4-Phenyl-1-(prop-2-yn-1-yl)-1H-1,5-benzodiazepin-2(3H)-one.

4-Phenyl-1H-1,5-benzodiazepin-2(3H)-one reacts in the pres-ence of a concentrated aqueous solution of sodium hydroxide and a quaternary ammonium salt (as catalyst) in benzene (phase transfer catalysis) with propargyl bromide, affording the title benzodiazepine derivative, C(18)H(14)N(2)O. In the mol-ecule, the mean plane of the propargyl substituent is almost perpendicular with that of the amide group [dihedral angle = 87.81 (8)°]. In the crystal, the molecules are linked by C-H⋯O and C-H⋯N inter-actions.

Related literature

For general background to applications of benzodiazepines, see: Ahmed et al. (1983 ▶); Bird (1996 ▶); Di Braccio et al. (1990 ▶, 2001 ▶); Goetzke et al. (1983 ▶); Kavita et al. (1988 ▶); Sieghart & Schuster (1984 ▶); Wolff (1996 ▶). For examples of benzodiazepines used as medicine, see: Wolff (1996 ▶). For the pharmacological effects of benzodiazepines, see: Meldrum & Chapman (1986 ▶). For examples of synthetic pathways of new benzodiazepines, see: Aatif et al. (2000 ▶); Baouid et al. (2001 ▶); Boudina et al. (2007 ▶); Nardi et al. (1973 ▶). For previous work from our groups on organic crystals, see: Fernandes et al. (2011 ▶); Amarante, Figueiredo et al. (2009); ▶ Amarante, Gonçalves & Almeida Paz (2009); ▶ Paz & Klinowski (2003); ▶ Paz et al. (2002) ▶.

Experimental

Crystal data

C18H14N2O

M = 274.31

Monoclinic,

a = 8.2574 (14) Å

b = 18.961 (3) Å

c = 9.0914 (15) Å

β = 102.962 (4)°

V = 1387.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 150 K

0.12 × 0.08 × 0.04 mm

Data collection

Bruker X8 Kappa CCD APEX II diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.990, T max = 0.997

11049 measured reflections

5228 independent reflections

3621 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.143

S = 1.05

5228 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811027371/tk2762sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027371/tk2762Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811027371/tk2762Isup3.cml

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

C18H14N2O	F(000) = 576
Mr = 274.31	Dx = 1.314 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2335 reflections
a = 8.2574 (14) Å	θ = 2.5–32.7°
b = 18.961 (3) Å	µ = 0.08 mm−1
c = 9.0914 (15) Å	T = 150 K
β = 102.962 (4)°	Block, yellow
V = 1387.1 (4) Å3	0.12 × 0.08 × 0.04 mm
Z = 4

Bruker X8 Kappa CCD APEX II diffractometer	5228 independent reflections
Radiation source: fine-focus sealed tube	3621 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω / φ scans	θmax = 33.1°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→11
Tmin = 0.990, Tmax = 0.997	k = −24→29
11049 measured reflections	l = −10→13

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0689P)2 + 0.095P] where P = (Fo2 + 2Fc2)/3
5228 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

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.

	x	y	z	Uiso*/Ueq
N1	0.81747 (12)	0.20787 (5)	0.66080 (10)	0.01806 (19)
N2	0.80660 (13)	0.05512 (5)	0.73647 (10)	0.0212 (2)
O1	0.73372 (11)	0.20477 (5)	0.40627 (9)	0.0263 (2)
C1	0.92473 (14)	0.26835 (6)	0.64614 (12)	0.0203 (2)
H1A	1.0213	0.2687	0.7333	0.024*
H1B	0.9675	0.2624	0.5535	0.024*
C2	0.83874 (16)	0.33625 (6)	0.63915 (12)	0.0247 (2)
C3	0.7724 (2)	0.39109 (7)	0.63764 (16)	0.0338 (3)
H3	0.7187	0.4355	0.6364	0.041*
C4	0.72159 (14)	0.18209 (6)	0.52947 (11)	0.0191 (2)
C5	0.60888 (14)	0.12224 (6)	0.54917 (13)	0.0218 (2)
H5A	0.5294	0.1118	0.4527	0.026*
H5B	0.5453	0.1343	0.6260	0.026*
C6	0.72038 (14)	0.05952 (6)	0.59981 (12)	0.0197 (2)
C7	0.73684 (14)	0.00310 (6)	0.49079 (12)	0.0203 (2)
C8	0.84549 (16)	−0.05308 (6)	0.53927 (14)	0.0250 (2)
H8	0.9068	−0.0547	0.6410	0.030*
C9	0.86457 (17)	−0.10638 (7)	0.44028 (15)	0.0289 (3)
H9	0.9375	−0.1446	0.4751	0.035*
C10	0.77807 (19)	−0.10440 (7)	0.29068 (15)	0.0318 (3)
H10	0.7916	−0.1410	0.2231	0.038*
C11	0.67212 (19)	−0.04871 (7)	0.24087 (14)	0.0318 (3)
H11	0.6135	−0.0468	0.1383	0.038*
C12	0.65061 (17)	0.00474 (7)	0.34008 (13)	0.0263 (3)
H12	0.5767	0.0426	0.3048	0.032*
C13	0.80668 (15)	0.11000 (6)	0.83976 (12)	0.0206 (2)
C14	0.81461 (17)	0.09009 (6)	0.99013 (13)	0.0265 (3)
H14	0.8139	0.0414	1.0143	0.032*
C15	0.82341 (17)	0.13908 (7)	1.10369 (13)	0.0285 (3)
H15	0.8261	0.1241	1.2039	0.034*
C16	0.82834 (16)	0.21074 (7)	1.07035 (13)	0.0259 (2)
H16	0.8353	0.2449	1.1480	0.031*
C17	0.82299 (15)	0.23177 (6)	0.92394 (12)	0.0221 (2)
H17	0.8267	0.2806	0.9020	0.026*
C18	0.81219 (14)	0.18262 (6)	0.80699 (11)	0.0187 (2)

	U11	U22	U33	U12	U13	U23
N1	0.0243 (5)	0.0140 (4)	0.0163 (4)	−0.0031 (4)	0.0055 (3)	−0.0011 (3)
N2	0.0281 (5)	0.0145 (4)	0.0223 (4)	0.0000 (4)	0.0083 (4)	−0.0004 (3)
O1	0.0319 (5)	0.0288 (5)	0.0172 (3)	−0.0007 (4)	0.0036 (3)	0.0012 (3)
C1	0.0248 (5)	0.0163 (5)	0.0207 (4)	−0.0036 (4)	0.0071 (4)	−0.0004 (4)
C2	0.0341 (6)	0.0196 (5)	0.0213 (5)	−0.0056 (5)	0.0083 (4)	0.0002 (4)
C3	0.0461 (8)	0.0222 (6)	0.0355 (6)	0.0045 (6)	0.0145 (6)	0.0060 (5)
C4	0.0209 (5)	0.0165 (5)	0.0192 (4)	0.0034 (4)	0.0033 (4)	−0.0012 (4)
C5	0.0213 (5)	0.0176 (5)	0.0258 (5)	−0.0010 (4)	0.0038 (4)	−0.0033 (4)
C6	0.0227 (5)	0.0138 (5)	0.0241 (5)	−0.0023 (4)	0.0082 (4)	−0.0015 (4)
C7	0.0241 (5)	0.0146 (5)	0.0242 (5)	−0.0042 (4)	0.0092 (4)	−0.0029 (4)
C8	0.0265 (6)	0.0189 (5)	0.0310 (5)	0.0004 (4)	0.0094 (4)	−0.0032 (5)
C9	0.0323 (6)	0.0204 (6)	0.0379 (6)	0.0021 (5)	0.0162 (5)	−0.0042 (5)
C10	0.0422 (8)	0.0240 (6)	0.0355 (6)	−0.0056 (6)	0.0224 (6)	−0.0095 (5)
C11	0.0438 (8)	0.0296 (7)	0.0243 (5)	−0.0063 (6)	0.0126 (5)	−0.0053 (5)
C12	0.0350 (7)	0.0198 (5)	0.0252 (5)	−0.0019 (5)	0.0088 (5)	−0.0005 (4)
C13	0.0263 (5)	0.0158 (5)	0.0208 (4)	0.0005 (4)	0.0074 (4)	−0.0009 (4)
C14	0.0387 (7)	0.0197 (5)	0.0229 (5)	0.0008 (5)	0.0105 (5)	0.0036 (4)
C15	0.0397 (7)	0.0290 (6)	0.0190 (5)	0.0015 (5)	0.0110 (4)	0.0023 (5)
C16	0.0346 (6)	0.0254 (6)	0.0194 (4)	0.0000 (5)	0.0099 (4)	−0.0038 (4)
C17	0.0299 (6)	0.0170 (5)	0.0204 (4)	−0.0007 (4)	0.0078 (4)	−0.0025 (4)
C18	0.0224 (5)	0.0174 (5)	0.0169 (4)	−0.0002 (4)	0.0060 (4)	0.0001 (4)

N1—C4	1.3665 (13)	C8—H8	0.9500
N1—C18	1.4226 (13)	C9—C10	1.388 (2)
N1—C1	1.4731 (14)	C9—H9	0.9500
N2—C6	1.2886 (14)	C10—C11	1.381 (2)
N2—C13	1.4017 (14)	C10—H10	0.9500
O1—C4	1.2246 (13)	C11—C12	1.3942 (17)
C1—C2	1.4648 (17)	C11—H11	0.9500
C1—H1A	0.9900	C12—H12	0.9500
C1—H1B	0.9900	C13—C14	1.4056 (16)
C2—C3	1.1739 (19)	C13—C18	1.4115 (16)
C3—H3	0.9500	C14—C15	1.3785 (17)
C4—C5	1.5037 (16)	C14—H14	0.9500
C5—C6	1.5112 (16)	C15—C16	1.3947 (18)
C5—H5A	0.9900	C15—H15	0.9500
C5—H5B	0.9900	C16—C17	1.3807 (16)
C6—C7	1.4851 (15)	C16—H16	0.9500
C7—C12	1.3956 (16)	C17—C18	1.4015 (15)
C7—C8	1.3988 (17)	C17—H17	0.9500
C8—C9	1.3855 (17)
C4—N1—C18	124.24 (10)	C8—C9—C10	120.56 (12)
C4—N1—C1	116.21 (9)	C8—C9—H9	119.7
C18—N1—C1	119.45 (9)	C10—C9—H9	119.7
C6—N2—C13	120.99 (10)	C11—C10—C9	119.40 (12)
C2—C1—N1	113.12 (10)	C11—C10—H10	120.3
C2—C1—H1A	109.0	C9—C10—H10	120.3
N1—C1—H1A	109.0	C10—C11—C12	120.45 (12)
C2—C1—H1B	109.0	C10—C11—H11	119.8
N1—C1—H1B	109.0	C12—C11—H11	119.8
H1A—C1—H1B	107.8	C11—C12—C7	120.53 (12)
C3—C2—C1	178.08 (13)	C11—C12—H12	119.7
C2—C3—H3	180.0	C7—C12—H12	119.7
O1—C4—N1	121.55 (11)	N2—C13—C14	116.43 (10)
O1—C4—C5	123.62 (10)	N2—C13—C18	125.31 (10)
N1—C4—C5	114.75 (9)	C14—C13—C18	118.07 (10)
C4—C5—C6	106.21 (9)	C15—C14—C13	122.04 (11)
C4—C5—H5A	110.5	C15—C14—H14	119.0
C6—C5—H5A	110.5	C13—C14—H14	119.0
C4—C5—H5B	110.5	C14—C15—C16	119.54 (11)
C6—C5—H5B	110.5	C14—C15—H15	120.2
H5A—C5—H5B	108.7	C16—C15—H15	120.2
N2—C6—C7	118.90 (10)	C17—C16—C15	119.64 (11)
N2—C6—C5	120.78 (10)	C17—C16—H16	120.2
C7—C6—C5	120.28 (9)	C15—C16—H16	120.2
C12—C7—C8	118.44 (11)	C16—C17—C18	121.48 (11)
C12—C7—C6	122.43 (11)	C16—C17—H17	119.3
C8—C7—C6	119.11 (10)	C18—C17—H17	119.3
C9—C8—C7	120.60 (12)	C17—C18—C13	119.22 (10)
C9—C8—H8	119.7	C17—C18—N1	118.34 (10)
C7—C8—H8	119.7	C13—C18—N1	122.33 (10)
C4—N1—C1—C2	84.64 (12)	C10—C11—C12—C7	0.6 (2)
C18—N1—C1—C2	−91.95 (12)	C8—C7—C12—C11	0.32 (18)
C18—N1—C4—O1	−178.39 (11)	C6—C7—C12—C11	178.80 (11)
C1—N1—C4—O1	5.21 (16)	C6—N2—C13—C14	144.00 (12)
C18—N1—C4—C5	−1.33 (15)	C6—N2—C13—C18	−41.08 (17)
C1—N1—C4—C5	−177.73 (9)	N2—C13—C14—C15	176.89 (12)
O1—C4—C5—C6	106.80 (12)	C18—C13—C14—C15	1.6 (2)
N1—C4—C5—C6	−70.19 (12)	C13—C14—C15—C16	−1.4 (2)
C13—N2—C6—C7	174.26 (10)	C14—C15—C16—C17	0.5 (2)
C13—N2—C6—C5	−3.54 (17)	C15—C16—C17—C18	0.18 (19)
C4—C5—C6—N2	75.83 (13)	C16—C17—C18—C13	−0.01 (18)
C4—C5—C6—C7	−101.94 (11)	C16—C17—C18—N1	−176.21 (11)
N2—C6—C7—C12	−178.58 (11)	N2—C13—C18—C17	−175.69 (11)
C5—C6—C7—C12	−0.77 (17)	C14—C13—C18—C17	−0.85 (17)
N2—C6—C7—C8	−0.12 (16)	N2—C13—C18—N1	0.36 (18)
C5—C6—C7—C8	177.70 (11)	C14—C13—C18—N1	175.20 (11)
C12—C7—C8—C9	−1.09 (18)	C4—N1—C18—C17	−140.25 (11)
C6—C7—C8—C9	−179.61 (11)	C1—N1—C18—C17	36.05 (15)
C7—C8—C9—C10	0.98 (19)	C4—N1—C18—C13	43.68 (17)
C8—C9—C10—C11	−0.1 (2)	C1—N1—C18—C13	−140.03 (11)
C9—C10—C11—C12	−0.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1i	0.99	2.14	3.1074 (15)	166
C3—H3···N2ii	0.95	2.58	3.4269 (18)	149

Plane	Atoms	Largest deviation/Å
A	C5 to C12 plus N2	-0.019 (1)
B	C13 to C18 plus N1, N2	-0.039 (1)
C	C1 to C5 plus O1, N1, C18	-0.026 (1)
D	C1 to C3 plus N1	-0.014 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1i	0.99	2.14	3.1074 (15)	166
C3—H3⋯N2ii	0.95	2.58	3.4269 (18)	149

Symmetry codes: (i) ; (ii) .