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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110049322/sk3397sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049322/sk3397Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049322/sk3397IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110049322/sk3397IIIsup4.hkl
Contains datablock III

CCDC references: 813491; 813492; 813493

Comment top

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 Rad(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 top

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).

Experimental top

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%).

Refinement top

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 Uiso(H) = 1.5Ueq(N) and a fixed N—H distance of 0.88 Å. In all structures, C-bound H atoms were refined as riding, with Uiso(H) = 1.2Ueq(C) [or 1.5Ueq (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 top

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 top
[Figure 1] Fig. 1. The asymmetric unit of (I) with displacement ellipsoids drawn at the 50% probability level. Dashed blue lines indicate hydrogen bonds.
[Figure 2] 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.
[Figure 3] Fig. 3. The intermolecular hydrogen bonding in (I). Dotted blue lines indicate hydrogen bonding and dotted red lines indicate hydrogen-bonding continuation.
[Figure 4] Fig. 4. The asymmetric unit of (II) with displacement ellipsoids drawn at the 30% probability level.
[Figure 5] Fig. 5. Hydrogen-bonding patterns in (II). Dotted blue lines indicate hydrogen bonding and dotted red lines indicate hydrogen-bonding continuation.
[Figure 6] 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 top
Crystal data top
C11H18N2O2F(000) = 912
Mr = 210.27Dx = 1.220 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 28727 reflections
a = 10.108 (2) Åθ = 2.9–27.5°
b = 21.824 (4) ŵ = 0.09 mm1
c = 10.393 (2) ÅT = 120 K
β = 92.52 (3)°Slab, colourless
V = 2290.4 (8) Å30.36 × 0.08 × 0.03 mm
Z = 8
Data collection top
Nonius KappaCCD
diffractometer
4030 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode3184 reflections with I > 2σ(I)
Mirror optics monochromatorRint = 0.110
ϕ and ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 1112
Tmin = 0.970, Tmax = 0.998k = 2525
37076 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.140 w = 1/[σ2(Fo2) + (0.0417P)2 + 2.3454P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
4030 reflectionsΔρmax = 0.26 e Å3
292 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0065 (10)
Crystal data top
C11H18N2O2V = 2290.4 (8) Å3
Mr = 210.27Z = 8
Monoclinic, P21/cMo Kα radiation
a = 10.108 (2) ŵ = 0.09 mm1
b = 21.824 (4) ÅT = 120 K
c = 10.393 (2) Å0.36 × 0.08 × 0.03 mm
β = 92.52 (3)°
Data collection top
Nonius KappaCCD
diffractometer
4030 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
3184 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.998Rint = 0.110
37076 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.26 e Å3
4030 reflectionsΔρmin = 0.23 e Å3
292 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.69715 (16)0.09347 (8)0.21980 (16)0.0295 (4)
O21.01230 (16)0.08578 (8)0.48868 (16)0.0291 (4)
N10.9204 (2)0.10154 (9)0.2397 (2)0.0250 (5)
H1N0.991 (3)0.0993 (13)0.285 (3)0.036 (8)*
N20.7945 (2)0.08685 (10)0.41984 (19)0.0252 (5)
H2N0.706 (3)0.0865 (11)0.455 (2)0.022 (6)*
C10.9357 (3)0.10554 (13)0.1019 (2)0.0336 (6)
H1A0.90420.06750.06070.050*
H1B1.02940.11160.08470.050*
H1C0.88390.14020.06700.050*
C20.8019 (2)0.09416 (10)0.2862 (2)0.0223 (5)
C30.8949 (2)0.08320 (11)0.5123 (2)0.0230 (5)
C40.8442 (2)0.07506 (11)0.6467 (2)0.0237 (5)
H40.77280.04330.64170.028*
C50.9531 (3)0.05215 (12)0.7400 (2)0.0301 (6)
H5A0.99200.01470.70570.045*
H5B0.91580.04330.82340.045*
H5C1.02180.08360.75090.045*
C60.7837 (2)0.13424 (11)0.6959 (2)0.0234 (5)
C70.8264 (3)0.18926 (12)0.6624 (2)0.0319 (6)
H70.89200.19140.59980.038*
C80.7779 (3)0.24788 (13)0.7169 (3)0.0412 (7)
H8A0.72280.26950.65020.049*
H8B0.85470.27430.74070.049*
C90.6967 (3)0.23779 (13)0.8350 (3)0.0462 (8)
H9A0.75680.22910.91070.055*
H9B0.64620.27550.85320.055*
C100.6028 (3)0.18529 (13)0.8137 (3)0.0423 (7)
H10A0.54220.19430.73860.051*
H10B0.54860.18050.89010.051*
C110.6762 (3)0.12600 (12)0.7900 (2)0.0307 (6)
H11A0.71580.11070.87270.037*
H11B0.61260.09480.75620.037*
O510.54140 (16)0.07316 (9)0.51051 (16)0.0313 (4)
O520.21841 (16)0.08453 (9)0.25643 (16)0.0334 (5)
N510.3185 (2)0.07093 (9)0.49911 (19)0.0240 (5)
H51N0.242 (3)0.0764 (13)0.452 (3)0.037 (8)*
N520.4386 (2)0.08232 (10)0.31293 (19)0.0251 (5)
H52N0.519 (3)0.0840 (10)0.281 (2)0.016 (6)*
C510.3115 (2)0.06391 (13)0.6379 (2)0.0297 (6)
H51A0.36300.02790.66620.045*
H51B0.21900.05850.66000.045*
H51C0.34780.10060.68100.045*
C520.4347 (2)0.07512 (11)0.4482 (2)0.0240 (5)
C530.3351 (2)0.08618 (11)0.2261 (2)0.0240 (5)
C540.3714 (2)0.09137 (11)0.0854 (2)0.0258 (6)
H540.47000.09470.08320.031*
C550.3297 (3)0.03268 (12)0.0171 (3)0.0348 (6)
H55A0.23350.02770.02060.052*
H55B0.37420.00220.05950.052*
H55C0.35420.03470.07300.052*
C560.3120 (2)0.14977 (11)0.0299 (2)0.0227 (5)
C570.2223 (2)0.15041 (12)0.0672 (2)0.0275 (6)
H570.19740.11230.10520.033*
C580.1577 (3)0.20738 (13)0.1208 (3)0.0376 (7)
H58A0.06130.20020.13340.045*
H58B0.19330.21640.20590.045*
C590.1809 (3)0.26257 (14)0.0323 (3)0.0459 (8)
H59A0.15750.30070.07970.055*
H59B0.12350.25940.04220.055*
C600.3254 (3)0.26508 (13)0.0150 (3)0.0415 (7)
H60A0.34050.30200.06910.050*
H60B0.38270.26800.05960.050*
C610.3614 (3)0.20780 (12)0.0933 (2)0.0311 (6)
H61A0.45890.20550.10610.037*
H61B0.32350.21130.17930.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0206 (9)0.0437 (11)0.0241 (9)0.0017 (7)0.0019 (7)0.0017 (8)
O20.0222 (9)0.0392 (11)0.0258 (9)0.0002 (7)0.0001 (7)0.0006 (8)
N10.0207 (11)0.0309 (12)0.0232 (11)0.0009 (9)0.0010 (9)0.0007 (9)
N20.0200 (11)0.0339 (12)0.0215 (11)0.0005 (9)0.0005 (8)0.0001 (9)
C10.0283 (14)0.0502 (18)0.0223 (13)0.0011 (12)0.0024 (10)0.0032 (12)
C20.0231 (13)0.0191 (12)0.0247 (13)0.0011 (9)0.0003 (10)0.0007 (10)
C30.0213 (13)0.0212 (12)0.0264 (13)0.0002 (10)0.0002 (10)0.0015 (10)
C40.0226 (12)0.0256 (13)0.0226 (13)0.0004 (10)0.0006 (9)0.0007 (10)
C50.0326 (14)0.0320 (15)0.0254 (13)0.0057 (11)0.0018 (11)0.0008 (11)
C60.0212 (12)0.0267 (13)0.0219 (12)0.0023 (10)0.0035 (9)0.0016 (10)
C70.0311 (14)0.0351 (16)0.0296 (14)0.0008 (11)0.0023 (11)0.0011 (12)
C80.0531 (18)0.0292 (15)0.0418 (17)0.0005 (13)0.0074 (13)0.0029 (13)
C90.068 (2)0.0331 (17)0.0384 (17)0.0066 (15)0.0127 (15)0.0071 (13)
C100.0441 (17)0.0416 (17)0.0427 (17)0.0090 (13)0.0182 (13)0.0006 (14)
C110.0316 (14)0.0317 (15)0.0288 (14)0.0014 (11)0.0024 (11)0.0006 (11)
O510.0188 (9)0.0511 (12)0.0236 (9)0.0018 (8)0.0021 (7)0.0022 (8)
O520.0199 (9)0.0530 (12)0.0270 (10)0.0007 (8)0.0008 (7)0.0057 (8)
N510.0192 (11)0.0333 (12)0.0195 (10)0.0004 (9)0.0004 (8)0.0009 (9)
N520.0222 (11)0.0314 (12)0.0216 (11)0.0002 (9)0.0001 (9)0.0023 (9)
C510.0261 (13)0.0400 (16)0.0232 (13)0.0011 (11)0.0033 (10)0.0001 (11)
C520.0239 (13)0.0233 (13)0.0246 (13)0.0001 (10)0.0006 (10)0.0008 (10)
C530.0251 (13)0.0222 (13)0.0246 (13)0.0003 (10)0.0013 (10)0.0028 (10)
C540.0244 (13)0.0299 (14)0.0228 (12)0.0006 (10)0.0007 (10)0.0018 (10)
C550.0445 (16)0.0302 (15)0.0294 (14)0.0023 (12)0.0003 (12)0.0001 (12)
C560.0230 (12)0.0265 (13)0.0188 (12)0.0011 (10)0.0032 (9)0.0019 (10)
C570.0288 (13)0.0327 (14)0.0209 (12)0.0024 (11)0.0008 (10)0.0021 (11)
C580.0343 (15)0.0445 (17)0.0334 (15)0.0026 (12)0.0030 (12)0.0114 (13)
C590.0521 (19)0.0385 (17)0.0471 (18)0.0163 (14)0.0019 (14)0.0090 (14)
C600.0521 (18)0.0263 (15)0.0459 (17)0.0015 (13)0.0008 (14)0.0020 (13)
C610.0361 (15)0.0302 (15)0.0267 (14)0.0024 (11)0.0018 (11)0.0031 (11)
Geometric parameters (Å, º) top
O1—C21.238 (3)O51—C521.234 (3)
O2—C31.224 (3)O52—C531.234 (3)
N1—H1N0.84 (3)N51—H51N0.90 (3)
N1—C11.451 (3)N51—C511.456 (3)
N1—C21.322 (3)N51—C521.313 (3)
N2—H2N0.98 (3)N52—H52N0.89 (3)
N2—C21.403 (3)N52—C521.417 (3)
N2—C31.369 (3)N52—C531.355 (3)
C1—H1A0.980C51—H51A0.980
C1—H1B0.980C51—H51B0.980
C1—H1C0.980C51—H51C0.980
C3—C41.519 (3)C53—C541.527 (3)
C4—H41.000C54—H541.000
C4—C51.519 (3)C54—C551.515 (4)
C4—C61.526 (3)C54—C561.513 (3)
C5—H5A0.980C55—H55A0.980
C5—H5B0.980C55—H55B0.980
C5—H5C0.980C55—H55C0.980
C6—C71.327 (4)C56—C571.326 (3)
C6—C111.505 (3)C56—C611.503 (3)
C7—H70.950C57—H570.950
C7—C81.491 (4)C57—C581.500 (4)
C8—H8A0.990C58—H58A0.990
C8—H8B0.990C58—H58B0.990
C8—C91.522 (4)C58—C591.527 (4)
C9—H9A0.990C59—H59A0.990
C9—H9B0.990C59—H59B0.990
C9—C101.499 (4)C59—C601.521 (4)
C10—H10A0.990C60—H60A0.990
C10—H10B0.990C60—H60B0.990
C10—C111.517 (4)C60—C611.527 (4)
C11—H11A0.990C61—H61A0.990
C11—H11B0.990C61—H61B0.990
H1N—N1—C1116 (2)H51N—N51—C51118.4 (18)
H1N—N1—C2123 (2)H51N—N51—C52121.9 (18)
C1—N1—C2120.4 (2)C51—N51—C52119.3 (2)
H2N—N2—C2117.4 (14)H52N—N52—C52116.2 (15)
H2N—N2—C3113.4 (14)H52N—N52—C53115.9 (15)
C2—N2—C3129.2 (2)C52—N52—C53127.9 (2)
N1—C1—H1A109.5N51—C51—H51A109.5
N1—C1—H1B109.5N51—C51—H51B109.5
N1—C1—H1C109.5N51—C51—H51C109.5
H1A—C1—H1B109.5H51A—C51—H51B109.5
H1A—C1—H1C109.5H51A—C51—H51C109.5
H1B—C1—H1C109.5H51B—C51—H51C109.5
O1—C2—N1124.3 (2)O51—C52—N51124.3 (2)
O1—C2—N2118.0 (2)O51—C52—N52117.6 (2)
N1—C2—N2117.6 (2)N51—C52—N52118.2 (2)
O2—C3—N2123.5 (2)O52—C53—N52123.1 (2)
O2—C3—C4124.0 (2)O52—C53—C54121.3 (2)
N2—C3—C4112.5 (2)N52—C53—C54115.5 (2)
C3—C4—H4107.8C53—C54—H54108.0
C3—C4—C5111.1 (2)C53—C54—C55108.2 (2)
C3—C4—C6111.42 (19)C53—C54—C56108.62 (19)
H4—C4—C5107.8H54—C54—C55108.0
H4—C4—C6107.8H54—C54—C56108.0
C5—C4—C6110.75 (19)C55—C54—C56115.8 (2)
C4—C5—H5A109.5C54—C55—H55A109.5
C4—C5—H5B109.5C54—C55—H55B109.5
C4—C5—H5C109.5C54—C55—H55C109.5
H5A—C5—H5B109.5H55A—C55—H55B109.5
H5A—C5—H5C109.5H55A—C55—H55C109.5
H5B—C5—H5C109.5H55B—C55—H55C109.5
C4—C6—C7122.6 (2)C54—C56—C57123.1 (2)
C4—C6—C11115.3 (2)C54—C56—C61115.1 (2)
C7—C6—C11122.1 (2)C57—C56—C61121.9 (2)
C6—C7—H7118.0C56—C57—H57117.9
C6—C7—C8124.1 (2)C56—C57—C58124.3 (2)
H7—C7—C8118.0H57—C57—C58117.9
C7—C8—H8A109.1C57—C58—H58A109.2
C7—C8—H8B109.1C57—C58—H58B109.2
C7—C8—C9112.4 (2)C57—C58—C59112.2 (2)
H8A—C8—H8B107.9H58A—C58—H58B107.9
H8A—C8—C9109.1H58A—C58—C59109.2
H8B—C8—C9109.1H58B—C58—C59109.2
C8—C9—H9A109.5C58—C59—H59A109.6
C8—C9—H9B109.5C58—C59—H59B109.6
C8—C9—C10110.6 (2)C58—C59—C60110.1 (2)
H9A—C9—H9B108.1H59A—C59—H59B108.2
H9A—C9—C10109.5H59A—C59—C60109.6
H9B—C9—C10109.5H59B—C59—C60109.6
C9—C10—H10A109.4C59—C60—H60A109.6
C9—C10—H10B109.4C59—C60—H60B109.6
C9—C10—C11111.4 (2)C59—C60—C61110.3 (2)
H10A—C10—H10B108.0H60A—C60—H60B108.1
H10A—C10—C11109.4H60A—C60—C61109.6
H10B—C10—C11109.4H60B—C60—C61109.6
C6—C11—C10112.1 (2)C56—C61—C60112.9 (2)
C6—C11—H11A109.2C56—C61—H61A109.0
C6—C11—H11B109.2C56—C61—H61B109.0
C10—C11—H11A109.2C60—C61—H61A109.0
C10—C11—H11B109.2C60—C61—H61B109.0
H11A—C11—H11B107.9H61A—C61—H61B107.8
C1—N1—C2—O14.0 (4)C51—N51—C52—O510.4 (4)
C1—N1—C2—N2176.2 (2)C51—N51—C52—N52179.6 (2)
C3—N2—C2—O1176.7 (2)C53—N52—C52—O51179.3 (2)
C3—N2—C2—N13.5 (4)C53—N52—C52—N510.7 (4)
C2—N2—C3—O20.3 (4)C52—N52—C53—O521.0 (4)
C2—N2—C3—C4179.8 (2)C52—N52—C53—C54177.7 (2)
O2—C3—C4—C516.7 (3)O52—C53—C54—C5567.0 (3)
O2—C3—C4—C6107.3 (3)O52—C53—C54—C5659.4 (3)
N2—C3—C4—C5162.8 (2)N52—C53—C54—C55111.7 (2)
N2—C3—C4—C673.2 (3)N52—C53—C54—C56121.9 (2)
C3—C4—C6—C731.4 (3)C53—C54—C56—C57117.7 (3)
C3—C4—C6—C11151.3 (2)C53—C54—C56—C6162.0 (3)
C5—C4—C6—C792.9 (3)C55—C54—C56—C574.2 (3)
C5—C4—C6—C1184.4 (3)C55—C54—C56—C61176.1 (2)
C4—C6—C7—C8174.6 (2)C54—C56—C57—C58177.5 (2)
C11—C6—C7—C82.6 (4)C61—C56—C57—C582.2 (4)
C6—C7—C8—C912.3 (4)C56—C57—C58—C5913.6 (4)
C7—C8—C9—C1043.4 (4)C57—C58—C59—C6044.9 (3)
C8—C9—C10—C1161.1 (3)C58—C59—C60—C6161.8 (3)
C4—C6—C11—C10168.6 (2)C54—C56—C61—C60166.0 (2)
C7—C6—C11—C1014.1 (3)C57—C56—C61—C6014.3 (3)
C9—C10—C11—C645.6 (3)C59—C60—C61—C5645.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.84 (3)2.14 (3)2.732 (3)127 (3)
N2—H2N···O510.98 (3)1.81 (3)2.781 (3)171 (2)
N51—H51N···O520.90 (3)2.04 (3)2.692 (3)128 (2)
N52—H52N···O10.89 (3)1.95 (3)2.837 (3)175 (2)
N1—H1N···O52i0.84 (3)2.35 (3)3.032 (3)139 (3)
N51—H51N···O2ii0.90 (3)2.38 (3)3.109 (3)138 (2)
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
(II) 2-ethyl-5-methylhexanamide top
Crystal data top
C9H19NOF(000) = 704
Mr = 157.25Dx = 1.036 Mg m3
Monoclinic, C2/cSynchrotron radiation, λ = 0.6933 Å
Hall symbol: -C 2ycCell parameters from 1361 reflections
a = 22.839 (6) Åθ = 3.5–28.5°
b = 5.0394 (13) ŵ = 0.07 mm1
c = 18.802 (5) ÅT = 120 K
β = 111.224 (4)°Plate, colourless
V = 2017.2 (9) Å30.20 × 0.10 × 0.05 mm
Z = 8
Data collection top
Bruker APEXII
diffractometer
1867 independent reflections
Radiation source: Daresbury SRS station 9.81456 reflections with I > 2σ(I)
Silicon 111 monochromatorRint = 0.042
thin–slice ω scansθmax = 25.0°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2727
Tmin = 0.987, Tmax = 0.997k = 66
5147 measured reflectionsl = 1922
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0931P)2 + 0.6424P]
where P = (Fo2 + 2Fc2)/3
1867 reflections(Δ/σ)max < 0.001
103 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C9H19NOV = 2017.2 (9) Å3
Mr = 157.25Z = 8
Monoclinic, C2/cSynchrotron radiation, λ = 0.6933 Å
a = 22.839 (6) ŵ = 0.07 mm1
b = 5.0394 (13) ÅT = 120 K
c = 18.802 (5) Å0.20 × 0.10 × 0.05 mm
β = 111.224 (4)°
Data collection top
Bruker APEXII
diffractometer
1867 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1456 reflections with I > 2σ(I)
Tmin = 0.987, Tmax = 0.997Rint = 0.042
5147 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 1.06Δρmax = 0.35 e Å3
1867 reflectionsΔρmin = 0.18 e Å3
103 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.18171 (5)0.5661 (2)0.00968 (7)0.0300 (4)
N10.19735 (6)1.0049 (3)0.01119 (8)0.0280 (4)
H1N0.23350.98490.00510.042*
H2N0.18341.16510.01500.042*
C10.20224 (10)0.8750 (6)0.31219 (13)0.0592 (7)
H1A0.24240.89000.30470.089*
H1B0.20860.77990.35990.089*
H1C0.18581.05280.31480.089*
C20.09442 (11)0.6835 (5)0.25804 (13)0.0540 (6)
H2A0.07370.85540.25550.081*
H2B0.10280.60340.30820.081*
H2C0.06710.56600.21830.081*
C30.15567 (9)0.7234 (4)0.24582 (12)0.0433 (5)
H30.17390.54370.24480.052*
C40.14781 (8)0.8585 (4)0.17060 (11)0.0351 (5)
H4A0.13261.04170.17210.042*
H4B0.18960.87120.16610.042*
C50.10312 (8)0.7221 (3)0.09961 (10)0.0317 (4)
H5A0.11530.53330.10080.038*
H5B0.06020.72820.10090.038*
C60.10179 (7)0.8441 (3)0.02515 (9)0.0259 (4)
H60.09591.04000.02760.031*
C70.04833 (8)0.7350 (4)0.04421 (11)0.0343 (5)
H7A0.05410.54120.04720.041*
H7B0.00810.76430.03680.041*
C80.04428 (9)0.8596 (4)0.11890 (11)0.0407 (5)
H8A0.03841.05160.11660.061*
H8B0.00860.78370.16050.061*
H8C0.08320.82420.12810.061*
C90.16398 (7)0.7946 (3)0.01469 (9)0.0237 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0273 (6)0.0208 (6)0.0486 (8)0.0005 (4)0.0217 (5)0.0003 (5)
N10.0257 (7)0.0198 (7)0.0454 (9)0.0022 (5)0.0212 (6)0.0002 (6)
C10.0441 (12)0.0943 (18)0.0369 (12)0.0056 (12)0.0118 (9)0.0064 (12)
C20.0571 (13)0.0699 (15)0.0424 (12)0.0130 (11)0.0270 (10)0.0006 (10)
C30.0436 (11)0.0523 (12)0.0377 (11)0.0015 (9)0.0193 (9)0.0058 (9)
C40.0332 (9)0.0402 (10)0.0363 (11)0.0016 (7)0.0179 (8)0.0018 (8)
C50.0276 (8)0.0354 (10)0.0378 (10)0.0019 (7)0.0186 (7)0.0005 (7)
C60.0225 (8)0.0255 (9)0.0334 (10)0.0006 (6)0.0144 (7)0.0014 (7)
C70.0238 (8)0.0396 (10)0.0408 (11)0.0014 (7)0.0134 (7)0.0033 (8)
C80.0331 (9)0.0507 (12)0.0364 (11)0.0010 (8)0.0105 (8)0.0021 (8)
C90.0232 (8)0.0225 (8)0.0278 (9)0.0013 (6)0.0122 (6)0.0005 (6)
Geometric parameters (Å, º) top
O1—C91.2354 (19)C4—H4A0.990
N1—C91.321 (2)C4—H4B0.990
N1—H1N0.880C5—C61.519 (2)
N1—H2N0.880C5—H5A0.990
C1—C31.520 (3)C5—H5B0.990
C1—H1A0.980C6—C91.523 (2)
C1—H1B0.980C6—C71.530 (2)
C1—H1C0.980C6—H61.000
C2—C31.511 (3)C7—C81.510 (3)
C2—H2A0.980C7—H7A0.990
C2—H2B0.980C7—H7B0.990
C2—H2C0.980C8—H8A0.980
C3—C41.521 (3)C8—H8B0.980
C3—H31.000C8—H8C0.980
C4—C51.520 (3)
C9—N1—H1N120.0C6—C5—C4114.18 (14)
C9—N1—H2N120.0C6—C5—H5A108.7
H1N—N1—H2N120.0C4—C5—H5A108.7
C3—C1—H1A109.5C6—C5—H5B108.7
C3—C1—H1B109.5C4—C5—H5B108.7
H1A—C1—H1B109.5H5A—C5—H5B107.6
C3—C1—H1C109.5C5—C6—C9110.14 (13)
H1A—C1—H1C109.5C5—C6—C7112.57 (14)
H1B—C1—H1C109.5C9—C6—C7108.96 (13)
C3—C2—H2A109.5C5—C6—H6108.4
C3—C2—H2B109.5C9—C6—H6108.4
H2A—C2—H2B109.5C7—C6—H6108.4
C3—C2—H2C109.5C8—C7—C6113.87 (15)
H2A—C2—H2C109.5C8—C7—H7A108.8
H2B—C2—H2C109.5C6—C7—H7A108.8
C2—C3—C1110.67 (18)C8—C7—H7B108.8
C2—C3—C4113.39 (17)C6—C7—H7B108.8
C1—C3—C4110.51 (17)H7A—C7—H7B107.7
C2—C3—H3107.3C7—C8—H8A109.5
C1—C3—H3107.3C7—C8—H8B109.5
C4—C3—H3107.3H8A—C8—H8B109.5
C5—C4—C3115.47 (16)C7—C8—H8C109.5
C5—C4—H4A108.4H8A—C8—H8C109.5
C3—C4—H4A108.4H8B—C8—H8C109.5
C5—C4—H4B108.4O1—C9—N1122.22 (14)
C3—C4—H4B108.4O1—C9—C6120.61 (14)
H4A—C4—H4B107.5N1—C9—C6117.17 (13)
C2—C3—C4—C556.1 (2)C9—C6—C7—C859.62 (19)
C1—C3—C4—C5178.95 (17)C5—C6—C9—O162.0 (2)
C3—C4—C5—C6173.54 (14)C7—C6—C9—O162.0 (2)
C4—C5—C6—C968.43 (18)C5—C6—C9—N1118.13 (16)
C4—C5—C6—C7169.75 (14)C7—C6—C9—N1117.94 (16)
C5—C6—C7—C8177.90 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.882.072.9488 (18)179
N1—H2N···O1ii0.882.022.8492 (18)156
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x, y+1, z.
(III) 2-ethylpentanamide top
Crystal data top
C8H17NOF(000) = 640
Mr = 143.23Dx = 1.019 Mg m3
Monoclinic, P21/cSynchrotron radiation, λ = 0.69330 Å
Hall symbol: -P 2ybcCell parameters from 2394 reflections
a = 21.597 (5) Åθ = 2.8–25.5°
b = 5.0469 (12) ŵ = 0.04 mm1
c = 18.424 (5) ÅT = 120 K
β = 111.529 (3)°Plate, colourless
V = 1868.0 (8) Å30.20 × 0.10 × 0.05 mm
Z = 8
Data collection top
Bruker APEXII
diffractometer
3250 independent reflections
Radiation source: Daresbury SRS station 9.82184 reflections with I > 2σ(I)
Silicon 111 monochromatorRint = 0.052
thin–slice ω scansθmax = 24.4°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2525
Tmin = 0.992, Tmax = 0.998k = 56
12823 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0678P)2 + 0.3705P]
where P = (Fo2 + 2Fc2)/3
3250 reflections(Δ/σ)max = 0.003
274 parametersΔρmax = 0.17 e Å3
19 restraintsΔρmin = 0.13 e Å3
Crystal data top
C8H17NOV = 1868.0 (8) Å3
Mr = 143.23Z = 8
Monoclinic, P21/cSynchrotron radiation, λ = 0.69330 Å
a = 21.597 (5) ŵ = 0.04 mm1
b = 5.0469 (12) ÅT = 120 K
c = 18.424 (5) Å0.20 × 0.10 × 0.05 mm
β = 111.529 (3)°
Data collection top
Bruker APEXII
diffractometer
3250 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2184 reflections with I > 2σ(I)
Tmin = 0.992, Tmax = 0.998Rint = 0.052
12823 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04919 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.02Δρmax = 0.17 e Å3
3250 reflectionsΔρmin = 0.13 e Å3
274 parameters
Special details top

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.1649 (4)0.4381 (19)0.4511 (5)0.0407 (14)0.559 (8)
N10.1914 (8)0.8732 (17)0.4601 (7)0.041 (2)0.559 (8)
H1N0.23020.83670.49660.061*0.559 (8)
H2N0.18101.03800.44500.061*0.559 (8)
C10.1979 (3)0.6082 (18)0.1629 (3)0.088 (2)0.559 (8)
H1A0.19270.52290.11320.132*0.559 (8)
H1B0.23920.54690.20340.132*0.559 (8)
H1C0.19970.80090.15730.132*0.559 (8)
C20.1392 (2)0.5369 (13)0.1857 (2)0.0670 (18)0.559 (8)
H2A0.09760.59540.14380.080*0.559 (8)
H2B0.13710.34180.18990.080*0.559 (8)
C30.1427 (3)0.6599 (13)0.2618 (3)0.0469 (14)0.559 (8)
H3A0.18560.61110.30310.056*0.559 (8)
H3B0.14160.85520.25640.056*0.559 (8)
C40.0865 (3)0.5733 (12)0.2863 (4)0.0394 (14)0.559 (8)
H4A0.09080.38050.29700.047*0.559 (8)
H4B0.04400.60220.24210.047*0.559 (8)
C50.0828 (4)0.712 (3)0.3570 (6)0.0328 (17)0.559 (8)
H50.07800.90610.34550.039*0.559 (8)
C60.0261 (4)0.6273 (17)0.3811 (5)0.050 (2)0.559 (8)
H6A0.01590.64220.33520.060*0.559 (8)
H6B0.03220.43810.39620.060*0.559 (8)
C70.0186 (6)0.7826 (17)0.4475 (6)0.072 (2)0.559 (8)
H7A0.02020.71690.45780.108*0.559 (8)
H7B0.01230.97060.43350.108*0.559 (8)
H7C0.05870.76090.49440.108*0.559 (8)
C80.1465 (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'0.21490.87410.50100.086*0.441 (8)
H2N'0.16481.03120.43460.086*0.441 (8)
C1'0.1773 (4)0.4144 (19)0.1617 (4)0.092 (3)0.441 (8)
H1'10.17910.38980.10970.138*0.441 (8)
H1'20.14310.29780.16750.138*0.441 (8)
H1'30.22060.37060.20150.138*0.441 (8)
C2'0.1605 (4)0.6961 (15)0.1712 (4)0.075 (2)0.441 (8)
H2'10.11590.73720.13190.090*0.441 (8)
H2'20.19310.81350.16100.090*0.441 (8)
C3'0.1605 (5)0.7539 (17)0.2521 (5)0.063 (2)0.441 (8)
H3'10.20390.69820.29110.075*0.441 (8)
H3'20.15670.94780.25740.075*0.441 (8)
C4'0.1066 (5)0.6222 (18)0.2711 (5)0.047 (2)0.441 (8)
H4'10.11550.42930.27580.057*0.441 (8)
H4'20.06400.64930.22690.057*0.441 (8)
C5'0.0985 (6)0.719 (4)0.3461 (8)0.041 (3)0.441 (8)
H5'0.09160.91530.34220.050*0.441 (8)
C6'0.0379 (6)0.591 (3)0.3566 (6)0.050 (2)0.441 (8)
H6'10.04530.39700.36280.060*0.441 (8)
H6'20.00170.62020.30860.060*0.441 (8)
C7'0.0235 (5)0.697 (2)0.4264 (7)0.067 (3)0.441 (8)
H7'10.01400.59890.43140.100*0.441 (8)
H7'20.01220.88520.41860.100*0.441 (8)
H7'30.06290.67380.47400.100*0.441 (8)
C8'0.1614 (6)0.661 (3)0.4166 (8)0.032 (2)0.441 (8)
O510.31437 (6)0.6957 (2)0.08876 (7)0.0499 (4)
N510.29846 (7)1.1342 (3)0.07592 (8)0.0445 (4)
H51A0.25901.11410.03890.053*
H51B0.31401.29420.09120.053*
C510.32418 (15)1.0964 (5)0.39915 (15)0.0863 (8)
H51C0.34471.27220.41090.104*
H51D0.32501.01270.44750.104*
H51E0.27801.11400.36290.104*
C520.36203 (12)0.9288 (5)0.36277 (12)0.0668 (6)
H52A0.34380.74670.35620.080*
H52B0.40910.91960.39880.080*
C530.35979 (9)1.0293 (4)0.28423 (10)0.0481 (5)
H53A0.31301.02730.24720.058*
H53B0.37531.21540.29010.058*
C540.40150 (9)0.8699 (4)0.25014 (10)0.0465 (5)
H54A0.38500.68500.24310.056*
H54B0.44790.86690.28820.056*
C550.40199 (8)0.9711 (3)0.17209 (9)0.0401 (4)
H550.41091.16600.17660.048*
C560.45567 (9)0.8372 (4)0.14969 (11)0.0513 (5)
H56A0.49920.86460.19240.062*
H56B0.44690.64420.14520.062*
C570.46062 (11)0.9339 (5)0.07468 (12)0.0664 (6)
H57A0.41920.89350.03110.080*
H57B0.49790.84530.06640.080*
H57C0.46811.12580.07770.080*
C580.33428 (8)0.9246 (3)0.10850 (9)0.0379 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.042 (3)0.0246 (16)0.044 (3)0.002 (2)0.0016 (17)0.0011 (17)
N10.055 (5)0.010 (3)0.042 (5)0.000 (2)0.001 (4)0.004 (3)
C10.075 (4)0.125 (7)0.067 (3)0.026 (4)0.030 (3)0.016 (3)
C20.068 (3)0.080 (4)0.051 (2)0.011 (3)0.021 (2)0.007 (2)
C30.047 (4)0.054 (4)0.039 (2)0.009 (3)0.014 (3)0.003 (2)
C40.042 (3)0.027 (3)0.037 (3)0.004 (2)0.000 (2)0.000 (2)
C50.026 (4)0.028 (2)0.036 (3)0.001 (3)0.001 (3)0.003 (2)
C60.045 (3)0.052 (4)0.050 (6)0.007 (3)0.013 (4)0.010 (4)
C70.092 (4)0.070 (5)0.065 (5)0.021 (4)0.041 (3)0.007 (4)
C80.032 (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)
O510.0568 (8)0.0235 (7)0.0465 (7)0.0007 (5)0.0079 (6)0.0009 (5)
N510.0482 (9)0.0240 (8)0.0418 (8)0.0023 (6)0.0068 (7)0.0013 (6)
C510.117 (2)0.091 (2)0.0681 (16)0.0194 (16)0.0536 (16)0.0006 (14)
C520.0857 (16)0.0651 (15)0.0509 (12)0.0127 (12)0.0265 (12)0.0058 (11)
C530.0566 (11)0.0417 (11)0.0387 (10)0.0103 (9)0.0088 (9)0.0018 (8)
C540.0496 (10)0.0394 (10)0.0366 (10)0.0057 (8)0.0007 (8)0.0050 (8)
C550.0449 (10)0.0306 (9)0.0337 (9)0.0018 (7)0.0015 (7)0.0004 (7)
C560.0489 (11)0.0480 (11)0.0474 (11)0.0013 (9)0.0061 (9)0.0015 (9)
C570.0668 (14)0.0781 (16)0.0527 (13)0.0053 (12)0.0201 (11)0.0064 (11)
C580.0469 (10)0.0271 (9)0.0312 (9)0.0008 (8)0.0045 (7)0.0005 (7)
Geometric parameters (Å, º) top
O1—C81.268 (12)C3'—C4'1.489 (8)
N1—H1N0.880C4'—H4'10.990
N1—H2N0.880C4'—H4'20.990
N1—C81.390 (14)C4'—C5'1.536 (14)
C1—H1A0.980C5'—H5'1.00
C1—H1B0.980C5'—C6'1.536 (12)
C1—H1C0.980C5'—C8'1.524 (16)
C1—C21.519 (10)C6'—H6'10.990
C2—H2A0.990C6'—H6'20.990
C2—H2B0.990C6'—C7'1.527 (9)
C2—C31.510 (7)C7'—H7'10.980
C3—H3A0.990C7'—H7'20.980
C3—H3B0.990C7'—H7'30.980
C3—C41.508 (6)O51—C581.2399 (19)
C4—H4A0.990N51—H51A0.880
C4—H4B0.990N51—H51B0.880
C4—C51.506 (13)N51—C581.318 (2)
C5—H51.00C51—H51C0.980
C5—C61.510 (10)C51—H51D0.980
C5—C81.510 (12)C51—H51E0.980
C6—H6A0.990C51—C521.495 (3)
C6—H6B0.990C52—H52A0.990
C6—C71.512 (7)C52—H52B0.990
C7—H7A0.980C52—C531.517 (3)
C7—H7B0.980C53—H53A0.990
C7—H7C0.980C53—H53B0.990
O1'—C8'1.210 (15)C53—C541.506 (3)
N1'—H1N'0.880C54—H54A0.990
N1'—H2N'0.880C54—H54B0.990
N1'—C8'1.294 (16)C54—C551.530 (2)
C1'—H1'10.980C55—H551.00
C1'—H1'20.980C55—C561.524 (3)
C1'—H1'30.980C55—C581.520 (2)
C1'—C2'1.494 (12)C56—H56A0.990
C2'—H2'10.990C56—H56B0.990
C2'—H2'20.990C56—C571.506 (3)
C2'—C3'1.519 (10)C57—H57A0.980
C3'—H3'10.990C57—H57B0.980
C3'—H3'20.990C57—H57C0.980
H1N—N1—H2N120.0H3'1—C3'—H3'2107.5
H1N—N1—C8120.0H3'1—C3'—C4'108.5
H2N—N1—C8120.0H3'2—C3'—C4'108.5
H1A—C1—H1B109.5C3'—C4'—H4'1108.5
H1A—C1—H1C109.5C3'—C4'—H4'2108.5
H1A—C1—C2109.5C3'—C4'—C5'115.2 (8)
H1B—C1—H1C109.5H4'1—C4'—H4'2107.5
H1B—C1—C2109.5H4'1—C4'—C5'108.5
H1C—C1—C2109.5H4'2—C4'—C5'108.5
C1—C2—H2A108.9C4'—C5'—H5'108.4
C1—C2—H2B108.9C4'—C5'—C6'111.2 (11)
C1—C2—C3113.4 (5)C4'—C5'—C8'110.2 (9)
H2A—C2—H2B107.7H5'—C5'—C6'108.4
H2A—C2—C3108.9H5'—C5'—C8'108.4
H2B—C2—C3108.9C6'—C5'—C8'110.3 (11)
C2—C3—H3A109.0C5'—C6'—H6'1108.8
C2—C3—H3B109.0C5'—C6'—H6'2108.8
C2—C3—C4112.8 (5)C5'—C6'—C7'113.9 (10)
H3A—C3—H3B107.8H6'1—C6'—H6'2107.7
H3A—C3—C4109.0H6'1—C6'—C7'108.8
H3B—C3—C4109.0H6'2—C6'—C7'108.8
C3—C4—H4A108.4C6'—C7'—H7'1109.5
C3—C4—H4B108.4C6'—C7'—H7'2109.5
C3—C4—C5115.4 (6)C6'—C7'—H7'3109.5
H4A—C4—H4B107.5H7'1—C7'—H7'2109.5
H4A—C4—C5108.4H7'1—C7'—H7'3109.5
H4B—C4—C5108.4H7'2—C7'—H7'3109.5
C4—C5—H5107.9O1'—C8'—N1'129.0 (14)
C4—C5—C6115.4 (7)O1'—C8'—C5'121.2 (14)
C4—C5—C8110.3 (8)N1'—C8'—C5'109.1 (14)
H5—C5—C6107.9H51A—N51—H51B120.0
H5—C5—C8107.9H51A—N51—C58120.0
C6—C5—C8107.3 (7)H51B—N51—C58120.0
C5—C6—H6A108.4C51—C52—H52A108.7
C5—C6—H6B108.4C51—C52—H52B108.7
C5—C6—C7115.5 (8)C51—C52—C53114.0 (2)
H6A—C6—H6B107.5H52A—C52—H52B107.6
H6A—C6—C7108.4H52A—C52—C53108.7
H6B—C6—C7108.4H52B—C52—C53108.7
C6—C7—H7A109.5C52—C53—H53A108.8
C6—C7—H7B109.5C52—C53—H53B108.8
C6—C7—H7C109.5C52—C53—C54113.87 (17)
H7A—C7—H7B109.5H53A—C53—H53B107.7
H7A—C7—H7C109.5H53A—C53—C54108.8
H7B—C7—H7C109.5H53B—C53—C54108.8
O1—C8—N1116.5 (10)C53—C54—H54A108.5
O1—C8—C5120.0 (10)C53—C54—H54B108.5
N1—C8—C5123.1 (11)C53—C54—C55115.17 (15)
H1N'—N1'—H2N'120.0H54A—C54—H54B107.5
H1N'—N1'—C8'120.0H54A—C54—C55108.5
H2N'—N1'—C8'120.0H54B—C54—C55108.5
H1'1—C1'—H1'2109.5C54—C55—H55108.5
H1'1—C1'—H1'3109.5C54—C55—C56112.02 (14)
H1'1—C1'—C2'109.5C54—C55—C58109.66 (14)
H1'2—C1'—H1'3109.5H55—C55—C56108.5
H1'2—C1'—C2'109.5H55—C55—C58108.5
H1'3—C1'—C2'109.5C56—C55—C58109.59 (14)
C1'—C2'—H2'1109.1C55—C56—H56A108.5
C1'—C2'—H2'2109.1C55—C56—H56B108.5
C1'—C2'—C3'112.6 (6)C55—C56—C57114.97 (16)
H2'1—C2'—H2'2107.8H56A—C56—H56B107.5
H2'1—C2'—C3'109.1H56A—C56—C57108.5
H2'2—C2'—C3'109.1H56B—C56—C57108.5
C2'—C3'—H3'1108.5O51—C58—N51122.14 (15)
C2'—C3'—H3'2108.5O51—C58—C55120.14 (14)
C2'—C3'—C4'115.2 (7)N51—C58—C55117.73 (14)
C1—C2—C3—C4176.3 (6)C8'—C5'—C6'—C7'62.4 (16)
C2—C3—C4—C5173.5 (7)C4'—C5'—C8'—O1'63.4 (15)
C3—C4—C5—C6179.3 (8)C4'—C5'—C8'—N1'125.3 (16)
C3—C4—C5—C858.8 (11)C6'—C5'—C8'—O1'59.8 (15)
C4—C5—C6—C7174.8 (8)C6'—C5'—C8'—N1'111.5 (17)
C8—C5—C6—C761.8 (12)C51—C52—C53—C54176.33 (19)
C4—C5—C8—O160.4 (11)C52—C53—C54—C55178.22 (16)
C4—C5—C8—N1111.7 (12)C53—C54—C55—C56168.19 (15)
C6—C5—C8—O166.1 (11)C53—C54—C55—C5869.91 (19)
C6—C5—C8—N1121.9 (11)C54—C55—C56—C57178.02 (16)
C1'—C2'—C3'—C4'67.7 (11)C58—C55—C56—C5760.0 (2)
C2'—C3'—C4'—C5'169.2 (9)C54—C55—C58—O5166.4 (2)
C3'—C4'—C5'—C6'174.7 (10)C54—C55—C58—N51113.64 (18)
C3'—C4'—C5'—C8'62.7 (15)C56—C55—C58—O5156.9 (2)
C4'—C5'—C6'—C7'175.0 (10)C56—C55—C58—N51123.01 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O51i0.881.992.858 (15)170
N1—H2N···O1ii0.882.062.901 (12)160
N1—H1N···O51i0.882.193.029 (19)159
N1—H2N···O1ii0.882.072.834 (18)145
N51—H51A···O1iii0.882.062.923 (12)166
N51—H51B···O51ii0.882.032.8539 (19)156
N51—H51A···O1iii0.882.102.980 (10)179
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1, z; (iii) x, y+3/2, z1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC11H18N2O2C9H19NOC8H17NO
Mr210.27157.25143.23
Crystal system, space groupMonoclinic, P21/cMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)120120120
a, b, c (Å)10.108 (2), 21.824 (4), 10.393 (2)22.839 (6), 5.0394 (13), 18.802 (5)21.597 (5), 5.0469 (12), 18.424 (5)
β (°) 92.52 (3) 111.224 (4) 111.529 (3)
V3)2290.4 (8)2017.2 (9)1868.0 (8)
Z888
Radiation typeMo KαSynchrotron, λ = 0.6933 ÅSynchrotron, λ = 0.69330 Å
µ (mm1)0.090.070.04
Crystal size (mm)0.36 × 0.08 × 0.030.20 × 0.10 × 0.050.20 × 0.10 × 0.05
Data collection
DiffractometerNonius KappaCCD
diffractometer
Bruker APEXII
diffractometer
Bruker APEXII
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Multi-scan
(SADABS; Sheldrick, 1996)
Multi-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.970, 0.9980.987, 0.9970.992, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections
37076, 4030, 3184 5147, 1867, 1456 12823, 3250, 2184
Rint0.1100.0420.052
(sin θ/λ)max1)0.5950.6100.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.140, 1.09 0.054, 0.159, 1.06 0.049, 0.141, 1.02
No. of reflections403018673250
No. of parameters292103274
No. of restraints0019
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.26, 0.230.35, 0.180.17, 0.13

Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2007), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DIAMOND (Brandenburg & Putz, 1999) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and local programs.

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.84 (3)2.14 (3)2.732 (3)127 (3)
N2—H2N···O510.98 (3)1.81 (3)2.781 (3)171 (2)
N51—H51N···O520.90 (3)2.04 (3)2.692 (3)128 (2)
N52—H52N···O10.89 (3)1.95 (3)2.837 (3)175 (2)
N1—H1N···O52i0.84 (3)2.35 (3)3.032 (3)139 (3)
N51—H51N···O2ii0.90 (3)2.38 (3)3.109 (3)138 (2)
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.882.072.9488 (18)179
N1—H2N···O1ii0.882.022.8492 (18)156
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O51i0.881.992.858 (15)170
N1—H2N···O1ii0.882.062.901 (12)160
N51—H51B···O51ii0.882.032.8539 (19)156
N51—H51A···O1iii0.882.102.980 (10)179
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1, z; (iii) x, y+3/2, z1/2.
 

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