Cytenamide trifluoro-acetic acid solvate.

Cytenamide forms a 1:1 solvate with trifluoro-acetic acid (systematic name: 5H-dibenzo[a,d]cyclo-hepta-triene-5-carboxamide trifluoro-acetic acid solvate), C(16)H(13)NO·C(2)HF(3)O(2). The compound crystallizes with one mol-ecule of cytenamide and one of trifluoro-acetic acid in the asymmetric unit; these are linked by O-H⋯O and N-H⋯O hydrogen bonds to form an R(2) (2)(8) motif. The trifluoro-methyl group of the solvent mol-ecule displays rotational disorder over two sites, with site-occupancy factors of 0.964 (4) and 0.036 (4).

Related literature

For details on the experimental methods used to obtain this form, see: Davis et al. (1964 ▶); Florence et al. (2003 ▶); Florence, Johnston, Fernandes et al. (2006 ▶). For literature on carbamazepine and other related structures, see: Cyr et al. (1987 ▶); Fleischman et al. (2003 ▶); Florence, Johnston, Price et al. (2006 ▶); Florence, Leech et al. (2006 ▶); Bandoli et al. (1992 ▶); Harrison et al. (2006 ▶); Leech et al. (2007 ▶); Florence, Bedford et al. (2008 ▶); Florence, Shankland et al. (2008 ▶); Fernandes et al. (2007 ▶). For hydrogen-bond motifs, see: Etter (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C16H13NO·C2HF3O2

M = 349.31

Monoclinic,

a = 12.1673 (11) Å

b = 6.3235 (6) Å

c = 21.4525 (15) Å

β = 101.932 (8)°

V = 1614.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 160 K

0.16 × 0.13 × 0.08 mm

Data collection

Oxford Diffraction Gemini S diffractometer

Absorption correction: multi-scan (ABSPACK/CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.83, T max = 0.99

10796 measured reflections

2995 independent reflections

1423 reflections with I > 2σ(I)

R int = 0.094

Refinement

R[F 2 > 2σ(F 2)] = 0.080

wR(F 2) = 0.178

S = 1.04

2984 reflections

236 parameters

24 restraints

H-atom parameters not refined

Δρmax = 0.73 e Å−3

Δρmin = −0.60 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶) and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808016577/cf2202sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016577/cf2202Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H13NO·C2HF3O2	F000 = 720
Mr = 349.31	Dx = 1.437 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1137 reflections
a = 12.1673 (11) Å	θ = 3–25º
b = 6.3235 (6) Å	µ = 0.12 mm−1
c = 21.4525 (15) Å	T = 160 K
β = 101.932 (8)º	Block, colourless
V = 1614.9 (2) Å3	0.16 × 0.13 × 0.08 mm
Z = 4

Oxford Diffraction Gemini S diffractometer	2995 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1423 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.094
Detector resolution: 15.9745 pixels mm-1	θmax = 25.5º
T = 160 K	θmin = 3.1º
φ and ω scans	h = −14→14
Absorption correction: multi-scan(ABSPACK/CrysAlis RED; Oxford Diffraction, 2006)	k = 0→7
Tmin = 0.83, Tmax = 0.99	l = 0→25
10796 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.080	H-atom parameters not refined
wR(F2) = 0.178	Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.06P)2 + 0.42P] ,where P = (max(Fo2,0) + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.0004
2984 reflections	Δρmax = 0.73 e Å−3
236 parameters	Δρmin = −0.60 e Å−3
24 restraints	Extinction correction: None

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.6284 (3)	0.6720 (7)	0.3296 (2)	0.0461
C2	0.5488 (4)	0.4854 (7)	0.31163 (18)	0.0431
C3	0.4806 (3)	0.4971 (7)	0.24379 (18)	0.0380
C4	0.4965 (4)	0.3481 (7)	0.1996 (2)	0.0507
C5	0.4406 (4)	0.3618 (8)	0.1366 (2)	0.0578
C6	0.3726 (4)	0.5332 (9)	0.1180 (2)	0.0576
C7	0.3553 (4)	0.6826 (8)	0.16104 (19)	0.0519
C8	0.4077 (3)	0.6646 (7)	0.22567 (17)	0.0393
C9	0.3794 (4)	0.8214 (7)	0.2691 (2)	0.0475
C10	0.3773 (3)	0.7968 (7)	0.33147 (19)	0.0456
C11	0.4028 (3)	0.6095 (7)	0.37105 (18)	0.0369
C12	0.3488 (4)	0.5854 (7)	0.42250 (19)	0.0470
C13	0.3646 (4)	0.4094 (8)	0.45999 (18)	0.0515
C14	0.4337 (4)	0.2524 (8)	0.4474 (2)	0.0570
C15	0.4912 (4)	0.2755 (7)	0.3988 (2)	0.0497
C16	0.4774 (3)	0.4536 (7)	0.36104 (17)	0.0374
C17	0.8909 (4)	0.3112 (8)	0.4387 (2)	0.0572
C18	0.8197 (3)	0.1386 (7)	0.4008 (2)	0.0461
N1	0.6679 (3)	0.7697 (6)	0.28446 (15)	0.0533
O1	0.7936 (2)	0.1490 (5)	0.34338 (13)	0.0564
O2	0.6593 (2)	0.7215 (5)	0.38684 (12)	0.0591
O3	0.7904 (3)	−0.0019 (5)	0.43735 (12)	0.0618
F1	0.9217 (4)	0.4524 (6)	0.40116 (15)	0.1040	0.964 (4)
F2	0.9828 (2)	0.2331 (5)	0.47540 (13)	0.0714	0.964 (4)
F3	0.8361 (3)	0.4082 (5)	0.47792 (16)	0.0845	0.964 (4)
F4	0.846 (3)	0.502 (2)	0.429 (3)	0.0800*	0.036 (4)
F5	0.992 (2)	0.330 (8)	0.425 (3)	0.0800*	0.036 (4)
F6	0.910 (5)	0.282 (6)	0.5010 (4)	0.0800*	0.036 (4)
H11	0.6461	0.7332	0.2450	0.0619*
H12	0.7150	0.8730	0.2945	0.0619*
H21	0.5969	0.3601	0.3139	0.0495*
H41	0.5449	0.2331	0.2125	0.0596*
H51	0.4499	0.2559	0.1077	0.0680*
H61	0.3386	0.5487	0.0754	0.0651*
H71	0.3068	0.7953	0.1473	0.0581*
H91	0.3579	0.9563	0.2521	0.0539*
H101	0.3556	0.9169	0.3516	0.0541*
H121	0.3022	0.6959	0.4312	0.0539*
H131	0.3278	0.3947	0.4943	0.0619*
H141	0.4423	0.1260	0.4713	0.0647*
H151	0.5414	0.1676	0.3914	0.0557*
H5	0.7404	−0.0935	0.4169	0.0888*

	U11	U22	U33	U12	U13	U23
C1	0.033 (2)	0.065 (3)	0.040 (3)	−0.002 (2)	0.005 (2)	0.003 (2)
C2	0.036 (2)	0.047 (3)	0.044 (2)	0.008 (2)	0.002 (2)	−0.006 (2)
C3	0.028 (2)	0.046 (3)	0.041 (2)	−0.007 (2)	0.0095 (19)	−0.007 (2)
C4	0.044 (3)	0.056 (3)	0.052 (3)	0.000 (2)	0.011 (2)	−0.009 (2)
C5	0.056 (3)	0.072 (4)	0.048 (3)	−0.012 (3)	0.015 (2)	−0.021 (3)
C6	0.053 (3)	0.081 (4)	0.036 (3)	−0.011 (3)	0.002 (2)	−0.003 (3)
C7	0.044 (3)	0.070 (3)	0.041 (3)	−0.004 (2)	0.004 (2)	0.002 (3)
C8	0.030 (2)	0.049 (3)	0.038 (2)	−0.003 (2)	0.0052 (19)	0.000 (2)
C9	0.047 (3)	0.041 (3)	0.055 (3)	0.002 (2)	0.009 (2)	−0.001 (2)
C10	0.047 (3)	0.045 (3)	0.047 (3)	0.003 (2)	0.013 (2)	−0.006 (2)
C11	0.036 (2)	0.037 (3)	0.035 (2)	−0.006 (2)	0.0022 (19)	−0.006 (2)
C12	0.047 (3)	0.056 (3)	0.038 (2)	−0.005 (2)	0.008 (2)	−0.011 (2)
C13	0.050 (3)	0.069 (4)	0.035 (2)	−0.014 (3)	0.007 (2)	0.006 (3)
C14	0.058 (3)	0.057 (3)	0.050 (3)	−0.010 (3)	−0.004 (2)	0.011 (3)
C15	0.043 (3)	0.055 (3)	0.048 (3)	−0.003 (2)	0.001 (2)	0.002 (2)
C16	0.040 (3)	0.036 (3)	0.032 (2)	−0.002 (2)	−0.0011 (19)	−0.003 (2)
C17	0.054 (3)	0.064 (4)	0.055 (3)	−0.003 (3)	0.014 (3)	−0.002 (3)
C18	0.034 (3)	0.060 (3)	0.044 (3)	0.002 (2)	0.007 (2)	0.008 (3)
N1	0.043 (2)	0.078 (3)	0.038 (2)	−0.017 (2)	0.0045 (17)	−0.009 (2)
O1	0.0488 (19)	0.082 (2)	0.0375 (17)	−0.0082 (17)	0.0064 (14)	0.0091 (17)
O2	0.054 (2)	0.090 (3)	0.0300 (17)	−0.0283 (18)	0.0024 (14)	−0.0002 (16)
O3	0.060 (2)	0.085 (2)	0.0362 (17)	−0.0297 (19)	−0.0009 (15)	0.0067 (17)
F1	0.132 (3)	0.101 (3)	0.074 (2)	−0.059 (3)	0.008 (2)	0.020 (2)
F2	0.0448 (18)	0.091 (2)	0.0715 (19)	−0.0066 (16)	−0.0045 (14)	−0.0160 (17)
F3	0.075 (2)	0.086 (2)	0.095 (2)	0.0090 (19)	0.0230 (19)	−0.027 (2)

C1—C2	1.525 (6)	C11—C16	1.386 (5)
C1—N1	1.321 (5)	C12—C13	1.363 (6)
C1—O2	1.247 (4)	C12—H121	0.942
C2—C3	1.521 (5)	C13—C14	1.364 (6)
C2—C16	1.517 (6)	C13—H131	0.942
C2—H21	0.980	C14—C15	1.378 (6)
C3—C4	1.379 (6)	C14—H141	0.945
C3—C8	1.384 (5)	C15—C16	1.376 (5)
C4—C5	1.383 (6)	C15—H151	0.951
C4—H41	0.941	C17—C18	1.520 (5)
C5—C6	1.372 (7)	C17—F1	1.307 (4)
C5—H51	0.936	C17—F2	1.322 (5)
C6—C7	1.368 (6)	C17—F3	1.328 (5)
C6—H61	0.928	C17—C18	1.520 (5)
C7—C8	1.406 (5)	C17—F4	1.323 (7)
C7—H71	0.934	C17—F5	1.323 (7)
C8—C9	1.451 (5)	C17—F6	1.323 (7)
C9—C10	1.352 (5)	C18—O1	1.209 (4)
C9—H91	0.944	C18—O3	1.283 (5)
C10—C11	1.453 (6)	N1—H11	0.865
C10—H101	0.938	N1—H12	0.867
C11—C12	1.405 (5)	O3—H5	0.887
C2—C1—N1	119.0 (4)	C12—C11—C16	118.2 (4)
C2—C1—O2	119.3 (4)	C11—C12—C13	121.4 (4)
N1—C1—O2	121.6 (4)	C11—C12—H121	118.3
C1—C2—C3	113.4 (4)	C13—C12—H121	120.4
C1—C2—C16	110.5 (3)	C12—C13—C14	119.6 (4)
C3—C2—C16	113.4 (3)	C12—C13—H131	120.7
C1—C2—H21	105.8	C14—C13—H131	119.7
C3—C2—H21	106.9	C13—C14—C15	120.2 (4)
C16—C2—H21	106.2	C13—C14—H141	120.7
C2—C3—C4	119.9 (4)	C15—C14—H141	119.0
C2—C3—C8	119.8 (4)	C14—C15—C16	120.8 (4)
C4—C3—C8	120.2 (4)	C14—C15—H151	119.6
C3—C4—C5	121.2 (4)	C16—C15—H151	119.6
C3—C4—H41	119.6	C2—C16—C11	120.1 (4)
C5—C4—H41	119.2	C2—C16—C15	120.1 (4)
C4—C5—C6	118.6 (4)	C11—C16—C15	119.7 (4)
C4—C5—H51	120.0	C18—C17—F1	111.5 (4)
C6—C5—H51	121.3	C18—C17—F2	111.6 (4)
C5—C6—C7	121.1 (4)	F1—C17—F2	107.9 (4)
C5—C6—H61	119.4	C18—C17—F3	111.4 (4)
C7—C6—H61	119.5	F1—C17—F3	108.7 (4)
C6—C7—C8	120.6 (4)	F2—C17—F3	105.6 (4)
C6—C7—H71	119.3	C18—C17—F4	113.56 (6)
C8—C7—H71	120.1	C18—C17—F5	113.57 (6)
C7—C8—C3	118.2 (4)	F4—C17—F5	105.08 (7)
C7—C8—C9	117.4 (4)	C18—C17—F6	113.57 (6)
C3—C8—C9	124.4 (4)	F4—C17—F6	105.08 (7)
C8—C9—C10	127.8 (4)	F5—C17—F6	105.08 (7)
C8—C9—H91	116.8	C17—C18—O1	120.4 (4)
C10—C9—H91	115.3	C17—C18—O3	111.8 (4)
C9—C10—C11	128.8 (4)	O1—C18—O3	127.8 (4)
C9—C10—H101	115.3	C1—N1—H11	120.6
C11—C10—H101	115.9	C1—N1—H12	119.5
C10—C11—C12	118.0 (4)	H11—N1—H12	119.9
C10—C11—C16	123.9 (4)	C18—O3—H5	113.5

D—H···A	D—H	H···A	D···A	D—H···A
O3—H5···O2i	0.89	1.58	2.462 (4)	173
N1—H11···O1ii	0.86	2.23	2.976 (4)	144
N1—H12···O1iii	0.87	2.16	2.982 (5)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H5⋯O2i	0.89	1.58	2.462 (4)	173
N1—H11⋯O1ii	0.86	2.23	2.976 (4)	144
N1—H12⋯O1iii	0.87	2.16	2.982 (5)	159

Symmetry codes: (i) ; (ii) ; (iii) .