5-Chloro­carbonyl-10,11-dihydro-5H-dibenz[b,f]azepine

In the title compound, C₁₅H₁₂ClNO, the central seven-membered azepine ring adopts a bent conformation, intermediate between the boat and chair forms. The overall structure of the mol­ecule is similar to a butterfly shape, which is commonly observed for carbamazepine analogues. The planes through the benzene rings on either side of the azepine ring inter­sect at an angle of 59.0 (1)°. The mol­ecular assembly is primarily stabilized by aromatic π–π inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.063
• wR factor = 0.119
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O17    -   C16     ..       5.73 su
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.93
           From the CIF: _reflns_number_total               2890
           Count of symmetry unique reflns         1662
           Completeness (_total/calc)            173.89%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1228
           Fraction of Friedel pairs measured     0.739
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

5-Chlorocarbonyl-10,11-dihydro-5H-dibenz[b,f]azepine

Crystal data

C15H12ClNO	Dx = 1.330 Mg m^−3
Mr = 257.71	Melting point: 425 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 870 reflections
a = 16.654 (3) Å	θ = 5–27°
b = 10.646 (2) Å	µ = 0.28 mm^−1
c = 7.2599 (14) Å	T = 295 K
V = 1287.1 (4) Å^3	Plate, colourless
Z = 4	0.58 × 0.20 × 0.12 mm
F(000) = 536

Data collection

Bruker SMART CCD area-detector diffractometer	2890 independent reflections
Radiation source: fine-focus sealed tube	2159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 27.9°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→21
Tmin = 0.926, Tmax = 0.971	k = −14→11
6801 measured reflections	l = −9→8

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)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.0447P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max < 0.001
2890 reflections	Δρmax = 0.29 e Å^−3
163 parameters	Δρmin = −0.18 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (10)

Special details

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.

Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d

Plane 1 m1 = -0.35730(0.00080) m2 = 0.89623(0.00034) m3 = -0.26289(0.00094) D = 0.49850(0.01487) Atom d s d/s (d/s)**2 N5 * -0.0168 0.0021 - 7.870 61.931 C1 * -0.0353 0.0034 - 10.400 108.164 C2 * -0.0180 0.0034 - 5.258 27.646 C3 * 0.0253 0.0031 8.247 68.018 C4 * 0.0126 0.0028 4.465 19.940 C11 * 0.0543 0.0036 15.102 228.077 C12 * 0.0075 0.0027 2.816 7.932 C13 * -0.0119 0.0031 - 3.874 15.005 C10 - 1.2038 0.0038 - 316.057 99892.266 C14 - 1.2532 0.0029 - 438.151 191975.984 ============ Sum((d/s)**2) for starred atoms 536.711 Chi-squared at 95% for 5 degrees of freedom: 11.10 The group of atoms deviates significantly from planarity

Plane 2 m1 = -0.80391(0.00054) m2 = 0.08071(0.00073) m3 = -0.58925(0.00076) D = -14.10585(0.00586) Atom d s d/s (d/s)**2 N5 * 0.0150 0.0022 6.928 47.995 C6 * -0.0349 0.0034 - 10.133 102.687 C7 * -0.0319 0.0036 - 8.774 76.991 C8 * 0.0004 0.0039 0.096 0.009 C9 * 0.0136 0.0034 4.055 16.441 C10 * 0.0138 0.0037 3.721 13.849 C11 * -0.0604 0.0035 - 17.273 298.351 C14 * 0.0176 0.0028 6.287 39.521 C15 * 0.0239 0.0030 7.918 62.692 C12 - 1.1067 0.0026 - 419.792 176225.094 C13 - 1.1753 0.0030 - 396.378 157115.313 ============ Sum((d/s)**2) for starred atoms 658.536 Chi-squared at 95% for 6 degrees of freedom: 12.60 The group of atoms deviates significantly from planarity

Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 59.04 (0.06) 120.96 (0.06)

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.

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

	x	y	z	Uiso*/Ueq
C1	1.06371 (18)	0.8464 (3)	0.6722 (5)	0.0566 (9)
H1	1.1011	0.8477	0.5771	0.068*
C2	1.08446 (19)	0.8949 (3)	0.8410 (6)	0.0573 (10)
H2	1.1355	0.9284	0.8588	0.069*
C3	1.03022 (18)	0.8942 (3)	0.9840 (6)	0.0526 (8)
H3	1.0439	0.9293	1.0970	0.063*
C4	0.95532 (16)	0.8411 (3)	0.9588 (5)	0.0445 (7)
H4	0.9189	0.8373	1.0558	0.053*
N5	0.85755 (11)	0.7369 (2)	0.7581 (4)	0.0409 (6)
C6	0.81351 (18)	0.5329 (3)	0.8666 (6)	0.0597 (9)
H6	0.7879	0.5736	0.9636	0.072*
C7	0.8097 (2)	0.4042 (4)	0.8518 (6)	0.0687 (11)
H7	0.7808	0.3576	0.9375	0.082*
C8	0.8488 (2)	0.3449 (3)	0.7101 (6)	0.0667 (11)
H8	0.8459	0.2580	0.6987	0.080*
C9	0.89168 (19)	0.4129 (3)	0.5865 (5)	0.0565 (9)
H9	0.9187	0.3709	0.4929	0.068*
C10	0.9478 (2)	0.6072 (4)	0.4499 (5)	0.0677 (10)
H10A	1.0005	0.5684	0.4535	0.081*
H10B	0.9247	0.5875	0.3307	0.081*
C11	0.9600 (2)	0.7481 (3)	0.4573 (5)	0.0605 (9)
H11A	0.9991	0.7717	0.3645	0.073*
H11B	0.9098	0.7892	0.4266	0.073*
C12	0.93523 (14)	0.7941 (3)	0.7887 (4)	0.0390 (7)
C13	0.98788 (17)	0.7952 (3)	0.6402 (4)	0.0450 (7)
C14	0.85570 (15)	0.6018 (3)	0.7362 (5)	0.0410 (7)
C15	0.89659 (17)	0.5431 (3)	0.5949 (5)	0.0473 (8)
C16	0.78835 (16)	0.8012 (3)	0.7413 (5)	0.0459 (7)
O17	0.72290 (12)	0.7592 (2)	0.7138 (4)	0.0661 (8)
Cl18	0.80023 (4)	0.96704 (7)	0.75942 (15)	0.0630 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0420 (18)	0.060 (2)	0.068 (3)	−0.0014 (16)	0.0137 (17)	0.0124 (18)
C2	0.0368 (17)	0.053 (2)	0.083 (3)	−0.0086 (15)	−0.0086 (18)	0.0079 (19)
C3	0.0519 (19)	0.0409 (19)	0.065 (2)	−0.0005 (15)	−0.0118 (18)	0.0005 (16)
C4	0.0415 (16)	0.0440 (18)	0.048 (2)	0.0022 (14)	0.0003 (14)	0.0007 (15)
N5	0.0310 (11)	0.0449 (14)	0.0468 (16)	0.0032 (9)	0.0034 (13)	−0.0082 (14)
C6	0.0480 (19)	0.054 (2)	0.077 (3)	0.0020 (17)	0.0134 (18)	−0.0048 (18)
C7	0.058 (2)	0.061 (3)	0.087 (3)	−0.0046 (18)	0.019 (2)	0.013 (2)
C8	0.059 (2)	0.042 (2)	0.099 (4)	0.0038 (16)	−0.004 (2)	−0.008 (2)
C9	0.055 (2)	0.053 (2)	0.061 (2)	0.0093 (16)	−0.0012 (17)	−0.011 (2)
C10	0.081 (2)	0.075 (3)	0.047 (2)	0.004 (2)	0.0126 (19)	−0.0117 (19)
C11	0.057 (2)	0.073 (3)	0.052 (2)	−0.0015 (18)	0.0132 (17)	0.0053 (19)
C12	0.0318 (14)	0.0425 (17)	0.0427 (18)	0.0025 (11)	−0.0016 (13)	0.0070 (14)
C13	0.0406 (16)	0.0469 (19)	0.0476 (19)	0.0003 (13)	0.0002 (14)	0.0075 (15)
C14	0.0310 (13)	0.0479 (18)	0.0442 (19)	0.0026 (12)	−0.0030 (14)	−0.0074 (15)
C15	0.0420 (16)	0.052 (2)	0.048 (2)	0.0079 (15)	−0.0058 (14)	−0.0080 (16)
C16	0.0420 (16)	0.0512 (17)	0.0446 (19)	0.0059 (13)	0.0034 (15)	−0.0037 (17)
O17	0.0303 (11)	0.0725 (16)	0.095 (2)	0.0011 (9)	−0.0081 (12)	−0.0121 (14)
Cl18	0.0497 (4)	0.0530 (5)	0.0863 (7)	0.0121 (3)	0.0037 (5)	0.0031 (6)

Geometric parameters (Å, º)

C1—C2	1.374 (5)	C7—H7	0.9300
C1—C13	1.395 (4)	C8—C9	1.355 (5)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.376 (5)	C9—C15	1.390 (4)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.381 (4)	C10—C11	1.515 (5)
C3—H3	0.9300	C10—C15	1.517 (5)
C4—C12	1.375 (5)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
N5—C16	1.346 (3)	C11—C13	1.493 (5)
N5—C12	1.447 (3)	C11—H11A	0.9700
N5—C14	1.448 (3)	C11—H11B	0.9700
C6—C7	1.376 (5)	C12—C13	1.390 (4)
C6—C14	1.389 (5)	C14—C15	1.381 (4)
C6—H6	0.9300	C16—O17	1.195 (3)
C7—C8	1.371 (5)	C16—Cl18	1.781 (3)
C2—C1—C13	121.6 (3)	C11—C10—C15	119.8 (3)
C2—C1—H1	119.2	C11—C10—H10A	107.4
C13—C1—H1	119.2	C15—C10—H10A	107.4
C1—C2—C3	120.4 (3)	C11—C10—H10B	107.4
C1—C2—H2	119.8	C15—C10—H10B	107.4
C3—C2—H2	119.8	H10A—C10—H10B	106.9
C2—C3—C4	119.7 (3)	C13—C11—C10	113.9 (3)
C2—C3—H3	120.2	C13—C11—H11A	108.8
C4—C3—H3	120.2	C10—C11—H11A	108.8
C12—C4—C3	119.2 (3)	C13—C11—H11B	108.8
C12—C4—H4	120.4	C10—C11—H11B	108.8
C3—C4—H4	120.4	H11A—C11—H11B	107.7
C16—N5—C12	124.5 (2)	C4—C12—C13	122.7 (2)
C16—N5—C14	118.5 (2)	C4—C12—N5	120.6 (3)
C12—N5—C14	116.97 (19)	C13—C12—N5	116.7 (3)
C7—C6—C14	119.7 (3)	C12—C13—C1	116.4 (3)
C7—C6—H6	120.1	C12—C13—C11	119.4 (3)
C14—C6—H6	120.1	C1—C13—C11	124.1 (3)
C8—C7—C6	119.7 (3)	C15—C14—C6	121.1 (3)
C8—C7—H7	120.2	C15—C14—N5	121.4 (3)
C6—C7—H7	120.2	C6—C14—N5	117.4 (3)
C9—C8—C7	120.1 (3)	C14—C15—C9	117.1 (3)
C9—C8—H8	120.0	C14—C15—C10	126.1 (3)
C7—C8—H8	120.0	C9—C15—C10	116.8 (3)
C8—C9—C15	122.3 (3)	O17—C16—N5	127.3 (3)
C8—C9—H9	118.9	O17—C16—Cl18	119.0 (2)
C15—C9—H9	118.9	N5—C16—Cl18	113.7 (2)
C13—C1—C2—C3	−0.1 (5)	C10—C11—C13—C1	112.3 (4)
C1—C2—C3—C4	1.9 (5)	C7—C6—C14—C15	−2.4 (5)
C2—C3—C4—C12	−2.4 (4)	C7—C6—C14—N5	179.9 (3)
C14—C6—C7—C8	1.1 (5)	C16—N5—C14—C15	116.7 (3)
C6—C7—C8—C9	0.8 (6)	C12—N5—C14—C15	−60.6 (4)
C7—C8—C9—C15	−1.4 (6)	C16—N5—C14—C6	−65.6 (4)
C15—C10—C11—C13	51.6 (5)	C12—N5—C14—C6	117.1 (3)
C3—C4—C12—C13	1.3 (4)	C6—C14—C15—C9	1.8 (4)
C3—C4—C12—N5	179.5 (3)	N5—C14—C15—C9	179.4 (3)
C16—N5—C12—C4	75.0 (4)	C6—C14—C15—C10	−177.0 (3)
C14—N5—C12—C4	−107.9 (3)	N5—C14—C15—C10	0.7 (5)
C16—N5—C12—C13	−106.7 (3)	C8—C9—C15—C14	0.1 (5)
C14—N5—C12—C13	70.4 (4)	C8—C9—C15—C10	179.0 (4)
C4—C12—C13—C1	0.4 (4)	C11—C10—C15—C14	2.4 (5)
N5—C12—C13—C1	−177.8 (3)	C11—C10—C15—C9	−176.3 (3)
C4—C12—C13—C11	−176.9 (3)	C12—N5—C16—O17	179.0 (4)
N5—C12—C13—C11	4.8 (4)	C14—N5—C16—O17	1.9 (6)
C2—C1—C13—C12	−1.0 (5)	C12—N5—C16—Cl18	0.2 (4)
C2—C1—C13—C11	176.1 (3)	C14—N5—C16—Cl18	−176.9 (2)
C10—C11—C13—C12	−70.6 (4)