Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041104/lh2481sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041104/lh2481Isup2.hkl |
CCDC reference: 660374
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (S-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.042
- wR factor = 0.114
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT301_ALERT_3_B Main Residue Disorder ......................... 40.00 Perc.
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT432_ALERT_2_C Short Inter X...Y Contact S1 .. C12A .. 3.29 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: All listed authours have made a significant contribution to this study. Johnston, Florence and Fernandes responsible for preparation and identification of sample. Shankland, K., Shankland, N. and Leech responsible for structure determination and refinement. |
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
For details on experimental methods used to obtain this form, see: Florence et al. (2003); Florence, Johnston, Fernandes et al. (2006). For related crystal structures of 10,11-dihydrocarbamazepine, see: Bandoli et al. (1992); Cyr et al. (1987); Harrison et al. (2006); Leech et al. (2007); Florence, Leech et al. (2006). For solvates of the related dibenzazepine compound carbamazepine, see: Fleischman et al. (2003); Florence, Johnston, Price et al. (2006).
For related literature, see: Etter (1990).
DHC was used as received from SigmaAldrich and a single-crystal sample was obtained by cooling a saturated DMSO solution, saturated at 298 K, to 273 K.
For the major component of the disorder and for the undisordered part of the structure all non-hydrogen atoms were located from the direct method solution, all hydrogen atoms were visible in a Fourier difference map. The –NH2 hydrogen atoms were located in a Fourier difference map and the atomic coordinates and Uiso values were refined freely. The rest of the hydrogen atoms were constrained to geometrically sensible positions in a riding-model approximation [SHELXL97; Sheldrick (1997)].
For the minor component of disorder, atoms C7A and C8A were visible in the Fourier difference map. The aromatic rings were constrained to a regular hexagon with C—C bond length of 1.39 Å and all hydrogen atoms were constrained to geometrically sensible positions in a riding-model approximation [SHELXL97; Sheldrick (1997)]. All atoms in the minor component of the disorder were refined isotropically with Uiso constrained to be identical for all C atoms. The Uiso value for the H atoms were constrained to be 1.2 times the value for the C atoms.
10,11-Dihydrocarbamazepine (DHC) is a recognized impurity in carbamazepine (CBZ), a dibenzazepine drug used to control seizures (Cyr et al., 1987). DHC is known to crystallize in three polymorphic forms: monoclinic form I (Bandoli et al., 1992), orthorhombic form II (Harrison et al., 2006) and triclinic form III (Leech et al., 2007a). The title compound, was produced during an automated parallel crystallization study (Florence, Johnston, Fernandes et al., 2006) on DHC as part of a wider investigation into the predicted and experimental structures of CBZ (Florence, Johnston, Price et al., 2006; Florence, Leech et al., 2006) and related molecules (Leech et al., 2007). The sample was identified as a new form using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003). Subsequent manual recrystallization, from a saturated dimethyl sulfoxide (DMSO) solution, by cooling to 273 K yielded single crystals suitable for X-ray diffraction. The molecular structure is shown in Fig. 1.
In the crystal structure, DHC molecules are partially disordered over two sites with the major component of this disorder being present at approximately 81%.
DHC molecules form a centrosymmetric hydrogen-bonded R22(8) dimer motif (Etter, 1990) via N2—H2A···O1i (symmetry code as in the Hydrogen Bond Geometry table) contacts in contrast to the C(4) catameric configuration observed in each of the three polymorphic forms. In the title structure, the DHC molecules form a second N—H···O hydrogen bond to atom O2 of the solvent molecule (Fig. 2) to form a packing motif also observed in the CBZ DMSO solvate (Fleischman et al., 2003).
For details on experimental methods used to obtain this form, see: Florence et al. (2003); Florence, Johnston, Fernandes et al. (2006). For related crystal structures of 10,11-dihydrocarbamazepine, see: Bandoli et al. (1992); Cyr et al. (1987); Harrison et al. (2006); Leech et al. (2007); Florence, Leech et al. (2006). For solvates of the related dibenzazepine compound carbamazepine, see: Fleischman et al. (2003); Florence, Johnston, Price et al. (2006).
For related literature, see: Etter (1990).
Data collection: CrysAlis CCD (Oxford Diffraction, 2000); cell refinement: CrysAlis RED (Oxford Diffraction, 2000); data reduction: CrysAlis RED (Oxford Diffraction, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 2003).
C15H14N2O·C2H6OS | F(000) = 672 |
Mr = 316.41 | Dx = 1.294 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7414 reflections |
a = 10.2696 (3) Å | θ = 2.6–28.6° |
b = 6.8543 (2) Å | µ = 0.21 mm−1 |
c = 23.3599 (6) Å | T = 123 K |
β = 98.932 (2)° | Block, colourless |
V = 1624.39 (8) Å3 | 0.24 × 0.10 × 0.07 mm |
Z = 4 |
Oxford Diffraction Gemini diffractometer | 3326 independent reflections |
Radiation source: Enhance (Mu) X-ray Source | 2627 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 15.9745 pixels mm-1 | θmax = 26.4°, θmin = 2.9° |
φ and ω scans | h = −10→12 |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2000), based on Clark & Reid (1995)] | k = −8→8 |
Tmin = 0.952, Tmax = 0.986 | l = −29→29 |
16299 measured reflections |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.0295P)2 + 2.9523P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.114 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.71 e Å−3 |
3326 reflections | Δρmin = −0.39 e Å−3 |
223 parameters |
C15H14N2O·C2H6OS | V = 1624.39 (8) Å3 |
Mr = 316.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.2696 (3) Å | µ = 0.21 mm−1 |
b = 6.8543 (2) Å | T = 123 K |
c = 23.3599 (6) Å | 0.24 × 0.10 × 0.07 mm |
β = 98.932 (2)° |
Oxford Diffraction Gemini diffractometer | 3326 independent reflections |
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2000), based on Clark & Reid (1995)] | 2627 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.986 | Rint = 0.029 |
16299 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 2 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.71 e Å−3 |
3326 reflections | Δρmin = −0.39 e Å−3 |
223 parameters |
Experimental. Absorption correction: CrysAlis RED (Oxford Diffraction, 2000), analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995). 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 > 2sigma(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. |
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 structure was refined using a disordered model in which the relative occupancy of the major component equals 81.1 (6)%. The disordered model is justified by the fact the refined structure using an ordered model showed 1) large residual peaks of electron density close to the C7—C8 bond which were assigned as atoms C7a and C8a, and 2) anomalous adps especially for atoms C3 C4 C5 and C12 C13 C14. Inclusion of disorder yielded adp values within normal ranges for these atoms. Overall, the disordered model resulted in significant improvements in the Rfactors (wR2 = 0.1426 and R1 = 0.0551 with no disorder). The major and minor components of the disorder are related conformers of DHC. The two confomers are related by an approximate inversion of the C6—C7—C8—C9 torsion angle, which leads to an associated shift in the position of the aromatic rings. This relationship can also be described as an approximate 180° rotation about the N1—C15 bond followed by an inversion of the whole molecule (note SG=P21/c contains an inversion center). For the major component of the disorder and for the undisordered part of the structure all non-hydrogen atoms were located from the direct method solution, all hydrogen atoms were visible in the Fourier difference map, the NH2 hydrogen atoms located from the Fourier difference map and the atomic coordinated and Uiso refined freely, the rest of the hydrogen atoms were constrained to geometrically sensible positions with a riding model (SHELX97). For the minor component of the disorder atoms C7A and C8A were visible in the Fourier difference map. The aromatic rings were constrained to a regular hexagon with C—C bond lenght of 1.39 Å and all hydrogen atoms were constrained to geometrically sensible positions with a riding model (SHELX97). All atoms in the minor component of the disorder were refined isotropically with Uiso constrained to be identical for all the carbon atoms. The Uiso for the hydrogen atoms was constrained to be 1.2 times the value for the hydrogen atoms. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 1.05951 (11) | 0.08903 (17) | 0.43941 (5) | 0.0227 (3) | |
N1 | 0.91771 (13) | 0.2552 (2) | 0.37293 (6) | 0.0189 (3) | |
C15 | 0.94794 (15) | 0.1576 (2) | 0.42506 (7) | 0.0189 (3) | |
N2 | 0.85194 (15) | 0.1394 (2) | 0.45751 (7) | 0.0236 (3) | |
H2A | 0.871 (2) | 0.077 (3) | 0.4893 (10) | 0.038 (6)* | |
H2B | 0.778 (2) | 0.186 (3) | 0.4494 (9) | 0.034 (6)* | |
C1 | 1.02405 (15) | 0.3029 (3) | 0.34188 (7) | 0.0207 (4) | |
C2A | 1.0637 (9) | 0.1930 (9) | 0.2976 (3) | 0.0203 (13)* | 0.189 (6) |
H2C | 1.0215 | 0.0725 | 0.2866 | 0.024* | 0.189 (6) |
C3A | 1.1650 (10) | 0.2595 (14) | 0.2696 (4) | 0.0203 (13)* | 0.189 (6) |
H3A | 1.1921 | 0.1844 | 0.2393 | 0.024* | 0.189 (6) |
C4A | 1.2268 (7) | 0.4358 (15) | 0.2858 (4) | 0.0203 (13)* | 0.189 (6) |
H4A | 1.2961 | 0.4812 | 0.2666 | 0.024* | 0.189 (6) |
C5A | 1.1872 (9) | 0.5457 (12) | 0.3300 (5) | 0.0203 (13)* | 0.189 (6) |
H5A | 1.2294 | 0.6662 | 0.3411 | 0.024* | 0.189 (6) |
C6A | 1.0858 (8) | 0.4793 (8) | 0.3581 (3) | 0.0203 (13)* | 0.189 (6) |
C2 | 1.0568 (3) | 0.1613 (4) | 0.30398 (11) | 0.0264 (6) | 0.811 (6) |
H2 | 1.0115 | 0.0400 | 0.3006 | 0.032* | 0.811 (6) |
C3 | 1.1561 (3) | 0.1974 (5) | 0.27098 (11) | 0.0300 (7) | 0.811 (6) |
H3 | 1.1799 | 0.1006 | 0.2454 | 0.036* | 0.811 (6) |
C4 | 1.2193 (2) | 0.3749 (5) | 0.27597 (11) | 0.0293 (7) | 0.811 (6) |
H4 | 1.2868 | 0.4012 | 0.2534 | 0.035* | 0.811 (6) |
C5 | 1.1859 (2) | 0.5136 (4) | 0.31305 (13) | 0.0313 (7) | 0.811 (6) |
H5 | 1.2310 | 0.6351 | 0.3157 | 0.038* | 0.811 (6) |
C6 | 1.0874 (3) | 0.4829 (4) | 0.34740 (11) | 0.0272 (6) | 0.811 (6) |
C7 | 1.0555 (3) | 0.6467 (4) | 0.38578 (16) | 0.0365 (7) | 0.811 (6) |
H7A | 1.0392 | 0.7646 | 0.3613 | 0.044* | 0.811 (6) |
H7B | 1.1357 | 0.6724 | 0.4142 | 0.044* | 0.811 (6) |
C8 | 0.9413 (3) | 0.6269 (4) | 0.41943 (13) | 0.0293 (7) | 0.811 (6) |
H8A | 0.9644 | 0.5291 | 0.4505 | 0.035* | 0.811 (6) |
H8B | 0.9274 | 0.7533 | 0.4380 | 0.035* | 0.811 (6) |
C9 | 0.8147 (2) | 0.5664 (3) | 0.38213 (10) | 0.0233 (5) | 0.811 (6) |
C10 | 0.80304 (16) | 0.3762 (3) | 0.36009 (7) | 0.0217 (4) | |
C11A | 0.6944 (4) | 0.2697 (6) | 0.3343 (3) | 0.0203 (13)* | 0.189 (6) |
H11A | 0.7023 | 0.1334 | 0.3283 | 0.024* | 0.189 (6) |
C12A | 0.5743 (3) | 0.3626 (12) | 0.3173 (4) | 0.0203 (13)* | 0.189 (6) |
H12A | 0.5001 | 0.2898 | 0.2996 | 0.024* | 0.189 (6) |
C13A | 0.5629 (4) | 0.5620 (12) | 0.3261 (4) | 0.0203 (13)* | 0.189 (6) |
H13A | 0.4808 | 0.6255 | 0.3144 | 0.024* | 0.189 (6) |
C14A | 0.6715 (7) | 0.6686 (7) | 0.3519 (4) | 0.0203 (13)* | 0.189 (6) |
H14A | 0.6636 | 0.8049 | 0.3579 | 0.024* | 0.189 (6) |
C9A | 0.7916 (5) | 0.5757 (3) | 0.3689 (3) | 0.0203 (13)* | 0.189 (6) |
C7A | 1.0462 (10) | 0.5949 (16) | 0.4089 (4) | 0.0203 (13)* | 0.189 (6) |
H7C | 1.0466 | 0.5061 | 0.4423 | 0.024* | 0.189 (6) |
H7D | 1.1127 | 0.6979 | 0.4204 | 0.024* | 0.189 (6) |
C8A | 0.9104 (8) | 0.6895 (16) | 0.3947 (5) | 0.0203 (13)* | 0.189 (6) |
H8C | 0.8902 | 0.7477 | 0.4311 | 0.024* | 0.189 (6) |
H8D | 0.9191 | 0.7991 | 0.3680 | 0.024* | 0.189 (6) |
C11 | 0.6906 (2) | 0.3133 (5) | 0.32519 (11) | 0.0319 (6) | 0.811 (6) |
H11 | 0.6850 | 0.1841 | 0.3103 | 0.038* | 0.811 (6) |
C12 | 0.5857 (2) | 0.4407 (6) | 0.31199 (11) | 0.0406 (8) | 0.811 (6) |
H12 | 0.5074 | 0.3989 | 0.2880 | 0.049* | 0.811 (6) |
C13 | 0.5945 (3) | 0.6268 (5) | 0.33340 (12) | 0.0397 (8) | 0.811 (6) |
H13 | 0.5221 | 0.7134 | 0.3241 | 0.048* | 0.811 (6) |
C14 | 0.7070 (3) | 0.6901 (4) | 0.36816 (12) | 0.0338 (7) | 0.811 (6) |
H14 | 0.7112 | 0.8197 | 0.3828 | 0.041* | 0.811 (6) |
S1 | 0.43861 (4) | 0.26487 (8) | 0.43255 (2) | 0.03643 (17) | |
O2 | 0.57765 (12) | 0.2223 (2) | 0.46042 (6) | 0.0429 (4) | |
C17 | 0.3694 (2) | 0.0384 (4) | 0.40614 (10) | 0.0453 (6) | |
H17A | 0.4117 | −0.0051 | 0.3736 | 0.068* | |
H17B | 0.2746 | 0.0546 | 0.3931 | 0.068* | |
H17C | 0.3836 | −0.0591 | 0.4372 | 0.068* | |
C16 | 0.34591 (19) | 0.2887 (3) | 0.49031 (10) | 0.0412 (5) | |
H16A | 0.3713 | 0.4093 | 0.5117 | 0.062* | |
H16B | 0.3635 | 0.1768 | 0.5165 | 0.062* | |
H16C | 0.2517 | 0.2932 | 0.4746 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0168 (6) | 0.0253 (6) | 0.0260 (6) | 0.0016 (5) | 0.0037 (5) | 0.0045 (5) |
N1 | 0.0165 (7) | 0.0214 (7) | 0.0193 (7) | 0.0003 (5) | 0.0043 (5) | 0.0004 (6) |
C15 | 0.0188 (8) | 0.0153 (8) | 0.0223 (8) | −0.0026 (6) | 0.0023 (6) | −0.0015 (7) |
N2 | 0.0182 (8) | 0.0283 (8) | 0.0250 (8) | 0.0038 (6) | 0.0055 (6) | 0.0081 (7) |
C1 | 0.0156 (8) | 0.0288 (9) | 0.0171 (8) | 0.0000 (7) | 0.0005 (6) | 0.0027 (7) |
C2 | 0.0210 (11) | 0.0389 (14) | 0.0193 (11) | −0.0028 (10) | 0.0036 (8) | −0.0018 (10) |
C3 | 0.0252 (12) | 0.0462 (18) | 0.0188 (11) | 0.0003 (12) | 0.0038 (8) | −0.0010 (12) |
C4 | 0.0195 (11) | 0.0475 (19) | 0.0209 (12) | −0.0017 (11) | 0.0031 (9) | 0.0063 (11) |
C5 | 0.0226 (11) | 0.0370 (15) | 0.0339 (16) | −0.0070 (11) | 0.0031 (12) | 0.0069 (12) |
C6 | 0.0211 (11) | 0.0333 (13) | 0.0270 (13) | −0.0001 (9) | 0.0031 (10) | 0.0036 (10) |
C7 | 0.0360 (14) | 0.0286 (14) | 0.0456 (18) | −0.0076 (11) | 0.0091 (12) | −0.0032 (12) |
C8 | 0.0363 (14) | 0.0229 (13) | 0.0293 (14) | −0.0010 (10) | 0.0072 (11) | −0.0035 (11) |
C9 | 0.0259 (12) | 0.0280 (12) | 0.0183 (11) | 0.0073 (9) | 0.0103 (9) | 0.0088 (9) |
C10 | 0.0207 (8) | 0.0290 (9) | 0.0164 (8) | 0.0042 (7) | 0.0064 (6) | 0.0042 (7) |
C11 | 0.0231 (12) | 0.0472 (16) | 0.0242 (12) | 0.0054 (10) | −0.0003 (9) | −0.0023 (11) |
C12 | 0.0234 (12) | 0.068 (2) | 0.0288 (14) | 0.0095 (13) | −0.0005 (10) | 0.0042 (15) |
C13 | 0.0337 (15) | 0.0553 (19) | 0.0314 (14) | 0.0211 (14) | 0.0092 (12) | 0.0109 (13) |
C14 | 0.0388 (15) | 0.0398 (15) | 0.0258 (14) | 0.0160 (11) | 0.0142 (11) | 0.0118 (11) |
S1 | 0.0212 (3) | 0.0496 (3) | 0.0390 (3) | 0.0011 (2) | 0.00652 (19) | 0.0107 (2) |
O2 | 0.0173 (7) | 0.0631 (10) | 0.0486 (9) | −0.0003 (6) | 0.0059 (6) | 0.0105 (8) |
C17 | 0.0315 (11) | 0.0599 (15) | 0.0430 (12) | 0.0056 (10) | 0.0013 (9) | −0.0136 (11) |
C16 | 0.0253 (10) | 0.0509 (14) | 0.0488 (12) | −0.0079 (9) | 0.0098 (9) | −0.0113 (10) |
O1—C15 | 1.2357 (19) | C9—C14 | 1.392 (3) |
N1—C15 | 1.382 (2) | C9—C10 | 1.399 (3) |
N1—C10 | 1.434 (2) | C10—C11 | 1.376 (3) |
N1—C1 | 1.439 (2) | C10—C11A | 1.3900 |
C15—N2 | 1.339 (2) | C10—C9A | 1.3900 |
N2—H2A | 0.85 (2) | C11A—C12A | 1.3900 |
N2—H2B | 0.82 (2) | C11A—H11A | 0.9500 |
C1—C2 | 1.390 (3) | C12A—C13A | 1.3900 |
C1—C2A | 1.3900 | C12A—H12A | 0.9500 |
C1—C6A | 1.3900 | C13A—C14A | 1.3900 |
C1—C6 | 1.391 (3) | C13A—H13A | 0.9500 |
C2A—C3A | 1.3900 | C14A—C9A | 1.3900 |
C2A—H2C | 0.9500 | C14A—H14A | 0.9500 |
C3A—C4A | 1.3900 | C9A—C8A | 1.494 (7) |
C3A—H3A | 0.9500 | C7A—C8A | 1.527 (14) |
C4A—C5A | 1.3900 | C7A—H7C | 0.9900 |
C4A—H4A | 0.9500 | C7A—H7D | 0.9900 |
C5A—C6A | 1.3900 | C8A—H8C | 0.9900 |
C5A—H5A | 0.9500 | C8A—H8D | 0.9900 |
C6A—C7A | 1.533 (8) | C11—C12 | 1.384 (4) |
C2—C3 | 1.393 (3) | C11—H11 | 0.9500 |
C2—H2 | 0.9500 | C12—C13 | 1.368 (4) |
C3—C4 | 1.376 (4) | C12—H12 | 0.9500 |
C3—H3 | 0.9500 | C13—C14 | 1.375 (4) |
C4—C5 | 1.365 (4) | C13—H13 | 0.9500 |
C4—H4 | 0.9500 | C14—H14 | 0.9500 |
C5—C6 | 1.401 (3) | S1—O2 | 1.5030 (14) |
C5—H5 | 0.9500 | S1—C16 | 1.776 (2) |
C6—C7 | 1.504 (3) | S1—C17 | 1.777 (2) |
C7—C8 | 1.516 (4) | C17—H17A | 0.9800 |
C7—H7A | 0.9900 | C17—H17B | 0.9800 |
C7—H7B | 0.9900 | C17—H17C | 0.9800 |
C8—C9 | 1.507 (3) | C16—H16A | 0.9800 |
C8—H8A | 0.9900 | C16—H16B | 0.9800 |
C8—H8B | 0.9900 | C16—H16C | 0.9800 |
C15—N1—C10 | 121.95 (13) | C11—C10—C9A | 108.3 (2) |
C15—N1—C1 | 118.02 (13) | C11A—C10—C9A | 120.0 |
C10—N1—C1 | 115.22 (13) | C11—C10—C9 | 121.72 (19) |
O1—C15—N2 | 122.95 (16) | C11A—C10—C9 | 131.7 (2) |
O1—C15—N1 | 119.68 (14) | C11—C10—N1 | 121.96 (19) |
N2—C15—N1 | 117.36 (14) | C11A—C10—N1 | 111.4 (2) |
C15—N2—H2A | 116.5 (14) | C9A—C10—N1 | 128.6 (2) |
C15—N2—H2B | 124.7 (15) | C9—C10—N1 | 116.20 (17) |
H2A—N2—H2B | 119 (2) | C10—C11A—C12A | 120.0 |
C2—C1—C6A | 129.5 (3) | C10—C11A—H11A | 120.0 |
C2A—C1—C6A | 120.0 | C12A—C11A—H11A | 120.0 |
C2—C1—C6 | 121.50 (18) | C13A—C12A—C11A | 120.0 |
C2A—C1—C6 | 111.3 (3) | C13A—C12A—H12A | 120.0 |
C2—C1—N1 | 116.10 (17) | C11A—C12A—H12A | 120.0 |
C2A—C1—N1 | 125.7 (3) | C12A—C13A—C14A | 120.0 |
C6A—C1—N1 | 114.2 (3) | C12A—C13A—H13A | 120.0 |
C6—C1—N1 | 122.35 (17) | C14A—C13A—H13A | 120.0 |
C1—C2A—C3A | 120.0 | C13A—C14A—C9A | 120.0 |
C1—C2A—H2C | 120.0 | C13A—C14A—H14A | 120.0 |
C3A—C2A—H2C | 120.0 | C9A—C14A—H14A | 120.0 |
C2A—C3A—C4A | 120.0 | C14A—C9A—C10 | 120.0 |
C2A—C3A—H3A | 120.0 | C14A—C9A—C8A | 120.6 (5) |
C4A—C3A—H3A | 120.0 | C10—C9A—C8A | 119.4 (5) |
C3A—C4A—C5A | 120.0 | C8A—C7A—C6A | 113.2 (8) |
C3A—C4A—H4A | 120.0 | C8A—C7A—H7C | 108.9 |
C5A—C4A—H4A | 120.0 | C6A—C7A—H7C | 108.9 |
C6A—C5A—C4A | 120.0 | C8A—C7A—H7D | 108.9 |
C6A—C5A—H5A | 120.0 | C6A—C7A—H7D | 108.9 |
C4A—C5A—H5A | 120.0 | H7C—C7A—H7D | 107.7 |
C5A—C6A—C1 | 120.0 | C9A—C8A—C7A | 121.8 (8) |
C5A—C6A—C7A | 120.2 (5) | C9A—C8A—H8C | 106.9 |
C1—C6A—C7A | 119.7 (5) | C7A—C8A—H8C | 106.9 |
C1—C2—C3 | 119.9 (2) | C9A—C8A—H8D | 106.9 |
C1—C2—H2 | 120.0 | C7A—C8A—H8D | 106.9 |
C3—C2—H2 | 120.0 | H8C—C8A—H8D | 106.7 |
C4—C3—C2 | 119.1 (2) | C10—C11—C12 | 119.2 (2) |
C4—C3—H3 | 120.4 | C10—C11—H11 | 120.4 |
C2—C3—H3 | 120.4 | C12—C11—H11 | 120.4 |
C5—C4—C3 | 120.5 (2) | C13—C12—C11 | 120.1 (2) |
C5—C4—H4 | 119.7 | C13—C12—H12 | 119.9 |
C3—C4—H4 | 119.7 | C11—C12—H12 | 119.9 |
C4—C5—C6 | 122.2 (2) | C12—C13—C14 | 120.8 (2) |
C4—C5—H5 | 118.9 | C12—C13—H13 | 119.6 |
C6—C5—H5 | 118.9 | C14—C13—H13 | 119.6 |
C1—C6—C5 | 116.7 (2) | C13—C14—C9 | 120.7 (2) |
C1—C6—C7 | 125.1 (2) | C13—C14—H14 | 119.7 |
C5—C6—C7 | 118.2 (2) | C9—C14—H14 | 119.7 |
C6—C7—C8 | 120.0 (2) | O2—S1—C16 | 105.90 (10) |
C6—C7—H7A | 107.3 | O2—S1—C17 | 106.44 (10) |
C8—C7—H7A | 107.3 | C16—S1—C17 | 96.39 (10) |
C6—C7—H7B | 107.3 | S1—C17—H17A | 109.5 |
C8—C7—H7B | 107.3 | S1—C17—H17B | 109.5 |
H7A—C7—H7B | 106.9 | H17A—C17—H17B | 109.5 |
C9—C8—C7 | 113.1 (2) | S1—C17—H17C | 109.5 |
C9—C8—H8A | 109.0 | H17A—C17—H17C | 109.5 |
C7—C8—H8A | 109.0 | H17B—C17—H17C | 109.5 |
C9—C8—H8B | 109.0 | S1—C16—H16A | 109.5 |
C7—C8—H8B | 109.0 | S1—C16—H16B | 109.5 |
H8A—C8—H8B | 107.8 | H16A—C16—H16B | 109.5 |
C14—C9—C10 | 117.5 (2) | S1—C16—H16C | 109.5 |
C14—C9—C8 | 123.4 (2) | H16A—C16—H16C | 109.5 |
C10—C9—C8 | 119.06 (19) | H16B—C16—H16C | 109.5 |
C10—N1—C1—C2 | −116.0 (2) | C3—C4—C5—C6 | 0.1 (4) |
C10—N1—C1—C6 | 61.5 (2) | C4—C5—C6—C1 | −0.2 (4) |
C15—N1—C1—C2 | 88.1 (2) | C4—C5—C6—C7 | −178.5 (3) |
C15—N1—C1—C6 | −94.5 (2) | C1—C6—C7—C8 | −3.8 (4) |
C1—N1—C10—C9 | −72.6 (2) | C5—C6—C7—C8 | 174.3 (3) |
C1—N1—C10—C11 | 103.6 (2) | C6—C7—C8—C9 | −51.3 (4) |
C15—N1—C10—C9 | 82.3 (2) | C7—C8—C9—C10 | 70.4 (3) |
C15—N1—C10—C11 | −101.5 (2) | C7—C8—C9—C14 | −109.7 (3) |
C1—N1—C15—O1 | −10.6 (2) | C8—C9—C10—N1 | −3.0 (3) |
C1—N1—C15—N2 | 170.45 (15) | C8—C9—C10—C11 | −179.1 (2) |
C10—N1—C15—O1 | −164.93 (15) | C14—C9—C10—N1 | 177.14 (19) |
C10—N1—C15—N2 | 16.2 (2) | C14—C9—C10—C11 | 1.0 (3) |
N1—C1—C2—C3 | 178.2 (2) | C8—C9—C14—C13 | 179.4 (3) |
C6—C1—C2—C3 | 0.8 (4) | C10—C9—C14—C13 | −0.8 (4) |
N1—C1—C6—C5 | −177.6 (2) | N1—C10—C11—C12 | −176.6 (2) |
N1—C1—C6—C7 | 0.6 (4) | C9—C10—C11—C12 | −0.7 (3) |
C2—C1—C6—C5 | −0.2 (4) | C10—C11—C12—C13 | 0.2 (4) |
C2—C1—C6—C7 | 177.9 (3) | C11—C12—C13—C14 | 0.0 (4) |
C1—C2—C3—C4 | −0.9 (4) | C12—C13—C14—C9 | 0.3 (4) |
C2—C3—C4—C5 | 0.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.85 (2) | 2.05 (2) | 2.8977 (19) | 171 (2) |
N2—H2B···O2 | 0.82 (2) | 2.13 (2) | 2.885 (2) | 154 (2) |
C16—H16C···O1ii | 0.98 | 2.45 | 3.294 (2) | 143 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H14N2O·C2H6OS |
Mr | 316.41 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 10.2696 (3), 6.8543 (2), 23.3599 (6) |
β (°) | 98.932 (2) |
V (Å3) | 1624.39 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.24 × 0.10 × 0.07 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini |
Absorption correction | Analytical [CrysAlis RED (Oxford Diffraction, 2000), based on Clark & Reid (1995)] |
Tmin, Tmax | 0.952, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16299, 3326, 2627 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.114, 1.06 |
No. of reflections | 3326 |
No. of parameters | 223 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.71, −0.39 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2000), CrysAlis RED (Oxford Diffraction, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.85 (2) | 2.05 (2) | 2.8977 (19) | 171 (2) |
N2—H2B···O2 | 0.82 (2) | 2.13 (2) | 2.885 (2) | 154 (2) |
C16—H16C···O1ii | 0.9800 | 2.4500 | 3.294 (2) | 143.00 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x−1, y, z. |
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10,11-Dihydrocarbamazepine (DHC) is a recognized impurity in carbamazepine (CBZ), a dibenzazepine drug used to control seizures (Cyr et al., 1987). DHC is known to crystallize in three polymorphic forms: monoclinic form I (Bandoli et al., 1992), orthorhombic form II (Harrison et al., 2006) and triclinic form III (Leech et al., 2007a). The title compound, was produced during an automated parallel crystallization study (Florence, Johnston, Fernandes et al., 2006) on DHC as part of a wider investigation into the predicted and experimental structures of CBZ (Florence, Johnston, Price et al., 2006; Florence, Leech et al., 2006) and related molecules (Leech et al., 2007). The sample was identified as a new form using multi-sample foil transmission X-ray powder diffraction analysis (Florence et al., 2003). Subsequent manual recrystallization, from a saturated dimethyl sulfoxide (DMSO) solution, by cooling to 273 K yielded single crystals suitable for X-ray diffraction. The molecular structure is shown in Fig. 1.
In the crystal structure, DHC molecules are partially disordered over two sites with the major component of this disorder being present at approximately 81%.
DHC molecules form a centrosymmetric hydrogen-bonded R22(8) dimer motif (Etter, 1990) via N2—H2A···O1i (symmetry code as in the Hydrogen Bond Geometry table) contacts in contrast to the C(4) catameric configuration observed in each of the three polymorphic forms. In the title structure, the DHC molecules form a second N—H···O hydrogen bond to atom O2 of the solvent molecule (Fig. 2) to form a packing motif also observed in the CBZ DMSO solvate (Fleischman et al., 2003).