2,4-Bis(4-fluoro-phen-yl)-2,3-dihydro-1H-1,5-benzodiazepine.

In the title compound, C(21)H(16)F(2)N(2), the seven-membered 1,4-diazepine ring of the benzodiazepine ring system adopts a distorted-boat conformation. The benzene ring of this system makes dihedral angles of 18.6 (2) and 78.8 (2)° with those of two fluoro-phenyl substituents. In the crystal, inversion dimers linked by two weak C-H⋯F hydrogen bonds generate R(2) (2)(20) ring motifs. There are also weak N-H⋯π and C-H⋯π inter-actions.

Related literature

For related structures, see: An et al. (2007 ▶); Bibila Mayaya Bisseyou et al. (2010 ▶); Harrison et al. (2005 ▶); Peeters et al. (1997 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For graph-set nomenclature of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C21H16F2N2

M = 334.36

Monoclinic,

a = 12.9151 (4) Å

b = 6.0438 (3) Å

c = 21.2851 (7) Å

β = 92.147 (3)°

V = 1660.27 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 294 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer

Absorption correction: refined from ΔF (XABS2; Parkin et al., 1995 ▶) T min = 0.981, T max = 0.981

3413 measured reflections

3413 independent reflections

1226 reflections with I > 2σ(I)

Refinement

R[F 2 > 2σ(F 2)] = 0.061

wR(F 2) = 0.151

S = 1.04

3413 reflections

233 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.18 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015455/hb5848sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015455/hb5848Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811015455/hb5848Isup3.cml

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

C21H16F2N2	F(000) = 696
Mr = 334.36	Dx = 1.338 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1691 reflections
a = 12.9151 (4) Å	θ = 2.5–26.3°
b = 6.0438 (3) Å	µ = 0.10 mm−1
c = 21.2851 (7) Å	T = 294 K
β = 92.147 (3)°	Block, pale yellow
V = 1660.27 (11) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Rigaku R-AXIS RAPID-S diffractometer	3413 independent reflections
Radiation source: Sealed Tube	1226 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.000
Detector resolution: 10.0000 pixels mm-1	θmax = 26.5°, θmin = 3.2°
dtprofit.ref scans	h = −16→16
Absorption correction: part of the refinement model (ΔF) [XABS2 (Parkin et al., 1995); Cubic fit to sinθ/λ, 24 parameters]	k = 0→7
Tmin = 0.981, Tmax = 0.981	l = 0→26
3413 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.P)2 + 1.2828P] where P = (Fo2 + 2Fc2)/3
3413 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.16 e Å−3
2 restraints	Δρmin = −0.18 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
F1	0.2985 (2)	0.5093 (5)	0.38988 (13)	0.1156 (16)
F2	0.6025 (2)	−0.0519 (5)	0.58369 (17)	0.1365 (18)
N1	−0.0014 (3)	0.2319 (7)	0.60658 (19)	0.0764 (17)
N2	0.1477 (3)	−0.0519 (6)	0.67436 (16)	0.0667 (16)
C1	0.0446 (4)	−0.0259 (7)	0.6923 (2)	0.0649 (17)
C2	0.0114 (4)	−0.1609 (7)	0.7400 (2)	0.0747 (19)
C3	−0.0881 (4)	−0.1566 (8)	0.7601 (2)	0.084 (2)
C4	−0.1587 (4)	−0.0156 (9)	0.7299 (2)	0.090 (2)
C5	−0.1280 (4)	0.1161 (8)	0.6815 (2)	0.083 (2)
C6	−0.0273 (4)	0.1150 (7)	0.6613 (2)	0.0669 (17)
C7	0.0768 (4)	0.4074 (7)	0.6097 (2)	0.0674 (17)
C8	0.1593 (3)	0.3499 (7)	0.66113 (19)	0.0675 (17)
C9	0.2006 (3)	0.1161 (7)	0.6576 (2)	0.0635 (17)
C10	0.3074 (3)	0.0767 (7)	0.6375 (2)	0.0652 (17)
C11	0.3591 (4)	0.2231 (8)	0.6009 (2)	0.080 (2)
C12	0.4584 (4)	0.1818 (9)	0.5813 (2)	0.095 (3)
C13	0.5044 (4)	−0.0120 (10)	0.6017 (3)	0.094 (3)
C14	0.4580 (4)	−0.1612 (8)	0.6392 (2)	0.085 (2)
C15	0.3579 (4)	−0.1181 (7)	0.6567 (2)	0.0735 (17)
C16	0.1258 (3)	0.4366 (7)	0.5464 (2)	0.0628 (17)
C17	0.1274 (3)	0.2722 (7)	0.5013 (2)	0.0710 (17)
C18	0.1843 (4)	0.2974 (9)	0.4478 (2)	0.083 (2)
C19	0.2394 (4)	0.4894 (10)	0.4416 (2)	0.081 (2)
C20	0.2382 (4)	0.6561 (8)	0.4837 (2)	0.080 (2)
C21	0.1800 (3)	0.6298 (7)	0.5363 (2)	0.0721 (17)
H1N	−0.060 (2)	0.265 (10)	0.588 (2)	0.1640*
H2	0.05840	−0.25840	0.75920	0.0900*
H3	−0.10780	−0.24590	0.79310	0.1010*
H4	−0.22690	−0.01050	0.74250	0.1080*
H5	−0.17630	0.20920	0.66170	0.1000*
H7	0.048 (4)	0.552 (4)	0.621 (2)	0.1640*
H8A	0.21670	0.45220	0.65810	0.0810*
H8B	0.12960	0.37130	0.70190	0.0810*
H11	0.32650	0.35440	0.58870	0.0960*
H12	0.49230	0.28040	0.55560	0.1140*
H14	0.49250	−0.28860	0.65270	0.1020*
H15	0.32380	−0.21960	0.68140	0.0880*
H17	0.08980	0.14290	0.50700	0.0850*
H18	0.18500	0.18780	0.41710	0.0990*
H20	0.27570	0.78520	0.47760	0.0960*
H21	0.17710	0.74420	0.56540	0.0860*

	U11	U22	U33	U12	U13	U23
F1	0.117 (3)	0.135 (3)	0.098 (2)	0.027 (2)	0.0457 (19)	0.034 (2)
F2	0.080 (2)	0.133 (3)	0.199 (4)	0.019 (2)	0.040 (2)	0.037 (3)
N1	0.065 (3)	0.093 (3)	0.071 (3)	−0.011 (2)	0.002 (2)	0.014 (2)
N2	0.063 (3)	0.064 (2)	0.073 (3)	0.001 (2)	0.003 (2)	0.001 (2)
C1	0.065 (3)	0.066 (3)	0.064 (3)	−0.005 (3)	0.006 (2)	0.001 (2)
C2	0.078 (4)	0.070 (3)	0.076 (3)	0.000 (3)	0.002 (3)	0.003 (3)
C3	0.088 (4)	0.088 (4)	0.077 (4)	0.001 (3)	0.020 (3)	0.014 (3)
C4	0.073 (4)	0.109 (4)	0.090 (4)	0.005 (3)	0.015 (3)	0.011 (3)
C5	0.069 (3)	0.098 (4)	0.083 (4)	0.009 (3)	0.013 (3)	0.012 (3)
C6	0.066 (3)	0.072 (3)	0.063 (3)	0.001 (3)	0.008 (2)	0.002 (2)
C7	0.069 (3)	0.069 (3)	0.064 (3)	0.004 (3)	0.000 (2)	0.004 (3)
C8	0.072 (3)	0.064 (3)	0.066 (3)	−0.001 (2)	−0.003 (2)	−0.003 (2)
C9	0.064 (3)	0.061 (3)	0.065 (3)	0.005 (2)	−0.004 (2)	0.000 (2)
C10	0.062 (3)	0.067 (3)	0.066 (3)	−0.004 (3)	−0.006 (2)	0.000 (2)
C11	0.062 (3)	0.082 (4)	0.096 (4)	0.001 (3)	0.000 (3)	0.015 (3)
C12	0.071 (4)	0.102 (4)	0.113 (5)	0.003 (3)	0.013 (3)	0.031 (3)
C13	0.056 (3)	0.105 (5)	0.123 (5)	0.012 (3)	0.015 (3)	0.010 (4)
C14	0.067 (4)	0.078 (4)	0.109 (4)	0.005 (3)	0.003 (3)	0.010 (3)
C15	0.069 (3)	0.067 (3)	0.084 (3)	−0.007 (3)	−0.002 (3)	−0.001 (3)
C16	0.061 (3)	0.061 (3)	0.066 (3)	0.004 (2)	−0.004 (2)	0.002 (2)
C17	0.073 (3)	0.068 (3)	0.072 (3)	0.003 (3)	0.003 (3)	0.001 (3)
C18	0.091 (4)	0.084 (4)	0.074 (4)	0.016 (3)	0.007 (3)	−0.006 (3)
C19	0.078 (4)	0.099 (4)	0.067 (3)	0.020 (3)	0.017 (3)	0.023 (3)
C20	0.080 (4)	0.074 (4)	0.085 (4)	0.006 (3)	0.006 (3)	0.017 (3)
C21	0.077 (3)	0.068 (3)	0.071 (3)	0.002 (3)	−0.002 (3)	0.001 (3)

F1—C19	1.368 (5)	C14—C15	1.384 (7)
F2—C13	1.359 (6)	C16—C21	1.382 (6)
N1—C6	1.413 (6)	C16—C17	1.382 (6)
N1—C7	1.464 (6)	C17—C18	1.387 (6)
N2—C1	1.408 (6)	C18—C19	1.370 (8)
N2—C9	1.282 (6)	C19—C20	1.349 (7)
N1—H1N	0.86 (3)	C20—C21	1.381 (6)
C1—C6	1.406 (7)	C2—H2	0.9300
C1—C2	1.383 (6)	C3—H3	0.9300
C2—C3	1.370 (7)	C4—H4	0.9300
C3—C4	1.388 (7)	C5—H5	0.9300
C4—C5	1.372 (7)	C7—H7	0.98 (3)
C5—C6	1.385 (7)	C8—H8A	0.9700
C7—C8	1.539 (6)	C8—H8B	0.9700
C7—C16	1.520 (6)	C11—H11	0.9300
C8—C9	1.513 (6)	C12—H12	0.9300
C9—C10	1.479 (6)	C14—H14	0.9300
C10—C11	1.369 (6)	C15—H15	0.9300
C10—C15	1.400 (6)	C17—H17	0.9300
C11—C12	1.386 (7)	C18—H18	0.9300
C12—C13	1.376 (8)	C20—H20	0.9300
C13—C14	1.358 (8)	C21—H21	0.9300
C6—N1—C7	120.6 (4)	F1—C19—C18	117.4 (4)
C1—N2—C9	120.4 (4)	C18—C19—C20	123.3 (4)
C7—N1—H1N	116 (4)	C19—C20—C21	118.2 (5)
C6—N1—H1N	105 (3)	C16—C21—C20	121.2 (4)
N2—C1—C6	123.7 (4)	C1—C2—H2	119.00
C2—C1—C6	119.0 (5)	C3—C2—H2	119.00
N2—C1—C2	117.1 (4)	C2—C3—H3	121.00
C1—C2—C3	122.6 (4)	C4—C3—H3	121.00
C2—C3—C4	118.3 (4)	C3—C4—H4	120.00
C3—C4—C5	120.0 (5)	C5—C4—H4	120.00
C4—C5—C6	122.1 (5)	C4—C5—H5	119.00
C1—C6—C5	117.9 (4)	C6—C5—H5	119.00
N1—C6—C1	121.1 (4)	N1—C7—H7	113 (3)
N1—C6—C5	120.5 (4)	C8—C7—H7	107 (3)
N1—C7—C16	110.7 (4)	C16—C7—H7	107 (2)
N1—C7—C8	109.1 (3)	C7—C8—H8A	109.00
C8—C7—C16	110.9 (4)	C7—C8—H8B	109.00
C7—C8—C9	114.3 (3)	C9—C8—H8A	109.00
N2—C9—C8	122.2 (4)	C9—C8—H8B	109.00
C8—C9—C10	119.9 (4)	H8A—C8—H8B	108.00
N2—C9—C10	117.8 (4)	C10—C11—H11	119.00
C9—C10—C15	118.7 (4)	C12—C11—H11	119.00
C9—C10—C11	122.7 (4)	C11—C12—H12	122.00
C11—C10—C15	118.6 (4)	C13—C12—H12	122.00
C10—C11—C12	122.1 (4)	C13—C14—H14	121.00
C11—C12—C13	116.9 (5)	C15—C14—H14	121.00
C12—C13—C14	123.8 (5)	C10—C15—H15	120.00
F2—C13—C14	119.0 (5)	C14—C15—H15	120.00
F2—C13—C12	117.3 (5)	C16—C17—H17	119.00
C13—C14—C15	118.1 (5)	C18—C17—H17	120.00
C10—C15—C14	120.7 (4)	C17—C18—H18	121.00
C17—C16—C21	118.6 (4)	C19—C18—H18	121.00
C7—C16—C17	123.3 (4)	C19—C20—H20	121.00
C7—C16—C21	117.8 (4)	C21—C20—H20	121.00
C16—C17—C18	120.9 (4)	C16—C21—H21	119.00
C17—C18—C19	117.7 (4)	C20—C21—H21	119.00
F1—C19—C20	119.3 (5)
C6—N1—C7—C8	32.4 (5)	C7—C8—C9—N2	−74.6 (5)
C6—N1—C7—C16	154.7 (4)	N2—C9—C10—C11	159.0 (4)
C7—N1—C6—C1	−67.0 (6)	N2—C9—C10—C15	−21.1 (6)
C7—N1—C6—C5	120.7 (5)	C8—C9—C10—C11	−24.2 (6)
C9—N2—C1—C6	40.9 (6)	C8—C9—C10—C15	155.7 (4)
C9—N2—C1—C2	−144.4 (4)	C9—C10—C11—C12	−178.6 (4)
C1—N2—C9—C8	5.1 (6)	C15—C10—C11—C12	1.5 (7)
C1—N2—C9—C10	−178.2 (4)	C9—C10—C15—C14	−179.7 (4)
N2—C1—C6—C5	176.5 (4)	C11—C10—C15—C14	0.2 (7)
N2—C1—C2—C3	−177.7 (4)	C10—C11—C12—C13	−1.6 (7)
C6—C1—C2—C3	−2.7 (7)	C11—C12—C13—F2	−178.8 (5)
N2—C1—C6—N1	3.9 (7)	C11—C12—C13—C14	0.1 (8)
C2—C1—C6—N1	−170.7 (4)	F2—C13—C14—C15	−179.6 (5)
C2—C1—C6—C5	1.8 (6)	C12—C13—C14—C15	1.5 (8)
C1—C2—C3—C4	2.0 (7)	C13—C14—C15—C10	−1.6 (7)
C2—C3—C4—C5	−0.5 (7)	C7—C16—C17—C18	−171.8 (4)
C3—C4—C5—C6	−0.3 (7)	C21—C16—C17—C18	1.7 (6)
C4—C5—C6—C1	−0.4 (7)	C7—C16—C21—C20	171.2 (4)
C4—C5—C6—N1	172.2 (4)	C17—C16—C21—C20	−2.6 (6)
N1—C7—C8—C9	48.6 (5)	C16—C17—C18—C19	0.6 (7)
N1—C7—C16—C21	163.2 (4)	C17—C18—C19—F1	177.5 (4)
C8—C7—C16—C17	97.9 (5)	C17—C18—C19—C20	−2.2 (8)
C8—C7—C16—C21	−75.6 (5)	F1—C19—C20—C21	−178.4 (4)
N1—C7—C16—C17	−23.3 (6)	C18—C19—C20—C21	1.3 (8)
C16—C7—C8—C9	−73.5 (4)	C19—C20—C21—C16	1.2 (7)
C7—C8—C9—C10	108.7 (4)

Cg1 and Cg2 are the centroids of the benzene rings of the two fluorophenyl substituents (C10–C15 and C16–C21, respectively).

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1i	0.93	2.54	3.469 (6)	175
N1—H1N···Cg2i	0.86 (3)	2.82 (5)	3.601 (4)	151 (4)
C2—H2···Cg1ii	0.93	2.89	3.640 (5)	138
C11—H11···Cg2	0.93	2.79	3.494 (5)	134

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the benzene rings of the two fluorophenyl substituents (C10–C15 and C16–C21, respectively).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F1i	0.93	2.54	3.469 (6)	175
N1—H1N⋯Cg2i	0.86 (3)	2.82 (5)	3.601 (4)	151 (4)
C2—H2⋯Cg1ii	0.93	2.89	3.640 (5)	138
C11—H11⋯Cg2	0.93	2.79	3.494 (5)	134

Symmetry codes: (i) ; (ii) .