Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105040928/ln1189sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105040928/ln1189Isup2.hkl |
CCDC reference: 299630
The synthesis of (I) was performed according to the method of Jain et al. (1967). A mixture of 7-bromoethoxy-4-methylcoumarin (566 mg, 2 mmol), 1-(4-methoxyphenyl)piperazine (457 mg, 2 mmol) and anhydrous K2CO3 (276 mg, 2 mmol) was stirred at reflux in acetone (5 ml) and anhydrous ethanol (5 ml) for 48 h. The precipitate was filtered off and washed with fresh chloroform. The solvent was evaporated under reduced pressure from the combined filtrate and washings. The residue was chromatographed on a silica gel column by eluting with a cyclohexane/acetone mixture (8:1 v/v) to give a colorless solid (170 mg, 21%, m.p 511 K); 1H NMR (500 MHz, CDCl3): δ 7.51 (d, 1H, H-5, J = 8.91 Hz), 6.95 (m, 4H, Ph), 6.86 (dd, 1H, H-6, J = 8.80 and 2.60 Hz), 6.82 (d, 1H, H-8, J = 2.60 Hz), 6.15 (s, 1H, H-3), 4.10 (t, 2H, CH2O, J = 6.30 Hz), 3.77 (s, 3H, OCH3), 3.10 [m, 4H, N4 (CH2)2], 2.85 [m, 4H, (CH2)2N1], 2.60 (m, 2H, N1CH2), 2.38 (s, 3H, CH3). A crystal suitable for diffraction analysis was obtained by slow evaporation of a solution of (I) in a mixture of ethanol and ethyl acetate (1:1 v/v) at room temperature.
The positions of the H atoms of the water molecule were located initially in a difference Fourier map and then constrained to ride on the parent O atom with Uiso(H) = 1.5Ueq(O). The methyl H atoms were constrained to an ideal geometry with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about the C—C bonds. All remaining H atoms were placed in geometrically idealized positions (C—H = 0.93–0.97 Å) and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL and WinGX (Version 1.7; Farrugia, 1999).
C23H26N2O4·H2O | F(000) = 880 |
Mr = 412.47 | Dx = 1.305 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2841 reflections |
a = 10.776 (7) Å | θ = 2.2–24.1° |
b = 7.483 (5) Å | µ = 0.09 mm−1 |
c = 26.381 (18) Å | T = 298 K |
β = 99.406 (10)° | Prism, colorless |
V = 2099 (2) Å3 | 0.53 × 0.48 × 0.27 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3684 independent reflections |
Radiation source: fine-focus sealed tube | 2296 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −12→10 |
Tmin = 0.962, Tmax = 0.985 | k = −8→8 |
10516 measured reflections | l = −31→31 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.28P] where P = (Fo2 + 2Fc2)/3 |
3684 reflections | (Δ/σ)max < 0.001 |
273 parameters | Δρmax = 0.17 e Å−3 |
2 restraints | Δρmin = −0.22 e Å−3 |
C23H26N2O4·H2O | V = 2099 (2) Å3 |
Mr = 412.47 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.776 (7) Å | µ = 0.09 mm−1 |
b = 7.483 (5) Å | T = 298 K |
c = 26.381 (18) Å | 0.53 × 0.48 × 0.27 mm |
β = 99.406 (10)° |
Bruker SMART CCD area-detector diffractometer | 3684 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2296 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.985 | Rint = 0.038 |
10516 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.17 e Å−3 |
3684 reflections | Δρmin = −0.22 e Å−3 |
273 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 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 | ||
N1 | 0.53174 (16) | 0.7986 (2) | 0.12525 (6) | 0.0505 (5) | |
N2 | 0.31370 (15) | 0.8865 (2) | 0.17170 (6) | 0.0456 (4) | |
O1 | 1.17834 (14) | 0.76897 (18) | −0.00482 (5) | 0.0523 (4) | |
O2 | 1.36372 (17) | 0.7424 (2) | −0.02888 (6) | 0.0759 (5) | |
O3 | 0.80421 (14) | 0.8368 (2) | 0.05953 (6) | 0.0619 (4) | |
O4 | −0.15187 (14) | 0.9134 (2) | 0.23986 (6) | 0.0660 (5) | |
O5 | 0.47771 (17) | 0.4188 (2) | 0.09991 (7) | 0.0875 (6) | |
H5A | 0.4900 | 0.5342 | 0.1045 | 0.105* | |
H5B | 0.5127 | 0.4031 | 0.0728 | 0.105* | |
C1 | 1.2518 (2) | 0.7162 (3) | −0.04013 (8) | 0.0562 (6) | |
C2 | 1.1882 (2) | 0.6361 (3) | −0.08669 (8) | 0.0579 (6) | |
H2 | 1.2357 | 0.6023 | −0.1116 | 0.069* | |
C3 | 1.0639 (2) | 0.6078 (3) | −0.09596 (7) | 0.0526 (6) | |
C4 | 0.9889 (2) | 0.6635 (2) | −0.05837 (7) | 0.0454 (5) | |
C5 | 0.8588 (2) | 0.6460 (3) | −0.06280 (8) | 0.0546 (6) | |
H5 | 0.8145 | 0.5948 | −0.0925 | 0.066* | |
C6 | 0.7934 (2) | 0.7013 (3) | −0.02513 (8) | 0.0541 (6) | |
H6 | 0.7066 | 0.6872 | −0.0293 | 0.065* | |
C7 | 0.8583 (2) | 0.7787 (3) | 0.01941 (8) | 0.0475 (5) | |
C8 | 0.9869 (2) | 0.7992 (3) | 0.02532 (7) | 0.0470 (5) | |
H8 | 1.0307 | 0.8503 | 0.0551 | 0.056* | |
C9 | 1.0498 (2) | 0.7438 (2) | −0.01305 (7) | 0.0443 (5) | |
C10 | 1.0030 (3) | 0.5162 (3) | −0.14454 (8) | 0.0743 (8) | |
H10A | 0.9370 | 0.5904 | −0.1621 | 0.111* | |
H10B | 0.9685 | 0.4038 | −0.1361 | 0.111* | |
H10C | 1.0648 | 0.4959 | −0.1663 | 0.111* | |
C11 | 0.6738 (2) | 0.8042 (3) | 0.05988 (8) | 0.0569 (6) | |
H11A | 0.6524 | 0.6810 | 0.0509 | 0.068* | |
H11B | 0.6219 | 0.8823 | 0.0359 | 0.068* | |
C12 | 0.6566 (2) | 0.8438 (3) | 0.11425 (8) | 0.0611 (6) | |
H12A | 0.7190 | 0.7775 | 0.1375 | 0.073* | |
H12B | 0.6718 | 0.9700 | 0.1210 | 0.073* | |
C13 | 0.5342 (2) | 0.8006 (3) | 0.18101 (8) | 0.0580 (6) | |
H13A | 0.5620 | 0.9172 | 0.1944 | 0.070* | |
H13B | 0.5945 | 0.7128 | 0.1969 | 0.070* | |
C14 | 0.4084 (2) | 0.7606 (3) | 0.19534 (8) | 0.0572 (6) | |
H14A | 0.3832 | 0.6403 | 0.1844 | 0.069* | |
H14B | 0.4145 | 0.7662 | 0.2324 | 0.069* | |
C15 | 0.3096 (2) | 0.8845 (3) | 0.11589 (7) | 0.0570 (6) | |
H15A | 0.2487 | 0.9719 | 0.1001 | 0.068* | |
H15B | 0.2823 | 0.7677 | 0.1026 | 0.068* | |
C16 | 0.4362 (2) | 0.9263 (3) | 0.10182 (8) | 0.0580 (6) | |
H16A | 0.4304 | 0.9226 | 0.0648 | 0.070* | |
H16B | 0.4612 | 1.0461 | 0.1133 | 0.070* | |
C17 | 0.19665 (19) | 0.8838 (2) | 0.18936 (7) | 0.0421 (5) | |
C18 | 0.1749 (2) | 0.7849 (3) | 0.23161 (7) | 0.0508 (5) | |
H18 | 0.2387 | 0.7119 | 0.2483 | 0.061* | |
C19 | 0.0613 (2) | 0.7915 (3) | 0.24977 (7) | 0.0517 (6) | |
H19 | 0.0506 | 0.7250 | 0.2785 | 0.062* | |
C20 | −0.0357 (2) | 0.8961 (3) | 0.22545 (7) | 0.0485 (5) | |
C21 | −0.0158 (2) | 0.9946 (3) | 0.18305 (8) | 0.0524 (6) | |
H21 | −0.0804 | 1.0653 | 0.1660 | 0.063* | |
C22 | 0.0970 (2) | 0.9897 (3) | 0.16589 (7) | 0.0499 (5) | |
H22 | 0.1078 | 1.0590 | 0.1377 | 0.060* | |
C23 | −0.1775 (2) | 0.8104 (4) | 0.28198 (9) | 0.0760 (8) | |
H23A | −0.2593 | 0.8406 | 0.2893 | 0.114* | |
H23B | −0.1153 | 0.8350 | 0.3116 | 0.114* | |
H23C | −0.1753 | 0.6857 | 0.2736 | 0.114* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0525 (11) | 0.0517 (11) | 0.0468 (10) | −0.0007 (9) | 0.0067 (8) | 0.0028 (8) |
N2 | 0.0516 (11) | 0.0458 (10) | 0.0379 (9) | 0.0043 (8) | 0.0028 (8) | 0.0063 (7) |
O1 | 0.0602 (10) | 0.0522 (9) | 0.0457 (8) | −0.0058 (7) | 0.0123 (7) | −0.0056 (7) |
O2 | 0.0662 (12) | 0.0896 (14) | 0.0756 (11) | −0.0065 (10) | 0.0226 (9) | −0.0157 (9) |
O3 | 0.0566 (10) | 0.0688 (11) | 0.0625 (9) | −0.0072 (8) | 0.0163 (8) | −0.0108 (8) |
O4 | 0.0641 (11) | 0.0767 (12) | 0.0598 (9) | 0.0069 (9) | 0.0180 (8) | 0.0089 (8) |
O5 | 0.0984 (14) | 0.0706 (12) | 0.0981 (13) | −0.0173 (10) | 0.0296 (11) | −0.0117 (10) |
C1 | 0.0703 (17) | 0.0490 (14) | 0.0525 (13) | −0.0014 (12) | 0.0197 (13) | 0.0026 (11) |
C2 | 0.0834 (18) | 0.0475 (14) | 0.0467 (13) | −0.0015 (12) | 0.0223 (12) | −0.0002 (10) |
C3 | 0.0856 (18) | 0.0316 (12) | 0.0414 (11) | −0.0044 (11) | 0.0125 (12) | 0.0024 (9) |
C4 | 0.0672 (15) | 0.0296 (11) | 0.0384 (11) | −0.0055 (10) | 0.0056 (10) | 0.0040 (9) |
C5 | 0.0731 (17) | 0.0442 (13) | 0.0429 (12) | −0.0119 (11) | −0.0019 (11) | 0.0014 (10) |
C6 | 0.0559 (14) | 0.0512 (14) | 0.0535 (13) | −0.0068 (11) | 0.0035 (11) | 0.0080 (11) |
C7 | 0.0588 (15) | 0.0368 (12) | 0.0471 (12) | −0.0017 (10) | 0.0091 (11) | 0.0041 (9) |
C8 | 0.0569 (14) | 0.0434 (13) | 0.0399 (11) | −0.0034 (10) | 0.0054 (10) | −0.0015 (9) |
C9 | 0.0547 (14) | 0.0322 (11) | 0.0451 (11) | −0.0045 (9) | 0.0058 (10) | 0.0061 (9) |
C10 | 0.110 (2) | 0.0630 (16) | 0.0500 (13) | −0.0117 (15) | 0.0134 (14) | −0.0141 (12) |
C11 | 0.0513 (14) | 0.0566 (14) | 0.0628 (14) | −0.0044 (11) | 0.0090 (11) | 0.0024 (11) |
C12 | 0.0591 (15) | 0.0631 (16) | 0.0614 (14) | −0.0040 (12) | 0.0111 (12) | −0.0027 (12) |
C13 | 0.0578 (15) | 0.0645 (15) | 0.0488 (12) | 0.0065 (12) | 0.0001 (11) | 0.0042 (11) |
C14 | 0.0591 (14) | 0.0654 (15) | 0.0452 (11) | 0.0092 (12) | 0.0033 (11) | 0.0141 (11) |
C15 | 0.0580 (14) | 0.0681 (15) | 0.0434 (12) | 0.0072 (12) | 0.0038 (10) | 0.0107 (11) |
C16 | 0.0637 (15) | 0.0589 (15) | 0.0519 (13) | 0.0050 (12) | 0.0114 (11) | 0.0132 (11) |
C17 | 0.0514 (13) | 0.0349 (11) | 0.0380 (10) | −0.0017 (10) | 0.0013 (10) | −0.0010 (9) |
C18 | 0.0602 (14) | 0.0445 (13) | 0.0451 (12) | 0.0035 (11) | 0.0007 (11) | 0.0076 (10) |
C19 | 0.0648 (15) | 0.0491 (13) | 0.0410 (11) | −0.0030 (11) | 0.0082 (11) | 0.0064 (10) |
C20 | 0.0547 (14) | 0.0456 (13) | 0.0442 (11) | −0.0021 (11) | 0.0054 (11) | −0.0041 (10) |
C21 | 0.0592 (15) | 0.0455 (13) | 0.0507 (12) | 0.0092 (11) | 0.0035 (11) | 0.0043 (10) |
C22 | 0.0630 (15) | 0.0429 (12) | 0.0428 (11) | 0.0038 (11) | 0.0055 (11) | 0.0075 (10) |
C23 | 0.0715 (17) | 0.096 (2) | 0.0632 (15) | −0.0050 (15) | 0.0203 (13) | 0.0125 (14) |
N1—C16 | 1.465 (3) | C10—H10B | 0.9600 |
N1—C12 | 1.461 (3) | C10—H10C | 0.9600 |
N1—C13 | 1.467 (3) | C11—C12 | 1.505 (3) |
N2—C17 | 1.414 (3) | C11—H11A | 0.9700 |
N2—C14 | 1.452 (2) | C11—H11B | 0.9700 |
N2—C15 | 1.466 (3) | C12—H12A | 0.9700 |
O1—C1 | 1.375 (3) | C12—H12B | 0.9700 |
O1—C9 | 1.380 (3) | C13—C14 | 1.496 (3) |
O2—C1 | 1.210 (3) | C13—H13A | 0.9700 |
O3—C7 | 1.360 (2) | C13—H13B | 0.9700 |
O3—C11 | 1.428 (3) | C14—H14A | 0.9700 |
O4—C20 | 1.373 (2) | C14—H14B | 0.9700 |
O4—C23 | 1.416 (3) | C15—C16 | 1.505 (3) |
O5—H5A | 0.8786 | C15—H15A | 0.9700 |
O5—H5B | 0.8689 | C15—H15B | 0.9700 |
C1—C2 | 1.436 (3) | C16—H16A | 0.9700 |
C2—C3 | 1.338 (3) | C16—H16B | 0.9700 |
C2—H2 | 0.9300 | C17—C18 | 1.389 (3) |
C3—C4 | 1.440 (3) | C17—C22 | 1.395 (3) |
C3—C10 | 1.506 (3) | C18—C19 | 1.386 (3) |
C4—C5 | 1.394 (3) | C18—H18 | 0.9300 |
C4—C9 | 1.401 (3) | C19—C20 | 1.377 (3) |
C5—C6 | 1.373 (3) | C19—H19 | 0.9300 |
C5—H5 | 0.9300 | C20—C21 | 1.385 (3) |
C6—C7 | 1.391 (3) | C21—C22 | 1.365 (3) |
C6—H6 | 0.9300 | C21—H21 | 0.9300 |
C7—C8 | 1.378 (3) | C22—H22 | 0.9300 |
C8—C9 | 1.371 (3) | C23—H23A | 0.9600 |
C8—H8 | 0.9300 | C23—H23B | 0.9600 |
C10—H10A | 0.9600 | C23—H23C | 0.9600 |
C16—N1—C12 | 111.81 (17) | N1—C12—H12B | 108.8 |
C16—N1—C13 | 108.22 (17) | C11—C12—H12B | 108.8 |
C12—N1—C13 | 109.31 (16) | H12A—C12—H12B | 107.7 |
C17—N2—C14 | 116.81 (15) | N1—C13—C14 | 112.53 (17) |
C17—N2—C15 | 116.63 (16) | N1—C13—H13A | 109.1 |
C14—N2—C15 | 109.19 (16) | C14—C13—H13A | 109.1 |
C1—O1—C9 | 121.91 (17) | N1—C13—H13B | 109.1 |
C7—O3—C11 | 119.84 (17) | C14—C13—H13B | 109.1 |
C20—O4—C23 | 118.00 (17) | H13A—C13—H13B | 107.8 |
H5A—O5—H5B | 99.9 | N2—C14—C13 | 111.34 (17) |
O2—C1—O1 | 116.6 (2) | N2—C14—H14A | 109.4 |
O2—C1—C2 | 126.5 (2) | C13—C14—H14A | 109.4 |
O1—C1—C2 | 116.9 (2) | N2—C14—H14B | 109.4 |
C3—C2—C1 | 123.1 (2) | C13—C14—H14B | 109.4 |
C3—C2—H2 | 118.5 | H14A—C14—H14B | 108.0 |
C1—C2—H2 | 118.5 | N2—C15—C16 | 111.45 (17) |
C2—C3—C4 | 119.1 (2) | N2—C15—H15A | 109.3 |
C2—C3—C10 | 120.8 (2) | C16—C15—H15A | 109.3 |
C4—C3—C10 | 120.1 (2) | N2—C15—H15B | 109.3 |
C5—C4—C9 | 115.84 (19) | C16—C15—H15B | 109.3 |
C5—C4—C3 | 125.8 (2) | H15A—C15—H15B | 108.0 |
C9—C4—C3 | 118.3 (2) | N1—C16—C15 | 111.33 (17) |
C6—C5—C4 | 122.6 (2) | N1—C16—H16A | 109.4 |
C6—C5—H5 | 118.7 | C15—C16—H16A | 109.4 |
C4—C5—H5 | 118.7 | N1—C16—H16B | 109.4 |
C5—C6—C7 | 119.4 (2) | C15—C16—H16B | 109.4 |
C5—C6—H6 | 120.3 | H16A—C16—H16B | 108.0 |
C7—C6—H6 | 120.3 | C18—C17—C22 | 116.11 (19) |
O3—C7—C8 | 115.28 (18) | C18—C17—N2 | 123.24 (18) |
O3—C7—C6 | 124.8 (2) | C22—C17—N2 | 120.59 (17) |
C8—C7—C6 | 119.9 (2) | C19—C18—C17 | 122.16 (19) |
C9—C8—C7 | 119.50 (19) | C19—C18—H18 | 118.9 |
C9—C8—H8 | 120.2 | C17—C18—H18 | 118.9 |
C7—C8—H8 | 120.2 | C20—C19—C18 | 120.34 (19) |
C8—C9—O1 | 116.58 (18) | C20—C19—H19 | 119.8 |
C8—C9—C4 | 122.7 (2) | C18—C19—H19 | 119.8 |
O1—C9—C4 | 120.70 (19) | O4—C20—C19 | 125.57 (19) |
C3—C10—H10A | 109.5 | O4—C20—C21 | 116.21 (19) |
C3—C10—H10B | 109.5 | C19—C20—C21 | 118.2 (2) |
H10A—C10—H10B | 109.5 | C22—C21—C20 | 121.1 (2) |
C3—C10—H10C | 109.5 | C22—C21—H21 | 119.4 |
H10A—C10—H10C | 109.5 | C20—C21—H21 | 119.4 |
H10B—C10—H10C | 109.5 | C21—C22—C17 | 122.04 (19) |
O3—C11—C12 | 104.33 (17) | C21—C22—H22 | 119.0 |
O3—C11—H11A | 110.9 | C17—C22—H22 | 119.0 |
C12—C11—H11A | 110.9 | O4—C23—H23A | 109.5 |
O3—C11—H11B | 110.9 | O4—C23—H23B | 109.5 |
C12—C11—H11B | 110.9 | H23A—C23—H23B | 109.5 |
H11A—C11—H11B | 108.9 | O4—C23—H23C | 109.5 |
N1—C12—C11 | 113.87 (18) | H23A—C23—H23C | 109.5 |
N1—C12—H12A | 108.8 | H23B—C23—H23C | 109.5 |
C11—C12—H12A | 108.8 | ||
C9—O1—C1—O2 | −179.06 (19) | C13—N1—C12—C11 | 166.38 (19) |
C9—O1—C1—C2 | 1.1 (3) | O3—C11—C12—N1 | −173.07 (17) |
O2—C1—C2—C3 | 178.4 (2) | C16—N1—C13—C14 | 56.4 (2) |
O1—C1—C2—C3 | −1.7 (3) | C12—N1—C13—C14 | 178.35 (18) |
C1—C2—C3—C4 | 1.5 (3) | C17—N2—C14—C13 | −168.91 (17) |
C1—C2—C3—C10 | −177.4 (2) | C15—N2—C14—C13 | 56.0 (2) |
C2—C3—C4—C5 | 178.9 (2) | N1—C13—C14—N2 | −57.7 (2) |
C10—C3—C4—C5 | −2.1 (3) | C17—N2—C15—C16 | 168.08 (17) |
C2—C3—C4—C9 | −0.7 (3) | C14—N2—C15—C16 | −56.8 (2) |
C10—C3—C4—C9 | 178.23 (19) | C12—N1—C16—C15 | −176.75 (17) |
C9—C4—C5—C6 | −0.8 (3) | C13—N1—C16—C15 | −56.3 (2) |
C3—C4—C5—C6 | 179.57 (19) | N2—C15—C16—N1 | 58.4 (2) |
C4—C5—C6—C7 | 0.2 (3) | C14—N2—C17—C18 | 8.4 (3) |
C11—O3—C7—C8 | −173.17 (18) | C15—N2—C17—C18 | 140.1 (2) |
C11—O3—C7—C6 | 6.2 (3) | C14—N2—C17—C22 | −174.68 (18) |
C5—C6—C7—O3 | −179.25 (19) | C15—N2—C17—C22 | −43.0 (3) |
C5—C6—C7—C8 | 0.0 (3) | C22—C17—C18—C19 | −0.5 (3) |
O3—C7—C8—C9 | 179.71 (18) | N2—C17—C18—C19 | 176.64 (18) |
C6—C7—C8—C9 | 0.3 (3) | C17—C18—C19—C20 | 1.1 (3) |
C7—C8—C9—O1 | 179.68 (17) | C23—O4—C20—C19 | −2.7 (3) |
C7—C8—C9—C4 | −1.0 (3) | C23—O4—C20—C21 | 177.91 (19) |
C1—O1—C9—C8 | 178.94 (18) | C18—C19—C20—O4 | −179.94 (19) |
C1—O1—C9—C4 | −0.4 (3) | C18—C19—C20—C21 | −0.6 (3) |
C5—C4—C9—C8 | 1.2 (3) | O4—C20—C21—C22 | 178.93 (18) |
C3—C4—C9—C8 | −179.13 (18) | C19—C20—C21—C22 | −0.5 (3) |
C5—C4—C9—O1 | −179.52 (17) | C20—C21—C22—C17 | 1.1 (3) |
C3—C4—C9—O1 | 0.2 (3) | C18—C17—C22—C21 | −0.6 (3) |
C7—O3—C11—C12 | 166.23 (18) | N2—C17—C22—C21 | −177.82 (18) |
C16—N1—C12—C11 | −73.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···N1 | 0.88 | 2.08 | 2.955 (3) | 172 |
O5—H5B···O2i | 0.87 | 2.19 | 2.989 (3) | 152 |
C6—H6···O5ii | 0.93 | 2.61 | 3.369 (3) | 139 |
C23—H23B···O5iii | 0.96 | 2.63 | 3.579 (4) | 170 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C23H26N2O4·H2O |
Mr | 412.47 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 10.776 (7), 7.483 (5), 26.381 (18) |
β (°) | 99.406 (10) |
V (Å3) | 2099 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.53 × 0.48 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.962, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10516, 3684, 2296 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.124, 1.03 |
No. of reflections | 3684 |
No. of parameters | 273 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.22 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL and WinGX (Version 1.7; Farrugia, 1999).
N1—C16 | 1.465 (3) | N2—C14 | 1.452 (2) |
N1—C12 | 1.461 (3) | N2—C15 | 1.466 (3) |
N1—C13 | 1.467 (3) | C13—C14 | 1.496 (3) |
N2—C17 | 1.414 (3) | C15—C16 | 1.505 (3) |
C16—N1—C12 | 111.81 (17) | C14—N2—C15 | 109.19 (16) |
C16—N1—C13 | 108.22 (17) | N1—C13—C14 | 112.53 (17) |
C12—N1—C13 | 109.31 (16) | N2—C14—C13 | 111.34 (17) |
C17—N2—C14 | 116.81 (15) | N2—C15—C16 | 111.45 (17) |
C17—N2—C15 | 116.63 (16) | N1—C16—C15 | 111.33 (17) |
N1—C13—C14—N2 | −57.7 (2) | C23—O4—C20—C19 | −2.7 (3) |
N2—C15—C16—N1 | 58.4 (2) | C23—O4—C20—C21 | 177.91 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···N1 | 0.88 | 2.08 | 2.955 (3) | 172 |
O5—H5B···O2i | 0.87 | 2.19 | 2.989 (3) | 152 |
C6—H6···O5ii | 0.93 | 2.61 | 3.369 (3) | 139 |
C23—H23B···O5iii | 0.96 | 2.63 | 3.579 (4) | 170 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
Coumarin is the parent organic compound of a class of naturally occurring phytochemicals with fragrance found in many plant species, and these compounds have received significant attention for many years. Natural or synthetic compounds comprising a coumarin backbone have a wide range of biological activities, such as anti-inflammatory (Kontogiorgis & Hadjipavlou-Litina, 2005), antitumour (Dexeus et al., 1990), anti-allergic (Buckle et al., 1979) and anti-HIV-1 (Lunney et al., 1994) activities. Compounds possessing a piperazine ring are being studied extensively as potential psychotropic agents (Lopez-Rodriguez et al., 1999). The neuroleptic and anxiolytic (tranquilizer) properties of these compounds are due to their interaction with dopamine and serotonin receptors. According to the hypothetical views on the topography of the α1-adrenoceptor antagonists (Kenny et al., 1997; Bremner et al., 2000; Dardonville et al., 2000), the basic pharmaphore of an α1-adrenoceptor antagonist should include a basic nitrogen center (BNC), hydrophobic groups (HP), an aromatic ring (AR) linked to the BNC directly and a hydrogen-bond donor or receptor (HB). We have designed and synthesized a series of coumarin derivatives containing a piperazine ring on the basis of the abovementioned structure–activity relationships. The structure elucidation of these compounds is important for understanding the molecular mechanisms of their biological activity. However, reports about the crystal structures of this kind of compounds are scarce (Estrada et al., 2000). In this context, the crystal structure of the monohydrate of one of the prepared novel coumarin derivatives, viz. the title compound, (I), is reported.
A view of the molecular structure of compound (I) is shown in Fig. 1. The bond lengths and angles in (I) are comparable to the average values reported in the literature for atoms in similar environments (Allen et al., 1987). The benzopyran ring (O1/C1–C9) is planar, with a mean deviation of the constituent atoms from their least-squares plane of 0.006 Å. The molecule of (I) has a fully extended conformation, like its analogue trans-1-(2-methoxyphenyl)-4-[4-(2-phthalimido)cyclohexyl]piperazine (Dalpiaz et al., 1996). In (I), the dihedral angle between the plane of the phenyl ring and the least-squares plane of the piperazine ring is 17.42 (10)°, while Kuipers et al. (1997) reported that the angle between the plane of the benzene and piperazine rings in bis(N-{2-[4-(2,3-dihydro-1,4-benzodioxin-5-yl)-cis-2,6-dimethyl- 1-piperazinyl]ethyl}-4-fluorobenzenecarboxamide)fumarate is approximately 30°. In (I), the distances from the central N atom, N1, to the centroid of the phenyl ring, to the hydrogen-bond donor C23 and to the centroid of the coumarin moiety, the hydrophobic centre, are 5.689 (4), 9.265 (7) and 7.175 (4) Å, respectively. The corresponding distances reported by Li & Xia (2005) for α1-adrenoceptor antagonists are 5.82, 9.08 and 7.53 Å, respectively. The angle between the coumarin moiety and the phenyl ring, D, is 65.44 (8)° in (I) and 67.8° in the report by Paluchowska et al. (1999). The similarity between the key geometric parameters of (I) and those given by Paluchowska et al. (1999) and Li & Xia (2005) suggests that the title compound may have potential biological activity. Actually, the bioassay results for tests of the α1-adrenoceptor antagonistic activity of (I) through in vitro animal experiments in the New Drugs Screening Center of Jiangsu province of China have shown a slightly lower activity than prozosin, the most accepted positive control substance for α1-adrenoceptor antagonistic activity (Ford et al., 1994).
The piperazine ring adopts an almost perfect chair conformation, as in the case of N,N'-dimethylpiperazine (Parkin & Parsons, 2002). This is confirmed by the puckering parameters [Q = 0.566 (2) Å, q2 = 0.008 (2) Å, q3 = −0.566 (2) Å, θ = 180.0 (2)° and ϕ2 = 108 (14)°] for the atom sequence N1—C13—C14—N2—C15—C16 (Cremer & Pople, 1975) and the intra-ring torsion angles shown in Table 1. The N atoms are substituted in equatorial positions, which meets the requirements for the bioactive conformation of an α1-adrenoceptor antagonist (Kuipers et al., 1997). The length of the C17—N2 bond is somewhat shorter (Table 1) than that of the C12—N1 bond as a result of conjugation between atom N2 and the 4-methoxyphenyl ring to which it is bonded. The methoxy group is coplanar with ring D (Table 1).
The title compound crystallized as a monohydrate. Each water molecule donates two hydrogen bonds to two adjacent piperazine molecules (Table 2). These interactions link two water molecules and two piperazine molecules alternately across a centre of inversion into a tetrameric unit. The interactions that lead to this unit can be described by an overall graph-set motif of R44(26) (Bernstein et al., 1995; Desiraju, 1995). In addition, each water molecule accepts two soft C—H···O interactions (Desiraju, 1996) from two piperazine molecules not involved in the original tetramer, so that each water molecule is surrounded by four piperazine molecules (Fig. 2).
Additional π–π stacking interactions are present between the pyran ring (A; π-electron deficient) and the benzyl ring (B; π-electron rich) of the adjacent centrosymmetrically related (symmetry code: 2 − x, 1 − y, −z) benzopyran group within the hydrogen-bonded tetrameric unit (Fig. 3). The plane of ring A makes an angle of 0.38° with that of ring B of the opposing molecule and the two rings overlap with an intercentroid distance of 3.643 (3) Å. The perpendicular distance from the centre of gravity of each ring to the plane of the opposing ring is 3.50 Å with a slippage from the centroid of the opposing ring of 0.85 Å.