Two polymorphs and the diethyl­ammonium salt of the barbiturate eldoral

Polymorph (Ia) of eldoral [5-ethyl-5-(piperidin-1-yl)barbituric acid or 5-ethyl-5-(piperidin-1-yl)-1,3-diazinane-2,4,6-trione], C₁₁H₁₇N₃O₃, displays a hydrogen-bonded layer structure parallel to (100). The piperidine N atom and the barbiturate carbonyl group in the 2-position are utilized in N-H...N and N-H...O=C hydrogen bonds, respectively. The structure of polymorph (Ib) contains pseudosymmetry elements. The two independent mol­ecules of (Ib) are connected via N-H...O=C(4/6-position) and N-H...N(piperidine) hydrogen bonds to give a chain structure in the [100] direction. The hydrogen-bonded layers, parallel to (010), formed in the salt di­ethyl­ammonium 5-ethyl-5-(piperidin-1-yl)barbiturate [or di­ethyl­ammonium 5-ethyl-2,4,6-trioxo-5-(piperidin-1-yl)-1,3-di­azinan-1-ide], C₄H₁₂N⁺·C₁₁H₁₆N₃O₃^-, (II), closely resemble the corresponding hydrogen-bonded structure in polymorph (Ia). Like many other 5,5-disubstituted derivatives of barbituric acid, polymorphs (Ia) and (Ib) contain the R₂²(8) N-H...O=C hydrogen-bond motif. However, the overall hydrogen-bonded chain and layer structures of (Ia) and (Ib) are unique because of the involvement of the hydrogen-bond acceptor function in the piperidine group.

S1. Comment

As part of a larger investigation of derivatives of barbituric acid (Gelbrich et al., 2007; Zencirci et al., 2009, 2010; Gelbrich et al., 2010a,b; Gelbrich, Zencirci et al., 2010; Gelbrich et al., 2011), we have studied two solid forms of 5-ethyl-5-piperidylbarbituric acid (I), CAS No. 509-87-5, and its diethylammonium salt, (II). Compound (I), also known as eldoral, has been marketed as a sedative and hypnotic drug since 1936 (Anders, 1954). According to Brandstätter-Kuhnert & Aepkers (1962), three distinct polymorphs of (I) grow from the melt. Their melting points were given as 490 K (form I), 483 K (form II; also the polymorph of the sublimate investigated by Fischer, 1939) and 477 K (form III). From sublimation experiments at 473 K we obtained polymorph (Ia) as long needles and polymorph (Ib) as blocks. Crystals of (Ia) and (Ib) also formed concomitantly from an ethanol solution. The results of thermomicroscopic and differential scanning calorimetry experiments confirmed (Ia) and (Ib) to be identical with forms I and II, respectively, studied by Brandstätter-Kuhnert & Aepkers (1962). The diethylammonium salt, (II), was obtained by slow evaporation of a solution of (I) in diethylamine.

As expected, the barbiturate entity adopts the same principle geometry (Fig. 1) in all three investigated crystal structures. The barbiturate ring is essentially planar and the piperidyl ring has a chair conformation. The ethyl conformation is such that the torsion angle C2···C5—C7—C8 is close to 0°, and C8—C7—C5—N9 is close to 180° (see Table 4).

The relative geometry of the five potential hydrogen-bond donor or acceptor functions of a barbiturate ring (two NH and three carbonyl groups, respectively) is inflexible. As a result, certain standard N—H···O═C bonded structures are frequently observed in 5,5-substituted derivatives of barbituric acid, usually one of four common chain structures (Gelbrich et al., 2011). In categorizing these structures, it is useful to distinguish between the two topologically equivalent carbonyl groups in the 4- and 6-positions on the one hand and the carbonyl group in the 2-position on the other. In the case of eldoral, (I), the piperidyl N atom can be utilized as an additional hydrogen-bond acceptor, which increases the number of feasible hydrogen-bond motifs.

The crystal structure of (Ia) contains one independent molecule (Fig. 1). Two barbiturate rings are N—H···O═C bonded to one another via a centrosymmetric R²₂(8) ring (Etter et al., 1990), and this interaction involves the C2 carbonyl group. One N—H···N bond links each barbiturate ring to the piperidyl group of a second molecule that is related to the first by a c-glide operation. Overall, the N—H···O═C and N—H···N interactions result in a corrugated layer structure parallel to (100) with p2₁/b layer symmetry. It contains larger R⁶₆(28) rings connecting four molecules (Fig. 2).

The asymmetric unit of the second polymorph, (Ib), consists of two molecules (denoted A and B, Fig. 3). The barbiturate rings of A- and B-type molecules are doubly N—H···O═C bonded to one another so that an R²₂(8) ring is formed. In contrast with the situation found in (Ia), one of the two equivalent C4/6 carbonyl groups in each molecule is utilized in this interaction (rather than the C2 group). The resulting `dimeric' N—H···O═C bonded unit is connected to two other units of the same kind via N—H···N(piperidyl) interactions, so that A- and B-type molecules are linked to one another as a consequence. An infinite hydrogen-bonded chain structure parallel to [100] is generated (Fig. 4), which contains centrosymmetric R₄⁴(18) rings that link four molecules together.

The nature of single-component crystal structures containing more than one (Z' > 1) independent molecule has been discussed by several authors in recent years (Steiner, 2000; Steed, 2003; Desiraju, 2007; Anderson & Steed, 2007; Bernstein, 2011). In order to gain a better understanding of such a crystal structure, it is useful to establish the geometric differences and commonalities between its Z' independent molecular environments, and thereby the presence (or absence) of local or peudo-symmetry elements in the crystal structure. For example, investigations with the computer program XPac (Gelbrich & Hursthouse, 2005) have revealed that local symmetry elements are present in a Z' = 4 form of carbamazepine (Gelbrich & Hursthouse, 2006), as well as in a Z' = 2 polymorph of sulfathiazole (Gelbrich et al., 2008).

An analogous XPac analysis for the structure of (Ib) reveals that its two complete molecular shells around A and B (each consisting of n = 15 molecules) exhibit roughly the same geometry, i.e. molecules A and B are related to one another by an approximate symmetry transformation. However, a relatively high XPac dissimilarity index x (Fabbiani et al., 2009) of 9.0 (calculated for n = 15) for the two independent molecular shells of A and B is obtained, which indicates that the deviation from proper symmetry relationships is considerable.

More details can be deduced from the diagram in Fig. 5. For each comparison between a pair of molecules in shell A with the matching pair in shell B, the individual dissimilarity parameter x_i is plotted against the corresponding distance parameter δ_d,i. The latter is the absolute difference of the distances between the two respective molecular centroids in the shells of A and B, and some of the differences are as high as 1 Å (data points encircled by a dashed line). However, a subset of data points (encircled by a dotted line) lies much closer to the origin than the rest, and it gives a combined x value of just 1.8 (for n = 5). These data points correspond to a shell fragment of five neighbouring molecules, which in turn represents the hydrogen-bonded chain shown in Fig. 4. Overall, the XPac results are consistent with an approximate C2/c pseudo-symmetry of (Ib), in which the pseudo-glide symmetry (perpendicular to [010]; glide vector parallel to [100]) between hydrogen-bonded A and B molecules is particularly well preserved.

Fig. 6 shows the asymmetric unit of the diethylammonium salt, (II). The NH group of the barbiturate ring is bonded to the piperidyl ring of the next molecule. This interaction alone results in an extended chain parallel to [100] (translation of 11.827 Å), as the two molecules are related by an a-glide plane perpendicular to [001] (Fig. 7). An XPac comparison reveals that it has the same geometry as the corresponding N—H···N bonded chain propagating along [001] (translation of 11.944 Å) in polymorph (Ia). The XPac dissimilarity index x for this one-dimensional supramolecular construct is 5.2 (for n = 2). The NH₂ group of the cation of (II) acts as a bridge between two anions, i.e. via an N—H···O═C bond to the C2 carbonyl group of the first anion and via an N—H···N bond to the 1-nitrogen of the second. Neighbouring anions are thereby doubly bridged so that a centrosymmetric R⁴₄(12) ring is formed. This interaction, in combination with the (anion)N—H···N(anion) bonds, results in a hydrogen-bonded layer which lies parallel to (001).

In Fig. 8, the hydrogen-bonded structures of (Ia), (Ib) and (II) are compared with those of two analogous 5,5-substituted barbituric acid derivatives with N—H···A bonds (A = hydrogen-bond acceptor), 3-oxocyclobarbital [Cambridge Structural Database (Allen, 2002) refcode BARCOX; Chentli-Benchikha et al., 1977) and bromo-meso-sarcosinuric acid (BMBARA10; Pascard-Billy, 1970). The barbiturate ring is represented as a hexagon, with NH groups drawn as arrows and the utilized hydrogen-bond acceptor sites as either circles (barbiturate carbonyl group), filled squares (5-substituted group, R) or open squares (deprotonated barbiturate N atom) (Figs. 8a and 8b). The close one-dimensional relationship between the hydrogen-bonded structures of (Ia) and (II) discussed above is apparent from Fig. 8(c). Moreover, the N—H···O═C R₂²(8) linkage between adjacent N—H···N(piperidyl) bonded chains in (Ia) is neatly substituted in (II) for two mutually opposite N···H—N—H···O bridges via a central cation. This similarity between (Ia) and (II) may also indicate a feasible transition mechanism for the removal of diethylamine from (II). Indeed, phase identification on the basis of FT–IR spectra has indicated that, upon solvent loss, the crystals of (II) transform exclusively into form (Ia).

For each structure, the configuration of utilized hydrogen-bond donor and acceptor sites is illustrated in Fig. 8(b). Polymorph (Ia) has the same configuration as BMBARA10, while (Ib) exhibits the same characteristics as BARCOX. However, quite different one- and two-dimensional hydrogen-bonded structures result from this within each of the two pairs. We note that there are only two recurring hydrogen-bonded motifs within this set. One is the C(5) chain motif found in (Ia) and (II), and the other is the R₂²(8) ring motif involving the A function of the C2 carbonyl group, which is present in (Ia) and in BMBARA10.

Related literature

For related literature, see: Allen (2002); Anders (1954); Anderson & Steed (2007); Bernstein (2011); Brandstätter-Kuhnert & Aepkers (1962); Chentli-Benchikha, Declercq, Germain, Van Meerssche, Bouché & Draguet-Brughmans (1977); Desiraju (2007); Etter et al. (1990); Fabbiani et al. (2009); Fischer (1939); Gelbrich & Hursthouse (2005, 2006); Gelbrich et al. (2007, 2008, 2010, 2010a, 2010b, 2011); Pascard-Billy (1970); Steed (2003); Steiner (2000); Zencirci et al. (2009, 2010).

S2. Experimental

Suitable crystals of (Ia) and (IIa) (Ib)? were obtained from an ethanol solution of the commercially available product [Source?]. Crystals of (II) were obtained in an NMR tube by evaporation of a dilute solution of (I) in diethylamine. The FT–IR spectra of (Ia) and (Ib) are available in the Supplementary materials. All XPac (Gelbrich & Hursthouse, 2005) calculations cited above were carried out with a complete set of 17 non-H atomic positions of the barbiturate molecule.

S3. Refinement

All H atoms were identified in a difference Fourier map. Methyl H atoms were idealized (C—H = 0.98 Å) and included as rigid groups allowed to rotate but not to tip, while methylene H atoms were positioned geometrically (C—H = 0.99 Å) and refined using a riding model. N-bound H atoms were refined with the N—H distances restrained to 0.88 (2) Å. The U_iso parameters of all H atoms were refined freely.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2003) for (Ia), (II); COLLECT (Nonius, 1998) for (Ib). Cell refinement: CrysAlis PRO (Oxford Diffraction, 2003) for (Ia), (II); SCALEPACK (Otwinowski & Minor, 1997) for (Ib). Data reduction: CrysAlis PRO (Oxford Diffraction, 2003) for (Ia), (II); DENZO and SCALEPACK (Otwinowski & Minor, 1997) for (Ib). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Bruker, 1998) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit of (Ia). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The hydrogen-bonded layer structure of (Ia). H, O and N atoms directly involved in N—H···O (dotted lines) or N—H···N (dashed lines) interactions are drawn as balls.
	Fig. 3. The asymmetric unit of (Ib). Displacement ellipsoids are drawn at the 50% probability level. [Is the primed molecule A or B?]
	Fig. 4. The hydrogen-bonded chain structure of (Ib), viewed along [010]. H, O and N atoms directly involved in N—H···O (dotted lines) or N—H···N (dashed lines) interactions are drawn as balls.
	Fig. 5. An XPac plot for the comparison of the geometrically similar shells of n = 15 molecules around molecules A and B of polymorph (Ib). A subset of data points for n = 5 (encircled by a dotted line) lies close to the origin (implying a high degree of similarity). It represents the hydrogen-bonded chain shown in Fig. 4, which has a noncrystallographic glide symmetry. A second subset of data points (encircled by a dashed line) indicates relatively large differences in the distances.
	Fig. 6. The asymmetric unit of (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 7. The two-dimensional hydrogen-bonded chain structure of (II). H, O and N atoms directly involved in O···H—N—H···O hydrogen bonds with the cation (dotted lines) or N—H···N(piperidine) interactions (dashed lines) are drawn as balls.
	Fig. 8. A comparison of hydrogen-bonded structures of 5,5-subsituted derivatives of barbituric acid with a single utilized hydrogen-bond acceptor function in a 5-substituted group. (a) Simplified representation of a barbiturate molecule, with N—H donor groups drawn as arrows and different types of hydrogen-bond acceptor (A) functions as either circles or squares. (b) The configuration of the utilized hydrogen-bond donor and acceptor functions in each molecule. (c) One-dimensional [(Ib) and BMBARA10] and two-dimensional [(Ia), (II) and BARCOX] extended hydrogen-bonded structures. Note the similarity between (Ia) and (II).

(Ia) 5-ethyl-5-(piperidin-1-yl)-1,3-diazinane-2,4,6-trione

Crystal data

C11H17N3O3	F(000) = 512
Mr = 239.28	Dx = 1.343 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 4404 reflections
a = 7.8761 (2) Å	θ = 3.5–67.2°
b = 12.7102 (4) Å	µ = 0.82 mm^−1
c = 11.9438 (3) Å	T = 173 K
β = 98.189 (3)°	Block, colourless
V = 1183.46 (6) Å^3	0.43 × 0.40 × 0.40 mm
Z = 4

Data collection

Oxford Xcalibur Ruby Gemini Ultra diffractometer	2111 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1900 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 10.3575 pixels mm^-1	θmax = 67.3°, θmin = 5.1°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003)	k = −15→14
Tmin = 0.719, Tmax = 0.735	l = −12→14
6405 measured reflections

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0823P)^2 + 0.3019P] where P = (Fo^2 + 2Fc^2)/3
2117 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.21 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

Special details

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

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

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

	x	y	z	Uiso*/Ueq
O2	0.36517 (13)	0.45037 (8)	0.58288 (8)	0.0228 (3)
O4	0.44593 (13)	0.31051 (8)	0.24714 (8)	0.0236 (3)
O6	0.16698 (14)	0.12057 (8)	0.51336 (8)	0.0243 (3)
N1	0.25601 (15)	0.28807 (10)	0.54236 (9)	0.0186 (3)
H1	0.226 (2)	0.2883 (15)	0.6090 (13)	0.029 (5)*
N3	0.41092 (15)	0.37557 (10)	0.41746 (10)	0.0189 (3)
H3	0.472 (3)	0.4313 (14)	0.4043 (17)	0.040 (5)*
N9	0.14381 (15)	0.18896 (9)	0.26946 (9)	0.0178 (3)
C2	0.34506 (17)	0.37528 (11)	0.51811 (11)	0.0182 (3)
C4	0.38837 (17)	0.29899 (11)	0.33517 (11)	0.0178 (3)
C5	0.29329 (17)	0.19810 (11)	0.36097 (11)	0.0175 (3)
C6	0.23423 (18)	0.19751 (11)	0.47846 (11)	0.0188 (3)
C7	0.42276 (18)	0.10750 (12)	0.35950 (12)	0.0208 (3)
H7A	0.3682	0.0409	0.3785	0.026 (4)*
H7B	0.4530	0.1004	0.2822	0.022 (4)*
C8	0.58668 (19)	0.12463 (13)	0.44271 (13)	0.0260 (4)
H8A	0.6449	0.1883	0.4216	0.035 (5)*
H8B	0.6627	0.0639	0.4405	0.035 (5)*
H8C	0.5575	0.1327	0.5193	0.033 (5)*
C10	0.06325 (19)	0.08342 (12)	0.25699 (12)	0.0231 (4)
H10A	0.0107	0.0665	0.3253	0.025 (4)*
H10B	0.1517	0.0297	0.2490	0.029 (5)*
C11	−0.0739 (2)	0.08171 (13)	0.15296 (13)	0.0283 (4)
H11A	−0.0192	0.0937	0.0844	0.025 (4)*
H11B	−0.1289	0.0115	0.1462	0.034 (5)*
C12	−0.2103 (2)	0.16542 (14)	0.15971 (14)	0.0298 (4)
H12A	−0.2906	0.1668	0.0880	0.035 (5)*
H12B	−0.2766	0.1481	0.2217	0.037 (5)*
C13	−0.12730 (19)	0.27285 (13)	0.18097 (13)	0.0267 (4)
H13A	−0.2155	0.3249	0.1946	0.035 (5)*
H13B	−0.0778	0.2953	0.1131	0.026 (4)*
C14	0.01334 (18)	0.26990 (12)	0.28261 (12)	0.0234 (4)
H14A	0.0694	0.3397	0.2920	0.027 (4)*
H14B	−0.0385	0.2549	0.3517	0.028 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0273 (6)	0.0227 (6)	0.0189 (5)	−0.0044 (4)	0.0051 (4)	−0.0040 (4)
O4	0.0255 (6)	0.0302 (6)	0.0161 (5)	−0.0054 (4)	0.0060 (4)	−0.0005 (4)
O6	0.0305 (6)	0.0223 (6)	0.0214 (5)	−0.0061 (4)	0.0079 (4)	0.0006 (4)
N1	0.0211 (6)	0.0209 (6)	0.0141 (6)	−0.0024 (5)	0.0036 (5)	−0.0001 (5)
N3	0.0209 (6)	0.0205 (7)	0.0158 (6)	−0.0039 (5)	0.0037 (5)	−0.0005 (5)
N9	0.0160 (6)	0.0196 (6)	0.0170 (6)	−0.0009 (5)	−0.0001 (5)	−0.0016 (4)
C2	0.0158 (6)	0.0217 (8)	0.0165 (7)	0.0006 (5)	−0.0003 (5)	0.0008 (5)
C5	0.0172 (7)	0.0202 (7)	0.0148 (7)	−0.0020 (6)	0.0013 (5)	−0.0011 (5)
C4	0.0147 (6)	0.0218 (7)	0.0162 (7)	0.0001 (5)	−0.0007 (5)	0.0004 (5)
C6	0.0170 (7)	0.0217 (7)	0.0172 (7)	0.0001 (5)	0.0006 (5)	0.0010 (5)
C7	0.0216 (7)	0.0210 (7)	0.0199 (7)	0.0018 (6)	0.0035 (6)	0.0001 (6)
C8	0.0232 (8)	0.0308 (9)	0.0233 (8)	0.0046 (6)	0.0007 (6)	0.0029 (6)
C10	0.0239 (8)	0.0211 (8)	0.0233 (7)	−0.0060 (6)	0.0001 (6)	0.0004 (6)
C11	0.0276 (8)	0.0288 (9)	0.0269 (8)	−0.0092 (7)	−0.0021 (6)	−0.0016 (6)
C12	0.0199 (7)	0.0409 (10)	0.0273 (8)	−0.0057 (7)	−0.0014 (6)	0.0018 (7)
C13	0.0191 (7)	0.0333 (9)	0.0268 (8)	0.0026 (6)	0.0000 (6)	0.0005 (7)
C14	0.0196 (7)	0.0264 (8)	0.0238 (7)	0.0023 (6)	0.0021 (6)	−0.0032 (6)

Geometric parameters (Å, º)

O2—C2	1.2246 (17)	C8—H8A	0.9800
O4—C4	1.2117 (17)	C8—H8B	0.9800
O6—C6	1.2139 (18)	C8—H8C	0.9800
N1—C2	1.3647 (18)	C10—C11	1.526 (2)
N1—C6	1.3782 (19)	C10—H10A	0.9900
N1—H1	0.862 (14)	C10—H10B	0.9900
N3—C2	1.3755 (18)	C11—C12	1.522 (2)
N3—C4	1.3767 (18)	C11—H11A	0.9900
N3—H3	0.881 (16)	C11—H11B	0.9900
N9—C14	1.4782 (18)	C12—C13	1.520 (2)
N9—C10	1.4824 (18)	C12—H12A	0.9900
N9—C5	1.4926 (17)	C12—H12B	0.9900
C5—C4	1.5381 (19)	C13—C14	1.523 (2)
C5—C7	1.5399 (19)	C13—H13A	0.9900
C5—C6	1.5400 (18)	C13—H13B	0.9900
C7—C8	1.529 (2)	C14—H14A	0.9900
C7—H7A	0.9900	C14—H14B	0.9900
C7—H7B	0.9900
C2—N1—C6	126.01 (12)	C7—C8—H8C	109.5
C2—N1—H1	114.2 (13)	H8A—C8—H8C	109.5
C6—N1—H1	119.0 (13)	H8B—C8—H8C	109.5
C2—N3—C4	126.56 (12)	N9—C10—C11	109.75 (12)
C2—N3—H3	116.1 (13)	N9—C10—H10A	109.7
C4—N3—H3	117.3 (13)	C11—C10—H10A	109.7
C14—N9—C10	110.27 (11)	N9—C10—H10B	109.7
C14—N9—C5	110.84 (10)	C11—C10—H10B	109.7
C10—N9—C5	115.19 (11)	H10A—C10—H10B	108.2
O2—C2—N1	121.54 (12)	C12—C11—C10	111.71 (13)
O2—C2—N3	121.27 (13)	C12—C11—H11A	109.3
N1—C2—N3	117.19 (12)	C10—C11—H11A	109.3
N9—C5—C4	105.90 (10)	C12—C11—H11B	109.3
N9—C5—C7	112.83 (11)	C10—C11—H11B	109.3
C4—C5—C7	106.21 (11)	H11A—C11—H11B	107.9
N9—C5—C6	110.96 (10)	C13—C12—C11	110.29 (12)
C4—C5—C6	113.92 (11)	C13—C12—H12A	109.6
C7—C5—C6	107.05 (11)	C11—C12—H12A	109.6
O4—C4—N3	120.52 (13)	C13—C12—H12B	109.6
O4—C4—C5	121.84 (12)	C11—C12—H12B	109.6
N3—C4—C5	117.61 (12)	H12A—C12—H12B	108.1
O6—C6—N1	120.57 (12)	C12—C13—C14	110.97 (13)
O6—C6—C5	121.34 (12)	C12—C13—H13A	109.4
N1—C6—C5	118.08 (12)	C14—C13—H13A	109.4
C8—C7—C5	112.67 (12)	C12—C13—H13B	109.4
C8—C7—H7A	109.1	C14—C13—H13B	109.4
C5—C7—H7A	109.1	H13A—C13—H13B	108.0
C8—C7—H7B	109.1	N9—C14—C13	111.72 (12)
C5—C7—H7B	109.1	N9—C14—H14A	109.3
H7A—C7—H7B	107.8	C13—C14—H14A	109.3
C7—C8—H8A	109.5	N9—C14—H14B	109.3
C7—C8—H8B	109.5	C13—C14—H14B	109.3
H8A—C8—H8B	109.5	H14A—C14—H14B	107.9
C2—C5—C7—C8	−4.38 (16)	C8—C7—C5—N9	172.30 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N9^i	0.86 (1)	2.13 (2)	2.9843 (16)	172 (2)
N3—H3···O2^ii	0.88 (2)	1.97 (2)	2.8295 (16)	165 (2)

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

(Ib) 5-ethyl-5-(piperidin-1-yl)-1,3-diazinane-2,4,6-trione

Crystal data

C11H17N3O3	F(000) = 1024
Mr = 239.28	Dx = 1.331 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 17714 reflections
a = 11.9311 (3) Å	θ = 2.9–26.0°
b = 15.9858 (4) Å	µ = 0.10 mm^−1
c = 13.0768 (3) Å	T = 120 K
β = 106.799 (1)°	Needle, colourless
V = 2387.68 (10) Å^3	0.25 × 0.04 × 0.04 mm
Z = 8

Data collection

Bruker Nonius Roper CCD camera on κ-goniostat diffractometer	4211 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 9.091 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ and ω scans	h = −12→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −18→19
Tmin = 0.976, Tmax = 0.996	l = −15→15
20817 measured reflections

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)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0304P)^2 + 4.2383P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4211 reflections	Δρmax = 0.30 e Å^−3
356 parameters	Δρmin = −0.25 e Å^−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (7)

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
O2	0.58310 (16)	−0.08070 (12)	0.04977 (15)	0.0249 (5)
O4	0.24412 (15)	−0.06590 (11)	0.13663 (14)	0.0196 (4)
O6	0.60661 (16)	0.01909 (12)	0.37828 (14)	0.0240 (5)
N1	0.59280 (19)	−0.02967 (14)	0.21411 (17)	0.0185 (5)
H1	0.6704 (16)	−0.0258 (17)	0.229 (2)	0.020 (7)*
N3	0.41502 (19)	−0.07521 (14)	0.09745 (17)	0.0188 (5)
H3	0.378 (3)	−0.0905 (18)	0.0315 (16)	0.029 (8)*
N9	0.35583 (18)	0.07015 (13)	0.26831 (17)	0.0174 (5)
C2	0.5341 (2)	−0.06227 (16)	0.1158 (2)	0.0178 (6)
C4	0.3496 (2)	−0.05345 (15)	0.1629 (2)	0.0167 (6)
C5	0.4111 (2)	−0.01423 (16)	0.2716 (2)	0.0170 (6)
C6	0.5444 (2)	−0.00695 (16)	0.2936 (2)	0.0175 (6)
C7	0.3875 (2)	−0.07105 (16)	0.3582 (2)	0.0184 (6)
H7A	0.4230	−0.0456	0.4292	0.029 (8)*
H7B	0.3019	−0.0748	0.3471	0.012 (6)*
C8	0.4370 (2)	−0.15919 (17)	0.3567 (2)	0.0235 (6)
H8A	0.4023	−0.1846	0.2864	0.031 (8)*
H8B	0.4182	−0.1934	0.4118	0.028 (8)*
H8C	0.5222	−0.1560	0.3709	0.030 (8)*
C10	0.3797 (2)	0.11192 (17)	0.3738 (2)	0.0215 (6)
H10A	0.4650	0.1212	0.4037	0.012 (6)*
H10B	0.3537	0.0754	0.4236	0.019 (7)*
C11	0.3158 (2)	0.19551 (17)	0.3630 (2)	0.0249 (6)
H11A	0.2303	0.1857	0.3391	0.019 (7)*
H11B	0.3353	0.2234	0.4336	0.040 (9)*
C12	0.3496 (3)	0.25213 (18)	0.2836 (2)	0.0288 (7)
H12A	0.4337	0.2666	0.3105	0.029 (8)*
H12B	0.3037	0.3046	0.2747	0.041 (9)*
C13	0.3257 (3)	0.20751 (17)	0.1768 (2)	0.0255 (6)
H13A	0.3513	0.2432	0.1259	0.019 (7)*
H13B	0.2405	0.1975	0.1471	0.012 (6)*
C14	0.3906 (2)	0.12458 (17)	0.1905 (2)	0.0234 (6)
H14A	0.3731	0.0958	0.1206	0.023 (8)*
H14B	0.4760	0.1350	0.2158	0.023 (7)*
O2'	1.07255 (17)	0.09236 (13)	0.02602 (15)	0.0290 (5)
O4'	0.73722 (15)	0.08890 (11)	0.11944 (14)	0.0207 (4)
O6'	1.10597 (16)	0.02770 (12)	0.36973 (14)	0.0231 (4)
N1'	1.08721 (19)	0.06082 (14)	0.19877 (17)	0.0191 (5)
H1'	1.1649 (16)	0.0575 (17)	0.212 (2)	0.017 (7)*
N3'	0.90611 (19)	0.09109 (14)	0.07617 (17)	0.0201 (5)
H3'	0.867 (2)	0.0961 (17)	0.0095 (15)	0.018 (7)*
N9'	0.85632 (19)	−0.03070 (13)	0.27545 (17)	0.0175 (5)
C2'	1.0258 (2)	0.08185 (17)	0.0960 (2)	0.0201 (6)
C4'	0.8430 (2)	0.07893 (15)	0.1466 (2)	0.0162 (6)
C5'	0.9080 (2)	0.05192 (16)	0.2611 (2)	0.0166 (6)
C6'	1.0416 (2)	0.04569 (15)	0.2816 (2)	0.0179 (6)
C7'	0.8853 (2)	0.11938 (16)	0.3364 (2)	0.0196 (6)
H7'1	0.7999	0.1241	0.3254	0.023 (7)*
H7'2	0.9219	0.1018	0.4112	0.021 (7)*
C8'	0.9335 (3)	0.20529 (17)	0.3188 (2)	0.0249 (6)
H8'1	1.0181	0.2011	0.3294	0.016 (7)*
H8'2	0.9184	0.2454	0.3700	0.042 (10)*
H8'3	0.8950	0.2243	0.2459	0.033 (9)*
C10'	0.8829 (2)	−0.05835 (18)	0.3883 (2)	0.0237 (6)
H10C	0.8548	−0.0157	0.4299	0.038 (9)*
H10D	0.9687	−0.0638	0.4194	0.026 (8)*
C11'	0.8244 (3)	−0.14213 (18)	0.3958 (2)	0.0276 (7)
H11C	0.8460	−0.1604	0.4713	0.034 (9)*
H11D	0.7383	−0.1352	0.3708	0.022 (7)*
C12'	0.8611 (3)	−0.20901 (18)	0.3286 (3)	0.0313 (7)
H12C	0.9460	−0.2204	0.3577	0.035 (9)*
H12D	0.8181	−0.2616	0.3309	0.037 (9)*
C13'	0.8343 (3)	−0.17848 (17)	0.2145 (2)	0.0270 (7)
H13C	0.7486	−0.1727	0.1834	0.011 (6)*
H13D	0.8625	−0.2201	0.1715	0.023 (7)*
C14'	0.8929 (2)	−0.09464 (17)	0.2097 (2)	0.0235 (6)
H14C	0.9790	−0.1016	0.2355	0.022 (7)*
H14D	0.8724	−0.0753	0.1346	0.023 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0222 (10)	0.0340 (11)	0.0205 (10)	0.0023 (9)	0.0093 (8)	−0.0018 (8)
O4	0.0156 (10)	0.0253 (10)	0.0169 (9)	0.0002 (8)	0.0032 (7)	0.0011 (7)
O6	0.0186 (10)	0.0309 (11)	0.0203 (10)	−0.0005 (8)	0.0020 (8)	−0.0064 (8)
N1	0.0136 (12)	0.0211 (12)	0.0204 (12)	−0.0009 (9)	0.0043 (9)	0.0003 (9)
N3	0.0185 (12)	0.0224 (12)	0.0144 (11)	−0.0005 (9)	0.0031 (9)	−0.0031 (9)
N9	0.0162 (11)	0.0191 (12)	0.0174 (11)	0.0015 (9)	0.0054 (9)	−0.0015 (9)
C2	0.0189 (14)	0.0195 (14)	0.0142 (13)	0.0029 (11)	0.0036 (11)	0.0012 (10)
C4	0.0153 (14)	0.0151 (13)	0.0191 (13)	0.0008 (10)	0.0043 (11)	0.0020 (10)
C5	0.0168 (14)	0.0171 (14)	0.0171 (13)	0.0005 (10)	0.0052 (11)	−0.0011 (10)
C6	0.0202 (14)	0.0139 (13)	0.0188 (14)	0.0006 (11)	0.0061 (11)	−0.0004 (10)
C7	0.0188 (14)	0.0185 (14)	0.0183 (13)	0.0003 (11)	0.0059 (11)	0.0011 (10)
C8	0.0239 (15)	0.0225 (15)	0.0217 (14)	−0.0018 (12)	0.0028 (12)	0.0026 (12)
C10	0.0210 (14)	0.0208 (14)	0.0221 (14)	−0.0018 (11)	0.0051 (11)	−0.0044 (11)
C11	0.0214 (15)	0.0230 (15)	0.0299 (16)	0.0007 (12)	0.0068 (12)	−0.0089 (12)
C12	0.0222 (16)	0.0186 (15)	0.0443 (18)	0.0021 (12)	0.0076 (14)	−0.0021 (13)
C13	0.0220 (15)	0.0220 (15)	0.0340 (16)	0.0015 (12)	0.0106 (13)	0.0077 (12)
C14	0.0253 (15)	0.0218 (15)	0.0254 (15)	0.0021 (12)	0.0110 (12)	0.0018 (12)
O2'	0.0213 (10)	0.0461 (13)	0.0209 (10)	−0.0012 (9)	0.0081 (8)	0.0033 (9)
O4'	0.0170 (10)	0.0255 (11)	0.0189 (9)	0.0008 (8)	0.0042 (8)	−0.0009 (8)
O6'	0.0164 (10)	0.0322 (11)	0.0183 (10)	−0.0005 (8)	0.0011 (8)	0.0032 (8)
N1'	0.0126 (12)	0.0260 (13)	0.0177 (12)	0.0007 (9)	0.0030 (9)	0.0001 (9)
N3'	0.0168 (12)	0.0279 (13)	0.0141 (11)	−0.0018 (10)	0.0018 (9)	0.0004 (10)
N9'	0.0181 (12)	0.0184 (12)	0.0164 (11)	−0.0015 (9)	0.0057 (9)	−0.0020 (9)
C2'	0.0202 (14)	0.0202 (14)	0.0212 (14)	−0.0026 (11)	0.0081 (12)	−0.0016 (11)
C4'	0.0172 (14)	0.0141 (13)	0.0166 (13)	−0.0013 (10)	0.0040 (11)	−0.0019 (10)
C5'	0.0157 (13)	0.0191 (14)	0.0159 (13)	−0.0027 (10)	0.0058 (10)	−0.0014 (10)
C6'	0.0210 (14)	0.0128 (13)	0.0202 (14)	−0.0004 (11)	0.0063 (12)	−0.0022 (10)
C7'	0.0170 (14)	0.0220 (14)	0.0199 (13)	0.0017 (11)	0.0055 (11)	0.0001 (11)
C8'	0.0221 (15)	0.0217 (15)	0.0287 (16)	−0.0013 (12)	0.0038 (12)	−0.0014 (12)
C10'	0.0236 (15)	0.0282 (16)	0.0174 (14)	−0.0024 (12)	0.0027 (11)	0.0038 (11)
C11'	0.0228 (15)	0.0291 (16)	0.0280 (16)	0.0001 (12)	0.0029 (12)	0.0107 (13)
C12'	0.0211 (15)	0.0225 (16)	0.0478 (19)	0.0013 (12)	0.0060 (14)	0.0084 (13)
C13'	0.0235 (15)	0.0199 (15)	0.0382 (17)	−0.0001 (12)	0.0099 (13)	−0.0030 (12)
C14'	0.0215 (15)	0.0225 (15)	0.0283 (15)	−0.0016 (11)	0.0103 (12)	−0.0052 (12)

Geometric parameters (Å, º)

O2—C2	1.211 (3)	O2'—C2'	1.213 (3)
O4—C4	1.221 (3)	O4'—C4'	1.218 (3)
O6—C6	1.214 (3)	O6'—C6'	1.220 (3)
N1—C6	1.376 (3)	N1'—C6'	1.368 (3)
N1—C2	1.376 (3)	N1'—C2'	1.374 (3)
N1—H1	0.892 (17)	N1'—H1'	0.894 (17)
N3—C4	1.360 (3)	N3'—C4'	1.361 (3)
N3—C2	1.386 (3)	N3'—C2'	1.383 (3)
N3—H3	0.883 (18)	N3'—H3'	0.867 (17)
N9—C10	1.484 (3)	N9'—C14'	1.480 (3)
N9—C14	1.486 (3)	N9'—C10'	1.484 (3)
N9—C5	1.497 (3)	N9'—C5'	1.492 (3)
C4—C5	1.533 (3)	C4'—C5'	1.537 (3)
C5—C6	1.536 (4)	C5'—C7'	1.536 (4)
C5—C7	1.540 (3)	C5'—C6'	1.541 (4)
C7—C8	1.530 (4)	C7'—C8'	1.532 (4)
C7—H7A	0.9900	C7'—H7'1	0.9900
C7—H7B	0.9900	C7'—H7'2	0.9900
C8—H8A	0.9800	C8'—H8'1	0.9800
C8—H8B	0.9800	C8'—H8'2	0.9800
C8—H8C	0.9800	C8'—H8'3	0.9800
C10—C11	1.525 (4)	C10'—C11'	1.527 (4)
C10—H10A	0.9900	C10'—H10C	0.9900
C10—H10B	0.9900	C10'—H10D	0.9900
C11—C12	1.518 (4)	C11'—C12'	1.527 (4)
C11—H11A	0.9900	C11'—H11C	0.9900
C11—H11B	0.9900	C11'—H11D	0.9900
C12—C13	1.520 (4)	C12'—C13'	1.514 (4)
C12—H12A	0.9900	C12'—H12C	0.9900
C12—H12B	0.9900	C12'—H12D	0.9900
C13—C14	1.520 (4)	C13'—C14'	1.521 (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
C6—N1—C2	126.5 (2)	C6'—N1'—C2'	126.6 (2)
C6—N1—H1	117.1 (18)	C6'—N1'—H1'	117.6 (18)
C2—N1—H1	116.3 (18)	C2'—N1'—H1'	115.8 (18)
C4—N3—C2	126.8 (2)	C4'—N3'—C2'	126.9 (2)
C4—N3—H3	118 (2)	C4'—N3'—H3'	116.5 (19)
C2—N3—H3	114 (2)	C2'—N3'—H3'	115.5 (19)
C10—N9—C14	110.9 (2)	C14'—N9'—C10'	111.0 (2)
C10—N9—C5	114.5 (2)	C14'—N9'—C5'	109.6 (2)
C14—N9—C5	109.84 (19)	C10'—N9'—C5'	114.3 (2)
O2—C2—N1	122.5 (2)	O2'—C2'—N1'	122.7 (3)
O2—C2—N3	121.5 (2)	O2'—C2'—N3'	121.3 (2)
N1—C2—N3	115.9 (2)	N1'—C2'—N3'	116.1 (2)
O4—C4—N3	120.9 (2)	O4'—C4'—N3'	120.9 (2)
O4—C4—C5	120.4 (2)	O4'—C4'—C5'	120.6 (2)
N3—C4—C5	118.7 (2)	N3'—C4'—C5'	118.5 (2)
N9—C5—C4	104.6 (2)	N9'—C5'—C7'	112.7 (2)
N9—C5—C6	111.2 (2)	N9'—C5'—C4'	105.09 (19)
C4—C5—C6	113.4 (2)	C7'—C5'—C4'	107.1 (2)
N9—C5—C7	112.3 (2)	N9'—C5'—C6'	111.4 (2)
C4—C5—C7	107.5 (2)	C7'—C5'—C6'	107.4 (2)
C6—C5—C7	107.9 (2)	C4'—C5'—C6'	113.2 (2)
O6—C6—N1	120.0 (2)	O6'—C6'—N1'	120.2 (2)
O6—C6—C5	121.6 (2)	O6'—C6'—C5'	121.1 (2)
N1—C6—C5	118.4 (2)	N1'—C6'—C5'	118.6 (2)
C8—C7—C5	112.3 (2)	C8'—C7'—C5'	113.0 (2)
C8—C7—H7A	109.1	C8'—C7'—H7'1	109.0
C5—C7—H7A	109.1	C5'—C7'—H7'1	109.0
C8—C7—H7B	109.1	C8'—C7'—H7'2	109.0
C5—C7—H7B	109.1	C5'—C7'—H7'2	109.0
H7A—C7—H7B	107.9	H7'1—C7'—H7'2	107.8
C7—C8—H8A	109.5	C7'—C8'—H8'1	109.5
C7—C8—H8B	109.5	C7'—C8'—H8'2	109.5
H8A—C8—H8B	109.5	H8'1—C8'—H8'2	109.5
C7—C8—H8C	109.5	C7'—C8'—H8'3	109.5
H8A—C8—H8C	109.5	H8'1—C8'—H8'3	109.5
H8B—C8—H8C	109.5	H8'2—C8'—H8'3	109.5
N9—C10—C11	110.6 (2)	N9'—C10'—C11'	110.8 (2)
N9—C10—H10A	109.5	N9'—C10'—H10C	109.5
C11—C10—H10A	109.5	C11'—C10'—H10C	109.5
N9—C10—H10B	109.5	N9'—C10'—H10D	109.5
C11—C10—H10B	109.5	C11'—C10'—H10D	109.5
H10A—C10—H10B	108.1	H10C—C10'—H10D	108.1
C12—C11—C10	111.2 (2)	C12'—C11'—C10'	111.4 (2)
C12—C11—H11A	109.4	C12'—C11'—H11C	109.4
C10—C11—H11A	109.4	C10'—C11'—H11C	109.4
C12—C11—H11B	109.4	C12'—C11'—H11D	109.4
C10—C11—H11B	109.4	C10'—C11'—H11D	109.4
H11A—C11—H11B	108.0	H11C—C11'—H11D	108.0
C11—C12—C13	109.4 (2)	C13'—C12'—C11'	109.1 (2)
C11—C12—H12A	109.8	C13'—C12'—H12C	109.9
C13—C12—H12A	109.8	C11'—C12'—H12C	109.9
C11—C12—H12B	109.8	C13'—C12'—H12D	109.9
C13—C12—H12B	109.8	C11'—C12'—H12D	109.9
H12A—C12—H12B	108.2	H12C—C12'—H12D	108.3
C12—C13—C14	110.3 (2)	C12'—C13'—C14'	110.8 (2)
C12—C13—H13A	109.6	C12'—C13'—H13C	109.5
C14—C13—H13A	109.6	C14'—C13'—H13C	109.5
C12—C13—H13B	109.6	C12'—C13'—H13D	109.5
C14—C13—H13B	109.6	C14'—C13'—H13D	109.5
H13A—C13—H13B	108.1	H13C—C13'—H13D	108.1
N9—C14—C13	111.0 (2)	N9'—C14'—C13'	111.6 (2)
N9—C14—H14A	109.4	N9'—C14'—H14C	109.3
C13—C14—H14A	109.4	C13'—C14'—H14C	109.3
N9—C14—H14B	109.4	N9'—C14'—H14D	109.3
C13—C14—H14B	109.4	C13'—C14'—H14D	109.3
H14A—C14—H14B	108.0	H14C—C14'—H14D	108.0
C2—C5—C7—C8	0.5 (3)	C2'—C5'—C7'—C8'	−1.4 (3)
C8—C7—C5—N9	176.2 (2)	C8'—C7'—C5'—N9'	−177.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N9′	0.89 (2)	2.13 (2)	3.012 (3)	173 (3)
N3—H3···O4′^i	0.88 (2)	2.05 (2)	2.901 (3)	161 (3)
N1′—H1′···N9^ii	0.89 (2)	2.19 (2)	3.072 (3)	168 (2)
N3′—H3′···O4^i	0.87 (2)	2.04 (2)	2.870 (3)	159 (3)

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

(II) diethylammonium 5-ethyl-2,4,6-trioxo-5-(piperidin-1-yl)-1,3-diazinan-1-ide

Crystal data

C4H12N^+·C11H16N3O3^−	F(000) = 1360
Mr = 312.41	Dx = 1.162 Mg m^−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 13761 reflections
a = 11.8270 (3) Å	θ = 3.6–67.3°
b = 16.1719 (4) Å	µ = 0.67 mm^−1
c = 18.6774 (5) Å	T = 173 K
V = 3572.35 (16) Å^3	Block, colourless
Z = 8	0.20 × 0.15 × 0.15 mm

Data collection

Oxford Xcalibur Ruby Gemini Ultra diffractometer	3209 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2921 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.034
Detector resolution: 10.3575 pixels mm^-1	θmax = 67.4°, θmin = 5.2°
ω scans	h = −14→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2003)	k = −17→19
Tmin = 0.880, Tmax = 1.000	l = −22→22
25972 measured reflections

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0561P)^2 + 0.9238P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3209 reflections	Δρmax = 0.34 e Å^−3
240 parameters	Δρmin = −0.21 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00061 (11)

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
O2	0.36833 (7)	0.04134 (6)	0.10261 (4)	0.0365 (2)
O4	0.69794 (7)	−0.01818 (5)	0.21295 (4)	0.0298 (2)
O6	0.39495 (7)	0.11518 (5)	0.33359 (4)	0.0267 (2)
N1	0.38581 (8)	0.07638 (6)	0.21795 (5)	0.0238 (2)
H1	0.3141 (11)	0.0885 (9)	0.2167 (8)	0.036 (4)*
N3	0.53698 (8)	0.01186 (6)	0.15455 (5)	0.0260 (2)
N9	0.64215 (7)	0.12923 (5)	0.29358 (5)	0.0202 (2)
C2	0.43096 (10)	0.04239 (7)	0.15588 (6)	0.0246 (3)
C4	0.60384 (9)	0.01384 (6)	0.21349 (6)	0.0224 (2)
C5	0.56512 (9)	0.05679 (6)	0.28353 (5)	0.0198 (2)
C6	0.44116 (9)	0.08508 (6)	0.28135 (6)	0.0208 (2)
C7	0.57601 (10)	−0.00660 (7)	0.34462 (6)	0.0241 (3)
H7A	0.6567	−0.0209	0.3512	0.029 (3)*
H7B	0.5484	0.0186	0.3897	0.029 (3)*
C8	0.50883 (11)	−0.08552 (8)	0.32946 (8)	0.0350 (3)
H8A	0.4294	−0.0714	0.3208	0.046 (4)*
H8B	0.5140	−0.1227	0.3708	0.049 (4)*
H8C	0.5400	−0.1131	0.2871	0.044 (4)*
C10	0.63744 (10)	0.16675 (7)	0.36570 (6)	0.0272 (3)
H10A	0.6535	0.1240	0.4022	0.032 (4)*
H10B	0.5605	0.1886	0.3746	0.029 (3)*
C11	0.72330 (11)	0.23676 (8)	0.37252 (8)	0.0373 (3)
H11A	0.7171	0.2619	0.4207	0.044 (4)*
H11B	0.8006	0.2141	0.3674	0.041 (4)*
C12	0.70400 (12)	0.30274 (8)	0.31597 (9)	0.0413 (3)
H12A	0.6296	0.3294	0.3235	0.045 (4)*
H12B	0.7633	0.3458	0.3195	0.053 (5)*
C13	0.70774 (11)	0.26256 (7)	0.24253 (8)	0.0361 (3)
H13A	0.7846	0.2408	0.2335	0.038 (4)*
H13B	0.6907	0.3044	0.2054	0.045 (4)*
C14	0.62223 (10)	0.19230 (7)	0.23768 (6)	0.0282 (3)
H14A	0.5449	0.2150	0.2430	0.031 (3)*
H14B	0.6276	0.1661	0.1899	0.031 (3)*
N1S	0.66644 (9)	−0.04274 (6)	0.04136 (5)	0.0259 (2)
H1SA	0.6156 (12)	−0.0228 (9)	0.0751 (8)	0.039 (4)*
H1SB	0.6371 (12)	−0.0403 (9)	−0.0033 (7)	0.035 (4)*
C1S	0.69010 (13)	−0.13007 (8)	0.05976 (8)	0.0408 (3)
H1S3	0.7188	−0.1334	0.1095	0.067 (6)*
H1S4	0.7492	−0.1520	0.0274	0.044 (4)*
C2S	0.58521 (19)	−0.18141 (11)	0.05292 (14)	0.0784 (7)
H2S1	0.5252	−0.1575	0.0826	0.091 (7)*
H2S2	0.6010	−0.2380	0.0689	0.096 (7)*
H2S3	0.5609	−0.1823	0.0028	0.129 (12)*
C3S	0.76908 (11)	0.01015 (9)	0.04231 (7)	0.0364 (3)
H3S1	0.8270	−0.0137	0.0101	0.049 (4)*
H3S2	0.8007	0.0116	0.0914	0.040 (4)*
C4S	0.74151 (18)	0.09649 (10)	0.01856 (9)	0.0592 (5)
H4S1	0.7129	0.0953	−0.0307	0.069 (6)*
H4S2	0.8099	0.1307	0.0207	0.090 (7)*
H4S3	0.6837	0.1199	0.0502	0.066 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0290 (5)	0.0592 (6)	0.0213 (4)	0.0039 (4)	−0.0060 (3)	−0.0060 (4)
O4	0.0222 (4)	0.0362 (5)	0.0308 (5)	0.0062 (3)	0.0006 (3)	−0.0078 (3)
O6	0.0224 (4)	0.0360 (4)	0.0218 (4)	0.0013 (3)	0.0033 (3)	−0.0055 (3)
N1	0.0166 (5)	0.0337 (5)	0.0211 (5)	0.0015 (4)	−0.0010 (4)	−0.0026 (4)
N3	0.0237 (5)	0.0333 (5)	0.0212 (5)	0.0022 (4)	0.0005 (4)	−0.0059 (4)
N9	0.0191 (4)	0.0202 (4)	0.0214 (5)	−0.0010 (3)	−0.0005 (3)	−0.0001 (3)
C2	0.0233 (6)	0.0309 (6)	0.0195 (5)	−0.0019 (4)	0.0002 (4)	−0.0018 (4)
C4	0.0213 (5)	0.0229 (5)	0.0230 (6)	−0.0010 (4)	0.0021 (4)	−0.0025 (4)
C5	0.0178 (5)	0.0223 (5)	0.0193 (5)	−0.0011 (4)	−0.0001 (4)	−0.0014 (4)
C6	0.0192 (5)	0.0230 (5)	0.0203 (5)	−0.0021 (4)	0.0011 (4)	0.0001 (4)
C7	0.0262 (6)	0.0230 (5)	0.0232 (5)	−0.0001 (4)	−0.0002 (4)	0.0021 (4)
C8	0.0361 (7)	0.0261 (6)	0.0428 (7)	−0.0056 (5)	0.0022 (6)	0.0031 (5)
C10	0.0293 (6)	0.0259 (6)	0.0265 (6)	−0.0018 (5)	−0.0009 (5)	−0.0057 (5)
C11	0.0356 (7)	0.0310 (6)	0.0454 (8)	−0.0060 (5)	−0.0037 (6)	−0.0114 (6)
C12	0.0377 (7)	0.0232 (6)	0.0630 (9)	−0.0075 (5)	0.0055 (7)	−0.0050 (6)
C13	0.0328 (6)	0.0252 (6)	0.0503 (8)	−0.0014 (5)	0.0095 (6)	0.0081 (5)
C14	0.0289 (6)	0.0254 (6)	0.0302 (6)	0.0006 (5)	0.0008 (5)	0.0062 (5)
N1S	0.0285 (5)	0.0296 (5)	0.0196 (5)	0.0025 (4)	0.0004 (4)	−0.0022 (4)
C1S	0.0560 (9)	0.0314 (7)	0.0351 (7)	0.0095 (6)	0.0108 (6)	0.0021 (5)
C2S	0.0853 (14)	0.0378 (9)	0.1121 (19)	−0.0165 (9)	0.0529 (14)	−0.0110 (10)
C3S	0.0343 (7)	0.0473 (8)	0.0276 (6)	−0.0096 (6)	−0.0006 (5)	−0.0024 (5)
C4S	0.0902 (13)	0.0427 (8)	0.0448 (9)	−0.0235 (9)	−0.0093 (9)	0.0048 (7)

Geometric parameters (Å, º)

O2—C2	1.2406 (14)	C11—H11B	0.9900
O4—C4	1.2275 (14)	C12—C13	1.518 (2)
O6—C6	1.2198 (13)	C12—H12A	0.9900
N1—C6	1.3603 (14)	C12—H12B	0.9900
N1—C2	1.3896 (14)	C13—C14	1.5238 (16)
N1—H1	0.871 (13)	C13—H13A	0.9900
N3—C2	1.3479 (15)	C13—H13B	0.9900
N3—C4	1.3558 (14)	C14—H14A	0.9900
N9—C10	1.4784 (14)	C14—H14B	0.9900
N9—C14	1.4784 (14)	N1S—C1S	1.4801 (16)
N9—C5	1.4959 (13)	N1S—C3S	1.4852 (16)
C4—C5	1.5503 (14)	N1S—H1SA	0.928 (13)
C5—C6	1.5364 (15)	N1S—H1SB	0.904 (13)
C5—C7	1.5393 (15)	C1S—C2S	1.498 (2)
C7—C8	1.5298 (16)	C1S—H1S3	0.9900
C7—H7A	0.9900	C1S—H1S4	0.9900
C7—H7B	0.9900	C2S—H2S1	0.9800
C8—H8A	0.9800	C2S—H2S2	0.9800
C8—H8B	0.9800	C2S—H2S3	0.9800
C8—H8C	0.9800	C3S—C4S	1.501 (2)
C10—C11	1.5262 (16)	C3S—H3S1	0.9900
C10—H10A	0.9900	C3S—H3S2	0.9900
C10—H10B	0.9900	C4S—H4S1	0.9800
C11—C12	1.519 (2)	C4S—H4S2	0.9800
C11—H11A	0.9900	C4S—H4S3	0.9800
C6—N1—C2	125.61 (10)	C13—C12—H12A	109.9
C6—N1—H1	118.0 (10)	C11—C12—H12A	109.9
C2—N1—H1	116.2 (10)	C13—C12—H12B	109.9
C2—N3—C4	121.25 (9)	C11—C12—H12B	109.9
C10—N9—C14	110.75 (9)	H12A—C12—H12B	108.3
C10—N9—C5	114.38 (8)	C12—C13—C14	110.71 (10)
C14—N9—C5	110.77 (8)	C12—C13—H13A	109.5
O2—C2—N3	122.39 (10)	C14—C13—H13A	109.5
O2—C2—N1	116.43 (10)	C12—C13—H13B	109.5
N3—C2—N1	121.19 (10)	C14—C13—H13B	109.5
O4—C4—N3	120.80 (10)	H13A—C13—H13B	108.1
O4—C4—C5	117.63 (9)	N9—C14—C13	111.51 (10)
N3—C4—C5	121.57 (9)	N9—C14—H14A	109.3
N9—C5—C6	110.57 (8)	C13—C14—H14A	109.3
N9—C5—C7	112.19 (8)	N9—C14—H14B	109.3
C6—C5—C7	107.32 (8)	C13—C14—H14B	109.3
N9—C5—C4	106.08 (8)	H14A—C14—H14B	108.0
C6—C5—C4	113.14 (9)	C1S—N1S—C3S	113.09 (11)
C7—C5—C4	107.60 (8)	C1S—N1S—H1SA	107.2 (9)
O6—C6—N1	121.48 (10)	C3S—N1S—H1SA	108.7 (9)
O6—C6—C5	121.68 (9)	C1S—N1S—H1SB	109.2 (9)
N1—C6—C5	116.84 (9)	C3S—N1S—H1SB	107.4 (9)
C8—C7—C5	112.03 (9)	H1SA—N1S—H1SB	111.3 (13)
C8—C7—H7A	109.2	N1S—C1S—C2S	110.63 (14)
C5—C7—H7A	109.2	N1S—C1S—H1S3	109.5
C8—C7—H7B	109.2	C2S—C1S—H1S3	109.5
C5—C7—H7B	109.2	N1S—C1S—H1S4	109.5
H7A—C7—H7B	107.9	C2S—C1S—H1S4	109.5
C7—C8—H8A	109.5	H1S3—C1S—H1S4	108.1
C7—C8—H8B	109.5	C1S—C2S—H2S1	109.5
H8A—C8—H8B	109.5	C1S—C2S—H2S2	109.5
C7—C8—H8C	109.5	H2S1—C2S—H2S2	109.5
H8A—C8—H8C	109.5	C1S—C2S—H2S3	109.5
H8B—C8—H8C	109.5	H2S1—C2S—H2S3	109.5
N9—C10—C11	110.82 (10)	H2S2—C2S—H2S3	109.5
N9—C10—H10A	109.5	N1S—C3S—C4S	110.78 (12)
C11—C10—H10A	109.5	N1S—C3S—H3S1	109.5
N9—C10—H10B	109.5	C4S—C3S—H3S1	109.5
C11—C10—H10B	109.5	N1S—C3S—H3S2	109.5
H10A—C10—H10B	108.1	C4S—C3S—H3S2	109.5
C12—C11—C10	111.29 (11)	H3S1—C3S—H3S2	108.1
C12—C11—H11A	109.4	C3S—C4S—H4S1	109.5
C10—C11—H11A	109.4	C3S—C4S—H4S2	109.5
C12—C11—H11B	109.4	H4S1—C4S—H4S2	109.5
C10—C11—H11B	109.4	C3S—C4S—H4S3	109.5
H11A—C11—H11B	108.0	H4S1—C4S—H4S3	109.5
C13—C12—C11	108.85 (10)	H4S2—C4S—H4S3	109.5
C2—C5—C7—C8	2.70 (14)	C8—C7—C5—N9	−172.63 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N9^i	0.87 (1)	2.15 (1)	3.0136 (13)	174 (1)
N1S—H1SA···N3	0.93 (1)	1.84 (1)	2.7555 (13)	169 (1)
N1S—H1SB···O2^ii	0.90 (1)	1.86 (1)	2.7204 (13)	159 (1)

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