Methane­sulfonic acid salt forms of carbamazepine and 10,11-di­hydro­carbamazepine

New methane­sulfonic acid salt forms of the anti­convulsant and analgesic active pharmaceutical ingredient carbamazepine and its closely related structural analogue 10,11-di­hydro­carbamazepine have been prepared and characterized by single-crystal X-ray diffraction at 120 and 100 K, respectively {namely [(5H-dibenzo[b,f]azepin-5-yl)(hy­droxy)methyl­idene]aza­nium methane­sulfonate, C₁₅H₁₃N₂O⁺·CH₃SO₃^-, and [(10,11-di­hydro-5H-dibenzo[b,f]azepin-5-yl)(hy­droxy)methyl­idene]aza­nium methane­sulfonate, C₁₅H₁₅N₂O⁺·CH₃SO₃^-}. In light of the structural information obtained, the crystal structure of the carbamazepine tri­fluoro­acetic acid monosol­vate [dibenzo[b,f]azepine-5-carboxamide-tri­fluoro­acetic acid (1/1), C₁₅H₁₂N₂O·CF₃COOH] was redetermined at 100 and 270 K, and from this data it was concluded that the protonation state for this solvate species is best described as in an `inter­mediate state' with the acidic proton located almost at the mid-point between the acid and base.

Computing details

Data collection: SMART (Bruker, 1999) for (3); CrysAlis PRO (Agilent, 2011) for (4), (5), (6). Cell refinement: SMART and SAINT (Bruker, 1999) for (3); CrysAlis PRO (Agilent, 2011) for (4), (5), (6). Data reduction: SAINT (Bruker, 1999) and SHELXTL (Sheldrick, 2008) for (3); CrysAlis PRO (Agilent, 2011) for (4), (5), (6). For all compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

(3) [(5H-Dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium methanesulfonate

Crystal data

C15H13N2O^+·CH3O3S^−	F(000) = 696
Mr = 332.37	Dx = 1.404 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.5673 (7) Å	Cell parameters from 876 reflections
b = 15.7196 (19) Å	θ = 2.6–27.9°
c = 18.125 (2) Å	µ = 0.23 mm^−1
β = 97.641 (4)°	T = 120 K
V = 1572.1 (3) Å^3	Prism, colourless
Z = 4	0.35 × 0.18 × 0.10 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer	2626 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 26.4°, θmin = 1.7°
Detector resolution: 8.192 pixels mm^-1	h = −6→6
ω scans	k = −19→19
13272 measured reflections	l = −22→22
3203 independent 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.750P] where P = (Fo^2 + 2Fc^2)/3
3203 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. Single-crystal X-ray data for (3) was measured at 120 K on a Bruker SMART 1 K X-ray diffractometer equipped with an Oxford Cryosystems Cryostream cooler using graphite-monochromated Mo Kα (λ = 0.71073 Å) radiation.

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

	x	y	z	Uiso*/Ueq
O1	0.7116 (2)	0.68279 (8)	0.37938 (6)	0.0228 (3)
H1A	0.784 (5)	0.6329 (19)	0.3586 (15)	0.061 (8)*
N1	0.5566 (3)	0.73258 (9)	0.47872 (8)	0.0194 (3)
N2	0.8099 (3)	0.61525 (10)	0.49083 (9)	0.0244 (3)
H2B	0.916 (4)	0.5868 (15)	0.4709 (13)	0.036 (6)*
H2C	0.799 (4)	0.6132 (15)	0.5370 (14)	0.039 (6)*
C1	0.4652 (3)	0.80545 (11)	0.43571 (10)	0.0221 (4)
C2	0.2549 (3)	0.79903 (13)	0.38618 (10)	0.0261 (4)
H2A	0.1664	0.7472	0.3815	0.031*
C3	0.1743 (4)	0.86908 (14)	0.34326 (11)	0.0333 (5)
H3A	0.0305	0.8654	0.3087	0.040*
C4	0.3046 (4)	0.94449 (14)	0.35096 (12)	0.0365 (5)
H4A	0.2497	0.9924	0.3215	0.044*
C5	0.5133 (4)	0.95038 (13)	0.40107 (12)	0.0342 (5)
H5A	0.6005	1.0025	0.4056	0.041*
C6	0.5995 (4)	0.88092 (12)	0.44550 (10)	0.0260 (4)
C7	0.8218 (4)	0.88805 (12)	0.49865 (11)	0.0297 (4)
H7A	0.9445	0.9242	0.4844	0.036*
C8	0.8718 (4)	0.84968 (12)	0.56468 (11)	0.0288 (4)
H8A	1.0266	0.8608	0.5918	0.035*
C9	0.7130 (3)	0.79217 (12)	0.59973 (10)	0.0237 (4)
C10	0.7161 (4)	0.79098 (13)	0.67723 (10)	0.0294 (4)
H10A	0.8281	0.8259	0.7076	0.035*
C11	0.5587 (4)	0.73972 (13)	0.70993 (10)	0.0302 (4)
H11A	0.5626	0.7402	0.7625	0.036*
C12	0.3952 (4)	0.68761 (13)	0.66703 (10)	0.0278 (4)
H12A	0.2854	0.6534	0.6899	0.033*
C13	0.3928 (3)	0.68570 (12)	0.59029 (10)	0.0235 (4)
H13A	0.2829	0.6496	0.5603	0.028*
C14	0.5517 (3)	0.73682 (11)	0.55793 (9)	0.0205 (4)
C15	0.6949 (3)	0.67510 (11)	0.44989 (9)	0.0197 (4)
S1	1.11791 (7)	0.52090 (3)	0.34676 (2)	0.01901 (13)
O2	0.8898 (2)	0.56267 (8)	0.31431 (7)	0.0261 (3)
O3	1.0868 (2)	0.43046 (8)	0.35405 (7)	0.0289 (3)
O4	1.2186 (2)	0.56268 (9)	0.41551 (7)	0.0278 (3)
C16	1.3180 (4)	0.53606 (15)	0.28087 (12)	0.0344 (5)
H16A	1.4767	0.5120	0.2998	0.052*
H16B	1.3353	0.5971	0.2717	0.052*
H16C	1.2540	0.5076	0.2343	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0302 (7)	0.0229 (7)	0.0155 (6)	0.0044 (5)	0.0041 (5)	0.0004 (5)
N1	0.0259 (8)	0.0173 (7)	0.0150 (7)	0.0002 (6)	0.0025 (6)	−0.0008 (6)
N2	0.0309 (9)	0.0258 (8)	0.0163 (8)	0.0070 (7)	0.0026 (6)	−0.0002 (7)
C1	0.0304 (10)	0.0188 (9)	0.0189 (9)	0.0039 (7)	0.0102 (7)	0.0005 (7)
C2	0.0276 (10)	0.0311 (10)	0.0210 (9)	0.0047 (8)	0.0082 (7)	0.0020 (8)
C3	0.0344 (11)	0.0426 (13)	0.0245 (10)	0.0155 (9)	0.0099 (8)	0.0054 (9)
C4	0.0508 (13)	0.0317 (11)	0.0302 (11)	0.0186 (10)	0.0173 (10)	0.0101 (9)
C5	0.0535 (13)	0.0215 (10)	0.0315 (11)	0.0043 (9)	0.0197 (10)	0.0029 (8)
C6	0.0365 (10)	0.0212 (9)	0.0227 (9)	0.0029 (8)	0.0130 (8)	−0.0002 (7)
C7	0.0388 (11)	0.0207 (9)	0.0319 (11)	−0.0100 (8)	0.0135 (9)	−0.0064 (8)
C8	0.0316 (10)	0.0252 (10)	0.0296 (10)	−0.0077 (8)	0.0043 (8)	−0.0072 (8)
C9	0.0277 (10)	0.0218 (9)	0.0220 (9)	−0.0009 (7)	0.0046 (7)	−0.0043 (7)
C10	0.0374 (11)	0.0287 (10)	0.0215 (9)	−0.0026 (8)	0.0018 (8)	−0.0089 (8)
C11	0.0401 (11)	0.0357 (11)	0.0154 (9)	0.0014 (9)	0.0059 (8)	−0.0032 (8)
C12	0.0307 (10)	0.0324 (11)	0.0219 (10)	−0.0007 (8)	0.0088 (8)	0.0003 (8)
C13	0.0239 (9)	0.0251 (10)	0.0214 (9)	−0.0016 (7)	0.0023 (7)	−0.0012 (7)
C14	0.0247 (9)	0.0211 (9)	0.0155 (8)	0.0033 (7)	0.0023 (7)	−0.0020 (7)
C15	0.0220 (8)	0.0190 (9)	0.0176 (8)	−0.0038 (7)	0.0006 (7)	−0.0020 (7)
S1	0.0188 (2)	0.0212 (2)	0.0170 (2)	0.00055 (16)	0.00206 (15)	−0.00143 (16)
O2	0.0258 (7)	0.0319 (7)	0.0196 (6)	0.0080 (5)	−0.0009 (5)	−0.0044 (5)
O3	0.0359 (8)	0.0240 (7)	0.0257 (7)	−0.0002 (6)	0.0006 (6)	0.0002 (5)
O4	0.0261 (7)	0.0329 (8)	0.0228 (7)	0.0017 (6)	−0.0024 (5)	−0.0066 (6)
C16	0.0296 (11)	0.0449 (13)	0.0308 (11)	−0.0090 (9)	0.0114 (8)	−0.0047 (9)

Geometric parameters (Å, º)

O1—C15	1.299 (2)	C7—H7A	0.9500
O1—H1A	0.98 (3)	C8—C9	1.467 (3)
N1—C15	1.338 (2)	C8—H8A	0.9500
N1—C1	1.440 (2)	C9—C14	1.399 (2)
N1—C14	1.441 (2)	C9—C10	1.403 (3)
N2—C15	1.311 (2)	C10—C11	1.381 (3)
N2—H2B	0.86 (3)	C10—H10A	0.9500
N2—H2C	0.85 (3)	C11—C12	1.384 (3)
C1—C2	1.381 (3)	C11—H11A	0.9500
C1—C6	1.401 (3)	C12—C13	1.390 (3)
C2—C3	1.388 (3)	C12—H12A	0.9500
C2—H2A	0.9500	C13—C14	1.382 (3)
C3—C4	1.387 (3)	C13—H13A	0.9500
C3—H3A	0.9500	S1—O3	1.4404 (14)
C4—C5	1.380 (3)	S1—O4	1.4534 (13)
C4—H4A	0.9500	S1—O2	1.4803 (13)
C5—C6	1.403 (3)	S1—C16	1.754 (2)
C5—H5A	0.9500	C16—H16A	0.9800
C6—C7	1.468 (3)	C16—H16B	0.9800
C7—C8	1.336 (3)	C16—H16C	0.9800
C15—O1—H1A	113.0 (16)	C14—C9—C8	121.97 (16)
C15—N1—C1	120.41 (14)	C10—C9—C8	120.93 (17)
C15—N1—C14	120.56 (14)	C11—C10—C9	120.90 (18)
C1—N1—C14	116.77 (13)	C11—C10—H10A	119.5
C15—N2—H2B	116.6 (15)	C9—C10—H10A	119.5
C15—N2—H2C	119.4 (16)	C10—C11—C12	120.78 (17)
H2B—N2—H2C	123 (2)	C10—C11—H11A	119.6
C2—C1—C6	122.42 (17)	C12—C11—H11A	119.6
C2—C1—N1	120.11 (16)	C11—C12—C13	119.56 (18)
C6—C1—N1	117.46 (16)	C11—C12—H12A	120.2
C1—C2—C3	119.30 (19)	C13—C12—H12A	120.2
C1—C2—H2A	120.4	C14—C13—C12	119.38 (17)
C3—C2—H2A	120.4	C14—C13—H13A	120.3
C4—C3—C2	119.7 (2)	C12—C13—H13A	120.3
C4—C3—H3A	120.1	C13—C14—C9	122.21 (16)
C2—C3—H3A	120.1	C13—C14—N1	119.58 (16)
C5—C4—C3	120.47 (19)	C9—C14—N1	118.20 (15)
C5—C4—H4A	119.8	O1—C15—N2	122.00 (16)
C3—C4—H4A	119.8	O1—C15—N1	116.21 (15)
C4—C5—C6	121.3 (2)	N2—C15—N1	121.78 (16)
C4—C5—H5A	119.4	O3—S1—O4	113.88 (8)
C6—C5—H5A	119.4	O3—S1—O2	111.52 (8)
C1—C6—C5	116.78 (19)	O4—S1—O2	110.66 (8)
C1—C6—C7	122.47 (17)	O3—S1—C16	106.95 (10)
C5—C6—C7	120.75 (18)	O4—S1—C16	108.35 (9)
C8—C7—C6	127.61 (18)	O2—S1—C16	104.96 (9)
C8—C7—H7A	116.2	S1—C16—H16A	109.5
C6—C7—H7A	116.2	S1—C16—H16B	109.5
C7—C8—C9	126.90 (18)	H16A—C16—H16B	109.5
C7—C8—H8A	116.6	S1—C16—H16C	109.5
C9—C8—H8A	116.6	H16A—C16—H16C	109.5
C14—C9—C10	117.10 (17)	H16B—C16—H16C	109.5
C15—N1—C1—C2	84.2 (2)	C14—C9—C10—C11	−2.7 (3)
C14—N1—C1—C2	−112.73 (18)	C8—C9—C10—C11	176.96 (19)
C15—N1—C1—C6	−94.7 (2)	C9—C10—C11—C12	0.6 (3)
C14—N1—C1—C6	68.3 (2)	C10—C11—C12—C13	1.2 (3)
C6—C1—C2—C3	1.2 (3)	C11—C12—C13—C14	−0.9 (3)
N1—C1—C2—C3	−177.70 (16)	C12—C13—C14—C9	−1.3 (3)
C1—C2—C3—C4	−0.4 (3)	C12—C13—C14—N1	177.54 (16)
C2—C3—C4—C5	−0.1 (3)	C10—C9—C14—C13	3.0 (3)
C3—C4—C5—C6	−0.1 (3)	C8—C9—C14—C13	−176.56 (18)
C2—C1—C6—C5	−1.4 (3)	C10—C9—C14—N1	−175.83 (16)
N1—C1—C6—C5	177.55 (15)	C8—C9—C14—N1	4.6 (3)
C2—C1—C6—C7	179.41 (17)	C15—N1—C14—C13	−86.7 (2)
N1—C1—C6—C7	−1.7 (3)	C1—N1—C14—C13	110.34 (19)
C4—C5—C6—C1	0.8 (3)	C15—N1—C14—C9	92.3 (2)
C4—C5—C6—C7	−179.96 (18)	C1—N1—C14—C9	−70.7 (2)
C1—C6—C7—C8	−34.2 (3)	C1—N1—C15—O1	−9.3 (2)
C5—C6—C7—C8	146.6 (2)	C14—N1—C15—O1	−171.65 (15)
C6—C7—C8—C9	−0.9 (3)	C1—N1—C15—N2	169.74 (16)
C7—C8—C9—C14	33.7 (3)	C14—N1—C15—N2	7.4 (3)
C7—C8—C9—C10	−145.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.98 (3)	1.53 (3)	2.5004 (18)	171 (3)
N2—H2C···O3^i	0.85 (3)	2.11 (3)	2.885 (2)	152 (2)
N2—H2B···O4	0.86 (3)	2.11 (3)	2.924 (2)	159 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

(4) [(9,10-Dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium methanesulfonate

Crystal data

C15H15N2O^+·CH3O3S^−	F(000) = 704
Mr = 334.38	Dx = 1.410 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.4477 (2) Å	Cell parameters from 3424 reflections
b = 15.7340 (7) Å	θ = 3.3–29.5°
c = 18.5034 (8) Å	µ = 0.23 mm^−1
β = 96.647 (4)°	T = 100 K
V = 1575.34 (11) Å^3	Lath, colourless
Z = 4	0.30 × 0.20 × 0.12 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3215 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2783 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.5598 pixels mm^-1	θmax = 26.4°, θmin = 1.7°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −19→18
Tmin = 0.766, Tmax = 1.000	l = −23→22
7104 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 0.7P] where P = (Fo^2 + 2Fc^2)/3
3215 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.8 (release 07-03-2011 CrysAlis171 .NET) (compiled Mar 7 2011,18:06:32) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Single-crystal X-ray data for structures (4), (5) and (6) were measured at 100 K [270 K for structure (6)], on an Oxford Diffraction (Agilent Technologies) SuperNova X-ray diffractometer equipped with an Oxford Cryosystems Cobra low-temperature device using either Mo Kα (λ = 0.71073 Å) radiation from a SuperNova Mo X-ray microsource (Nova) for (4) or Cu Kα (λ = 1.54173 Å) radiation from a SuperNova Cu X-ray microsource (Nova) for (5) and (6) and focusing mirror optics (Agilent, 2011).

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

	x	y	z	Uiso*/Ueq
O1	0.73850 (19)	0.67537 (7)	0.37232 (5)	0.0155 (2)
H1A	0.816 (4)	0.6288 (17)	0.3548 (14)	0.056 (7)*
N1	0.5897 (2)	0.73580 (8)	0.46781 (6)	0.0129 (3)
N2	0.8547 (2)	0.62104 (8)	0.48580 (7)	0.0159 (3)
H2B	0.959 (3)	0.5867 (12)	0.4689 (10)	0.019 (4)*
H2C	0.848 (3)	0.6210 (11)	0.5304 (11)	0.017 (4)*
C1	0.4756 (3)	0.80112 (10)	0.42031 (8)	0.0141 (3)
C2	0.2727 (3)	0.77834 (10)	0.37107 (8)	0.0162 (3)
H2A	0.2165	0.7211	0.3687	0.019*
C3	0.1533 (3)	0.83903 (10)	0.32569 (8)	0.0187 (3)
H3A	0.0153	0.8238	0.2920	0.022*
C4	0.2370 (3)	0.92249 (10)	0.32975 (8)	0.0194 (3)
H4A	0.1570	0.9646	0.2986	0.023*
C5	0.4381 (3)	0.94424 (10)	0.37942 (8)	0.0173 (3)
H5A	0.4923	1.0017	0.3819	0.021*
C7	0.7832 (3)	0.91600 (10)	0.47730 (8)	0.0167 (3)
H7A	0.7252	0.9644	0.5050	0.020*
H7B	0.9061	0.9389	0.4470	0.020*
C8	0.9199 (3)	0.85443 (10)	0.53251 (8)	0.0182 (3)
H8A	1.0093	0.8120	0.5059	0.022*
H8B	1.0443	0.8867	0.5648	0.022*
C6	0.5634 (3)	0.88445 (9)	0.42593 (8)	0.0140 (3)
C9	0.7518 (3)	0.80844 (10)	0.57854 (8)	0.0158 (3)
C10	0.7465 (3)	0.82293 (10)	0.65272 (8)	0.0203 (3)
H10A	0.8565	0.8631	0.6774	0.024*
C11	0.5815 (3)	0.77906 (10)	0.69067 (8)	0.0219 (3)
H11A	0.5794	0.7896	0.7411	0.026*
C12	0.4196 (3)	0.72000 (10)	0.65603 (8)	0.0195 (3)
H12A	0.3063	0.6908	0.6825	0.023*
C13	0.4238 (3)	0.70375 (10)	0.58226 (8)	0.0162 (3)
H13A	0.3159	0.6628	0.5579	0.019*
C14	0.5882 (3)	0.74844 (9)	0.54505 (8)	0.0137 (3)
C15	0.7298 (2)	0.67538 (9)	0.44226 (8)	0.0129 (3)
S1	1.14613 (6)	0.50621 (2)	0.351758 (19)	0.01365 (11)
O2	0.95704 (19)	0.56144 (7)	0.31122 (5)	0.0181 (2)
O3	1.0521 (2)	0.42143 (7)	0.36193 (6)	0.0201 (2)
O4	1.25031 (19)	0.54714 (7)	0.41908 (6)	0.0203 (2)
C16	1.3818 (3)	0.49719 (11)	0.29503 (9)	0.0213 (3)
H16A	1.5215	0.4660	0.3205	0.032*
H16B	1.4364	0.5540	0.2823	0.032*
H16C	1.3190	0.4666	0.2506	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0183 (5)	0.0182 (5)	0.0099 (5)	0.0029 (4)	0.0014 (4)	−0.0011 (4)
N1	0.0144 (6)	0.0143 (6)	0.0097 (6)	0.0004 (5)	0.0005 (5)	−0.0005 (5)
N2	0.0192 (6)	0.0185 (7)	0.0099 (6)	0.0047 (5)	0.0011 (5)	0.0000 (5)
C1	0.0142 (7)	0.0177 (7)	0.0109 (7)	0.0028 (6)	0.0038 (5)	0.0010 (6)
C2	0.0139 (7)	0.0200 (8)	0.0150 (7)	−0.0011 (6)	0.0026 (6)	−0.0010 (6)
C3	0.0153 (7)	0.0285 (9)	0.0122 (7)	0.0020 (6)	0.0002 (6)	0.0002 (6)
C4	0.0203 (7)	0.0249 (8)	0.0136 (7)	0.0077 (6)	0.0037 (6)	0.0049 (6)
C5	0.0212 (7)	0.0169 (7)	0.0151 (7)	0.0015 (6)	0.0070 (6)	0.0021 (6)
C7	0.0184 (7)	0.0163 (7)	0.0155 (7)	−0.0030 (6)	0.0026 (6)	−0.0003 (6)
C8	0.0153 (7)	0.0211 (8)	0.0174 (7)	−0.0029 (6)	−0.0011 (6)	−0.0015 (6)
C6	0.0145 (7)	0.0175 (7)	0.0108 (7)	0.0012 (6)	0.0050 (5)	−0.0003 (6)
C9	0.0152 (7)	0.0167 (7)	0.0148 (7)	0.0026 (6)	−0.0010 (6)	0.0010 (6)
C10	0.0246 (8)	0.0187 (8)	0.0162 (8)	0.0014 (6)	−0.0035 (6)	−0.0023 (6)
C11	0.0315 (8)	0.0230 (8)	0.0114 (7)	0.0067 (7)	0.0024 (6)	−0.0005 (6)
C12	0.0214 (7)	0.0230 (8)	0.0151 (7)	0.0048 (6)	0.0068 (6)	0.0042 (6)
C13	0.0149 (7)	0.0168 (7)	0.0164 (7)	0.0012 (6)	−0.0001 (6)	0.0013 (6)
C14	0.0146 (7)	0.0156 (7)	0.0109 (7)	0.0043 (6)	0.0009 (5)	0.0001 (5)
C15	0.0120 (6)	0.0139 (7)	0.0126 (7)	−0.0032 (5)	0.0006 (5)	−0.0010 (5)
S1	0.01256 (18)	0.0164 (2)	0.01192 (19)	0.00119 (13)	0.00112 (14)	−0.00096 (13)
O2	0.0180 (5)	0.0222 (6)	0.0136 (5)	0.0051 (4)	−0.0008 (4)	−0.0021 (4)
O3	0.0220 (5)	0.0204 (6)	0.0179 (5)	−0.0028 (4)	0.0023 (4)	0.0019 (4)
O4	0.0183 (5)	0.0247 (6)	0.0169 (5)	0.0033 (4)	−0.0028 (4)	−0.0040 (5)
C16	0.0162 (7)	0.0262 (9)	0.0227 (8)	−0.0004 (6)	0.0078 (6)	−0.0010 (7)

Geometric parameters (Å, º)

O1—C15	1.3005 (17)	C7—H7B	0.9900
O1—H1A	0.92 (3)	C8—C9	1.506 (2)
N1—C15	1.3390 (19)	C8—H8A	0.9900
N1—C14	1.4440 (18)	C8—H8B	0.9900
N1—C1	1.4452 (18)	C9—C14	1.394 (2)
N2—C15	1.3101 (19)	C9—C10	1.395 (2)
N2—H2B	0.87 (2)	C10—C11	1.387 (2)
N2—H2C	0.830 (19)	C10—H10A	0.9500
C1—C2	1.395 (2)	C11—C12	1.386 (2)
C1—C6	1.396 (2)	C11—H11A	0.9500
C2—C3	1.383 (2)	C12—C13	1.392 (2)
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.389 (2)	C13—C14	1.383 (2)
C3—H3A	0.9500	C13—H13A	0.9500
C4—C5	1.389 (2)	S1—O3	1.4489 (11)
C4—H4A	0.9500	S1—O4	1.4578 (11)
C5—C6	1.399 (2)	S1—O2	1.4833 (11)
C5—H5A	0.9500	S1—C16	1.7556 (15)
C7—C6	1.523 (2)	C16—H16A	0.9800
C7—C8	1.536 (2)	C16—H16B	0.9800
C7—H7A	0.9900	C16—H16C	0.9800
C15—O1—H1A	114.8 (16)	C1—C6—C7	126.21 (13)
C15—N1—C14	121.07 (12)	C5—C6—C7	117.22 (13)
C15—N1—C1	120.84 (12)	C14—C9—C10	117.59 (14)
C14—N1—C1	116.91 (11)	C14—C9—C8	118.27 (13)
C15—N2—H2B	119.9 (12)	C10—C9—C8	124.13 (14)
C15—N2—H2C	122.2 (12)	C11—C10—C9	120.35 (14)
H2B—N2—H2C	117.6 (17)	C11—C10—H10A	119.8
C2—C1—C6	121.93 (14)	C9—C10—H10A	119.8
C2—C1—N1	117.83 (13)	C12—C11—C10	120.98 (14)
C6—C1—N1	120.21 (13)	C12—C11—H11A	119.5
C3—C2—C1	120.02 (14)	C10—C11—H11A	119.5
C3—C2—H2A	120.0	C11—C12—C13	119.65 (14)
C1—C2—H2A	120.0	C11—C12—H12A	120.2
C2—C3—C4	119.42 (14)	C13—C12—H12A	120.2
C2—C3—H3A	120.3	C14—C13—C12	118.68 (14)
C4—C3—H3A	120.3	C14—C13—H13A	120.7
C5—C4—C3	119.85 (14)	C12—C13—H13A	120.7
C5—C4—H4A	120.1	C13—C14—C9	122.75 (13)
C3—C4—H4A	120.1	C13—C14—N1	120.05 (13)
C4—C5—C6	122.21 (14)	C9—C14—N1	117.17 (13)
C4—C5—H5A	118.9	O1—C15—N2	122.38 (13)
C6—C5—H5A	118.9	O1—C15—N1	116.06 (13)
C6—C7—C8	119.66 (13)	N2—C15—N1	121.53 (13)
C6—C7—H7A	107.4	O3—S1—O4	113.84 (7)
C8—C7—H7A	107.4	O3—S1—O2	111.70 (6)
C6—C7—H7B	107.4	O4—S1—O2	110.63 (6)
C8—C7—H7B	107.4	O3—S1—C16	107.30 (7)
H7A—C7—H7B	106.9	O4—S1—C16	107.90 (7)
C9—C8—C7	113.54 (12)	O2—S1—C16	104.95 (7)
C9—C8—H8A	108.9	S1—C16—H16A	109.5
C7—C8—H8A	108.9	S1—C16—H16B	109.5
C9—C8—H8B	108.9	H16A—C16—H16B	109.5
C7—C8—H8B	108.9	S1—C16—H16C	109.5
H8A—C8—H8B	107.7	H16A—C16—H16C	109.5
C1—C6—C5	116.57 (13)	H16B—C16—H16C	109.5
C15—N1—C1—C2	73.83 (17)	C14—C9—C10—C11	−0.5 (2)
C14—N1—C1—C2	−118.42 (14)	C8—C9—C10—C11	178.48 (14)
C15—N1—C1—C6	−108.14 (16)	C9—C10—C11—C12	0.2 (2)
C14—N1—C1—C6	59.61 (17)	C10—C11—C12—C13	0.6 (2)
C6—C1—C2—C3	0.4 (2)	C11—C12—C13—C14	−1.1 (2)
N1—C1—C2—C3	178.40 (13)	C12—C13—C14—C9	0.7 (2)
C1—C2—C3—C4	−0.1 (2)	C12—C13—C14—N1	−177.29 (13)
C2—C3—C4—C5	−0.4 (2)	C10—C9—C14—C13	0.1 (2)
C3—C4—C5—C6	0.6 (2)	C8—C9—C14—C13	−179.01 (13)
C6—C7—C8—C9	−52.33 (18)	C10—C9—C14—N1	178.13 (13)
C2—C1—C6—C5	−0.2 (2)	C8—C9—C14—N1	−0.93 (19)
N1—C1—C6—C5	−178.17 (12)	C15—N1—C14—C13	−88.80 (17)
C2—C1—C6—C7	−179.67 (13)	C1—N1—C14—C13	103.48 (15)
N1—C1—C6—C7	2.4 (2)	C15—N1—C14—C9	93.07 (16)
C4—C5—C6—C1	−0.3 (2)	C1—N1—C14—C9	−74.65 (16)
C4—C5—C6—C7	179.23 (13)	C14—N1—C15—O1	−172.74 (12)
C8—C7—C6—C1	−3.8 (2)	C1—N1—C15—O1	−5.50 (19)
C8—C7—C6—C5	176.77 (13)	C14—N1—C15—N2	5.7 (2)
C7—C8—C9—C14	68.68 (18)	C1—N1—C15—N2	172.91 (13)
C7—C8—C9—C10	−110.31 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.92 (3)	1.58 (3)	2.4941 (15)	168 (2)
N2—H2C···O3^i	0.830 (19)	2.112 (19)	2.8830 (17)	154.4 (17)
N2—H2B···O4	0.87 (2)	2.02 (2)	2.8523 (17)	159.5 (17)

Symmetry code: (i) −x+2, −y+1, −z+1.

(5) Dibenzo[b,f]azepine-5-carboxamide–trifluoroacetic acid (1/1)

Crystal data

C15H12N2O·C2HF3O2	F(000) = 720
Mr = 350.29	Dx = 1.493 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 14.9968 (12) Å	Cell parameters from 3607 reflections
b = 5.2660 (3) Å	θ = 3.0–75.6°
c = 20.1911 (12) Å	µ = 1.10 mm^−1
β = 102.191 (7)°	T = 100 K
V = 1558.60 (18) Å^3	Lath, colourless
Z = 4	0.45 × 0.20 × 0.10 mm

Data collection

SuperNova, Dual, Cu at zero, Atlas diffractometer	3189 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2937 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 10.5598 pixels mm^-1	θmax = 74.5°, θmin = 3.4°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −3→6
Tmin = 0.650, Tmax = 1.000	l = −25→25
7053 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0945P)^2 + 0.550P] where P = (Fo^2 + 2Fc^2)/3
3189 reflections	(Δ/σ)max = 0.001
266 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Single-crystal X-ray data for structures (4), (5) and (6) were measured at 100 K [270 K for structure (6)], on an Oxford Diffraction (Agilent Technologies) SuperNova X-ray diffractometer equipped with an Oxford Cryosystems Cobra low-temperature device using either Mo Kα (λ = 0.71073 Å) radiation from a SuperNova Mo X-ray microsource (Nova) for (4) or Cu Kα (λ = 1.54173 Å) radiation from a SuperNova Cu X-ray microsource (Nova) for (5) and (6) and focusing mirror optics (Agilent, 2011).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	1.01040 (8)	0.3899 (2)	−0.19315 (5)	0.0204 (3)
N2	1.13634 (9)	0.1950 (3)	−0.22083 (6)	0.0247 (3)
H2B	1.1857 (14)	0.109 (4)	−0.2068 (10)	0.029 (5)*
H2C	1.1209 (13)	0.258 (4)	−0.2615 (11)	0.030 (5)*
O1	1.11508 (7)	0.1982 (2)	−0.11242 (5)	0.0244 (2)
C1	0.95601 (9)	0.4422 (3)	−0.14367 (6)	0.0197 (3)
C2	0.97975 (10)	0.6438 (3)	−0.09929 (7)	0.0230 (3)
H2A	1.0290	0.7522	−0.1033	0.028*
C3	0.93124 (10)	0.6866 (3)	−0.04891 (7)	0.0249 (3)
H3A	0.9468	0.8254	−0.0186	0.030*
C4	0.85989 (10)	0.5256 (3)	−0.04289 (7)	0.0256 (3)
H4A	0.8276	0.5520	−0.0078	0.031*
C5	0.83597 (9)	0.3273 (3)	−0.08796 (7)	0.0243 (3)
H5A	0.7872	0.2182	−0.0833	0.029*
C6	0.88225 (9)	0.2835 (3)	−0.14061 (7)	0.0208 (3)
C7	0.85101 (9)	0.0800 (3)	−0.18921 (7)	0.0232 (3)
H7A	0.8226	−0.0608	−0.1727	0.028*
C8	0.85782 (9)	0.0688 (3)	−0.25451 (7)	0.0233 (3)
H8A	0.8345	−0.0801	−0.2786	0.028*
C9	0.89710 (9)	0.2598 (3)	−0.29261 (7)	0.0215 (3)
C10	0.86126 (10)	0.2862 (3)	−0.36231 (7)	0.0248 (3)
H10A	0.8153	0.1720	−0.3841	0.030*
C11	0.89142 (10)	0.4749 (3)	−0.40005 (7)	0.0266 (3)
H11A	0.8658	0.4899	−0.4471	0.032*
C12	0.95892 (10)	0.6419 (3)	−0.36917 (7)	0.0269 (3)
H12A	0.9787	0.7735	−0.3949	0.032*
C13	0.99757 (10)	0.6168 (3)	−0.30068 (7)	0.0242 (3)
H13A	1.0442	0.7300	−0.2794	0.029*
C14	0.96744 (9)	0.4245 (3)	−0.26327 (6)	0.0204 (3)
C15	1.08910 (9)	0.2580 (3)	−0.17442 (7)	0.0204 (3)
O2	1.23590 (7)	−0.1025 (2)	−0.06761 (5)	0.0278 (3)
H2D	1.1757 (19)	0.053 (6)	−0.0964 (13)	0.067 (8)*
O3	1.28746 (8)	−0.1351 (3)	−0.16402 (6)	0.0371 (3)
C16	1.28569 (10)	−0.1916 (3)	−0.10585 (7)	0.0253 (3)
C17A	1.35264 (11)	−0.3987 (3)	−0.07195 (8)	0.0311 (4)	0.738 (15)
F1A	1.3372 (3)	−0.4807 (8)	−0.01191 (14)	0.0412 (7)	0.738 (15)
F2A	1.34620 (19)	−0.6059 (4)	−0.11052 (17)	0.0452 (8)	0.738 (15)
F3A	1.4373 (2)	−0.3211 (7)	−0.0597 (3)	0.0433 (8)	0.738 (15)
C17B	1.35264 (11)	−0.3987 (3)	−0.07195 (8)	0.0311 (4)	0.262 (15)
F1B	1.3244 (10)	−0.536 (3)	−0.0352 (13)	0.084 (5)	0.262 (15)
F2B	1.3867 (17)	−0.507 (5)	−0.1213 (4)	0.109 (9)	0.262 (15)
F3B	1.4281 (7)	−0.257 (3)	−0.0392 (8)	0.060 (3)	0.262 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0196 (5)	0.0241 (6)	0.0183 (5)	0.0002 (4)	0.0055 (4)	0.0007 (4)
N2	0.0222 (6)	0.0325 (6)	0.0202 (6)	0.0037 (5)	0.0064 (5)	0.0020 (5)
O1	0.0245 (5)	0.0302 (5)	0.0189 (5)	0.0061 (4)	0.0057 (4)	0.0013 (4)
C1	0.0203 (6)	0.0212 (6)	0.0178 (6)	0.0035 (5)	0.0048 (5)	0.0035 (5)
C2	0.0255 (7)	0.0220 (6)	0.0210 (6)	−0.0005 (5)	0.0035 (5)	0.0021 (5)
C3	0.0298 (7)	0.0244 (7)	0.0196 (6)	0.0051 (6)	0.0028 (5)	−0.0011 (5)
C4	0.0241 (6)	0.0337 (7)	0.0198 (6)	0.0082 (6)	0.0066 (5)	0.0018 (5)
C5	0.0201 (6)	0.0307 (7)	0.0227 (6)	0.0020 (5)	0.0057 (5)	0.0045 (5)
C6	0.0207 (6)	0.0213 (6)	0.0203 (6)	0.0036 (5)	0.0042 (5)	0.0038 (5)
C7	0.0209 (6)	0.0219 (6)	0.0273 (7)	−0.0015 (5)	0.0060 (5)	0.0033 (5)
C8	0.0222 (6)	0.0211 (6)	0.0259 (7)	−0.0022 (5)	0.0035 (5)	−0.0019 (5)
C9	0.0223 (6)	0.0207 (6)	0.0220 (6)	0.0024 (5)	0.0063 (5)	−0.0009 (5)
C10	0.0228 (7)	0.0291 (7)	0.0225 (6)	0.0014 (6)	0.0045 (5)	−0.0036 (5)
C11	0.0276 (7)	0.0339 (8)	0.0183 (6)	0.0056 (6)	0.0048 (5)	0.0019 (5)
C12	0.0307 (7)	0.0275 (7)	0.0242 (7)	0.0024 (6)	0.0099 (6)	0.0048 (5)
C13	0.0257 (7)	0.0239 (7)	0.0240 (7)	−0.0009 (5)	0.0073 (5)	0.0000 (5)
C14	0.0213 (6)	0.0215 (6)	0.0193 (6)	0.0028 (5)	0.0062 (5)	0.0001 (5)
C15	0.0204 (6)	0.0206 (6)	0.0208 (6)	−0.0030 (5)	0.0053 (5)	−0.0013 (5)
O2	0.0280 (5)	0.0332 (6)	0.0238 (5)	0.0095 (4)	0.0094 (4)	0.0020 (4)
O3	0.0386 (6)	0.0493 (7)	0.0260 (5)	0.0165 (5)	0.0129 (5)	0.0021 (5)
C16	0.0240 (7)	0.0279 (7)	0.0246 (7)	0.0026 (6)	0.0061 (5)	−0.0040 (5)
C17A	0.0282 (7)	0.0329 (8)	0.0335 (8)	0.0054 (6)	0.0091 (6)	−0.0017 (6)
F1A	0.0432 (14)	0.0448 (14)	0.0396 (12)	0.0211 (11)	0.0180 (9)	0.0185 (8)
F2A	0.0524 (13)	0.0290 (10)	0.0523 (12)	0.0110 (9)	0.0066 (8)	−0.0112 (7)
F3A	0.0210 (8)	0.0354 (13)	0.0723 (19)	0.0016 (8)	0.0071 (10)	0.0129 (11)
C17B	0.0282 (7)	0.0329 (8)	0.0335 (8)	0.0054 (6)	0.0091 (6)	−0.0017 (6)
F1B	0.056 (5)	0.059 (7)	0.141 (13)	0.012 (5)	0.032 (8)	0.063 (8)
F2B	0.139 (14)	0.134 (14)	0.049 (3)	0.117 (13)	0.009 (5)	−0.008 (5)
F3B	0.036 (3)	0.068 (5)	0.067 (6)	0.019 (3)	−0.007 (3)	0.011 (4)

Geometric parameters (Å, º)

N1—C15	1.3529 (18)	C7—H7A	0.9500
N1—C14	1.4380 (16)	C8—C9	1.4636 (19)
N1—C1	1.4433 (16)	C8—H8A	0.9500
N2—C15	1.3306 (18)	C9—C14	1.3971 (19)
N2—H2B	0.86 (2)	C9—C10	1.4034 (19)
N2—H2C	0.87 (2)	C10—C11	1.385 (2)
O1—C15	1.2696 (17)	C10—H10A	0.9500
O1—H2D	1.18 (3)	C11—C12	1.386 (2)
C1—C2	1.3865 (19)	C11—H11A	0.9500
C1—C6	1.3980 (19)	C12—C13	1.388 (2)
C2—C3	1.388 (2)	C12—H12A	0.9500
C2—H2A	0.9500	C13—C14	1.3944 (19)
C3—C4	1.390 (2)	C13—H13A	0.9500
C3—H3A	0.9500	O2—C16	1.2718 (18)
C4—C5	1.382 (2)	O2—H2D	1.27 (3)
C4—H4A	0.9500	O3—C16	1.2174 (19)
C5—C6	1.4059 (19)	C16—C17A	1.541 (2)
C5—H5A	0.9500	C17A—F3A	1.306 (3)
C6—C7	1.4618 (19)	C17A—F2A	1.332 (3)
C7—C8	1.345 (2)	C17A—F1A	1.352 (4)
C15—N1—C14	121.55 (11)	C14—C9—C10	117.30 (12)
C15—N1—C1	119.45 (11)	C14—C9—C8	123.75 (12)
C14—N1—C1	117.14 (10)	C10—C9—C8	118.92 (12)
C15—N2—H2B	116.5 (13)	C11—C10—C9	121.48 (13)
C15—N2—H2C	119.6 (13)	C11—C10—H10A	119.3
H2B—N2—H2C	123.3 (18)	C9—C10—H10A	119.3
C15—O1—H2D	119.3 (13)	C10—C11—C12	120.01 (13)
C2—C1—C6	121.78 (12)	C10—C11—H11A	120.0
C2—C1—N1	119.21 (12)	C12—C11—H11A	120.0
C6—C1—N1	118.99 (12)	C11—C12—C13	119.97 (13)
C1—C2—C3	119.67 (13)	C11—C12—H12A	120.0
C1—C2—H2A	120.2	C13—C12—H12A	120.0
C3—C2—H2A	120.2	C12—C13—C14	119.59 (13)
C2—C3—C4	119.82 (13)	C12—C13—H13A	120.2
C2—C3—H3A	120.1	C14—C13—H13A	120.2
C4—C3—H3A	120.1	C13—C14—C9	121.55 (12)
C5—C4—C3	120.05 (13)	C13—C14—N1	119.75 (12)
C5—C4—H4A	120.0	C9—C14—N1	118.68 (12)
C3—C4—H4A	120.0	O1—C15—N2	122.30 (13)
C4—C5—C6	121.39 (13)	O1—C15—N1	118.10 (12)
C4—C5—H5A	119.3	N2—C15—N1	119.60 (12)
C6—C5—H5A	119.3	C16—O2—H2D	114.4 (12)
C1—C6—C5	117.20 (13)	O3—C16—O2	129.11 (14)
C1—C6—C7	123.57 (12)	O3—C16—C17A	117.16 (13)
C5—C6—C7	119.23 (12)	O2—C16—C17A	113.73 (12)
C8—C7—C6	127.61 (13)	F3A—C17A—F2A	108.4 (2)
C8—C7—H7A	116.2	F3A—C17A—F1A	105.9 (3)
C6—C7—H7A	116.2	F2A—C17A—F1A	104.9 (2)
C7—C8—C9	127.39 (13)	F3A—C17A—C16	112.24 (19)
C7—C8—H8A	116.3	F2A—C17A—C16	111.09 (16)
C9—C8—H8A	116.3	F1A—C17A—C16	113.91 (19)
C15—N1—C1—C2	81.15 (16)	C10—C11—C12—C13	1.3 (2)
C14—N1—C1—C2	−114.12 (14)	C11—C12—C13—C14	−0.6 (2)
C15—N1—C1—C6	−97.09 (15)	C12—C13—C14—C9	−1.9 (2)
C14—N1—C1—C6	67.64 (16)	C12—C13—C14—N1	176.91 (12)
C6—C1—C2—C3	2.0 (2)	C10—C9—C14—C13	3.5 (2)
N1—C1—C2—C3	−176.17 (12)	C8—C9—C14—C13	−174.75 (13)
C1—C2—C3—C4	0.6 (2)	C10—C9—C14—N1	−175.30 (11)
C2—C3—C4—C5	−1.5 (2)	C8—C9—C14—N1	6.4 (2)
C3—C4—C5—C6	−0.2 (2)	C15—N1—C14—C13	−82.35 (17)
C2—C1—C6—C5	−3.64 (19)	C1—N1—C14—C13	113.26 (14)
N1—C1—C6—C5	174.56 (11)	C15—N1—C14—C9	96.48 (15)
C2—C1—C6—C7	175.64 (12)	C1—N1—C14—C9	−67.91 (16)
N1—C1—C6—C7	−6.17 (19)	C14—N1—C15—O1	−168.32 (12)
C4—C5—C6—C1	2.7 (2)	C1—N1—C15—O1	−4.28 (19)
C4—C5—C6—C7	−176.59 (12)	C14—N1—C15—N2	11.6 (2)
C1—C6—C7—C8	−28.7 (2)	C1—N1—C15—N2	175.60 (12)
C5—C6—C7—C8	150.59 (15)	O3—C16—C17A—F3A	69.8 (3)
C6—C7—C8—C9	−0.9 (2)	O2—C16—C17A—F3A	−109.9 (3)
C7—C8—C9—C14	29.8 (2)	O3—C16—C17A—F2A	−51.7 (3)
C7—C8—C9—C10	−148.46 (15)	O2—C16—C17A—F2A	128.6 (2)
C14—C9—C10—C11	−2.8 (2)	O3—C16—C17A—F1A	−169.9 (2)
C8—C9—C10—C11	175.55 (13)	O2—C16—C17A—F1A	10.4 (3)
C9—C10—C11—C12	0.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3	0.86 (2)	2.04 (2)	2.8941 (18)	169.1 (18)
N2—H2C···O3^i	0.87 (2)	2.31 (2)	2.9383 (16)	129.1 (16)
O1—H2D···O2	1.18 (3)	1.27 (3)	2.4322 (14)	168 (2)
O1—H2D···O3	1.18 (3)	2.57 (3)	3.4622 (15)	130.9 (17)

Symmetry code: (i) −x+5/2, y+1/2, −z−1/2.

(6) Dibenzo[b,f]azepine-5-carboxamide–trifluoroacetic acid (1/1)

Crystal data

C15H12N2O·C2HF3O2	F(000) = 720
Mr = 350.29	Dx = 1.442 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 14.9970 (3) Å	Cell parameters from 3984 reflections
b = 5.3712 (1) Å	θ = 3.0–75.8°
c = 20.4441 (4) Å	µ = 1.06 mm^−1
β = 101.529 (2)°	T = 270 K
V = 1613.58 (5) Å^3	Lath, colourless
Z = 4	0.45 × 0.25 × 0.18 mm

Data collection

SuperNova, Dual, Cu at zero, Atlas diffractometer	3302 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2957 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.5598 pixels mm^-1	θmax = 74.5°, θmin = 3.4°
ω scans	h = −18→17
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −4→6
Tmin = 0.738, Tmax = 1.000	l = −24→25
7096 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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.155	w = 1/[σ^2(Fo^2) + (0.0975P)^2 + 0.320P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3302 reflections	Δρmax = 0.34 e Å^−3
267 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (7)

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET) (compiled Oct 27 2011,15:02:11) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Single-crystal X-ray data for structures (4), (5) and (6) were measured at 100 K [270 K for structure (6)], on an Oxford Diffraction (Agilent Technologies) SuperNova X-ray diffractometer equipped with an Oxford Cryosystems Cobra low-temperature device using either Mo Kα (λ = 0.71073 Å) radiation from a SuperNova Mo X-ray microsource (Nova) for (4) or Cu Kα (λ = 1.54173 Å) radiation from a SuperNova Cu X-ray microsource (Nova) for (5) and (6) and focusing mirror optics (Agilent, 2011).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	1.00960 (8)	0.3794 (2)	−0.19199 (6)	0.0445 (3)
N2	1.13368 (10)	0.1840 (3)	−0.22070 (7)	0.0594 (4)
H2B	1.1836 (16)	0.095 (4)	−0.2079 (10)	0.061 (5)*
H2C	1.1187 (15)	0.251 (4)	−0.2610 (12)	0.068 (6)*
O1	1.11367 (8)	0.1877 (2)	−0.11365 (5)	0.0561 (3)
C1	0.95582 (9)	0.4336 (3)	−0.14274 (7)	0.0438 (3)
C2	0.97930 (12)	0.6319 (3)	−0.09996 (8)	0.0541 (4)
H2A	1.0276	0.7349	−0.1044	0.065*
C3	0.93064 (14)	0.6769 (4)	−0.05025 (8)	0.0626 (5)
H3A	0.9458	0.8114	−0.0215	0.075*
C4	0.85988 (12)	0.5224 (4)	−0.04340 (8)	0.0641 (5)
H4A	0.8282	0.5502	−0.0094	0.077*
C5	0.83609 (11)	0.3274 (4)	−0.08673 (8)	0.0595 (4)
H5A	0.7883	0.2240	−0.0815	0.071*
C6	0.88219 (10)	0.2802 (3)	−0.13878 (7)	0.0477 (3)
C7	0.85093 (11)	0.0798 (3)	−0.18596 (9)	0.0544 (4)
H7A	0.8229	−0.0541	−0.1694	0.065*
C8	0.85761 (11)	0.0651 (3)	−0.25014 (9)	0.0533 (4)
H8A	0.8347	−0.0788	−0.2727	0.064*
C9	0.89671 (10)	0.2486 (3)	−0.28882 (7)	0.0465 (3)
C10	0.86112 (11)	0.2709 (3)	−0.35739 (8)	0.0559 (4)
H10A	0.8162	0.1608	−0.3777	0.067*
C11	0.89126 (12)	0.4521 (4)	−0.39514 (8)	0.0610 (4)
H11A	0.8669	0.4630	−0.4406	0.073*
C12	0.95721 (14)	0.6172 (4)	−0.36603 (9)	0.0626 (4)
H12A	0.9761	0.7428	−0.3915	0.075*
C13	0.99580 (12)	0.5967 (3)	−0.29858 (8)	0.0550 (4)
H13A	1.0412	0.7067	−0.2789	0.066*
C14	0.96626 (9)	0.4112 (3)	−0.26084 (7)	0.0441 (3)
C15	1.08751 (9)	0.2478 (3)	−0.17424 (7)	0.0449 (3)
O2	1.23698 (9)	−0.0982 (3)	−0.06931 (6)	0.0671 (4)
H2D	1.179 (2)	0.035 (5)	−0.0965 (13)	0.098 (8)*
O3	1.28638 (13)	−0.1342 (4)	−0.16454 (7)	0.0975 (6)
C16	1.28630 (12)	−0.1862 (4)	−0.10722 (9)	0.0605 (4)
C17A	1.35519 (16)	−0.3780 (5)	−0.07339 (12)	0.0776 (6)	0.505 (9)
F1A	1.3430 (5)	−0.4494 (14)	−0.0135 (3)	0.118 (2)	0.505 (9)
F2A	1.3469 (6)	−0.5914 (9)	−0.1084 (3)	0.141 (3)	0.505 (9)
F3A	1.4339 (3)	−0.3150 (14)	−0.0614 (6)	0.152 (4)	0.505 (9)
C17B	1.35519 (16)	−0.3780 (5)	−0.07339 (12)	0.0776 (6)	0.495 (9)
F1B	1.3224 (6)	−0.5483 (14)	−0.0464 (6)	0.160 (5)	0.495 (9)
F2B	1.4066 (4)	−0.4498 (14)	−0.11635 (19)	0.112 (3)	0.495 (9)
F3B	1.4203 (4)	−0.2479 (14)	−0.0311 (2)	0.136 (3)	0.495 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0373 (6)	0.0557 (7)	0.0402 (6)	−0.0012 (5)	0.0068 (4)	0.0028 (5)
N2	0.0486 (7)	0.0859 (10)	0.0458 (7)	0.0122 (7)	0.0141 (6)	0.0052 (7)
O1	0.0484 (6)	0.0776 (8)	0.0420 (5)	0.0165 (5)	0.0083 (4)	0.0035 (5)
C1	0.0400 (7)	0.0505 (7)	0.0403 (7)	0.0070 (5)	0.0063 (5)	0.0077 (6)
C2	0.0574 (9)	0.0565 (8)	0.0457 (8)	0.0018 (7)	0.0043 (6)	0.0040 (6)
C3	0.0728 (11)	0.0676 (10)	0.0448 (8)	0.0186 (9)	0.0054 (7)	−0.0014 (7)
C4	0.0544 (9)	0.0928 (13)	0.0461 (8)	0.0238 (9)	0.0127 (7)	0.0066 (8)
C5	0.0423 (8)	0.0840 (12)	0.0539 (9)	0.0081 (7)	0.0137 (6)	0.0154 (8)
C6	0.0392 (7)	0.0551 (8)	0.0488 (8)	0.0063 (6)	0.0087 (6)	0.0109 (6)
C7	0.0464 (8)	0.0545 (8)	0.0624 (9)	−0.0065 (6)	0.0114 (7)	0.0101 (7)
C8	0.0476 (8)	0.0488 (8)	0.0616 (9)	−0.0067 (6)	0.0064 (7)	−0.0008 (7)
C9	0.0409 (7)	0.0494 (7)	0.0481 (8)	0.0023 (6)	0.0065 (5)	−0.0009 (6)
C10	0.0459 (8)	0.0685 (10)	0.0505 (8)	−0.0022 (7)	0.0027 (6)	−0.0059 (7)
C11	0.0580 (9)	0.0786 (11)	0.0441 (8)	0.0077 (8)	0.0048 (7)	0.0052 (7)
C12	0.0711 (11)	0.0667 (10)	0.0512 (9)	−0.0015 (8)	0.0155 (8)	0.0130 (7)
C13	0.0564 (9)	0.0580 (9)	0.0509 (8)	−0.0092 (7)	0.0114 (7)	0.0037 (7)
C14	0.0408 (7)	0.0504 (7)	0.0407 (7)	0.0014 (5)	0.0073 (5)	0.0026 (5)
C15	0.0386 (7)	0.0540 (8)	0.0420 (7)	−0.0033 (6)	0.0077 (5)	0.0003 (6)
O2	0.0637 (7)	0.0861 (9)	0.0551 (7)	0.0268 (7)	0.0202 (6)	0.0084 (6)
O3	0.0980 (12)	0.1415 (15)	0.0589 (8)	0.0577 (11)	0.0295 (8)	0.0087 (9)
C16	0.0546 (9)	0.0746 (11)	0.0536 (9)	0.0118 (8)	0.0142 (7)	−0.0039 (8)
C17A	0.0693 (12)	0.0863 (15)	0.0803 (14)	0.0246 (11)	0.0225 (11)	0.0025 (11)
F1A	0.122 (5)	0.134 (5)	0.104 (3)	0.070 (4)	0.037 (3)	0.049 (3)
F2A	0.160 (6)	0.082 (3)	0.175 (5)	0.039 (3)	0.018 (4)	−0.033 (3)
F3A	0.0488 (17)	0.137 (5)	0.267 (10)	0.008 (2)	0.026 (4)	0.089 (6)
C17B	0.0693 (12)	0.0863 (15)	0.0803 (14)	0.0246 (11)	0.0225 (11)	0.0025 (11)
F1B	0.118 (4)	0.102 (5)	0.276 (13)	0.035 (4)	0.080 (7)	0.099 (7)
F2B	0.107 (4)	0.138 (5)	0.094 (2)	0.074 (4)	0.031 (2)	−0.001 (2)
F3B	0.097 (4)	0.216 (6)	0.081 (2)	0.072 (4)	−0.021 (2)	−0.028 (3)

Geometric parameters (Å, º)

N1—C15	1.3516 (19)	C7—H7A	0.9300
N1—C14	1.4378 (18)	C8—C9	1.458 (2)
N1—C1	1.4401 (18)	C8—H8A	0.9300
N2—C15	1.327 (2)	C9—C14	1.393 (2)
N2—H2B	0.88 (2)	C9—C10	1.402 (2)
N2—H2C	0.89 (2)	C10—C11	1.374 (3)
O1—C15	1.2643 (18)	C10—H10A	0.9300
O1—H2D	1.27 (3)	C11—C12	1.372 (3)
C1—C2	1.378 (2)	C11—H11A	0.9300
C1—C6	1.393 (2)	C12—C13	1.389 (2)
C2—C3	1.386 (2)	C12—H12A	0.9300
C2—H2A	0.9300	C13—C14	1.386 (2)
C3—C4	1.376 (3)	C13—H13A	0.9300
C3—H3A	0.9300	O2—C16	1.265 (2)
C4—C5	1.372 (3)	O2—H2D	1.17 (3)
C4—H4A	0.9300	O3—C16	1.205 (2)
C5—C6	1.403 (2)	C16—C17A	1.524 (3)
C5—H5A	0.9300	C17A—F3A	1.205 (5)
C6—C7	1.459 (2)	C17A—F1A	1.331 (6)
C7—C8	1.338 (2)	C17A—F2A	1.344 (5)
C15—N1—C14	121.49 (12)	C14—C9—C10	117.47 (14)
C15—N1—C1	119.54 (11)	C14—C9—C8	123.41 (14)
C14—N1—C1	116.98 (11)	C10—C9—C8	119.09 (14)
C15—N2—H2B	117.4 (13)	C11—C10—C9	121.34 (16)
C15—N2—H2C	119.3 (15)	C11—C10—H10A	119.3
H2B—N2—H2C	123 (2)	C9—C10—H10A	119.3
C15—O1—H2D	120.3 (12)	C12—C11—C10	120.25 (15)
C2—C1—C6	121.67 (14)	C12—C11—H11A	119.9
C2—C1—N1	119.48 (14)	C10—C11—H11A	119.9
C6—C1—N1	118.84 (13)	C11—C12—C13	120.03 (16)
C1—C2—C3	119.67 (17)	C11—C12—H12A	120.0
C1—C2—H2A	120.2	C13—C12—H12A	120.0
C3—C2—H2A	120.2	C14—C13—C12	119.58 (16)
C4—C3—C2	119.95 (17)	C14—C13—H13A	120.2
C4—C3—H3A	120.0	C12—C13—H13A	120.2
C2—C3—H3A	120.0	C13—C14—C9	121.25 (14)
C5—C4—C3	120.06 (16)	C13—C14—N1	119.89 (13)
C5—C4—H4A	120.0	C9—C14—N1	118.84 (13)
C3—C4—H4A	120.0	O1—C15—N2	122.09 (14)
C4—C5—C6	121.57 (17)	O1—C15—N1	118.60 (13)
C4—C5—H5A	119.2	N2—C15—N1	119.31 (13)
C6—C5—H5A	119.2	C16—O2—H2D	113.8 (13)
C1—C6—C5	116.98 (16)	O3—C16—O2	128.58 (18)
C1—C6—C7	123.47 (14)	O3—C16—C17A	117.77 (17)
C5—C6—C7	119.53 (15)	O2—C16—C17A	113.64 (16)
C8—C7—C6	127.95 (15)	F3A—C17A—F1A	101.7 (6)
C8—C7—H7A	116.0	F3A—C17A—F2A	109.3 (5)
C6—C7—H7A	116.0	F1A—C17A—F2A	103.3 (4)
C7—C8—C9	127.52 (15)	F3A—C17A—C16	116.7 (3)
C7—C8—H8A	116.2	F1A—C17A—C16	114.0 (3)
C9—C8—H8A	116.2	F2A—C17A—C16	110.7 (3)
C15—N1—C1—C2	81.92 (18)	C10—C11—C12—C13	2.0 (3)
C14—N1—C1—C2	−113.89 (15)	C11—C12—C13—C14	−1.0 (3)
C15—N1—C1—C6	−96.79 (16)	C12—C13—C14—C9	−1.8 (3)
C14—N1—C1—C6	67.40 (17)	C12—C13—C14—N1	176.28 (15)
C6—C1—C2—C3	2.0 (2)	C10—C9—C14—C13	3.4 (2)
N1—C1—C2—C3	−176.65 (13)	C8—C9—C14—C13	−174.33 (15)
C1—C2—C3—C4	0.7 (2)	C10—C9—C14—N1	−174.70 (13)
C2—C3—C4—C5	−1.5 (3)	C8—C9—C14—N1	7.6 (2)
C3—C4—C5—C6	−0.2 (3)	C15—N1—C14—C13	−82.98 (19)
C2—C1—C6—C5	−3.6 (2)	C1—N1—C14—C13	113.15 (16)
N1—C1—C6—C5	175.03 (13)	C15—N1—C14—C9	95.12 (17)
C2—C1—C6—C7	175.40 (14)	C1—N1—C14—C9	−68.75 (18)
N1—C1—C6—C7	−5.9 (2)	C14—N1—C15—O1	−167.38 (14)
C4—C5—C6—C1	2.7 (2)	C1—N1—C15—O1	−3.9 (2)
C4—C5—C6—C7	−176.33 (15)	C14—N1—C15—N2	12.1 (2)
C1—C6—C7—C8	−28.7 (3)	C1—N1—C15—N2	175.53 (14)
C5—C6—C7—C8	150.31 (18)	O3—C16—C17A—F3A	70.1 (8)
C6—C7—C8—C9	−1.0 (3)	O2—C16—C17A—F3A	−108.5 (7)
C7—C8—C9—C14	29.1 (3)	O3—C16—C17A—F1A	−171.6 (5)
C7—C8—C9—C10	−148.54 (18)	O2—C16—C17A—F1A	9.8 (5)
C14—C9—C10—C11	−2.4 (2)	O3—C16—C17A—F2A	−55.7 (6)
C8—C9—C10—C11	175.46 (16)	O2—C16—C17A—F2A	125.7 (5)
C9—C10—C11—C12	−0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3	0.88 (2)	2.03 (2)	2.904 (2)	169.1 (19)
N2—H2C···O3^i	0.89 (2)	2.36 (2)	3.003 (2)	129.2 (19)
O2—H2D···O1	1.17 (3)	1.27 (3)	2.4349 (16)	168 (2)
O1—H2D···O3	1.27 (3)	2.50 (3)	3.4435 (18)	128.9 (17)

Symmetry code: (i) −x+5/2, y+1/2, −z−1/2.