10-Methoxy­dibenz­[b,f]­azepine-5-carbox­amide

Nagaraj, B.; Yathirajan, H.S.; Narasegowda, R.S.; Nagaraja, P.; Lynch, D.E.

doi:10.1107/S1600536805014601

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 6| June 2005| Pages o1760-o1761

https://doi.org/10.1107/S1600536805014601

10-Methoxydibenz[b,f]azepine-5-carboxamide

Basavegowda Nagaraj,^a Hemmige S. Yathirajan,^a Rajenahally S. Narasegowda,^a Padmarajaiah Nagaraja ^a and Daniel E. Lynch ^b ^*

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^bSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 28 April 2005; accepted 9 May 2005; online 14 May 2005)

The structure of the title compound, C₁₆H₁₄N₂O₂, contains a seven-membered ring that adopts a boat conformation, and the overall molecular shape is that of a butterfly. In the packing, the molecules form a convoluted hydrogen-bonded polymer via a typical R₂²(8) graph-set dimer, between carboxamide groups, and an R₂²(16) graph-set dimer formed through an interaction between the second carboxamide NH group and an adjacent methoxy O atom (in each molecule). The dihedral angle between the benzene rings is 56.09 (5)°.

Comment

The title compound, (I), is an intermediate in the synthesis of the anticonvulsant drug oxcarbazepine (Kricka & Ledwith, 1974 ), being the next step on from 10-methoxy-5H-dibenz[b,f]azepine, the structure of which we reported recently (Nagaraj et al., 2005 ).

The structure of (I) (Fig. 1) contains a seven-membered ring that adopts a boat conformation (Cremer & Pople, 1975 ), and the overall molecular shape is that of a butterfly. In the packing of (I), the molecules form two types of dimers, thus creating a convoluted hydrogen-bonded polymer (Fig. 2). A typical R₂²(8) graph-set (Etter, 1990 ) dimer is formed by interaction between carboxamide groups, while an interaction between the second carboxamide NH group and an adjacent methoxy O atom (in each molecule) creates an R₂²(16) graph-set dimer, listed in Table 1. The dihedral angle between the benzene rings is 56.09 (5)°.

Figure 1
The molecular structure and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary radii.

Figure 2
Partial packing diagram for (I

), showing the hydrogen-bonding interactions as dashed lines. For clarity, H atoms not involved in the hydrogen-bonding interactions have been omitted. [Symmetry codes: (i) −x, 1 − y, −z; (ii) 1 − x, 1 − y, −z.]

Experimental

The title compound was prepared by heating 10-methoxy-5H-dibenz[b,f]azepine (2.23 g, 10 mmol) with NaOCN (0.65 g, 10 mmol) in the presence of monochloracetic acid (2.95 g, 10 mmol) in toluene (5 ml). The compound was recrystallized from a dichloromethane–ethanol solution (1:1 v/v).

Crystal data

C₁₆H₁₄N₂O₂
M_r = 266.29
Triclinic, $[P\overline 1]$
a = 8.8003 (2) Å
b = 9.2012 (2) Å
c = 9.3735 (3) Å
α = 64.6999 (16)°
β = 76.0520 (15)°
γ = 83.7398 (18)°
V = 665.95 (3) Å³
Z = 2
D_x = 1.328 Mg m⁻³
Mo Kα radiation
Cell parameters from 3002 reflections
θ = 2.9–27.5°
μ = 0.09 mm⁻¹
T = 120 (2) K
Block, colourless
0.54 × 0.36 × 0.19 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.953, T_max = 0.983
14 982 measured reflections
3054 independent reflections
2527 reflections with I > 2σ(I)
R_int = 0.030
θ_max = 27.6°
h = −11 → 11
k = −11 → 11
l = −11 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.136
S = 1.07
3054 reflections
189 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0757P)² + 0.2176P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.155 (14)

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N51—H51⋯O51ⁱ	0.893 (19)	2.05 (2)	2.9426 (16)	174.1 (16)
N51—H52⋯O10ⁱⁱ	0.893 (19)	2.339 (18)	3.0720 (16)	139.4 (15)
Symmetry codes: (i) -x,1-y,-z; (ii) 1-x,1-y,-z.

All H atoms not included in the hydrogen-bonding associations were included in the refinement at calculated positions, in the riding-model approximation, with C—H distances of 0.95 (ArH) and 0.98 Å (CH₃). The isotropic displacement parameters for the aromatic H atoms were set equal to 1.2U_eq of the carrier atom while the methyl H atoms were set equal to 1.5U_eq of the carrier atom. The two amide H atoms were located in difference syntheses and their positional parameters were refined. The isotropic displacement parameters for these located H atoms were set equal to 1.2U_eq of the carrier N atom.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805014601/nc6031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805014601/nc6031Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; 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.

10-Methoxydibenz[b,f]azepine-5-carboxamide top

Crystal data top

C₁₆H₁₄N₂O₂	Z = 2
M_r = 266.29	F(000) = 280
Triclinic, P1	D_x = 1.328 Mg m⁻³
Hall symbol: -P 1	Melting point: 454 K
a = 8.8003 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2012 (2) Å	Cell parameters from 3002 reflections
c = 9.3735 (3) Å	θ = 2.9–27.5°
α = 64.6999 (16)°	µ = 0.09 mm⁻¹
β = 76.0520 (15)°	T = 120 K
γ = 83.7398 (18)°	Plate, colourless
V = 665.95 (3) Å³	0.54 × 0.36 × 0.19 mm

Data collection top

Nonius KappaCCD diffractometer	3054 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2527 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.030
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.2°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
T_min = 0.953, T_max = 0.983	l = −11→12
14982 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0757P)² + 0.2176P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3054 reflections	Δρ_max = 0.43 e Å⁻³
189 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.155 (14)

Special details top

Experimental. The minimum and maximum absorption values stated above are those calculated in SHELXL97 from the given crystal dimensions. The ratio of minimum to maximum apparent transmission was determined experimentally as 0.901594.

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

6.9149 (0.0032) x + 6.2794 (0.0038) y + 2.8138 (0.0054) z = 6.2902 (0.0039)

* -0.0076 (0.0010) C1 * -0.0032 (0.0011) C2 * 0.0079 (0.0010) C3 * -0.0015 (0.0010) C4 * -0.0093 (0.0009) C13 * 0.0137 (0.0010) C12

Rms deviation of fitted atoms = 0.0083

1.3249 (0.0049) x + 7.9732 (0.0027) y + 7.6776 (0.0032) z = 6.9179 (0.0032)

Angle to previous plane (with approximate e.s.d.) = 56.09 (0.05)

* 0.0084 (0.0010) C6 * -0.0071 (0.0010) C7 * -0.0005 (0.0010) C8 * 0.0068 (0.0010) C9 * -0.0054 (0.0010) C15 * -0.0021 (0.0009) C14

Rms deviation of fitted atoms = 0.0058

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O10	0.50862 (12)	0.41544 (12)	0.28982 (13)	0.0319 (3)
O51	−0.03722 (11)	0.62828 (12)	0.10931 (12)	0.0237 (3)
N5	0.18124 (13)	0.75306 (14)	0.08902 (13)	0.0193 (3)
N51	0.17788 (15)	0.63327 (16)	−0.08401 (15)	0.0245 (3)
H51	0.131 (2)	0.559 (2)	−0.097 (2)	0.029*
H52	0.282 (2)	0.642 (2)	−0.113 (2)	0.029*
C1	0.08186 (18)	0.6754 (2)	0.52440 (18)	0.0288 (3)
H1	0.1064	0.6010	0.6238	0.035*
C2	−0.02650 (19)	0.7956 (2)	0.52389 (19)	0.0315 (4)
H2	−0.0748	0.8039	0.6224	0.038*
C3	−0.06553 (17)	0.90457 (19)	0.3807 (2)	0.0292 (4)
H3	−0.1393	0.9881	0.3805	0.035*
C4	0.00404 (16)	0.89061 (18)	0.23750 (18)	0.0243 (3)
H4	−0.0229	0.9642	0.1391	0.029*
C6	0.40025 (16)	0.91305 (17)	−0.11514 (17)	0.0233 (3)
H6	0.3276	0.9834	−0.1734	0.028*
C7	0.55957 (17)	0.94138 (18)	−0.17407 (18)	0.0267 (3)
H7	0.5965	1.0296	−0.2740	0.032*
C8	0.66488 (17)	0.84024 (18)	−0.08635 (19)	0.0265 (3)
H8	0.7740	0.8603	−0.1261	0.032*
C9	0.61233 (16)	0.71044 (17)	0.05846 (18)	0.0251 (3)
H9	0.6857	0.6428	0.1177	0.030*
C10	0.39947 (17)	0.53775 (17)	0.27309 (18)	0.0237 (3)
C11	0.27161 (17)	0.53113 (18)	0.38749 (18)	0.0258 (3)
H11	0.2537	0.4333	0.4821	0.031*
C12	0.15683 (16)	0.66085 (17)	0.38017 (17)	0.0223 (3)
C13	0.11316 (15)	0.76916 (16)	0.23758 (16)	0.0197 (3)
C14	0.34680 (15)	0.78133 (16)	0.02951 (16)	0.0193 (3)
C15	0.45189 (16)	0.67769 (16)	0.11857 (17)	0.0209 (3)
C16	0.4869 (2)	0.2772 (2)	0.4403 (2)	0.0380 (4)
H161	0.3880	0.2253	0.4591	0.057*
H162	0.4840	0.3097	0.5278	0.057*
H163	0.5738	0.2015	0.4373	0.057*
C51	0.10077 (15)	0.66637 (15)	0.04191 (16)	0.0185 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O10	0.0265 (6)	0.0258 (6)	0.0348 (6)	0.0025 (4)	−0.0049 (5)	−0.0061 (5)
O51	0.0152 (5)	0.0325 (6)	0.0283 (5)	−0.0029 (4)	−0.0031 (4)	−0.0172 (4)
N5	0.0133 (5)	0.0258 (6)	0.0214 (6)	−0.0025 (4)	−0.0014 (4)	−0.0129 (5)
N51	0.0188 (6)	0.0330 (7)	0.0282 (7)	−0.0046 (5)	−0.0012 (5)	−0.0198 (6)
C1	0.0283 (8)	0.0365 (8)	0.0224 (7)	−0.0084 (6)	−0.0013 (6)	−0.0132 (6)
C2	0.0290 (8)	0.0415 (9)	0.0294 (8)	−0.0102 (7)	0.0043 (6)	−0.0231 (7)
C3	0.0211 (7)	0.0325 (8)	0.0389 (9)	−0.0030 (6)	0.0013 (6)	−0.0229 (7)
C4	0.0187 (7)	0.0276 (7)	0.0281 (7)	−0.0025 (5)	−0.0027 (5)	−0.0137 (6)
C6	0.0210 (7)	0.0266 (7)	0.0235 (7)	−0.0008 (5)	−0.0040 (5)	−0.0118 (6)
C7	0.0253 (8)	0.0276 (7)	0.0242 (7)	−0.0066 (6)	0.0021 (6)	−0.0105 (6)
C8	0.0160 (7)	0.0291 (7)	0.0359 (8)	−0.0047 (5)	0.0018 (6)	−0.0179 (7)
C9	0.0179 (7)	0.0244 (7)	0.0351 (8)	0.0000 (5)	−0.0053 (6)	−0.0146 (6)
C10	0.0210 (7)	0.0215 (7)	0.0296 (7)	−0.0003 (5)	−0.0085 (6)	−0.0100 (6)
C11	0.0256 (7)	0.0249 (7)	0.0247 (7)	−0.0043 (6)	−0.0061 (6)	−0.0069 (6)
C12	0.0205 (7)	0.0250 (7)	0.0229 (7)	−0.0068 (5)	−0.0018 (5)	−0.0113 (6)
C13	0.0160 (6)	0.0247 (7)	0.0219 (7)	−0.0060 (5)	−0.0006 (5)	−0.0133 (6)
C14	0.0150 (6)	0.0237 (7)	0.0225 (7)	−0.0020 (5)	−0.0019 (5)	−0.0134 (6)
C15	0.0172 (7)	0.0219 (7)	0.0261 (7)	−0.0021 (5)	−0.0026 (5)	−0.0128 (6)
C16	0.0371 (9)	0.0293 (8)	0.0372 (9)	0.0033 (7)	−0.0083 (7)	−0.0048 (7)
C51	0.0169 (6)	0.0189 (6)	0.0205 (6)	0.0006 (5)	−0.0066 (5)	−0.0079 (5)

Geometric parameters (Å, º) top

O10—C10	1.3784 (17)	C6—C7	1.3864 (19)
O10—C16	1.4262 (19)	C6—C14	1.3931 (19)
O51—C51	1.2371 (16)	C6—H6	0.95
N5—C51	1.3812 (17)	C7—C8	1.388 (2)
N5—C14	1.4382 (16)	C7—H7	0.95
N5—C13	1.4404 (17)	C8—C9	1.384 (2)
N51—C51	1.3500 (18)	C8—H8	0.95
N51—H51	0.893 (19)	C9—C15	1.4021 (19)
N51—H52	0.893 (19)	C9—H9	0.95
C1—C2	1.379 (2)	C10—C11	1.341 (2)
C1—C12	1.409 (2)	C10—C15	1.4772 (19)
C1—H1	0.95	C11—C12	1.466 (2)
C2—C3	1.387 (2)	C11—H11	0.95
C2—H2	0.95	C12—C13	1.397 (2)
C3—C4	1.388 (2)	C14—C15	1.4004 (19)
C3—H3	0.95	C16—H161	0.98
C4—C13	1.392 (2)	C16—H162	0.98
C4—H4	0.95	C16—H163	0.98

C10—O10—C16	117.75 (12)	C8—C9—H9	119.7
C51—N5—C14	122.20 (11)	C15—C9—H9	119.7
C51—N5—C13	118.35 (11)	C11—C10—O10	123.75 (13)
C14—N5—C13	116.23 (10)	C11—C10—C15	126.28 (13)
C51—N51—H51	113.9 (11)	O10—C10—C15	109.81 (12)
C51—N51—H52	119.3 (11)	C10—C11—C12	126.05 (13)
H51—N51—H52	119.2 (16)	C10—C11—H11	117.0
C2—C1—C12	121.18 (14)	C12—C11—H11	117.0
C2—C1—H1	119.4	C13—C12—C1	117.54 (13)
C12—C1—H1	119.4	C13—C12—C11	123.48 (13)
C1—C2—C3	120.48 (14)	C1—C12—C11	118.94 (13)
C1—C2—H2	119.8	C4—C13—C12	121.06 (13)
C3—C2—H2	119.8	C4—C13—N5	119.73 (12)
C2—C3—C4	119.45 (14)	C12—C13—N5	119.20 (12)
C2—C3—H3	120.3	C6—C14—C15	120.90 (12)
C4—C3—H3	120.3	C6—C14—N5	119.41 (12)
C3—C4—C13	120.24 (14)	C15—C14—N5	119.69 (12)
C3—C4—H4	119.9	C14—C15—C9	118.19 (13)
C13—C4—H4	119.9	C14—C15—C10	122.41 (12)
C7—C6—C14	119.98 (13)	C9—C15—C10	119.40 (13)
C7—C6—H6	120.0	O10—C16—H161	109.5
C14—C6—H6	120.0	O10—C16—H162	109.5
C6—C7—C8	119.67 (13)	H161—C16—H162	109.5
C6—C7—H7	120.2	O10—C16—H163	109.5
C8—C7—H7	120.2	H161—C16—H163	109.5
C9—C8—C7	120.58 (13)	H162—C16—H163	109.5
C9—C8—H8	119.7	O51—C51—N51	122.82 (12)
C7—C8—H8	119.7	O51—C51—N5	120.43 (12)
C8—C9—C15	120.66 (13)	N51—C51—N5	116.68 (12)

C12—C1—C2—C3	0.7 (2)	C51—N5—C13—C12	94.38 (15)
C1—C2—C3—C4	0.8 (2)	C14—N5—C13—C12	−65.81 (16)
C2—C3—C4—C13	−0.6 (2)	C7—C6—C14—C15	1.1 (2)
C14—C6—C7—C8	−1.5 (2)	C7—C6—C14—N5	−179.81 (12)
C6—C7—C8—C9	0.7 (2)	C51—N5—C14—C6	86.66 (16)
C7—C8—C9—C15	0.6 (2)	C13—N5—C14—C6	−113.98 (14)
C16—O10—C10—C11	−2.7 (2)	C51—N5—C14—C15	−94.23 (16)
C16—O10—C10—C15	172.88 (13)	C13—N5—C14—C15	65.13 (17)
O10—C10—C11—C12	176.14 (13)	C6—C14—C15—C9	0.2 (2)
C15—C10—C11—C12	1.3 (2)	N5—C14—C15—C9	−178.88 (11)
C2—C1—C12—C13	−2.3 (2)	C6—C14—C15—C10	179.44 (13)
C2—C1—C12—C11	179.75 (13)	N5—C14—C15—C10	0.3 (2)
C10—C11—C12—C13	35.0 (2)	C8—C9—C15—C14	−1.1 (2)
C10—C11—C12—C1	−147.14 (15)	C8—C9—C15—C10	179.68 (13)
C3—C4—C13—C12	−1.0 (2)	C11—C10—C15—C14	−37.2 (2)
C3—C4—C13—N5	178.23 (12)	O10—C10—C15—C14	147.39 (13)
C1—C12—C13—C4	2.4 (2)	C11—C10—C15—C9	142.05 (15)
C11—C12—C13—C4	−179.69 (13)	O10—C10—C15—C9	−33.39 (18)
C1—C12—C13—N5	−176.85 (12)	C14—N5—C51—O51	171.50 (12)
C11—C12—C13—N5	1.0 (2)	C13—N5—C51—O51	12.56 (18)
C51—N5—C13—C4	−84.90 (16)	C14—N5—C51—N51	−11.43 (18)
C14—N5—C13—C4	114.91 (14)	C13—N5—C51—N51	−170.38 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51···O51ⁱ	0.893 (19)	2.05 (2)	2.9426 (16)	174.1 (16)
N51—H52···O10ⁱⁱ	0.893 (19)	2.339 (18)	3.0720 (16)	139.4 (15)

Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z.

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England).

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