The title compound, C
21H
20ClN
5, has been synthesized in two steps from (
RS)-4-chloro-6,11-dimethyl-6,11-dihydro-5
H-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
Pna2
1, (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
CCDC references: 1913610; 1913609
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-5
H-benzo[
b]pyrimido[5,4-
f]azepine (I)
top
Crystal data top
C21H20ClN5 | F(000) = 792 |
Mr = 377.87 | Dx = 1.332 Mg m−3 |
Monoclinic, Cc | Cu Kα radiation, λ = 1.54178 Å |
a = 12.9010 (15) Å | Cell parameters from 3250 reflections |
b = 20.055 (3) Å | θ = 4.4–67.2° |
c = 8.7001 (13) Å | µ = 1.91 mm−1 |
β = 123.161 (7)° | T = 100 K |
V = 1884.4 (5) Å3 | Plate, colourless |
Z = 4 | 0.11 × 0.10 × 0.06 mm |
Data collection top
Bruker D8 Venture diffractometer | 3280 independent reflections |
Radiation source: INCOATEC high brilliance microfocus sealed tube | 2886 reflections with I > 2σ(I) |
Multilayer mirror monochromator | Rint = 0.063 |
φ and ω scans | θmax = 67.2°, θmin = 4.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −15→15 |
Tmin = 0.707, Tmax = 0.892 | k = −23→23 |
11068 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | H 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) = 0.105 | Δρmax = 0.26 e Å−3 |
S = 1.05 | Δρmin = −0.29 e Å−3 |
3280 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
250 parameters | Extinction coefficient: 0.0033 (5) |
2 restraints | Absolute structure: Flack x determined using 1264 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Primary atom site location: difference Fourier map | Absolute 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.5994 (3) | 0.66938 (16) | 0.4852 (5) | 0.0322 (8) | |
C2 | 0.5047 (4) | 0.6376 (2) | 0.3464 (5) | 0.0304 (9) | |
H2 | 0.4738 | 0.6560 | 0.2283 | 0.037* | |
N3 | 0.4468 (3) | 0.58323 (17) | 0.3493 (4) | 0.0303 (8) | |
C4 | 0.4840 (3) | 0.56256 (19) | 0.5203 (5) | 0.0272 (9) | |
C4A | 0.5808 (3) | 0.59193 (19) | 0.6811 (5) | 0.0264 (8) | |
C5 | 0.6061 (4) | 0.5688 (2) | 0.8646 (5) | 0.0298 (9) | |
H5B | 0.6215 | 0.5202 | 0.8744 | 0.036* | |
H5A | 0.5302 | 0.5761 | 0.8644 | 0.036* | |
C6 | 0.7134 (4) | 0.6016 (2) | 1.0353 (6) | 0.0303 (9) | |
H6 | 0.6987 | 0.6508 | 1.0241 | 0.036* | |
C6A | 0.8297 (4) | 0.58849 (19) | 1.0391 (5) | 0.0293 (9) | |
C7 | 0.9162 (4) | 0.5405 (2) | 1.1488 (6) | 0.0359 (10) | |
H7 | 0.9036 | 0.5144 | 1.2283 | 0.043* | |
C8 | 1.0212 (4) | 0.5298 (2) | 1.1448 (6) | 0.0411 (10) | |
H8 | 1.0783 | 0.4957 | 1.2180 | 0.049* | |
C9 | 1.0419 (4) | 0.5690 (3) | 1.0340 (7) | 0.0452 (12) | |
H9 | 1.1158 | 0.5636 | 1.0361 | 0.054* | |
C10 | 0.9549 (4) | 0.6165 (2) | 0.9192 (6) | 0.0404 (10) | |
H10 | 0.9684 | 0.6427 | 0.8407 | 0.049* | |
C10A | 0.8489 (4) | 0.6253 (2) | 0.9200 (5) | 0.0308 (9) | |
N11 | 0.7533 (3) | 0.67116 (17) | 0.7941 (5) | 0.0339 (8) | |
C11A | 0.6438 (4) | 0.6435 (2) | 0.6544 (5) | 0.0289 (9) | |
N41 | 0.4196 (3) | 0.50956 (17) | 0.5290 (5) | 0.0282 (7) | |
H41 | 0.437 (4) | 0.496 (2) | 0.637 (6) | 0.034* | |
N42 | 0.3456 (3) | 0.47120 (16) | 0.3750 (4) | 0.0279 (7) | |
C43 | 0.2932 (4) | 0.42124 (19) | 0.3977 (5) | 0.0281 (9) | |
H43 | 0.3051 | 0.4142 | 0.5143 | 0.034* | |
C431 | 0.2160 (3) | 0.37515 (19) | 0.2485 (5) | 0.0273 (8) | |
C432 | 0.1910 (4) | 0.3823 (2) | 0.0712 (6) | 0.0324 (9) | |
H432 | 0.2276 | 0.4181 | 0.0457 | 0.039* | |
C433 | 0.1144 (4) | 0.3382 (2) | −0.0670 (6) | 0.0336 (9) | |
H433 | 0.0984 | 0.3436 | −0.1866 | 0.040* | |
C434 | 0.0614 (4) | 0.2864 (2) | −0.0296 (6) | 0.0350 (10) | |
Cl4 | −0.04196 (11) | 0.23272 (5) | −0.20597 (16) | 0.0488 (4) | |
C435 | 0.0849 (4) | 0.2770 (2) | 0.1440 (7) | 0.0420 (11) | |
H435 | 0.0488 | 0.2407 | 0.1684 | 0.050* | |
C436 | 0.1622 (4) | 0.3215 (2) | 0.2820 (6) | 0.0364 (10) | |
H436 | 0.1789 | 0.3153 | 0.4018 | 0.044* | |
C61 | 0.7195 (4) | 0.5779 (2) | 1.2067 (6) | 0.0408 (10) | |
H61B | 0.7283 | 0.5293 | 1.2162 | 0.061* | |
H61A | 0.6433 | 0.5907 | 1.1983 | 0.061* | |
H61C | 0.7907 | 0.5985 | 1.3156 | 0.061* | |
C111 | 0.7959 (5) | 0.7324 (2) | 0.7539 (6) | 0.0466 (12) | |
H11A | 0.8660 | 0.7508 | 0.8682 | 0.070* | |
H11C | 0.7283 | 0.7649 | 0.6969 | 0.070* | |
H11B | 0.8219 | 0.7223 | 0.6696 | 0.070* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.035 (2) | 0.0314 (18) | 0.0330 (19) | 0.0005 (15) | 0.0206 (17) | 0.0039 (15) |
C2 | 0.031 (2) | 0.032 (2) | 0.027 (2) | −0.0020 (17) | 0.0157 (18) | 0.0018 (17) |
N3 | 0.0325 (19) | 0.0307 (18) | 0.0297 (18) | 0.0006 (15) | 0.0183 (16) | 0.0016 (15) |
C4 | 0.023 (2) | 0.030 (2) | 0.032 (2) | 0.0044 (16) | 0.0171 (18) | 0.0029 (17) |
C4A | 0.024 (2) | 0.029 (2) | 0.029 (2) | 0.0007 (17) | 0.0157 (18) | 0.0005 (17) |
C5 | 0.027 (2) | 0.033 (2) | 0.030 (2) | −0.0009 (17) | 0.0161 (19) | 0.0011 (17) |
C6 | 0.032 (2) | 0.031 (2) | 0.031 (2) | −0.0015 (17) | 0.0196 (19) | 0.0011 (17) |
C6A | 0.025 (2) | 0.031 (2) | 0.030 (2) | −0.0031 (17) | 0.0132 (18) | −0.0021 (17) |
C7 | 0.031 (2) | 0.035 (2) | 0.035 (2) | −0.0024 (18) | 0.014 (2) | −0.0018 (18) |
C8 | 0.030 (2) | 0.041 (2) | 0.044 (3) | 0.0067 (19) | 0.016 (2) | −0.008 (2) |
C9 | 0.029 (2) | 0.064 (3) | 0.045 (3) | −0.002 (2) | 0.022 (2) | −0.014 (2) |
C10 | 0.033 (2) | 0.058 (3) | 0.036 (2) | −0.010 (2) | 0.022 (2) | −0.008 (2) |
C10A | 0.027 (2) | 0.034 (2) | 0.029 (2) | −0.0062 (17) | 0.0139 (18) | −0.0036 (17) |
N11 | 0.0336 (19) | 0.0321 (19) | 0.0304 (17) | −0.0067 (15) | 0.0139 (16) | 0.0012 (15) |
C11A | 0.028 (2) | 0.031 (2) | 0.029 (2) | −0.0032 (16) | 0.0166 (19) | −0.0018 (17) |
N41 | 0.0256 (18) | 0.0329 (19) | 0.0248 (17) | −0.0047 (14) | 0.0129 (16) | −0.0009 (14) |
N42 | 0.0215 (16) | 0.0318 (18) | 0.0275 (18) | −0.0004 (14) | 0.0115 (15) | −0.0026 (14) |
C43 | 0.025 (2) | 0.032 (2) | 0.031 (2) | 0.0005 (17) | 0.0182 (18) | 0.0016 (18) |
C431 | 0.0230 (19) | 0.028 (2) | 0.032 (2) | 0.0030 (16) | 0.0159 (18) | 0.0047 (16) |
C432 | 0.033 (2) | 0.031 (2) | 0.034 (2) | −0.0054 (17) | 0.0182 (19) | 0.0008 (18) |
C433 | 0.031 (2) | 0.034 (2) | 0.031 (2) | −0.0020 (18) | 0.0145 (19) | −0.0013 (18) |
C434 | 0.030 (2) | 0.025 (2) | 0.043 (3) | 0.0001 (17) | 0.015 (2) | −0.0036 (18) |
Cl4 | 0.0444 (7) | 0.0354 (6) | 0.0580 (7) | −0.0100 (5) | 0.0225 (6) | −0.0138 (6) |
C435 | 0.043 (3) | 0.032 (2) | 0.055 (3) | −0.011 (2) | 0.029 (2) | −0.001 (2) |
C436 | 0.038 (2) | 0.035 (2) | 0.042 (2) | −0.003 (2) | 0.026 (2) | 0.003 (2) |
C61 | 0.042 (3) | 0.050 (3) | 0.033 (2) | −0.007 (2) | 0.022 (2) | −0.002 (2) |
C111 | 0.050 (3) | 0.044 (3) | 0.039 (3) | −0.019 (2) | 0.020 (2) | 0.003 (2) |
Geometric parameters (Å, º) top
N1—C2 | 1.320 (5) | C10A—N11 | 1.446 (5) |
N1—C11A | 1.358 (5) | N11—C11A | 1.379 (5) |
C2—N3 | 1.330 (5) | N11—C111 | 1.463 (5) |
C2—H2 | 0.9500 | N41—N42 | 1.378 (5) |
N3—C4 | 1.354 (5) | N41—H41 | 0.88 (5) |
C4—N41 | 1.377 (5) | N42—C43 | 1.283 (5) |
C4—C4A | 1.397 (5) | C43—C431 | 1.455 (6) |
C4A—C11A | 1.411 (5) | C43—H43 | 0.9500 |
C4A—C5 | 1.516 (5) | C431—C436 | 1.394 (5) |
C5—C6 | 1.518 (6) | C431—C432 | 1.400 (5) |
C5—H5B | 0.9900 | C432—C433 | 1.379 (6) |
C5—H5A | 0.9900 | C432—H432 | 0.9500 |
C6—C6A | 1.505 (5) | C433—C434 | 1.378 (6) |
C6—C61 | 1.525 (6) | C433—H433 | 0.9500 |
C6—H6 | 1.0000 | C434—C435 | 1.380 (6) |
C6A—C7 | 1.384 (6) | C434—Cl4 | 1.747 (4) |
C6A—C10A | 1.400 (5) | C435—C436 | 1.387 (6) |
C7—C8 | 1.390 (6) | C435—H435 | 0.9500 |
C7—H7 | 0.9500 | C436—H436 | 0.9500 |
C8—C9 | 1.378 (7) | C61—H61B | 0.9800 |
C8—H8 | 0.9500 | C61—H61A | 0.9800 |
C9—C10 | 1.392 (7) | C61—H61C | 0.9800 |
C9—H9 | 0.9500 | C111—H11A | 0.9800 |
C10—C10A | 1.383 (6) | C111—H11C | 0.9800 |
C10—H10 | 0.9500 | C111—H11B | 0.9800 |
| | | |
C2—N1—C11A | 116.0 (3) | C11A—N11—C111 | 117.7 (3) |
N1—C2—N3 | 128.8 (4) | C10A—N11—C111 | 116.0 (3) |
N1—C2—H2 | 115.6 | N1—C11A—N11 | 115.0 (3) |
N3—C2—H2 | 115.6 | N1—C11A—C4A | 121.3 (4) |
C2—N3—C4 | 114.0 (3) | N11—C11A—C4A | 123.7 (3) |
N3—C4—N41 | 115.8 (3) | C4—N41—N42 | 119.7 (3) |
N3—C4—C4A | 123.8 (3) | C4—N41—H41 | 119 (3) |
N41—C4—C4A | 120.4 (3) | N42—N41—H41 | 120 (3) |
C4—C4A—C11A | 115.1 (3) | C43—N42—N41 | 115.4 (3) |
C4—C4A—C5 | 119.0 (3) | N42—C43—C431 | 121.3 (3) |
C11A—C4A—C5 | 125.8 (3) | N42—C43—H43 | 119.3 |
C4A—C5—C6 | 117.0 (3) | C431—C43—H43 | 119.3 |
C4A—C5—H5B | 108.0 | C436—C431—C432 | 117.9 (4) |
C6—C5—H5B | 108.0 | C436—C431—C43 | 118.7 (3) |
C4A—C5—H5A | 108.0 | C432—C431—C43 | 123.4 (3) |
C6—C5—H5A | 108.0 | C433—C432—C431 | 121.2 (4) |
H5B—C5—H5A | 107.3 | C433—C432—H432 | 119.4 |
C6A—C6—C5 | 108.1 (3) | C431—C432—H432 | 119.4 |
C6A—C6—C61 | 114.0 (4) | C434—C433—C432 | 119.2 (4) |
C5—C6—C61 | 110.7 (3) | C434—C433—H433 | 120.4 |
C6A—C6—H6 | 108.0 | C432—C433—H433 | 120.4 |
C5—C6—H6 | 108.0 | C433—C434—C435 | 121.4 (4) |
C61—C6—H6 | 108.0 | C433—C434—Cl4 | 119.7 (3) |
C7—C6A—C10A | 118.3 (3) | C435—C434—Cl4 | 118.8 (3) |
C7—C6A—C6 | 123.7 (3) | C434—C435—C436 | 118.9 (4) |
C10A—C6A—C6 | 118.0 (3) | C434—C435—H435 | 120.6 |
C6A—C7—C8 | 121.3 (4) | C436—C435—H435 | 120.6 |
C6A—C7—H7 | 119.4 | C435—C436—C431 | 121.3 (4) |
C8—C7—H7 | 119.4 | C435—C436—H436 | 119.3 |
C9—C8—C7 | 119.6 (4) | C431—C436—H436 | 119.3 |
C9—C8—H8 | 120.2 | C6—C61—H61B | 109.5 |
C7—C8—H8 | 120.2 | C6—C61—H61A | 109.5 |
C8—C9—C10 | 120.2 (4) | H61B—C61—H61A | 109.5 |
C8—C9—H9 | 119.9 | C6—C61—H61C | 109.5 |
C10—C9—H9 | 119.9 | H61B—C61—H61C | 109.5 |
C10A—C10—C9 | 119.6 (4) | H61A—C61—H61C | 109.5 |
C10A—C10—H10 | 120.2 | N11—C111—H11A | 109.5 |
C9—C10—H10 | 120.2 | N11—C111—H11C | 109.5 |
C10—C10A—C6A | 120.8 (4) | H11A—C111—H11C | 109.5 |
C10—C10A—N11 | 120.9 (3) | N11—C111—H11B | 109.5 |
C6A—C10A—N11 | 118.2 (3) | H11A—C111—H11B | 109.5 |
C11A—N11—C10A | 116.7 (3) | H11C—C111—H11B | 109.5 |
| | | |
C11A—N1—C2—N3 | −0.3 (6) | C10—C10A—N11—C111 | −36.3 (5) |
N1—C2—N3—C4 | 6.9 (6) | C6A—C10A—N11—C111 | 145.6 (4) |
C2—N3—C4—N41 | 175.1 (3) | C2—N1—C11A—N11 | 170.8 (3) |
C2—N3—C4—C4A | −4.6 (5) | C2—N1—C11A—C4A | −9.0 (5) |
N3—C4—C4A—C11A | −3.5 (5) | C10A—N11—C11A—N1 | −133.2 (3) |
N41—C4—C4A—C11A | 176.8 (3) | C111—N11—C11A—N1 | 11.7 (5) |
N3—C4—C4A—C5 | 174.2 (3) | C10A—N11—C11A—C4A | 46.6 (5) |
N41—C4—C4A—C5 | −5.5 (5) | C111—N11—C11A—C4A | −168.5 (4) |
C4—C4A—C5—C6 | 179.1 (3) | C4—C4A—C11A—N1 | 10.6 (5) |
C11A—C4A—C5—C6 | −3.5 (5) | C5—C4A—C11A—N1 | −166.9 (4) |
C4A—C5—C6—C6A | −59.8 (4) | C4—C4A—C11A—N11 | −169.2 (3) |
C4A—C5—C6—C61 | 174.7 (3) | C5—C4A—C11A—N11 | 13.3 (6) |
C5—C6—C6A—C7 | −101.8 (4) | N3—C4—N41—N42 | 15.6 (5) |
C61—C6—C6A—C7 | 21.7 (6) | C4A—C4—N41—N42 | −164.7 (3) |
C5—C6—C6A—C10A | 75.8 (4) | C4—N41—N42—C43 | 177.2 (3) |
C61—C6—C6A—C10A | −160.7 (4) | N41—N42—C43—C431 | −177.9 (3) |
C10A—C6A—C7—C8 | 1.4 (6) | N42—C43—C431—C436 | 179.5 (4) |
C6—C6A—C7—C8 | 179.0 (4) | N42—C43—C431—C432 | −1.4 (6) |
C6A—C7—C8—C9 | 2.1 (7) | C436—C431—C432—C433 | 0.9 (6) |
C7—C8—C9—C10 | −3.6 (7) | C43—C431—C432—C433 | −178.2 (4) |
C8—C9—C10—C10A | 1.5 (7) | C431—C432—C433—C434 | 0.1 (6) |
C9—C10—C10A—C6A | 2.0 (6) | C432—C433—C434—C435 | −1.1 (6) |
C9—C10—C10A—N11 | −176.0 (4) | C432—C433—C434—Cl4 | 176.8 (3) |
C7—C6A—C10A—C10 | −3.5 (6) | C433—C434—C435—C436 | 1.0 (6) |
C6—C6A—C10A—C10 | 178.8 (4) | Cl4—C434—C435—C436 | −176.9 (3) |
C7—C6A—C10A—N11 | 174.7 (4) | C434—C435—C436—C431 | 0.1 (6) |
C6—C6A—C10A—N11 | −3.1 (5) | C432—C431—C436—C435 | −1.0 (6) |
C10—C10A—N11—C11A | 109.3 (4) | C43—C431—C436—C435 | 178.2 (4) |
C6A—C10A—N11—C11A | −68.9 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41···N3i | 0.88 (4) | 2.39 (5) | 3.207 (5) | 155 (4) |
C5—H5A···N42i | 0.99 | 2.61 | 3.504 (7) | 150 |
C43—H43···N3i | 0.95 | 2.45 | 3.295 (5) | 148 |
C433—H433···Cg1ii | 0.95 | 2.68 | 3.378 (5) | 131 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x−1, −y+1, z−3/2. |
(
RS)-(
E)-4-[2-(4-Chlorobenzylidene)hydrazinyl]-6,11-dimethyl-6,11-dihydro-5
H-benzo[
b]pyrimido[5,4-
f]azepine (II)
top
Crystal data top
C21H20ClN5 | Dx = 1.372 Mg m−3 |
Mr = 377.87 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pna21 | Cell parameters from 3084 reflections |
a = 8.8623 (4) Å | θ = 4.4–67.0° |
b = 14.4656 (7) Å | µ = 1.97 mm−1 |
c = 14.2723 (7) Å | T = 100 K |
V = 1829.69 (15) Å3 | Plate, colourless |
Z = 4 | 0.12 × 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 tube | 2669 reflections with I > 2σ(I) |
Multilayer mirror monochromator | Rint = 0.062 |
φ and ω scans | θmax = 66.9°, θmin = 4.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −9→10 |
Tmin = 0.726, Tmax = 0.871 | k = −17→17 |
22910 measured reflections | l = −15→16 |
Refinement top
Refinement on F2 | H 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) = 0.089 | Δρmax = 0.29 e Å−3 |
S = 1.06 | Δρmin = −0.23 e Å−3 |
3083 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
250 parameters | Extinction coefficient: 0.0057 (6) |
1 restraint | Absolute structure: Flack x determined using 1075 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
Primary atom site location: difference Fourier map | Absolute 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.6254 (3) | 0.4527 (2) | 0.6504 (2) | 0.0276 (7) | |
C2 | 0.6661 (4) | 0.4156 (2) | 0.5697 (2) | 0.0316 (8) | |
H2 | 0.7591 | 0.4371 | 0.5446 | 0.038* | |
N3 | 0.5950 (3) | 0.35249 (19) | 0.51894 (18) | 0.0272 (7) | |
C4 | 0.4589 (4) | 0.3292 (2) | 0.5520 (2) | 0.0249 (8) | |
C4A | 0.3975 (4) | 0.3621 (2) | 0.6370 (2) | 0.0252 (7) | |
C5 | 0.2391 (4) | 0.3341 (2) | 0.6622 (2) | 0.0287 (8) | |
H5A | 0.2395 | 0.2673 | 0.6772 | 0.034* | |
H5B | 0.1748 | 0.3425 | 0.6061 | 0.034* | |
C6 | 0.1651 (4) | 0.3856 (2) | 0.7439 (2) | 0.0280 (8) | |
H6 | 0.1737 | 0.4533 | 0.7308 | 0.034* | |
C6A | 0.2487 (4) | 0.3665 (2) | 0.8338 (2) | 0.0284 (8) | |
C7 | 0.1855 (5) | 0.3138 (2) | 0.9061 (3) | 0.0337 (9) | |
H7 | 0.0893 | 0.2862 | 0.8975 | 0.040* | |
C8 | 0.2625 (5) | 0.3013 (2) | 0.9908 (3) | 0.0361 (9) | |
H8 | 0.2185 | 0.2655 | 1.0395 | 0.043* | |
C9 | 0.4011 (4) | 0.3408 (2) | 1.0032 (3) | 0.0361 (9) | |
H9 | 0.4524 | 0.3333 | 1.0611 | 0.043* | |
C10 | 0.4676 (5) | 0.3918 (3) | 0.9322 (3) | 0.0338 (9) | |
H10 | 0.5644 | 0.4185 | 0.9415 | 0.041* | |
C10A | 0.3925 (4) | 0.4041 (2) | 0.8469 (2) | 0.0268 (8) | |
N11 | 0.4618 (3) | 0.4585 (2) | 0.7752 (2) | 0.0269 (7) | |
C11A | 0.4935 (4) | 0.4224 (2) | 0.6864 (2) | 0.0245 (8) | |
N41 | 0.3745 (3) | 0.27030 (18) | 0.4969 (2) | 0.0289 (6) | |
H41 | 0.274 (5) | 0.253 (2) | 0.514 (3) | 0.035* | |
N42 | 0.4331 (3) | 0.23699 (19) | 0.41314 (19) | 0.0277 (7) | |
C43 | 0.3317 (4) | 0.2050 (2) | 0.3577 (2) | 0.0264 (8) | |
H43 | 0.2286 | 0.2097 | 0.3753 | 0.032* | |
C431 | 0.3700 (4) | 0.1616 (2) | 0.2683 (2) | 0.0257 (8) | |
C432 | 0.5153 (5) | 0.1333 (3) | 0.2439 (3) | 0.0290 (8) | |
H432 | 0.5966 | 0.1451 | 0.2857 | 0.035* | |
C433 | 0.5433 (4) | 0.0887 (2) | 0.1602 (2) | 0.0299 (8) | |
H433 | 0.6427 | 0.0697 | 0.1443 | 0.036* | |
C434 | 0.4238 (4) | 0.0719 (2) | 0.0994 (2) | 0.0295 (8) | |
Cl4 | 0.45257 (10) | 0.01049 (6) | −0.00398 (7) | 0.0372 (3) | |
C435 | 0.2793 (5) | 0.0993 (2) | 0.1208 (2) | 0.0313 (8) | |
H435 | 0.1988 | 0.0876 | 0.0785 | 0.038* | |
C436 | 0.2525 (4) | 0.1446 (2) | 0.2059 (2) | 0.0294 (8) | |
H436 | 0.1530 | 0.1640 | 0.2211 | 0.035* | |
C61 | −0.0023 (5) | 0.3618 (3) | 0.7470 (3) | 0.0311 (8) | |
H61A | −0.0502 | 0.3952 | 0.7989 | 0.047* | |
H61B | −0.0145 | 0.2952 | 0.7565 | 0.047* | |
H61C | −0.0498 | 0.3799 | 0.6878 | 0.047* | |
C111 | 0.5616 (4) | 0.5329 (3) | 0.8079 (3) | 0.0337 (9) | |
H11A | 0.5775 | 0.5775 | 0.7571 | 0.051* | |
H11C | 0.6588 | 0.5067 | 0.8269 | 0.051* | |
H11B | 0.5150 | 0.5643 | 0.8614 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0238 (17) | 0.0353 (15) | 0.0238 (15) | −0.0030 (13) | 0.0007 (13) | −0.0023 (13) |
C2 | 0.027 (2) | 0.0346 (19) | 0.033 (2) | −0.0032 (15) | 0.0018 (16) | 0.0028 (16) |
N3 | 0.0212 (16) | 0.0349 (15) | 0.0257 (17) | −0.0033 (12) | 0.0016 (12) | 0.0017 (12) |
C4 | 0.0206 (19) | 0.0264 (17) | 0.0275 (18) | −0.0001 (14) | −0.0022 (15) | 0.0024 (15) |
C4A | 0.0247 (19) | 0.0272 (16) | 0.0238 (17) | 0.0021 (14) | −0.0005 (15) | 0.0018 (14) |
C5 | 0.022 (2) | 0.037 (2) | 0.026 (2) | −0.0011 (15) | 0.0008 (15) | −0.0001 (16) |
C6 | 0.027 (2) | 0.0320 (18) | 0.0254 (18) | 0.0005 (16) | 0.0005 (16) | 0.0006 (15) |
C6A | 0.030 (2) | 0.0311 (18) | 0.0242 (18) | 0.0026 (16) | 0.0024 (15) | 0.0008 (15) |
C7 | 0.035 (2) | 0.0345 (19) | 0.032 (2) | −0.0035 (17) | 0.0017 (17) | 0.0010 (16) |
C8 | 0.046 (2) | 0.0351 (18) | 0.0273 (19) | 0.0043 (16) | 0.0028 (18) | 0.0070 (19) |
C9 | 0.042 (2) | 0.044 (2) | 0.0225 (18) | 0.0095 (17) | −0.0022 (19) | 0.0027 (18) |
C10 | 0.029 (2) | 0.045 (2) | 0.0277 (19) | 0.0009 (17) | −0.0028 (16) | −0.0058 (17) |
C10A | 0.027 (2) | 0.0301 (18) | 0.0228 (18) | 0.0024 (15) | 0.0005 (15) | 0.0007 (15) |
N11 | 0.0248 (17) | 0.0318 (15) | 0.0239 (16) | −0.0037 (13) | 0.0000 (12) | −0.0040 (13) |
C11A | 0.0220 (19) | 0.0285 (18) | 0.0231 (18) | 0.0021 (14) | 0.0002 (14) | 0.0005 (14) |
N41 | 0.0236 (16) | 0.0388 (15) | 0.0242 (14) | −0.0023 (13) | 0.0050 (14) | −0.0041 (15) |
N42 | 0.0262 (18) | 0.0323 (16) | 0.0247 (16) | 0.0000 (13) | 0.0046 (13) | −0.0023 (13) |
C43 | 0.0224 (18) | 0.0313 (17) | 0.0255 (19) | −0.0005 (15) | 0.0037 (15) | 0.0014 (15) |
C431 | 0.026 (2) | 0.0269 (18) | 0.0238 (19) | −0.0019 (14) | 0.0003 (15) | 0.0028 (14) |
C432 | 0.025 (2) | 0.034 (2) | 0.0275 (18) | −0.0010 (17) | 0.0027 (16) | −0.0014 (16) |
C433 | 0.026 (2) | 0.0342 (19) | 0.029 (2) | −0.0002 (15) | 0.0051 (15) | 0.0013 (15) |
C434 | 0.036 (2) | 0.0298 (19) | 0.0230 (19) | 0.0025 (16) | 0.0051 (15) | 0.0017 (16) |
Cl4 | 0.0421 (6) | 0.0447 (5) | 0.0249 (4) | 0.0037 (4) | 0.0013 (5) | −0.0060 (4) |
C435 | 0.036 (2) | 0.0329 (18) | 0.0253 (19) | 0.0019 (16) | −0.0042 (16) | 0.0025 (15) |
C436 | 0.028 (2) | 0.0338 (19) | 0.0268 (18) | 0.0022 (16) | 0.0020 (16) | 0.0011 (16) |
C61 | 0.0257 (19) | 0.040 (2) | 0.0272 (17) | −0.0001 (19) | 0.0022 (15) | −0.0020 (17) |
C111 | 0.030 (2) | 0.038 (2) | 0.033 (2) | −0.0064 (17) | −0.0003 (17) | −0.0089 (17) |
Geometric parameters (Å, º) top
N1—C2 | 1.322 (5) | C10A—N11 | 1.430 (4) |
N1—C11A | 1.350 (5) | N11—C11A | 1.400 (4) |
C2—N3 | 1.324 (4) | N11—C111 | 1.469 (5) |
C2—H2 | 0.9500 | N41—N42 | 1.390 (4) |
N3—C4 | 1.338 (4) | N41—H41 | 0.96 (4) |
C4—N41 | 1.380 (4) | N42—C43 | 1.284 (4) |
C4—C4A | 1.413 (5) | C43—C431 | 1.461 (5) |
C4A—C11A | 1.408 (5) | C43—H43 | 0.9500 |
C4A—C5 | 1.505 (5) | C431—C436 | 1.393 (5) |
C5—C6 | 1.531 (5) | C431—C432 | 1.396 (5) |
C5—H5A | 0.9900 | C432—C433 | 1.381 (5) |
C5—H5B | 0.9900 | C432—H432 | 0.9500 |
C6—C6A | 1.507 (5) | C433—C434 | 1.390 (5) |
C6—C61 | 1.523 (5) | C433—H433 | 0.9500 |
C6—H6 | 1.0000 | C434—C435 | 1.375 (5) |
C6A—C10A | 1.398 (5) | C434—Cl4 | 1.741 (4) |
C6A—C7 | 1.400 (5) | C435—C436 | 1.400 (5) |
C7—C8 | 1.401 (5) | C435—H435 | 0.9500 |
C7—H7 | 0.9500 | C436—H436 | 0.9500 |
C8—C9 | 1.366 (5) | C61—H61A | 0.9800 |
C8—H8 | 0.9500 | C61—H61B | 0.9800 |
C9—C10 | 1.385 (5) | C61—H61C | 0.9800 |
C9—H9 | 0.9500 | C111—H11A | 0.9800 |
C10—C10A | 1.399 (5) | C111—H11C | 0.9800 |
C10—H10 | 0.9500 | C111—H11B | 0.9800 |
| | | |
C2—N1—C11A | 115.9 (3) | C11A—N11—C111 | 116.1 (3) |
N1—C2—N3 | 128.8 (3) | C10A—N11—C111 | 115.8 (3) |
N1—C2—H2 | 115.6 | N1—C11A—N11 | 113.4 (3) |
N3—C2—H2 | 115.6 | N1—C11A—C4A | 122.3 (3) |
C2—N3—C4 | 114.2 (3) | N11—C11A—C4A | 124.3 (3) |
N3—C4—N41 | 116.4 (3) | C4—N41—N42 | 120.1 (3) |
N3—C4—C4A | 124.4 (3) | C4—N41—H41 | 122 (2) |
N41—C4—C4A | 119.2 (3) | N42—N41—H41 | 118 (2) |
C11A—C4A—C4 | 114.0 (3) | C43—N42—N41 | 113.1 (3) |
C11A—C4A—C5 | 127.7 (3) | N42—C43—C431 | 122.0 (3) |
C4—C4A—C5 | 118.3 (3) | N42—C43—H43 | 119.0 |
C4A—C5—C6 | 116.8 (3) | C431—C43—H43 | 119.0 |
C4A—C5—H5A | 108.1 | C436—C431—C432 | 118.6 (3) |
C6—C5—H5A | 108.1 | C436—C431—C43 | 117.4 (3) |
C4A—C5—H5B | 108.1 | C432—C431—C43 | 123.9 (3) |
C6—C5—H5B | 108.1 | C433—C432—C431 | 121.3 (4) |
H5A—C5—H5B | 107.3 | C433—C432—H432 | 119.4 |
C6A—C6—C61 | 114.4 (3) | C431—C432—H432 | 119.4 |
C6A—C6—C5 | 110.4 (3) | C432—C433—C434 | 119.0 (3) |
C61—C6—C5 | 109.3 (3) | C432—C433—H433 | 120.5 |
C6A—C6—H6 | 107.5 | C434—C433—H433 | 120.5 |
C61—C6—H6 | 107.5 | C435—C434—C433 | 121.4 (3) |
C5—C6—H6 | 107.5 | C435—C434—Cl4 | 118.2 (3) |
C10A—C6A—C7 | 118.5 (3) | C433—C434—Cl4 | 120.4 (3) |
C10A—C6A—C6 | 119.4 (3) | C434—C435—C436 | 119.1 (4) |
C7—C6A—C6 | 122.0 (3) | C434—C435—H435 | 120.5 |
C6A—C7—C8 | 120.8 (4) | C436—C435—H435 | 120.5 |
C6A—C7—H7 | 119.6 | C431—C436—C435 | 120.7 (3) |
C8—C7—H7 | 119.6 | C431—C436—H436 | 119.6 |
C9—C8—C7 | 119.7 (4) | C435—C436—H436 | 119.6 |
C9—C8—H8 | 120.2 | C6—C61—H61A | 109.5 |
C7—C8—H8 | 120.2 | C6—C61—H61B | 109.5 |
C8—C9—C10 | 120.8 (4) | H61A—C61—H61B | 109.5 |
C8—C9—H9 | 119.6 | C6—C61—H61C | 109.5 |
C10—C9—H9 | 119.6 | H61A—C61—H61C | 109.5 |
C9—C10—C10A | 120.1 (4) | H61B—C61—H61C | 109.5 |
C9—C10—H10 | 119.9 | N11—C111—H11A | 109.5 |
C10A—C10—H10 | 119.9 | N11—C111—H11C | 109.5 |
C6A—C10A—C10 | 120.1 (3) | H11A—C111—H11C | 109.5 |
C6A—C10A—N11 | 120.6 (3) | N11—C111—H11B | 109.5 |
C10—C10A—N11 | 119.2 (3) | H11A—C111—H11B | 109.5 |
C11A—N11—C10A | 121.9 (3) | H11C—C111—H11B | 109.5 |
| | | |
C11A—N1—C2—N3 | 0.0 (5) | C6A—C10A—N11—C111 | 147.7 (3) |
N1—C2—N3—C4 | 5.2 (5) | C10—C10A—N11—C111 | −29.8 (5) |
C2—N3—C4—N41 | 174.1 (3) | C2—N1—C11A—N11 | 175.3 (3) |
C2—N3—C4—C4A | −4.6 (5) | C2—N1—C11A—C4A | −6.1 (5) |
N3—C4—C4A—C11A | −0.6 (5) | C10A—N11—C11A—N1 | −141.9 (3) |
N41—C4—C4A—C11A | −179.3 (3) | C111—N11—C11A—N1 | 9.3 (4) |
N3—C4—C4A—C5 | 176.4 (3) | C10A—N11—C11A—C4A | 39.6 (5) |
N41—C4—C4A—C5 | −2.2 (5) | C111—N11—C11A—C4A | −169.3 (3) |
C11A—C4A—C5—C6 | 8.2 (5) | C4—C4A—C11A—N1 | 6.3 (5) |
C4—C4A—C5—C6 | −168.3 (3) | C5—C4A—C11A—N1 | −170.4 (3) |
C4A—C5—C6—C6A | −64.2 (4) | C4—C4A—C11A—N11 | −175.2 (3) |
C4A—C5—C6—C61 | 169.1 (3) | C5—C4A—C11A—N11 | 8.1 (6) |
C61—C6—C6A—C10A | −165.6 (3) | N3—C4—N41—N42 | 1.4 (4) |
C5—C6—C6A—C10A | 70.6 (4) | C4A—C4—N41—N42 | −179.8 (3) |
C61—C6—C6A—C7 | 12.9 (5) | C4—N41—N42—C43 | −161.9 (3) |
C5—C6—C6A—C7 | −110.9 (4) | N41—N42—C43—C431 | −176.3 (3) |
C10A—C6A—C7—C8 | 1.9 (5) | N42—C43—C431—C436 | −168.5 (3) |
C6—C6A—C7—C8 | −176.5 (3) | N42—C43—C431—C432 | 14.0 (5) |
C6A—C7—C8—C9 | −0.1 (5) | C436—C431—C432—C433 | −0.6 (5) |
C7—C8—C9—C10 | −1.2 (5) | C43—C431—C432—C433 | 176.9 (3) |
C8—C9—C10—C10A | 0.6 (5) | C431—C432—C433—C434 | 0.1 (5) |
C7—C6A—C10A—C10 | −2.5 (5) | C432—C433—C434—C435 | 0.3 (5) |
C6—C6A—C10A—C10 | 176.0 (3) | C432—C433—C434—Cl4 | −176.6 (3) |
C7—C6A—C10A—N11 | −179.9 (3) | C433—C434—C435—C436 | −0.2 (5) |
C6—C6A—C10A—N11 | −1.4 (5) | Cl4—C434—C435—C436 | 176.8 (3) |
C9—C10—C10A—C6A | 1.3 (5) | C432—C431—C436—C435 | 0.7 (5) |
C9—C10—C10A—N11 | 178.7 (3) | C43—C431—C436—C435 | −176.9 (3) |
C6A—C10A—N11—C11A | −61.1 (5) | C434—C435—C436—C431 | −0.3 (5) |
C10—C10A—N11—C11A | 121.5 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N41—H41···N3i | 0.96 (4) | 2.20 (4) | 3.064 (4) | 149 (3) |
C43—H43···N3i | 0.95 | 2.53 | 3.223 (4) | 130 |
C6—H6···Cg2ii | 1.00 | 2.54 | 3.496 (3) | 161 |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) −x+1/2, y+1/2, z+1/2. |
Hydrogen-bond parameters (Å, °) for (I) and (II) topCompound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | N41—H41···N3i | 0.88 (4) | 2.39 (5) | 3.207 (5) | 155 (4) |
| C5—H5A···N42i | 0.99 | 2.61 | 3.504 (7) | 150 |
| C43—H43···N3i | 0.95 | 2.45 | 3.295 (5) | 148 |
| C433—H433···Cg1ii | 0.95 | 2.68 | 3.378 (5) | 131 |
(II) | N41—H41···N3iii | 0.96 (4) | 2.20 (4) | 3.064 (4) | 149 (3) |
| C43—H43···N3iii | 0.95 | 2.53 | 3.223 (4) | 130 |
| C6—H6···Cg2iv | 1.00 | 2.54 | 3.496 (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) topParameter | (I) | (II) |
Torsion and dihedral angles | | |
C4—N41—N42—C43 | 177.2 (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 1 | 65.35 (13) | 50.60 (10) |
Dihedral 2 | 16.64 (19) | 36.26 (12) |
| | |
Ring-puckering parameters | | |
Q | 0.935 (5) | 0.824 (3) |
φ2 | 31.8 (3) | 37.9 (2) |
φ3 | 293.6 (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) topC—Cl···Cg | C—Cl | Cl···Cg | C···Cg | C—Cl···Cg |
C434—Cl4···Cg2i | 1.747 (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. |