Buy article online - an online subscription or single-article purchase is required to access this article.
Two polymorphic forms of the title compound, C
24H
20Cl
2N
4, were obtained and characterized using X-ray crystal structure analysis. Colourless crystals of polymorph (I
a) were obtained from the oily mother residue. Recrystallization of polymorph (I
a) from an acetone-methanol mixture resulted in pale-yellow crystals of polymorph (I
b). The major feature distinguishing the two polymorphic forms is their interaction modes, and hence their packing arrangements. In the crystal structure of polymorph (I
a), there are N-H
N hydrogen bonds and also aromatic
-
stacking interactions between molecules. The molecules of polymorph (I
b) are linked by N-H
Cl hydrogen bonds only.
Supporting information
CCDC references: 609416; 609417
Compound (I) was obtained as a yellowish oil using the procedure described previously by Cieplik et al. (1995). Colourless crystals of polymorph (Ia) were grown by slow evaporation of a solution of the oily residue in an acetone–methanol mixture (1:4 v/v). Pale-yellow crystals of polymorph (Ib) were obtained via recrystallization of (Ia) from an acetone–methanol mixture (4:1 v/v).
The N-bonded H atoms were found in difference Fourier maps and refined with Uiso(H) = 1.2Ueq(N). The remaining H atoms were treated as riding, with C—H distances in the range 0.95–0.99 Å, and refined with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl H.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998); software used to prepare material for publication: SHELXL97.
(Ia)
N-(4-chlorophenyl)-5-{[(4-chlorophenyl)amino]methyl}-6-methyl-2- phenylpyrimidin-4-amine
top
Crystal data top
C24H20Cl2N4 | Dx = 1.369 Mg m−3 |
Mr = 435.34 | Melting point: 190 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 12344 reflections |
a = 7.378 (3) Å | θ = 4.5–27.5° |
b = 23.875 (6) Å | µ = 0.33 mm−1 |
c = 23.984 (6) Å | T = 100 K |
V = 4225 (2) Å3 | Plate, colourless |
Z = 8 | 0.50 × 0.15 × 0.05 mm |
F(000) = 1808 | |
Data collection top
Kuma KM4 CCD κ-geometry diffractometer | 3240 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.075 |
Graphite monochromator | θmax = 27.5°, θmin = 4.5° |
Detector resolution: 0 pixels mm-1 | h = −7→9 |
ω scans | k = −24→31 |
34892 measured reflections | l = −31→29 |
4829 independent reflections | |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | w = 1/[σ2(Fo2) + (0.0597P)2 where P = (Fo2 + 2Fc2)/3 |
4829 reflections | (Δ/σ)max < 0.001 |
278 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C24H20Cl2N4 | V = 4225 (2) Å3 |
Mr = 435.34 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.378 (3) Å | µ = 0.33 mm−1 |
b = 23.875 (6) Å | T = 100 K |
c = 23.984 (6) Å | 0.50 × 0.15 × 0.05 mm |
Data collection top
Kuma KM4 CCD κ-geometry diffractometer | 3240 reflections with I > 2σ(I) |
34892 measured reflections | Rint = 0.075 |
4829 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.075 | 0 restraints |
wR(F2) = 0.148 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.15 | Δρmax = 0.58 e Å−3 |
4829 reflections | Δρmin = −0.30 e Å−3 |
278 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Diffraction data for I were collected on a Xcalibur PX ω-geometry diffractometer equipped with an Oxford Cryosystems low-temperature device. The crystal structure was solved by direct methods using the SHELXS97 program (Sheldrick, 1990) and refined using SHELXL97 (Sheldrick, 1997). The full-matrix least-squares were completed, using anisotropic parameters for all non H-atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl4 | 0.20555 (11) | 0.71671 (3) | 0.36059 (3) | 0.0266 (2) | |
Cl5 | 0.28914 (12) | 0.28069 (4) | 0.61868 (3) | 0.0399 (3) | |
C61 | 0.5135 (4) | 0.29693 (11) | 0.24457 (12) | 0.0242 (7) | |
H61A | 0.5318 | 0.2846 | 0.2060 | 0.036* | |
H61B | 0.4252 | 0.2723 | 0.2628 | 0.036* | |
H61C | 0.6289 | 0.2953 | 0.2647 | 0.036* | |
C6 | 0.4434 (4) | 0.35619 (11) | 0.24487 (12) | 0.0184 (6) | |
N1 | 0.4188 (3) | 0.37939 (9) | 0.19362 (9) | 0.0198 (6) | |
C2 | 0.3554 (4) | 0.43214 (11) | 0.19285 (11) | 0.0181 (6) | |
C21 | 0.3198 (4) | 0.45829 (11) | 0.13745 (12) | 0.0191 (6) | |
C22 | 0.3602 (4) | 0.43067 (12) | 0.08810 (12) | 0.0225 (7) | |
H22 | 0.4138 | 0.3945 | 0.0893 | 0.027* | |
C23 | 0.3233 (4) | 0.45521 (13) | 0.03712 (12) | 0.0301 (8) | |
H23 | 0.3531 | 0.4360 | 0.0037 | 0.036* | |
C24 | 0.2433 (4) | 0.50742 (14) | 0.03453 (13) | 0.0333 (8) | |
H24 | 0.2171 | 0.5241 | −0.0005 | 0.040* | |
C25 | 0.2015 (4) | 0.53532 (13) | 0.08368 (13) | 0.0322 (8) | |
H25 | 0.1460 | 0.5712 | 0.0823 | 0.039* | |
C26 | 0.2406 (4) | 0.51102 (12) | 0.13485 (12) | 0.0250 (7) | |
H26 | 0.2130 | 0.5306 | 0.1683 | 0.030* | |
N3 | 0.3180 (3) | 0.46380 (9) | 0.23722 (9) | 0.0186 (5) | |
C4 | 0.3440 (4) | 0.44081 (11) | 0.28706 (11) | 0.0183 (6) | |
N4 | 0.3069 (3) | 0.47235 (10) | 0.33327 (10) | 0.0212 (6) | |
H4 | 0.293 (4) | 0.4552 (12) | 0.3635 (13) | 0.025* | |
C41 | 0.2765 (4) | 0.53068 (11) | 0.33572 (11) | 0.0192 (6) | |
C42 | 0.3541 (4) | 0.56818 (12) | 0.29829 (12) | 0.0243 (7) | |
H42 | 0.4231 | 0.5546 | 0.2677 | 0.029* | |
C43 | 0.3311 (4) | 0.62540 (12) | 0.30549 (12) | 0.0263 (7) | |
H43 | 0.3849 | 0.6511 | 0.2801 | 0.032* | |
C44 | 0.2293 (4) | 0.64472 (11) | 0.34990 (11) | 0.0202 (7) | |
C45 | 0.1504 (4) | 0.60820 (12) | 0.38682 (12) | 0.0221 (7) | |
H45 | 0.0793 | 0.6220 | 0.4168 | 0.026* | |
C46 | 0.1753 (4) | 0.55118 (12) | 0.38001 (11) | 0.0209 (7) | |
H46 | 0.1226 | 0.5258 | 0.4059 | 0.025* | |
C5 | 0.4077 (4) | 0.38528 (11) | 0.29363 (11) | 0.0179 (6) | |
C57 | 0.4425 (4) | 0.36231 (12) | 0.35113 (11) | 0.0215 (7) | |
H57A | 0.4923 | 0.3239 | 0.3480 | 0.026* | |
H57B | 0.5341 | 0.3859 | 0.3701 | 0.026* | |
N5 | 0.2776 (4) | 0.36087 (10) | 0.38460 (10) | 0.0209 (6) | |
H5 | 0.187 (4) | 0.3505 (13) | 0.3662 (12) | 0.025* | |
C51 | 0.2840 (4) | 0.34056 (11) | 0.43936 (11) | 0.0189 (6) | |
C52 | 0.4367 (4) | 0.34795 (12) | 0.47281 (12) | 0.0227 (7) | |
H52 | 0.5409 | 0.3659 | 0.4580 | 0.027* | |
C53 | 0.4378 (4) | 0.32925 (12) | 0.52777 (12) | 0.0255 (7) | |
H53 | 0.5427 | 0.3341 | 0.5502 | 0.031* | |
C54 | 0.2867 (4) | 0.30373 (12) | 0.54934 (12) | 0.0256 (7) | |
C55 | 0.1341 (4) | 0.29545 (12) | 0.51717 (12) | 0.0247 (7) | |
H55 | 0.0305 | 0.2775 | 0.5324 | 0.030* | |
C56 | 0.1338 (4) | 0.31362 (11) | 0.46229 (12) | 0.0224 (7) | |
H56 | 0.0294 | 0.3076 | 0.4399 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl4 | 0.0333 (5) | 0.0167 (3) | 0.0299 (4) | 0.0014 (3) | 0.0024 (4) | 0.0000 (3) |
Cl5 | 0.0367 (5) | 0.0634 (6) | 0.0194 (4) | 0.0065 (5) | 0.0023 (4) | 0.0129 (4) |
C61 | 0.0252 (17) | 0.0197 (14) | 0.0276 (17) | 0.0006 (13) | 0.0053 (14) | −0.0007 (13) |
C6 | 0.0139 (16) | 0.0172 (13) | 0.0241 (16) | −0.0026 (12) | 0.0025 (12) | 0.0010 (13) |
N1 | 0.0199 (14) | 0.0196 (12) | 0.0201 (13) | −0.0018 (11) | 0.0044 (11) | 0.0007 (10) |
C2 | 0.0129 (15) | 0.0216 (15) | 0.0197 (15) | −0.0042 (13) | 0.0021 (12) | −0.0001 (12) |
C21 | 0.0147 (16) | 0.0215 (15) | 0.0213 (15) | −0.0028 (13) | −0.0006 (13) | 0.0033 (12) |
C22 | 0.0238 (18) | 0.0221 (15) | 0.0216 (16) | −0.0016 (14) | 0.0015 (13) | 0.0008 (13) |
C23 | 0.035 (2) | 0.0368 (19) | 0.0184 (16) | −0.0079 (16) | 0.0007 (14) | −0.0033 (14) |
C24 | 0.037 (2) | 0.0411 (19) | 0.0217 (17) | −0.0039 (17) | −0.0049 (15) | 0.0088 (15) |
C25 | 0.032 (2) | 0.0312 (17) | 0.0332 (19) | 0.0064 (16) | 0.0012 (16) | 0.0097 (15) |
C26 | 0.0246 (18) | 0.0296 (16) | 0.0208 (16) | 0.0039 (15) | 0.0020 (13) | 0.0002 (13) |
N3 | 0.0207 (14) | 0.0178 (12) | 0.0172 (12) | −0.0019 (10) | 0.0000 (11) | 0.0000 (10) |
C4 | 0.0154 (16) | 0.0218 (15) | 0.0178 (15) | −0.0046 (13) | 0.0015 (12) | −0.0025 (12) |
N4 | 0.0322 (15) | 0.0179 (12) | 0.0135 (12) | −0.0013 (11) | 0.0023 (12) | 0.0006 (10) |
C41 | 0.0237 (17) | 0.0178 (13) | 0.0163 (14) | −0.0029 (13) | −0.0038 (13) | −0.0012 (11) |
C42 | 0.0282 (18) | 0.0229 (15) | 0.0217 (16) | −0.0002 (14) | 0.0046 (14) | −0.0030 (13) |
C43 | 0.0332 (19) | 0.0256 (16) | 0.0200 (16) | −0.0058 (15) | 0.0029 (14) | 0.0044 (13) |
C44 | 0.0244 (17) | 0.0148 (13) | 0.0214 (15) | −0.0007 (13) | −0.0042 (13) | −0.0011 (12) |
C45 | 0.0233 (17) | 0.0241 (15) | 0.0188 (15) | −0.0010 (14) | 0.0033 (13) | −0.0025 (12) |
C46 | 0.0240 (18) | 0.0216 (14) | 0.0171 (15) | −0.0060 (14) | 0.0007 (13) | 0.0020 (12) |
C5 | 0.0150 (15) | 0.0186 (14) | 0.0200 (15) | −0.0042 (12) | 0.0018 (12) | 0.0011 (12) |
C57 | 0.0210 (17) | 0.0203 (15) | 0.0231 (16) | −0.0009 (13) | 0.0004 (13) | 0.0027 (12) |
N5 | 0.0194 (14) | 0.0254 (13) | 0.0179 (13) | −0.0025 (12) | −0.0021 (11) | 0.0032 (10) |
C51 | 0.0255 (17) | 0.0145 (13) | 0.0167 (14) | 0.0003 (14) | 0.0002 (14) | −0.0006 (11) |
C52 | 0.0248 (18) | 0.0230 (16) | 0.0204 (16) | 0.0007 (14) | 0.0032 (13) | 0.0012 (13) |
C53 | 0.0282 (19) | 0.0279 (17) | 0.0204 (16) | 0.0041 (15) | −0.0025 (14) | −0.0014 (13) |
C54 | 0.0342 (19) | 0.0263 (15) | 0.0163 (15) | 0.0059 (15) | 0.0028 (15) | 0.0026 (13) |
C55 | 0.0287 (18) | 0.0206 (16) | 0.0246 (16) | 0.0031 (14) | 0.0066 (14) | 0.0005 (13) |
C56 | 0.0279 (18) | 0.0180 (15) | 0.0214 (16) | 0.0030 (14) | −0.0021 (13) | −0.0010 (12) |
Geometric parameters (Å, º) top
Cl4—C44 | 1.746 (3) | C41—C46 | 1.388 (4) |
Cl5—C54 | 1.752 (3) | C41—C42 | 1.391 (4) |
C61—C6 | 1.506 (4) | C42—C43 | 1.387 (4) |
C61—H61A | 0.9800 | C42—H42 | 0.9500 |
C61—H61B | 0.9800 | C43—C44 | 1.383 (4) |
C61—H61C | 0.9800 | C43—H43 | 0.9500 |
C6—N1 | 1.360 (3) | C44—C45 | 1.372 (4) |
C6—C5 | 1.385 (4) | C45—C46 | 1.383 (4) |
N1—C2 | 1.344 (3) | C45—H45 | 0.9500 |
C2—N3 | 1.334 (3) | C46—H46 | 0.9500 |
C2—C21 | 1.491 (4) | C5—C57 | 1.506 (4) |
C21—C22 | 1.387 (4) | C57—N5 | 1.458 (4) |
C21—C26 | 1.390 (4) | C57—H57A | 0.9900 |
C22—C23 | 1.383 (4) | C57—H57B | 0.9900 |
C22—H22 | 0.9500 | N5—C51 | 1.401 (3) |
C23—C24 | 1.381 (4) | N5—H5 | 0.84 (3) |
C23—H23 | 0.9500 | C51—C56 | 1.394 (4) |
C24—C25 | 1.389 (5) | C51—C52 | 1.394 (4) |
C24—H24 | 0.9500 | C52—C53 | 1.392 (4) |
C25—C26 | 1.388 (4) | C52—H52 | 0.9500 |
C25—H25 | 0.9500 | C53—C54 | 1.372 (4) |
C26—H26 | 0.9500 | C53—H53 | 0.9500 |
N3—C4 | 1.329 (3) | C54—C55 | 1.379 (4) |
C4—N4 | 1.368 (3) | C55—C56 | 1.386 (4) |
C4—C5 | 1.416 (4) | C55—H55 | 0.9500 |
N4—C41 | 1.412 (3) | C56—H56 | 0.9500 |
N4—H4 | 0.84 (3) | | |
| | | |
C6—C61—H61A | 109.5 | C41—C42—H42 | 119.9 |
C6—C61—H61B | 109.5 | C44—C43—C42 | 119.4 (3) |
H61A—C61—H61B | 109.5 | C44—C43—H43 | 120.3 |
C6—C61—H61C | 109.5 | C42—C43—H43 | 120.3 |
H61A—C61—H61C | 109.5 | C45—C44—C43 | 121.0 (3) |
H61B—C61—H61C | 109.5 | C45—C44—Cl4 | 119.2 (2) |
N1—C6—C5 | 122.2 (2) | C43—C44—Cl4 | 119.7 (2) |
N1—C6—C61 | 115.1 (2) | C44—C45—C46 | 119.5 (3) |
C5—C6—C61 | 122.7 (3) | C44—C45—H45 | 120.2 |
C2—N1—C6 | 116.1 (2) | C46—C45—H45 | 120.2 |
N3—C2—N1 | 126.3 (3) | C45—C46—C41 | 120.6 (3) |
N3—C2—C21 | 115.9 (2) | C45—C46—H46 | 119.7 |
N1—C2—C21 | 117.8 (2) | C41—C46—H46 | 119.7 |
C22—C21—C26 | 118.9 (3) | C6—C5—C4 | 116.0 (3) |
C22—C21—C2 | 121.6 (2) | C6—C5—C57 | 123.9 (2) |
C26—C21—C2 | 119.6 (3) | C4—C5—C57 | 120.0 (2) |
C23—C22—C21 | 120.7 (3) | N5—C57—C5 | 111.7 (2) |
C23—C22—H22 | 119.6 | N5—C57—H57A | 109.3 |
C21—C22—H22 | 119.6 | C5—C57—H57A | 109.3 |
C24—C23—C22 | 120.4 (3) | N5—C57—H57B | 109.3 |
C24—C23—H23 | 119.8 | C5—C57—H57B | 109.3 |
C22—C23—H23 | 119.8 | H57A—C57—H57B | 107.9 |
C23—C24—C25 | 119.3 (3) | C51—N5—C57 | 119.8 (2) |
C23—C24—H24 | 120.3 | C51—N5—H5 | 115 (2) |
C25—C24—H24 | 120.3 | C57—N5—H5 | 112 (2) |
C26—C25—C24 | 120.3 (3) | C56—C51—C52 | 118.3 (3) |
C26—C25—H25 | 119.9 | C56—C51—N5 | 120.2 (3) |
C24—C25—H25 | 119.9 | C52—C51—N5 | 121.5 (3) |
C25—C26—C21 | 120.4 (3) | C53—C52—C51 | 120.6 (3) |
C25—C26—H26 | 119.8 | C53—C52—H52 | 119.7 |
C21—C26—H26 | 119.8 | C51—C52—H52 | 119.7 |
C4—N3—C2 | 117.0 (2) | C54—C53—C52 | 119.7 (3) |
N3—C4—N4 | 118.2 (2) | C54—C53—H53 | 120.2 |
N3—C4—C5 | 122.3 (2) | C52—C53—H53 | 120.2 |
N4—C4—C5 | 119.5 (3) | C53—C54—C55 | 121.1 (3) |
C4—N4—C41 | 127.5 (2) | C53—C54—Cl5 | 119.3 (2) |
C4—N4—H4 | 117 (2) | C55—C54—Cl5 | 119.7 (2) |
C41—N4—H4 | 115 (2) | C54—C55—C56 | 119.2 (3) |
C46—C41—C42 | 119.2 (3) | C54—C55—H55 | 120.4 |
C46—C41—N4 | 117.7 (2) | C56—C55—H55 | 120.4 |
C42—C41—N4 | 122.9 (3) | C55—C56—C51 | 121.2 (3) |
C43—C42—C41 | 120.2 (3) | C55—C56—H56 | 119.4 |
C43—C42—H42 | 119.9 | C51—C56—H56 | 119.4 |
| | | |
C5—C6—N1—C2 | −0.8 (4) | C43—C44—C45—C46 | 0.9 (4) |
C61—C6—N1—C2 | 179.6 (2) | Cl4—C44—C45—C46 | −177.2 (2) |
C6—N1—C2—N3 | 1.4 (4) | C44—C45—C46—C41 | −1.1 (4) |
C6—N1—C2—C21 | −177.7 (2) | C42—C41—C46—C45 | 0.4 (4) |
N3—C2—C21—C22 | 177.2 (3) | N4—C41—C46—C45 | 175.8 (3) |
N1—C2—C21—C22 | −3.6 (4) | N1—C6—C5—C4 | −0.1 (4) |
N3—C2—C21—C26 | −4.3 (4) | C61—C6—C5—C4 | 179.5 (3) |
N1—C2—C21—C26 | 174.9 (3) | N1—C6—C5—C57 | −176.6 (3) |
C26—C21—C22—C23 | 0.3 (4) | C61—C6—C5—C57 | 3.0 (4) |
C2—C21—C22—C23 | 178.8 (3) | N3—C4—C5—C6 | 0.6 (4) |
C21—C22—C23—C24 | −0.8 (5) | N4—C4—C5—C6 | −179.5 (2) |
C22—C23—C24—C25 | 0.5 (5) | N3—C4—C5—C57 | 177.3 (2) |
C23—C24—C25—C26 | 0.3 (5) | N4—C4—C5—C57 | −2.9 (4) |
C24—C25—C26—C21 | −0.8 (5) | C6—C5—C57—N5 | −121.7 (3) |
C22—C21—C26—C25 | 0.5 (4) | C4—C5—C57—N5 | 61.9 (3) |
C2—C21—C26—C25 | −178.1 (3) | C5—C57—N5—C51 | 179.8 (2) |
N1—C2—N3—C4 | −0.8 (4) | C57—N5—C51—C56 | −148.8 (3) |
C21—C2—N3—C4 | 178.2 (2) | C57—N5—C51—C52 | 33.1 (4) |
C2—N3—C4—N4 | 179.9 (2) | C56—C51—C52—C53 | −0.5 (4) |
C2—N3—C4—C5 | −0.2 (4) | N5—C51—C52—C53 | 177.6 (3) |
N3—C4—N4—C41 | −13.3 (4) | C51—C52—C53—C54 | −0.6 (4) |
C5—C4—N4—C41 | 166.9 (3) | C52—C53—C54—C55 | 1.0 (4) |
C4—N4—C41—C46 | 155.5 (3) | C52—C53—C54—Cl5 | −179.7 (2) |
C4—N4—C41—C42 | −29.3 (5) | C53—C54—C55—C56 | −0.4 (4) |
C46—C41—C42—C43 | 0.4 (4) | Cl5—C54—C55—C56 | −179.7 (2) |
N4—C41—C42—C43 | −174.8 (3) | C54—C55—C56—C51 | −0.7 (4) |
C41—C42—C43—C44 | −0.5 (4) | C52—C51—C56—C55 | 1.1 (4) |
C42—C43—C44—C45 | −0.1 (4) | N5—C51—C56—C55 | −177.0 (3) |
C42—C43—C44—Cl4 | 178.0 (2) | | |
(Ib)
N-(4-chlorophenyl)-5-{[(4-chlorophenyl)amino]methyl}-6-methyl-2- phenylpyrimidin-4-amine
top
Crystal data top
C24H20Cl2N4 | F(000) = 904 |
Mr = 435.34 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/c | Melting point: 190 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 15.332 (4) Å | Cell parameters from 16673 reflections |
b = 7.993 (2) Å | θ = 4.7–28.1° |
c = 17.235 (4) Å | µ = 0.34 mm−1 |
β = 104.06 (3)° | T = 100 K |
V = 2048.9 (9) Å3 | Plate, pale yellow |
Z = 4 | 0.16 × 0.15 × 0.10 mm |
Data collection top
Kuma KM4 CCD κ-geometry diffractometr | 3895 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 28.1°, θmin = 4.7° |
Detector resolution: 0 pixels mm-1 | h = −20→20 |
ω scans | k = −8→10 |
26386 measured reflections | l = −22→22 |
4952 independent reflections | |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0769P)2 + 0.4721P] where P = (Fo2 + 2Fc2)/3 |
4952 reflections | (Δ/σ)max = 0.001 |
278 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C24H20Cl2N4 | V = 2048.9 (9) Å3 |
Mr = 435.34 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.332 (4) Å | µ = 0.34 mm−1 |
b = 7.993 (2) Å | T = 100 K |
c = 17.235 (4) Å | 0.16 × 0.15 × 0.10 mm |
β = 104.06 (3)° | |
Data collection top
Kuma KM4 CCD κ-geometry diffractometr | 3895 reflections with I > 2σ(I) |
26386 measured reflections | Rint = 0.043 |
4952 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.49 e Å−3 |
4952 reflections | Δρmin = −0.30 e Å−3 |
278 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Diffraction data for I were collected on a Xcalibur PX ω-geometry diffractometer equipped with an Oxford Cryosystems low-temperature device. The crystal structure was solved by direct methods using the SHELXS97 program (Sheldrick, 1990) and refined using SHELXL97 (Sheldrick, 1997). The full-matrix least-squares were completed, using anisotropic parameters for all non H-atoms. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl4 | 0.66123 (4) | 0.33111 (7) | 0.37837 (3) | 0.02978 (17) | |
Cl5 | 0.33415 (4) | 0.49845 (8) | 0.89159 (4) | 0.03679 (18) | |
N1 | 0.88258 (12) | 0.3531 (2) | 0.91081 (10) | 0.0211 (4) | |
C2 | 0.86547 (13) | 0.2882 (3) | 0.83714 (12) | 0.0186 (4) | |
C21 | 0.90082 (13) | 0.1179 (3) | 0.82712 (12) | 0.0189 (4) | |
C22 | 0.95206 (14) | 0.0301 (3) | 0.89212 (13) | 0.0247 (5) | |
H22 | 0.9675 | 0.0811 | 0.9434 | 0.030* | |
C23 | 0.98096 (15) | −0.1325 (3) | 0.88235 (14) | 0.0276 (5) | |
H23 | 1.0151 | −0.1922 | 0.9272 | 0.033* | |
C24 | 0.96003 (15) | −0.2073 (3) | 0.80745 (15) | 0.0270 (5) | |
H24 | 0.9801 | −0.3177 | 0.8009 | 0.032* | |
C25 | 0.90980 (16) | −0.1202 (3) | 0.74239 (14) | 0.0266 (5) | |
H25 | 0.8957 | −0.1711 | 0.6910 | 0.032* | |
C26 | 0.87980 (15) | 0.0411 (3) | 0.75156 (13) | 0.0230 (5) | |
H26 | 0.8450 | 0.0994 | 0.7066 | 0.028* | |
N3 | 0.81732 (12) | 0.3611 (2) | 0.77059 (10) | 0.0194 (4) | |
C4 | 0.78123 (14) | 0.5096 (2) | 0.77805 (12) | 0.0187 (4) | |
N4 | 0.73384 (12) | 0.5890 (2) | 0.70989 (10) | 0.0215 (4) | |
H4 | 0.7017 (17) | 0.676 (3) | 0.7178 (15) | 0.026* | |
C41 | 0.72011 (14) | 0.5287 (3) | 0.63102 (12) | 0.0206 (4) | |
C42 | 0.78666 (15) | 0.4462 (3) | 0.60340 (13) | 0.0232 (5) | |
H42 | 0.8444 | 0.4303 | 0.6382 | 0.028* | |
C43 | 0.76924 (15) | 0.3872 (3) | 0.52539 (13) | 0.0245 (5) | |
H43 | 0.8144 | 0.3296 | 0.5068 | 0.029* | |
C44 | 0.68490 (15) | 0.4135 (3) | 0.47504 (12) | 0.0226 (5) | |
C45 | 0.61949 (15) | 0.5026 (3) | 0.50023 (13) | 0.0250 (5) | |
H45 | 0.5629 | 0.5240 | 0.4644 | 0.030* | |
C46 | 0.63733 (15) | 0.5600 (3) | 0.57807 (13) | 0.0233 (5) | |
H46 | 0.5927 | 0.6215 | 0.5957 | 0.028* | |
C5 | 0.78988 (14) | 0.5870 (3) | 0.85380 (12) | 0.0201 (4) | |
C57 | 0.74856 (15) | 0.7570 (3) | 0.86288 (13) | 0.0239 (5) | |
H57A | 0.7455 | 0.7706 | 0.9192 | 0.029* | |
H57B | 0.7889 | 0.8453 | 0.8512 | 0.029* | |
N5 | 0.65831 (13) | 0.7829 (2) | 0.81104 (11) | 0.0244 (4) | |
H5 | 0.6506 (17) | 0.890 (3) | 0.7994 (15) | 0.029* | |
C51 | 0.58325 (15) | 0.7165 (3) | 0.83278 (12) | 0.0217 (4) | |
C52 | 0.58972 (14) | 0.5813 (3) | 0.88475 (13) | 0.0224 (4) | |
H52 | 0.6470 | 0.5346 | 0.9083 | 0.027* | |
C53 | 0.51332 (15) | 0.5139 (3) | 0.90247 (13) | 0.0237 (5) | |
H53 | 0.5183 | 0.4210 | 0.9376 | 0.028* | |
C54 | 0.42980 (15) | 0.5828 (3) | 0.86870 (13) | 0.0258 (5) | |
C55 | 0.42173 (16) | 0.7183 (3) | 0.81736 (13) | 0.0270 (5) | |
H55 | 0.3643 | 0.7655 | 0.7948 | 0.032* | |
C56 | 0.49781 (16) | 0.7847 (3) | 0.79899 (13) | 0.0261 (5) | |
H56 | 0.4922 | 0.8769 | 0.7633 | 0.031* | |
C6 | 0.84411 (14) | 0.5028 (3) | 0.91826 (13) | 0.0209 (4) | |
C61 | 0.86469 (16) | 0.5710 (3) | 1.00255 (13) | 0.0288 (5) | |
H61A | 0.9119 | 0.5032 | 1.0370 | 0.043* | |
H61B | 0.8103 | 0.5669 | 1.0228 | 0.043* | |
H61C | 0.8853 | 0.6871 | 1.0025 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl4 | 0.0434 (4) | 0.0247 (3) | 0.0194 (3) | −0.0037 (2) | 0.0041 (2) | −0.0016 (2) |
Cl5 | 0.0213 (3) | 0.0443 (4) | 0.0447 (4) | −0.0003 (2) | 0.0078 (3) | −0.0010 (3) |
N1 | 0.0212 (9) | 0.0237 (9) | 0.0178 (9) | −0.0022 (7) | 0.0034 (7) | 0.0006 (7) |
C2 | 0.0169 (10) | 0.0205 (10) | 0.0196 (10) | −0.0035 (8) | 0.0066 (8) | 0.0012 (8) |
C21 | 0.0160 (10) | 0.0189 (10) | 0.0225 (10) | −0.0019 (8) | 0.0058 (8) | 0.0023 (8) |
C22 | 0.0202 (11) | 0.0289 (11) | 0.0233 (11) | −0.0001 (9) | 0.0018 (9) | 0.0021 (9) |
C23 | 0.0199 (11) | 0.0282 (12) | 0.0341 (13) | 0.0031 (9) | 0.0051 (9) | 0.0065 (10) |
C24 | 0.0227 (11) | 0.0206 (11) | 0.0410 (13) | 0.0028 (9) | 0.0142 (10) | 0.0022 (10) |
C25 | 0.0307 (12) | 0.0237 (11) | 0.0283 (12) | −0.0031 (9) | 0.0127 (10) | −0.0040 (9) |
C26 | 0.0237 (11) | 0.0239 (11) | 0.0220 (11) | 0.0003 (9) | 0.0066 (9) | 0.0032 (9) |
N3 | 0.0208 (9) | 0.0198 (9) | 0.0176 (8) | −0.0005 (7) | 0.0047 (7) | 0.0008 (7) |
C4 | 0.0181 (10) | 0.0198 (10) | 0.0188 (10) | −0.0025 (8) | 0.0055 (8) | 0.0009 (8) |
N4 | 0.0251 (10) | 0.0211 (9) | 0.0180 (9) | 0.0050 (8) | 0.0050 (7) | −0.0005 (7) |
C41 | 0.0247 (11) | 0.0204 (10) | 0.0174 (10) | 0.0005 (8) | 0.0065 (8) | 0.0026 (8) |
C42 | 0.0218 (11) | 0.0269 (11) | 0.0206 (10) | 0.0048 (9) | 0.0044 (9) | 0.0040 (9) |
C43 | 0.0295 (12) | 0.0236 (11) | 0.0220 (11) | 0.0048 (9) | 0.0094 (9) | 0.0027 (9) |
C44 | 0.0321 (12) | 0.0197 (10) | 0.0158 (10) | −0.0038 (9) | 0.0055 (9) | 0.0025 (8) |
C45 | 0.0220 (11) | 0.0298 (12) | 0.0209 (11) | −0.0006 (9) | 0.0010 (9) | 0.0050 (9) |
C46 | 0.0223 (11) | 0.0255 (11) | 0.0225 (11) | 0.0042 (9) | 0.0063 (9) | 0.0037 (9) |
C5 | 0.0201 (10) | 0.0203 (10) | 0.0212 (10) | −0.0042 (8) | 0.0077 (8) | −0.0013 (8) |
C57 | 0.0263 (11) | 0.0216 (10) | 0.0248 (11) | −0.0047 (9) | 0.0083 (9) | −0.0036 (9) |
N5 | 0.0304 (10) | 0.0183 (9) | 0.0261 (10) | 0.0043 (8) | 0.0102 (8) | 0.0029 (8) |
C51 | 0.0278 (11) | 0.0212 (10) | 0.0170 (10) | 0.0028 (9) | 0.0072 (9) | −0.0059 (8) |
C52 | 0.0208 (11) | 0.0225 (10) | 0.0228 (11) | 0.0050 (9) | 0.0032 (9) | −0.0033 (9) |
C53 | 0.0250 (11) | 0.0235 (11) | 0.0221 (11) | 0.0017 (9) | 0.0048 (9) | 0.0008 (9) |
C54 | 0.0219 (11) | 0.0286 (12) | 0.0267 (11) | −0.0003 (9) | 0.0058 (9) | −0.0081 (9) |
C55 | 0.0258 (12) | 0.0326 (12) | 0.0196 (10) | 0.0103 (10) | 0.0000 (9) | −0.0057 (9) |
C56 | 0.0334 (13) | 0.0261 (11) | 0.0180 (10) | 0.0083 (10) | 0.0045 (9) | −0.0025 (9) |
C6 | 0.0219 (11) | 0.0233 (10) | 0.0185 (10) | −0.0072 (8) | 0.0073 (8) | −0.0029 (8) |
C61 | 0.0358 (13) | 0.0321 (12) | 0.0171 (11) | −0.0020 (10) | 0.0039 (9) | −0.0039 (9) |
Geometric parameters (Å, º) top
Cl4—C44 | 1.746 (2) | C43—H43 | 0.9500 |
Cl5—C54 | 1.744 (2) | C44—C45 | 1.383 (3) |
N1—C2 | 1.337 (3) | C45—C46 | 1.381 (3) |
N1—C6 | 1.353 (3) | C45—H45 | 0.9500 |
C2—N3 | 1.337 (3) | C46—H46 | 0.9500 |
C2—C21 | 1.491 (3) | C5—C6 | 1.389 (3) |
C21—C22 | 1.392 (3) | C5—C57 | 1.524 (3) |
C21—C26 | 1.405 (3) | C57—N5 | 1.468 (3) |
C22—C23 | 1.397 (3) | C57—H57A | 0.9900 |
C22—H22 | 0.9500 | C57—H57B | 0.9900 |
C23—C24 | 1.388 (3) | N5—C51 | 1.399 (3) |
C23—H23 | 0.9500 | N5—H5 | 0.88 (3) |
C24—C25 | 1.384 (3) | C51—C52 | 1.392 (3) |
C24—H24 | 0.9500 | C51—C56 | 1.408 (3) |
C25—C26 | 1.391 (3) | C52—C53 | 1.389 (3) |
C25—H25 | 0.9500 | C52—H52 | 0.9500 |
C26—H26 | 0.9500 | C53—C54 | 1.386 (3) |
N3—C4 | 1.329 (3) | C53—H53 | 0.9500 |
C4—N4 | 1.377 (3) | C54—C55 | 1.385 (3) |
C4—C5 | 1.421 (3) | C55—C56 | 1.386 (3) |
N4—C41 | 1.409 (3) | C55—H55 | 0.9500 |
N4—H4 | 0.88 (3) | C56—H56 | 0.9500 |
C41—C42 | 1.392 (3) | C6—C61 | 1.511 (3) |
C41—C46 | 1.394 (3) | C61—H61A | 0.9800 |
C42—C43 | 1.388 (3) | C61—H61B | 0.9800 |
C42—H42 | 0.9500 | C61—H61C | 0.9800 |
C43—C44 | 1.387 (3) | | |
| | | |
C2—N1—C6 | 116.32 (18) | C44—C45—H45 | 120.4 |
N1—C2—N3 | 125.84 (19) | C45—C46—C41 | 120.7 (2) |
N1—C2—C21 | 118.12 (18) | C45—C46—H46 | 119.7 |
N3—C2—C21 | 116.03 (18) | C41—C46—H46 | 119.7 |
C22—C21—C26 | 118.9 (2) | C6—C5—C4 | 115.33 (19) |
C22—C21—C2 | 121.16 (19) | C6—C5—C57 | 122.22 (19) |
C26—C21—C2 | 119.93 (19) | C4—C5—C57 | 122.29 (19) |
C21—C22—C23 | 120.4 (2) | N5—C57—C5 | 114.66 (17) |
C21—C22—H22 | 119.8 | N5—C57—H57A | 108.6 |
C23—C22—H22 | 119.8 | C5—C57—H57A | 108.6 |
C24—C23—C22 | 120.3 (2) | N5—C57—H57B | 108.6 |
C24—C23—H23 | 119.8 | C5—C57—H57B | 108.6 |
C22—C23—H23 | 119.8 | H57A—C57—H57B | 107.6 |
C25—C24—C23 | 119.6 (2) | C51—N5—C57 | 119.91 (18) |
C25—C24—H24 | 120.2 | C51—N5—H5 | 110.9 (17) |
C23—C24—H24 | 120.2 | C57—N5—H5 | 109.3 (17) |
C24—C25—C26 | 120.6 (2) | C52—C51—N5 | 122.18 (19) |
C24—C25—H25 | 119.7 | C52—C51—C56 | 118.7 (2) |
C26—C25—H25 | 119.7 | N5—C51—C56 | 119.1 (2) |
C25—C26—C21 | 120.2 (2) | C53—C52—C51 | 120.7 (2) |
C25—C26—H26 | 119.9 | C53—C52—H52 | 119.6 |
C21—C26—H26 | 119.9 | C51—C52—H52 | 119.6 |
C4—N3—C2 | 117.52 (18) | C54—C53—C52 | 119.8 (2) |
N3—C4—N4 | 118.35 (19) | C54—C53—H53 | 120.1 |
N3—C4—C5 | 121.96 (19) | C52—C53—H53 | 120.1 |
N4—C4—C5 | 119.69 (18) | C55—C54—C53 | 120.6 (2) |
C4—N4—C41 | 126.11 (18) | C55—C54—Cl5 | 119.83 (18) |
C4—N4—H4 | 115.5 (16) | C53—C54—Cl5 | 119.57 (18) |
C41—N4—H4 | 117.5 (16) | C54—C55—C56 | 119.7 (2) |
C42—C41—C46 | 119.17 (19) | C54—C55—H55 | 120.1 |
C42—C41—N4 | 122.80 (19) | C56—C55—H55 | 120.1 |
C46—C41—N4 | 117.97 (19) | C55—C56—C51 | 120.5 (2) |
C43—C42—C41 | 120.5 (2) | C55—C56—H56 | 119.8 |
C43—C42—H42 | 119.7 | C51—C56—H56 | 119.8 |
C41—C42—H42 | 119.7 | N1—C6—C5 | 122.84 (19) |
C44—C43—C42 | 119.0 (2) | N1—C6—C61 | 114.58 (19) |
C44—C43—H43 | 120.5 | C5—C6—C61 | 122.6 (2) |
C42—C43—H43 | 120.5 | C6—C61—H61A | 109.5 |
C45—C44—C43 | 121.2 (2) | C6—C61—H61B | 109.5 |
C45—C44—Cl4 | 119.70 (17) | H61A—C61—H61B | 109.5 |
C43—C44—Cl4 | 119.07 (17) | C6—C61—H61C | 109.5 |
C46—C45—C44 | 119.2 (2) | H61A—C61—H61C | 109.5 |
C46—C45—H45 | 120.4 | H61B—C61—H61C | 109.5 |
| | | |
C6—N1—C2—N3 | 3.0 (3) | C44—C45—C46—C41 | −0.1 (3) |
C6—N1—C2—C21 | −175.53 (17) | C42—C41—C46—C45 | 3.4 (3) |
N1—C2—C21—C22 | −1.5 (3) | N4—C41—C46—C45 | −179.33 (19) |
N3—C2—C21—C22 | 179.81 (19) | N3—C4—C5—C6 | 4.7 (3) |
N1—C2—C21—C26 | 176.16 (19) | N4—C4—C5—C6 | −175.66 (18) |
N3—C2—C21—C26 | −2.5 (3) | N3—C4—C5—C57 | −179.88 (19) |
C26—C21—C22—C23 | −0.8 (3) | N4—C4—C5—C57 | −0.2 (3) |
C2—C21—C22—C23 | 176.88 (19) | C6—C5—C57—N5 | −144.4 (2) |
C21—C22—C23—C24 | 1.0 (3) | C4—C5—C57—N5 | 40.5 (3) |
C22—C23—C24—C25 | −0.4 (3) | C5—C57—N5—C51 | 80.5 (2) |
C23—C24—C25—C26 | −0.3 (3) | C57—N5—C51—C52 | −22.9 (3) |
C24—C25—C26—C21 | 0.5 (3) | C57—N5—C51—C56 | 159.35 (19) |
C22—C21—C26—C25 | 0.1 (3) | N5—C51—C52—C53 | −177.28 (19) |
C2—C21—C26—C25 | −177.63 (19) | C56—C51—C52—C53 | 0.5 (3) |
N1—C2—N3—C4 | −1.7 (3) | C51—C52—C53—C54 | −0.6 (3) |
C21—C2—N3—C4 | 176.86 (17) | C52—C53—C54—C55 | 0.0 (3) |
C2—N3—C4—N4 | 177.95 (18) | C52—C53—C54—Cl5 | −179.65 (16) |
C2—N3—C4—C5 | −2.4 (3) | C53—C54—C55—C56 | 0.6 (3) |
N3—C4—N4—C41 | −0.8 (3) | Cl5—C54—C55—C56 | −179.74 (16) |
C5—C4—N4—C41 | 179.56 (19) | C54—C55—C56—C51 | −0.6 (3) |
C4—N4—C41—C42 | −39.4 (3) | C52—C51—C56—C55 | 0.1 (3) |
C4—N4—C41—C46 | 143.4 (2) | N5—C51—C56—C55 | 177.96 (19) |
C46—C41—C42—C43 | −3.7 (3) | C2—N1—C6—C5 | −0.2 (3) |
N4—C41—C42—C43 | 179.1 (2) | C2—N1—C6—C61 | 179.62 (18) |
C41—C42—C43—C44 | 0.9 (3) | C4—C5—C6—N1 | −3.3 (3) |
C42—C43—C44—C45 | 2.5 (3) | C57—C5—C6—N1 | −178.75 (19) |
C42—C43—C44—Cl4 | −177.11 (16) | C4—C5—C6—C61 | 176.85 (19) |
C43—C44—C45—C46 | −2.8 (3) | C57—C5—C6—C61 | 1.4 (3) |
Cl4—C44—C45—C46 | 176.75 (17) | | |
Experimental details
| (Ia) | (Ib) |
Crystal data |
Chemical formula | C24H20Cl2N4 | C24H20Cl2N4 |
Mr | 435.34 | 435.34 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.378 (3), 23.875 (6), 23.984 (6) | 15.332 (4), 7.993 (2), 17.235 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 104.06 (3), 90 |
V (Å3) | 4225 (2) | 2048.9 (9) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 0.34 |
Crystal size (mm) | 0.50 × 0.15 × 0.05 | 0.16 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Kuma KM4 CCD κ-geometry diffractometer | Kuma KM4 CCD κ-geometry diffractometr |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34892, 4829, 3240 | 26386, 4952, 3895 |
Rint | 0.075 | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 | 0.662 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.148, 1.15 | 0.057, 0.145, 1.12 |
No. of reflections | 4829 | 4952 |
No. of parameters | 278 | 278 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.30 | 0.49, −0.30 |
Comparison of bond lengths and torsion angles for polymorphs (Ia) and (Ib) (Å, °) topParameter | (Ia) | (Ib) |
N1-C2 | 1.344 (3) | 1.337 (2) |
C2-N3 | 1.334 (3) | 1.337 (3) |
N3-C4 | 1.329 (3) | 1.329 (3) |
C4-C5 | 1.416 (4) | 1.421 (3) |
C5-C6 | 1.385 (4) | 1.389 (3) |
C6-N1 | 1.360 (3) | 1.353 (3) |
C4-N4 | 1.368 (3) | 1.377 (3) |
N4-C41 | 1.412 (3) | 1.409 (3) |
C5-C57 | 1.506 (4) | 1.524 (3) |
C57-N5 | 1.458 (4) | 1.468 (3) |
N5-C51 | 1.401 (3) | 1.399 (3) |
N1-C2-C21-C22 | -3.6 (4) | -1.5 (3) |
N3-C4-N4-C41 | -13.3 (4) | -0.8 (3) |
C5-C4-N4-C41 | 166.9 (3) | 179.6 (2) |
C4-N4-C41-C42 | -29.3 (5) | -39.4 (3) |
C4-C5-C57-N5 | 61.9 (3) | 40.5 (3) |
C6-C5-C57-N5 | -121.7 (3) | -144.4 (2) |
C5-C57-N5-C51 | 179.8 (2) | 80.5 (2) |
C57-N5-C51-C52 | 33.1 (4) | -22.9 (3) |
C57-N5-C51-C56 | -148.8 (3) | 159.4 (2) |
Hydrogen-bonding geometry for polymorphs (Ia) and (Ib) (Å, °) top | D-H···A | D-H | H···A | D···A | D-H···A |
(Ia) | N4-H4···N5 | 0.84 (3) | 2.31 (3) | 2.940 (3) | 132 (3) |
| N5-H5···N1i | 0.84 (3) | 2.54 (3) | 3.274 (4) | 147 (3) |
(Ib) | N4-H4···N5 | 0.88 (3) | 2.07 (3) | 2.786 (3) | 138 (2) |
| N5-H5···Cl4ii | 0.88 (3) | 2.60 (3) | 3.292 (2) | 137 (2) |
Symmetry codes: (i) x − 1/2, y, 1/2 − z; (ii) x, −y + 3/2, z + 1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Pyrimidine derivatives have very interesting biological properties and many applications in the areas of pharmaceuticals. For example, alkoxy- and amino-substitued O6-benzyloxy-5-nitropyrimidines are important as potential inhibitors of the human DNA-repair protein O6-alkylguanine-DNA-transferase (Quesada et al., 2002; Glidewell et al., 2003). Several pyrimidine derivatives have been developed as agrochemicals (Maeno et al., 1990), antiviral agents, such as AZT, which is the most widely used anti-HIV drug (Gilchrist, 1997), or antifolate drugs, such as TMP and DHFR (Feeney, 2000).
In order to discover more active pyrimidine compounds displaying immunomodulatory activity, we synthesized new 6-methyl-2-phenyl-5-substitued pyrimidine derivatives (Cieplik et al., 1995). We report here the structures of two polymorphic forms of N-(4-chlorophenyl)-5-{[(4-chlorophenyl)amino]methyl}-6-methyl-2-phenylpyrimidin-4-amine, (Ia) and (Ib).
The polymorphs (Ia) (Fig. 1) and (Ib) (Fig. 2) crystallize in space group Pbca with Z = 8 and in P21/c with Z = 4, respectively. The bond lengths and angles for (Ia) and (Ib) are in accordance with anticipated values (Reference for standard values?). However, pronounced differences between these polymorphs are apparent in the conformation of the 4-chlorophenylamino group about atom C51.
In both cases, the orientation of N amide atoms with respect to each other is the result of an intramolecular N—H···N hydrogen bond between atoms N4 and N5, which generates an S(6) motif (Bernstein et al., 1995). The C—N distances are in the ranges 1.329 (3)–1.360 (3) Å in (Ia) and 1.329 (3)–1.353 (3) Å in (Ib) (Table 1), with no significant bond fixation within the pyrimidine ring. In addition, the pyrimidine ring distances are comparable with the corresponding bonds in 4,6-disubstitued 2-aminopyrimidines (Quesada et al., 2004). The phenyl ring is nearly coplanar with the pyrimidine ring: the angle between the least-squares planes through the pyrimidine and phenyl rings is 5.2 (2)° in (Ia) and 6.4 (2)° in (Ib). Aromatic atom C41 of the N-(4-chlorophenyl)-4-amine group is also nearly coplanar with the pyrimidine ring, whereas atom C51 of the 5-[(4-chlorophenyl)amino]methyl group deviates from the pyrimidine ring plane by −1.20 (1) Å in (Ia) and −2.19 (1) Å in (Ib). The C5—C57—N5—C51 torsion angle describing the orientation of aromatic atom C51 with respect to the pyrimidine atom C5 is 179.8 (2)° in (Ia) and 80.5 (2)° in (Ib).
The molecules of (Ia) are linked by N—H···N hydrogen bonds (Table 2), with amide atom N5 as a donor and ring atom N1 of the molecule at (x − 1/2, y, −z + 1/2) as acceptor in this linkage. Propagation of the hydrogen-bonding C(7) motif generates a chain running along the a axis (Fig. 3). Between pyrimidine rings of adjacent molecules within a chain there is also an aromatic π–π stacking interaction, with an interplanar spacing of 3.47 (4) Å, a centroid-to-centroid separation of 3.71 (3) Å and a centroid offset of 1.31 Å. These chains run through each unit cell, but there is no direction-specific interaction between adjacent chains.
It is interesting to note that the aromatic π–π stacking interactions found in (Ia) are absent in the structure of (Ib) and molecules are linked by N—H···Cl hydrogen bonds only (Table 2). Amide atom N5 acts as a hydrogen-bond donor to atom Cl4 in the molecule at (x, −y + 1/2, z − 1/2). This hydrogen-bond motif, which can be described as C(11), generates a chain running along the c axis (Fig. 4).