Ethyl 2-(2-oxo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-1-yl)acetate

Ballo, D.; Ahabchane, N.H.; Zouihri, H.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810028278

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2070

https://doi.org/10.1107/S1600536810028278

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Ethyl 2-(2-oxo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-1-yl)acetate

Daouda Ballo,^a Noureddine Hamou Ahabchane,^a Hafid Zouihri,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bCNRST Division UATRS, Angle Allal Fassi/FAR, BP 8027 Hay Riad, Rabat, Morocco, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 7 July 2010; accepted 15 July 2010; online 21 July 2010)

The seven-membered ring in the title compound, C₁₉H₁₈N₂O₃, adopts a boat conformation with the two phenylene C atoms representing the stern and the methylene C atom the prow. The dihedral angle between the best plane through the seven-membered ring (r.m.s deviation = 0.343 Å) and the phenyl substituent is 31.9 (1)°. The dihedral angle between this best plane and the best plane through the ethoxycarbonylmethyl substituent (r.m.s. deviation = 0.058 Å) is 72.2 (1)°.

Related literature

For the background to 2,3-dihydro-1H-1,5-benzodiazepin-2-ones, see: Ahabchane et al. (1999 ). For a related structure, see: Ballo et al. (2010 ).

Experimental

Crystal data

C₁₉H₁₈N₂O₃
M_r = 322.35
Monoclinic, P 2₁ /c
a = 12.5198 (4) Å
b = 11.7911 (3) Å
c = 11.2058 (3) Å
β = 97.843 (2)°
V = 1638.75 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.15 × 0.10 mm

Data collection

Bruker X8 APEXII diffractometer
13943 measured reflections
3029 independent reflections
2195 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.114
S = 1.00
3029 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810028278/zs2051sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028278/zs2051Isup2.hkl

checkCIF report

Comment top

The background to the class of 2,3-dihydro-1H-1,5-benzodiazepin-2-ones is given in an earlier report (Ahabchane et al., 1999). A recent study presents the crystal structure of 1-allyl-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one (Ballo et al., 2010). The present study has an ethoxycarbonylmethyl group in place of the allyl group (Scheme I, Fig. 1). The principal feature is the seven-membered ring that is fused to a phenylene ring. This ring adopts a boat-shaped conformation, two phenylene carbons representing the stern and the methylene carbon atom the prow [r.m.s deviation 0.343 Å]. The methyl carbon deviates by 0.604 Å from the best plane.

Related literature top

For the background to 2,3-dihydro-1H-1,5-benzodiazepin-2-ones, see: Ahabchane et al. (1999). For a related structure, see: Ballo et al. (2010).

Experimental top

To a solution of 4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-2-one (1 g, 4.2 mmol) in DMF (20 ml) was added ethyl chloroacetate (0.5 g, 4.2 mmol), potassium carbonate (1 g, 7.4 mmol) and a catalytic quantity of tetra-n-butylammonium bromide. The mixture was stirred at room temperature for 24 h. The solution was filtered and the solvent removed under reduced pressure. The residue was recrystallized from ethanol to afford the title compound as yellow crystals.

Structure description top

For the background to 2,3-dihydro-1H-1,5-benzodiazepin-2-ones, see: Ahabchane et al. (1999). For a related structure, see: Ballo et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the molecule of C₁₉H₁₈N₂O₃ at the 50% probability level.

Ethyl 2-(2-oxo-4-phenyl-2,3-dihydro-1H-1,5-benzodiazepin-1-yl)acetate top

Crystal data top

C₁₉H₁₈N₂O₃	F(000) = 680
M_r = 322.35	D_x = 1.307 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3291 reflections
a = 12.5198 (4) Å	θ = 2.4–23.1°
b = 11.7911 (3) Å	µ = 0.09 mm⁻¹
c = 11.2058 (3) Å	T = 293 K
β = 97.843 (2)°	Prism, yellow
V = 1638.75 (8) Å³	0.30 × 0.15 × 0.10 mm
Z = 4

Data collection top

Bruker X8 APEXII diffractometer	2195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 25.5°, θ_min = 2.5°
φ and ω scans	h = −15→15
13943 measured reflections	k = −14→14
3029 independent reflections	l = −13→13

Refinement top

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0707P)²] where P = (F_o² + 2F_c²)/3
3029 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₉H₁₈N₂O₃	V = 1638.75 (8) Å³
M_r = 322.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5198 (4) Å	µ = 0.09 mm⁻¹
b = 11.7911 (3) Å	T = 293 K
c = 11.2058 (3) Å	0.30 × 0.15 × 0.10 mm
β = 97.843 (2)°

Data collection top

Bruker X8 APEXII diffractometer	2195 reflections with I > 2σ(I)
13943 measured reflections	R_int = 0.033
3029 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.00	Δρ_max = 0.12 e Å⁻³
3029 reflections	Δρ_min = −0.15 e Å⁻³
217 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.45383 (9)	0.67927 (10)	0.34251 (11)	0.0662 (4)
O2	0.43414 (9)	0.64804 (9)	0.06491 (11)	0.0604 (3)
O3	0.60915 (8)	0.69533 (8)	0.08966 (10)	0.0488 (3)
N1	0.39095 (10)	0.82128 (10)	0.21765 (12)	0.0460 (3)
N2	0.16060 (9)	0.76218 (10)	0.14862 (11)	0.0438 (3)
C1	0.15443 (12)	0.57820 (13)	0.23365 (13)	0.0452 (4)
C2	0.21662 (14)	0.49224 (14)	0.29222 (16)	0.0599 (5)
H2	0.2822	0.5097	0.3381	0.072*
C3	0.18218 (17)	0.38119 (15)	0.28306 (18)	0.0690 (5)
H3	0.2253	0.3242	0.3214	0.083*
C4	0.08518 (16)	0.35429 (14)	0.21804 (18)	0.0648 (5)
H4	0.0618	0.2793	0.2132	0.078*
C5	0.02215 (14)	0.43823 (15)	0.15974 (18)	0.0631 (5)
H5	−0.0440	0.4202	0.1156	0.076*
C6	0.05711 (13)	0.54944 (13)	0.16671 (15)	0.0525 (4)
H6	0.0147	0.6057	0.1259	0.063*
C7	0.19264 (11)	0.69709 (12)	0.23782 (13)	0.0423 (4)
C8	0.27085 (12)	0.73756 (13)	0.34441 (13)	0.0483 (4)
H8A	0.2497	0.8118	0.3702	0.058*
H8B	0.2715	0.6853	0.4113	0.058*
C9	0.38018 (12)	0.74323 (13)	0.30496 (14)	0.0478 (4)
C10	0.49294 (13)	0.81974 (13)	0.16772 (16)	0.0536 (4)
H10A	0.5523	0.8288	0.2323	0.064*
H10B	0.4948	0.8828	0.1124	0.064*
C11	0.50622 (12)	0.71043 (12)	0.10251 (13)	0.0431 (4)
C12	0.63354 (14)	0.59312 (14)	0.02606 (16)	0.0592 (5)
H12A	0.6050	0.5992	−0.0586	0.071*
H12B	0.6010	0.5277	0.0593	0.071*
C13	0.75293 (14)	0.58019 (15)	0.04048 (16)	0.0669 (5)
H13A	0.7712	0.5132	−0.0011	0.100*
H13B	0.7803	0.5736	0.1245	0.100*
H13C	0.7843	0.6453	0.0074	0.100*
C14	0.31063 (11)	0.90246 (12)	0.17520 (12)	0.0414 (4)
C15	0.34293 (13)	1.01399 (12)	0.15912 (14)	0.0511 (4)
H15	0.4153	1.0333	0.1776	0.061*
C16	0.26962 (15)	1.09539 (14)	0.11653 (16)	0.0595 (5)
H16	0.2924	1.1694	0.1066	0.071*
C17	0.16234 (15)	1.06815 (14)	0.08833 (15)	0.0596 (5)
H17	0.1125	1.1238	0.0604	0.072*
C18	0.12908 (13)	0.95835 (13)	0.10160 (14)	0.0528 (4)
H18	0.0566	0.9402	0.0810	0.063*
C19	0.20182 (12)	0.87328 (12)	0.14543 (12)	0.0418 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0551 (8)	0.0761 (8)	0.0638 (8)	0.0232 (6)	−0.0050 (6)	0.0014 (6)
O2	0.0439 (7)	0.0632 (7)	0.0729 (8)	−0.0078 (6)	0.0036 (5)	−0.0194 (6)
O3	0.0384 (6)	0.0511 (6)	0.0573 (7)	0.0031 (4)	0.0083 (5)	−0.0115 (5)
N1	0.0373 (7)	0.0501 (7)	0.0512 (8)	0.0040 (5)	0.0081 (6)	−0.0036 (6)
N2	0.0392 (7)	0.0486 (7)	0.0432 (7)	0.0003 (5)	0.0037 (5)	0.0044 (6)
C1	0.0456 (9)	0.0518 (9)	0.0405 (9)	0.0050 (7)	0.0138 (7)	0.0039 (7)
C2	0.0617 (11)	0.0583 (11)	0.0589 (11)	0.0074 (8)	0.0049 (8)	0.0115 (8)
C3	0.0826 (14)	0.0581 (11)	0.0687 (12)	0.0148 (10)	0.0184 (10)	0.0180 (9)
C4	0.0781 (13)	0.0476 (10)	0.0750 (13)	−0.0020 (9)	0.0333 (10)	0.0026 (9)
C5	0.0538 (11)	0.0612 (11)	0.0772 (13)	−0.0070 (8)	0.0189 (9)	−0.0040 (9)
C6	0.0464 (9)	0.0532 (9)	0.0594 (10)	0.0026 (7)	0.0123 (7)	0.0050 (8)
C7	0.0364 (8)	0.0518 (9)	0.0398 (8)	0.0053 (6)	0.0088 (6)	0.0034 (7)
C8	0.0523 (10)	0.0549 (9)	0.0372 (8)	0.0053 (7)	0.0047 (7)	0.0028 (7)
C9	0.0441 (9)	0.0546 (9)	0.0421 (9)	0.0077 (7)	−0.0031 (7)	−0.0086 (7)
C10	0.0390 (9)	0.0538 (9)	0.0696 (11)	−0.0012 (7)	0.0129 (8)	−0.0137 (8)
C11	0.0364 (8)	0.0487 (8)	0.0433 (9)	0.0009 (7)	0.0025 (6)	−0.0019 (7)
C12	0.0610 (11)	0.0597 (10)	0.0570 (11)	0.0105 (8)	0.0082 (8)	−0.0162 (8)
C13	0.0651 (12)	0.0721 (12)	0.0681 (12)	0.0205 (9)	0.0253 (9)	0.0010 (9)
C14	0.0413 (8)	0.0456 (8)	0.0383 (8)	0.0031 (6)	0.0085 (6)	−0.0049 (6)
C15	0.0521 (10)	0.0487 (9)	0.0536 (10)	−0.0049 (7)	0.0108 (7)	−0.0090 (7)
C16	0.0766 (13)	0.0426 (9)	0.0599 (11)	−0.0012 (8)	0.0115 (9)	−0.0004 (8)
C17	0.0711 (12)	0.0516 (10)	0.0552 (10)	0.0119 (9)	0.0053 (9)	0.0088 (8)
C18	0.0480 (9)	0.0592 (10)	0.0498 (10)	0.0056 (7)	0.0019 (7)	0.0078 (8)
C19	0.0430 (8)	0.0473 (8)	0.0349 (8)	0.0009 (7)	0.0050 (6)	−0.0007 (6)

Geometric parameters (Å, º) top

O1—C9	1.2207 (17)	C8—C9	1.496 (2)
O2—C11	1.1955 (17)	C8—H8A	0.9700
O3—C11	1.3281 (17)	C8—H8B	0.9700
O3—C12	1.4537 (17)	C10—C11	1.502 (2)
N1—C9	1.363 (2)	C10—H10A	0.9700
N1—C14	1.4224 (17)	C10—H10B	0.9700
N1—C10	1.4625 (19)	C12—C13	1.489 (2)
N2—C7	1.2805 (18)	C12—H12A	0.9700
N2—C19	1.4102 (18)	C12—H12B	0.9700
C1—C6	1.383 (2)	C13—H13A	0.9600
C1—C2	1.387 (2)	C13—H13B	0.9600
C1—C7	1.480 (2)	C13—H13C	0.9600
C2—C3	1.378 (2)	C14—C15	1.395 (2)
C2—H2	0.9300	C14—C19	1.4005 (19)
C3—C4	1.366 (3)	C15—C16	1.368 (2)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.374 (2)	C16—C17	1.375 (2)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.381 (2)	C17—C18	1.374 (2)
C5—H5	0.9300	C17—H17	0.9300
C6—H6	0.9300	C18—C19	1.398 (2)
C7—C8	1.515 (2)	C18—H18	0.9300

C11—O3—C12	115.86 (12)	C11—C10—H10A	109.5
C9—N1—C14	124.03 (13)	N1—C10—H10B	109.5
C9—N1—C10	116.31 (12)	C11—C10—H10B	109.5
C14—N1—C10	119.65 (12)	H10A—C10—H10B	108.0
C7—N2—C19	119.99 (13)	O2—C11—O3	125.19 (14)
C6—C1—C2	118.26 (15)	O2—C11—C10	124.83 (14)
C6—C1—C7	120.43 (14)	O3—C11—C10	109.95 (12)
C2—C1—C7	121.26 (14)	O3—C12—C13	107.85 (13)
C3—C2—C1	120.61 (17)	O3—C12—H12A	110.1
C3—C2—H2	119.7	C13—C12—H12A	110.1
C1—C2—H2	119.7	O3—C12—H12B	110.1
C4—C3—C2	120.46 (17)	C13—C12—H12B	110.1
C4—C3—H3	119.8	H12A—C12—H12B	108.4
C2—C3—H3	119.8	C12—C13—H13A	109.5
C3—C4—C5	119.83 (17)	C12—C13—H13B	109.5
C3—C4—H4	120.1	H13A—C13—H13B	109.5
C5—C4—H4	120.1	C12—C13—H13C	109.5
C4—C5—C6	119.99 (17)	H13A—C13—H13C	109.5
C4—C5—H5	120.0	H13B—C13—H13C	109.5
C6—C5—H5	120.0	C15—C14—C19	119.38 (13)
C5—C6—C1	120.83 (16)	C15—C14—N1	118.26 (13)
C5—C6—H6	119.6	C19—C14—N1	122.32 (13)
C1—C6—H6	119.6	C16—C15—C14	120.93 (16)
N2—C7—C1	118.53 (13)	C16—C15—H15	119.5
N2—C7—C8	121.78 (13)	C14—C15—H15	119.5
C1—C7—C8	119.65 (13)	C15—C16—C17	120.26 (15)
C9—C8—C7	107.47 (12)	C15—C16—H16	119.9
C9—C8—H8A	110.2	C17—C16—H16	119.9
C7—C8—H8A	110.2	C18—C17—C16	119.74 (16)
C9—C8—H8B	110.2	C18—C17—H17	120.1
C7—C8—H8B	110.2	C16—C17—H17	120.1
H8A—C8—H8B	108.5	C17—C18—C19	121.43 (16)
O1—C9—N1	121.36 (15)	C17—C18—H18	119.3
O1—C9—C8	123.30 (15)	C19—C18—H18	119.3
N1—C9—C8	115.23 (13)	C18—C19—C14	118.24 (13)
N1—C10—C11	110.92 (12)	C18—C19—N2	116.89 (13)
N1—C10—H10A	109.5	C14—C19—N2	124.72 (13)

C6—C1—C2—C3	0.4 (2)	C14—N1—C10—C11	−116.19 (14)
C7—C1—C2—C3	−177.05 (15)	C12—O3—C11—O2	−1.0 (2)
C1—C2—C3—C4	−1.3 (3)	C12—O3—C11—C10	−179.08 (14)
C2—C3—C4—C5	1.0 (3)	N1—C10—C11—O2	20.5 (2)
C3—C4—C5—C6	0.2 (3)	N1—C10—C11—O3	−161.39 (13)
C4—C5—C6—C1	−1.1 (3)	C11—O3—C12—C13	−169.68 (13)
C2—C1—C6—C5	0.9 (2)	C9—N1—C14—C15	135.77 (15)
C7—C1—C6—C5	178.28 (15)	C10—N1—C14—C15	−43.45 (18)
C19—N2—C7—C1	−175.16 (12)	C9—N1—C14—C19	−46.5 (2)
C19—N2—C7—C8	2.8 (2)	C10—N1—C14—C19	134.31 (15)
C6—C1—C7—N2	−26.6 (2)	C19—C14—C15—C16	1.0 (2)
C2—C1—C7—N2	150.72 (15)	N1—C14—C15—C16	178.85 (13)
C6—C1—C7—C8	155.40 (14)	C14—C15—C16—C17	−0.2 (2)
C2—C1—C7—C8	−27.3 (2)	C15—C16—C17—C18	−0.8 (3)
N2—C7—C8—C9	−74.71 (17)	C16—C17—C18—C19	1.2 (3)
C1—C7—C8—C9	103.20 (15)	C17—C18—C19—C14	−0.4 (2)
C14—N1—C9—O1	−176.16 (13)	C17—C18—C19—N2	−176.23 (14)
C10—N1—C9—O1	3.1 (2)	C15—C14—C19—C18	−0.7 (2)
C14—N1—C9—C8	7.5 (2)	N1—C14—C19—C18	−178.44 (13)
C10—N1—C9—C8	−173.24 (12)	C15—C14—C19—N2	174.79 (14)
C7—C8—C9—O1	−111.25 (16)	N1—C14—C19—N2	−2.9 (2)
C7—C8—C9—N1	65.00 (16)	C7—N2—C19—C18	−140.71 (15)
C9—N1—C10—C11	64.53 (18)	C7—N2—C19—C14	43.7 (2)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈N₂O₃
M_r	322.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.5198 (4), 11.7911 (3), 11.2058 (3)
β (°)	97.843 (2)
V (Å³)	1638.75 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.15 × 0.10

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13943, 3029, 2195
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.114, 1.00
No. of reflections	3029
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.15

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

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