Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807000633/ya2037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807000633/ya20375sup2.hkl |
CCDC reference: 636844
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C)= 0.003 Å
- R factor = 0.055
- wR factor = 0.124
- Data-to-parameter ratio = 18.7
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.
C18H14Cl2N2O | F(000) = 712 |
Mr = 345.21 | Dx = 1.465 Mg m−3 |
Monoclinic, P21/c | Melting point: 371 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 19.1362 (5) Å | Cell parameters from 6273 reflections |
b = 7.2803 (2) Å | θ = 2.9–32.2° |
c = 11.2860 (3) Å | µ = 0.42 mm−1 |
β = 95.377 (1)° | T = 150 K |
V = 1565.42 (7) Å3 | Block, colorless |
Z = 4 | 0.22 × 0.18 × 0.11 mm |
Bruker SMART 6000 CCD diffractometer | 3889 independent reflections |
Radiation source: sealed tube | 3188 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 0.75 pixels mm-1 | θmax = 28.3°, θmin = 1.1° |
ω scans | h = −25→21 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | k = −9→9 |
Tmin = 0.822, Tmax = 0.955 | l = −15→15 |
13291 measured reflections |
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)] = 0.055 | Hydrogen site location: mixed |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0325P)2 + 1.3572P] where P = (Fo2 + 2Fc2)/3 |
3889 reflections | (Δ/σ)max = 0.001 |
208 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Experimental. Single crystals were obtained from ethanol. A suitable crystal was mounted on the tip of a glass fiber with paratone-N. The first 50 frames of data were recollected for a decay correction. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size. Spectroscopic details for (4): IR (KBr) 2923, 1685, 1589, 1400, 1092 cm-16. 1H NMR (250 MHz, CDCl3) δ 3.59 (t, 2H, 7 Hz, –CO—CH2–), 4.51 (t, 2H, 7 Hz, –CH2—N<), 6.27 (d, 1H, 2 Hz, C-4pyrazoleH), 7.38–7.43 (m, 6H, aromatic H), 7.53 (d, 1H, 2 Hz, C-3pyrazoleH), 7.86 (d, 2H, 7.5 Hz, aromatic H) p.p.m. 13C NMR (75 MHz, CDCl3) δ 196.2 (C=O), 142.7 C-5pyrazoleC), 140.0 (aromatic C), 139.9 (C3-pyrazoleC), 134.9, 134.7 (aromatic C), 130.3, 129.5, 129.1, 129.0 (aromatic C), 106.5 (C-4pyrazoleC), 44.3, 38.3 (CH2) p.p.m. MS (ESI, M+) calcd. for C18H14N2OCl2, 344.0483, found 344.0477 Spectroscopic details for (5): IR (KBr) 3447, 3132, 1682, 1590, 1098 cm-1 1H NMR (250 MHz, CDCl3) δ 3.61(t, 2H, 7 Hz, –CO—CH2–), 4.61 (t, 2H, 7 Hz, –CH2—N<), 6.47 (d, 1H, 2 Hz, C-4pyrazoleH), 7.33 (d, 2H, 8 Hz, aromatic H), 7.37 (d, 2H, 8 Hz, aromatic H), 7.51 (d, 1H, 3 Hz, C-5pyrazoleH), 7.68 (d, 2H, 8 Hz, aromatic H), 7.89 (d, 2H, 8 Hz, aromatic H) p.p.m. 13C NMR (75 MHz, CDCl3) δ 196.3 (C=O), 150.8 (C-3pyrazoleC), 140.0, 134.7, 132.1 (aromatic C), 131.8 (C-5pyrazoleC), 129.5, 129.0, 128.8, 126.8 (aromatic C), 102.6 (C-4pyrazoleC), 46.9, 38.8 (CH2) p.p.m. MS (ESI, M+) calcd. for C18H14N2OCl2, 344.0483, found 344.0502 |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) -1.5903 (154)x + 6.8634 (21)y + 3.7176 (90)z = 3.5593 (47) * 0.0013 (0.0014) C1 * 0.0044 (0.0014) C2 * -0.0054 (0.0015) C3 * 0.0005 (0.0015) C4 * 0.0053 (0.0015) C5 * -0.0061 (0.0014) C6 Rms deviation of fitted atoms = 0.0044 -2.3188 (203)x + 7.1421 (15)y + 1.8291 (117)z = 2.8504 (36) Angle to previous plane (with approximate e.s.d.) = 10.32 (7) * 0.0010 (0.0012) C7 * 0.0005 (0.0013) C8 * -0.0018 (0.0013) C9 * 0.0025 (0.0012) N10 * -0.0022 (0.0011) N11 Rms deviation of fitted atoms = 0.0018 0.5565 (162)x + 7.0399 (16)y - 2.8757 (96)z = 2.1353 (57) Angle to previous plane (with approximate e.s.d.) = 24.94 (4) * -0.0041 (0.0014) C15 * 0.0012 (0.0015) C16 * 0.0046 (0.0015) C17 * -0.0076 (0.0015) C18 * 0.0045 (0.0015) C19 * 0.0013 (0.0015) C20 Rms deviation of fitted atoms = 0.0045 - 2.3188 (203) x + 7.1421 (15) y + 1.8291 (117) z = 2.8504 (36) * 0.0010 (0.0012) C7 * 0.0025 (0.0012) N10 * 0.0005 (0.0013) C8 * -0.0022 (0.0011) N11 * -0.0018 (0.0013) C9 Rms deviation of fitted atoms = 0.0018 2.1589 (174) x + 7.1466 (32) y - 1.8475 (253) z = 1.9057 (72) Angle to previous plane (with approximate e.s.d.) = 22.17 (0.07) * -0.0044 (0.0010) N10 * 0.0254 (0.0013) C14 * -0.0200 (0.0012) C12 * -0.0263 (0.0011) C15 * 0.0252 (0.0015) C13 Rms deviation of fitted atoms = 0.0219 0.5565 (162) x + 7.0399 (16) y - 2.8757 (96) z = 2.1353 (57) Angle to previous plane (with approximate e.s.d.) = 7.50 (0.10) * -0.0041 (0.0014) C15 * -0.0076 (0.0015) C18 * 0.0012 (0.0015) C16 * 0.0045 (0.0015) C19 * 0.0046 (0.0015) C17 * 0.0013 (0.0015) C20 Rms deviation of fitted atoms = 0.0045 |
Refinement. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.22305 (11) | 0.4214 (3) | 0.27525 (17) | 0.0207 (4) | |
H1 | 0.1991 | 0.4564 | 0.2012 | 0.025* | |
C2 | 0.29563 (11) | 0.4303 (3) | 0.29067 (19) | 0.0235 (4) | |
H2 | 0.3213 | 0.4716 | 0.2277 | 0.028* | |
Cl3 | 0.42157 (3) | 0.38898 (9) | 0.41830 (6) | 0.03759 (17) | |
C3 | 0.33051 (11) | 0.3784 (3) | 0.3987 (2) | 0.0236 (4) | |
C4 | 0.29395 (11) | 0.3204 (3) | 0.49185 (19) | 0.0252 (4) | |
H4 | 0.3183 | 0.2861 | 0.5657 | 0.030* | |
C5 | 0.22148 (11) | 0.3127 (3) | 0.47622 (18) | 0.0229 (4) | |
H5 | 0.1962 | 0.2738 | 0.5403 | 0.027* | |
C6 | 0.18454 (10) | 0.3613 (3) | 0.36767 (17) | 0.0186 (4) | |
C7 | 0.10761 (10) | 0.3438 (3) | 0.35279 (17) | 0.0183 (4) | |
C8 | 0.06191 (11) | 0.3065 (3) | 0.44014 (18) | 0.0241 (4) | |
H8 | 0.0739 | 0.2894 | 0.5230 | 0.029* | |
C9 | −0.00366 (11) | 0.3003 (3) | 0.38031 (17) | 0.0242 (4) | |
H9 | −0.0465 | 0.2772 | 0.4138 | 0.029* | |
N10 | 0.00423 (8) | 0.3331 (2) | 0.26438 (14) | 0.0194 (3) | |
N11 | 0.07216 (9) | 0.3596 (2) | 0.24465 (15) | 0.0195 (3) | |
C12 | −0.04835 (10) | 0.3203 (3) | 0.16175 (17) | 0.0207 (4) | |
H12A | −0.0468 | 0.1959 | 0.1267 | 0.025* | |
H12B | −0.0370 | 0.4101 | 0.1005 | 0.025* | |
C13 | −0.12186 (10) | 0.3578 (3) | 0.19656 (17) | 0.0200 (4) | |
H13A | −0.1234 | 0.4817 | 0.2324 | 0.024* | |
H13B | −0.1336 | 0.2671 | 0.2570 | 0.024* | |
C14 | −0.17585 (10) | 0.3464 (3) | 0.08904 (18) | 0.0204 (4) | |
O14 | −0.15794 (8) | 0.3182 (2) | −0.00984 (13) | 0.0308 (4) | |
C15 | −0.25147 (10) | 0.3671 (3) | 0.10904 (18) | 0.0199 (4) | |
C16 | −0.27366 (11) | 0.4147 (3) | 0.21927 (18) | 0.0234 (4) | |
H16 | −0.2400 | 0.4389 | 0.2847 | 0.028* | |
C17 | −0.34459 (11) | 0.4267 (3) | 0.23383 (19) | 0.0255 (4) | |
H17 | −0.3596 | 0.4600 | 0.3088 | 0.031* | |
Cl18 | −0.48173 (3) | 0.39787 (9) | 0.15999 (6) | 0.03929 (18) | |
C18 | −0.39355 (11) | 0.3898 (3) | 0.1383 (2) | 0.0252 (4) | |
C19 | −0.37282 (11) | 0.3445 (3) | 0.0272 (2) | 0.0267 (5) | |
H19 | −0.4067 | 0.3219 | −0.0383 | 0.032* | |
C20 | −0.30176 (11) | 0.3330 (3) | 0.01395 (18) | 0.0227 (4) | |
H20 | −0.2869 | 0.3013 | −0.0614 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0233 (10) | 0.0194 (10) | 0.0191 (9) | 0.0025 (8) | 0.0013 (7) | −0.0021 (7) |
C2 | 0.0246 (10) | 0.0215 (10) | 0.0252 (10) | 0.0000 (8) | 0.0063 (8) | −0.0015 (8) |
Cl3 | 0.0187 (3) | 0.0380 (3) | 0.0550 (4) | 0.0020 (2) | −0.0017 (2) | −0.0005 (3) |
C3 | 0.0175 (9) | 0.0195 (10) | 0.0333 (11) | 0.0013 (8) | −0.0008 (8) | −0.0038 (8) |
C4 | 0.0277 (11) | 0.0231 (10) | 0.0230 (10) | 0.0011 (8) | −0.0069 (8) | 0.0000 (8) |
C5 | 0.0265 (10) | 0.0231 (10) | 0.0187 (9) | −0.0010 (8) | 0.0000 (8) | 0.0013 (8) |
C6 | 0.0210 (9) | 0.0157 (9) | 0.0188 (9) | −0.0007 (7) | 0.0008 (7) | −0.0029 (7) |
C7 | 0.0206 (9) | 0.0166 (9) | 0.0176 (9) | 0.0012 (7) | 0.0014 (7) | −0.0016 (7) |
C8 | 0.0243 (10) | 0.0310 (11) | 0.0171 (9) | −0.0013 (9) | 0.0022 (8) | 0.0014 (8) |
C9 | 0.0235 (10) | 0.0312 (11) | 0.0184 (9) | −0.0022 (8) | 0.0050 (8) | 0.0007 (8) |
N10 | 0.0167 (8) | 0.0236 (9) | 0.0177 (8) | −0.0005 (6) | 0.0002 (6) | −0.0002 (7) |
N11 | 0.0175 (8) | 0.0212 (8) | 0.0197 (8) | −0.0008 (6) | 0.0020 (6) | 0.0012 (6) |
C12 | 0.0203 (9) | 0.0259 (10) | 0.0160 (9) | −0.0020 (8) | 0.0018 (7) | 0.0007 (8) |
C13 | 0.0191 (9) | 0.0217 (10) | 0.0192 (9) | −0.0011 (7) | 0.0014 (7) | 0.0013 (7) |
C14 | 0.0203 (9) | 0.0188 (9) | 0.0218 (9) | −0.0007 (7) | 0.0000 (8) | 0.0024 (7) |
O14 | 0.0248 (8) | 0.0476 (10) | 0.0200 (7) | 0.0013 (7) | 0.0022 (6) | 0.0004 (7) |
C15 | 0.0207 (9) | 0.0173 (9) | 0.0212 (9) | −0.0010 (7) | −0.0002 (7) | 0.0038 (7) |
C16 | 0.0231 (10) | 0.0238 (10) | 0.0227 (10) | −0.0004 (8) | −0.0010 (8) | −0.0012 (8) |
C17 | 0.0260 (10) | 0.0255 (11) | 0.0255 (10) | 0.0022 (9) | 0.0056 (8) | −0.0026 (8) |
Cl18 | 0.0203 (3) | 0.0497 (4) | 0.0485 (4) | 0.0002 (2) | 0.0062 (2) | −0.0026 (3) |
C18 | 0.0188 (10) | 0.0229 (10) | 0.0341 (11) | 0.0013 (8) | 0.0032 (8) | 0.0026 (9) |
C19 | 0.0226 (10) | 0.0288 (11) | 0.0278 (11) | −0.0018 (9) | −0.0023 (8) | 0.0012 (9) |
C20 | 0.0246 (10) | 0.0228 (10) | 0.0205 (9) | −0.0001 (8) | 0.0003 (8) | 0.0016 (8) |
C1—C2 | 1.385 (3) | C12—C13 | 1.520 (3) |
C1—C6 | 1.402 (3) | C12—H12A | 0.9900 |
C1—H1 | 0.9500 | C12—H12B | 0.9900 |
C2—C3 | 1.386 (3) | C13—C14 | 1.521 (3) |
C2—H2 | 0.9500 | C13—H13A | 0.9900 |
Cl3—C3 | 1.738 (2) | C13—H13B | 0.9900 |
C3—C4 | 1.383 (3) | C14—O14 | 1.215 (3) |
C4—C5 | 1.382 (3) | C14—C15 | 1.493 (3) |
C4—H4 | 0.9500 | C15—C20 | 1.395 (3) |
C5—C6 | 1.401 (3) | C15—C16 | 1.395 (3) |
C5—H5 | 0.9500 | C16—C17 | 1.385 (3) |
C6—C7 | 1.471 (3) | C16—H16 | 0.9500 |
C7—N11 | 1.344 (2) | C17—C18 | 1.387 (3) |
C7—C8 | 1.404 (3) | C17—H17 | 0.9500 |
C8—C9 | 1.369 (3) | Cl18—C18 | 1.729 (2) |
C8—H8 | 0.9500 | C18—C19 | 1.390 (3) |
C9—N10 | 1.352 (3) | C19—C20 | 1.384 (3) |
C9—H9 | 0.9500 | C19—H19 | 0.9500 |
N10—N11 | 1.353 (2) | C20—H20 | 0.9500 |
N10—C12 | 1.464 (2) | ||
C2—C1—C6 | 120.79 (18) | N10—C12—H12A | 109.3 |
C2—C1—H1 | 119.6 | C13—C12—H12A | 109.3 |
C6—C1—H1 | 119.6 | N10—C12—H12B | 109.3 |
C1—C2—C3 | 119.49 (19) | C13—C12—H12B | 109.3 |
C1—C2—H2 | 120.3 | H12A—C12—H12B | 108.0 |
C3—C2—H2 | 120.3 | C12—C13—C14 | 111.09 (16) |
C4—C3—C2 | 121.04 (19) | C12—C13—H13A | 109.4 |
C4—C3—Cl3 | 119.32 (16) | C14—C13—H13A | 109.4 |
C2—C3—Cl3 | 119.63 (17) | C12—C13—H13B | 109.4 |
C5—C4—C3 | 119.23 (19) | C14—C13—H13B | 109.4 |
C5—C4—H4 | 120.4 | H13A—C13—H13B | 108.0 |
C3—C4—H4 | 120.4 | O14—C14—C15 | 121.11 (18) |
C4—C5—C6 | 121.29 (19) | O14—C14—C13 | 120.88 (18) |
C4—C5—H5 | 119.4 | C15—C14—C13 | 118.00 (17) |
C6—C5—H5 | 119.4 | C20—C15—C16 | 118.98 (19) |
C5—C6—C1 | 118.15 (19) | C20—C15—C14 | 118.30 (18) |
C5—C6—C7 | 119.69 (18) | C16—C15—C14 | 122.69 (18) |
C1—C6—C7 | 122.14 (17) | C17—C16—C15 | 120.32 (19) |
N11—C7—C8 | 111.06 (17) | C17—C16—H16 | 119.8 |
N11—C7—C6 | 120.69 (17) | C15—C16—H16 | 119.8 |
C8—C7—C6 | 128.23 (18) | C16—C17—C18 | 119.6 (2) |
C9—C8—C7 | 105.22 (17) | C16—C17—H17 | 120.2 |
C9—C8—H8 | 127.4 | C18—C17—H17 | 120.2 |
C7—C8—H8 | 127.4 | C17—C18—C19 | 121.2 (2) |
N10—C9—C8 | 106.92 (18) | C17—C18—Cl18 | 118.70 (17) |
N10—C9—H9 | 126.5 | C19—C18—Cl18 | 120.07 (17) |
C8—C9—H9 | 126.5 | C20—C19—C18 | 118.55 (19) |
C9—N10—N11 | 112.36 (16) | C20—C19—H19 | 120.7 |
C9—N10—C12 | 128.55 (17) | C18—C19—H19 | 120.7 |
N11—N10—C12 | 118.59 (15) | C19—C20—C15 | 121.3 (2) |
C7—N11—N10 | 104.44 (16) | C19—C20—H20 | 119.3 |
N10—C12—C13 | 111.59 (16) | C15—C20—H20 | 119.3 |
C6—C1—C2—C3 | 0.3 (3) | C9—N10—N11—C7 | −0.5 (2) |
C1—C2—C3—C4 | −0.9 (3) | C12—N10—N11—C7 | −173.05 (17) |
C1—C2—C3—Cl3 | 179.87 (15) | C9—N10—C12—C13 | 28.8 (3) |
C2—C3—C4—C5 | 0.5 (3) | N11—N10—C12—C13 | −160.02 (16) |
Cl3—C3—C4—C5 | 179.75 (16) | N10—C12—C13—C14 | 179.32 (16) |
C3—C4—C5—C6 | 0.5 (3) | C12—C13—C14—O14 | −2.9 (3) |
C4—C5—C6—C1 | −1.1 (3) | C12—C13—C14—C15 | 175.93 (17) |
C4—C5—C6—C7 | 177.37 (19) | O14—C14—C15—C20 | 7.1 (3) |
C2—C1—C6—C5 | 0.7 (3) | C13—C14—C15—C20 | −171.74 (18) |
C2—C1—C6—C7 | −177.72 (18) | O14—C14—C15—C16 | −174.5 (2) |
C5—C6—C7—N11 | −168.74 (18) | C13—C14—C15—C16 | 6.6 (3) |
C1—C6—C7—N11 | 9.7 (3) | C20—C15—C16—C17 | 0.3 (3) |
C5—C6—C7—C8 | 9.7 (3) | C14—C15—C16—C17 | −178.04 (19) |
C1—C6—C7—C8 | −171.9 (2) | C15—C16—C17—C18 | 0.5 (3) |
N11—C7—C8—C9 | −0.1 (2) | C16—C17—C18—C19 | −1.3 (3) |
C6—C7—C8—C9 | −178.6 (2) | C16—C17—C18—Cl18 | 177.75 (16) |
C7—C8—C9—N10 | −0.2 (2) | C17—C18—C19—C20 | 1.3 (3) |
C8—C9—N10—N11 | 0.4 (2) | Cl18—C18—C19—C20 | −177.76 (16) |
C8—C9—N10—C12 | 172.1 (2) | C18—C19—C20—C15 | −0.5 (3) |
C8—C7—N11—N10 | 0.3 (2) | C16—C15—C20—C19 | −0.3 (3) |
C6—C7—N11—N10 | 178.97 (17) | C14—C15—C20—C19 | 178.10 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O14i | 0.95 | 2.47 | 3.418 (3) | 173 |
Symmetry code: (i) x, −y+1/2, z+1/2. |