. The crude tosylate was used in the next step without further purification. The tosylate was reacted with sodium azide (0.60 g, 9.23 mmol) in DMF (30 ml). The reaction mixture was heated for 1 h at 100 °C, and stirred overnight at room temperature. The salt was removed by filtration and the filtrate evaporated under reduced pressure. The remaining solid was purified by ash chromatography using petroleum ether/ethyl acetate (5:2) as eluent. Compound (I) was obtained as a white solid (0.96 g, 73.1% total yield; m.p. 380–381 K; from ethanol). Single crystals suitable for X-ray analysis were obtained by slow evaporation of a dilute ethanol solution of (I). [α]_D²⁰ = −90 (c = 1 in CH₂Cl₂); ¹H NMR (CDCl₃, 300 MHz, δ, p.p.m.): 7.53 (d, J = 9.1 Hz, 2H, NH), 4.13 (dt, J = 9.5 Hz, J' = 4.7 Hz, 2H, CH_α), 3.46 (m, 4H, CH₂), 1.65–1.39 (m, 6H, CH_γ and CH_β), 0.95/0.94 (2 d, J = 5.1 Hz, 6H each, CH₃); ¹³C NMR (CDCl₃, 75 MHz, δ, p.p.m.): 159.3 (CONH), 54.6 (CH₂) 47.8 (CH_α), 40.8 (CH_β), 24.7 (CH_γ), 23.0 and 22.0 (CH₃); IR (KBr, ν_max, cm^{-1_{): 3295 (NH), 2099 (azide), 1654 (amide 1), 1522 (amide 2).}}

S3. Refinement

Atomic scattering factors were those included in SHELXL97. The H-atom coordinates were calculated geometrically and refined using the SHELXL97 riding model.

Computing details

Data collection: COLLECT (Nonius BV, 1997–2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 1999).

Figures

	Fig. 1. The molecular structure of (I) with two molecules in the asymmetric unit, viz. A and B. Displacement ellipsoids are shown at the 50% probability level. Intramolecular N—H···O hydrogen bonds form a pseudo-C5 type typical of retropeptides, whereas intermolecular hydrogen bonds between A and B form a dimer.
	Fig. 2. An overlap diagram of molecules A and B, illustrating different conformations of the leucyl and azide groups (a least-square fit through the oxalamide bridges was used). Molecule A reveals an approximate twofold axis bisecting the C—C bond of the oxalamide group, whereas molecule B exibits no symmetry at all.
	Fig. 3. The crystal packing of (I). Intermolecular and intramolecular hydrogen bonds between oxalamide groups generate a ladder pattern of α-network with the molecular sequence AB—BA—AB—BA. A twofold axis relates dimers A···A and B···B, whereas the A···B dimer reveals an approximate diagonal symmetry. For clarity, only those H atoms that act as donors are shown.

(I)

Crystal data

C14H26N8O2	F(000) = 1456
Mr = 338.43	Dx = 1.225 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: C 2y	Cell parameters from 4035 reflections
a = 24.0235 (5) Å	θ = 2.9–27.1°
b = 7.9361 (2) Å	µ = 0.09 mm^−1
c = 20.2167 (5) Å	T = 150 K
β = 107.824 (1)°	Prism, colorless
V = 3669.37 (15) Å^3	0.25 × 0.25 × 0.12 mm
Z = 8

Data collection

KappaCCD diffractometer	Rint = 0
CCD rotation images, thick slices scans	θmax = 27.1°, θmin = 3.3°
7645 measured reflections	h = −30→30
7645 independent reflections	k = −10→10
5889 reflections with I > 2σ(I)	l = −25→25

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.054	w = 1/[σ^2(Fo^2) + (0.0475P)^2 + 3.569P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.129	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.21 e Å^−3
7645 reflections	Δρmin = −0.29 e Å^−3
449 parameters

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.

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

	x	y	z	Uiso*/Ueq
O13	0.94280 (8)	0.4182 (2)	0.91922 (9)	0.0340 (4)
O1	0.94218 (7)	0.4575 (2)	0.66378 (8)	0.0289 (4)
O12	1.03112 (8)	0.5700 (2)	0.82281 (8)	0.0346 (4)
N11	1.04680 (9)	0.6132 (3)	0.68753 (10)	0.0242 (5)
N1	0.93215 (9)	0.4428 (3)	0.54865 (10)	0.0241 (4)
O11	1.04798 (7)	0.5308 (2)	0.58041 (8)	0.0315 (4)
N12	1.05454 (10)	0.5287 (3)	0.93906 (11)	0.0317 (5)
N13	0.92591 (9)	0.4302 (3)	0.80212 (11)	0.0281 (5)
C2	0.87294 (10)	0.3753 (3)	0.52703 (13)	0.0265 (5)
H2	0.8571	0.3854	0.5662	0.032*
C1	0.96135 (10)	0.4757 (3)	0.61449 (12)	0.0224 (5)
C13	0.95800 (11)	0.4499 (3)	0.86784 (12)	0.0265 (5)
N21	1.20955 (10)	0.6180 (3)	0.77775 (13)	0.0373 (5)
C11	1.02356 (10)	0.5428 (3)	0.62557 (12)	0.0225 (5)
C4	0.83261 (11)	0.4716 (4)	0.46543 (13)	0.0295 (6)
H4A	0.7934	0.4264	0.4556	0.035*
H4B	0.8453	0.4505	0.425	0.035*
C23	0.86768 (11)	0.3572 (3)	0.77892 (13)	0.0293 (6)
H23	0.8552	0.3298	0.8195	0.035*
C12	1.01901 (11)	0.5224 (3)	0.87473 (12)	0.0275 (6)
N23	0.91222 (13)	0.0748 (4)	0.78074 (13)	0.0496 (7)
C41	1.10451 (12)	0.8488 (3)	0.75174 (13)	0.0276 (5)
H41A	1.0904	0.8217	0.7906	0.033*
H41B	1.1444	0.8886	0.7707	0.033*
C51	1.06744 (12)	0.9915 (3)	0.71073 (13)	0.0312 (6)
H51	1.0277	0.9484	0.6898	0.037*
C53	0.81026 (12)	0.6387 (4)	0.76647 (14)	0.0345 (6)
H53	0.8473	0.6881	0.7948	0.041*
C21	1.10508 (11)	0.6874 (3)	0.71088 (13)	0.0274 (6)
H21	1.117	0.7156	0.67	0.033*
C31	1.14696 (11)	0.5542 (3)	0.75314 (13)	0.0321 (6)
H31A	1.1349	0.5228	0.7931	0.039*
H31B	1.145	0.4544	0.7248	0.039*
C6	0.81837 (12)	0.7088 (4)	0.54283 (14)	0.0382 (7)
H6A	0.8171	0.8291	0.5468	0.057*
H6B	0.8491	0.6644	0.5813	0.057*
H6C	0.7816	0.6618	0.5431	0.057*
C33	0.86818 (12)	0.1972 (3)	0.73754 (14)	0.0346 (6)
H33A	0.8296	0.1462	0.7239	0.042*
H33B	0.878	0.2247	0.6957	0.042*
N33	0.92140 (11)	−0.0423 (4)	0.75094 (15)	0.0459 (6)
C43	0.82392 (11)	0.4803 (3)	0.73210 (13)	0.0316 (6)
H43A	0.8389	0.5142	0.6946	0.038*
H43B	0.7876	0.4204	0.7113	0.038*
C22	1.11408 (12)	0.5955 (4)	0.95643 (13)	0.0356 (6)
H22	1.1188	0.6481	0.9146	0.043*
C5	0.82999 (11)	0.6628 (3)	0.47530 (13)	0.0319 (6)
H5	0.868	0.7103	0.4766	0.038*
N22	1.15505 (14)	0.3468 (4)	0.91575 (13)	0.0531 (7)
N32	1.17922 (12)	0.2187 (5)	0.92676 (14)	0.0578 (8)
N2	0.90824 (14)	0.0881 (3)	0.57360 (13)	0.0473 (7)
C3	0.87373 (13)	0.1891 (4)	0.50872 (14)	0.0370 (6)
H3A	0.8919	0.1751	0.4723	0.044*
H3B	0.834	0.1469	0.4917	0.044*
C71	1.08958 (15)	1.0554 (4)	0.65219 (16)	0.0480 (8)
H71A	1.0647	1.1448	0.6279	0.072*
H71B	1.0891	0.9649	0.6205	0.072*
H71C	1.1288	1.0967	0.6713	0.072*
C63	0.77265 (14)	0.6005 (5)	0.81405 (16)	0.0487 (8)
H63A	0.7648	0.7034	0.8345	0.073*
H63B	0.7933	0.5242	0.8501	0.073*
H63C	0.7364	0.5502	0.7872	0.073*
N43	0.93402 (14)	−0.1639 (4)	0.72698 (19)	0.0658 (9)
N31	1.22629 (11)	0.6502 (4)	0.83772 (17)	0.0518 (7)
C42	1.12641 (14)	0.7288 (4)	1.01360 (15)	0.0440 (7)
H42A	1.1313	0.6717	1.0574	0.053*
H42B	1.1634	0.7822	1.0164	0.053*
C61	1.06429 (15)	1.1373 (4)	0.75922 (16)	0.0461 (8)
H61A	1.0407	1.2262	0.7326	0.069*
H61B	1.103	1.1788	0.7818	0.069*
H61C	1.0472	1.098	0.7935	0.069*
C32	1.15806 (13)	0.4541 (4)	0.97808 (15)	0.0449 (7)
H32A	1.1971	0.5003	0.9971	0.054*
H32B	1.1495	0.3862	1.0137	0.054*
C73	0.77896 (14)	0.7676 (4)	0.71150 (17)	0.0453 (8)
H73A	0.7705	0.8668	0.7339	0.068*
H73B	0.7431	0.72	0.6823	0.068*
H73C	0.8036	0.7969	0.6837	0.068*
C52	1.08105 (17)	0.8664 (4)	1.00621 (17)	0.0548 (9)
H52	1.0468	0.8157	1.015	0.066*
N42	1.20105 (16)	0.0862 (5)	0.93030 (18)	0.0794 (11)
N4	0.96361 (18)	−0.1333 (5)	0.55828 (19)	0.0867 (12)
C7	0.78316 (13)	0.7401 (4)	0.41299 (16)	0.0475 (8)
H7A	0.7815	0.8597	0.4194	0.071*
H7B	0.7458	0.6913	0.4094	0.071*
H7C	0.7929	0.7177	0.3712	0.071*
C62	1.06080 (19)	0.9483 (5)	0.93493 (19)	0.0680 (11)
H62A	1.0321	1.033	0.9343	0.102*
H62B	1.0439	0.8643	0.9005	0.102*
H62C	1.0936	0.9992	0.925	0.102*
C72	1.1056 (3)	1.0000 (6)	1.0624 (2)	0.0927 (15)
H72A	1.0771	1.0873	1.0583	0.139*
H72B	1.1405	1.0475	1.0566	0.139*
H72C	1.1145	0.9487	1.1074	0.139*
N3	0.93357 (14)	−0.0144 (5)	0.56273 (15)	0.0600 (8)
N41	1.24793 (15)	0.6881 (5)	0.89497 (18)	0.0839 (11)
H11N	1.0281 (11)	0.602 (3)	0.7161 (13)	0.022 (7)*
H1N	0.9496 (12)	0.459 (4)	0.5192 (14)	0.028 (7)*
H13N	0.9407 (11)	0.456 (3)	0.7725 (13)	0.019 (6)*
H12N	1.0426 (11)	0.494 (3)	0.9707 (14)	0.024 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O13	0.0394 (11)	0.0418 (11)	0.0225 (9)	−0.0107 (9)	0.0118 (8)	−0.0018 (8)
O1	0.0320 (10)	0.0361 (10)	0.0200 (8)	−0.0061 (8)	0.0100 (7)	−0.0021 (8)
O12	0.0367 (10)	0.0467 (11)	0.0199 (9)	−0.0118 (9)	0.0079 (7)	0.0022 (8)
N11	0.0258 (11)	0.0297 (12)	0.0191 (10)	−0.0048 (9)	0.0097 (9)	−0.0034 (9)
N1	0.0235 (11)	0.0307 (12)	0.0187 (10)	−0.0019 (9)	0.0073 (9)	0.0004 (9)
O11	0.0273 (9)	0.0453 (11)	0.0229 (9)	−0.0045 (8)	0.0092 (7)	−0.0085 (8)
N12	0.0342 (13)	0.0410 (14)	0.0196 (11)	−0.0125 (10)	0.0076 (9)	0.0004 (10)
N13	0.0286 (12)	0.0372 (13)	0.0190 (11)	−0.0074 (10)	0.0081 (9)	0.0017 (9)
C2	0.0239 (13)	0.0321 (14)	0.0236 (12)	−0.0040 (11)	0.0073 (10)	−0.0007 (11)
C1	0.0265 (13)	0.0199 (12)	0.0211 (12)	0.0004 (10)	0.0078 (10)	−0.0008 (10)
C13	0.0328 (14)	0.0260 (13)	0.0216 (12)	−0.0023 (11)	0.0096 (10)	0.0002 (10)
N21	0.0296 (12)	0.0419 (14)	0.0408 (14)	0.0046 (11)	0.0114 (11)	−0.0046 (11)
C11	0.0245 (12)	0.0224 (12)	0.0197 (12)	0.0029 (10)	0.0053 (9)	0.0021 (10)
C4	0.0233 (13)	0.0412 (15)	0.0229 (12)	−0.0032 (12)	0.0056 (10)	−0.0024 (11)
C23	0.0312 (14)	0.0351 (15)	0.0218 (12)	−0.0074 (12)	0.0081 (11)	0.0005 (11)
C12	0.0364 (15)	0.0246 (13)	0.0214 (13)	−0.0038 (11)	0.0086 (11)	−0.0018 (10)
N23	0.0645 (18)	0.0473 (17)	0.0329 (14)	0.0023 (15)	0.0090 (12)	0.0051 (13)
C41	0.0321 (14)	0.0267 (13)	0.0232 (12)	−0.0068 (11)	0.0074 (10)	−0.0006 (10)
C51	0.0323 (14)	0.0301 (14)	0.0305 (14)	−0.0008 (12)	0.0085 (11)	0.0030 (11)
C53	0.0329 (14)	0.0402 (16)	0.0329 (14)	−0.0077 (13)	0.0136 (12)	−0.0089 (12)
C21	0.0272 (13)	0.0305 (14)	0.0240 (12)	−0.0051 (11)	0.0070 (10)	−0.0009 (11)
C31	0.0318 (14)	0.0314 (14)	0.0308 (14)	−0.0010 (12)	0.0059 (11)	−0.0044 (12)
C6	0.0358 (15)	0.0397 (16)	0.0386 (16)	0.0070 (13)	0.0108 (12)	−0.0021 (13)
C33	0.0365 (15)	0.0323 (15)	0.0313 (14)	−0.0062 (13)	0.0049 (12)	−0.0001 (12)
N33	0.0388 (15)	0.0407 (17)	0.0637 (18)	0.0060 (13)	0.0237 (13)	0.0199 (15)
C43	0.0288 (14)	0.0378 (15)	0.0264 (13)	−0.0067 (12)	0.0059 (11)	−0.0032 (12)
C22	0.0355 (15)	0.0447 (17)	0.0238 (13)	−0.0106 (13)	0.0046 (11)	−0.0016 (12)
C5	0.0263 (14)	0.0371 (15)	0.0305 (14)	0.0024 (12)	0.0061 (11)	0.0065 (11)
N22	0.071 (2)	0.0502 (17)	0.0302 (14)	0.0069 (16)	0.0035 (13)	0.0018 (13)
N32	0.0382 (16)	0.096 (3)	0.0390 (16)	0.0067 (18)	0.0122 (12)	−0.0010 (17)
N2	0.078 (2)	0.0301 (15)	0.0348 (14)	−0.0128 (15)	0.0192 (14)	−0.0107 (11)
C3	0.0430 (16)	0.0312 (15)	0.0330 (15)	−0.0052 (13)	0.0060 (13)	−0.0034 (12)
C71	0.059 (2)	0.0445 (18)	0.0446 (17)	0.0056 (16)	0.0218 (15)	0.0182 (15)
C63	0.0443 (18)	0.061 (2)	0.0463 (18)	−0.0041 (16)	0.0214 (14)	−0.0073 (16)
N43	0.059 (2)	0.0431 (17)	0.102 (3)	0.0081 (15)	0.0354 (19)	0.0031 (17)
N31	0.0378 (15)	0.0484 (17)	0.060 (2)	−0.0007 (13)	0.0009 (14)	0.0048 (14)
C42	0.0489 (18)	0.0517 (19)	0.0292 (15)	−0.0180 (16)	0.0086 (13)	−0.0062 (13)
C61	0.064 (2)	0.0293 (15)	0.0443 (17)	0.0047 (15)	0.0149 (16)	0.0013 (13)
C32	0.0380 (16)	0.058 (2)	0.0332 (15)	−0.0017 (16)	0.0036 (12)	−0.0008 (15)
C73	0.0458 (18)	0.0385 (17)	0.054 (2)	0.0056 (14)	0.0181 (15)	0.0002 (14)
C52	0.074 (2)	0.048 (2)	0.0439 (19)	−0.0026 (19)	0.0201 (17)	−0.0032 (16)
N42	0.071 (2)	0.101 (3)	0.069 (2)	0.040 (2)	0.0269 (18)	0.008 (2)
N4	0.089 (3)	0.068 (2)	0.081 (3)	0.025 (2)	−0.008 (2)	−0.010 (2)
C7	0.0405 (17)	0.058 (2)	0.0385 (17)	0.0130 (16)	0.0034 (13)	0.0098 (15)
C62	0.091 (3)	0.047 (2)	0.063 (2)	0.000 (2)	0.018 (2)	0.0016 (19)
C72	0.147 (5)	0.066 (3)	0.061 (3)	0.004 (3)	0.025 (3)	−0.019 (2)
N3	0.0560 (19)	0.057 (2)	0.0481 (17)	−0.0150 (18)	−0.0115 (14)	0.0091 (16)
N41	0.076 (2)	0.098 (3)	0.055 (2)	−0.028 (2)	−0.0134 (17)	−0.009 (2)

Geometric parameters (Å, º)

O13—C13	1.228 (3)	C6—H6C	0.96
O1—C1	1.227 (3)	C33—H33A	0.97
O12—C12	1.231 (3)	C33—H33B	0.97
N11—C11	1.328 (3)	N33—N43	1.161 (4)
N11—C21	1.458 (3)	C43—H43A	0.97
N11—H11N	0.84 (3)	C43—H43B	0.97
N1—C1	1.327 (3)	C22—C32	1.511 (4)
N1—C2	1.456 (3)	C22—C42	1.528 (4)
N1—H1N	0.84 (3)	C22—H22	0.98
O11—C11	1.231 (3)	C5—C7	1.537 (4)
N12—C12	1.320 (3)	C5—H5	0.98
N12—C22	1.464 (3)	N22—N32	1.158 (4)
N12—H12N	0.82 (3)	N22—C32	1.504 (4)
N13—C13	1.325 (3)	N32—N42	1.168 (5)
N13—C23	1.453 (3)	N2—N3	1.078 (4)
N13—H13N	0.81 (3)	N2—C3	1.544 (4)
C2—C3	1.525 (4)	C3—H3A	0.97
C2—C4	1.528 (3)	C3—H3B	0.97
C2—H2	0.98	C71—H71A	0.96
C1—C11	1.537 (3)	C71—H71B	0.96
C13—C12	1.541 (4)	C71—H71C	0.96
N21—N31	1.183 (4)	C63—H63A	0.96
N21—C31	1.519 (4)	C63—H63B	0.96
C4—C5	1.534 (4)	C63—H63C	0.96
C4—H4A	0.97	N31—N41	1.154 (4)
C4—H4B	0.97	C42—C52	1.517 (5)
C23—C33	1.523 (4)	C42—H42A	0.97
C23—C43	1.532 (4)	C42—H42B	0.97
C23—H23	0.98	C61—H61A	0.96
N23—N33	1.165 (4)	C61—H61B	0.96
N23—C33	1.503 (4)	C61—H61C	0.96
C41—C51	1.520 (4)	C32—H32A	0.97
C41—C21	1.527 (4)	C32—H32B	0.97
C41—H41A	0.97	C73—H73A	0.96
C41—H41B	0.97	C73—H73B	0.96
C51—C71	1.525 (4)	C73—H73C	0.96
C51—C61	1.533 (4)	C52—C62	1.519 (5)
C51—H51	0.98	C52—C72	1.533 (5)
C53—C43	1.520 (4)	C52—H52	0.98
C53—C73	1.528 (4)	N4—N3	1.208 (5)
C53—C63	1.538 (4)	C7—H7A	0.96
C53—H53	0.98	C7—H7B	0.96
C21—C31	1.527 (4)	C7—H7C	0.96
C21—H21	0.98	C62—H62A	0.96
C31—H31A	0.97	C62—H62B	0.96
C31—H31B	0.97	C62—H62C	0.96
C6—C5	1.519 (4)	C72—H72A	0.96
C6—H6A	0.96	C72—H72B	0.96
C6—H6B	0.96	C72—H72C	0.96
C11—N11—C21	124.0 (2)	C53—C43—H43A	108.1
C11—N11—H11N	116.4 (18)	C23—C43—H43A	108.1
C21—N11—H11N	119.0 (18)	C53—C43—H43B	108.1
C1—N1—C2	122.8 (2)	C23—C43—H43B	108.1
C1—N1—H1N	117.2 (18)	H43A—C43—H43B	107.3
C2—N1—H1N	120.0 (18)	N12—C22—C32	110.2 (2)
C12—N12—C22	122.7 (2)	N12—C22—C42	112.4 (2)
C12—N12—H12N	118.5 (18)	C32—C22—C42	109.8 (2)
C22—N12—H12N	118.8 (18)	N12—C22—H22	108.1
C13—N13—C23	125.3 (2)	C32—C22—H22	108.1
C13—N13—H13N	117.3 (18)	C42—C22—H22	108.1
C23—N13—H13N	117.4 (18)	C6—C5—C4	112.4 (2)
N1—C2—C3	110.2 (2)	C6—C5—C7	110.5 (2)
N1—C2—C4	112.2 (2)	C4—C5—C7	109.7 (2)
C3—C2—C4	109.8 (2)	C6—C5—H5	108
N1—C2—H2	108.2	C4—C5—H5	108
C3—C2—H2	108.2	C7—C5—H5	108
C4—C2—H2	108.2	N32—N22—C32	116.3 (3)
O1—C1—N1	125.2 (2)	N22—N32—N42	172.7 (4)
O1—C1—C11	120.8 (2)	N3—N2—C3	114.1 (3)
N1—C1—C11	113.98 (19)	C2—C3—N2	109.9 (2)
O13—C13—N13	126.3 (2)	C2—C3—H3A	109.7
O13—C13—C12	121.4 (2)	N2—C3—H3A	109.7
N13—C13—C12	112.3 (2)	C2—C3—H3B	109.7
N31—N21—C31	113.6 (2)	N2—C3—H3B	109.7
O11—C11—N11	125.0 (2)	H3A—C3—H3B	108.2
O11—C11—C1	121.9 (2)	C51—C71—H71A	109.5
N11—C11—C1	113.1 (2)	C51—C71—H71B	109.5
C2—C4—C5	115.4 (2)	H71A—C71—H71B	109.5
C2—C4—H4A	108.4	C51—C71—H71C	109.5
C5—C4—H4A	108.4	H71A—C71—H71C	109.5
C2—C4—H4B	108.4	H71B—C71—H71C	109.5
C5—C4—H4B	108.4	C53—C63—H63A	109.5
H4A—C4—H4B	107.5	C53—C63—H63B	109.5
N13—C23—C33	110.0 (2)	H63A—C63—H63B	109.5
N13—C23—C43	110.8 (2)	C53—C63—H63C	109.5
C33—C23—C43	108.2 (2)	H63A—C63—H63C	109.5
N13—C23—H23	109.3	H63B—C63—H63C	109.5
C33—C23—H23	109.3	N41—N31—N21	172.7 (4)
C43—C23—H23	109.3	C52—C42—C22	117.2 (3)
O12—C12—N12	125.3 (2)	C52—C42—H42A	108
O12—C12—C13	120.3 (2)	C22—C42—H42A	108
N12—C12—C13	114.4 (2)	C52—C42—H42B	108
N33—N23—C33	115.2 (3)	C22—C42—H42B	108
C51—C41—C21	115.5 (2)	H42A—C42—H42B	107.2
C51—C41—H41A	108.4	C51—C61—H61A	109.5
C21—C41—H41A	108.4	C51—C61—H61B	109.5
C51—C41—H41B	108.4	H61A—C61—H61B	109.5
C21—C41—H41B	108.4	C51—C61—H61C	109.5
H41A—C41—H41B	107.5	H61A—C61—H61C	109.5
C41—C51—C71	112.7 (2)	H61B—C61—H61C	109.5
C41—C51—C61	110.4 (2)	N22—C32—C22	109.1 (2)
C71—C51—C61	110.0 (2)	N22—C32—H32A	109.9
C41—C51—H51	107.8	C22—C32—H32A	109.9
C71—C51—H51	107.8	N22—C32—H32B	109.9
C61—C51—H51	107.8	C22—C32—H32B	109.9
C43—C53—C73	110.4 (2)	H32A—C32—H32B	108.3
C43—C53—C63	111.9 (2)	C53—C73—H73A	109.5
C73—C53—C63	109.5 (2)	C53—C73—H73B	109.5
C43—C53—H53	108.3	H73A—C73—H73B	109.5
C73—C53—H53	108.3	C53—C73—H73C	109.5
C63—C53—H53	108.3	H73A—C73—H73C	109.5
N11—C21—C41	110.3 (2)	H73B—C73—H73C	109.5
N11—C21—C31	107.7 (2)	C62—C52—C42	114.4 (3)
C41—C21—C31	113.0 (2)	C62—C52—C72	110.2 (3)
N11—C21—H21	108.5	C42—C52—C72	108.8 (3)
C41—C21—H21	108.5	C62—C52—H52	107.7
C31—C21—H21	108.5	C42—C52—H52	107.7
N21—C31—C21	111.7 (2)	C72—C52—H52	107.7
N21—C31—H31A	109.3	C5—C7—H7A	109.5
C21—C31—H31A	109.3	C5—C7—H7B	109.5
N21—C31—H31B	109.3	H7A—C7—H7B	109.5
C21—C31—H31B	109.3	C5—C7—H7C	109.5
H31A—C31—H31B	107.9	H7A—C7—H7C	109.5
C5—C6—H6A	109.5	H7B—C7—H7C	109.5
C5—C6—H6B	109.5	C52—C62—H62A	109.5
H6A—C6—H6B	109.5	C52—C62—H62B	109.5
C5—C6—H6C	109.5	H62A—C62—H62B	109.5
H6A—C6—H6C	109.5	C52—C62—H62C	109.5
H6B—C6—H6C	109.5	H62A—C62—H62C	109.5
N23—C33—C23	110.0 (2)	H62B—C62—H62C	109.5
N23—C33—H33A	109.7	C52—C72—H72A	109.5
C23—C33—H33A	109.7	C52—C72—H72B	109.5
N23—C33—H33B	109.7	H72A—C72—H72B	109.5
C23—C33—H33B	109.7	C52—C72—H72C	109.5
H33A—C33—H33B	108.2	H72A—C72—H72C	109.5
N43—N33—N23	173.7 (4)	H72B—C72—H72C	109.5
C53—C43—C23	116.6 (2)	N2—N3—N4	172.8 (4)
C1—N1—C2—C4	132.2 (2)	C12—N12—C22—C42	128.4 (3)
C2—N1—C1—O1	−1.7 (4)	C2—C4—C5—C6	−50.6 (3)
C23—N13—C13—O13	−4.1 (4)	C2—C4—C5—C7	−173.9 (2)
C21—N11—C11—O11	0.3 (4)	C4—C2—C3—N2	−173.0 (2)
O1—C1—C11—O11	165.2 (2)	N3—N2—C3—C2	−143.6 (3)
N1—C1—C11—O11	−15.3 (3)	C32—C22—C42—C52	−170.5 (3)
O1—C1—C11—N11	−15.0 (3)	N32—N22—C32—C22	−167.6 (3)
N1—C1—C11—N11	164.5 (2)	C42—C22—C32—N22	−166.3 (2)
C3—C2—C4—C5	−177.1 (2)	C22—C42—C52—C62	−48.0 (4)
C13—N13—C23—C43	123.2 (3)	C22—C42—C52—C72	−171.8 (3)
C22—N12—C12—O12	0.2 (4)	C2—N1—C1—C11	178.8 (2)
O13—C13—C12—O12	−172.2 (2)	C1—N1—C2—C3	−105.1 (3)
N13—C13—C12—O12	6.9 (3)	N1—C2—C3—N2	62.8 (3)
O13—C13—C12—N12	7.2 (4)	N1—C2—C4—C5	−54.1 (3)
N13—C13—C12—N12	−173.7 (2)	C21—N11—C11—C1	−179.6 (2)
C21—C41—C51—C71	−63.6 (3)	C11—N11—C21—C31	−95.9 (3)
C21—C41—C51—C61	172.9 (2)	N11—C21—C31—N21	178.0 (2)
C11—N11—C21—C41	140.3 (2)	C51—C41—C21—N11	−64.1 (3)
C51—C41—C21—C31	175.2 (2)	C23—N13—C13—C12	176.9 (2)
N31—N21—C31—C21	106.0 (3)	C12—N12—C22—C32	−108.8 (3)
C41—C21—C31—N21	−59.8 (3)	N12—C22—C32—N22	69.4 (3)
N33—N23—C33—C23	−170.5 (3)	N12—C22—C42—C52	−47.4 (4)
C43—C23—C33—N23	178.0 (2)	C22—N12—C12—C13	−179.2 (2)
C73—C53—C43—C23	165.7 (2)	C13—N13—C23—C33	−117.3 (3)
C63—C53—C43—C23	−72.0 (3)	N13—C23—C33—N23	56.8 (3)
C33—C23—C43—C53	171.6 (2)	N13—C23—C43—C53	−67.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11N···O12	0.84 (3)	2.15 (3)	2.893 (3)	147 (2)
N1—H1N···O11^i	0.84 (3)	2.11 (3)	2.879 (3)	153 (2)
N13—H13N···O1	0.81 (3)	2.21 (3)	2.948 (3)	152 (2)
N13—H13N···O12	0.81 (3)	2.28 (3)	2.673 (3)	110 (2)
N12—H12N···O13^ii	0.82 (3)	2.23 (3)	2.978 (3)	152 (2)
N1—H1N···O11	0.84 (3)	2.38 (3)	2.748 (3)	108 (2)
N12—H12N···O13	0.82 (3)	2.38 (3)	2.734 (4)	107 (2)
N11—H11N···O1	0.84 (3)	2.31 (3)	2.708 (3)	109 (2)

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