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The title compound, C21H20ClN5, has been synthesized in two steps from (RS)-4-chloro-6,11-dimethyl-6,11-di­hydro-5H-benzo[b]pyrimido[5,4-f]azepine and char­acterized by 1H and 13C NMR spectroscopy and by high-resolution mass spectrometry. Crystallization from hexa­ne–ethyl acetate yields approximately equal qu­anti­ties of a monoclinic polymorph in the space group Cc, (I), and an ortho­rhom­bic polymorph in the space group Pna21, (II). The mol­ecules in polymorphs (I) and (II) show small differences in their mol­ecular conformations, particularly in the shape of the azepine ring and the orientation of the chloro­phenyl substituent. The mol­ecules in polymorph (I) are linked by C—H...N and C—H...π(arene) hydrogen bonds to form sheets, which are linked into a three-dimensional framework structure by C—Cl...π(arene) inter­actions. There are no C—Cl...π(arene) inter­actions between the mol­ecules in polymorph (II) and the supra­molecular assembly takes the form of sheets built from C—H...N and C—H...π(arene) hydrogen bonds. Comparisons are made with some related structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961900617X/ov3128sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961900617X/ov3128Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961900617X/ov3128IIsup3.hkl
Contains datablock II

CCDC references: 1913610; 1913609

Computing details top

For both structures, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(RS)-(E)-4-[2-(4-Chlorobenzylidene)hydrazinyl]-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine (I) top
Crystal data top
C21H20ClN5F(000) = 792
Mr = 377.87Dx = 1.332 Mg m3
Monoclinic, CcCu Kα radiation, λ = 1.54178 Å
a = 12.9010 (15) ÅCell parameters from 3250 reflections
b = 20.055 (3) Åθ = 4.4–67.2°
c = 8.7001 (13) ŵ = 1.91 mm1
β = 123.161 (7)°T = 100 K
V = 1884.4 (5) Å3Plate, colourless
Z = 40.11 × 0.10 × 0.06 mm
Data collection top
Bruker D8 Venture
diffractometer
3280 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube2886 reflections with I > 2σ(I)
Multilayer mirror monochromatorRint = 0.063
φ and ω scansθmax = 67.2°, θmin = 4.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = 1515
Tmin = 0.707, Tmax = 0.892k = 2323
11068 measured reflectionsl = 1010
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0435P)2 + 0.640P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.042(Δ/σ)max < 0.001
wR(F2) = 0.105Δρmax = 0.26 e Å3
S = 1.05Δρmin = 0.29 e Å3
3280 reflectionsExtinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
250 parametersExtinction coefficient: 0.0033 (5)
2 restraintsAbsolute structure: Flack x determined using 1264 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: difference Fourier mapAbsolute structure parameter: 0.011 (11)
Hydrogen site location: mixed
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.5994 (3)0.66938 (16)0.4852 (5)0.0322 (8)
C20.5047 (4)0.6376 (2)0.3464 (5)0.0304 (9)
H20.47380.65600.22830.037*
N30.4468 (3)0.58323 (17)0.3493 (4)0.0303 (8)
C40.4840 (3)0.56256 (19)0.5203 (5)0.0272 (9)
C4A0.5808 (3)0.59193 (19)0.6811 (5)0.0264 (8)
C50.6061 (4)0.5688 (2)0.8646 (5)0.0298 (9)
H5B0.62150.52020.87440.036*
H5A0.53020.57610.86440.036*
C60.7134 (4)0.6016 (2)1.0353 (6)0.0303 (9)
H60.69870.65081.02410.036*
C6A0.8297 (4)0.58849 (19)1.0391 (5)0.0293 (9)
C70.9162 (4)0.5405 (2)1.1488 (6)0.0359 (10)
H70.90360.51441.22830.043*
C81.0212 (4)0.5298 (2)1.1448 (6)0.0411 (10)
H81.07830.49571.21800.049*
C91.0419 (4)0.5690 (3)1.0340 (7)0.0452 (12)
H91.11580.56361.03610.054*
C100.9549 (4)0.6165 (2)0.9192 (6)0.0404 (10)
H100.96840.64270.84070.049*
C10A0.8489 (4)0.6253 (2)0.9200 (5)0.0308 (9)
N110.7533 (3)0.67116 (17)0.7941 (5)0.0339 (8)
C11A0.6438 (4)0.6435 (2)0.6544 (5)0.0289 (9)
N410.4196 (3)0.50956 (17)0.5290 (5)0.0282 (7)
H410.437 (4)0.496 (2)0.637 (6)0.034*
N420.3456 (3)0.47120 (16)0.3750 (4)0.0279 (7)
C430.2932 (4)0.42124 (19)0.3977 (5)0.0281 (9)
H430.30510.41420.51430.034*
C4310.2160 (3)0.37515 (19)0.2485 (5)0.0273 (8)
C4320.1910 (4)0.3823 (2)0.0712 (6)0.0324 (9)
H4320.22760.41810.04570.039*
C4330.1144 (4)0.3382 (2)0.0670 (6)0.0336 (9)
H4330.09840.34360.18660.040*
C4340.0614 (4)0.2864 (2)0.0296 (6)0.0350 (10)
Cl40.04196 (11)0.23272 (5)0.20597 (16)0.0488 (4)
C4350.0849 (4)0.2770 (2)0.1440 (7)0.0420 (11)
H4350.04880.24070.16840.050*
C4360.1622 (4)0.3215 (2)0.2820 (6)0.0364 (10)
H4360.17890.31530.40180.044*
C610.7195 (4)0.5779 (2)1.2067 (6)0.0408 (10)
H61B0.72830.52931.21620.061*
H61A0.64330.59071.19830.061*
H61C0.79070.59851.31560.061*
C1110.7959 (5)0.7324 (2)0.7539 (6)0.0466 (12)
H11A0.86600.75080.86820.070*
H11C0.72830.76490.69690.070*
H11B0.82190.72230.66960.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.035 (2)0.0314 (18)0.0330 (19)0.0005 (15)0.0206 (17)0.0039 (15)
C20.031 (2)0.032 (2)0.027 (2)0.0020 (17)0.0157 (18)0.0018 (17)
N30.0325 (19)0.0307 (18)0.0297 (18)0.0006 (15)0.0183 (16)0.0016 (15)
C40.023 (2)0.030 (2)0.032 (2)0.0044 (16)0.0171 (18)0.0029 (17)
C4A0.024 (2)0.029 (2)0.029 (2)0.0007 (17)0.0157 (18)0.0005 (17)
C50.027 (2)0.033 (2)0.030 (2)0.0009 (17)0.0161 (19)0.0011 (17)
C60.032 (2)0.031 (2)0.031 (2)0.0015 (17)0.0196 (19)0.0011 (17)
C6A0.025 (2)0.031 (2)0.030 (2)0.0031 (17)0.0132 (18)0.0021 (17)
C70.031 (2)0.035 (2)0.035 (2)0.0024 (18)0.014 (2)0.0018 (18)
C80.030 (2)0.041 (2)0.044 (3)0.0067 (19)0.016 (2)0.008 (2)
C90.029 (2)0.064 (3)0.045 (3)0.002 (2)0.022 (2)0.014 (2)
C100.033 (2)0.058 (3)0.036 (2)0.010 (2)0.022 (2)0.008 (2)
C10A0.027 (2)0.034 (2)0.029 (2)0.0062 (17)0.0139 (18)0.0036 (17)
N110.0336 (19)0.0321 (19)0.0304 (17)0.0067 (15)0.0139 (16)0.0012 (15)
C11A0.028 (2)0.031 (2)0.029 (2)0.0032 (16)0.0166 (19)0.0018 (17)
N410.0256 (18)0.0329 (19)0.0248 (17)0.0047 (14)0.0129 (16)0.0009 (14)
N420.0215 (16)0.0318 (18)0.0275 (18)0.0004 (14)0.0115 (15)0.0026 (14)
C430.025 (2)0.032 (2)0.031 (2)0.0005 (17)0.0182 (18)0.0016 (18)
C4310.0230 (19)0.028 (2)0.032 (2)0.0030 (16)0.0159 (18)0.0047 (16)
C4320.033 (2)0.031 (2)0.034 (2)0.0054 (17)0.0182 (19)0.0008 (18)
C4330.031 (2)0.034 (2)0.031 (2)0.0020 (18)0.0145 (19)0.0013 (18)
C4340.030 (2)0.025 (2)0.043 (3)0.0001 (17)0.015 (2)0.0036 (18)
Cl40.0444 (7)0.0354 (6)0.0580 (7)0.0100 (5)0.0225 (6)0.0138 (6)
C4350.043 (3)0.032 (2)0.055 (3)0.011 (2)0.029 (2)0.001 (2)
C4360.038 (2)0.035 (2)0.042 (2)0.003 (2)0.026 (2)0.003 (2)
C610.042 (3)0.050 (3)0.033 (2)0.007 (2)0.022 (2)0.002 (2)
C1110.050 (3)0.044 (3)0.039 (3)0.019 (2)0.020 (2)0.003 (2)
Geometric parameters (Å, º) top
N1—C21.320 (5)C10A—N111.446 (5)
N1—C11A1.358 (5)N11—C11A1.379 (5)
C2—N31.330 (5)N11—C1111.463 (5)
C2—H20.9500N41—N421.378 (5)
N3—C41.354 (5)N41—H410.88 (5)
C4—N411.377 (5)N42—C431.283 (5)
C4—C4A1.397 (5)C43—C4311.455 (6)
C4A—C11A1.411 (5)C43—H430.9500
C4A—C51.516 (5)C431—C4361.394 (5)
C5—C61.518 (6)C431—C4321.400 (5)
C5—H5B0.9900C432—C4331.379 (6)
C5—H5A0.9900C432—H4320.9500
C6—C6A1.505 (5)C433—C4341.378 (6)
C6—C611.525 (6)C433—H4330.9500
C6—H61.0000C434—C4351.380 (6)
C6A—C71.384 (6)C434—Cl41.747 (4)
C6A—C10A1.400 (5)C435—C4361.387 (6)
C7—C81.390 (6)C435—H4350.9500
C7—H70.9500C436—H4360.9500
C8—C91.378 (7)C61—H61B0.9800
C8—H80.9500C61—H61A0.9800
C9—C101.392 (7)C61—H61C0.9800
C9—H90.9500C111—H11A0.9800
C10—C10A1.383 (6)C111—H11C0.9800
C10—H100.9500C111—H11B0.9800
C2—N1—C11A116.0 (3)C11A—N11—C111117.7 (3)
N1—C2—N3128.8 (4)C10A—N11—C111116.0 (3)
N1—C2—H2115.6N1—C11A—N11115.0 (3)
N3—C2—H2115.6N1—C11A—C4A121.3 (4)
C2—N3—C4114.0 (3)N11—C11A—C4A123.7 (3)
N3—C4—N41115.8 (3)C4—N41—N42119.7 (3)
N3—C4—C4A123.8 (3)C4—N41—H41119 (3)
N41—C4—C4A120.4 (3)N42—N41—H41120 (3)
C4—C4A—C11A115.1 (3)C43—N42—N41115.4 (3)
C4—C4A—C5119.0 (3)N42—C43—C431121.3 (3)
C11A—C4A—C5125.8 (3)N42—C43—H43119.3
C4A—C5—C6117.0 (3)C431—C43—H43119.3
C4A—C5—H5B108.0C436—C431—C432117.9 (4)
C6—C5—H5B108.0C436—C431—C43118.7 (3)
C4A—C5—H5A108.0C432—C431—C43123.4 (3)
C6—C5—H5A108.0C433—C432—C431121.2 (4)
H5B—C5—H5A107.3C433—C432—H432119.4
C6A—C6—C5108.1 (3)C431—C432—H432119.4
C6A—C6—C61114.0 (4)C434—C433—C432119.2 (4)
C5—C6—C61110.7 (3)C434—C433—H433120.4
C6A—C6—H6108.0C432—C433—H433120.4
C5—C6—H6108.0C433—C434—C435121.4 (4)
C61—C6—H6108.0C433—C434—Cl4119.7 (3)
C7—C6A—C10A118.3 (3)C435—C434—Cl4118.8 (3)
C7—C6A—C6123.7 (3)C434—C435—C436118.9 (4)
C10A—C6A—C6118.0 (3)C434—C435—H435120.6
C6A—C7—C8121.3 (4)C436—C435—H435120.6
C6A—C7—H7119.4C435—C436—C431121.3 (4)
C8—C7—H7119.4C435—C436—H436119.3
C9—C8—C7119.6 (4)C431—C436—H436119.3
C9—C8—H8120.2C6—C61—H61B109.5
C7—C8—H8120.2C6—C61—H61A109.5
C8—C9—C10120.2 (4)H61B—C61—H61A109.5
C8—C9—H9119.9C6—C61—H61C109.5
C10—C9—H9119.9H61B—C61—H61C109.5
C10A—C10—C9119.6 (4)H61A—C61—H61C109.5
C10A—C10—H10120.2N11—C111—H11A109.5
C9—C10—H10120.2N11—C111—H11C109.5
C10—C10A—C6A120.8 (4)H11A—C111—H11C109.5
C10—C10A—N11120.9 (3)N11—C111—H11B109.5
C6A—C10A—N11118.2 (3)H11A—C111—H11B109.5
C11A—N11—C10A116.7 (3)H11C—C111—H11B109.5
C11A—N1—C2—N30.3 (6)C10—C10A—N11—C11136.3 (5)
N1—C2—N3—C46.9 (6)C6A—C10A—N11—C111145.6 (4)
C2—N3—C4—N41175.1 (3)C2—N1—C11A—N11170.8 (3)
C2—N3—C4—C4A4.6 (5)C2—N1—C11A—C4A9.0 (5)
N3—C4—C4A—C11A3.5 (5)C10A—N11—C11A—N1133.2 (3)
N41—C4—C4A—C11A176.8 (3)C111—N11—C11A—N111.7 (5)
N3—C4—C4A—C5174.2 (3)C10A—N11—C11A—C4A46.6 (5)
N41—C4—C4A—C55.5 (5)C111—N11—C11A—C4A168.5 (4)
C4—C4A—C5—C6179.1 (3)C4—C4A—C11A—N110.6 (5)
C11A—C4A—C5—C63.5 (5)C5—C4A—C11A—N1166.9 (4)
C4A—C5—C6—C6A59.8 (4)C4—C4A—C11A—N11169.2 (3)
C4A—C5—C6—C61174.7 (3)C5—C4A—C11A—N1113.3 (6)
C5—C6—C6A—C7101.8 (4)N3—C4—N41—N4215.6 (5)
C61—C6—C6A—C721.7 (6)C4A—C4—N41—N42164.7 (3)
C5—C6—C6A—C10A75.8 (4)C4—N41—N42—C43177.2 (3)
C61—C6—C6A—C10A160.7 (4)N41—N42—C43—C431177.9 (3)
C10A—C6A—C7—C81.4 (6)N42—C43—C431—C436179.5 (4)
C6—C6A—C7—C8179.0 (4)N42—C43—C431—C4321.4 (6)
C6A—C7—C8—C92.1 (7)C436—C431—C432—C4330.9 (6)
C7—C8—C9—C103.6 (7)C43—C431—C432—C433178.2 (4)
C8—C9—C10—C10A1.5 (7)C431—C432—C433—C4340.1 (6)
C9—C10—C10A—C6A2.0 (6)C432—C433—C434—C4351.1 (6)
C9—C10—C10A—N11176.0 (4)C432—C433—C434—Cl4176.8 (3)
C7—C6A—C10A—C103.5 (6)C433—C434—C435—C4361.0 (6)
C6—C6A—C10A—C10178.8 (4)Cl4—C434—C435—C436176.9 (3)
C7—C6A—C10A—N11174.7 (4)C434—C435—C436—C4310.1 (6)
C6—C6A—C10A—N113.1 (5)C432—C431—C436—C4351.0 (6)
C10—C10A—N11—C11A109.3 (4)C43—C431—C436—C435178.2 (4)
C6A—C10A—N11—C11A68.9 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N41—H41···N3i0.88 (4)2.39 (5)3.207 (5)155 (4)
C5—H5A···N42i0.992.613.504 (7)150
C43—H43···N3i0.952.453.295 (5)148
C433—H433···Cg1ii0.952.683.378 (5)131
Symmetry codes: (i) x, y+1, z+1/2; (ii) x1, y+1, z3/2.
(RS)-(E)-4-[2-(4-Chlorobenzylidene)hydrazinyl]-6,11-dimethyl-6,11-dihydro-5H-benzo[b]pyrimido[5,4-f]azepine (II) top
Crystal data top
C21H20ClN5Dx = 1.372 Mg m3
Mr = 377.87Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pna21Cell parameters from 3084 reflections
a = 8.8623 (4) Åθ = 4.4–67.0°
b = 14.4656 (7) ŵ = 1.97 mm1
c = 14.2723 (7) ÅT = 100 K
V = 1829.69 (15) Å3Plate, colourless
Z = 40.12 × 0.12 × 0.07 mm
F(000) = 792
Data collection top
Bruker D8 Venture
diffractometer
3083 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube2669 reflections with I > 2σ(I)
Multilayer mirror monochromatorRint = 0.062
φ and ω scansθmax = 66.9°, θmin = 4.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2015)
h = 910
Tmin = 0.726, Tmax = 0.871k = 1717
22910 measured reflectionsl = 1516
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0509P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.037(Δ/σ)max < 0.001
wR(F2) = 0.089Δρmax = 0.29 e Å3
S = 1.06Δρmin = 0.23 e Å3
3083 reflectionsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
250 parametersExtinction coefficient: 0.0057 (6)
1 restraintAbsolute structure: Flack x determined using 1075 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: difference Fourier mapAbsolute structure parameter: 0.048 (9)
Hydrogen site location: mixed
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.6254 (3)0.4527 (2)0.6504 (2)0.0276 (7)
C20.6661 (4)0.4156 (2)0.5697 (2)0.0316 (8)
H20.75910.43710.54460.038*
N30.5950 (3)0.35249 (19)0.51894 (18)0.0272 (7)
C40.4589 (4)0.3292 (2)0.5520 (2)0.0249 (8)
C4A0.3975 (4)0.3621 (2)0.6370 (2)0.0252 (7)
C50.2391 (4)0.3341 (2)0.6622 (2)0.0287 (8)
H5A0.23950.26730.67720.034*
H5B0.17480.34250.60610.034*
C60.1651 (4)0.3856 (2)0.7439 (2)0.0280 (8)
H60.17370.45330.73080.034*
C6A0.2487 (4)0.3665 (2)0.8338 (2)0.0284 (8)
C70.1855 (5)0.3138 (2)0.9061 (3)0.0337 (9)
H70.08930.28620.89750.040*
C80.2625 (5)0.3013 (2)0.9908 (3)0.0361 (9)
H80.21850.26551.03950.043*
C90.4011 (4)0.3408 (2)1.0032 (3)0.0361 (9)
H90.45240.33331.06110.043*
C100.4676 (5)0.3918 (3)0.9322 (3)0.0338 (9)
H100.56440.41850.94150.041*
C10A0.3925 (4)0.4041 (2)0.8469 (2)0.0268 (8)
N110.4618 (3)0.4585 (2)0.7752 (2)0.0269 (7)
C11A0.4935 (4)0.4224 (2)0.6864 (2)0.0245 (8)
N410.3745 (3)0.27030 (18)0.4969 (2)0.0289 (6)
H410.274 (5)0.253 (2)0.514 (3)0.035*
N420.4331 (3)0.23699 (19)0.41314 (19)0.0277 (7)
C430.3317 (4)0.2050 (2)0.3577 (2)0.0264 (8)
H430.22860.20970.37530.032*
C4310.3700 (4)0.1616 (2)0.2683 (2)0.0257 (8)
C4320.5153 (5)0.1333 (3)0.2439 (3)0.0290 (8)
H4320.59660.14510.28570.035*
C4330.5433 (4)0.0887 (2)0.1602 (2)0.0299 (8)
H4330.64270.06970.14430.036*
C4340.4238 (4)0.0719 (2)0.0994 (2)0.0295 (8)
Cl40.45257 (10)0.01049 (6)0.00398 (7)0.0372 (3)
C4350.2793 (5)0.0993 (2)0.1208 (2)0.0313 (8)
H4350.19880.08760.07850.038*
C4360.2525 (4)0.1446 (2)0.2059 (2)0.0294 (8)
H4360.15300.16400.22110.035*
C610.0023 (5)0.3618 (3)0.7470 (3)0.0311 (8)
H61A0.05020.39520.79890.047*
H61B0.01450.29520.75650.047*
H61C0.04980.37990.68780.047*
C1110.5616 (4)0.5329 (3)0.8079 (3)0.0337 (9)
H11A0.57750.57750.75710.051*
H11C0.65880.50670.82690.051*
H11B0.51500.56430.86140.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0238 (17)0.0353 (15)0.0238 (15)0.0030 (13)0.0007 (13)0.0023 (13)
C20.027 (2)0.0346 (19)0.033 (2)0.0032 (15)0.0018 (16)0.0028 (16)
N30.0212 (16)0.0349 (15)0.0257 (17)0.0033 (12)0.0016 (12)0.0017 (12)
C40.0206 (19)0.0264 (17)0.0275 (18)0.0001 (14)0.0022 (15)0.0024 (15)
C4A0.0247 (19)0.0272 (16)0.0238 (17)0.0021 (14)0.0005 (15)0.0018 (14)
C50.022 (2)0.037 (2)0.026 (2)0.0011 (15)0.0008 (15)0.0001 (16)
C60.027 (2)0.0320 (18)0.0254 (18)0.0005 (16)0.0005 (16)0.0006 (15)
C6A0.030 (2)0.0311 (18)0.0242 (18)0.0026 (16)0.0024 (15)0.0008 (15)
C70.035 (2)0.0345 (19)0.032 (2)0.0035 (17)0.0017 (17)0.0010 (16)
C80.046 (2)0.0351 (18)0.0273 (19)0.0043 (16)0.0028 (18)0.0070 (19)
C90.042 (2)0.044 (2)0.0225 (18)0.0095 (17)0.0022 (19)0.0027 (18)
C100.029 (2)0.045 (2)0.0277 (19)0.0009 (17)0.0028 (16)0.0058 (17)
C10A0.027 (2)0.0301 (18)0.0228 (18)0.0024 (15)0.0005 (15)0.0007 (15)
N110.0248 (17)0.0318 (15)0.0239 (16)0.0037 (13)0.0000 (12)0.0040 (13)
C11A0.0220 (19)0.0285 (18)0.0231 (18)0.0021 (14)0.0002 (14)0.0005 (14)
N410.0236 (16)0.0388 (15)0.0242 (14)0.0023 (13)0.0050 (14)0.0041 (15)
N420.0262 (18)0.0323 (16)0.0247 (16)0.0000 (13)0.0046 (13)0.0023 (13)
C430.0224 (18)0.0313 (17)0.0255 (19)0.0005 (15)0.0037 (15)0.0014 (15)
C4310.026 (2)0.0269 (18)0.0238 (19)0.0019 (14)0.0003 (15)0.0028 (14)
C4320.025 (2)0.034 (2)0.0275 (18)0.0010 (17)0.0027 (16)0.0014 (16)
C4330.026 (2)0.0342 (19)0.029 (2)0.0002 (15)0.0051 (15)0.0013 (15)
C4340.036 (2)0.0298 (19)0.0230 (19)0.0025 (16)0.0051 (15)0.0017 (16)
Cl40.0421 (6)0.0447 (5)0.0249 (4)0.0037 (4)0.0013 (5)0.0060 (4)
C4350.036 (2)0.0329 (18)0.0253 (19)0.0019 (16)0.0042 (16)0.0025 (15)
C4360.028 (2)0.0338 (19)0.0268 (18)0.0022 (16)0.0020 (16)0.0011 (16)
C610.0257 (19)0.040 (2)0.0272 (17)0.0001 (19)0.0022 (15)0.0020 (17)
C1110.030 (2)0.038 (2)0.033 (2)0.0064 (17)0.0003 (17)0.0089 (17)
Geometric parameters (Å, º) top
N1—C21.322 (5)C10A—N111.430 (4)
N1—C11A1.350 (5)N11—C11A1.400 (4)
C2—N31.324 (4)N11—C1111.469 (5)
C2—H20.9500N41—N421.390 (4)
N3—C41.338 (4)N41—H410.96 (4)
C4—N411.380 (4)N42—C431.284 (4)
C4—C4A1.413 (5)C43—C4311.461 (5)
C4A—C11A1.408 (5)C43—H430.9500
C4A—C51.505 (5)C431—C4361.393 (5)
C5—C61.531 (5)C431—C4321.396 (5)
C5—H5A0.9900C432—C4331.381 (5)
C5—H5B0.9900C432—H4320.9500
C6—C6A1.507 (5)C433—C4341.390 (5)
C6—C611.523 (5)C433—H4330.9500
C6—H61.0000C434—C4351.375 (5)
C6A—C10A1.398 (5)C434—Cl41.741 (4)
C6A—C71.400 (5)C435—C4361.400 (5)
C7—C81.401 (5)C435—H4350.9500
C7—H70.9500C436—H4360.9500
C8—C91.366 (5)C61—H61A0.9800
C8—H80.9500C61—H61B0.9800
C9—C101.385 (5)C61—H61C0.9800
C9—H90.9500C111—H11A0.9800
C10—C10A1.399 (5)C111—H11C0.9800
C10—H100.9500C111—H11B0.9800
C2—N1—C11A115.9 (3)C11A—N11—C111116.1 (3)
N1—C2—N3128.8 (3)C10A—N11—C111115.8 (3)
N1—C2—H2115.6N1—C11A—N11113.4 (3)
N3—C2—H2115.6N1—C11A—C4A122.3 (3)
C2—N3—C4114.2 (3)N11—C11A—C4A124.3 (3)
N3—C4—N41116.4 (3)C4—N41—N42120.1 (3)
N3—C4—C4A124.4 (3)C4—N41—H41122 (2)
N41—C4—C4A119.2 (3)N42—N41—H41118 (2)
C11A—C4A—C4114.0 (3)C43—N42—N41113.1 (3)
C11A—C4A—C5127.7 (3)N42—C43—C431122.0 (3)
C4—C4A—C5118.3 (3)N42—C43—H43119.0
C4A—C5—C6116.8 (3)C431—C43—H43119.0
C4A—C5—H5A108.1C436—C431—C432118.6 (3)
C6—C5—H5A108.1C436—C431—C43117.4 (3)
C4A—C5—H5B108.1C432—C431—C43123.9 (3)
C6—C5—H5B108.1C433—C432—C431121.3 (4)
H5A—C5—H5B107.3C433—C432—H432119.4
C6A—C6—C61114.4 (3)C431—C432—H432119.4
C6A—C6—C5110.4 (3)C432—C433—C434119.0 (3)
C61—C6—C5109.3 (3)C432—C433—H433120.5
C6A—C6—H6107.5C434—C433—H433120.5
C61—C6—H6107.5C435—C434—C433121.4 (3)
C5—C6—H6107.5C435—C434—Cl4118.2 (3)
C10A—C6A—C7118.5 (3)C433—C434—Cl4120.4 (3)
C10A—C6A—C6119.4 (3)C434—C435—C436119.1 (4)
C7—C6A—C6122.0 (3)C434—C435—H435120.5
C6A—C7—C8120.8 (4)C436—C435—H435120.5
C6A—C7—H7119.6C431—C436—C435120.7 (3)
C8—C7—H7119.6C431—C436—H436119.6
C9—C8—C7119.7 (4)C435—C436—H436119.6
C9—C8—H8120.2C6—C61—H61A109.5
C7—C8—H8120.2C6—C61—H61B109.5
C8—C9—C10120.8 (4)H61A—C61—H61B109.5
C8—C9—H9119.6C6—C61—H61C109.5
C10—C9—H9119.6H61A—C61—H61C109.5
C9—C10—C10A120.1 (4)H61B—C61—H61C109.5
C9—C10—H10119.9N11—C111—H11A109.5
C10A—C10—H10119.9N11—C111—H11C109.5
C6A—C10A—C10120.1 (3)H11A—C111—H11C109.5
C6A—C10A—N11120.6 (3)N11—C111—H11B109.5
C10—C10A—N11119.2 (3)H11A—C111—H11B109.5
C11A—N11—C10A121.9 (3)H11C—C111—H11B109.5
C11A—N1—C2—N30.0 (5)C6A—C10A—N11—C111147.7 (3)
N1—C2—N3—C45.2 (5)C10—C10A—N11—C11129.8 (5)
C2—N3—C4—N41174.1 (3)C2—N1—C11A—N11175.3 (3)
C2—N3—C4—C4A4.6 (5)C2—N1—C11A—C4A6.1 (5)
N3—C4—C4A—C11A0.6 (5)C10A—N11—C11A—N1141.9 (3)
N41—C4—C4A—C11A179.3 (3)C111—N11—C11A—N19.3 (4)
N3—C4—C4A—C5176.4 (3)C10A—N11—C11A—C4A39.6 (5)
N41—C4—C4A—C52.2 (5)C111—N11—C11A—C4A169.3 (3)
C11A—C4A—C5—C68.2 (5)C4—C4A—C11A—N16.3 (5)
C4—C4A—C5—C6168.3 (3)C5—C4A—C11A—N1170.4 (3)
C4A—C5—C6—C6A64.2 (4)C4—C4A—C11A—N11175.2 (3)
C4A—C5—C6—C61169.1 (3)C5—C4A—C11A—N118.1 (6)
C61—C6—C6A—C10A165.6 (3)N3—C4—N41—N421.4 (4)
C5—C6—C6A—C10A70.6 (4)C4A—C4—N41—N42179.8 (3)
C61—C6—C6A—C712.9 (5)C4—N41—N42—C43161.9 (3)
C5—C6—C6A—C7110.9 (4)N41—N42—C43—C431176.3 (3)
C10A—C6A—C7—C81.9 (5)N42—C43—C431—C436168.5 (3)
C6—C6A—C7—C8176.5 (3)N42—C43—C431—C43214.0 (5)
C6A—C7—C8—C90.1 (5)C436—C431—C432—C4330.6 (5)
C7—C8—C9—C101.2 (5)C43—C431—C432—C433176.9 (3)
C8—C9—C10—C10A0.6 (5)C431—C432—C433—C4340.1 (5)
C7—C6A—C10A—C102.5 (5)C432—C433—C434—C4350.3 (5)
C6—C6A—C10A—C10176.0 (3)C432—C433—C434—Cl4176.6 (3)
C7—C6A—C10A—N11179.9 (3)C433—C434—C435—C4360.2 (5)
C6—C6A—C10A—N111.4 (5)Cl4—C434—C435—C436176.8 (3)
C9—C10—C10A—C6A1.3 (5)C432—C431—C436—C4350.7 (5)
C9—C10—C10A—N11178.7 (3)C43—C431—C436—C435176.9 (3)
C6A—C10A—N11—C11A61.1 (5)C434—C435—C436—C4310.3 (5)
C10—C10A—N11—C11A121.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N41—H41···N3i0.96 (4)2.20 (4)3.064 (4)149 (3)
C43—H43···N3i0.952.533.223 (4)130
C6—H6···Cg2ii1.002.543.496 (3)161
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond parameters (Å, °) for (I) and (II) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)N41—H41···N3i0.88 (4)2.39 (5)3.207 (5)155 (4)
C5—H5A···N42i0.992.613.504 (7)150
C43—H43···N3i0.952.453.295 (5)148
C433—H433···Cg1ii0.952.683.378 (5)131
(II)N41—H41···N3iii0.96 (4)2.20 (4)3.064 (4)149 (3)
C43—H43···N3iii0.952.533.223 (4)130
C6—H6···Cg2iv1.002.543.496 (3)161
Symmetry codes: (i) x, -y+1, z+1/2; (ii) x-1, -y+1, z-3/2; (iii) x-1/2, -y+1/2, z; (iv) -x+1/2, y+1/2, z+1/2.

Cg1 and Cg2 represent the centroids of the C6A/C7–C10/C10A and C431–C436 rings, respectively.
Selected geometric parameters (Å, °) for (I) and (II) top
Parameter(I)(II)
Torsion and dihedral angles
C4—N41—N42—C43177.2 (3)-161.9 (3)
N41—N42—C43—C431-177.9 (3)-176.3 (3)
N42—C43—C431—C432-1.4 (6)14.0 (5)
Dihedral 165.35 (13)50.60 (10)
Dihedral 216.64 (19)36.26 (12)
Ring-puckering parameters
Q0.935 (5)0.824 (3)
φ231.8 (3)37.9 (2)
φ3293.6 (10)290.1 (6)
Dihedral 1 represents the dihedral angle between the two rings fused to the azepine ring and dihedral 2 represents the dihedral angle between the pyrimidine ring and the chlorinated C431–C436 ring.

Ring-puckering angles are calculated for the atom sequence N11–C10A–C6A–C6–C5–C4A–C11A.
Geometric parameters (Å, °) for the C—Cl···π interaction in the monoclinic polymorph (I) top
C—Cl···CgC—ClCl···CgC···CgC—Cl···Cg
C434—Cl4···Cg2i1.747 (4)3.731 (3)5.1356 (5)136.1 (2)(4)
Symmetry code: (i) x-1/2, -y+1/2, z-1/2.

Cg2 represents the centroid of the C431–C436 ring.
 

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