Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680200747X/ob6126sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680200747X/ob6126Isup2.hkl |
CCDC reference: 185807
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.003 Å
- R factor = 0.033
- wR factor = 0.082
- Data-to-parameter ratio = 14.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSTM_02 Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.682 0.962 Tmin' and Tmax expected: 0.852 0.956 RR' = 0.795 Please check that your absorption correction is appropriate.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
An ice-cold solution of sodium hydroxide (0.005 mol) in water (0.25 ml) and methanol (50 ml) was added to an ice-cold solution of 2,4-dichlorobenzaldehyde (0.01 mol) and 1-tetralone (0.01 mol) in methanol (75 ml). After stirring at room temperature for 2 d, the mixture was refrigerated (268 K) for 1 d and the precipitate collected and dried. Column chromatography using keiselgel 60 and an eluting solvent of toluene afforded (I) (m.p. 381–383 K) in 56% yield, while an eluting solvent of 1% methanol in toluene led to 2-(2,4-dichlorophenyl-hydroxymethyl)-1-tetralone, (II) (m.p. 444–446 K) in 13% yield. Elemental analysis, calculated for C17H12Cl2O: C 67.35, H 3.99%; found: C 67.21, H 3.73%. The cytotoxicity of (I) was determined using murine P388 and L1210 cells, as well as human Molt 4/C8 and CEM T-lymphocytes. The IC50 values of (I) were 17.2±0.5, 34.4±5.4, 28.4±7.6 and 8.73±1.24 µM, respectively.
All H atoms were placed in calculated positions on their parent C atoms (C—H = 0.99 Å on aliphatic C atoms and 0.95 Å on aromatic C atoms). The Uiso value of each H atom was assigned as equal to 1.2 times the Ueq of the attached C atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal3.7 (Hall et al., 2000); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. |
C17H12Cl2O | F(000) = 624 |
Mr = 303.17 | Dx = 1.435 Mg m−3 |
Monoclinic, P21/c | Melting point = 381–383 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.3695 (9) Å | Cell parameters from 5425 reflections |
b = 13.7644 (10) Å | θ = 2.5–25° |
c = 8.2403 (6) Å | µ = 0.45 mm−1 |
β = 90.01 (1)° | T = 193 K |
V = 1402.98 (18) Å3 | Prism, colourless |
Z = 4 | 0.35 × 0.10 × 0.10 mm |
Bruker SMART1000 CCD diffractometer | 2668 independent reflections |
Radiation source: fine-focus sealed tube | 2022 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 17 pixels mm-1 | θmax = 25.8°, θmin = 1.7° |
CCD scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | k = −16→15 |
Tmin = 0.682, Tmax = 0.962 | l = −10→9 |
8415 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0418P)2] where P = (Fo2 + 2Fc2)/3 |
2668 reflections | (Δ/σ)max = 0.005 |
181 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C17H12Cl2O | V = 1402.98 (18) Å3 |
Mr = 303.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.3695 (9) Å | µ = 0.45 mm−1 |
b = 13.7644 (10) Å | T = 193 K |
c = 8.2403 (6) Å | 0.35 × 0.10 × 0.10 mm |
β = 90.01 (1)° |
Bruker SMART1000 CCD diffractometer | 2668 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 2022 reflections with I > 2σ(I) |
Tmin = 0.682, Tmax = 0.962 | Rint = 0.047 |
8415 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.21 e Å−3 |
2668 reflections | Δρmin = −0.19 e Å−3 |
181 parameters |
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. Refinement was by full-matrix least-squares methods. Refinement of F2 against ALL reflections. 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 | ||
Cl1 | 0.53090 (4) | 0.24397 (4) | 0.41220 (7) | 0.04201 (16) | |
Cl2 | 0.64505 (4) | −0.04634 (4) | 0.80642 (6) | 0.03862 (15) | |
O | 0.16014 (9) | 0.36507 (9) | 0.45961 (17) | 0.0375 (3) | |
C1 | 0.12921 (13) | 0.28081 (14) | 0.4465 (2) | 0.0282 (4) | |
C2 | 0.19817 (13) | 0.19697 (13) | 0.4989 (2) | 0.0266 (4) | |
C3 | 0.14545 (13) | 0.09859 (14) | 0.5011 (2) | 0.0306 (4) | |
H3A | 0.1008 | 0.0922 | 0.6001 | 0.037* | |
H3B | 0.2019 | 0.0477 | 0.5042 | 0.037* | |
C4 | 0.07426 (14) | 0.08367 (14) | 0.3512 (2) | 0.0336 (5) | |
H4A | 0.1205 | 0.0812 | 0.2532 | 0.040* | |
H4B | 0.0360 | 0.0207 | 0.3605 | 0.040* | |
C5 | −0.00700 (14) | 0.16379 (15) | 0.3329 (2) | 0.0337 (5) | |
C6 | −0.10931 (15) | 0.14709 (17) | 0.2676 (3) | 0.0446 (6) | |
H6 | −0.1293 | 0.0832 | 0.2358 | 0.053* | |
C7 | −0.18195 (17) | 0.2225 (2) | 0.2486 (3) | 0.0553 (7) | |
H7 | −0.2512 | 0.2101 | 0.2032 | 0.066* | |
C8 | −0.15467 (16) | 0.3155 (2) | 0.2951 (3) | 0.0544 (7) | |
H8 | −0.2053 | 0.3668 | 0.2827 | 0.065* | |
C9 | −0.05385 (15) | 0.33414 (16) | 0.3597 (2) | 0.0412 (5) | |
H9 | −0.0350 | 0.3983 | 0.3913 | 0.049* | |
C10 | 0.02048 (14) | 0.25846 (14) | 0.3787 (2) | 0.0316 (5) | |
C11 | 0.30183 (14) | 0.21563 (13) | 0.5357 (2) | 0.0271 (4) | |
H11 | 0.3252 | 0.2807 | 0.5199 | 0.033* | |
C12 | 0.38339 (13) | 0.14768 (12) | 0.5974 (2) | 0.0255 (4) | |
C13 | 0.49238 (13) | 0.15561 (13) | 0.5509 (2) | 0.0257 (4) | |
C14 | 0.57174 (13) | 0.09564 (13) | 0.6111 (2) | 0.0271 (4) | |
H14 | 0.6444 | 0.1018 | 0.5751 | 0.032* | |
C15 | 0.54406 (14) | 0.02651 (13) | 0.7244 (2) | 0.0276 (4) | |
C16 | 0.43831 (14) | 0.01589 (14) | 0.7764 (2) | 0.0301 (4) | |
H16 | 0.4200 | −0.0321 | 0.8546 | 0.036* | |
C17 | 0.35992 (14) | 0.07620 (13) | 0.7127 (2) | 0.0285 (4) | |
H17 | 0.2874 | 0.0689 | 0.7484 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0294 (2) | 0.0449 (3) | 0.0518 (4) | 0.0006 (2) | 0.0041 (2) | 0.0214 (3) |
Cl2 | 0.0382 (3) | 0.0394 (3) | 0.0383 (3) | 0.0128 (2) | −0.0011 (2) | 0.0065 (2) |
O | 0.0330 (7) | 0.0261 (8) | 0.0534 (10) | 0.0024 (6) | 0.0024 (6) | 0.0010 (6) |
C1 | 0.0251 (8) | 0.0312 (11) | 0.0282 (11) | 0.0016 (8) | 0.0081 (8) | 0.0006 (8) |
C2 | 0.0261 (9) | 0.0270 (10) | 0.0268 (10) | −0.0001 (8) | 0.0044 (8) | −0.0009 (8) |
C3 | 0.0267 (9) | 0.0286 (10) | 0.0365 (11) | −0.0023 (8) | 0.0018 (8) | 0.0017 (9) |
C4 | 0.0293 (9) | 0.0325 (11) | 0.0388 (12) | −0.0070 (8) | 0.0011 (8) | −0.0014 (9) |
C5 | 0.0266 (9) | 0.0444 (12) | 0.0300 (11) | −0.0033 (8) | 0.0035 (8) | 0.0040 (9) |
C6 | 0.0315 (10) | 0.0576 (15) | 0.0445 (14) | −0.0066 (10) | −0.0024 (9) | 0.0030 (11) |
C7 | 0.0284 (11) | 0.084 (2) | 0.0530 (16) | −0.0002 (12) | −0.0090 (10) | 0.0073 (14) |
C8 | 0.0330 (11) | 0.0735 (18) | 0.0566 (16) | 0.0166 (11) | −0.0033 (10) | 0.0107 (14) |
C9 | 0.0331 (10) | 0.0475 (13) | 0.0429 (13) | 0.0084 (9) | 0.0030 (9) | 0.0056 (11) |
C10 | 0.0241 (9) | 0.0402 (12) | 0.0306 (11) | 0.0008 (8) | 0.0055 (8) | 0.0075 (9) |
C11 | 0.0286 (9) | 0.0220 (9) | 0.0309 (11) | 0.0002 (8) | 0.0024 (8) | −0.0028 (8) |
C12 | 0.0250 (8) | 0.0246 (10) | 0.0271 (10) | −0.0010 (7) | −0.0014 (7) | −0.0049 (8) |
C13 | 0.0281 (9) | 0.0253 (10) | 0.0237 (10) | −0.0034 (7) | −0.0003 (7) | 0.0012 (8) |
C14 | 0.0237 (8) | 0.0313 (10) | 0.0262 (10) | 0.0011 (8) | 0.0012 (7) | −0.0030 (8) |
C15 | 0.0316 (9) | 0.0265 (10) | 0.0247 (10) | 0.0063 (8) | −0.0027 (8) | −0.0043 (8) |
C16 | 0.0354 (10) | 0.0277 (10) | 0.0272 (11) | −0.0001 (8) | 0.0019 (8) | −0.0008 (8) |
C17 | 0.0256 (8) | 0.0295 (10) | 0.0304 (11) | −0.0019 (8) | 0.0031 (8) | −0.0038 (8) |
Cl1—C13 | 1.7357 (18) | C7—C8 | 1.378 (3) |
Cl2—C15 | 1.7386 (17) | C7—H7 | 0.9500 |
O—C1 | 1.226 (2) | C8—C9 | 1.380 (3) |
C1—C10 | 1.488 (2) | C8—H8 | 0.9500 |
C1—C2 | 1.499 (3) | C9—C10 | 1.398 (3) |
C2—C11 | 1.342 (2) | C9—H9 | 0.9500 |
C2—C3 | 1.503 (2) | C11—C12 | 1.467 (2) |
C3—C4 | 1.530 (2) | C11—H11 | 0.9500 |
C3—H3A | 0.9900 | C12—C17 | 1.398 (2) |
C3—H3B | 0.9900 | C12—C13 | 1.406 (2) |
C4—C5 | 1.500 (3) | C13—C14 | 1.375 (2) |
C4—H4A | 0.9900 | C14—C15 | 1.376 (3) |
C4—H4B | 0.9900 | C14—H14 | 0.9500 |
C5—C6 | 1.394 (3) | C15—C16 | 1.384 (2) |
C5—C10 | 1.398 (3) | C16—C17 | 1.380 (2) |
C6—C7 | 1.382 (3) | C16—H16 | 0.9500 |
C6—H6 | 0.9500 | C17—H17 | 0.9500 |
O—C1—C10 | 120.71 (16) | C9—C8—H8 | 120.0 |
O—C1—C2 | 121.69 (16) | C8—C9—C10 | 119.9 (2) |
C10—C1—C2 | 117.60 (16) | C8—C9—H9 | 120.0 |
C11—C2—C1 | 117.48 (16) | C10—C9—H9 | 120.0 |
C11—C2—C3 | 125.74 (16) | C9—C10—C5 | 120.29 (17) |
C1—C2—C3 | 116.76 (15) | C9—C10—C1 | 118.82 (18) |
C2—C3—C4 | 111.16 (16) | C5—C10—C1 | 120.89 (16) |
C2—C3—H3A | 109.4 | C2—C11—C12 | 127.83 (17) |
C4—C3—H3A | 109.4 | C2—C11—H11 | 116.1 |
C2—C3—H3B | 109.4 | C12—C11—H11 | 116.1 |
C4—C3—H3B | 109.4 | C17—C12—C13 | 116.05 (15) |
H3A—C3—H3B | 108.0 | C17—C12—C11 | 122.77 (15) |
C5—C4—C3 | 111.60 (16) | C13—C12—C11 | 121.04 (16) |
C5—C4—H4A | 109.3 | C14—C13—C12 | 122.65 (16) |
C3—C4—H4A | 109.3 | C14—C13—Cl1 | 117.53 (13) |
C5—C4—H4B | 109.3 | C12—C13—Cl1 | 119.82 (13) |
C3—C4—H4B | 109.3 | C13—C14—C15 | 118.82 (16) |
H4A—C4—H4B | 108.0 | C13—C14—H14 | 120.6 |
C6—C5—C10 | 118.57 (18) | C15—C14—H14 | 120.6 |
C6—C5—C4 | 121.73 (19) | C14—C15—C16 | 121.22 (16) |
C10—C5—C4 | 119.68 (16) | C14—C15—Cl2 | 118.92 (13) |
C7—C6—C5 | 120.7 (2) | C16—C15—Cl2 | 119.84 (15) |
C7—C6—H6 | 119.7 | C17—C16—C15 | 118.84 (17) |
C5—C6—H6 | 119.7 | C17—C16—H16 | 120.6 |
C8—C7—C6 | 120.5 (2) | C15—C16—H16 | 120.6 |
C8—C7—H7 | 119.8 | C16—C17—C12 | 122.40 (16) |
C6—C7—H7 | 119.8 | C16—C17—H17 | 118.8 |
C7—C8—C9 | 120.1 (2) | C12—C17—H17 | 118.8 |
C7—C8—H8 | 120.0 | ||
O—C1—C2—C11 | −10.8 (3) | C2—C1—C10—C9 | 167.10 (17) |
C10—C1—C2—C11 | 169.74 (17) | O—C1—C10—C5 | 167.00 (18) |
O—C1—C2—C3 | 170.81 (18) | C2—C1—C10—C5 | −13.6 (3) |
C10—C1—C2—C3 | −8.6 (2) | C1—C2—C11—C12 | 176.61 (17) |
C11—C2—C3—C4 | −136.25 (19) | C3—C2—C11—C12 | −5.2 (3) |
C1—C2—C3—C4 | 42.0 (2) | C2—C11—C12—C17 | −39.6 (3) |
C2—C3—C4—C5 | −54.3 (2) | C2—C11—C12—C13 | 144.8 (2) |
C3—C4—C5—C6 | −146.85 (18) | C17—C12—C13—C14 | 1.5 (3) |
C3—C4—C5—C10 | 34.6 (2) | C11—C12—C13—C14 | 177.41 (16) |
C10—C5—C6—C7 | 0.0 (3) | C17—C12—C13—Cl1 | −178.44 (13) |
C4—C5—C6—C7 | −178.6 (2) | C11—C12—C13—Cl1 | −2.6 (2) |
C5—C6—C7—C8 | −0.5 (4) | C12—C13—C14—C15 | −1.6 (3) |
C6—C7—C8—C9 | 0.6 (4) | Cl1—C13—C14—C15 | 178.36 (14) |
C7—C8—C9—C10 | −0.3 (3) | C13—C14—C15—C16 | 0.8 (3) |
C8—C9—C10—C5 | −0.2 (3) | C13—C14—C15—Cl2 | −177.58 (13) |
C8—C9—C10—C1 | 179.13 (19) | C14—C15—C16—C17 | 0.0 (3) |
C6—C5—C10—C9 | 0.4 (3) | Cl2—C15—C16—C17 | 178.35 (13) |
C4—C5—C10—C9 | 178.93 (18) | C15—C16—C17—C12 | 0.0 (3) |
C6—C5—C10—C1 | −178.96 (18) | C13—C12—C17—C16 | −0.7 (3) |
C4—C5—C10—C1 | −0.4 (3) | C11—C12—C17—C16 | −176.51 (16) |
O—C1—C10—C9 | −12.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O | 0.95 | 2.40 | 2.774 (2) | 103 |
C4—H4A···Oi | 0.99 | 2.58 | 3.470 (2) | 150 |
C11—H11···Cl2ii | 0.95 | 2.80 | 3.5858 (18) | 140 |
C17—H17···Oiii | 0.95 | 2.52 | 3.302 (2) | 140 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H12Cl2O |
Mr | 303.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 12.3695 (9), 13.7644 (10), 8.2403 (6) |
β (°) | 90.01 (1) |
V (Å3) | 1402.98 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.35 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.682, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8415, 2668, 2022 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.612 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.082, 0.98 |
No. of reflections | 2668 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.19 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Xtal3.7 (Hall et al., 2000), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···O | 0.95 | 2.40 | 2.774 (2) | 103.1 |
C4—H4A···Oi | 0.99 | 2.58 | 3.470 (2) | 150.0 |
C11—H11···Cl2ii | 0.95 | 2.80 | 3.5858 (18) | 140.4 |
C17—H17···Oiii | 0.95 | 2.52 | 3.302 (2) | 140.1 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+1/2, z+1/2. |
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Recently, the synthesis and cytotoxic properties of a series of 2-arylidenebenzocycloalkanones were reported (Dimmock et al., 1999), which revealed, inter alia, that the relative positions of the two aryl rings influenced bioactivity. In order to develop structure–activity relationships in this group of compounds, analogues with ortho substituents were required, including 2-(2,4-dichlorophenylmethylene)-1-tetralone, (I). During the synthesis of (I), a second product was isolated which was shown by X-ray crystallography to be 2-(2,4-dichlorophenyl-hydroxymethyl)-1-tetralone, (II) (Oloo et al., 2002).
The cyclohexenone (C1—C2—C3—C4—C5—C10) ring of (I) has one multiple bond shared with the phenyl moiety and two external double bonds (the carbonyl O and C11 attached to C2). The atoms in the cyclohexenone ring adopted a conformation, with C2 and C3 on the same side of the plane determined by the other four atoms. Conjugation of the dichlorophenyl group with the α,β-unsaturated ketone should favor coplanarity, but steric effects interfere. The torsion angle C2—C11—C12—C17 is -39.6 (3)°, indicating that the aryl ring (C12–C17) is twisted out of the plane of the α,β-unsaturated ketone. This effect may be due to the Cl1···H11 and O···H11 non-bonded repulsions, since these interatomic distances are 2.72 and 2.40 Å, respectively. In addition, the distance between H17 and the pseudo-equatorial H atom on atom C3 is 2.29 Å, which may also contribute to the torsion angle observed.
Compound (I) has no possibility of classical hydrogen bonding. In Table 1, a non-classical intramolecular hydrogen bond is shown between H11 and O. In addition, intermolecular hydrogen bonds are listed between H4 and O, between H11 and Cl2, and between H17 and O, which link the molecules into a three-dimensional network.