Literature DB >> 21754822

7-Chloro-5-cyclo-propyl-9-methyl-5H-4,5,6,10-tetra-aza-dibenzo[a,d]cyclo-hepten-11(10H)-one.

S Naveen, N R Thimmegowda, H R Manjunath, M A Sridhar, J Shashidhara Prasad, K S Rangappa.   

Abstract

In the title compound, C(15)H(13)ClN(4)O, which is a chloro derivative of the drug Nevirapine, the diazepine ring is in a twisted boat conformation. The pyridine rings fused to the diazepine fragment form a dihedral angle of 58.44 (10)° and the mol-ecule adopts a butterfly shape. The mol-ecules are joined via N-H⋯N hydrogen bonding into polymeric chains down the b axis. All weaker C-H⋯O inter-actions involve the carbonyl O atom as acceptor.

Entities:  

Year:  2011        PMID： 21754822      PMCID： PMC3120426          DOI： 10.1107/S1600536811018022

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For background to the chemistry of azepines, see: Le Count (1996 ▶). The title compound is a chloro derivative of the anti-HIV drug nevirapine (systematic name 11-cyclo­propyl-4-methyl-5,11-dihydro-6H-dipyrido[3,2-b:2′,3′-e][1,4]diazepin-6-one) and was synthesised as a basic scaffold, see: Matsumoto et al. (1984 ▶). We have also synthesized its derivatives and tested for secretory phospho­lipase A2 with anti-inflammatory activity, see: Thimmegowda et al. (2007 ▶). For a related structure, see: Thimmegowda et al. (2008 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H13ClN4O M = 300.74 Orthorhombic, a = 12.7750 (6) Å b = 13.5870 (7) Å c = 16.4920 (9) Å V = 2862.6 (3) Å3 Z = 8 Mo Kα radiation μ = 0.27 mm−1 T = 293 K 0.27 × 0.25 × 0.25 mm

Data collection

MacScience DIPLabo 32001 diffractometer 4721 measured reflections 2525 independent reflections 2155 reflections with I > 2σ(I) R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.040 wR(F 2) = 0.114 S = 1.03 2525 reflections 192 parameters H-atom parameters constrained Δρmax = 0.34 e Å−3 Δρmin = −0.39 e Å−3 Data collection: XPRESS (MacScience, 2002 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811018022/gk2369sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018022/gk2369Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536811018022/gk2369Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C15H13ClN4OF(000) = 1248
Mr = 300.74Dx = 1.396 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4721 reflections
a = 12.7750 (6) Åθ = 2.5–25.0°
b = 13.5870 (7) ŵ = 0.27 mm−1
c = 16.4920 (9) ÅT = 293 K
V = 2862.6 (3) Å3Block, brown
Z = 80.27 × 0.25 × 0.25 mm
MacScience DIPLabo 32001 diffractometer2155 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
graphiteθmax = 25.0°, θmin = 3.2°
Detector resolution: 10.0 pixels mm-1h = −15→15
ω scansk = −16→16
4721 measured reflectionsl = −19→19
2525 independent reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.114w = 1/[σ2(Fo2) + (0.059P)2 + 1.1189P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.013
2525 reflectionsΔρmax = 0.34 e Å−3
192 parametersΔρmin = −0.39 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0027 (7)
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.
xyzUiso*/Ueq
Cl190.26118 (5)0.13670 (5)0.51234 (4)0.0776 (3)
O210.00487 (10)−0.08660 (9)0.11274 (8)0.0483 (4)
N1−0.00616 (11)0.11150 (10)0.29568 (8)0.0364 (4)
N30.12574 (12)0.11681 (11)0.39490 (9)0.0434 (5)
N80.07762 (12)−0.06760 (11)0.23540 (9)0.0421 (5)
N14−0.01401 (12)0.23835 (11)0.19903 (9)0.0445 (5)
C20.08540 (13)0.07028 (12)0.33068 (10)0.0360 (5)
C40.21102 (16)0.07779 (15)0.42695 (12)0.0490 (6)
C50.26156 (16)−0.00449 (16)0.39890 (12)0.0524 (7)
C60.22027 (15)−0.05343 (14)0.33216 (12)0.0462 (6)
C70.12823 (14)−0.01540 (12)0.29831 (10)0.0378 (5)
C90.03801 (13)−0.03110 (13)0.16565 (10)0.0365 (5)
C100.03435 (13)0.07739 (13)0.15357 (10)0.0371 (5)
C110.04651 (16)0.11305 (14)0.07545 (11)0.0449 (6)
C120.03218 (17)0.21156 (15)0.05952 (12)0.0521 (7)
C130.00047 (17)0.27026 (15)0.12274 (12)0.0530 (7)
C150.00547 (13)0.14368 (12)0.21449 (10)0.0344 (5)
C16−0.07237 (15)0.16871 (13)0.34905 (10)0.0419 (5)
C17−0.18729 (17)0.15434 (18)0.33813 (13)0.0600 (7)
C18−0.13242 (19)0.11117 (17)0.41005 (13)0.0626 (8)
C200.27121 (18)−0.14459 (17)0.29923 (18)0.0685 (8)
H50.32220−0.027100.424000.0630*
H80.07130−0.130100.242300.0510*
H110.064400.070300.033700.0540*
H120.043500.237300.008000.0630*
H13−0.011800.336500.112000.0640*
H16−0.048000.234400.364800.0500*
H17A−0.210300.109700.295800.0720*
H17B−0.232700.210500.347200.0720*
H18A−0.144700.141200.462500.0750*
H18B−0.122400.040400.411200.0750*
H20A0.33340−0.158600.329800.1030*
H20B0.28930−0.134500.243300.1030*
H20C0.22350−0.199000.303500.1030*
U11U22U33U12U13U23
Cl190.0725 (4)0.0946 (5)0.0656 (4)0.0017 (3)−0.0270 (3)−0.0291 (3)
O210.0605 (9)0.0418 (7)0.0425 (7)0.0021 (6)−0.0068 (6)−0.0094 (6)
N10.0424 (8)0.0363 (8)0.0306 (7)0.0038 (6)0.0007 (6)0.0004 (6)
N30.0483 (9)0.0435 (9)0.0384 (8)−0.0026 (7)−0.0034 (7)−0.0029 (6)
N80.0541 (9)0.0305 (7)0.0417 (8)−0.0012 (6)−0.0085 (7)−0.0020 (6)
N140.0589 (9)0.0352 (8)0.0393 (8)0.0042 (7)0.0000 (7)0.0018 (6)
C20.0397 (9)0.0355 (9)0.0327 (8)−0.0036 (7)−0.0003 (7)0.0023 (7)
C40.0498 (11)0.0538 (12)0.0435 (10)−0.0054 (9)−0.0078 (9)−0.0036 (9)
C50.0459 (11)0.0594 (12)0.0520 (11)0.0021 (9)−0.0134 (9)−0.0010 (10)
C60.0451 (10)0.0427 (10)0.0508 (11)0.0018 (8)−0.0051 (8)0.0015 (8)
C70.0435 (9)0.0337 (9)0.0363 (9)−0.0023 (7)−0.0044 (7)0.0027 (7)
C90.0378 (9)0.0380 (9)0.0338 (9)0.0012 (7)0.0005 (7)−0.0042 (7)
C100.0389 (9)0.0388 (9)0.0337 (9)−0.0011 (7)−0.0017 (7)−0.0010 (7)
C110.0526 (11)0.0495 (11)0.0326 (9)−0.0007 (9)0.0012 (8)−0.0032 (8)
C120.0684 (13)0.0528 (11)0.0351 (10)−0.0018 (10)0.0012 (9)0.0085 (9)
C130.0744 (14)0.0393 (11)0.0454 (11)0.0031 (9)0.0005 (10)0.0091 (8)
C150.0373 (9)0.0336 (8)0.0324 (8)−0.0004 (7)−0.0018 (7)0.0000 (7)
C160.0513 (10)0.0386 (9)0.0359 (9)0.0038 (8)0.0054 (8)−0.0023 (7)
C170.0479 (11)0.0705 (14)0.0615 (13)0.0062 (10)0.0079 (10)−0.0075 (11)
C180.0743 (15)0.0587 (13)0.0549 (13)0.0029 (11)0.0254 (11)0.0067 (10)
C200.0592 (13)0.0570 (13)0.0892 (17)0.0176 (11)−0.0199 (12)−0.0173 (13)
Cl19—C41.742 (2)C10—C111.385 (2)
O21—C91.229 (2)C11—C121.376 (3)
N1—C21.420 (2)C12—C131.374 (3)
N1—C151.416 (2)C16—C181.487 (3)
N1—C161.447 (2)C16—C171.492 (3)
N3—C21.337 (2)C17—C181.497 (3)
N3—C41.322 (3)C5—H50.9300
N8—C71.413 (2)C11—H110.9300
N8—C91.351 (2)C12—H120.9300
N14—C131.344 (2)C13—H130.9300
N14—C151.335 (2)C16—H160.9800
N8—H80.8600C17—H17A0.9700
C2—C71.393 (2)C17—H17B0.9700
C4—C51.371 (3)C18—H18A0.9700
C5—C61.390 (3)C18—H18B0.9700
C6—C201.501 (3)C20—H20A0.9600
C6—C71.400 (3)C20—H20B0.9600
C9—C101.488 (2)C20—H20C0.9600
C10—C151.399 (2)
Cl19···H17Bi3.1100C7···H13iv2.9100
O21···C12ii3.343 (2)C7···H17Avii3.0900
O21···C11ii3.193 (2)C13···H8v2.7600
O21···C20iii3.412 (3)C15···H17A3.1000
O21···C5iii3.308 (2)C20···H82.7300
O21···H16iv2.5200H5···H20A2.3700
O21···H11ii2.5800H5···H11viii2.3900
O21···H112.6100H5···O21vii2.5400
O21···H5iii2.5400H8···C202.7300
O21···H20Aiii2.5800H8···H20C2.3800
N1···N82.838 (2)H8···N14iv2.1600
N3···C183.308 (3)H8···C13iv2.7600
N8···C13iv3.365 (3)H8···H13iv2.5600
N8···N12.838 (2)H8···H16iv2.5700
N8···N14iv2.963 (2)H11···O212.6100
N14···C173.386 (3)H11···H5ix2.3900
N14···N8v2.963 (2)H11···O21ii2.5800
N3···H12vi2.9200H12···N3x2.9200
N3···H162.7800H13···C7v2.9100
N8···H20C2.8100H13···H8v2.5600
N8···H20B2.8600H16···N32.7800
N14···H162.7700H16···N142.7700
N14···H8v2.1600H16···O21v2.5200
N14···H20Cv2.8100H16···H8v2.5700
C5···O21vii3.308 (2)H17A···C153.1000
C7···C13iv3.589 (3)H17A···C7iii3.0900
C11···O21ii3.193 (2)H17B···Cl19xi3.1100
C12···O21ii3.343 (2)H18B···C23.0000
C13···N8v3.365 (3)H20A···H52.3700
C13···C7v3.589 (3)H20A···O21vii2.5800
C17···N143.386 (3)H20B···N82.8600
C18···N33.308 (3)H20C···N82.8100
C20···O21vii3.412 (3)H20C···H82.3800
C2···H18B3.0000H20C···N14iv2.8100
C2—N1—C15114.82 (13)N1—C16—C18115.50 (16)
C2—N1—C16116.50 (13)N1—C16—C17115.56 (15)
C15—N1—C16118.07 (13)C17—C16—C1860.35 (14)
C2—N3—C4116.41 (16)C16—C17—C1859.67 (14)
C7—N8—C9127.75 (15)C16—C18—C1759.98 (14)
C13—N14—C15117.66 (16)C4—C5—H5121.00
C9—N8—H8116.00C6—C5—H5121.00
C7—N8—H8116.00C10—C11—H11120.00
N3—C2—C7123.20 (16)C12—C11—H11120.00
N1—C2—N3116.95 (14)C11—C12—H12121.00
N1—C2—C7119.85 (15)C13—C12—H12121.00
Cl19—C4—C5118.30 (16)N14—C13—H13118.00
Cl19—C4—N3116.24 (15)C12—C13—H13118.00
N3—C4—C5125.46 (18)N1—C16—H16118.00
C4—C5—C6118.59 (19)C17—C16—H16118.00
C5—C6—C7117.25 (17)C18—C16—H16118.00
C7—C6—C20121.62 (18)C16—C17—H17A118.00
C5—C6—C20121.12 (19)C16—C17—H17B118.00
N8—C7—C6119.44 (15)C18—C17—H17A118.00
N8—C7—C2121.41 (15)C18—C17—H17B118.00
C2—C7—C6119.04 (16)H17A—C17—H17B115.00
O21—C9—C10120.14 (15)C16—C18—H18A118.00
O21—C9—N8120.57 (16)C16—C18—H18B118.00
N8—C9—C10119.30 (15)C17—C18—H18A118.00
C11—C10—C15118.19 (16)C17—C18—H18B118.00
C9—C10—C15123.36 (15)H18A—C18—H18B115.00
C9—C10—C11117.87 (15)C6—C20—H20A109.00
C10—C11—C12120.19 (17)C6—C20—H20B110.00
C11—C12—C13117.32 (18)C6—C20—H20C109.00
N14—C13—C12124.33 (19)H20A—C20—H20B109.00
N1—C15—N14117.29 (14)H20A—C20—H20C110.00
N14—C15—C10122.17 (15)H20B—C20—H20C109.00
N1—C15—C10120.52 (15)
C15—N1—C2—N3117.40 (16)N3—C2—C7—N8173.78 (16)
C15—N1—C2—C7−63.2 (2)N3—C2—C7—C6−2.5 (3)
C16—N1—C2—N3−26.7 (2)Cl19—C4—C5—C6178.23 (15)
C16—N1—C2—C7152.68 (16)N3—C4—C5—C6−1.3 (3)
C2—N1—C15—N14−121.30 (16)C4—C5—C6—C7−0.6 (3)
C2—N1—C15—C1059.9 (2)C4—C5—C6—C20−179.2 (2)
C16—N1—C15—N1422.2 (2)C5—C6—C7—N8−174.00 (17)
C16—N1—C15—C10−156.65 (16)C5—C6—C7—C22.4 (3)
C2—N1—C16—C17−139.70 (16)C20—C6—C7—N84.6 (3)
C2—N1—C16—C18−72.0 (2)C20—C6—C7—C2−179.04 (18)
C15—N1—C16—C1777.4 (2)O21—C9—C10—C11−32.9 (2)
C15—N1—C16—C18145.11 (17)O21—C9—C10—C15138.19 (18)
C4—N3—C2—N1−179.96 (16)N8—C9—C10—C11147.41 (17)
C4—N3—C2—C70.7 (3)N8—C9—C10—C15−41.5 (2)
C2—N3—C4—Cl19−178.26 (13)C9—C10—C11—C12172.74 (18)
C2—N3—C4—C51.2 (3)C15—C10—C11—C121.2 (3)
C9—N8—C7—C248.6 (3)C9—C10—C15—N110.1 (2)
C9—N8—C7—C6−135.18 (19)C9—C10—C15—N14−168.66 (16)
C7—N8—C9—O21173.00 (16)C11—C10—C15—N1−178.83 (16)
C7—N8—C9—C10−7.3 (3)C11—C10—C15—N142.4 (3)
C15—N14—C13—C121.2 (3)C10—C11—C12—C13−3.3 (3)
C13—N14—C15—N1177.66 (16)C11—C12—C13—N142.2 (3)
C13—N14—C15—C10−3.5 (3)N1—C16—C17—C18106.08 (18)
N1—C2—C7—N8−5.5 (2)N1—C16—C18—C17−106.17 (18)
N1—C2—C7—C6178.18 (16)
D—H···AD—HH···AD···AD—H···A
N8—H8···N14iv0.862.162.963 (2)155
C5—H5···O21vii0.932.543.308 (2)140
C11—H11···O21ii0.932.583.193 (2)124
C16—H16···O21v0.982.523.492 (2)171
C20—H20A···O21vii0.962.583.412 (3)145
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N8—H8⋯N14i0.862.162.963 (2)155
C5—H5⋯O21ii0.932.543.308 (2)140
C11—H11⋯O21iii0.932.583.193 (2)124
C16—H16⋯O21iv0.982.523.492 (2)171
C20—H20A⋯O21ii0.962.583.412 (3)145

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

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