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The enantiomerically pure (S) title compound, C19H17ClN2O3, was crystallized from a 1:1 mixture of ethanol and di­chloro­methane. The 1,4-diazepine ring has a boat conformation with the C atom in position 3 displaced by 0.729 (4) Å from the plane defined by the atoms in positions 1, 2, 4 and 5. A weak C—H...O interaction, the most prominent feature of the crystal packing, links the mol­ecules into infinite chains stretched along the c axis. The title compound, as well as other 1,4-benzodiazepin-2-one derivatives, are suitable precursors for the synthesis of enantiomerically pure α-amino acids and their congeners.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802000338/ya6083sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802000338/ya6083Isup2.hkl
Contains datablock I

CCDC reference: 180788

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.012 Å
  • R factor = 0.052
  • wR factor = 0.154
  • Data-to-parameter ratio = 7.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.113 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 26.30 From the CIF: _reflns_number_total 1796 Count of symmetry unique reflns 1801 Completeness (_total/calc) 99.72% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: SET4 and CELDIM in CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 1990).

3-acetoxymethyl-7-chloro-1,3-dihydro-1-methyl-5-phenyl- 2H-1,4-benzodiazepin-2-one top
Crystal data top
C19H17ClN2O3Dx = 1.371 Mg m3
Mr = 356.80Mo Kα radiation, λ = 0.71069 Å
Hexagonal, P61Cell parameters from 20 reflections
Hall symbol: P 61θ = 4.9–20.3°
a = 11.075 (5) ŵ = 0.24 mm1
c = 24.40 (4) ÅT = 293 K
V = 2592 (5) Å3Prismatic, colourless
Z = 60.20 × 0.20 × 0.18 mm
F(000) = 1116
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.113
Radiation source: X-ray tubeθmax = 26.3°, θmin = 2.1°
Graphite monochromatorh = 130
θ/2θ scansk = 013
2904 measured reflectionsl = 300
1796 independent reflections3 standard reflections every 120 min
798 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0712P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.052(Δ/σ)max < 0.001
wR(F2) = 0.154Δρmax = 0.29 e Å3
S = 0.97Δρmin = 0.27 e Å3
1796 reflectionsAbsolute structure: Flack,1983; no Friedel pairs
236 parametersAbsolute structure parameter: 0.1 (2)
1 restraint
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'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 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 (Å2) top
xyzUiso*/Ueq
Cl11.3483 (2)0.6783 (2)0.04034 (10)0.0625 (8)
O110.5970 (6)0.0037 (6)0.0462 (2)0.069 (2)
O130.7799 (11)0.1407 (9)0.0113 (3)0.125 (4)
O150.7377 (13)0.3463 (10)0.0369 (5)0.155 (6)
N10.7595 (6)0.2235 (6)0.0471 (2)0.041 (2)
N40.8783 (6)0.1035 (6)0.1236 (2)0.041 (2)
C20.7190 (9)0.0863 (9)0.0516 (2)0.044 (3)
C30.8305 (9)0.0529 (9)0.0674 (3)0.050 (3)
C50.9538 (8)0.2331 (8)0.1311 (3)0.039 (3)
C61.1323 (8)0.4451 (7)0.0831 (2)0.039 (3)
C71.1763 (7)0.5436 (8)0.0422 (3)0.042 (2)
C81.0842 (8)0.5374 (9)0.0040 (3)0.048 (3)
C90.9480 (9)0.4317 (9)0.0055 (3)0.045 (3)
C100.6536 (9)0.2586 (12)0.0310 (4)0.075 (4)
C120.7848 (11)0.1001 (9)0.0678 (3)0.065 (3)
C140.7525 (14)0.2625 (14)0.0009 (5)0.098 (6)
C160.7363 (18)0.2960 (15)0.0590 (5)0.150 (8)
C171.0038 (7)0.2829 (9)0.1872 (2)0.039 (3)
C181.0346 (8)0.2022 (9)0.2223 (3)0.050 (3)
C191.0691 (9)0.2414 (10)0.2761 (3)0.056 (3)
C201.0753 (9)0.3583 (11)0.2950 (3)0.072 (4)
C211.0480 (9)0.4412 (10)0.2615 (3)0.058 (3)
C221.0163 (8)0.4044 (8)0.2067 (3)0.047 (3)
C510.9963 (7)0.3388 (7)0.0859 (3)0.032 (2)
C910.9007 (7)0.3280 (8)0.0462 (3)0.038 (3)
H30.90930.10100.04220.0601*
H61.19580.45050.10930.0465*
H81.11360.60490.02330.0565*
H90.88580.42860.02070.0545*
H10A0.64760.25880.00820.1128*
H10B0.67860.34920.04490.1128*
H10C0.56490.19070.04580.1128*
H12A0.85060.11610.08820.0785*
H12B0.69360.15340.08460.0785*
H16A0.81940.29210.07260.2241*
H16B0.72030.22980.07840.2241*
H16C0.65830.38800.06430.2241*
H181.03170.12190.20920.0602*
H191.08820.18670.29940.0675*
H201.09850.38340.33150.0862*
H211.05070.52080.27510.0696*
H221.00330.46290.18310.0563*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0503 (14)0.0509 (13)0.0695 (13)0.0126 (11)0.0062 (12)0.0174 (12)
O110.057 (4)0.064 (4)0.048 (4)0.002 (3)0.013 (3)0.001 (3)
O130.215 (10)0.067 (5)0.068 (5)0.052 (6)0.032 (6)0.022 (4)
O150.233 (13)0.077 (6)0.134 (9)0.062 (7)0.011 (9)0.011 (7)
N10.037 (4)0.045 (4)0.032 (4)0.013 (3)0.002 (3)0.003 (3)
N40.044 (4)0.035 (4)0.035 (4)0.013 (3)0.003 (3)0.002 (3)
C20.041 (5)0.051 (6)0.025 (5)0.011 (4)0.005 (3)0.002 (4)
C30.052 (5)0.057 (6)0.029 (4)0.018 (5)0.001 (4)0.001 (4)
C50.038 (5)0.048 (5)0.033 (4)0.022 (4)0.002 (4)0.005 (4)
C60.041 (5)0.037 (4)0.037 (5)0.018 (4)0.001 (4)0.003 (4)
C70.045 (4)0.041 (4)0.037 (4)0.020 (4)0.008 (4)0.000 (4)
C80.056 (6)0.045 (5)0.040 (5)0.024 (5)0.003 (4)0.006 (4)
C90.047 (5)0.054 (5)0.038 (5)0.028 (5)0.005 (4)0.003 (4)
C100.054 (6)0.114 (8)0.072 (7)0.053 (6)0.007 (5)0.016 (6)
C120.099 (7)0.039 (5)0.042 (5)0.023 (5)0.008 (5)0.018 (4)
C140.104 (10)0.071 (9)0.097 (11)0.027 (8)0.007 (8)0.025 (8)
C160.182 (16)0.101 (11)0.110 (12)0.029 (11)0.010 (10)0.054 (9)
C170.032 (4)0.042 (5)0.032 (4)0.011 (4)0.003 (3)0.000 (4)
C180.046 (5)0.059 (5)0.041 (6)0.023 (4)0.001 (4)0.007 (4)
C190.049 (5)0.061 (6)0.039 (5)0.013 (5)0.013 (4)0.001 (4)
C200.060 (7)0.079 (8)0.030 (5)0.000 (6)0.010 (5)0.005 (5)
C210.062 (6)0.061 (6)0.038 (5)0.021 (5)0.001 (4)0.019 (5)
C220.044 (4)0.047 (5)0.043 (4)0.017 (4)0.006 (4)0.002 (5)
C510.037 (4)0.032 (4)0.026 (4)0.017 (4)0.001 (3)0.003 (3)
C910.044 (4)0.049 (5)0.030 (4)0.030 (4)0.002 (4)0.007 (4)
Geometric parameters (Å, º) top
Cl1—C71.736 (9)C18—C191.375 (11)
O11—C21.221 (12)C19—C201.343 (14)
O13—C121.443 (11)C20—C211.371 (14)
O13—C141.261 (17)C21—C221.391 (11)
O15—C141.260 (17)C51—C911.395 (12)
N1—C21.357 (11)C3—H30.9792
N1—C101.462 (14)C6—H60.9299
N1—C911.406 (11)C8—H80.9307
N4—C31.476 (9)C9—H90.9291
N4—C51.262 (10)C10—H10A0.9591
C2—C31.506 (15)C10—H10B0.9604
C3—C121.507 (13)C10—H10C0.9602
C5—C171.476 (10)C12—H12A0.9708
C5—C511.502 (11)C12—H12B0.9701
C6—C71.375 (10)C16—H16A0.9600
C6—C511.373 (11)C16—H16B0.9605
C7—C81.358 (12)C16—H16C0.9600
C8—C91.372 (14)C18—H180.9301
C9—C911.406 (11)C19—H190.9299
C14—C161.454 (18)C20—H200.9304
C17—C181.398 (12)C21—H210.9291
C17—C221.367 (12)C22—H220.9296
Cl1···O11i3.211 (8)C9···H10B2.8168
Cl1···C22ii3.565 (13)C10···H6x3.1000
Cl1···H10Aiii2.9622C10···H92.6297
Cl1···H20iv3.0652C17···H62.7632
O11···Cl1v3.211 (8)C18···H3vi2.9626
O11···O133.194 (15)C20···H8xi3.0908
O11···C9vi3.171 (11)C22···H62.9743
O11···C8vi3.320 (11)C51···H32.5418
O13···O113.194 (15)C51···H222.7233
O15···C16vi3.39 (3)C91···H32.5648
O15···C22vii3.380 (17)H3···C512.5418
O15···C21vii3.410 (18)H3···C912.5648
O11···H10C2.3509H3···N4ii2.8086
O11···H12B2.5598H3···C18ii2.9626
O11···H21viii2.8288H3···H18ii2.4167
O11···H9vi2.8134H6···C172.7632
O13···H12Aii2.7581H6···C222.9743
O15···H12A2.5382H6···C10iii3.1000
O15···H16Bvi2.4319H6···H10Aiii2.4705
O15···H12B2.6830H8···C20iv3.0908
O15···H21vii2.8405H8···H10Cii2.4983
O15···H22vii2.7550H9···C102.6297
N1···N42.955 (10)H9···H10A2.3726
N4···N12.955 (10)H9···H10B2.5676
N4···H182.6355H9···O11ii2.8134
N4···H3vi2.8086H10A···C92.9111
C2···C8vi3.469 (14)H10A···H92.3726
C2···C9vi3.550 (13)H10A···Cl1x2.9622
C6···C223.220 (11)H10A···H6x2.4705
C6···C18ii3.588 (15)H10B···C92.8168
C6···C22ii3.534 (15)H10B···H92.5676
C6···C17ii3.400 (15)H10C···O112.3509
C8···C16ix3.58 (2)H10C···H8vi2.4983
C8···O11ii3.320 (11)H12A···O152.5382
C8···C2ii3.469 (12)H12A···O13vi2.7581
C9···O11ii3.171 (11)H12A···H16Bvi2.5474
C9···C2ii3.550 (13)H12B···O112.5598
C16···O15ii3.39 (2)H12B···O152.6830
C16···C8vii3.584 (18)H16B···O15ii2.4319
C17···C6vi3.400 (15)H16B···H12Aii2.5474
C18···C6vi3.588 (17)H16C···C6vii2.9915
C21···O15ix3.410 (18)H16C···C7vii2.7685
C22···Cl1vi3.565 (12)H16C···C8vii2.8786
C22···C6vi3.534 (14)H18···N42.6355
C22···C63.220 (11)H18···H3vi2.4167
C22···O15ix3.380 (17)H20···Cl1xi3.0652
C6···H222.8841H21···O15ix2.8405
C6···H16Cix2.9915H21···O11xii2.8288
C7···H16Cix2.7685H22···C62.8841
C8···H16Cix2.8786H22···C512.7233
C9···H10A2.9111H22···O15ix2.7550
C12—O13—C14120.7 (9)C9—C91—C51117.6 (8)
C2—N1—C10117.4 (8)N4—C3—H3108.85
C2—N1—C91122.2 (8)C2—C3—H3108.88
C10—N1—C91119.2 (7)C12—C3—H3108.84
C3—N4—C5118.3 (6)C7—C6—H6119.37
O11—C2—N1121.1 (9)C51—C6—H6119.44
O11—C2—C3122.4 (8)C7—C8—H8119.92
N1—C2—C3116.3 (8)C9—C8—H8119.91
N4—C3—C2109.1 (7)C8—C9—H9119.42
N4—C3—C12106.0 (6)C91—C9—H9119.41
C2—C3—C12115.0 (9)N1—C10—H10A109.55
N4—C5—C17118.1 (7)N1—C10—H10B109.41
N4—C5—C51123.4 (7)N1—C10—H10C109.41
C17—C5—C51118.5 (7)H10A—C10—H10B109.52
C7—C6—C51121.2 (7)H10A—C10—H10C109.53
Cl1—C7—C6120.1 (6)H10B—C10—H10C109.42
Cl1—C7—C8119.9 (6)O13—C12—H12A110.43
C6—C7—C8119.9 (8)O13—C12—H12B110.46
C7—C8—C9120.2 (8)C3—C12—H12A110.42
C8—C9—C91121.2 (8)C3—C12—H12B110.49
O13—C12—C3106.5 (7)H12A—C12—H12B108.56
O13—C14—O15119.2 (11)C14—C16—H16A109.49
O13—C14—C16115.9 (12)C14—C16—H16B109.46
O15—C14—C16124.9 (13)C14—C16—H16C109.52
C5—C17—C18119.7 (7)H16A—C16—H16B109.44
C5—C17—C22121.7 (7)H16A—C16—H16C109.47
C18—C17—C22118.6 (6)H16B—C16—H16C109.44
C17—C18—C19120.1 (8)C17—C18—H18119.87
C18—C19—C20120.3 (9)C19—C18—H18120.06
C19—C20—C21121.2 (8)C18—C19—H19119.85
C20—C21—C22119.0 (9)C20—C19—H19119.88
C17—C22—C21120.6 (8)C19—C20—H20119.37
C5—C51—C6119.1 (7)C21—C20—H20119.40
C5—C51—C91120.9 (7)C20—C21—H21120.59
C6—C51—C91119.9 (7)C22—C21—H21120.41
N1—C91—C9119.4 (7)C17—C22—H22119.71
N1—C91—C51122.9 (7)C21—C22—H22119.66
C12—O13—C14—C16173.9 (14)C51—C5—C17—C18145.6 (9)
C14—O13—C12—C3175.8 (13)N4—C5—C51—C6135.4 (9)
C12—O13—C14—O154 (2)N4—C5—C51—C9142.9 (13)
C91—N1—C2—O11171.8 (6)C51—C5—C17—C2236.7 (13)
C91—N1—C2—C312.4 (8)C51—C6—C7—Cl1179.0 (6)
C10—N1—C2—C3179.1 (6)C7—C6—C51—C5179.5 (7)
C10—N1—C2—O115.1 (9)C7—C6—C51—C911.2 (12)
C10—N1—C91—C934.8 (10)C51—C6—C7—C80.6 (12)
C2—N1—C91—C9131.7 (7)Cl1—C7—C8—C9179.6 (7)
C10—N1—C91—C51141.6 (8)C6—C7—C8—C91.2 (13)
C2—N1—C91—C5152.0 (10)C7—C8—C9—C910.0 (14)
C3—N4—C5—C17178.7 (8)C8—C9—C91—C511.8 (13)
C3—N4—C5—C510.7 (14)C8—C9—C91—N1178.4 (8)
C5—N4—C3—C12162.3 (9)C18—C17—C22—C215.1 (14)
C5—N4—C3—C273.3 (10)C5—C17—C22—C21172.5 (9)
N1—C2—C3—N465.6 (8)C5—C17—C18—C19174.1 (9)
O11—C2—C3—N4110.2 (7)C22—C17—C18—C193.6 (14)
O11—C2—C3—C128.7 (9)C17—C18—C19—C200.9 (16)
N1—C2—C3—C12175.5 (6)C18—C19—C20—C210.2 (17)
N4—C3—C12—O13162.4 (9)C19—C20—C21—C221.4 (17)
C2—C3—C12—O1377.0 (11)C20—C21—C22—C174.1 (15)
C17—C5—C51—C91137.7 (9)C6—C51—C91—N1178.8 (7)
C17—C5—C51—C644.1 (12)C6—C51—C91—C92.4 (12)
N4—C5—C17—C1833.8 (13)C5—C51—C91—C9179.4 (8)
N4—C5—C17—C22143.8 (9)C5—C51—C91—N13.0 (12)
Symmetry codes: (i) x+1, y+1, z; (ii) y+1, x+y+1, z1/6; (iii) xy+1, x, z+1/6; (iv) x+y+2, x+2, z1/3; (v) x1, y1, z; (vi) xy, x1, z+1/6; (vii) y, x+y, z1/6; (viii) x+y+1, x+1, z1/3; (ix) xy, x, z+1/6; (x) y, x+y+1, z1/6; (xi) y+2, xy, z+1/3; (xii) y+1, xy, z+1/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C16—H16B···O15ii0.96052.43193.39 (2)173.53
Symmetry code: (ii) y+1, x+y+1, z1/6.
 

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