Two polymorphs of 5-cyclo­hexyl-5-ethyl­barbituric acid and their packing relationships with other barbiturates

Polymorph (Ia) (m.p. 474 K) of the title compound, C₁₂H₁₈N₂O₃, displays an N—H...O=C hydrogen-bonded layer structure which contains R₆⁶(28) rings connecting six mol­ecules, as well as R₂²(8) rings linking two mol­ecules. The 3-connected hydrogen-bonded net resulting from these inter­actions has the hcb topology. Form (Ib) (m.p. 471 K) displays N—H...O=C hydrogen-bonded looped chains in which neighbouring mol­ecules are linked to one another by two different R₂²(8) rings. Polymorph (Ia) is isostructural with the previously reported form II of 5-(2-bromo­all­yl)-5-iso­propyl­barbituric acid (noctal) and polymorph (Ib) is isostructural with the known crystal structures of four other barbiturates.

S1. Introduction

The title compound [systematic name: 5-cyclo­hexyl-5-ethyl­pyrimidine-2,4,6(1H,3H,5H)-trione], (I) (see scheme), was investigated as part of a wider study of solid forms of barbiturates, 5-substituted derivatives of barbituric acid (Zencirci et al., 2009, 2010, 2014; Rossi et al., 2012). Barbiturates have been used as sedative, hypnotic and anti­convulsant agents, and the polymorphism and isomorphic relationships of selected members of this class have been investigated for several decades [see, for example, Brandstätter-Kuhnert & Aepkers (1961, 1962a,b, 1963)]. The core pyrimidine-2,4,6-trione unit contains a rigid arrangement of two N—H and three carbonyl groups, which can serve as donor and acceptor groups, respectively, for hydrogen bonds. This imposes limitations on the connectivity modes and geometries that are feasible for the formation of inter­molecular N—H···O═C hydrogen-bonded structures, especially if no other functional groups for classical hydrogen bonding are available. The Cambridge Structural Database (CSD, Version 3.35; Groom & Allen, 2014) and the recent literature contain 51 unique crystal structures of barbiturates which have these characteristics, and the hydrogen-bonded structures (HBSs) formed in this set can be assigned to 12 distinct connectivity modes (Gelbrich et al., 2011). For a classification of the observed HBSs, one has to distinguish between the carbonyl group at position C2 on the one hand and the two topologically equivalent C4 and C6 carbonyl groups on the other (Fig. 1a). This set of barbiturate structures is dominated by four HBS types which are periodic in one dimension, e.g. two kinds of looped chain, a tape and a ladder structure (Gelbrich et al., 2011). The looped chains C-1 and C-2 (Figs. 1b and 1c) are the most important of these one-dimensional structures (see Table S1 of the Supporting information). By comparison, N—H···O═C hydrogen-bonded layers and frameworks are rarely encountered in this group, with the exception of the subset of 5,5-dihalogen-substituted barbituric acid derivatives, which tend to form more complex HBSs (DesMarteau et al., 1994; Gelbrich et al., 2011).

S2. Experimental

S2.1. Synthesis and crystallisation

The synthesis of (I) was described by Kindler & Lührs (1965), who reported a melting point of 470 K. There is no previous report about the polymorphism of (I). The sample in our archive, synthesized by Kindler and co-workers more than 70 years ago, contained hexagonal plates of polymorph (Ia) and oblong prisms of form (Ib). It was characterised by hot-stage microscopy, FT–IR spectroscopy, powder X-ray crystallography and differential scanning calorimetry (for details, see the Supporting information). Sublimation experiments were carried out on a hot bench at 393, 423 and 463 K. A small amount of sample was placed on a glass slide and covered by a cylindrical-shaped glass bowl (diameter 6 mm, height 5 mm). After 1 d, the experiment at 393 K yielded isometric crystals of (Ia) in the hot section, close to the surface of the hot bench, and long prisms of form (Ib) in the cold section, on the surface of the inner bottom of the glass bowl. The other experiments resulted exclusively in form (Ib).

S2.2. Hot-stage microscopy

Heating of the original sample above 433 K on a hot stage resulted in intense sublimation, followed by the formation of secondary needle-shaped crystals. The oblong prisms of polymorph (Ib) melted at 469–473 K and the hexagonal plates of (Ia) at 473–476 K. The melt, still containing residual seeds of form (Ia), was left to cool, and at about 453 K the seeds grew rapidly into hexagonal or lath-shaped aggregates. Characteristic patterns of cracks appeared in these aggregates on further cooling below 396 K. A fraction of the remaining noncrystalline islands (undercooled melt) transformed into crystalline spherulitic aggregates at approximately the same temperature. These aggregates belong to a third polymorph, form (Ic), and show a distinct inter­nal feather pattern. The remaining islands of undercooled melt crystallized below 384 K as very fine needles which were arranged into a fuzzy pattern and represented a fourth polymorph, form (Id). On reheating, the transformations of the aggregates of forms (Ic) and (Id) into form (Ib) occur at about 393 and 413 K, respectively. With a very fast heating rate, melting of untransformed crystals was observed at approximately 443 K. It was not possible to produce larger qu­anti­ties of forms (Ic) and (Id) nor single crystals of these polymorphs suitable for X-ray crystallography.

S2.3. Differential scanning calorimetry (DSC) and thermodynamic stability

The DSC trace of the original sample containing a mixture of forms (Ia) and (Ib) shows two overlapping endothermic events (see Fig. S4 in the Supporting information). These indicate the melting process of form (Ib) with an onset temperature of about 469 K, followed by the melting of form (Ia), the main component of this sample, at about 474 K (onset temperature).

The melting endotherms of the two phase-pure forms (see Fig. S5 in the Supporting information) confirm that form (Ib) is the lower-melting polymorph. From a series of DSC experiments, the heats of fusion (Δ_fusH) of forms (Ia) and (Ib) were determined to be 28.8±0.6 and 28.0±0.6 kJ mol^-1 (95% c.i.), respectively, indicating that there is very little energy difference between the two forms. Form (Ia) has the higher melting point, as well as the higher heat of fusion. Application of the heat of fusion rule (Burger & Ramberger, 1979) would suggest a monotropic relationship in which form (Ia) is the more stable polymorph over the entire temperature range, but the statistical certainty associated with our data does not permit a reliable assessment in this regard. However, polymorph (Ib) is clearly more dense than (Ia) (by 1.9%). The density rule (Burger & Ramberger, 1979), which postulates that the denser phase should have a lower free energy at absolute zero, may not be applicable for polymorphs with strong hydrogen bonds and different Z'.

The available data do not permit a definitive assessment of the relative thermodynamic stability of forms (Ia) and (Ib). The co-existence of forms (Ia) and (Ib) in a 70-year-old sample investigated in this study indicates that both these polymorphs are kinetically highly stable.

S2.4. Refinement

Crystal data, data collection and structure refinement details are summarised in Table 1. All H atoms were identified in difference maps. Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip, with C—H = 0.98 Å. Other C-bound H atoms were positioned geometrically, with C—H = 0.99 Å for secondary (CH₂) and tertiary (CH) C atoms. For all C-bound H atoms, U_iso(H) = 1.2U_eq(C) for CH and CH₂ groups, or 1.5U_eq(C) for methyl groups. N-bound H atoms were refined with restrained distances N—H = 0.86 (2) Å, and their U_iso(H) parameters were refined freely.

S3. Results and discussion

Polymorph (Ia) crystallizes in the space group P2₁/c and contains two independent molecules (Fig. 2), denoted A and B, which adopt the same principle geometry. The cyclo­hexyl ring displays an almost ideal chair conformation, with an equatorial C5 substituent and with the ethyl group oriented trans relative to the C9—C5 bond (Fig. 3). The largest difference between molecules A and B occurs in the corresponding torsion angles C8—C7—C5—C9 (in molecule A) and C8'—C7'—C5'—C9' (in molecule B) of -173.8 (2) and -179.7 (2)°, respectively. The pyrimidine-2,4,6-trione units of molecules A and B are essentially planar, with the largest deviation shown by their C4 and C4' carbonyl groups, so that atoms O4 and O4' lie 0.109 (3) and 0.158 (3) Å, respectively, from the mean plane of the respective C₄N₂ ring.

Each molecule is bonded to two molecules of the same type via N1—H1···O4(x, -y + 3/2, z + 1/2) and N1'—H1'···O4'(x, -y + 1/2, z + 1/2) inter­actions which involve a glide mirror operation. Additionally, two A and B molecules are connected to one another by two anti­parallel inter­actions, (A)N3—H3···O2'(B) and (B)N3'—H3'···O2(A). Altogether, a hydrogen-bonded layer structure is formed (Fig. 4) which lies parallel to (100) and belongs to the L-4 type (Fig. 1d). It contains rings comprising six molecules, as well as dimeric units, which may be described in graph-set notation (Etter et al., 1990; Bernstein et al., 1995) as R₆⁶(28) and R₂²(8), respectively. There is only one previous example of this kind of N—H···O hydrogen-bonded layer among the 51 published crystal structures of analogous barbiturates. The underlying net of this HBS has the hcb topology (O'Keeffe et al., 2008), and the A and B molecules both serve as three-connected nodes and are topologically equivalent. The L-4 units of polymorph (Ia) are corrugated sheets with an inter­nal glide mirror symmetry, which are stacked along the a axis via inversion and 2₁ operations.

An XPac comparison (Gelbrich & Hursthouse, 2005) revealed that the crystal structure of form (Ia) is closely related to that of polymorph II of no­ctal [systematic name: 5-(2-bromo­allyl)-5-iso­propyl­barbituric acid; Gelbrich et al., 2011], the other known L-4 example, not just with regard to the topology of its HBS but indeed in its complete crystal packing arrangement (Fig. 5). Geometric differences between these two crystal structures result from shape and size differences in their substituent pairs at atom C5. This is reflected in the core dissimilarity index x₁₁ (Gelbrich et al., 2012) of 10.9, calculated with parameters derived from matching non-H-atom positions of the pyrimidine-2,4,6-trione unit and the first C atom of each C5 substituent. Furthermore, the difference between the β angles of polymorph (Ia) and the no­ctal structure is 9.9° (see Table S2 of the Supporting information).

The space-group symmetry of the no­ctal structure is also P2₁/c, but its asymmetric unit contains just one molecule. Closer inspection shows that polymorph (Ia) has an approximate pseudosymmetry and is related to the no­ctal structure via a doubling of the a axis. In Fig. 5(a) (right), the break in the translation symmetry between neighbouring A and B molecules along [100] is visible as a slight offset between the two molecule types.

The molecular geometry of the C2/c polymorph, (Ib) (Fig. 6), is similar to that found in form (Ia) (Fig. 3). However, the ethyl group of (Ib) is oriented somewhat out-of-plane and the torsion angle C8—C7—C5—C9 = -160.77 (9)° is 13.0 and 18.9° smaller than the analogous values for molecules A and B of form (Ia). The C4 carbonyl group shows the largest deviation from the essentially planar pyrimidine ring, and the distance between atom O4 and the mean plane of the C₄N₂ ring is 0.162 (2) Å. Each molecule of polymorph (Ib) is bonded to two other molecules by two distinct anti­parallel two-point connections, viz. N1—H1···O2(-x + 1, y, -z - 1/2) and N3—H3···O4(-x + 1, y, -z + 1/2). These hydrogen bonds result in two independent R₂²(8) rings, the centres of which are inter­sected by crystallographic twofold axes. A looped hydrogen-bonded chain is formed, in which the two ring types alternate, and which runs parallel to [001]. This chain belongs to the C-1 type (Fig. 1b), the most common HBS for barbiturates (22 previous examples, see the Supporting information), which is distinct from the C-2 looped chain (eight examples). Neighbouring C-1 chains of polymorph (Ia) are arranged into centrosymmetric pairs in such a way that their mean planes, defined by C₄N₂ pyrimidine units, are parallel and the ethyl and cyclo­hexyl substituents are oriented towards the centre and the surface, respectively, of the resulting chain pair unit (Fig. 8a).

The formation of this kind of chain pair is a common feature in C-1 structures and an XPac analysis revealed that form (Ib) belongs to a larger subset characterized by extensive packing relationships. It is isostructural with the other four crystal structures listed in Table 4 and additionally with polymorph X of phenobarbital (Zencirci et al., 2009). Only two of the listed crystal structures have the maximum space-group symmetry (C2/c; Z' = 1), namely form (Ib) and polymorph I of ipral (systematic name: 5-ethyl-5-iso­propyl­barbituric acid). The unit-cell transformation between this structure and the two distinct P2₁/c (Z' = 2) settings of pseudosymmetric isostructures (CSD refcodes AMYTAL and BECLIE) was previously discussed by Zencirci et al. (2009). These lower-symmetry crystal structures are characterized by the absence of crystallographic twofold axes in their C-1 chains. XPac dissimilarity indices x₁₂ were calculated for the comparison of form (Ib) with each of the other four structures listed in Table 4, using the matching non-H-atom positions of the pyrimidine-2,4,6-trione unit and the ethyl group, and additionally the C atom of the R^5' substituent which is bonded to the pyrimidine ring. The x₁₂ values obtained lie between 6.8 and 9.2, and are consistent with the accommodation of R^5' substituents of different shapes and sizes in the same packing arrangement. Moreover, the isostructures listed in Table 4 show a two-dimensional packing similarity with each of the forms I and II of pentobarbital [systematic name: 5-ethyl-5-(1-methyl­butyl)­barbituric acid; Rossi et al., 2012], due to a common stacking mode of C-1 chain pairs.

In summary, the title compound exemplifies the propensity of barbiturates to crystallize in multiple solid forms, as well as their tendency to form isomorphic relationships. The specific energy contributions associated with competing hydrogen-bond motifs in the barbiturate class are currently being investigated in our laboratory and will be the topic of a future report.

Computing details

Data collection: COLLECT (Nonius, 1998) for (Ia); CrysAlis PRO (Oxford Diffraction, 2010) for (Ib). Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (Ia); CrysAlis PRO (Oxford Diffraction, 2010) for (Ib). Data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for (Ia); CrysAlis PRO (Oxford Diffraction, 2010) for (Ib). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP (Bruker, 1998) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. (a) A simplified representation of a barbiturate molecule (additional circles denote carbonyl groups engaged in hydrogen bonding), used for the depiction of the hydrogen-bonded chain and layer structures, (b) C-1, polymorph (Ib), (c) C-2 and (d) L-4, polymorph (Ia).
	Fig. 2. The asymmetric unit of polymorph (Ia), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. An overlay of the molecular geometries of polymorphs (Ia) and (Ib). The largest conformational differences occur in the torsion angle C9—C5—C8—C7, with a value of -173.9 (2)° for molecule A of (Ia), -179.7 (2)° for molecule B of (Ia) and -160.77 (9)° for (Ib). The r.m.s. distances are 0.061 Å for molecule A of (Ia) versus molecule B of (Ia), 0.090 Å for molecule A of (Ia) versus (Ib), and 0.1123 Å for molecule B of (Ia) versus (Ib).
	Fig. 4. The hydrogen-bonded L-4 structure of (Ia), viewed along [100]. H and O atoms engaged in hydrogen bonding are depicted as balls and all other H atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds. The two graph sets are highlighted.
	Fig. 5. The three-dimensional packing similarity between (Ia) (top row) and polymorph II of noctal (bottom row). The crystal structures are shown in three matching views along corresponding lattice directions, and the core atoms used for XPac calculations (Gelbrich & Hursthouse, 2005) are drawn as balls. All other non-H atoms are drawn as capped sticks in the left-hand column of diagrams. In the centre and right-hand rows they have been omitted for clarity. Dashed lines indicate hydrogen bonds.
	Fig. 6. The asymmetric unit of form (Ib), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 7. The hydrogen-bonded C-1 chain structure of polymorph (Ib). H and O atoms engaged in hydrogen bonding are depicted as balls and all other H atoms have been omitted for clarity. Dashed lines indicate hydrogen bonds. The graph set is highlighted. [Symmetry codes: (i) -x + 1, y, -z - 1/2; (ii) -x + 1, y, -z + 1/2. Please check]
	Fig. 8. The packing similarity between (a) form (Ib) and (b) polymorph I of ipral. Each crystal structure is viewed along its b axis. The core atoms used for the XPac calculations (Gelbrich & Hursthouse, 2005) are drawn as balls and all the other non-H atoms are drawn as capped sticks.

(Ia) 5-Cyclohexyl-5-ethylpyrimidine-2,4,6(1H,3H,5H)-trione

Crystal data

C12H18N2O3	Dx = 1.281 Mg m^−3
Mr = 238.28	Melting point: 473 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.9322 (4) Å	Cell parameters from 12888 reflections
b = 10.4961 (3) Å	θ = 2.9–25.4°
c = 13.2006 (4) Å	µ = 0.09 mm^−1
β = 95.896 (2)°	T = 120 K
V = 2471.45 (12) Å^3	Plate, colourless
Z = 8	0.12 × 0.12 × 0.02 mm
F(000) = 1024

Data collection

Bruker Nonius APEXII CCD camera on κ-goniostat diffractometer	3416 reflections with I > 2σ(I)
Detector resolution: 65.3 pixels mm^-1	Rint = 0.054
ϕ and ω scans	θmax = 25.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS2007; Sheldrick, 2007)	h = −21→21
Tmin = 0.989, Tmax = 0.998	k = −12→12
18686 measured reflections	l = −14→15
4513 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.061	w = 1/[σ^2(Fo^2) + 3.5813P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.125	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.28 e Å^−3
4513 reflections	Δρmin = −0.22 e Å^−3
326 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
4 restraints	Extinction coefficient: 0.0025 (4)

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
O2	0.26316 (9)	0.61775 (17)	0.62922 (12)	0.0242 (4)
O4	0.33419 (10)	0.66952 (17)	0.31516 (13)	0.0252 (4)
O6	0.41779 (10)	0.94798 (17)	0.58705 (13)	0.0291 (4)
N1	0.34212 (12)	0.7818 (2)	0.60629 (16)	0.0221 (5)
H1	0.3412 (16)	0.800 (3)	0.6700 (14)	0.038 (9)*
N3	0.30390 (11)	0.6441 (2)	0.47334 (15)	0.0207 (5)
H3	0.2791 (14)	0.577 (2)	0.453 (2)	0.028 (8)*
C2	0.30070 (13)	0.6774 (2)	0.57355 (18)	0.0194 (5)
C4	0.34150 (13)	0.7068 (2)	0.40309 (18)	0.0191 (5)
C5	0.39087 (13)	0.8194 (2)	0.43796 (18)	0.0188 (5)
C6	0.38503 (13)	0.8564 (2)	0.54859 (19)	0.0207 (5)
C7	0.36728 (14)	0.9357 (2)	0.36998 (19)	0.0244 (6)
H7A	0.4032	1.0059	0.3875	0.029*
H7B	0.3710	0.9123	0.2980	0.029*
C8	0.28861 (17)	0.9841 (3)	0.3797 (2)	0.0405 (8)
H8A	0.2527	0.9143	0.3659	0.061*
H8B	0.2767	1.0529	0.3305	0.061*
H8C	0.2857	1.0163	0.4488	0.061*
C9	0.47565 (13)	0.7868 (2)	0.43101 (19)	0.0217 (6)
H9	0.5046	0.8654	0.4526	0.026*
C10	0.49536 (15)	0.7552 (3)	0.3234 (2)	0.0304 (6)
H10A	0.4689	0.6765	0.2989	0.037*
H10B	0.4785	0.8254	0.2764	0.037*
C11	0.57990 (15)	0.7363 (3)	0.3235 (2)	0.0371 (7)
H11A	0.5913	0.7127	0.2542	0.044*
H11B	0.6060	0.8174	0.3422	0.044*
C12	0.60870 (16)	0.6328 (3)	0.3983 (3)	0.0408 (8)
H12A	0.5865	0.5499	0.3757	0.049*
H12B	0.6638	0.6259	0.3994	0.049*
C13	0.58859 (15)	0.6626 (3)	0.5045 (2)	0.0375 (7)
H13A	0.6153	0.7406	0.5299	0.045*
H13B	0.6052	0.5916	0.5509	0.045*
C14	0.50427 (14)	0.6821 (3)	0.5056 (2)	0.0291 (6)
H14A	0.4933	0.7056	0.5752	0.035*
H14B	0.4778	0.6014	0.4868	0.035*
O2'	0.21369 (10)	0.42669 (18)	0.42118 (13)	0.0278 (4)
O4'	0.15416 (10)	0.34154 (17)	0.73713 (12)	0.0253 (4)
O6'	0.09393 (11)	0.05615 (17)	0.46154 (14)	0.0300 (4)
N1'	0.15211 (11)	0.2426 (2)	0.44330 (15)	0.0203 (5)
H1'	0.1556 (15)	0.225 (3)	0.3808 (14)	0.027 (8)*
N3'	0.17635 (11)	0.3859 (2)	0.57713 (15)	0.0207 (5)
H3'	0.1993 (14)	0.453 (2)	0.599 (2)	0.029 (8)*
C2'	0.18263 (13)	0.3560 (2)	0.47667 (18)	0.0200 (5)
C4'	0.14797 (13)	0.3089 (2)	0.64810 (18)	0.0192 (5)
C5'	0.11057 (13)	0.1851 (2)	0.61185 (18)	0.0190 (5)
C6'	0.11752 (13)	0.1541 (2)	0.50050 (19)	0.0207 (5)
C7'	0.14867 (14)	0.0756 (3)	0.67532 (19)	0.0255 (6)
H7C	0.1397	0.0875	0.7475	0.031*
H7D	0.1250	−0.0058	0.6518	0.031*
C8'	0.23292 (17)	0.0662 (4)	0.6689 (2)	0.0478 (9)
H8D	0.2424	0.0535	0.5978	0.072*
H8E	0.2532	−0.0060	0.7100	0.072*
H8F	0.2572	0.1451	0.6947	0.072*
C9'	0.02403 (13)	0.1901 (2)	0.62223 (19)	0.0214 (5)
H9A	0.0031	0.1067	0.5960	0.026*
C10'	−0.01589 (14)	0.2926 (3)	0.5551 (2)	0.0287 (6)
H10C	−0.0034	0.2821	0.4843	0.034*
H10D	0.0018	0.3776	0.5794	0.034*
C11'	−0.10068 (15)	0.2844 (3)	0.5571 (2)	0.0347 (7)
H11C	−0.1251	0.3545	0.5159	0.042*
H11D	−0.1191	0.2027	0.5267	0.042*
C12'	−0.12154 (16)	0.2937 (3)	0.6659 (2)	0.0399 (8)
H12C	−0.1079	0.3792	0.6936	0.048*
H12D	−0.1764	0.2832	0.6657	0.048*
C13'	−0.08176 (15)	0.1929 (3)	0.7335 (2)	0.0365 (7)
H13C	−0.0991	0.1074	0.7098	0.044*
H13D	−0.0945	0.2040	0.8042	0.044*
C14'	0.00338 (14)	0.2020 (3)	0.7318 (2)	0.0299 (6)
H14C	0.0281	0.1333	0.7742	0.036*
H14D	0.0214	0.2848	0.7608	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0277 (9)	0.0275 (10)	0.0183 (9)	−0.0075 (8)	0.0064 (7)	0.0026 (8)
O4	0.0294 (10)	0.0299 (10)	0.0165 (10)	−0.0063 (8)	0.0036 (7)	−0.0013 (8)
O6	0.0365 (11)	0.0266 (10)	0.0243 (10)	−0.0101 (8)	0.0040 (8)	−0.0043 (8)
N1	0.0295 (12)	0.0228 (12)	0.0145 (11)	−0.0049 (9)	0.0055 (9)	−0.0024 (9)
N3	0.0234 (11)	0.0211 (11)	0.0178 (11)	−0.0072 (9)	0.0034 (9)	−0.0024 (9)
C2	0.0194 (12)	0.0199 (13)	0.0188 (13)	−0.0001 (10)	0.0017 (10)	0.0000 (11)
C4	0.0193 (12)	0.0200 (13)	0.0180 (13)	0.0016 (10)	0.0019 (10)	0.0007 (10)
C5	0.0197 (12)	0.0217 (13)	0.0153 (12)	−0.0009 (10)	0.0031 (9)	−0.0015 (10)
C6	0.0210 (12)	0.0184 (13)	0.0225 (14)	0.0017 (10)	0.0008 (10)	0.0006 (11)
C7	0.0310 (14)	0.0199 (13)	0.0220 (14)	0.0022 (11)	0.0017 (11)	0.0029 (11)
C8	0.0434 (18)	0.0451 (19)	0.0335 (17)	0.0199 (15)	0.0063 (14)	0.0067 (14)
C9	0.0208 (13)	0.0190 (13)	0.0254 (14)	−0.0024 (10)	0.0036 (10)	0.0002 (11)
C10	0.0276 (14)	0.0353 (16)	0.0296 (15)	0.0052 (12)	0.0084 (12)	−0.0018 (13)
C11	0.0256 (15)	0.0434 (18)	0.0449 (18)	0.0004 (13)	0.0163 (13)	−0.0066 (15)
C12	0.0245 (15)	0.0367 (17)	0.062 (2)	0.0059 (13)	0.0057 (14)	−0.0028 (16)
C13	0.0259 (15)	0.0345 (17)	0.051 (2)	0.0052 (12)	−0.0035 (13)	−0.0023 (15)
C14	0.0251 (14)	0.0264 (15)	0.0353 (16)	0.0042 (11)	0.0006 (11)	0.0011 (12)
O2'	0.0354 (10)	0.0312 (11)	0.0172 (9)	−0.0125 (8)	0.0051 (8)	0.0022 (8)
O4'	0.0297 (10)	0.0311 (10)	0.0152 (9)	−0.0099 (8)	0.0028 (7)	−0.0020 (8)
O6'	0.0428 (11)	0.0235 (10)	0.0245 (10)	−0.0085 (9)	0.0079 (8)	−0.0053 (8)
N1'	0.0249 (11)	0.0238 (12)	0.0126 (11)	−0.0044 (9)	0.0043 (9)	−0.0019 (9)
N3'	0.0247 (11)	0.0219 (11)	0.0153 (11)	−0.0065 (9)	0.0009 (8)	−0.0009 (9)
C2'	0.0201 (12)	0.0239 (14)	0.0156 (12)	−0.0002 (10)	−0.0003 (10)	0.0006 (11)
C4'	0.0164 (12)	0.0236 (13)	0.0178 (13)	−0.0005 (10)	0.0024 (9)	0.0024 (11)
C5'	0.0206 (12)	0.0206 (13)	0.0159 (12)	−0.0003 (10)	0.0028 (10)	−0.0013 (10)
C6'	0.0207 (12)	0.0215 (13)	0.0203 (13)	0.0015 (10)	0.0033 (10)	0.0006 (11)
C7'	0.0320 (14)	0.0248 (14)	0.0201 (14)	0.0056 (11)	0.0044 (11)	0.0036 (11)
C8'	0.0411 (18)	0.069 (2)	0.0347 (18)	0.0292 (17)	0.0124 (14)	0.0163 (17)
C9'	0.0168 (12)	0.0237 (13)	0.0237 (13)	−0.0025 (10)	0.0021 (10)	−0.0032 (11)
C10'	0.0269 (14)	0.0314 (15)	0.0272 (15)	0.0042 (11)	−0.0003 (11)	−0.0004 (12)
C11'	0.0243 (14)	0.0417 (18)	0.0370 (17)	0.0060 (12)	−0.0027 (12)	−0.0076 (14)
C12'	0.0253 (15)	0.0480 (19)	0.0468 (19)	0.0039 (13)	0.0060 (13)	−0.0162 (15)
C13'	0.0253 (14)	0.056 (2)	0.0295 (16)	−0.0035 (14)	0.0073 (12)	−0.0075 (14)
C14'	0.0229 (13)	0.0416 (17)	0.0258 (15)	−0.0030 (12)	0.0054 (11)	−0.0037 (13)

Geometric parameters (Å, º)

O2—C2	1.219 (3)	O2'—C2'	1.217 (3)
O4—C4	1.219 (3)	O4'—C4'	1.218 (3)
O6—C6	1.210 (3)	O6'—C6'	1.207 (3)
N1—C2	1.369 (3)	N1'—C2'	1.364 (3)
N1—C6	1.381 (3)	N1'—C6'	1.383 (3)
N1—H1	0.865 (17)	N1'—H1'	0.854 (17)
N3—C4	1.370 (3)	N3'—C4'	1.374 (3)
N3—C2	1.375 (3)	N3'—C2'	1.379 (3)
N3—H3	0.862 (17)	N3'—H3'	0.853 (17)
C4—C5	1.520 (3)	C4'—C5'	1.517 (3)
C5—C6	1.525 (3)	C5'—C6'	1.523 (3)
C5—C7	1.548 (3)	C5'—C7'	1.540 (3)
C5—C9	1.570 (3)	C5'—C9'	1.573 (3)
C7—C8	1.517 (4)	C7'—C8'	1.525 (4)
C7—H7A	0.9900	C7'—H7C	0.9900
C7—H7B	0.9900	C7'—H7D	0.9900
C8—H8A	0.9800	C8'—H8D	0.9800
C8—H8B	0.9800	C8'—H8E	0.9800
C8—H8C	0.9800	C8'—H8F	0.9800
C9—C14	1.529 (4)	C9'—C10'	1.524 (4)
C9—C10	1.535 (3)	C9'—C14'	1.534 (3)
C9—H9	1.0000	C9'—H9A	1.0000
C10—C11	1.529 (4)	C10'—C11'	1.526 (4)
C10—H10A	0.9900	C10'—H10C	0.9900
C10—H10B	0.9900	C10'—H10D	0.9900
C11—C12	1.523 (4)	C11'—C12'	1.523 (4)
C11—H11A	0.9900	C11'—H11C	0.9900
C11—H11B	0.9900	C11'—H11D	0.9900
C12—C13	1.516 (4)	C12'—C13'	1.515 (4)
C12—H12A	0.9900	C12'—H12C	0.9900
C12—H12B	0.9900	C12'—H12D	0.9900
C13—C14	1.527 (4)	C13'—C14'	1.532 (4)
C13—H13A	0.9900	C13'—H13C	0.9900
C13—H13B	0.9900	C13'—H13D	0.9900
C14—H14A	0.9900	C14'—H14C	0.9900
C14—H14B	0.9900	C14'—H14D	0.9900
C2—N1—C6	126.5 (2)	C2'—N1'—C6'	126.7 (2)
C2—N1—H1	115 (2)	C2'—N1'—H1'	115.7 (19)
C6—N1—H1	118 (2)	C6'—N1'—H1'	117.7 (19)
C4—N3—C2	126.9 (2)	C4'—N3'—C2'	126.5 (2)
C4—N3—H3	116.9 (19)	C4'—N3'—H3'	117.5 (19)
C2—N3—H3	116.2 (19)	C2'—N3'—H3'	115.1 (19)
O2—C2—N1	122.4 (2)	O2'—C2'—N1'	122.1 (2)
O2—C2—N3	121.9 (2)	O2'—C2'—N3'	121.8 (2)
N1—C2—N3	115.6 (2)	N1'—C2'—N3'	116.1 (2)
O4—C4—N3	118.6 (2)	O4'—C4'—N3'	119.3 (2)
O4—C4—C5	122.7 (2)	O4'—C4'—C5'	122.6 (2)
N3—C4—C5	118.7 (2)	N3'—C4'—C5'	118.1 (2)
C4—C5—C6	113.13 (19)	C4'—C5'—C6'	114.2 (2)
C4—C5—C7	108.8 (2)	C4'—C5'—C7'	108.1 (2)
C6—C5—C7	108.2 (2)	C6'—C5'—C7'	106.9 (2)
C4—C5—C9	110.50 (19)	C4'—C5'—C9'	110.64 (19)
C6—C5—C9	105.88 (19)	C6'—C5'—C9'	105.70 (19)
C7—C5—C9	110.28 (19)	C7'—C5'—C9'	111.3 (2)
O6—C6—N1	119.5 (2)	O6'—C6'—N1'	119.8 (2)
O6—C6—C5	121.7 (2)	O6'—C6'—C5'	122.2 (2)
N1—C6—C5	118.7 (2)	N1'—C6'—C5'	118.0 (2)
C8—C7—C5	114.6 (2)	C8'—C7'—C5'	113.9 (2)
C8—C7—H7A	108.6	C8'—C7'—H7C	108.8
C5—C7—H7A	108.6	C5'—C7'—H7C	108.8
C8—C7—H7B	108.6	C8'—C7'—H7D	108.8
C5—C7—H7B	108.6	C5'—C7'—H7D	108.8
H7A—C7—H7B	107.6	H7C—C7'—H7D	107.7
C7—C8—H8A	109.5	C7'—C8'—H8D	109.5
C7—C8—H8B	109.5	C7'—C8'—H8E	109.5
H8A—C8—H8B	109.5	H8D—C8'—H8E	109.5
C7—C8—H8C	109.5	C7'—C8'—H8F	109.5
H8A—C8—H8C	109.5	H8D—C8'—H8F	109.5
H8B—C8—H8C	109.5	H8E—C8'—H8F	109.5
C14—C9—C10	110.3 (2)	C10'—C9'—C14'	110.2 (2)
C14—C9—C5	112.5 (2)	C10'—C9'—C5'	112.4 (2)
C10—C9—C5	114.7 (2)	C14'—C9'—C5'	114.9 (2)
C14—C9—H9	106.3	C10'—C9'—H9A	106.2
C10—C9—H9	106.3	C14'—C9'—H9A	106.2
C5—C9—H9	106.3	C5'—C9'—H9A	106.2
C11—C10—C9	110.5 (2)	C9'—C10'—C11'	111.1 (2)
C11—C10—H10A	109.6	C9'—C10'—H10C	109.4
C9—C10—H10A	109.6	C11'—C10'—H10C	109.4
C11—C10—H10B	109.6	C9'—C10'—H10D	109.4
C9—C10—H10B	109.6	C11'—C10'—H10D	109.4
H10A—C10—H10B	108.1	H10C—C10'—H10D	108.0
C12—C11—C10	111.3 (2)	C12'—C11'—C10'	110.7 (2)
C12—C11—H11A	109.4	C12'—C11'—H11C	109.5
C10—C11—H11A	109.4	C10'—C11'—H11C	109.5
C12—C11—H11B	109.4	C12'—C11'—H11D	109.5
C10—C11—H11B	109.4	C10'—C11'—H11D	109.5
H11A—C11—H11B	108.0	H11C—C11'—H11D	108.1
C13—C12—C11	110.8 (2)	C13'—C12'—C11'	111.4 (2)
C13—C12—H12A	109.5	C13'—C12'—H12C	109.4
C11—C12—H12A	109.5	C11'—C12'—H12C	109.4
C13—C12—H12B	109.5	C13'—C12'—H12D	109.4
C11—C12—H12B	109.5	C11'—C12'—H12D	109.4
H12A—C12—H12B	108.1	H12C—C12'—H12D	108.0
C12—C13—C14	111.5 (2)	C12'—C13'—C14'	110.9 (2)
C12—C13—H13A	109.3	C12'—C13'—H13C	109.5
C14—C13—H13A	109.3	C14'—C13'—H13C	109.5
C12—C13—H13B	109.3	C12'—C13'—H13D	109.5
C14—C13—H13B	109.3	C14'—C13'—H13D	109.5
H13A—C13—H13B	108.0	H13C—C13'—H13D	108.0
C13—C14—C9	110.9 (2)	C13'—C14'—C9'	110.3 (2)
C13—C14—H14A	109.5	C13'—C14'—H14C	109.6
C9—C14—H14A	109.5	C9'—C14'—H14C	109.6
C13—C14—H14B	109.5	C13'—C14'—H14D	109.6
C9—C14—H14B	109.5	C9'—C14'—H14D	109.6
H14A—C14—H14B	108.0	H14C—C14'—H14D	108.1
C6—N1—C2—O2	−178.7 (2)	C6'—N1'—C2'—N3'	−1.8 (4)
C6—N1—C2—N3	1.1 (4)	C4'—N3'—C2'—O2'	−174.4 (2)
C4—N3—C2—O2	177.1 (2)	C4'—N3'—C2'—N1'	5.5 (4)
C4—N3—C2—N1	−2.7 (4)	C2'—N3'—C4'—O4'	171.1 (2)
C2—N3—C4—O4	−174.8 (2)	C2'—N3'—C4'—C5'	−8.3 (4)
C2—N3—C4—C5	5.5 (4)	O4'—C4'—C5'—C6'	−172.5 (2)
O4—C4—C5—C6	174.2 (2)	N3'—C4'—C5'—C6'	6.9 (3)
N3—C4—C5—C6	−6.1 (3)	O4'—C4'—C5'—C7'	−53.8 (3)
O4—C4—C5—C7	53.9 (3)	N3'—C4'—C5'—C7'	125.7 (2)
N3—C4—C5—C7	−126.4 (2)	O4'—C4'—C5'—C9'	68.4 (3)
O4—C4—C5—C9	−67.3 (3)	N3'—C4'—C5'—C9'	−112.2 (2)
N3—C4—C5—C9	112.4 (2)	C2'—N1'—C6'—O6'	−178.8 (2)
C2—N1—C6—O6	178.5 (2)	C2'—N1'—C6'—C5'	1.3 (4)
C2—N1—C6—C5	−2.5 (4)	C4'—C5'—C6'—O6'	176.3 (2)
C4—C5—C6—O6	−176.3 (2)	C7'—C5'—C6'—O6'	56.9 (3)
C7—C5—C6—O6	−55.7 (3)	C9'—C5'—C6'—O6'	−61.8 (3)
C9—C5—C6—O6	62.5 (3)	C4'—C5'—C6'—N1'	−3.8 (3)
C4—C5—C6—N1	4.8 (3)	C7'—C5'—C6'—N1'	−123.2 (2)
C7—C5—C6—N1	125.4 (2)	C9'—C5'—C6'—N1'	118.1 (2)
C9—C5—C6—N1	−116.4 (2)	C4'—C5'—C7'—C8'	−58.0 (3)
C4—C5—C7—C8	64.9 (3)	C6'—C5'—C7'—C8'	65.4 (3)
C6—C5—C7—C8	−58.4 (3)	C9'—C5'—C7'—C8'	−179.7 (2)
C9—C5—C7—C8	−173.8 (2)	C4'—C5'—C9'—C10'	63.3 (3)
C4—C5—C9—C14	−66.0 (3)	C6'—C5'—C9'—C10'	−60.9 (3)
C6—C5—C9—C14	56.8 (3)	C7'—C5'—C9'—C10'	−176.5 (2)
C7—C5—C9—C14	173.7 (2)	C4'—C5'—C9'—C14'	−63.9 (3)
C4—C5—C9—C10	61.0 (3)	C6'—C5'—C9'—C14'	172.0 (2)
C6—C5—C9—C10	−176.1 (2)	C7'—C5'—C9'—C14'	56.3 (3)
C7—C5—C9—C10	−59.3 (3)	C14'—C9'—C10'—C11'	−57.3 (3)
C14—C9—C10—C11	−56.8 (3)	C5'—C9'—C10'—C11'	173.2 (2)
C5—C9—C10—C11	175.1 (2)	C9'—C10'—C11'—C12'	56.3 (3)
C9—C10—C11—C12	56.8 (3)	C10'—C11'—C12'—C13'	−55.8 (3)
C10—C11—C12—C13	−56.1 (3)	C11'—C12'—C13'—C14'	56.4 (3)
C11—C12—C13—C14	55.7 (3)	C12'—C13'—C14'—C9'	−57.0 (3)
C12—C13—C14—C9	−56.3 (3)	C10'—C9'—C14'—C13'	57.3 (3)
C10—C9—C14—C13	56.5 (3)	C5'—C9'—C14'—C13'	−174.5 (2)
C5—C9—C14—C13	−174.2 (2)	C9—C5—C7—C8	−173.8 (2)
C6'—N1'—C2'—O2'	178.2 (2)	C9'—C5'—C7'—C8'	−179.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.87 (2)	1.96 (2)	2.822 (3)	175 (3)
N3—H3···O2′	0.86 (2)	1.98 (2)	2.840 (3)	172 (3)
N1′—H1′···O4′^ii	0.85 (2)	2.02 (2)	2.865 (3)	171 (3)
N3′—H3′···O2	0.85 (2)	2.09 (2)	2.932 (3)	171 (3)

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

(Ib) 5-Cyclohexyl-5-ethylpyrimidine-2,4,6(1H,3H,5H)-trione

Crystal data

C12H18N2O3	Dx = 1.305 Mg m^−3
Mr = 238.28	Melting point: 462 K
Monoclinic, C2/c	Cu Kα radiation, λ = 1.5418 Å
a = 12.5071 (7) Å	Cell parameters from 4171 reflections
b = 21.0741 (9) Å	θ = 4.0–67.3°
c = 10.3310 (5) Å	µ = 0.77 mm^−1
β = 116.989 (5)°	T = 173 K
V = 2426.4 (2) Å^3	Prism, colourless
Z = 8	0.60 × 0.08 × 0.08 mm
F(000) = 1024

Data collection

Oxford Xcalibur diffractometer with Gemini Ultra Ruby CCD detector [OK?]	2188 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1897 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
Detector resolution: 10.3575 pixels mm^-1	θmax = 67.4°, θmin = 4.2°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −25→24
Tmin = 0.932, Tmax = 1.000	l = −12→11
6607 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.7034P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2188 reflections	Δρmax = 0.29 e Å^−3
164 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00111 (15)

Special details

Experimental. CrysAlisPro (Oxford Diffraction, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
O2	0.44099 (7)	0.07368 (4)	−0.13883 (9)	0.0313 (2)
O4	0.65981 (7)	0.06726 (4)	0.34585 (8)	0.0293 (2)
O6	0.84171 (7)	0.08917 (5)	0.03118 (9)	0.0344 (3)
N1	0.64283 (9)	0.07951 (5)	−0.05071 (11)	0.0246 (2)
H1	0.6315 (14)	0.0791 (7)	−0.1393 (19)	0.036 (4)*
N3	0.55393 (8)	0.07662 (5)	0.10429 (10)	0.0222 (2)
H3	0.4920 (14)	0.0726 (6)	0.1154 (15)	0.028 (4)*
C2	0.54014 (10)	0.07646 (5)	−0.03538 (12)	0.0218 (3)
C4	0.66090 (10)	0.07439 (5)	0.22940 (12)	0.0215 (3)
C5	0.77686 (10)	0.08310 (5)	0.21676 (12)	0.0229 (3)
C6	0.75865 (10)	0.08392 (5)	0.06019 (12)	0.0241 (3)
C7	0.86557 (10)	0.02881 (6)	0.29951 (12)	0.0259 (3)
H7A	0.9477	0.0426	0.3212	0.031*
H7B	0.8639	0.0221	0.3934	0.031*
C8	0.84039 (11)	−0.03426 (6)	0.21941 (14)	0.0323 (3)
H8A	0.7582	−0.0477	0.1937	0.049*
H8B	0.8970	−0.0663	0.2821	0.049*
H8C	0.8498	−0.0294	0.1308	0.049*
C9	0.83334 (11)	0.14932 (6)	0.28090 (13)	0.0294 (3)
H9	0.9047	0.1538	0.2623	0.035*
C10	0.88127 (14)	0.15489 (7)	0.44579 (15)	0.0421 (4)
H10A	0.8139	0.1522	0.4710	0.051*
H10B	0.9373	0.1195	0.4946	0.051*
C11	0.9462 (2)	0.21825 (9)	0.4979 (2)	0.0684 (6)
H11A	0.9734	0.2226	0.6036	0.082*
H11B	1.0180	0.2190	0.4810	0.082*
C12	0.8653 (2)	0.27382 (9)	0.4192 (2)	0.0776 (7)
H12A	0.9115	0.3138	0.4520	0.093*
H12B	0.7981	0.2758	0.4447	0.093*
C13	0.81515 (19)	0.26823 (8)	0.2552 (2)	0.0594 (5)
H3A	0.8813	0.2716	0.2280	0.071*
H3B	0.7583	0.3034	0.2077	0.071*
C14	0.75063 (14)	0.20474 (6)	0.20239 (18)	0.0428 (4)
H14A	0.6791	0.2035	0.2199	0.051*
H14B	0.7231	0.2007	0.0965	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0191 (4)	0.0515 (6)	0.0207 (4)	−0.0027 (4)	0.0069 (3)	−0.0022 (3)
O4	0.0211 (4)	0.0490 (5)	0.0200 (4)	0.0010 (4)	0.0113 (3)	0.0032 (3)
O6	0.0213 (4)	0.0601 (6)	0.0262 (4)	0.0023 (4)	0.0146 (4)	0.0049 (4)
N1	0.0204 (5)	0.0377 (6)	0.0170 (5)	0.0013 (4)	0.0096 (4)	0.0010 (4)
N3	0.0149 (5)	0.0328 (5)	0.0209 (5)	0.0003 (4)	0.0099 (4)	0.0009 (4)
C2	0.0199 (6)	0.0242 (6)	0.0214 (6)	0.0003 (4)	0.0095 (5)	−0.0005 (4)
C4	0.0191 (6)	0.0259 (6)	0.0205 (6)	0.0010 (4)	0.0098 (4)	0.0005 (4)
C5	0.0161 (5)	0.0338 (6)	0.0192 (6)	0.0003 (4)	0.0083 (4)	0.0011 (4)
C6	0.0196 (6)	0.0318 (6)	0.0221 (6)	0.0024 (4)	0.0106 (5)	0.0023 (4)
C7	0.0166 (5)	0.0396 (7)	0.0211 (6)	0.0031 (5)	0.0083 (4)	0.0035 (5)
C8	0.0244 (6)	0.0372 (7)	0.0355 (7)	0.0022 (5)	0.0137 (5)	0.0025 (5)
C9	0.0247 (6)	0.0368 (7)	0.0305 (6)	−0.0066 (5)	0.0158 (5)	−0.0036 (5)
C10	0.0479 (8)	0.0474 (8)	0.0338 (7)	−0.0158 (7)	0.0209 (6)	−0.0125 (6)
C11	0.0898 (14)	0.0702 (12)	0.0513 (10)	−0.0469 (11)	0.0374 (10)	−0.0285 (9)
C12	0.1261 (19)	0.0433 (10)	0.0931 (15)	−0.0387 (11)	0.0757 (15)	−0.0294 (10)
C13	0.0767 (12)	0.0370 (9)	0.0809 (12)	−0.0130 (8)	0.0499 (10)	−0.0039 (8)
C14	0.0423 (8)	0.0332 (7)	0.0584 (9)	−0.0018 (6)	0.0276 (7)	0.0015 (6)

Geometric parameters (Å, º)

O2—C2	1.2168 (14)	C8—H8C	0.9800
O4—C4	1.2186 (14)	C9—C14	1.5267 (19)
O6—C6	1.2098 (14)	C9—C10	1.5323 (17)
N1—C2	1.3651 (15)	C9—H9	1.0000
N1—C6	1.3832 (15)	C10—C11	1.528 (2)
N1—H1	0.860 (18)	C10—H10A	0.9900
N3—C2	1.3733 (15)	C10—H10B	0.9900
N3—C4	1.3759 (15)	C11—C12	1.520 (3)
N3—H3	0.838 (16)	C11—H11A	0.9900
C4—C5	1.5252 (15)	C11—H11B	0.9900
C5—C6	1.5278 (15)	C12—C13	1.521 (3)
C5—C7	1.5523 (15)	C12—H12A	0.9900
C5—C9	1.5687 (16)	C12—H12B	0.9900
C7—C8	1.5213 (18)	C13—C14	1.529 (2)
C7—H7A	0.9900	C13—H3A	0.9900
C7—H7B	0.9900	C13—H3B	0.9900
C8—H8A	0.9800	C14—H14A	0.9900
C8—H8B	0.9800	C14—H14B	0.9900
C2—N1—C6	126.43 (10)	C10—C9—C5	114.32 (10)
C2—N1—H1	114.4 (11)	C14—C9—H9	105.9
C6—N1—H1	119.1 (10)	C10—C9—H9	105.9
C2—N3—C4	126.29 (10)	C5—C9—H9	105.9
C2—N3—H3	117.4 (10)	C11—C10—C9	109.62 (12)
C4—N3—H3	115.7 (10)	C11—C10—H10A	109.7
O2—C2—N1	122.54 (10)	C9—C10—H10A	109.7
O2—C2—N3	121.00 (10)	C11—C10—H10B	109.7
N1—C2—N3	116.46 (10)	C9—C10—H10B	109.7
O4—C4—N3	119.33 (10)	H10A—C10—H10B	108.2
O4—C4—C5	122.44 (10)	C12—C11—C10	111.51 (16)
N3—C4—C5	118.20 (9)	C12—C11—H11A	109.3
C4—C5—C6	113.67 (9)	C10—C11—H11A	109.3
C4—C5—C7	109.51 (9)	C12—C11—H11B	109.3
C6—C5—C7	108.50 (9)	C10—C11—H11B	109.3
C4—C5—C9	109.53 (9)	H11A—C11—H11B	108.0
C6—C5—C9	105.03 (9)	C11—C12—C13	111.98 (15)
C7—C5—C9	110.53 (9)	C11—C12—H12A	109.2
O6—C6—N1	119.68 (10)	C13—C12—H12A	109.2
O6—C6—C5	122.08 (10)	C11—C12—H12B	109.2
N1—C6—C5	118.23 (10)	C13—C12—H12B	109.2
C8—C7—C5	115.12 (9)	H12A—C12—H12B	107.9
C8—C7—H7A	108.5	C12—C13—C14	110.45 (14)
C5—C7—H7A	108.5	C12—C13—H3A	109.6
C8—C7—H7B	108.5	C14—C13—H3A	109.6
C5—C7—H7B	108.5	C12—C13—H3B	109.6
H7A—C7—H7B	107.5	C14—C13—H3B	109.6
C7—C8—H8A	109.5	H3A—C13—H3B	108.1
C7—C8—H8B	109.5	C9—C14—C13	111.05 (13)
H8A—C8—H8B	109.5	C9—C14—H14A	109.4
C7—C8—H8C	109.5	C13—C14—H14A	109.4
H8A—C8—H8C	109.5	C9—C14—H14B	109.4
H8B—C8—H8C	109.5	C13—C14—H14B	109.4
C14—C9—C10	111.16 (11)	H14A—C14—H14B	108.0
C14—C9—C5	112.93 (10)
C8—C7—C5—C9	−160.77 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.86 (2)	2.05 (2)	2.8896 (13)	165 (2)
N3—H3···O4^ii	0.84 (2)	2.11 (2)	2.9497 (13)	176 (1)

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