1-(2-Cyclo­hex-2-enylpropion­yl)-3-methyl­urea, 2-ethyl-5-methyl­hexa­namide and 2-ethyl­penta­namide: three products of barbiturate decomposition

The three title compounds were obtained by reactions which mimic, with more extreme conditions, the in vivo metabolism of barbiturates. 1-(2-Cyclo­hex-2-enylpropion­yl)-3-methyl­urea, C₁₁H₁₈N₂O₂, (I), and 2-ethyl­penta­namide, C₈H₁₇NO, (III), both crystallize with two unique mol­ecules in the asymmetric unit; in the case of (III), one unique mol­ecule exhibits whole-mol­ecule disorder. 2-Ethyl-5-methyl­hexa­namide, C₉H₁₉NO, (II), crystallizes as a fully ordered mol­ecule with Z' = 1. In the crystal structures, three different hydrogen-bonding motifs are observed: in (I) a combination of R₂²(4) and R₂²(8) motifs, and in (II) and (III) a combination of R₄²(8) and R₂²(8) motifs. In all three structures, one-dimensional ribbons are formed by N-H...O hydrogen-bonding inter­actions.

S1. Comment

Substituted barbiturates have for decades been used as sedatives in the treatment of anxiety disorders (Volwiler & Tabern, 1930; Schwartz et al., 2005). Their chemical and structural properties are much studied, polymorphism in particular (Zencirci et al., 2009; Gryl et al., 2008; Bernstein, 2002). Despite their widespread medical use and the extensive structural characterization of the drug molecules, charting the in vivo metabolic pathway and the subsequent identification of the resulting metabolites seems to have received much less attention, at least in terms of published material. A search of SciFinder Scholar in November 2010 for `barbiturate metabolism' returned just 50 hits. In 1961 Freifelder and co-workers charted the synthetic route of the ring opening and subsequent hydrolysis of 5,5-disubstituted barbiturates (Scheme); they had thus described a chemical model for the in vivo metabolism of barbiturates (Freifelder et al., 1961).

Our interest in barbiturate crystal packing has revealed phase transitions (Nichol & Clegg, 2005a,b), metal complexes (Nichol & Clegg, 2005c), hydrogen-bonding interactions in organic co-crystals (Nichol & Clegg, 2006, 2009) and now the products of barbiturate hydrolysis. To investigate how the hydrogen-bonding motifs vary among barbiturate metabolites, we synthesized and characterized by X-ray crystallography the decomposition products of three 5,5-disubstituted barbituric acids (hexobarbitone, amylobarbitone and butobarbitone; Scheme) according to the mechanism reported by Freifelder. In each case the crystals obtained were of good size and sufficient quality that one would reasonably expect standard laboratory X-ray equipment to be satisfactory for data collection. This turned out to be incorrect and much higher intensity radiation was necessary; data for one compound were collected using radiation from a rotating anode amplified by mirror optics (Coles & Hursthouse, 2004) at Southampton University via the EPSRC National X-ray Crystallography Service, and data for the other two compounds were collected at Station 9.8 of the SRS at Daresbury Laboratory.

The discussion below describes the hydrogen-bonding motifs in terms of graph-set notation (Bernstein et al., 1995). The most pertinent pattern in this study is the R^a_d(n) notation, where R = ring, a = number of acceptors, d = number of donors and n = total number of atoms in the ring. In addition there are motifs of type S (intramolecular hydrogen bonding).

The synthesis of compound (I), 1-(2-cyclohex-2-enylpropionyl)-3-methylurea, is slightly different from that of the other two compounds, (II) and (III). The presence of an N-methyl group means that hydrolysis (step 2 of the reaction) cannot proceed, so instead crystals of the product of the first decarboxylation are obtained. The molecular structure of (I) is presented in Fig. 1 and hydrogen-bonding details are given in Table 1. There are two crystallographically unique molecules in the asymmetric unit; the molecule composed of atoms O1 to C11 will henceforth be referred to as `molecule A' and the molecule composed of atoms O51 to C61 as `molecule B'. Discussion is focused on molecule A with results for molecule B given in square brackets. Within the molecule, the urea group is essentially planar, with an r.m.s. deviation of 0.022Å [0.016 Å]; the two molecules differ in the orientations of the cyclohex-2-enyl groups, as a result of free rotation about the C3—C4 [C53—C54] bond. Fig. 2 shows a least-squares overlay formed by fitting the the urea groups of molecule A (orange) and B (black) with an r.m.s. deviation of 0.04; the differences in the cyclohex-2-enyl orientations are clear. Both cyclohex-2-enyl rings adopt a half-chair conformation.

In the crystal structure, N—H···O hydrogen bonding links adjacent unique molecules to form a one-dimensional ribbon which propagates parallel with the a axis (Fig. 3). In addition to an S(6) interaction found in both molecules, two intermolecular hydrogen-bonding motifs are present: an R₂²(8) motif, common between amide groups, and a second R₂²(4) motif. This combination of ring motifs, to yield a one-dimensional ribbon, has also been observed in other urea derivatives (Hashizume et al., 2003; Chen et al., 2005). Bond angles around the carbonyl C atom deviate significantly from 120°; this is also consistent with other urea derivates with the same hydrogen-bonding pattern.

Compound (II), 2-ethyl-5-methylhexanoic acid amide, was synthesized from amylobarbitone; in amylobarbitone there is no N-methyl group and so hydrolysis can proceed to give the final acid amide product. As a result there are only one hydrogen-bond acceptor and two donor sites, which means that the range of potential motifs is much more limited than those possible in compound (I). The molecular structure of (II) is shown in Fig. 4, and molecular dimensions are unexceptional. Hydrogen-bonding details are given in Table 2. In the crystal structure, each carbonyl group acts as a bifurcated hydrogen-bond acceptor and both hydrogen atoms of each amine group act as hydrogen-bond donors; thus all potential hydrogen-bonding donors and acceptors are satisfied. Two different hydrogen-bonding motifs are present (Fig. 5): an R₂²(8) interaction is found as in (I), and an R₄²(8) motif links the dimers into an infinite tape which runs parallel to the b axis.

Compound (III), 2-ethylpentanamide, was synthesized from butobarbitone; as with amylobarbitone, butobarbitone contains no N-methyl group and consequently the product of hydrolysis, (III), is analogous to (II). The molecular structure of (III) is presented in Fig. 6 and hydrogen-bonding geometry is given in Table 3. The unit-cell parameters for (III) are also similar to those of (II). However, where (II) crystallizes in space group C2/c, (III) crystallizes in space group P2₁/c with two crystallographically independent molecules (`molecule A' formed by atoms O1 to C8; `molecule B' formed by atoms O51 to C58) in the asymmetric unit and overall Z = 8. There are no exact or approximate systematic absences in the data for (III) which would suggest a centred unit cell. Molecule A exhibits whole-molecule disorder; this was modelled over two sites and refined with occupancies of 0.559: 0.441 (8). Molecule B is fully ordered. Hydrogen-bonding patterns are the same as for (II) (Fig. 5) and the overall crystal packing is broadly similar.

Related literature

For related literature, see: Bernstein (2002); Bernstein et al. (1995); Chen et al. (2005); Coles & Hursthouse (2004); Farrugia (1999); Freifelder et al. (1961); Gryl et al. (2008); Hashizume et al. (2003); Nichol & Clegg (2005a, 2005b, 2005c, 2006, 2009); Schwartz et al. (2005); Volwiler & Tabern (1930); Zencirci et al. (2009).

S2. Experimental

The 5,5-disubstituted barbituric acids were obtained as commercial samples from Professor Roger Griffin, Newcastle University. Caesium hydroxide monohydrate was purchased from Lancaster Chemicals. All reagents were used without further purification.

For the preparation of (I), 1-(2-cyclohex-2-enylpropionyl)-3-methylurea, hexobarbitone (0.223 g, 0.94 mmol) and CsOH.H₂O (0.169 g, 1 mmol) were dissolved in boiling distilled water (40 ml). The solution was boiled until ca 15 ml remained when the hot solution was transferred to a separate sample vial and set aside to cool undisturbed at room temperature. Large, colourless, lath crystals of (I) appeared after approximately 2 weeks (yield 35 mg, 17.7%).

For the preparation of (II), 2-ethyl-5-methylhexanamide, amylobarbitone (0.228 g, 1 mmol) was placed in a Teflon-lined steel autoclave along with distilled water (10 ml). The sealed autoclave was placed in an oven and kept at 453 K for 48 h after which time the oven temperature was cooled slowly to 298 K over a period of 18 h. Large, colourless, lath-shaped crystals of (II) were removed from the autoclave and stored in distilled water (yield 55 mg, 35.03%).

For the preparation of (III), 2-ethylpentanamide, butobarbitone (0.219 g, 1 mmol) was placed in a Teflon-lined steel autoclave along with distilled water (10 ml). The sealed autoclave was placed in an oven and kept at 453 K for 48 h after which time the oven temperature was cooled slowly to 298 K over a period of 18 h. Large, colourless, lath-shaped crystals of (III) were removed from the autoclave and stored in distilled water (yield 45 mg, 32.59%).

S3. Refinement

All H atoms were first located in a difference Fourier map. In (I) N-bound H atoms were freely refined. In (II) and (III) N-bound H atoms were refined as riding atoms with U_iso(H) = 1.5U_eq(N) and a fixed N—H distance of 0.88 Å. In all structures, C-bound H atoms were refined as riding, with U_iso(H) = 1.2U_eq(C) [or 1.5U_eq (C) for methyl hydrogen atoms] and fixed C—H distances (0.95–1.00 Å). Molecule A in the asymmetric unit of compound (III) exhibits whole-molecule disorder, which was refined over two positions with occupancies of 0.559:0.441 (8). Bond distance restraints were used to control the refinement of the disordered molecule. Real and imaginary components of the anomalous scattering factors for (II) and (III) were calculated using WinGX (Farrugia, 1999).

Computing details

Data collection: COLLECT (Nonius, 1998) for (I); APEX2 (Bruker, 2007) for (II), (III). Cell refinement: DENZO (Otwinowski & Minor, 1997) for (I); APEX2 (Bruker, 2007) for (II), (III). Data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (I); APEX2 (Bruker, 2007) for (II), (III). For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 1999) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and local programs.

Figures

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 50% probability level. Dashed blue lines indicate hydrogen bonds.
	Fig. 2. A least-squares overlay formed by fitting the urea groups of molecule A (orange) and B (black) in (I) with an r.m.s. deviation of 0.04 Å. H atoms are omitted.
	Fig. 3. The intermolecular hydrogen bonding in (I). Dotted blue lines indicate hydrogen bonding and dotted red lines indicate hydrogen-bonding continuation.
	Fig. 4. The asymmetric unit of (II) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 5. Hydrogen-bonding patterns in (II). Dotted blue lines indicate hydrogen bonding and dotted red lines indicate hydrogen-bonding continuation.
	Fig. 6. The asymmetric unit of (III) with displacement ellipsoids drawn at the 30% probability level; the minor disorder component is omitted.

(I) 1-(2-Cyclohex-2-enylpropionyl)-3-methylurea

Crystal data

C11H18N2O2	F(000) = 912
Mr = 210.27	Dx = 1.220 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 28727 reflections
a = 10.108 (2) Å	θ = 2.9–27.5°
b = 21.824 (4) Å	µ = 0.09 mm^−1
c = 10.393 (2) Å	T = 120 K
β = 92.52 (3)°	Slab, colourless
V = 2290.4 (8) Å^3	0.36 × 0.08 × 0.03 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	4030 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode	3184 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.110
ϕ and ω scans	θmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −11→12
Tmin = 0.970, Tmax = 0.998	k = −25→25
37076 measured reflections	l = −12→12

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)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0417P)^2 + 2.3454P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
4030 reflections	Δρmax = 0.26 e Å^−3
292 parameters	Δρmin = −0.23 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (10)

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
O1	0.69715 (16)	0.09347 (8)	0.21980 (16)	0.0295 (4)
O2	1.01230 (16)	0.08578 (8)	0.48868 (16)	0.0291 (4)
N1	0.9204 (2)	0.10154 (9)	0.2397 (2)	0.0250 (5)
H1N	0.991 (3)	0.0993 (13)	0.285 (3)	0.036 (8)*
N2	0.7945 (2)	0.08685 (10)	0.41984 (19)	0.0252 (5)
H2N	0.706 (3)	0.0865 (11)	0.455 (2)	0.022 (6)*
C1	0.9357 (3)	0.10554 (13)	0.1019 (2)	0.0336 (6)
H1A	0.9042	0.0675	0.0607	0.050*
H1B	1.0294	0.1116	0.0847	0.050*
H1C	0.8839	0.1402	0.0670	0.050*
C2	0.8019 (2)	0.09416 (10)	0.2862 (2)	0.0223 (5)
C3	0.8949 (2)	0.08320 (11)	0.5123 (2)	0.0230 (5)
C4	0.8442 (2)	0.07506 (11)	0.6467 (2)	0.0237 (5)
H4	0.7728	0.0433	0.6417	0.028*
C5	0.9531 (3)	0.05215 (12)	0.7400 (2)	0.0301 (6)
H5A	0.9920	0.0147	0.7057	0.045*
H5B	0.9158	0.0433	0.8234	0.045*
H5C	1.0218	0.0836	0.7509	0.045*
C6	0.7837 (2)	0.13424 (11)	0.6959 (2)	0.0234 (5)
C7	0.8264 (3)	0.18926 (12)	0.6624 (2)	0.0319 (6)
H7	0.8920	0.1914	0.5998	0.038*
C8	0.7779 (3)	0.24788 (13)	0.7169 (3)	0.0412 (7)
H8A	0.7228	0.2695	0.6502	0.049*
H8B	0.8547	0.2743	0.7407	0.049*
C9	0.6967 (3)	0.23779 (13)	0.8350 (3)	0.0462 (8)
H9A	0.7568	0.2291	0.9107	0.055*
H9B	0.6462	0.2755	0.8532	0.055*
C10	0.6028 (3)	0.18529 (13)	0.8137 (3)	0.0423 (7)
H10A	0.5422	0.1943	0.7386	0.051*
H10B	0.5486	0.1805	0.8901	0.051*
C11	0.6762 (3)	0.12600 (12)	0.7900 (2)	0.0307 (6)
H11A	0.7158	0.1107	0.8727	0.037*
H11B	0.6126	0.0948	0.7562	0.037*
O51	0.54140 (16)	0.07316 (9)	0.51051 (16)	0.0313 (4)
O52	0.21841 (16)	0.08453 (9)	0.25643 (16)	0.0334 (5)
N51	0.3185 (2)	0.07093 (9)	0.49911 (19)	0.0240 (5)
H51N	0.242 (3)	0.0764 (13)	0.452 (3)	0.037 (8)*
N52	0.4386 (2)	0.08232 (10)	0.31293 (19)	0.0251 (5)
H52N	0.519 (3)	0.0840 (10)	0.281 (2)	0.016 (6)*
C51	0.3115 (2)	0.06391 (13)	0.6379 (2)	0.0297 (6)
H51A	0.3630	0.0279	0.6662	0.045*
H51B	0.2190	0.0585	0.6600	0.045*
H51C	0.3478	0.1006	0.6810	0.045*
C52	0.4347 (2)	0.07512 (11)	0.4482 (2)	0.0240 (5)
C53	0.3351 (2)	0.08618 (11)	0.2261 (2)	0.0240 (5)
C54	0.3714 (2)	0.09137 (11)	0.0854 (2)	0.0258 (6)
H54	0.4700	0.0947	0.0832	0.031*
C55	0.3297 (3)	0.03268 (12)	0.0171 (3)	0.0348 (6)
H55A	0.2335	0.0277	0.0206	0.052*
H55B	0.3742	−0.0022	0.0595	0.052*
H55C	0.3542	0.0347	−0.0730	0.052*
C56	0.3120 (2)	0.14977 (11)	0.0299 (2)	0.0227 (5)
C57	0.2223 (2)	0.15041 (12)	−0.0672 (2)	0.0275 (6)
H57	0.1974	0.1123	−0.1052	0.033*
C58	0.1577 (3)	0.20738 (13)	−0.1208 (3)	0.0376 (7)
H58A	0.0613	0.2002	−0.1334	0.045*
H58B	0.1933	0.2164	−0.2059	0.045*
C59	0.1809 (3)	0.26257 (14)	−0.0323 (3)	0.0459 (8)
H59A	0.1575	0.3007	−0.0797	0.055*
H59B	0.1235	0.2594	0.0422	0.055*
C60	0.3254 (3)	0.26508 (13)	0.0150 (3)	0.0415 (7)
H60A	0.3405	0.3020	0.0691	0.050*
H60B	0.3827	0.2680	−0.0596	0.050*
C61	0.3614 (3)	0.20780 (12)	0.0933 (2)	0.0311 (6)
H61A	0.4589	0.2055	0.1061	0.037*
H61B	0.3235	0.2113	0.1793	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0206 (9)	0.0437 (11)	0.0241 (9)	−0.0017 (7)	−0.0019 (7)	0.0017 (8)
O2	0.0222 (9)	0.0392 (11)	0.0258 (9)	−0.0002 (7)	0.0001 (7)	−0.0006 (8)
N1	0.0207 (11)	0.0309 (12)	0.0232 (11)	0.0009 (9)	−0.0010 (9)	0.0007 (9)
N2	0.0200 (11)	0.0339 (12)	0.0215 (11)	0.0005 (9)	−0.0005 (8)	0.0001 (9)
C1	0.0283 (14)	0.0502 (18)	0.0223 (13)	0.0011 (12)	0.0024 (10)	0.0032 (12)
C2	0.0231 (13)	0.0191 (12)	0.0247 (13)	0.0011 (9)	0.0003 (10)	−0.0007 (10)
C3	0.0213 (13)	0.0212 (12)	0.0264 (13)	−0.0002 (10)	−0.0002 (10)	−0.0015 (10)
C4	0.0226 (12)	0.0256 (13)	0.0226 (13)	−0.0004 (10)	−0.0006 (9)	−0.0007 (10)
C5	0.0326 (14)	0.0320 (15)	0.0254 (13)	0.0057 (11)	−0.0018 (11)	0.0008 (11)
C6	0.0212 (12)	0.0267 (13)	0.0219 (12)	0.0023 (10)	−0.0035 (9)	0.0016 (10)
C7	0.0311 (14)	0.0351 (16)	0.0296 (14)	−0.0008 (11)	0.0023 (11)	−0.0011 (12)
C8	0.0531 (18)	0.0292 (15)	0.0418 (17)	−0.0005 (13)	0.0074 (13)	−0.0029 (13)
C9	0.068 (2)	0.0331 (17)	0.0384 (17)	0.0066 (15)	0.0127 (15)	−0.0071 (13)
C10	0.0441 (17)	0.0416 (17)	0.0427 (17)	0.0090 (13)	0.0182 (13)	−0.0006 (14)
C11	0.0316 (14)	0.0317 (15)	0.0288 (14)	0.0014 (11)	0.0024 (11)	0.0006 (11)
O51	0.0188 (9)	0.0511 (12)	0.0236 (9)	−0.0018 (8)	−0.0021 (7)	0.0022 (8)
O52	0.0199 (9)	0.0530 (12)	0.0270 (10)	−0.0007 (8)	−0.0008 (7)	0.0057 (8)
N51	0.0192 (11)	0.0333 (12)	0.0195 (10)	0.0004 (9)	−0.0004 (8)	−0.0009 (9)
N52	0.0222 (11)	0.0314 (12)	0.0216 (11)	0.0002 (9)	0.0001 (9)	0.0023 (9)
C51	0.0261 (13)	0.0400 (16)	0.0232 (13)	−0.0011 (11)	0.0033 (10)	−0.0001 (11)
C52	0.0239 (13)	0.0233 (13)	0.0246 (13)	−0.0001 (10)	0.0006 (10)	0.0008 (10)
C53	0.0251 (13)	0.0222 (13)	0.0246 (13)	0.0003 (10)	−0.0013 (10)	0.0028 (10)
C54	0.0244 (13)	0.0299 (14)	0.0228 (12)	0.0006 (10)	−0.0007 (10)	0.0018 (10)
C55	0.0445 (16)	0.0302 (15)	0.0294 (14)	0.0023 (12)	−0.0003 (12)	0.0001 (12)
C56	0.0230 (12)	0.0265 (13)	0.0188 (12)	−0.0011 (10)	0.0032 (9)	0.0019 (10)
C57	0.0288 (13)	0.0327 (14)	0.0209 (12)	−0.0024 (11)	−0.0008 (10)	0.0021 (11)
C58	0.0343 (15)	0.0445 (17)	0.0334 (15)	0.0026 (12)	−0.0030 (12)	0.0114 (13)
C59	0.0521 (19)	0.0385 (17)	0.0471 (18)	0.0163 (14)	0.0019 (14)	0.0090 (14)
C60	0.0521 (18)	0.0263 (15)	0.0459 (17)	−0.0015 (13)	−0.0008 (14)	−0.0020 (13)
C61	0.0361 (15)	0.0302 (15)	0.0267 (14)	−0.0024 (11)	−0.0018 (11)	−0.0031 (11)

Geometric parameters (Å, º)

O1—C2	1.238 (3)	O51—C52	1.234 (3)
O2—C3	1.224 (3)	O52—C53	1.234 (3)
N1—H1N	0.84 (3)	N51—H51N	0.90 (3)
N1—C1	1.451 (3)	N51—C51	1.456 (3)
N1—C2	1.322 (3)	N51—C52	1.313 (3)
N2—H2N	0.98 (3)	N52—H52N	0.89 (3)
N2—C2	1.403 (3)	N52—C52	1.417 (3)
N2—C3	1.369 (3)	N52—C53	1.355 (3)
C1—H1A	0.980	C51—H51A	0.980
C1—H1B	0.980	C51—H51B	0.980
C1—H1C	0.980	C51—H51C	0.980
C3—C4	1.519 (3)	C53—C54	1.527 (3)
C4—H4	1.000	C54—H54	1.000
C4—C5	1.519 (3)	C54—C55	1.515 (4)
C4—C6	1.526 (3)	C54—C56	1.513 (3)
C5—H5A	0.980	C55—H55A	0.980
C5—H5B	0.980	C55—H55B	0.980
C5—H5C	0.980	C55—H55C	0.980
C6—C7	1.327 (4)	C56—C57	1.326 (3)
C6—C11	1.505 (3)	C56—C61	1.503 (3)
C7—H7	0.950	C57—H57	0.950
C7—C8	1.491 (4)	C57—C58	1.500 (4)
C8—H8A	0.990	C58—H58A	0.990
C8—H8B	0.990	C58—H58B	0.990
C8—C9	1.522 (4)	C58—C59	1.527 (4)
C9—H9A	0.990	C59—H59A	0.990
C9—H9B	0.990	C59—H59B	0.990
C9—C10	1.499 (4)	C59—C60	1.521 (4)
C10—H10A	0.990	C60—H60A	0.990
C10—H10B	0.990	C60—H60B	0.990
C10—C11	1.517 (4)	C60—C61	1.527 (4)
C11—H11A	0.990	C61—H61A	0.990
C11—H11B	0.990	C61—H61B	0.990
H1N—N1—C1	116 (2)	H51N—N51—C51	118.4 (18)
H1N—N1—C2	123 (2)	H51N—N51—C52	121.9 (18)
C1—N1—C2	120.4 (2)	C51—N51—C52	119.3 (2)
H2N—N2—C2	117.4 (14)	H52N—N52—C52	116.2 (15)
H2N—N2—C3	113.4 (14)	H52N—N52—C53	115.9 (15)
C2—N2—C3	129.2 (2)	C52—N52—C53	127.9 (2)
N1—C1—H1A	109.5	N51—C51—H51A	109.5
N1—C1—H1B	109.5	N51—C51—H51B	109.5
N1—C1—H1C	109.5	N51—C51—H51C	109.5
H1A—C1—H1B	109.5	H51A—C51—H51B	109.5
H1A—C1—H1C	109.5	H51A—C51—H51C	109.5
H1B—C1—H1C	109.5	H51B—C51—H51C	109.5
O1—C2—N1	124.3 (2)	O51—C52—N51	124.3 (2)
O1—C2—N2	118.0 (2)	O51—C52—N52	117.6 (2)
N1—C2—N2	117.6 (2)	N51—C52—N52	118.2 (2)
O2—C3—N2	123.5 (2)	O52—C53—N52	123.1 (2)
O2—C3—C4	124.0 (2)	O52—C53—C54	121.3 (2)
N2—C3—C4	112.5 (2)	N52—C53—C54	115.5 (2)
C3—C4—H4	107.8	C53—C54—H54	108.0
C3—C4—C5	111.1 (2)	C53—C54—C55	108.2 (2)
C3—C4—C6	111.42 (19)	C53—C54—C56	108.62 (19)
H4—C4—C5	107.8	H54—C54—C55	108.0
H4—C4—C6	107.8	H54—C54—C56	108.0
C5—C4—C6	110.75 (19)	C55—C54—C56	115.8 (2)
C4—C5—H5A	109.5	C54—C55—H55A	109.5
C4—C5—H5B	109.5	C54—C55—H55B	109.5
C4—C5—H5C	109.5	C54—C55—H55C	109.5
H5A—C5—H5B	109.5	H55A—C55—H55B	109.5
H5A—C5—H5C	109.5	H55A—C55—H55C	109.5
H5B—C5—H5C	109.5	H55B—C55—H55C	109.5
C4—C6—C7	122.6 (2)	C54—C56—C57	123.1 (2)
C4—C6—C11	115.3 (2)	C54—C56—C61	115.1 (2)
C7—C6—C11	122.1 (2)	C57—C56—C61	121.9 (2)
C6—C7—H7	118.0	C56—C57—H57	117.9
C6—C7—C8	124.1 (2)	C56—C57—C58	124.3 (2)
H7—C7—C8	118.0	H57—C57—C58	117.9
C7—C8—H8A	109.1	C57—C58—H58A	109.2
C7—C8—H8B	109.1	C57—C58—H58B	109.2
C7—C8—C9	112.4 (2)	C57—C58—C59	112.2 (2)
H8A—C8—H8B	107.9	H58A—C58—H58B	107.9
H8A—C8—C9	109.1	H58A—C58—C59	109.2
H8B—C8—C9	109.1	H58B—C58—C59	109.2
C8—C9—H9A	109.5	C58—C59—H59A	109.6
C8—C9—H9B	109.5	C58—C59—H59B	109.6
C8—C9—C10	110.6 (2)	C58—C59—C60	110.1 (2)
H9A—C9—H9B	108.1	H59A—C59—H59B	108.2
H9A—C9—C10	109.5	H59A—C59—C60	109.6
H9B—C9—C10	109.5	H59B—C59—C60	109.6
C9—C10—H10A	109.4	C59—C60—H60A	109.6
C9—C10—H10B	109.4	C59—C60—H60B	109.6
C9—C10—C11	111.4 (2)	C59—C60—C61	110.3 (2)
H10A—C10—H10B	108.0	H60A—C60—H60B	108.1
H10A—C10—C11	109.4	H60A—C60—C61	109.6
H10B—C10—C11	109.4	H60B—C60—C61	109.6
C6—C11—C10	112.1 (2)	C56—C61—C60	112.9 (2)
C6—C11—H11A	109.2	C56—C61—H61A	109.0
C6—C11—H11B	109.2	C56—C61—H61B	109.0
C10—C11—H11A	109.2	C60—C61—H61A	109.0
C10—C11—H11B	109.2	C60—C61—H61B	109.0
H11A—C11—H11B	107.9	H61A—C61—H61B	107.8
C1—N1—C2—O1	−4.0 (4)	C51—N51—C52—O51	0.4 (4)
C1—N1—C2—N2	176.2 (2)	C51—N51—C52—N52	−179.6 (2)
C3—N2—C2—O1	176.7 (2)	C53—N52—C52—O51	−179.3 (2)
C3—N2—C2—N1	−3.5 (4)	C53—N52—C52—N51	0.7 (4)
C2—N2—C3—O2	−0.3 (4)	C52—N52—C53—O52	1.0 (4)
C2—N2—C3—C4	−179.8 (2)	C52—N52—C53—C54	−177.7 (2)
O2—C3—C4—C5	−16.7 (3)	O52—C53—C54—C55	−67.0 (3)
O2—C3—C4—C6	107.3 (3)	O52—C53—C54—C56	59.4 (3)
N2—C3—C4—C5	162.8 (2)	N52—C53—C54—C55	111.7 (2)
N2—C3—C4—C6	−73.2 (3)	N52—C53—C54—C56	−121.9 (2)
C3—C4—C6—C7	−31.4 (3)	C53—C54—C56—C57	−117.7 (3)
C3—C4—C6—C11	151.3 (2)	C53—C54—C56—C61	62.0 (3)
C5—C4—C6—C7	92.9 (3)	C55—C54—C56—C57	4.2 (3)
C5—C4—C6—C11	−84.4 (3)	C55—C54—C56—C61	−176.1 (2)
C4—C6—C7—C8	−174.6 (2)	C54—C56—C57—C58	177.5 (2)
C11—C6—C7—C8	2.6 (4)	C61—C56—C57—C58	−2.2 (4)
C6—C7—C8—C9	12.3 (4)	C56—C57—C58—C59	−13.6 (4)
C7—C8—C9—C10	−43.4 (4)	C57—C58—C59—C60	44.9 (3)
C8—C9—C10—C11	61.1 (3)	C58—C59—C60—C61	−61.8 (3)
C4—C6—C11—C10	−168.6 (2)	C54—C56—C61—C60	166.0 (2)
C7—C6—C11—C10	14.1 (3)	C57—C56—C61—C60	−14.3 (3)
C9—C10—C11—C6	−45.6 (3)	C59—C60—C61—C56	45.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.84 (3)	2.14 (3)	2.732 (3)	127 (3)
N2—H2N···O51	0.98 (3)	1.81 (3)	2.781 (3)	171 (2)
N51—H51N···O52	0.90 (3)	2.04 (3)	2.692 (3)	128 (2)
N52—H52N···O1	0.89 (3)	1.95 (3)	2.837 (3)	175 (2)
N1—H1N···O52^i	0.84 (3)	2.35 (3)	3.032 (3)	139 (3)
N51—H51N···O2^ii	0.90 (3)	2.38 (3)	3.109 (3)	138 (2)

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

(II) 2-ethyl-5-methylhexanamide

Crystal data

C9H19NO	F(000) = 704
Mr = 157.25	Dx = 1.036 Mg m^−3
Monoclinic, C2/c	Synchrotron radiation, λ = 0.6933 Å
Hall symbol: -C 2yc	Cell parameters from 1361 reflections
a = 22.839 (6) Å	θ = 3.5–28.5°
b = 5.0394 (13) Å	µ = 0.07 mm^−1
c = 18.802 (5) Å	T = 120 K
β = 111.224 (4)°	Plate, colourless
V = 2017.2 (9) Å^3	0.20 × 0.10 × 0.05 mm
Z = 8

Data collection

Bruker APEXII diffractometer	1867 independent reflections
Radiation source: Daresbury SRS station 9.8	1456 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.042
thin–slice ω scans	θmax = 25.0°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −27→27
Tmin = 0.987, Tmax = 0.997	k = −6→6
5147 measured reflections	l = −19→22

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0931P)^2 + 0.6424P] where P = (Fo^2 + 2Fc^2)/3
1867 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.18 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
O1	0.18171 (5)	0.5661 (2)	0.00968 (7)	0.0300 (4)
N1	0.19735 (6)	1.0049 (3)	0.01119 (8)	0.0280 (4)
H1N	0.2335	0.9849	0.0051	0.042*
H2N	0.1834	1.1651	0.0150	0.042*
C1	0.20224 (10)	0.8750 (6)	0.31219 (13)	0.0592 (7)
H1A	0.2424	0.8900	0.3047	0.089*
H1B	0.2086	0.7799	0.3599	0.089*
H1C	0.1858	1.0528	0.3148	0.089*
C2	0.09442 (11)	0.6835 (5)	0.25804 (13)	0.0540 (6)
H2A	0.0737	0.8554	0.2555	0.081*
H2B	0.1028	0.6034	0.3082	0.081*
H2C	0.0671	0.5660	0.2183	0.081*
C3	0.15567 (9)	0.7234 (4)	0.24582 (12)	0.0433 (5)
H3	0.1739	0.5437	0.2448	0.052*
C4	0.14781 (8)	0.8585 (4)	0.17060 (11)	0.0351 (5)
H4A	0.1326	1.0417	0.1721	0.042*
H4B	0.1896	0.8712	0.1661	0.042*
C5	0.10312 (8)	0.7221 (3)	0.09961 (10)	0.0317 (4)
H5A	0.1153	0.5333	0.1008	0.038*
H5B	0.0602	0.7282	0.1009	0.038*
C6	0.10179 (7)	0.8441 (3)	0.02515 (9)	0.0259 (4)
H6	0.0959	1.0400	0.0276	0.031*
C7	0.04833 (8)	0.7350 (4)	−0.04421 (11)	0.0343 (5)
H7A	0.0541	0.5412	−0.0472	0.041*
H7B	0.0081	0.7643	−0.0368	0.041*
C8	0.04428 (9)	0.8596 (4)	−0.11890 (11)	0.0407 (5)
H8A	0.0384	1.0516	−0.1166	0.061*
H8B	0.0086	0.7837	−0.1605	0.061*
H8C	0.0832	0.8242	−0.1281	0.061*
C9	0.16398 (7)	0.7946 (3)	0.01469 (9)	0.0237 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0273 (6)	0.0208 (6)	0.0486 (8)	−0.0005 (4)	0.0217 (5)	−0.0003 (5)
N1	0.0257 (7)	0.0198 (7)	0.0454 (9)	0.0022 (5)	0.0212 (6)	−0.0002 (6)
C1	0.0441 (12)	0.0943 (18)	0.0369 (12)	−0.0056 (12)	0.0118 (9)	0.0064 (12)
C2	0.0571 (13)	0.0699 (15)	0.0424 (12)	−0.0130 (11)	0.0270 (10)	0.0006 (10)
C3	0.0436 (11)	0.0523 (12)	0.0377 (11)	0.0015 (9)	0.0193 (9)	0.0058 (9)
C4	0.0332 (9)	0.0402 (10)	0.0363 (11)	−0.0016 (7)	0.0179 (8)	0.0018 (8)
C5	0.0276 (8)	0.0354 (10)	0.0378 (10)	−0.0019 (7)	0.0186 (7)	0.0005 (7)
C6	0.0225 (8)	0.0255 (9)	0.0334 (10)	0.0006 (6)	0.0144 (7)	−0.0014 (7)
C7	0.0238 (8)	0.0396 (10)	0.0408 (11)	−0.0014 (7)	0.0134 (7)	−0.0033 (8)
C8	0.0331 (9)	0.0507 (12)	0.0364 (11)	0.0010 (8)	0.0105 (8)	−0.0021 (8)
C9	0.0232 (8)	0.0225 (8)	0.0278 (9)	0.0013 (6)	0.0122 (6)	−0.0005 (6)

Geometric parameters (Å, º)

O1—C9	1.2354 (19)	C4—H4A	0.990
N1—C9	1.321 (2)	C4—H4B	0.990
N1—H1N	0.880	C5—C6	1.519 (2)
N1—H2N	0.880	C5—H5A	0.990
C1—C3	1.520 (3)	C5—H5B	0.990
C1—H1A	0.980	C6—C9	1.523 (2)
C1—H1B	0.980	C6—C7	1.530 (2)
C1—H1C	0.980	C6—H6	1.000
C2—C3	1.511 (3)	C7—C8	1.510 (3)
C2—H2A	0.980	C7—H7A	0.990
C2—H2B	0.980	C7—H7B	0.990
C2—H2C	0.980	C8—H8A	0.980
C3—C4	1.521 (3)	C8—H8B	0.980
C3—H3	1.000	C8—H8C	0.980
C4—C5	1.520 (3)
C9—N1—H1N	120.0	C6—C5—C4	114.18 (14)
C9—N1—H2N	120.0	C6—C5—H5A	108.7
H1N—N1—H2N	120.0	C4—C5—H5A	108.7
C3—C1—H1A	109.5	C6—C5—H5B	108.7
C3—C1—H1B	109.5	C4—C5—H5B	108.7
H1A—C1—H1B	109.5	H5A—C5—H5B	107.6
C3—C1—H1C	109.5	C5—C6—C9	110.14 (13)
H1A—C1—H1C	109.5	C5—C6—C7	112.57 (14)
H1B—C1—H1C	109.5	C9—C6—C7	108.96 (13)
C3—C2—H2A	109.5	C5—C6—H6	108.4
C3—C2—H2B	109.5	C9—C6—H6	108.4
H2A—C2—H2B	109.5	C7—C6—H6	108.4
C3—C2—H2C	109.5	C8—C7—C6	113.87 (15)
H2A—C2—H2C	109.5	C8—C7—H7A	108.8
H2B—C2—H2C	109.5	C6—C7—H7A	108.8
C2—C3—C1	110.67 (18)	C8—C7—H7B	108.8
C2—C3—C4	113.39 (17)	C6—C7—H7B	108.8
C1—C3—C4	110.51 (17)	H7A—C7—H7B	107.7
C2—C3—H3	107.3	C7—C8—H8A	109.5
C1—C3—H3	107.3	C7—C8—H8B	109.5
C4—C3—H3	107.3	H8A—C8—H8B	109.5
C5—C4—C3	115.47 (16)	C7—C8—H8C	109.5
C5—C4—H4A	108.4	H8A—C8—H8C	109.5
C3—C4—H4A	108.4	H8B—C8—H8C	109.5
C5—C4—H4B	108.4	O1—C9—N1	122.22 (14)
C3—C4—H4B	108.4	O1—C9—C6	120.61 (14)
H4A—C4—H4B	107.5	N1—C9—C6	117.17 (13)
C2—C3—C4—C5	−56.1 (2)	C9—C6—C7—C8	−59.62 (19)
C1—C3—C4—C5	178.95 (17)	C5—C6—C9—O1	62.0 (2)
C3—C4—C5—C6	−173.54 (14)	C7—C6—C9—O1	−62.0 (2)
C4—C5—C6—C9	68.43 (18)	C5—C6—C9—N1	−118.13 (16)
C4—C5—C6—C7	−169.75 (14)	C7—C6—C9—N1	117.94 (16)
C5—C6—C7—C8	177.90 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.88	2.07	2.9488 (18)	179
N1—H2N···O1^ii	0.88	2.02	2.8492 (18)	156

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

(III) 2-ethylpentanamide

Crystal data

C8H17NO	F(000) = 640
Mr = 143.23	Dx = 1.019 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.69330 Å
Hall symbol: -P 2ybc	Cell parameters from 2394 reflections
a = 21.597 (5) Å	θ = 2.8–25.5°
b = 5.0469 (12) Å	µ = 0.04 mm^−1
c = 18.424 (5) Å	T = 120 K
β = 111.529 (3)°	Plate, colourless
V = 1868.0 (8) Å^3	0.20 × 0.10 × 0.05 mm
Z = 8

Data collection

Bruker APEXII diffractometer	3250 independent reflections
Radiation source: Daresbury SRS station 9.8	2184 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.052
thin–slice ω scans	θmax = 24.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→25
Tmin = 0.992, Tmax = 0.998	k = −5→6
12823 measured reflections	l = −21→21

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) = 0.141	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0678P)^2 + 0.3705P] where P = (Fo^2 + 2Fc^2)/3
3250 reflections	(Δ/σ)max = 0.003
274 parameters	Δρmax = 0.17 e Å^−3
19 restraints	Δρmin = −0.13 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	Occ. (<1)
O1	0.1649 (4)	0.4381 (19)	0.4511 (5)	0.0407 (14)	0.559 (8)
N1	0.1914 (8)	0.8732 (17)	0.4601 (7)	0.041 (2)	0.559 (8)
H1N	0.2302	0.8367	0.4966	0.061*	0.559 (8)
H2N	0.1810	1.0380	0.4450	0.061*	0.559 (8)
C1	0.1979 (3)	0.6082 (18)	0.1629 (3)	0.088 (2)	0.559 (8)
H1A	0.1927	0.5229	0.1132	0.132*	0.559 (8)
H1B	0.2392	0.5469	0.2034	0.132*	0.559 (8)
H1C	0.1997	0.8009	0.1573	0.132*	0.559 (8)
C2	0.1392 (2)	0.5369 (13)	0.1857 (2)	0.0670 (18)	0.559 (8)
H2A	0.0976	0.5954	0.1438	0.080*	0.559 (8)
H2B	0.1371	0.3418	0.1899	0.080*	0.559 (8)
C3	0.1427 (3)	0.6599 (13)	0.2618 (3)	0.0469 (14)	0.559 (8)
H3A	0.1856	0.6111	0.3031	0.056*	0.559 (8)
H3B	0.1416	0.8552	0.2564	0.056*	0.559 (8)
C4	0.0865 (3)	0.5733 (12)	0.2863 (4)	0.0394 (14)	0.559 (8)
H4A	0.0908	0.3805	0.2970	0.047*	0.559 (8)
H4B	0.0440	0.6022	0.2421	0.047*	0.559 (8)
C5	0.0828 (4)	0.712 (3)	0.3570 (6)	0.0328 (17)	0.559 (8)
H5	0.0780	0.9061	0.3455	0.039*	0.559 (8)
C6	0.0261 (4)	0.6273 (17)	0.3811 (5)	0.050 (2)	0.559 (8)
H6A	−0.0159	0.6422	0.3352	0.060*	0.559 (8)
H6B	0.0322	0.4381	0.3962	0.060*	0.559 (8)
C7	0.0186 (6)	0.7826 (17)	0.4475 (6)	0.072 (2)	0.559 (8)
H7A	−0.0202	0.7169	0.4578	0.108*	0.559 (8)
H7B	0.0123	0.9706	0.4335	0.108*	0.559 (8)
H7C	0.0587	0.7609	0.4944	0.108*	0.559 (8)
C8	0.1465 (5)	0.670 (2)	0.4264 (7)	0.033 (2)	0.559 (8)
O1'	0.1798 (5)	0.436 (2)	0.4351 (7)	0.0428 (19)	0.441 (8)
N1'	0.1826 (10)	0.879 (3)	0.4548 (11)	0.057 (5)	0.441 (8)
H1N'	0.2149	0.8741	0.5010	0.086*	0.441 (8)
H2N'	0.1648	1.0312	0.4346	0.086*	0.441 (8)
C1'	0.1773 (4)	0.4144 (19)	0.1617 (4)	0.092 (3)	0.441 (8)
H1'1	0.1791	0.3898	0.1097	0.138*	0.441 (8)
H1'2	0.1431	0.2978	0.1675	0.138*	0.441 (8)
H1'3	0.2206	0.3706	0.2015	0.138*	0.441 (8)
C2'	0.1605 (4)	0.6961 (15)	0.1712 (4)	0.075 (2)	0.441 (8)
H2'1	0.1159	0.7372	0.1319	0.090*	0.441 (8)
H2'2	0.1931	0.8135	0.1610	0.090*	0.441 (8)
C3'	0.1605 (5)	0.7539 (17)	0.2521 (5)	0.063 (2)	0.441 (8)
H3'1	0.2039	0.6982	0.2911	0.075*	0.441 (8)
H3'2	0.1567	0.9478	0.2574	0.075*	0.441 (8)
C4'	0.1066 (5)	0.6222 (18)	0.2711 (5)	0.047 (2)	0.441 (8)
H4'1	0.1155	0.4293	0.2758	0.057*	0.441 (8)
H4'2	0.0640	0.6493	0.2269	0.057*	0.441 (8)
C5'	0.0985 (6)	0.719 (4)	0.3461 (8)	0.041 (3)	0.441 (8)
H5'	0.0916	0.9153	0.3422	0.050*	0.441 (8)
C6'	0.0379 (6)	0.591 (3)	0.3566 (6)	0.050 (2)	0.441 (8)
H6'1	0.0453	0.3970	0.3628	0.060*	0.441 (8)
H6'2	−0.0017	0.6202	0.3086	0.060*	0.441 (8)
C7'	0.0235 (5)	0.697 (2)	0.4264 (7)	0.067 (3)	0.441 (8)
H7'1	−0.0140	0.5989	0.4314	0.100*	0.441 (8)
H7'2	0.0122	0.8852	0.4186	0.100*	0.441 (8)
H7'3	0.0629	0.6738	0.4740	0.100*	0.441 (8)
C8'	0.1614 (6)	0.661 (3)	0.4166 (8)	0.032 (2)	0.441 (8)
O51	0.31437 (6)	0.6957 (2)	0.08876 (7)	0.0499 (4)
N51	0.29846 (7)	1.1342 (3)	0.07592 (8)	0.0445 (4)
H51A	0.2590	1.1141	0.0389	0.053*
H51B	0.3140	1.2942	0.0912	0.053*
C51	0.32418 (15)	1.0964 (5)	0.39915 (15)	0.0863 (8)
H51C	0.3447	1.2722	0.4109	0.104*
H51D	0.3250	1.0127	0.4475	0.104*
H51E	0.2780	1.1140	0.3629	0.104*
C52	0.36203 (12)	0.9288 (5)	0.36277 (12)	0.0668 (6)
H52A	0.3438	0.7467	0.3562	0.080*
H52B	0.4091	0.9196	0.3988	0.080*
C53	0.35979 (9)	1.0293 (4)	0.28423 (10)	0.0481 (5)
H53A	0.3130	1.0273	0.2472	0.058*
H53B	0.3753	1.2154	0.2901	0.058*
C54	0.40150 (9)	0.8699 (4)	0.25014 (10)	0.0465 (5)
H54A	0.3850	0.6850	0.2431	0.056*
H54B	0.4479	0.8669	0.2882	0.056*
C55	0.40199 (8)	0.9711 (3)	0.17209 (9)	0.0401 (4)
H55	0.4109	1.1660	0.1766	0.048*
C56	0.45567 (9)	0.8372 (4)	0.14969 (11)	0.0513 (5)
H56A	0.4992	0.8646	0.1924	0.062*
H56B	0.4469	0.6442	0.1452	0.062*
C57	0.46062 (11)	0.9339 (5)	0.07468 (12)	0.0664 (6)
H57A	0.4192	0.8935	0.0311	0.080*
H57B	0.4979	0.8453	0.0664	0.080*
H57C	0.4681	1.1258	0.0777	0.080*
C58	0.33428 (8)	0.9246 (3)	0.10850 (9)	0.0379 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.042 (3)	0.0246 (16)	0.044 (3)	0.002 (2)	0.0016 (17)	−0.0011 (17)
N1	0.055 (5)	0.010 (3)	0.042 (5)	0.000 (2)	0.001 (4)	−0.004 (3)
C1	0.075 (4)	0.125 (7)	0.067 (3)	−0.026 (4)	0.030 (3)	−0.016 (3)
C2	0.068 (3)	0.080 (4)	0.051 (2)	−0.011 (3)	0.021 (2)	−0.007 (2)
C3	0.047 (4)	0.054 (4)	0.039 (2)	−0.009 (3)	0.014 (3)	0.003 (2)
C4	0.042 (3)	0.027 (3)	0.037 (3)	−0.004 (2)	0.000 (2)	0.000 (2)
C5	0.026 (4)	0.028 (2)	0.036 (3)	−0.001 (3)	0.001 (3)	0.003 (2)
C6	0.045 (3)	0.052 (4)	0.050 (6)	0.007 (3)	0.013 (4)	0.010 (4)
C7	0.092 (4)	0.070 (5)	0.065 (5)	0.021 (4)	0.041 (3)	0.007 (4)
C8	0.032 (4)	0.023 (2)	0.040 (3)	0.008 (3)	0.010 (3)	−0.001 (2)
O1'	0.038 (4)	0.024 (2)	0.050 (5)	0.004 (3)	−0.002 (2)	0.000 (3)
N1'	0.048 (5)	0.046 (7)	0.038 (5)	0.003 (3)	−0.030 (3)	0.007 (4)
C1'	0.085 (5)	0.116 (7)	0.082 (5)	0.014 (5)	0.039 (4)	−0.007 (5)
C2'	0.075 (5)	0.070 (5)	0.076 (4)	−0.003 (4)	0.024 (4)	0.013 (3)
C3'	0.074 (5)	0.063 (5)	0.055 (4)	−0.010 (4)	0.030 (3)	0.002 (4)
C4'	0.046 (6)	0.048 (5)	0.037 (4)	−0.007 (4)	0.002 (4)	0.005 (3)
C5'	0.026 (5)	0.030 (3)	0.061 (6)	0.000 (4)	0.007 (3)	0.005 (4)
C6'	0.046 (5)	0.050 (4)	0.045 (5)	0.005 (4)	0.006 (3)	0.005 (4)
C7'	0.065 (4)	0.076 (8)	0.069 (8)	0.003 (5)	0.036 (5)	−0.001 (5)
C8'	0.023 (4)	0.031 (3)	0.037 (4)	0.006 (3)	0.006 (3)	−0.005 (3)
O51	0.0568 (8)	0.0235 (7)	0.0465 (7)	−0.0007 (5)	−0.0079 (6)	−0.0009 (5)
N51	0.0482 (9)	0.0240 (8)	0.0418 (8)	−0.0023 (6)	−0.0068 (7)	−0.0013 (6)
C51	0.117 (2)	0.091 (2)	0.0681 (16)	−0.0194 (16)	0.0536 (16)	−0.0006 (14)
C52	0.0857 (16)	0.0651 (15)	0.0509 (12)	−0.0127 (12)	0.0265 (12)	0.0058 (11)
C53	0.0566 (11)	0.0417 (11)	0.0387 (10)	−0.0103 (9)	0.0088 (9)	0.0018 (8)
C54	0.0496 (10)	0.0394 (10)	0.0366 (10)	−0.0057 (8)	−0.0007 (8)	0.0050 (8)
C55	0.0449 (10)	0.0306 (9)	0.0337 (9)	−0.0018 (7)	0.0015 (7)	−0.0004 (7)
C56	0.0489 (11)	0.0480 (11)	0.0474 (11)	0.0013 (9)	0.0061 (9)	−0.0015 (9)
C57	0.0668 (14)	0.0781 (16)	0.0527 (13)	0.0053 (12)	0.0201 (11)	−0.0064 (11)
C58	0.0469 (10)	0.0271 (9)	0.0312 (9)	−0.0008 (8)	0.0045 (7)	−0.0005 (7)

Geometric parameters (Å, º)

O1—C8	1.268 (12)	C3'—C4'	1.489 (8)
N1—H1N	0.880	C4'—H4'1	0.990
N1—H2N	0.880	C4'—H4'2	0.990
N1—C8	1.390 (14)	C4'—C5'	1.536 (14)
C1—H1A	0.980	C5'—H5'	1.00
C1—H1B	0.980	C5'—C6'	1.536 (12)
C1—H1C	0.980	C5'—C8'	1.524 (16)
C1—C2	1.519 (10)	C6'—H6'1	0.990
C2—H2A	0.990	C6'—H6'2	0.990
C2—H2B	0.990	C6'—C7'	1.527 (9)
C2—C3	1.510 (7)	C7'—H7'1	0.980
C3—H3A	0.990	C7'—H7'2	0.980
C3—H3B	0.990	C7'—H7'3	0.980
C3—C4	1.508 (6)	O51—C58	1.2399 (19)
C4—H4A	0.990	N51—H51A	0.880
C4—H4B	0.990	N51—H51B	0.880
C4—C5	1.506 (13)	N51—C58	1.318 (2)
C5—H5	1.00	C51—H51C	0.980
C5—C6	1.510 (10)	C51—H51D	0.980
C5—C8	1.510 (12)	C51—H51E	0.980
C6—H6A	0.990	C51—C52	1.495 (3)
C6—H6B	0.990	C52—H52A	0.990
C6—C7	1.512 (7)	C52—H52B	0.990
C7—H7A	0.980	C52—C53	1.517 (3)
C7—H7B	0.980	C53—H53A	0.990
C7—H7C	0.980	C53—H53B	0.990
O1'—C8'	1.210 (15)	C53—C54	1.506 (3)
N1'—H1N'	0.880	C54—H54A	0.990
N1'—H2N'	0.880	C54—H54B	0.990
N1'—C8'	1.294 (16)	C54—C55	1.530 (2)
C1'—H1'1	0.980	C55—H55	1.00
C1'—H1'2	0.980	C55—C56	1.524 (3)
C1'—H1'3	0.980	C55—C58	1.520 (2)
C1'—C2'	1.494 (12)	C56—H56A	0.990
C2'—H2'1	0.990	C56—H56B	0.990
C2'—H2'2	0.990	C56—C57	1.506 (3)
C2'—C3'	1.519 (10)	C57—H57A	0.980
C3'—H3'1	0.990	C57—H57B	0.980
C3'—H3'2	0.990	C57—H57C	0.980
H1N—N1—H2N	120.0	H3'1—C3'—H3'2	107.5
H1N—N1—C8	120.0	H3'1—C3'—C4'	108.5
H2N—N1—C8	120.0	H3'2—C3'—C4'	108.5
H1A—C1—H1B	109.5	C3'—C4'—H4'1	108.5
H1A—C1—H1C	109.5	C3'—C4'—H4'2	108.5
H1A—C1—C2	109.5	C3'—C4'—C5'	115.2 (8)
H1B—C1—H1C	109.5	H4'1—C4'—H4'2	107.5
H1B—C1—C2	109.5	H4'1—C4'—C5'	108.5
H1C—C1—C2	109.5	H4'2—C4'—C5'	108.5
C1—C2—H2A	108.9	C4'—C5'—H5'	108.4
C1—C2—H2B	108.9	C4'—C5'—C6'	111.2 (11)
C1—C2—C3	113.4 (5)	C4'—C5'—C8'	110.2 (9)
H2A—C2—H2B	107.7	H5'—C5'—C6'	108.4
H2A—C2—C3	108.9	H5'—C5'—C8'	108.4
H2B—C2—C3	108.9	C6'—C5'—C8'	110.3 (11)
C2—C3—H3A	109.0	C5'—C6'—H6'1	108.8
C2—C3—H3B	109.0	C5'—C6'—H6'2	108.8
C2—C3—C4	112.8 (5)	C5'—C6'—C7'	113.9 (10)
H3A—C3—H3B	107.8	H6'1—C6'—H6'2	107.7
H3A—C3—C4	109.0	H6'1—C6'—C7'	108.8
H3B—C3—C4	109.0	H6'2—C6'—C7'	108.8
C3—C4—H4A	108.4	C6'—C7'—H7'1	109.5
C3—C4—H4B	108.4	C6'—C7'—H7'2	109.5
C3—C4—C5	115.4 (6)	C6'—C7'—H7'3	109.5
H4A—C4—H4B	107.5	H7'1—C7'—H7'2	109.5
H4A—C4—C5	108.4	H7'1—C7'—H7'3	109.5
H4B—C4—C5	108.4	H7'2—C7'—H7'3	109.5
C4—C5—H5	107.9	O1'—C8'—N1'	129.0 (14)
C4—C5—C6	115.4 (7)	O1'—C8'—C5'	121.2 (14)
C4—C5—C8	110.3 (8)	N1'—C8'—C5'	109.1 (14)
H5—C5—C6	107.9	H51A—N51—H51B	120.0
H5—C5—C8	107.9	H51A—N51—C58	120.0
C6—C5—C8	107.3 (7)	H51B—N51—C58	120.0
C5—C6—H6A	108.4	C51—C52—H52A	108.7
C5—C6—H6B	108.4	C51—C52—H52B	108.7
C5—C6—C7	115.5 (8)	C51—C52—C53	114.0 (2)
H6A—C6—H6B	107.5	H52A—C52—H52B	107.6
H6A—C6—C7	108.4	H52A—C52—C53	108.7
H6B—C6—C7	108.4	H52B—C52—C53	108.7
C6—C7—H7A	109.5	C52—C53—H53A	108.8
C6—C7—H7B	109.5	C52—C53—H53B	108.8
C6—C7—H7C	109.5	C52—C53—C54	113.87 (17)
H7A—C7—H7B	109.5	H53A—C53—H53B	107.7
H7A—C7—H7C	109.5	H53A—C53—C54	108.8
H7B—C7—H7C	109.5	H53B—C53—C54	108.8
O1—C8—N1	116.5 (10)	C53—C54—H54A	108.5
O1—C8—C5	120.0 (10)	C53—C54—H54B	108.5
N1—C8—C5	123.1 (11)	C53—C54—C55	115.17 (15)
H1N'—N1'—H2N'	120.0	H54A—C54—H54B	107.5
H1N'—N1'—C8'	120.0	H54A—C54—C55	108.5
H2N'—N1'—C8'	120.0	H54B—C54—C55	108.5
H1'1—C1'—H1'2	109.5	C54—C55—H55	108.5
H1'1—C1'—H1'3	109.5	C54—C55—C56	112.02 (14)
H1'1—C1'—C2'	109.5	C54—C55—C58	109.66 (14)
H1'2—C1'—H1'3	109.5	H55—C55—C56	108.5
H1'2—C1'—C2'	109.5	H55—C55—C58	108.5
H1'3—C1'—C2'	109.5	C56—C55—C58	109.59 (14)
C1'—C2'—H2'1	109.1	C55—C56—H56A	108.5
C1'—C2'—H2'2	109.1	C55—C56—H56B	108.5
C1'—C2'—C3'	112.6 (6)	C55—C56—C57	114.97 (16)
H2'1—C2'—H2'2	107.8	H56A—C56—H56B	107.5
H2'1—C2'—C3'	109.1	H56A—C56—C57	108.5
H2'2—C2'—C3'	109.1	H56B—C56—C57	108.5
C2'—C3'—H3'1	108.5	O51—C58—N51	122.14 (15)
C2'—C3'—H3'2	108.5	O51—C58—C55	120.14 (14)
C2'—C3'—C4'	115.2 (7)	N51—C58—C55	117.73 (14)
C1—C2—C3—C4	−176.3 (6)	C8'—C5'—C6'—C7'	62.4 (16)
C2—C3—C4—C5	−173.5 (7)	C4'—C5'—C8'—O1'	−63.4 (15)
C3—C4—C5—C6	179.3 (8)	C4'—C5'—C8'—N1'	125.3 (16)
C3—C4—C5—C8	−58.8 (11)	C6'—C5'—C8'—O1'	59.8 (15)
C4—C5—C6—C7	−174.8 (8)	C6'—C5'—C8'—N1'	−111.5 (17)
C8—C5—C6—C7	61.8 (12)	C51—C52—C53—C54	176.33 (19)
C4—C5—C8—O1	−60.4 (11)	C52—C53—C54—C55	−178.22 (16)
C4—C5—C8—N1	111.7 (12)	C53—C54—C55—C56	168.19 (15)
C6—C5—C8—O1	66.1 (11)	C53—C54—C55—C58	−69.91 (19)
C6—C5—C8—N1	−121.9 (11)	C54—C55—C56—C57	−178.02 (16)
C1'—C2'—C3'—C4'	−67.7 (11)	C58—C55—C56—C57	60.0 (2)
C2'—C3'—C4'—C5'	−169.2 (9)	C54—C55—C58—O51	−66.4 (2)
C3'—C4'—C5'—C6'	174.7 (10)	C54—C55—C58—N51	113.64 (18)
C3'—C4'—C5'—C8'	−62.7 (15)	C56—C55—C58—O51	56.9 (2)
C4'—C5'—C6'—C7'	−175.0 (10)	C56—C55—C58—N51	−123.01 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O51^i	0.88	1.99	2.858 (15)	170
N1—H2N···O1^ii	0.88	2.06	2.901 (12)	160
N1′—H1N′···O51^i	0.88	2.19	3.029 (19)	159
N1′—H2N′···O1′^ii	0.88	2.07	2.834 (18)	145
N51—H51A···O1′^iii	0.88	2.06	2.923 (12)	166
N51—H51B···O51^ii	0.88	2.03	2.8539 (19)	156
N51—H51A···O1^iii	0.88	2.10	2.980 (10)	179

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