Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801017421/wn6060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801017421/wn6060Isup2.hkl |
CCDC reference: 176026
Key indicators
- Single-crystal X-ray study
- T = 200 K
- Mean (C-C) = 0.002 Å
- R factor = 0.042
- wR factor = 0.105
- Data-to-parameter ratio = 15.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Compound (III) was prepared by passing a rapid stream of dry HCl gas through a solution of (II) (2 g, 9.0 mmol), fused zinc chloride (10 g) and resorcinol (1.01 g, 9.0 mmol) in dry ether (25 ml). The mixture was stored in an ice-chest for 2 d and the supernatant ethereal layer was decanted. The dark-brown sticky mass was washed twice with dry ether and refluxed with water (20 ml) for 2 h, when a light-brown solid precipitated out. It was filtered off, washed with water and crystallized from acetone to get a white solid (1.4 g, 46.6%), m.p. 553–555 K. Compound (I) was prepared by adding dimethyl sulfate (0.315 g) to a mixture of (III) (0.82 g) and fused potassium carbonate (4 g) in anhydrous acetone (60 ml) and refluxing for 5 h. The potassium carbonate was filtered off and the filtrate was evaporated to dryness, the residue was macerated with ice and the mixture extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, the solid obtained on evaporation of the solvent was purified by column chromatography using ethyl acetate/petrol (333–353 K, 1:4) as eluent to obtain (I). The title compound crystallized from acetone as yellow needles (0.59, 70% yield), m.p. 426–427 K.
Physical properties of (I): IR νmax (KBr): 3331, 2925, 2854, 2364, 1628, 1507, 1443, 1358, 1221 and 781 cm-1; UV λmax (MeOH): 202 and 238 nm; 1H NMR (300 MHz, acetone-d6) δ: 3.88 (3H, s, OCH3), 4.45 (2H, s, C2—H), 6.46 (1H, d, J = 1.3 Hz, C3'-H), 6.53 (1 h, dd, J = 1.3 and 9 Hz each, C5'-H), 6.64 (1H, s, C4"-H), 7.57 (2H, d, J = 8.4 Hz, C2"'-H and C62'-H), 7.76 (2H, d, J = 8.4 Hz, C3"'-H and C5"'-H) and 8.03 (1H, d, J = 9 Hz, C6'-H). EIMS, m/z (% relative intensity): 345 [M+2] (35), 343 [M+] (100), 179 (23), 167 (20), 151 (18), 91 (20), 74 (30).
Most of the H atoms were added at calculated positions and refined using a riding model; however, those bonded to N1 and O1 were located from electron-density maps and allowed to refine freely. H atoms were given isotropic displacement parameters equal to 1.2 (or 1.5 for methyl-H atoms) times the equivalent isotropic displacement parameter of their parent atoms.
Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Siemens, 1994); software used to prepare material for publication: SHELXTL/PC.
C18H15ClN2O3 | F(000) = 1424 |
Mr = 342.77 | Dx = 1.448 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 30.1055 (18) Å | Cell parameters from 3596 reflections |
b = 7.5383 (11) Å | θ = 2.7–27.0° |
c = 13.8612 (14) Å | µ = 0.26 mm−1 |
β = 90.338 (4)° | T = 200 K |
V = 3145.7 (6) Å3 | Plate, yellow |
Z = 8 | 0.40 × 0.40 × 0.08 mm |
Siemens SMART CCD area-detector diffractometer | 3425 independent reflections |
Radiation source: normal-focus sealed tube | 2145 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.192 pixels mm-1 | θmax = 27.0°, θmin = 2.7° |
ω scans | h = −38→34 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.902, Tmax = 0.979 | l = −17→10 |
8778 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0562P)2] where P = (Fo2 + 2Fc2)/3 |
3425 reflections | (Δ/σ)max < 0.001 |
226 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C18H15ClN2O3 | V = 3145.7 (6) Å3 |
Mr = 342.77 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.1055 (18) Å | µ = 0.26 mm−1 |
b = 7.5383 (11) Å | T = 200 K |
c = 13.8612 (14) Å | 0.40 × 0.40 × 0.08 mm |
β = 90.338 (4)° |
Siemens SMART CCD area-detector diffractometer | 3425 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2145 reflections with I > 2σ(I) |
Tmin = 0.902, Tmax = 0.979 | Rint = 0.037 |
8778 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.105 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.23 e Å−3 |
3425 reflections | Δρmin = −0.27 e Å−3 |
226 parameters |
Experimental. The temperature of the crystal was controlled using the Oxford Cryosystem Cryostream Cooler (Cosier & Glazer, 1986). Data were collected over a hemisphere of reciprocal space, by a combination of three sets of exposures. Each set had a different ϕ angle for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal to detector distance was 5.01 cm. Crystal decay was monitored by repeating the initial frames at the end of the data collection and analyzing the duplicate reflections. |
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 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 | 0.038277 (18) | 0.04558 (8) | 0.33182 (4) | 0.0644 (2) | |
O1 | 0.26052 (4) | 0.12928 (17) | 0.90110 (9) | 0.0462 (3) | |
O2 | 0.30704 (4) | 0.06150 (17) | 1.04683 (9) | 0.0443 (3) | |
H2 | 0.2848 (7) | 0.077 (3) | 1.0047 (18) | 0.079 (8)* | |
O3 | 0.46303 (4) | 0.1403 (2) | 1.02449 (10) | 0.0599 (4) | |
N1 | 0.20464 (5) | 0.2725 (2) | 0.76611 (11) | 0.0420 (4) | |
H1 | 0.2061 (6) | 0.311 (3) | 0.8304 (15) | 0.064 (6)* | |
N2 | 0.16585 (4) | 0.2512 (2) | 0.71830 (10) | 0.0418 (4) | |
C1 | 0.29386 (5) | 0.1709 (2) | 0.85314 (12) | 0.0358 (4) | |
C2 | 0.28723 (5) | 0.2386 (2) | 0.75169 (12) | 0.0369 (4) | |
H2A | 0.2964 | 0.3647 | 0.7495 | 0.044* | |
H2B | 0.3071 | 0.1716 | 0.7082 | 0.044* | |
C1' | 0.33797 (5) | 0.1605 (2) | 0.89635 (12) | 0.0337 (4) | |
C2' | 0.34283 (5) | 0.1065 (2) | 0.99283 (12) | 0.0349 (4) | |
C3' | 0.38389 (6) | 0.0970 (2) | 1.03825 (13) | 0.0387 (4) | |
H3'A | 0.3863 | 0.0593 | 1.1035 | 0.046* | |
C4' | 0.42118 (6) | 0.1434 (2) | 0.98684 (14) | 0.0440 (5) | |
C5' | 0.41779 (6) | 0.1987 (3) | 0.89104 (14) | 0.0502 (5) | |
H5'A | 0.4437 | 0.2313 | 0.8566 | 0.060* | |
C6' | 0.37724 (5) | 0.2061 (2) | 0.84693 (14) | 0.0427 (5) | |
H6'A | 0.3754 | 0.2426 | 0.7814 | 0.051* | |
C7' | 0.46876 (7) | 0.0764 (3) | 1.12064 (16) | 0.0625 (6) | |
H7'A | 0.5003 | 0.0810 | 1.1383 | 0.094* | |
H7'B | 0.4582 | −0.0463 | 1.1246 | 0.094* | |
H7'C | 0.4517 | 0.1508 | 1.1651 | 0.094* | |
C3" | 0.17761 (5) | 0.1909 (2) | 0.63156 (12) | 0.0345 (4) | |
C4" | 0.22404 (5) | 0.1724 (2) | 0.62598 (12) | 0.0362 (4) | |
H4"A | 0.2406 | 0.1320 | 0.5722 | 0.043* | |
C5" | 0.24036 (5) | 0.2245 (2) | 0.71353 (12) | 0.0350 (4) | |
C1"' | 0.14354 (5) | 0.1523 (2) | 0.55815 (12) | 0.0354 (4) | |
C2"' | 0.15438 (6) | 0.0798 (2) | 0.46912 (13) | 0.0400 (4) | |
H2"A | 0.1846 | 0.0538 | 0.4556 | 0.048* | |
C3"' | 0.12251 (6) | 0.0444 (2) | 0.39991 (14) | 0.0431 (5) | |
H3"A | 0.1305 | −0.0059 | 0.3396 | 0.052* | |
C4"' | 0.07886 (6) | 0.0835 (2) | 0.41979 (14) | 0.0442 (5) | |
C5"' | 0.06649 (6) | 0.1524 (3) | 0.50759 (14) | 0.0492 (5) | |
H5"A | 0.0361 | 0.1760 | 0.5207 | 0.059* | |
C6"' | 0.09861 (6) | 0.1869 (2) | 0.57632 (13) | 0.0451 (5) | |
H6"A | 0.0902 | 0.2348 | 0.6369 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0522 (3) | 0.0821 (4) | 0.0588 (4) | −0.0039 (3) | −0.0188 (3) | 0.0014 (3) |
O1 | 0.0280 (6) | 0.0703 (9) | 0.0405 (7) | −0.0013 (6) | 0.0062 (6) | 0.0058 (7) |
O2 | 0.0296 (7) | 0.0665 (9) | 0.0369 (7) | 0.0002 (6) | 0.0075 (6) | 0.0018 (6) |
O3 | 0.0299 (7) | 0.0867 (10) | 0.0631 (10) | −0.0054 (7) | −0.0064 (7) | 0.0179 (8) |
N1 | 0.0324 (8) | 0.0613 (10) | 0.0323 (8) | 0.0048 (7) | 0.0014 (7) | −0.0013 (8) |
N2 | 0.0323 (8) | 0.0602 (10) | 0.0329 (8) | 0.0059 (7) | 0.0013 (7) | 0.0034 (7) |
C1 | 0.0313 (9) | 0.0365 (9) | 0.0396 (10) | −0.0015 (7) | 0.0072 (8) | −0.0051 (8) |
C2 | 0.0306 (9) | 0.0443 (10) | 0.0359 (10) | −0.0019 (8) | 0.0044 (8) | −0.0016 (8) |
C1' | 0.0283 (9) | 0.0354 (9) | 0.0374 (10) | −0.0001 (7) | 0.0046 (8) | −0.0009 (8) |
C2' | 0.0288 (9) | 0.0358 (9) | 0.0401 (10) | −0.0003 (7) | 0.0077 (8) | −0.0052 (8) |
C3' | 0.0363 (10) | 0.0422 (10) | 0.0375 (10) | 0.0015 (8) | 0.0015 (8) | 0.0006 (8) |
C4' | 0.0304 (10) | 0.0481 (11) | 0.0535 (12) | −0.0003 (8) | −0.0034 (9) | 0.0048 (9) |
C5' | 0.0282 (10) | 0.0654 (13) | 0.0572 (13) | −0.0051 (9) | 0.0043 (9) | 0.0142 (11) |
C6' | 0.0337 (10) | 0.0509 (11) | 0.0434 (11) | −0.0029 (8) | 0.0059 (8) | 0.0082 (9) |
C7' | 0.0412 (12) | 0.0838 (17) | 0.0623 (15) | −0.0024 (11) | −0.0158 (11) | 0.0132 (13) |
C3" | 0.0330 (9) | 0.0377 (10) | 0.0329 (9) | 0.0035 (7) | 0.0037 (8) | 0.0056 (8) |
C4" | 0.0321 (9) | 0.0429 (10) | 0.0338 (10) | 0.0037 (8) | 0.0063 (8) | 0.0012 (8) |
C5" | 0.0308 (9) | 0.0372 (9) | 0.0370 (10) | 0.0012 (7) | 0.0057 (8) | 0.0038 (8) |
C1"' | 0.0328 (9) | 0.0368 (9) | 0.0367 (10) | 0.0028 (8) | 0.0041 (8) | 0.0084 (8) |
C2"' | 0.0330 (10) | 0.0469 (11) | 0.0403 (11) | 0.0031 (8) | 0.0048 (8) | 0.0068 (9) |
C3"' | 0.0446 (11) | 0.0479 (11) | 0.0367 (10) | 0.0016 (9) | 0.0027 (9) | 0.0024 (9) |
C4"' | 0.0375 (10) | 0.0495 (11) | 0.0456 (11) | −0.0017 (8) | −0.0059 (9) | 0.0075 (9) |
C5"' | 0.0322 (10) | 0.0647 (13) | 0.0507 (12) | 0.0075 (9) | 0.0013 (9) | 0.0042 (10) |
C6"' | 0.0367 (10) | 0.0592 (12) | 0.0395 (11) | 0.0097 (9) | 0.0039 (9) | 0.0027 (9) |
Cl1—C4"' | 1.7445 (19) | C5'—C6' | 1.363 (2) |
O1—C1 | 1.2475 (19) | C5'—H5'A | 0.9500 |
O2—C2' | 1.3587 (19) | C6'—H6'A | 0.9500 |
O2—H2 | 0.89 (2) | C7'—H7'A | 0.9800 |
O3—C4' | 1.361 (2) | C7'—H7'B | 0.9800 |
O3—C7' | 1.426 (2) | C7'—H7'C | 0.9800 |
N1—N2 | 1.3488 (19) | C3"—C4" | 1.407 (2) |
N1—C5" | 1.352 (2) | C3"—C1"' | 1.470 (2) |
N1—H1 | 0.94 (2) | C4"—C5" | 1.364 (2) |
N2—C3" | 1.335 (2) | C4"—H4"A | 0.9500 |
C1—C1' | 1.455 (2) | C1"'—C2"' | 1.391 (2) |
C1—C2 | 1.508 (2) | C1"'—C6"' | 1.402 (2) |
C2—C5" | 1.508 (2) | C2"'—C3"' | 1.379 (2) |
C2—H2A | 0.9900 | C2"'—H2"A | 0.9500 |
C2—H2B | 0.9900 | C3"'—C4"' | 1.376 (2) |
C1'—C2' | 1.405 (2) | C3"'—H3"A | 0.9500 |
C1'—C6' | 1.412 (2) | C4"'—C5"' | 1.377 (3) |
C2'—C3' | 1.386 (2) | C5"'—C6"' | 1.378 (3) |
C3'—C4' | 1.378 (2) | C5"'—H5"A | 0.9500 |
C3'—H3'A | 0.9500 | C6"'—H6"A | 0.9500 |
C4'—C5' | 1.395 (3) | ||
C2'—O2—H2 | 101.6 (15) | O3—C7'—H7'A | 109.5 |
C4'—O3—C7' | 118.07 (14) | O3—C7'—H7'B | 109.5 |
N2—N1—C5" | 113.10 (14) | H7'A—C7'—H7'B | 109.5 |
N2—N1—H1 | 122.6 (12) | O3—C7'—H7'C | 109.5 |
C5"—N1—H1 | 124.2 (12) | H7'A—C7'—H7'C | 109.5 |
C3"—N2—N1 | 104.45 (13) | H7'B—C7'—H7'C | 109.5 |
O1—C1—C1' | 120.15 (15) | N2—C3"—C4" | 110.61 (15) |
O1—C1—C2 | 118.66 (15) | N2—C3"—C1"' | 120.21 (15) |
C1'—C1—C2 | 121.15 (14) | C4"—C3"—C1"' | 129.18 (15) |
C5"—C2—C1 | 114.94 (13) | C5"—C4"—C3" | 105.97 (15) |
C5"—C2—H2A | 108.5 | C5"—C4"—H4"A | 127.0 |
C1—C2—H2A | 108.5 | C3"—C4"—H4"A | 127.0 |
C5"—C2—H2B | 108.5 | N1—C5"—C4" | 105.85 (15) |
C1—C2—H2B | 108.5 | N1—C5"—C2 | 122.53 (15) |
H2A—C2—H2B | 107.5 | C4"—C5"—C2 | 131.59 (15) |
C2'—C1'—C6' | 116.70 (15) | C2"'—C1"'—C6"' | 117.67 (17) |
C2'—C1'—C1 | 119.81 (14) | C2"'—C1"'—C3" | 121.72 (15) |
C6'—C1'—C1 | 123.48 (15) | C6"'—C1"'—C3" | 120.60 (16) |
O2—C2'—C3' | 116.43 (15) | C3"'—C2"'—C1"' | 121.84 (16) |
O2—C2'—C1' | 121.22 (15) | C3"'—C2"'—H2"A | 119.1 |
C3'—C2'—C1' | 122.36 (15) | C1"'—C2"'—H2"A | 119.1 |
C4'—C3'—C2' | 118.62 (17) | C4"'—C3"'—C2"' | 118.74 (18) |
C4'—C3'—H3'A | 120.7 | C4"'—C3"'—H3"A | 120.6 |
C2'—C3'—H3'A | 120.7 | C2"'—C3"'—H3"A | 120.6 |
O3—C4'—C3' | 123.52 (17) | C3"'—C4"'—C5"' | 121.41 (18) |
O3—C4'—C5' | 115.62 (15) | C3"'—C4"'—Cl1 | 119.38 (16) |
C3'—C4'—C5' | 120.86 (17) | C5"'—C4"'—Cl1 | 119.20 (14) |
C6'—C5'—C4' | 119.94 (16) | C4"'—C5"'—C6"' | 119.35 (17) |
C6'—C5'—H5'A | 120.0 | C4"'—C5"'—H5"A | 120.3 |
C4'—C5'—H5'A | 120.0 | C6"'—C5"'—H5"A | 120.3 |
C5'—C6'—C1' | 121.51 (17) | C5"'—C6"'—C1"' | 120.96 (18) |
C5'—C6'—H6'A | 119.2 | C5"'—C6"'—H6"A | 119.5 |
C1'—C6'—H6'A | 119.2 | C1"'—C6"'—H6"A | 119.5 |
C5"—N1—N2—C3" | −1.3 (2) | N1—N2—C3"—C1"' | −179.76 (14) |
O1—C1—C2—C5" | −8.3 (2) | N2—C3"—C4"—C5" | −0.1 (2) |
C1'—C1—C2—C5" | 174.18 (14) | C1"'—C3"—C4"—C5" | −179.47 (16) |
O1—C1—C1'—C2' | −1.1 (2) | N2—N1—C5"—C4" | 1.2 (2) |
C2—C1—C1'—C2' | 176.39 (15) | N2—N1—C5"—C2 | 179.31 (15) |
O1—C1—C1'—C6' | −179.72 (16) | C3"—C4"—C5"—N1 | −0.68 (19) |
C2—C1—C1'—C6' | −2.2 (3) | C3"—C4"—C5"—C2 | −178.50 (16) |
C6'—C1'—C2'—O2 | 179.40 (15) | C1—C2—C5"—N1 | 45.3 (2) |
C1—C1'—C2'—O2 | 0.7 (2) | C1—C2—C5"—C4" | −137.16 (19) |
C6'—C1'—C2'—C3' | −0.2 (2) | N2—C3"—C1"'—C2"' | −176.21 (16) |
C1—C1'—C2'—C3' | −178.88 (15) | C4"—C3"—C1"'—C2"' | 3.1 (3) |
O2—C2'—C3'—C4' | −179.24 (15) | N2—C3"—C1"'—C6"' | 3.4 (3) |
C1'—C2'—C3'—C4' | 0.4 (3) | C4"—C3"—C1"'—C6"' | −177.29 (16) |
C7'—O3—C4'—C3' | 3.5 (3) | C6"'—C1"'—C2"'—C3"' | 0.8 (3) |
C7'—O3—C4'—C5' | −176.97 (18) | C3"—C1"'—C2"'—C3"' | −179.60 (15) |
C2'—C3'—C4'—O3 | 179.49 (16) | C1"'—C2"'—C3"'—C4"' | 0.4 (3) |
C2'—C3'—C4'—C5' | 0.0 (3) | C2"'—C3"'—C4"'—C5"' | −1.6 (3) |
O3—C4'—C5'—C6' | 179.92 (17) | C2"'—C3"'—C4"'—Cl1 | 178.19 (13) |
C3'—C4'—C5'—C6' | −0.5 (3) | C3"'—C4"'—C5"'—C6"' | 1.5 (3) |
C4'—C5'—C6'—C1' | 0.7 (3) | Cl1—C4"'—C5"'—C6"' | −178.30 (14) |
C2'—C1'—C6'—C5' | −0.4 (3) | C4"'—C5"'—C6"'—C1"' | −0.2 (3) |
C1—C1'—C6'—C5' | 178.26 (17) | C2"'—C1"'—C6"'—C5"' | −0.9 (3) |
N1—N2—C3"—C4" | 0.77 (19) | C3"—C1"'—C6"'—C5"' | 179.48 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.89 (2) | 1.66 (2) | 2.5040 (18) | 157 (2) |
N1—H1···O1 | 0.94 (2) | 2.347 (19) | 2.7311 (19) | 104.0 (14) |
N1—H1···O2i | 0.94 (2) | 1.99 (2) | 2.902 (2) | 162.0 (17) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C18H15ClN2O3 |
Mr | 342.77 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 200 |
a, b, c (Å) | 30.1055 (18), 7.5383 (11), 13.8612 (14) |
β (°) | 90.338 (4) |
V (Å3) | 3145.7 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.26 |
Crystal size (mm) | 0.40 × 0.40 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.902, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8778, 3425, 2145 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.105, 0.91 |
No. of reflections | 3425 |
No. of parameters | 226 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.27 |
Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Siemens, 1994), SHELXTL/PC.
O1—C1—C2—C5" | −8.3 (2) | O1—C1—C1'—C2' | −1.1 (2) |
C1'—C1—C2—C5" | 174.18 (14) | C1—C1'—C2'—O2 | 0.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.89 (2) | 1.66 (2) | 2.5040 (18) | 157 (2) |
N1—H1···O1 | 0.94 (2) | 2.347 (19) | 2.7311 (19) | 104.0 (14) |
N1—H1···O2i | 0.94 (2) | 1.99 (2) | 2.902 (2) | 162.0 (17) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+2. |
Pyrazole derivatives are used in various forms in medicines as they have shown quite significant bacteriostatic, anti-inflammatory, anticonvulsive and antihypertensive activities (Mahajan et al., 1991; Biere et al., 1982; Lepage & Hublot, 1992; Nakamura et al., 1993). We have synthesized a series of pyrazoles to study structure–activity relationships. In the process of their derivatization, we condensed (II) (Ram et al., 1991) with resorcinol in the presence of dry HCl gas and anhydrous zinc chloride to obtain the corresponding ketone (III); methylation of (III) gave the title compound, (I).
The structure of (I) is illustrated in Fig. 1. The planes of the chlorophenyl and hydroxymethoxyphenyl groups are inclined at angles of 3.13 (8) and 38.80 (4)° with respect to the plane of the pyrazole ring. The bond lengths and angles are largely unremarkable. The H atoms with a high potential to hydrogen bond (i.e. those bonded to N1 and O2) were located from electron-density maps and allowed to refine freely. The O1···O2 separation of 2.5040 (18) Å (cf. sum of van der Waals radii = 3.04 Å) is indicative of hydrogen bonding, which restrains the atoms O1, C1, C1', C2', O2 and H2 to form an essentially planar unit (r.m.s. deviation = 0.0034). The H atom directly bonded to N1 is involved in bifurcated hydrogen bonding intramolecularly to O1 and intermolecularly to O2 (-x + 0.5, -y + 0.5, -z + 2); the sum of the angles about this H atom is 360° as required in the ideal situation. The overall effect of the hydrogen bonding in this system is to produce dimeric units as illustrated in Fig. 2. There are also significant intermolecular interactions which result in Cl···Cl separations of 3.224 (1) Å (cf. sum of van der Waals radii = 3.50 Å) and a C—Cl···Cl(-x, y, 0.5 - z) angle of 170.6 (1)°.