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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 206-209

Crystal structure of the α-racemate of methohexital

aInstitute of Pharmacy, University of Innsbruck, Innrain 52c, 6020 Innsbruck, Austria
*Correspondence e-mail: thomas.gelbrich@uibk.ac.at

Edited by M. Weil, Vienna University of Technology, Austria (Received 15 December 2014; accepted 18 January 2015; online 24 January 2015)

Mol­ecules of the title compound, C14H18N2O3 [systematic name: 5-allyl-5-(hex-3-yn-2-yl)-1-methylpyrimidine-2,4,6(1H,3H,5H)-trione in the (RbSh)/(SbRh) racemic form], are connected by mutual N—H⋯O=C hydrogen bonds in which the carbonyl group at the 2-position of the pyrimidine­trione ring is employed. These inter­actions result in an inversion dimer which displays a central R22(8) ring motif. This dimer is topologically distinct from that of the previously reported (SbRh) form, which is, however, also based on an R22(8) motif. The methyl group at the 1-position of the pyrimidine­trione ring in the title structure is disordered over two sets of sites in a 0.57 (2):0.43 (2) ratio.

1. Chemical context

The title compound is a barbiturate derivative, the Na salt of which (trade name Brevimytal, Eli Lilly) is a widely used short-acting anaesthetic with a rapid onset of action. The mol­ecule contains two asymmetric centres and can exist as two diastereomeric enanti­omer pairs. Its stereoisomerism is known to affect the anaesthetic activity and possible side effects of the drug (Gibson et al., 1959[Gibson, W. R., Doran, W. J., Wood, W. C. & Swanson, E. E. (1959). J. Pharmacol. Exp. Ther. 125, 23-27.]). The crystal structure of the (SbRh) form of methohexital was previously reported by Brunner et al. (2003[Brunner, H., Ittner, K.-P., Lunz, D., Schmatloch, S., Schmidt, T. & Zabel, M. (2003). Eur. J. Org. Chem. pp. 855-862.]), who also established that the commercial product (α-racemate) consists of the (RbSh) and (SbRh) isomers.

[Scheme 1]

2. Structural commentary

This study confirmed the presence of the (RbSh)/(SbRh) racemate. The mol­ecule (Fig. 1[link]) displays an approximately planar pyrimidine­trione unit in which the oxygen atoms of the C2 and C4 carbonyl groups lie at distances of −0.160 (2) and 0.156 (2) Å from the mean plane of the six-membered ring (r.m.s. deviation = 0.046 Å). The conformation of the two 5-substituents of the ring is characterized by three parameters, the torsion angles C5—C7—C8—C9 of −103.3 (2) and C10—C5—C7—C8 of −171.51 (13)° and the pseudo-torsion angle C5—C10⋯C13–C14 of 23.2 (2)°.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary size.

The previously reported (SbRh) form contains two independent mol­ecules (denoted A and B), which differ from the mol­ecule of the title structure in the conformation adopted by the terminal groups of both 5-substituents (Fig. 2[link]). Specifically, in mol­ecule A, the torsion angle analogous to C5—C7—C8—C9 in the present α-racemate is 125.3°, and the pseudo-torsion angles analogous to C5—C10⋯C13—C14 of the title structure are −15.4° (A) and −26.3° (B).

[Figure 2]
Figure 2
Overlay of the mol­ecule of the α-racemate (denoted X) with the two independent mol­ecules (A, B) of the previously reported (SbRh) form, generated by least-squares fits of their 1-methyl-2,4,6-pyrimidine­trione units (ten non-H atomic positions).

3. Supra­molecular features

Two mol­ecules are linked to one another by two mutual anti­parallel N—H⋯O=C bonds so that an inversion dimer is formed (Table 1[link], Fig. 3[link]), which displays a central [R_{2}^{2}](8) ring motif (Etter et al., 1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]; Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]). This inter­action involves the carbonyl group at the 2-position of the ring. The [R_{2}^{2}](8) ring motif is also present in the (SbRh) form (Brunner et al., 2003[Brunner, H., Ittner, K.-P., Lunz, D., Schmatloch, S., Schmidt, T. & Zabel, M. (2003). Eur. J. Org. Chem. pp. 855-862.]) where it connects the two crystallographically independent mol­ecules. However, in this case the dimer is based on two topologically distinct N—H⋯O=C inter­actions which involve the carbonyl groups at the 4-position of the ring of mol­ecule A and at the 2-position of mol­ecule B.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H3⋯O2i 0.85 (2) 2.03 (2) 2.8826 (17) 173.2 (17)
Symmetry code: (i) -x, -y, -z+1.
[Figure 3]
Figure 3
The N—H⋯O=C hydrogen-bonded inversion dimer displaying a central [R_{2}^{2}](8) ring. These inter­actions (dotted lines) involve the carbonyl group at the 2-position of the six-membered ring. O and H atoms engaged in hydrogen bonding are drawn as spheres.

4. Database survey

The Cambridge Structural Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 115-121.]; Version 3.35) contains 11 unique entries for derivatives of barbituric acid which are analogous to the title compound and substituted at the 1-position, but not at the 3-position of the six-membered ring. A common characteristic of these compounds is the presence of one hydrogen-bond donor group (NH) and three potential acceptor groups, viz. the carbonyl groups at the ring positions 2, 4 and 6. Thus, three topologically distinct hydrogen-bonding acceptor inter­actions are possible. Additionally, there is a competition between possible dimer and catemer motifs, which is similar to the competition between hydrogen-bonded dimer and catemer motifs between carboxyl groups (Beyer & Price; 2000[Beyer, T. & Price, S. L. (2000). J. Phys. Chem. B, 104, 2647-2655.]) or carboxamide groups (Arlin et al., 2010[Arlin, J.-B., Johnston, A., Miller, G. J., Kennedy, A. R., Price, S. L. & Florence, A. J. (2010). CrystEngComm 12, 64-66.], 2011[Arlin, J.-B., Price, L. S., Price, S. L. & Florence, A. J. (2011). Chem. Commun. 47, 7074-7076.]).

Closer inspection of the geometric possibilities (Fig. 4[link]) shows that dimer formation is feasible for N—H⋯O=C2 and N—H⋯O=C4 connections only, whereas N—H⋯O=C6 should be the preferred connection mode for chain formation. Indeed, five crystal structures containing N—H⋯O=C6 chain motifs are known and their CSD refcodes are DMCYBA01 (Nichol & Clegg, 2005[Nichol, G. S. & Clegg, W. (2005). Acta Cryst. E61, o1004-o1006.]), DULMED (Gelbrich et al., 2010[Gelbrich, T., Zencirci, N. & Griesser, U. J. (2010). Acta Cryst. C66, o55-o58.]), MDEBAR (Wunderlich, 1973[Wunderlich, H. (1973). Acta Cryst. B29, 168-173.]), MIBABA (Wilhelm & Fischer, 1976[Wilhelm, E. & Fischer, K. F. (1976). Cryst. Struct. Commun. 5, 507-510.]), OBIPUM (Gelbrich & Griesser, 2009[Gelbrich, T. & Griesser, U. (2009). Private communication (refcode OBIPUM). CCDC, Cambridge, England.]). So far, the crystal structure with refcode VEMQUB (Savechenkov et al., 2012[Savechenkov, P. Y., Zhang, X., Chiara, D. C., Stewart, D. S., Ge, R., Zhou, X., Raines, D. E., Cohen, J. B., Forman, S. A., Miller, K. W. & Bruzik, K. S. (2012). J. Med. Chem. 55, 6554-6565.]) is the only example in the set where another chain type, viz. N—H⋯O=C2, is present.

[Figure 4]
Figure 4
The three fundamental connection modes for the formation of N—H⋯O=C bonds in 1-substituted derivatives of barbituric acid arising from the involvement of different carbonyl groups, and the corresponding numbers of observed dimer and catemer isomers. The (SbRh) form of methohexithal contains a dimer with mixed N—H⋯O=C2/N—H⋯O=C4 connectivity and was therefore not included.

Apart from the title structure, two analogues with refcodes CXALBA (Dideberg et al., 1975[Dideberg, O., Dupont, L. & Pyzalska, D. (1975). Acta Cryst. B31, 685-688.]) and DULMAZ (Gelbrich et al., 2010[Gelbrich, T., Zencirci, N. & Griesser, U. J. (2010). Acta Cryst. C66, o55-o58.]) also form N—H⋯O=C2 bonded dimers. The alternative N—H⋯O=C4 dimer was observed in the two structures with refcodes ALLBTC (Pyżalska et al., 1980[Pyżalska, D., Pyżalski, R. & Borowiak, T. (1980). Acta Cryst. B36, 1672-1675.]) and MEPBAB01 (Lewis et al., 2005[Lewis, W., McKeown, R. H. & Robinson, W. T. (2005). Acta Cryst. E61, o799-o800.]). The (SbRh) form of methohexital provides the only case of a dimer based on a mixed N—H⋯O=C2/N—H⋯O=C4 connectivity.

5. Synthesis and crystallization

The crystals investigated in this study were obtained at room temperature, by slow evaporation from an aqueous solution of the α-racemate of methohexital (Lilly Research Centre Ltd., Windlesham, England).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. H atoms were identified in difference maps. The H atoms of the C14 methyl group and disordered C1 methyl group [occupancy ratio 0.57 (2):0.43 (2)] were idealized and included as rigid groups allowed to rotate but not tip (C—H = 0.96 Å) and refined with Uiso set to 1.5Ueq(C) of the parent carbon atom. H atoms bonded to secondary CH2 (C—H = 0.97 Å), tertiary CH (C—H = 0.98 Å) carbon and aromatic CH carbon atoms (C—H = 0.93 Å) were positioned geometrically and refined with Uiso set to 1.2Ueq(C) of the parent carbon atom. The NH hydrogen atom was refined with a restrained distance [N—H = 0.86 (2) Å] and its Uiso parameter was freely refined.

Table 2
Experimental details

Crystal data
Chemical formula C14H18N2O3
Mr 262.30
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 293
a, b, c (Å) 7.7502 (6), 7.9792 (5), 12.6881 (10)
α, β, γ (°) 93.713 (6), 96.226 (6), 113.314 (7)
V3) 711.32 (10)
Z 2
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.35 × 0.20 × 0.20
 
Data collection
Diffractometer Agilent Xcalibur (Ruby, Gemini ultra)
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.883, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 6896, 3363, 2462
Rint 0.022
(sin θ/λ)max−1) 0.690
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.135, 1.05
No. of reflections 3363
No. of parameters 180
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.22, −0.20
Computer programs: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/6 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

The title compound is a barbiturate derivative, the Na salt of which (trade name Brevimytal, Eli Lilly) is a widely used short-acting anaesthetic with a rapid onset of action. The molecule contains two asymmetric centres and can exist as two diastereomeric enanti­omer pairs. Its stereoisomerism is known to affect the anaesthetic activity and possible side effects of the drug (Gibson et al., 1959). The crystal structure of the (SbRh) form of methohexital was previously reported by Brunner et al. (2003), who also established that the commercial product (α-racemate) consists of the (RbSh) and (SbRh) isomers.

Structural commentary top

This study confirmed the presence of the (RbSh)/(SbRh) racemate. The molecule (Fig. 1) displays an approximately planar pyrimidine­trione unit in which the oxygen atoms of the C2 and C4 carbonyl groups lie at distances of –0.160 (2) and 0.156 (2) Å from the least-squares plane of the six-membered ring (r.m.s. deviation = 0.046 Å). The conformation of the two 5-substituents of the ring is characterized by three parameters, the torsion angles C5—C7—C8—C9 of –103.3 (2) and C10—C5—C7—C8 of –171.51 (13)° and the pseudo-torsion angle C5—C10···C13–C14 of 23.2 (2)°.

The previously reported (SbRh) form contains two independent molecules (denoted A and B), which differ from the molecule of the title structure in the conformation adopted by the terminal groups of both 5-substituents (Fig. 2). Specifically, in molecule A, the torsion angle analogous to C5—C7—C8—C9 in the present α-racemate is 125.3°, and the pseudo-torsion angles analogous to C5—C10···C13—C14 of the title structure are –15.4° (A) and –26.3° (B).

Supra­molecular features top

Two molecules are linked to one another by two mutual anti­parallel N—H···O C bonds so that an inversion dimer is formed (Table 1, Fig. 3), which displays a central R22(8) ring motif (Etter et al., 1990; Bernstein et al., 1995). This inter­action involves the carbonyl group at the 2-position of the ring. The R22(8) ring motif is also present in the (SbRh) form (Brunner et al., 2003) where it connects the two crystallographically independent molecules. However, in this case the dimer is based on two topologically distinct N—H···OC inter­actions which involve the carbonyl groups at the 4-position of the ring of molecule A and at the 2-position of molecule B.

Database survey top

The Cambridge Structural Database (Groom & Allen, 2014; Version 3.35) contains 11 unique entries for derivatives of barbituric acid which are analogous to the title compound and substituted at the 1-position, but not at the 3-position of the six-membered ring. A common characteristic of these compounds is the presence of one hydrogen-bond donor group (NH) and three potential acceptor groups, viz. the carbonyl groups at the ring positions 2, 4 and 6. Thus, three topologically distinct hydrogen-bonding acceptor inter­actions are possible. Additionally, there is a competition between possible dimer and catemer motifs, which are similar to the competition between hydrogen-bonded dimer and catemer motifs between carboxyl groups (Beyer & Price; 2000) or carboxamide groups (Arlin et al., 2010, 2011).

Closer inspection of the geometric possibilities (Fig. 4) shows that dimer formation is feasible for N—H···OC2 and N—H···OC4 connections only, whereas N—H···OC6 should be the preferred connection mode for chain formation. Indeed, five crystal structures containing N—H···OC6 chain motifs are known and their CSD refcodes are DMCYBA01 (Nichol & Clegg, 2005), DULMED (Gelbrich et al., 2010), MDEBAR (Wunderlich, 1973), MIBABA (Wilhelm & Fischer, 1976), OBIPUM (Gelbrich & Griesser, 2009). So far, the crystal structure with refcode VEMQUB (Savechenkov et al., 2012) is the only example in the set where another chain type, viz. N—H···OC2, is present.

Apart from the title structure, two analogues with refcodes CXALBA (Dideberg et al., 1975) and DULMAZ (Gelbrich et al., 2010) also form N—H···OC2 bonded dimers. The alternative N—H···OC4 dimer was observed in the two structures with refcodes ALLBTC (Pyżalska et al., 1980) and MEPBAB01 (Lewis et al., 2005). The (SbRh) form of methohexital provides the only case of a dimer based on a mixed N—H···O C2/N—H···OC4 connectivity.

Synthesis and crystallization top

The crystals investigated in this study were obtained at room temperature, by slow evaporation from an aqueous solution of the α-racemate of methohexital (Lilly Research Centre Ltd., Windlesham, England).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were identified in difference maps. The H atoms of the C14 methyl group and disordered C1 methyl group [occupancy ratio 0.57 (2):0.43 (2)] were idealized and included as rigid groups allowed to rotate but not tip (C—H = 0.96 Å) and refined with Uiso set to 1.5Ueq(C) of the parent carbon atom. H atoms bonded to secondary CH2 (C—H = 0.97 Å), tertiary CH (C—H = 0.98 Å) carbon and aromatic CH carbon atoms (C—H = 0.93 Å) were positioned geometrically and refined with Uiso set to 1.2Ueq(C) of the parent carbon atom. The NH hydrogen atom was refined with a restrained distance [N—H = 0.86 (2) Å] and its Uiso parameter was refined freely.

Related literature top

For related literature, see: Arlin et al. (2010, 2011); Bernstein et al. (1995); Beyer & Price (2000); Brunner et al. (2003); Dideberg et al. (1975); Etter et al. (1990); Gelbrich & Griesser (2009); Gelbrich et al. (2010); Gibson et al. (1959); Groom & Allen (2014); Lewis et al. (2005); Nichol & Clegg (2005); Pyżalska et al. (1980); Savechenkov et al. (2012); Wilhelm & Fischer (1976); Wunderlich (1973).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary size.
[Figure 2] Fig. 2. Overlay of the molecule of the α-racemate (denoted X) with the two independent molecules (A, B) of the previously reported (SbRh) form, generated by least-squares fits of their 1-methyl-2,4,6-pyrimidinetrione units (ten non-H atomic positions).
[Figure 3] Fig. 3. The N—H···OC hydrogen-bonded inversion dimer displaying a central R22(8) ring. These interactions (dotted lines) involve the carbonyl group at the 2-position of the six-membered ring. O and H atoms engaged in hydrogen bonding are drawn as spheres.
[Figure 4] Fig. 4. The three fundamental connection modes for the formation of N—H···OC bonds in 1-substituted derivatives of barbituric acid arising from the involvement of different carbonyl groups, and the corresponding numbers of observed dimer and catemer isomers. The (SbRh) form of methohexithal contains a dimer with mixed N—H···OC2/N—H···OC4 connectivity and was therefore not included.
5-Allyl-5-(hex-3-yn-2-yl)-1-methylpyrimidine-2,4,6(1H,3H,5H)-trione top
Crystal data top
C14H18N2O3Z = 2
Mr = 262.30F(000) = 280
Triclinic, P1Dx = 1.225 Mg m3
a = 7.7502 (6) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.9792 (5) ÅCell parameters from 1814 reflections
c = 12.6881 (10) Åθ = 4.4–28.8°
α = 93.713 (6)°µ = 0.09 mm1
β = 96.226 (6)°T = 293 K
γ = 113.314 (7)°Prism, colourless
V = 711.32 (10) Å30.35 × 0.20 × 0.20 mm
Data collection top
Agilent Xcalibur (Ruby, Gemini ultra)
diffractometer
3363 independent reflections
Radiation source: Enhance (Mo) X-ray Source2462 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
Detector resolution: 10.3575 pixels mm-1θmax = 29.4°, θmin = 2.8°
ω scansh = 910
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 119
Tmin = 0.883, Tmax = 1.000l = 1615
6896 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.135 w = 1/[σ2(Fo2) + (0.0572P)2 + 0.1234P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3363 reflectionsΔρmax = 0.22 e Å3
180 parametersΔρmin = 0.20 e Å3
Crystal data top
C14H18N2O3γ = 113.314 (7)°
Mr = 262.30V = 711.32 (10) Å3
Triclinic, P1Z = 2
a = 7.7502 (6) ÅMo Kα radiation
b = 7.9792 (5) ŵ = 0.09 mm1
c = 12.6881 (10) ÅT = 293 K
α = 93.713 (6)°0.35 × 0.20 × 0.20 mm
β = 96.226 (6)°
Data collection top
Agilent Xcalibur (Ruby, Gemini ultra)
diffractometer
3363 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
2462 reflections with I > 2σ(I)
Tmin = 0.883, Tmax = 1.000Rint = 0.022
6896 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.135H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.22 e Å3
3363 reflectionsΔρmin = 0.20 e Å3
180 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. The C1 methyl group is disordered over two positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.00769 (16)0.12155 (16)0.75511 (9)0.0382 (3)
N30.15035 (17)0.08665 (17)0.63981 (10)0.0412 (3)
H30.145 (2)0.115 (2)0.5763 (16)0.055 (5)*
O20.12784 (15)0.15309 (16)0.58085 (9)0.0582 (4)
O40.42793 (15)0.32706 (15)0.69135 (9)0.0546 (3)
O60.12730 (17)0.09825 (17)0.92461 (9)0.0589 (3)
C10.1759 (2)0.2810 (2)0.77286 (14)0.0550 (4)
H1A0.16240.30360.84610.082*0.43 (2)
H1B0.28710.25660.75700.082*0.43 (2)
H1C0.18810.38700.72720.082*0.43 (2)
H1D0.26270.32790.70740.082*0.57 (2)
H1E0.13800.37490.79650.082*0.57 (2)
H1F0.23700.24450.82630.082*0.57 (2)
C20.0015 (2)0.06791 (19)0.65385 (11)0.0393 (3)
C40.30668 (19)0.18923 (19)0.71322 (11)0.0376 (3)
C50.32002 (19)0.11774 (19)0.82021 (11)0.0368 (3)
C60.1393 (2)0.04093 (19)0.83867 (11)0.0383 (3)
C70.3687 (2)0.2764 (2)0.90965 (12)0.0460 (4)
H7A0.39930.23750.97750.055*
H7B0.48020.38030.89700.055*
C80.2092 (2)0.3359 (2)0.91640 (13)0.0527 (4)
H80.10680.26230.94790.063*
C90.2045 (3)0.4828 (3)0.88144 (18)0.0759 (6)
H9A0.30470.55940.84960.091*
H9B0.10100.51180.88820.091*
C100.4766 (2)0.0383 (2)0.82568 (12)0.0463 (4)
H100.46800.02530.88970.057 (5)*
C110.4322 (2)0.1006 (2)0.73331 (14)0.0510 (4)
C120.3973 (3)0.2041 (3)0.65519 (17)0.0620 (5)
C130.3521 (4)0.3299 (3)0.55608 (19)0.0882 (7)
H13A0.46990.32040.53190.106*
H13B0.28580.45510.57160.106*
C140.2356 (5)0.2930 (4)0.4700 (2)0.1143 (10)
H14A0.20910.38090.40860.171*
H14B0.30270.17140.45180.171*
H14C0.11850.30250.49310.171*
C150.6801 (2)0.1819 (3)0.83485 (16)0.0640 (5)
H15A0.76560.12170.83530.096*
H15B0.71060.26280.89990.096*
H15C0.69220.25170.77510.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0343 (6)0.0402 (6)0.0336 (6)0.0085 (5)0.0022 (5)0.0091 (5)
N30.0409 (7)0.0458 (7)0.0270 (6)0.0083 (5)0.0027 (5)0.0108 (5)
O20.0463 (6)0.0661 (7)0.0372 (6)0.0001 (5)0.0087 (5)0.0094 (5)
O40.0494 (6)0.0501 (6)0.0469 (7)0.0019 (5)0.0011 (5)0.0168 (5)
O60.0592 (7)0.0696 (8)0.0345 (6)0.0109 (6)0.0028 (5)0.0210 (5)
C10.0428 (8)0.0541 (9)0.0541 (10)0.0037 (7)0.0054 (7)0.0182 (8)
C20.0366 (7)0.0430 (8)0.0328 (8)0.0117 (6)0.0010 (6)0.0069 (6)
C40.0357 (7)0.0389 (7)0.0326 (7)0.0100 (6)0.0014 (6)0.0072 (6)
C50.0351 (7)0.0424 (7)0.0276 (7)0.0115 (6)0.0017 (5)0.0054 (5)
C60.0396 (7)0.0429 (8)0.0302 (7)0.0143 (6)0.0026 (6)0.0081 (6)
C70.0433 (8)0.0508 (9)0.0329 (8)0.0110 (7)0.0046 (6)0.0011 (6)
C80.0504 (9)0.0550 (10)0.0433 (9)0.0138 (8)0.0031 (7)0.0034 (7)
C90.0711 (13)0.0635 (12)0.0904 (16)0.0273 (10)0.0032 (11)0.0041 (11)
C100.0434 (8)0.0571 (9)0.0387 (8)0.0215 (7)0.0007 (6)0.0112 (7)
C110.0491 (9)0.0562 (10)0.0533 (10)0.0268 (8)0.0064 (8)0.0122 (8)
C120.0633 (11)0.0639 (11)0.0663 (12)0.0352 (9)0.0044 (9)0.0051 (9)
C130.1023 (18)0.0897 (16)0.0816 (16)0.0565 (14)0.0012 (14)0.0187 (13)
C140.146 (3)0.130 (2)0.0667 (16)0.064 (2)0.0027 (17)0.0222 (15)
C150.0396 (9)0.0777 (12)0.0671 (12)0.0194 (9)0.0034 (8)0.0029 (10)
Geometric parameters (Å, º) top
N1—C21.3800 (18)C7—H7A0.9700
N1—C61.3804 (17)C7—H7B0.9700
N1—C11.4687 (18)C8—C91.292 (3)
N3—C21.3648 (18)C8—H80.9300
N3—C41.3701 (17)C9—H9A0.9300
N3—H30.85 (2)C9—H9B0.9300
O2—C21.2140 (16)C10—C111.471 (2)
O4—C41.2032 (17)C10—C151.526 (2)
O6—C61.2083 (17)C10—H100.9800
C1—H1A0.9600C11—C121.182 (2)
C1—H1B0.9600C12—C131.474 (3)
C1—H1C0.9600C13—C141.460 (3)
C1—H1D0.9600C13—H13A0.9700
C1—H1E0.9600C13—H13B0.9700
C1—H1F0.9600C14—H14A0.9600
C4—C51.5151 (18)C14—H14B0.9600
C5—C61.5248 (19)C14—H14C0.9600
C5—C71.541 (2)C15—H15A0.9600
C5—C101.574 (2)C15—H15B0.9600
C7—C81.498 (2)C15—H15C0.9600
C2—N1—C6123.81 (12)O6—C6—C5120.29 (12)
C2—N1—C1117.84 (12)N1—C6—C5119.14 (12)
C6—N1—C1118.24 (12)C8—C7—C5112.61 (12)
C2—N3—C4127.42 (12)C8—C7—H7A109.1
C2—N3—H3113.2 (12)C5—C7—H7A109.1
C4—N3—H3119.3 (12)C8—C7—H7B109.1
N1—C1—H1A109.5C5—C7—H7B109.1
N1—C1—H1B109.5H7A—C7—H7B107.8
H1A—C1—H1B109.5C9—C8—C7124.36 (18)
N1—C1—H1C109.5C9—C8—H8117.8
H1A—C1—H1C109.5C7—C8—H8117.8
H1B—C1—H1C109.5C8—C9—H9A120.0
N1—C1—H1D109.5C8—C9—H9B120.0
H1A—C1—H1D141.1H9A—C9—H9B120.0
H1B—C1—H1D56.3C11—C10—C15110.95 (15)
H1C—C1—H1D56.3C11—C10—C5109.25 (12)
N1—C1—H1E109.5C15—C10—C5114.96 (14)
H1A—C1—H1E56.3C11—C10—H10107.1
H1B—C1—H1E141.1C15—C10—H10107.1
H1C—C1—H1E56.3C5—C10—H10107.1
H1D—C1—H1E109.5C12—C11—C10176.00 (18)
N1—C1—H1F109.5C11—C12—C13178.4 (2)
H1A—C1—H1F56.3C14—C13—C12113.7 (2)
H1B—C1—H1F56.3C14—C13—H13A108.8
H1C—C1—H1F141.1C12—C13—H13A108.8
H1D—C1—H1F109.5C14—C13—H13B108.8
H1E—C1—H1F109.5C12—C13—H13B108.8
O2—C2—N3121.50 (13)H13A—C13—H13B107.7
O2—C2—N1121.22 (13)C13—C14—H14A109.5
N3—C2—N1117.27 (12)C13—C14—H14B109.5
O4—C4—N3120.57 (12)H14A—C14—H14B109.5
O4—C4—C5122.59 (12)C13—C14—H14C109.5
N3—C4—C5116.82 (12)H14A—C14—H14C109.5
C4—C5—C6114.41 (11)H14B—C14—H14C109.5
C4—C5—C7108.82 (12)C10—C15—H15A109.5
C6—C5—C7108.29 (12)C10—C15—H15B109.5
C4—C5—C10108.59 (12)H15A—C15—H15B109.5
C6—C5—C10105.19 (11)C10—C15—H15C109.5
C7—C5—C10111.55 (11)H15A—C15—H15C109.5
O6—C6—N1120.54 (13)H15B—C15—H15C109.5
C10—C5—C7—C8171.51 (13)C5—C7—C8—C9103.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O2i0.85 (2)2.03 (2)2.8826 (17)173.2 (17)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O2i0.85 (2)2.03 (2)2.8826 (17)173.2 (17)
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC14H18N2O3
Mr262.30
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.7502 (6), 7.9792 (5), 12.6881 (10)
α, β, γ (°)93.713 (6), 96.226 (6), 113.314 (7)
V3)711.32 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.35 × 0.20 × 0.20
Data collection
DiffractometerAgilent Xcalibur (Ruby, Gemini ultra)
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.883, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6896, 3363, 2462
Rint0.022
(sin θ/λ)max1)0.690
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.135, 1.05
No. of reflections3363
No. of parameters180
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.20

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014/6 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

 

Acknowledgements

We thank Volker Kahlenberg for access to the X-ray diffraction instrument used in this study.

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Volume 71| Part 2| February 2015| Pages 206-209
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