Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041049/wn2194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041049/wn2194Isup2.hkl |
CCDC reference: 660350
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- R factor = 0.074
- wR factor = 0.193
- Data-to-parameter ratio = 63.7
checkCIF/PLATON results
No syntax errors found
Alert level A REFLT03_ALERT_3_A Reflection count > 15% excess reflns - sys abs data present? From the CIF: _diffrn_reflns_theta_max 26.00 From the CIF: _diffrn_reflns_theta_full 26.00 From the CIF: _reflns_number_total 13441 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2824 Completeness (_total/calc) 475.96%
Author Response: Twinned crystal. Data treated using the HKLF 5 convention. The number given for reflection count thus refers to all reflections from BOTH twin components. |
PLAT021_ALERT_1_A Ratio Unique / Expected Reflections too High ... 4.76
Author Response: See above response. |
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.624 1.000 Tmin(prime) and Tmax expected: 0.993 0.998 RR(prime) = 0.628 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ............. 0.63
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.106 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.11 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 40 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.998 Tmax scaled 0.998 Tmin scaled 0.623
2 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For details of experimental methods used to obtain this compound, see: Florence et al. (2003); Florence, Johnston, Fernandes et al. (2006). For related crystal structures, see: Bandoli et al. (1992); Cyr et al. (1987); Harrison et al. (2006); Leech et al. (2007); Fleischman et al. (2003); Florence, Johnston, Price et al. (2006); Florence, Leech et al. (2006); Johnston et al. (2006, 2007). For related literature, see: Etter (1990).
DHC was used as received from SigmaAldrich and a single-crystal sample of the title compound was obtained by isothermal solvent evaporation of a saturated formamide solution at 298 K.
All crystals examined were twinned by a 180° rotation about -1 1 0. The model reported utilized the SHELX HKLF 5 convention where the ratio of the two twin components refined to 0.518 (3):0.482 (3). H atoms in the formamide solvent and the NH2 group of the DHC molecule were found by difference synthesis and refined isotropically; C—H = 1.026 (19) and N—H = 0.87 (2)–0.94 (2) Å. All other H atoms were constrained to idealized geometry with riding models: Uiso(H) = 1.2Ueq(C); C—H distances = 0.95 and 0.99 Å for CH and CH2 groups, respectively.
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., 2007). The title compound was produced during an automated parallel crystallization study (Florence, Johnston, Fernandes et al., 2006) on DHC as part of a wider study 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 formamide solution by slow evaporation at 298 K, yielded single crystals suitable for X-ray diffraction (Fig. 1).
The molecules adopt a hydrogen-bonded arrangement similar to that observed in the DHC acetic acid (1/1) (Johnston et al., 2006) and DHC formic acid (1/1) solvates (Johnston et al., 2007). Specifically, the DHC and formamide molecules are connected via N2—H2N···O2 and N3—H4N···O1 hydrogen bonds to form an R22(8) (Etter, 1990) dimer motif (Table 1). Two further hydrogen bonds, N2—H1···O2i and N3—H3N···O1ii form centrosymmetric R24(8) motifs that link the R22(8) DHC/formamide dimers in a ladder arrangement running parallel to the c axis (Fig. 2).
For details of experimental methods used to obtain this compound, see: Florence et al. (2003); Florence, Johnston, Fernandes et al. (2006). For related crystal structures, see: Bandoli et al. (1992); Cyr et al. (1987); Harrison et al. (2006); Leech et al. (2007); Fleischman et al. (2003); Florence, Johnston, Price et al. (2006); Florence, Leech et al. (2006); Johnston et al. (2006, 2007). For related literature, see: Etter (1990).
Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C15H14N2O·CH3NO | Z = 2 |
Mr = 283.33 | F(000) = 300 |
Triclinic, P1 | Dx = 1.313 Mg m−3 |
a = 8.4690 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.0215 (4) Å | Cell parameters from 3115 reflections |
c = 10.3137 (4) Å | θ = 2.9–27.5° |
α = 74.363 (3)° | µ = 0.09 mm−1 |
β = 83.630 (3)° | T = 120 K |
γ = 70.847 (3)° | Slab, colourless |
V = 716.61 (5) Å3 | 0.08 × 0.06 × 0.02 mm |
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 13441 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 7956 reflections with I > 2σ(I) |
10cm confocal mirrors monochromator | Rint = 0.106 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.0°, θmin = 2.9° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −11→11 |
Tmin = 0.624, Tmax = 1 | l = −12→12 |
16142 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.074 | w = 1/[σ2(Fo2) + (0.0295P)2 + 2.9523P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.194 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.37 e Å−3 |
13441 reflections | Δρmin = −0.34 e Å−3 |
211 parameters |
C15H14N2O·CH3NO | γ = 70.847 (3)° |
Mr = 283.33 | V = 716.61 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.4690 (4) Å | Mo Kα radiation |
b = 9.0215 (4) Å | µ = 0.09 mm−1 |
c = 10.3137 (4) Å | T = 120 K |
α = 74.363 (3)° | 0.08 × 0.06 × 0.02 mm |
β = 83.630 (3)° |
Bruker Nonius 95mm CCD camera on κ-goniostat diffractometer | 13441 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 7956 reflections with I > 2σ(I) |
Tmin = 0.624, Tmax = 1 | Rint = 0.106 |
16142 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.194 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.37 e Å−3 |
13441 reflections | Δρmin = −0.34 e Å−3 |
211 parameters |
Experimental. Data collection at Soton service 2006src1503. Data treated as twinned (180 ° rot) about -1 1 0 hklf 5 file created. SADABS does not output Tmin and Tmax - but the ratio is reported as 0.62441. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.66395 (16) | 0.07647 (16) | 0.62574 (12) | 0.0278 (3) | |
N1 | 0.78725 (19) | 0.21960 (19) | 0.70960 (15) | 0.0228 (4) | |
N2 | 0.6485 (2) | 0.0536 (2) | 0.85028 (17) | 0.0318 (4) | |
C1 | 0.8002 (2) | 0.2875 (2) | 0.81820 (18) | 0.0237 (5) | |
C2 | 0.9315 (2) | 0.2155 (2) | 0.90536 (18) | 0.0269 (5) | |
H2 | 1.0145 | 0.1178 | 0.8963 | 0.032* | |
C3 | 0.9412 (3) | 0.2868 (3) | 1.00620 (19) | 0.0305 (5) | |
H3 | 1.0299 | 0.2375 | 1.0680 | 0.037* | |
C4 | 0.8201 (3) | 0.4309 (3) | 1.01629 (19) | 0.0339 (5) | |
H4 | 0.8263 | 0.4801 | 1.0854 | 0.041* | |
C5 | 0.6905 (3) | 0.5036 (3) | 0.92678 (19) | 0.0303 (5) | |
H5 | 0.6095 | 0.6031 | 0.9339 | 0.036* | |
C6 | 0.6782 (2) | 0.4316 (2) | 0.82621 (19) | 0.0268 (5) | |
C7 | 0.5462 (2) | 0.5087 (2) | 0.72184 (18) | 0.0279 (5) | |
H7A | 0.4567 | 0.5968 | 0.7510 | 0.034* | |
H7B | 0.4959 | 0.4270 | 0.7134 | 0.034* | |
C8 | 0.6176 (2) | 0.5775 (2) | 0.58525 (19) | 0.0287 (5) | |
H8A | 0.5250 | 0.6264 | 0.5210 | 0.034* | |
H8B | 0.6566 | 0.6663 | 0.5941 | 0.034* | |
C9 | 0.7598 (2) | 0.4634 (2) | 0.52278 (19) | 0.0247 (5) | |
C10 | 0.8252 (2) | 0.5318 (3) | 0.39736 (19) | 0.0273 (5) | |
H10 | 0.7784 | 0.6443 | 0.3579 | 0.033* | |
C11 | 0.9537 (3) | 0.4415 (3) | 0.33078 (19) | 0.0293 (5) | |
H11 | 0.9953 | 0.4917 | 0.2469 | 0.035* | |
C12 | 1.0230 (3) | 0.2771 (3) | 0.38566 (19) | 0.0294 (5) | |
H12 | 1.1098 | 0.2130 | 0.3386 | 0.035* | |
C13 | 0.9645 (2) | 0.2072 (2) | 0.50968 (19) | 0.0249 (5) | |
H13 | 1.0139 | 0.0950 | 0.5491 | 0.030* | |
C14 | 0.8346 (2) | 0.2986 (2) | 0.57749 (18) | 0.0223 (4) | |
C15 | 0.6970 (2) | 0.1151 (2) | 0.72422 (18) | 0.0244 (5) | |
O2 | 0.36473 (18) | −0.07760 (18) | 0.86899 (13) | 0.0367 (4) | |
N3 | 0.3791 (2) | −0.0440 (2) | 0.64367 (17) | 0.0297 (4) | |
C16 | 0.3135 (3) | −0.0850 (3) | 0.7648 (2) | 0.0286 (5) | |
H1N | 0.659 (3) | 0.095 (2) | 0.921 (2) | 0.037 (6)* | |
H2N | 0.575 (3) | 0.004 (2) | 0.859 (2) | 0.032 (6)* | |
H3N | 0.347 (3) | −0.065 (2) | 0.573 (2) | 0.036 (6)* | |
H4N | 0.475 (3) | −0.010 (3) | 0.631 (2) | 0.043 (7)* | |
H16 | 0.214 (2) | −0.127 (2) | 0.7653 (18) | 0.028 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0350 (8) | 0.0344 (9) | 0.0213 (7) | −0.0180 (7) | −0.0003 (6) | −0.0100 (6) |
N1 | 0.0284 (9) | 0.0260 (10) | 0.0166 (8) | −0.0136 (8) | 0.0009 (7) | −0.0039 (7) |
N2 | 0.0453 (12) | 0.0383 (12) | 0.0207 (10) | −0.0262 (10) | 0.0015 (9) | −0.0065 (9) |
C1 | 0.0292 (11) | 0.0288 (12) | 0.0173 (10) | −0.0165 (10) | 0.0022 (9) | −0.0043 (9) |
C2 | 0.0290 (11) | 0.0297 (12) | 0.0235 (11) | −0.0142 (10) | −0.0022 (9) | −0.0023 (9) |
C3 | 0.0292 (12) | 0.0422 (14) | 0.0228 (11) | −0.0193 (11) | −0.0046 (9) | −0.0009 (10) |
C4 | 0.0455 (14) | 0.0485 (15) | 0.0197 (11) | −0.0292 (12) | 0.0012 (10) | −0.0106 (10) |
C5 | 0.0314 (12) | 0.0349 (13) | 0.0270 (12) | −0.0131 (10) | 0.0051 (9) | −0.0106 (10) |
C6 | 0.0289 (12) | 0.0341 (13) | 0.0217 (11) | −0.0166 (10) | 0.0014 (9) | −0.0064 (9) |
C7 | 0.0272 (11) | 0.0329 (12) | 0.0247 (11) | −0.0095 (9) | −0.0027 (9) | −0.0079 (9) |
C8 | 0.0259 (11) | 0.0300 (12) | 0.0296 (12) | −0.0072 (10) | −0.0027 (9) | −0.0075 (9) |
C9 | 0.0240 (11) | 0.0312 (12) | 0.0236 (11) | −0.0130 (9) | −0.0074 (9) | −0.0066 (9) |
C10 | 0.0291 (12) | 0.0299 (12) | 0.0242 (11) | −0.0128 (10) | −0.0076 (9) | −0.0014 (9) |
C11 | 0.0337 (12) | 0.0433 (14) | 0.0179 (10) | −0.0239 (11) | −0.0006 (9) | −0.0041 (10) |
C12 | 0.0312 (12) | 0.0369 (14) | 0.0259 (12) | −0.0131 (10) | 0.0015 (9) | −0.0150 (10) |
C13 | 0.0279 (11) | 0.0252 (11) | 0.0241 (11) | −0.0103 (9) | −0.0035 (9) | −0.0068 (9) |
C14 | 0.0248 (11) | 0.0277 (12) | 0.0196 (10) | −0.0150 (9) | −0.0023 (8) | −0.0052 (9) |
C15 | 0.0285 (11) | 0.0251 (12) | 0.0204 (11) | −0.0105 (9) | −0.0021 (9) | −0.0037 (9) |
O2 | 0.0442 (9) | 0.0517 (10) | 0.0228 (8) | −0.0262 (8) | 0.0016 (7) | −0.0103 (7) |
N3 | 0.0329 (11) | 0.0411 (12) | 0.0199 (10) | −0.0177 (9) | 0.0018 (8) | −0.0088 (8) |
C16 | 0.0294 (12) | 0.0319 (13) | 0.0272 (12) | −0.0128 (10) | −0.0004 (10) | −0.0079 (10) |
O1—C15 | 1.245 (2) | C7—H7B | 0.9900 |
N1—C15 | 1.366 (2) | C8—C9 | 1.515 (3) |
N1—C14 | 1.438 (2) | C8—H8A | 0.9900 |
N1—C1 | 1.444 (2) | C8—H8B | 0.9900 |
N2—C15 | 1.345 (2) | C9—C14 | 1.393 (3) |
N2—H1N | 0.93 (2) | C9—C10 | 1.413 (3) |
N2—H2N | 0.87 (2) | C10—C11 | 1.369 (3) |
C1—C2 | 1.378 (3) | C10—H10 | 0.9500 |
C1—C6 | 1.386 (3) | C11—C12 | 1.384 (3) |
C2—C3 | 1.384 (3) | C11—H11 | 0.9500 |
C2—H2 | 0.9500 | C12—C13 | 1.382 (3) |
C3—C4 | 1.389 (3) | C12—H12 | 0.9500 |
C3—H3 | 0.9500 | C13—C14 | 1.387 (3) |
C4—C5 | 1.383 (3) | C13—H13 | 0.9500 |
C4—H4 | 0.9500 | O2—C16 | 1.228 (2) |
C5—C6 | 1.393 (3) | N3—C16 | 1.318 (3) |
C5—H5 | 0.9500 | N3—H3N | 0.88 (2) |
C6—C7 | 1.499 (3) | N3—H4N | 0.94 (2) |
C7—C8 | 1.524 (3) | C16—H16 | 1.026 (19) |
C7—H7A | 0.9900 | ||
C15—N1—C14 | 120.22 (14) | C7—C8—H8A | 107.8 |
C15—N1—C1 | 121.60 (15) | C9—C8—H8B | 107.8 |
C14—N1—C1 | 116.19 (14) | C7—C8—H8B | 107.8 |
C15—N2—H1N | 120.6 (13) | H8A—C8—H8B | 107.1 |
C15—N2—H2N | 117.3 (13) | C14—C9—C10 | 116.65 (19) |
H1N—N2—H2N | 117.9 (19) | C14—C9—C8 | 126.67 (17) |
C2—C1—C6 | 122.17 (18) | C10—C9—C8 | 116.67 (19) |
C2—C1—N1 | 121.25 (18) | C11—C10—C9 | 122.3 (2) |
C6—C1—N1 | 116.52 (17) | C11—C10—H10 | 118.9 |
C1—C2—C3 | 119.3 (2) | C9—C10—H10 | 118.9 |
C1—C2—H2 | 120.3 | C10—C11—C12 | 119.96 (18) |
C3—C2—H2 | 120.3 | C10—C11—H11 | 120.0 |
C2—C3—C4 | 119.43 (19) | C12—C11—H11 | 120.0 |
C2—C3—H3 | 120.3 | C13—C12—C11 | 119.20 (19) |
C4—C3—H3 | 120.3 | C13—C12—H12 | 120.4 |
C5—C4—C3 | 120.70 (19) | C11—C12—H12 | 120.4 |
C5—C4—H4 | 119.6 | C12—C13—C14 | 120.90 (19) |
C3—C4—H4 | 119.6 | C12—C13—H13 | 119.5 |
C4—C5—C6 | 120.3 (2) | C14—C13—H13 | 119.5 |
C4—C5—H5 | 119.8 | C13—C14—C9 | 120.99 (17) |
C6—C5—H5 | 119.8 | C13—C14—N1 | 117.68 (18) |
C1—C6—C5 | 118.01 (18) | C9—C14—N1 | 121.21 (17) |
C1—C6—C7 | 119.05 (17) | O1—C15—N2 | 121.61 (18) |
C5—C6—C7 | 122.8 (2) | O1—C15—N1 | 121.52 (17) |
C6—C7—C8 | 111.57 (16) | N2—C15—N1 | 116.85 (16) |
C6—C7—H7A | 109.3 | C16—N3—H3N | 121.0 (13) |
C8—C7—H7A | 109.3 | C16—N3—H4N | 121.2 (13) |
C6—C7—H7B | 109.3 | H3N—N3—H4N | 116.8 (19) |
C8—C7—H7B | 109.3 | O2—C16—N3 | 124.7 (2) |
H7A—C7—H7B | 108.0 | O2—C16—H16 | 121.8 (10) |
C9—C8—C7 | 118.16 (17) | N3—C16—H16 | 113.5 (10) |
C9—C8—H8A | 107.8 | ||
C15—N1—C1—C2 | 93.5 (2) | C14—C9—C10—C11 | 1.1 (3) |
C14—N1—C1—C2 | −102.6 (2) | C8—C9—C10—C11 | 179.94 (17) |
C15—N1—C1—C6 | −89.2 (2) | C9—C10—C11—C12 | 0.5 (3) |
C14—N1—C1—C6 | 74.8 (2) | C10—C11—C12—C13 | −2.0 (3) |
C6—C1—C2—C3 | 1.3 (3) | C11—C12—C13—C14 | 1.9 (3) |
N1—C1—C2—C3 | 178.50 (16) | C12—C13—C14—C9 | −0.2 (3) |
C1—C2—C3—C4 | −1.1 (3) | C12—C13—C14—N1 | −176.34 (16) |
C2—C3—C4—C5 | 0.0 (3) | C10—C9—C14—C13 | −1.3 (2) |
C3—C4—C5—C6 | 1.0 (3) | C8—C9—C14—C13 | −179.96 (18) |
C2—C1—C6—C5 | −0.3 (3) | C10—C9—C14—N1 | 174.74 (15) |
N1—C1—C6—C5 | −177.66 (16) | C8—C9—C14—N1 | −4.0 (3) |
C2—C1—C6—C7 | 175.70 (17) | C15—N1—C14—C13 | −75.5 (2) |
N1—C1—C6—C7 | −1.6 (3) | C1—N1—C14—C13 | 120.26 (19) |
C4—C5—C6—C1 | −0.8 (3) | C15—N1—C14—C9 | 108.3 (2) |
C4—C5—C6—C7 | −176.68 (18) | C1—N1—C14—C9 | −55.9 (2) |
C1—C6—C7—C8 | −70.4 (2) | C14—N1—C15—O1 | 5.3 (3) |
C5—C6—C7—C8 | 105.5 (2) | C1—N1—C15—O1 | 168.59 (18) |
C6—C7—C8—C9 | 57.7 (2) | C14—N1—C15—N2 | −176.03 (18) |
C7—C8—C9—C14 | −0.1 (3) | C1—N1—C15—N2 | −12.7 (3) |
C7—C8—C9—C10 | −178.80 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2 | 0.87 (2) | 2.12 (2) | 2.975 (2) | 170.0 (19) |
N2—H1N···O2i | 0.93 (2) | 2.12 (2) | 2.948 (2) | 147.6 (17) |
N3—H4N···O1 | 0.94 (2) | 1.99 (2) | 2.924 (2) | 172.2 (19) |
N3—H3N···O1ii | 0.88 (2) | 2.10 (2) | 2.945 (2) | 159.7 (18) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H14N2O·CH3NO |
Mr | 283.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 8.4690 (4), 9.0215 (4), 10.3137 (4) |
α, β, γ (°) | 74.363 (3), 83.630 (3), 70.847 (3) |
V (Å3) | 716.61 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.08 × 0.06 × 0.02 |
Data collection | |
Diffractometer | Bruker Nonius 95mm CCD camera on κ-goniostat |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.624, 1 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16142, 13441, 7956 |
Rint | 0.106 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.194, 1.04 |
No. of reflections | 13441 |
No. of parameters | 211 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.34 |
Computer programs: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997), COLLECT and DENZO, DENZO, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O2 | 0.87 (2) | 2.12 (2) | 2.975 (2) | 170.0 (19) |
N2—H1N···O2i | 0.93 (2) | 2.12 (2) | 2.948 (2) | 147.6 (17) |
N3—H4N···O1 | 0.94 (2) | 1.99 (2) | 2.924 (2) | 172.2 (19) |
N3—H3N···O1ii | 0.88 (2) | 2.10 (2) | 2.945 (2) | 159.7 (18) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1. |
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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., 2007). The title compound was produced during an automated parallel crystallization study (Florence, Johnston, Fernandes et al., 2006) on DHC as part of a wider study 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 formamide solution by slow evaporation at 298 K, yielded single crystals suitable for X-ray diffraction (Fig. 1).
The molecules adopt a hydrogen-bonded arrangement similar to that observed in the DHC acetic acid (1/1) (Johnston et al., 2006) and DHC formic acid (1/1) solvates (Johnston et al., 2007). Specifically, the DHC and formamide molecules are connected via N2—H2N···O2 and N3—H4N···O1 hydrogen bonds to form an R22(8) (Etter, 1990) dimer motif (Table 1). Two further hydrogen bonds, N2—H1···O2i and N3—H3N···O1ii form centrosymmetric R24(8) motifs that link the R22(8) DHC/formamide dimers in a ladder arrangement running parallel to the c axis (Fig. 2).