The title compound, C
27H
27N
5O
3·H
2O, is built up from pyrazolinone, phenyl and acetophenone oxime moieties. The 2-phenyl substituent is nearly perpendicular to the pyrazolinone ring, with a dihedral angle of 87.66 (1)°. The acetophenone oxime moieties are twisted out of the pyrazolinone-ring plane by 47.04 (1)°. The molecules in the crystal pack in an antiparallel fashion and are held together by hydrogen-bonded water molecules and intermolecular O—H
O and O—H
N hydrogen bonds.
Supporting information
CCDC reference: 192303
4-Aminoantipyrine (4-ATP; 1 mol) and α-bromoacetophenone oxime (2 mol), alternatively called (E)-2-bromo-1-phenylethanone oxime, were mixed in ethanol-water (50 ml; 1:1 v/v) and heated at 343 K for 2 h with vigorous stirring. The resulting beige-coloured precipitate was filtered off and washed three times with EtOH-H2O (1:1 v/v) and finally with diethyl ether, then air dried (yield 82.5%). Recrystallization from ethanol (95%) gave colourless block-shaped crystals of (I) suitable for single-crystal X-ray analysis. IR (KBr, ν, cm−1): 3280 (O—H), 3153 (Ar CH), 2885 (N—CH3, CH2), 1605 and 1612 (C ═N, C ═O), 1548 (C ═C), 964 (N—O), 895, 840, 691, 557. ESI-MS (m/z): 470.
The water H atoms were refined isotropically, with Uiso values in the range 0.105 (12)–0.110 (14) Å2. The other H atoms were treated using a riding model, with fixed C—H distances of 0.93–0.97 Å for C—H bonds, 0.97 Å for C—H2 bonds and 0.96 Å for C—H3 (HFIX 137, 33), and with an O—H distance of 0.82 Å (HFIX 83). The Uiso(H) values for these H atoms were fixed at either 1.2 or 1.5Ueq(parent).
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
4-[
N,
N-Bis(2-hydroxyimino-2-phenylethyl)amino]-2,3-dimethyl-2-phenyl- 2,3-dihydropyrazol-3-one monohydrate
top
Crystal data top
C27H27N5O3·H2O | F(000) = 1032 |
Mr = 487.55 | Dx = 1.243 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 10.385 (6) Å | θ = 1.8–25.0° |
b = 18.024 (4) Å | µ = 0.09 mm−1 |
c = 14.229 (5) Å | T = 293 K |
β = 102.05 (5)° | Block, colourless |
V = 2604.6 (19) Å3 | 0.46 × 0.38 × 0.12 mm |
Z = 4 | |
Data collection top
Siemens P4 diffractometer | Rint = 0.025 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.9° |
Graphite monochromator | h = −1→12 |
ω scans | k = −1→21 |
4862 measured reflections | l = −16→16 |
4592 independent reflections | 3 standard reflections every 97 reflections |
2956 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0636P)2 + 0.8613P] where P = (Fo2 + 2Fc2)/3 |
4592 reflections | (Δ/σ)max = 0.006 |
334 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C27H27N5O3·H2O | V = 2604.6 (19) Å3 |
Mr = 487.55 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.385 (6) Å | µ = 0.09 mm−1 |
b = 18.024 (4) Å | T = 293 K |
c = 14.229 (5) Å | 0.46 × 0.38 × 0.12 mm |
β = 102.05 (5)° | |
Data collection top
Siemens P4 diffractometer | Rint = 0.025 |
4862 measured reflections | 3 standard reflections every 97 reflections |
4592 independent reflections | intensity decay: none |
2956 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.23 e Å−3 |
4592 reflections | Δρmin = −0.22 e Å−3 |
334 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. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.79733 (16) | 0.51577 (9) | 0.65611 (14) | 0.0607 (5) | |
O2 | 0.8724 (2) | 0.62651 (11) | 0.46281 (16) | 0.0762 (6) | |
H2A | 0.9457 | 0.6203 | 0.4510 | 0.114* | |
O3 | 0.37695 (18) | 0.55068 (11) | 0.48587 (16) | 0.0771 (6) | |
H3A | 0.3248 | 0.5310 | 0.4417 | 0.116* | |
O4 | 0.9227 (2) | 0.38534 (12) | 0.62181 (18) | 0.0665 (6) | |
N1 | 0.95406 (19) | 0.59910 (11) | 0.73126 (16) | 0.0521 (5) | |
N2 | 0.96913 (19) | 0.67647 (11) | 0.73522 (16) | 0.0531 (5) | |
N3 | 0.63728 (18) | 0.66453 (11) | 0.59783 (14) | 0.0460 (5) | |
N4 | 0.8328 (2) | 0.70004 (13) | 0.44280 (17) | 0.0641 (6) | |
N5 | 0.3219 (2) | 0.61558 (12) | 0.51331 (18) | 0.0591 (6) | |
C1 | 0.7660 (2) | 0.65145 (13) | 0.65488 (17) | 0.0437 (6) | |
C2 | 0.8315 (2) | 0.58191 (13) | 0.67607 (18) | 0.0459 (6) | |
C3 | 1.0674 (2) | 0.55223 (13) | 0.74864 (19) | 0.0486 (6) | |
C4 | 1.1043 (3) | 0.51588 (17) | 0.8343 (2) | 0.0728 (9) | |
H4A | 1.0554 | 0.5211 | 0.8817 | 0.087* | |
C5 | 1.2172 (4) | 0.47049 (19) | 0.8501 (3) | 0.0935 (12) | |
H5A | 1.2435 | 0.4451 | 0.9079 | 0.112* | |
C6 | 1.2864 (3) | 0.46445 (19) | 0.7807 (4) | 0.0964 (14) | |
H6A | 1.3611 | 0.4346 | 0.7915 | 0.116* | |
C7 | 1.2513 (3) | 0.5003 (2) | 0.6950 (4) | 0.0928 (12) | |
H7A | 1.3010 | 0.4950 | 0.6481 | 0.111* | |
C8 | 1.1404 (3) | 0.54478 (17) | 0.6789 (2) | 0.0682 (8) | |
H8A | 1.1151 | 0.5697 | 0.6207 | 0.082* | |
C9 | 1.0771 (3) | 0.70939 (17) | 0.8032 (2) | 0.0760 (9) | |
H9A | 1.1471 | 0.6739 | 0.8198 | 0.114* | |
H9B | 1.0474 | 0.7239 | 0.8600 | 0.114* | |
H9C | 1.1086 | 0.7522 | 0.7748 | 0.114* | |
C10 | 0.8519 (2) | 0.70648 (13) | 0.69319 (17) | 0.0475 (6) | |
C11 | 0.8297 (3) | 0.78829 (14) | 0.6921 (2) | 0.0638 (8) | |
H11A | 0.8475 | 0.8067 | 0.7569 | 0.096* | |
H11B | 0.7399 | 0.7988 | 0.6621 | 0.096* | |
H11C | 0.8874 | 0.8120 | 0.6568 | 0.096* | |
C12 | 0.6340 (3) | 0.65588 (16) | 0.49395 (18) | 0.0552 (7) | |
H12A | 0.5441 | 0.6606 | 0.4582 | 0.066* | |
H12B | 0.6653 | 0.6068 | 0.4820 | 0.066* | |
C13 | 0.7183 (3) | 0.71329 (15) | 0.45984 (18) | 0.0548 (7) | |
C14 | 0.6711 (3) | 0.79160 (16) | 0.44144 (18) | 0.0588 (7) | |
C15 | 0.5494 (3) | 0.81370 (19) | 0.4557 (2) | 0.0779 (9) | |
H15A | 0.4959 | 0.7796 | 0.4781 | 0.093* | |
C16 | 0.5054 (4) | 0.8863 (2) | 0.4369 (3) | 0.0940 (11) | |
H16A | 0.4230 | 0.9000 | 0.4471 | 0.113* | |
C17 | 0.5814 (4) | 0.9374 (2) | 0.4038 (2) | 0.0881 (11) | |
H17A | 0.5512 | 0.9856 | 0.3908 | 0.106* | |
C18 | 0.7034 (4) | 0.91686 (19) | 0.3897 (2) | 0.0839 (10) | |
H18A | 0.7563 | 0.9515 | 0.3674 | 0.101* | |
C19 | 0.7477 (3) | 0.84501 (18) | 0.4087 (2) | 0.0707 (8) | |
H19A | 0.8307 | 0.8321 | 0.3992 | 0.085* | |
C20 | 0.5344 (2) | 0.62061 (15) | 0.6297 (2) | 0.0530 (6) | |
H20A | 0.5462 | 0.6238 | 0.6990 | 0.064* | |
H20B | 0.5421 | 0.5689 | 0.6126 | 0.064* | |
C21 | 0.3990 (2) | 0.64947 (14) | 0.58272 (19) | 0.0505 (6) | |
C22 | 0.3499 (3) | 0.72072 (15) | 0.61589 (19) | 0.0531 (6) | |
C23 | 0.2294 (4) | 0.7503 (2) | 0.5720 (3) | 0.0906 (11) | |
H23A | 0.1772 | 0.7251 | 0.5208 | 0.109* | |
C24 | 0.1851 (4) | 0.8167 (2) | 0.6028 (3) | 0.1092 (14) | |
H24A | 0.1038 | 0.8356 | 0.5722 | 0.131* | |
C25 | 0.2601 (4) | 0.8548 (2) | 0.6781 (3) | 0.0938 (12) | |
H25A | 0.2309 | 0.8996 | 0.6984 | 0.113* | |
C26 | 0.3784 (4) | 0.8257 (2) | 0.7226 (3) | 0.0947 (11) | |
H26A | 0.4296 | 0.8507 | 0.7744 | 0.114* | |
C27 | 0.4228 (3) | 0.76018 (19) | 0.6920 (2) | 0.0811 (10) | |
H27A | 0.5041 | 0.7418 | 0.7233 | 0.097* | |
H4C | 0.908 (4) | 0.427 (2) | 0.647 (3) | 0.110 (14)* | |
H4B | 0.842 (4) | 0.380 (2) | 0.571 (3) | 0.105 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0463 (10) | 0.0394 (10) | 0.0877 (14) | −0.0009 (8) | −0.0062 (9) | −0.0082 (9) |
O2 | 0.0706 (13) | 0.0650 (13) | 0.0983 (16) | 0.0198 (11) | 0.0296 (12) | 0.0072 (11) |
O3 | 0.0526 (11) | 0.0605 (13) | 0.1075 (17) | 0.0122 (9) | −0.0079 (11) | −0.0270 (11) |
O4 | 0.0519 (12) | 0.0530 (12) | 0.0906 (16) | 0.0146 (9) | 0.0053 (11) | −0.0023 (11) |
N1 | 0.0426 (11) | 0.0392 (12) | 0.0686 (14) | 0.0008 (9) | −0.0021 (10) | −0.0076 (10) |
N2 | 0.0471 (12) | 0.0389 (11) | 0.0662 (14) | −0.0023 (9) | −0.0043 (10) | −0.0082 (10) |
N3 | 0.0401 (11) | 0.0491 (12) | 0.0461 (11) | 0.0039 (9) | 0.0027 (9) | −0.0018 (9) |
N4 | 0.0680 (15) | 0.0604 (15) | 0.0656 (15) | 0.0155 (12) | 0.0175 (12) | 0.0042 (12) |
N5 | 0.0433 (12) | 0.0501 (13) | 0.0795 (16) | 0.0073 (10) | 0.0030 (11) | −0.0078 (12) |
C1 | 0.0389 (12) | 0.0431 (14) | 0.0463 (13) | 0.0036 (11) | 0.0027 (10) | −0.0028 (11) |
C2 | 0.0392 (13) | 0.0420 (14) | 0.0525 (14) | −0.0007 (11) | 0.0008 (11) | −0.0048 (11) |
C3 | 0.0417 (13) | 0.0386 (13) | 0.0588 (16) | −0.0031 (11) | −0.0045 (12) | 0.0024 (12) |
C4 | 0.073 (2) | 0.068 (2) | 0.070 (2) | −0.0018 (16) | −0.0024 (16) | 0.0083 (16) |
C5 | 0.095 (3) | 0.063 (2) | 0.100 (3) | 0.002 (2) | −0.032 (2) | 0.0217 (19) |
C6 | 0.056 (2) | 0.052 (2) | 0.167 (4) | −0.0011 (16) | −0.009 (3) | −0.003 (3) |
C7 | 0.066 (2) | 0.068 (2) | 0.151 (4) | −0.0011 (18) | 0.038 (2) | −0.012 (2) |
C8 | 0.0582 (17) | 0.0624 (19) | 0.084 (2) | 0.0054 (14) | 0.0158 (16) | 0.0036 (16) |
C9 | 0.0610 (18) | 0.0554 (18) | 0.097 (2) | −0.0099 (14) | −0.0165 (16) | −0.0170 (16) |
C10 | 0.0482 (14) | 0.0402 (13) | 0.0510 (14) | 0.0037 (11) | 0.0035 (12) | −0.0041 (11) |
C11 | 0.0692 (18) | 0.0424 (15) | 0.0741 (19) | 0.0035 (13) | 0.0019 (15) | −0.0093 (13) |
C12 | 0.0506 (15) | 0.0630 (17) | 0.0492 (15) | 0.0032 (13) | 0.0036 (12) | −0.0078 (13) |
C13 | 0.0547 (16) | 0.0631 (17) | 0.0450 (14) | 0.0105 (14) | 0.0071 (12) | 0.0004 (13) |
C14 | 0.0642 (17) | 0.0671 (18) | 0.0440 (14) | 0.0139 (14) | 0.0089 (13) | 0.0041 (13) |
C15 | 0.068 (2) | 0.081 (2) | 0.087 (2) | 0.0245 (17) | 0.0208 (17) | 0.0133 (18) |
C16 | 0.082 (2) | 0.096 (3) | 0.105 (3) | 0.039 (2) | 0.021 (2) | 0.009 (2) |
C17 | 0.114 (3) | 0.073 (2) | 0.072 (2) | 0.032 (2) | 0.009 (2) | 0.0076 (18) |
C18 | 0.117 (3) | 0.065 (2) | 0.072 (2) | 0.017 (2) | 0.026 (2) | 0.0093 (17) |
C19 | 0.083 (2) | 0.071 (2) | 0.0635 (18) | 0.0124 (17) | 0.0268 (16) | 0.0045 (16) |
C20 | 0.0442 (14) | 0.0528 (15) | 0.0586 (16) | 0.0016 (12) | 0.0030 (12) | 0.0033 (12) |
C21 | 0.0437 (14) | 0.0503 (15) | 0.0572 (16) | 0.0024 (12) | 0.0100 (12) | 0.0024 (12) |
C22 | 0.0521 (15) | 0.0538 (15) | 0.0551 (16) | 0.0036 (12) | 0.0150 (13) | 0.0005 (13) |
C23 | 0.092 (2) | 0.081 (2) | 0.088 (2) | 0.037 (2) | −0.007 (2) | −0.0171 (19) |
C24 | 0.122 (3) | 0.090 (3) | 0.107 (3) | 0.056 (3) | 0.006 (3) | −0.012 (2) |
C25 | 0.129 (3) | 0.064 (2) | 0.098 (3) | 0.018 (2) | 0.046 (3) | −0.012 (2) |
C26 | 0.107 (3) | 0.087 (3) | 0.093 (3) | −0.001 (2) | 0.027 (2) | −0.035 (2) |
C27 | 0.075 (2) | 0.087 (2) | 0.079 (2) | 0.0054 (18) | 0.0092 (17) | −0.0228 (18) |
Geometric parameters (Å, º) top
O1—C2 | 1.259 (3) | C11—H11A | 0.9600 |
O2—N4 | 1.399 (3) | C11—H11B | 0.9600 |
O2—H2A | 0.8200 | C11—H11C | 0.9600 |
O3—N5 | 1.393 (3) | C12—C13 | 1.500 (4) |
O3—H3A | 0.8200 | C12—H12A | 0.9700 |
O4—H4C | 0.86 (4) | C12—H12B | 0.9700 |
O4—H4B | 0.99 (4) | C13—C14 | 1.499 (4) |
N1—C2 | 1.384 (3) | C14—C15 | 1.380 (4) |
N1—N2 | 1.403 (3) | C14—C19 | 1.390 (4) |
N1—C3 | 1.428 (3) | C15—C16 | 1.394 (5) |
N2—C10 | 1.352 (3) | C15—H15A | 0.9300 |
N2—C9 | 1.446 (3) | C16—C17 | 1.359 (5) |
N3—C1 | 1.431 (3) | C16—H16A | 0.9300 |
N3—C20 | 1.475 (3) | C17—C18 | 1.373 (5) |
N3—C12 | 1.480 (3) | C17—H17A | 0.9300 |
N4—C13 | 1.285 (3) | C18—C19 | 1.382 (4) |
N5—C21 | 1.288 (3) | C18—H18A | 0.9300 |
C1—C10 | 1.369 (3) | C19—H19A | 0.9300 |
C1—C2 | 1.428 (3) | C20—C21 | 1.517 (4) |
C3—C4 | 1.366 (4) | C20—H20A | 0.9700 |
C3—C8 | 1.376 (4) | C20—H20B | 0.9700 |
C4—C5 | 1.409 (5) | C21—C22 | 1.494 (4) |
C4—H4A | 0.9300 | C22—C27 | 1.382 (4) |
C5—C6 | 1.342 (6) | C22—C23 | 1.383 (4) |
C5—H5A | 0.9300 | C23—C24 | 1.387 (5) |
C6—C7 | 1.361 (6) | C23—H23A | 0.9300 |
C6—H6A | 0.9300 | C24—C25 | 1.370 (5) |
C7—C8 | 1.382 (5) | C24—H24A | 0.9300 |
C7—H7A | 0.9300 | C25—C26 | 1.364 (5) |
C8—H8A | 0.9300 | C25—H25A | 0.9300 |
C9—H9A | 0.9600 | C26—C27 | 1.372 (5) |
C9—H9B | 0.9600 | C26—H26A | 0.9300 |
C9—H9C | 0.9600 | C27—H27A | 0.9300 |
C10—C11 | 1.492 (3) | | |
| | | |
N4—O2—H2A | 109.5 | N3—C12—H12A | 109.4 |
N5—O3—H3A | 109.5 | C13—C12—H12A | 109.5 |
H4C—O4—H4B | 101 (3) | N3—C12—H12B | 109.5 |
C2—N1—N2 | 109.08 (18) | C13—C12—H12B | 109.5 |
C2—N1—C3 | 126.4 (2) | H12A—C12—H12B | 108.0 |
N2—N1—C3 | 120.00 (19) | N4—C13—C14 | 115.1 (3) |
C10—N2—N1 | 107.28 (19) | N4—C13—C12 | 124.0 (3) |
C10—N2—C9 | 129.2 (2) | C14—C13—C12 | 121.0 (2) |
N1—N2—C9 | 119.9 (2) | C15—C14—C19 | 117.1 (3) |
C1—N3—C20 | 112.83 (19) | C15—C14—C13 | 121.5 (3) |
C1—N3—C12 | 111.90 (19) | C19—C14—C13 | 121.5 (3) |
C20—N3—C12 | 112.5 (2) | C14—C15—C16 | 121.1 (3) |
C13—N4—O2 | 112.4 (2) | C14—C15—H15A | 119.4 |
C21—N5—O3 | 112.8 (2) | C16—C15—H15A | 119.4 |
C10—C1—C2 | 108.0 (2) | C17—C16—C15 | 120.7 (3) |
C10—C1—N3 | 124.1 (2) | C17—C16—H16A | 119.6 |
C2—C1—N3 | 127.7 (2) | C15—C16—H16A | 119.6 |
O1—C2—N1 | 121.5 (2) | C16—C17—C18 | 119.3 (3) |
O1—C2—C1 | 133.1 (2) | C16—C17—H17A | 120.4 |
N1—C2—C1 | 105.3 (2) | C18—C17—H17A | 120.4 |
C4—C3—C8 | 120.2 (3) | C17—C18—C19 | 120.2 (4) |
C4—C3—N1 | 120.4 (3) | C17—C18—H18A | 119.9 |
C8—C3—N1 | 119.4 (2) | C19—C18—H18A | 119.9 |
C3—C4—C5 | 119.4 (3) | C18—C19—C14 | 121.6 (3) |
C3—C4—H4A | 120.3 | C18—C19—H19A | 119.2 |
C5—C4—H4A | 120.3 | C14—C19—H19A | 119.2 |
C6—C5—C4 | 119.0 (3) | N3—C20—C21 | 110.2 (2) |
C6—C5—H5A | 120.5 | N3—C20—H20A | 109.6 |
C4—C5—H5A | 120.5 | C21—C20—H20A | 109.6 |
C5—C6—C7 | 122.5 (4) | N3—C20—H20B | 109.6 |
C5—C6—H6A | 118.8 | C21—C20—H20B | 109.6 |
C7—C6—H6A | 118.8 | H20A—C20—H20B | 108.1 |
C6—C7—C8 | 118.8 (4) | N5—C21—C22 | 116.8 (2) |
C6—C7—H7A | 120.6 | N5—C21—C20 | 123.1 (2) |
C8—C7—H7A | 120.6 | C22—C21—C20 | 120.1 (2) |
C3—C8—C7 | 120.2 (3) | C27—C22—C23 | 116.8 (3) |
C3—C8—H8A | 119.9 | C27—C22—C21 | 121.5 (3) |
C7—C8—H8A | 119.9 | C23—C22—C21 | 121.6 (3) |
N2—C9—H9A | 109.5 | C22—C23—C24 | 121.2 (3) |
N2—C9—H9B | 109.5 | C22—C23—H23A | 119.4 |
H9A—C9—H9B | 109.5 | C24—C23—H23A | 119.4 |
N2—C9—H9C | 109.5 | C25—C24—C23 | 120.6 (4) |
H9A—C9—H9C | 109.5 | C25—C24—H24A | 119.7 |
H9B—C9—H9C | 109.5 | C23—C24—H24A | 119.7 |
N2—C10—C1 | 109.8 (2) | C26—C25—C24 | 118.7 (3) |
N2—C10—C11 | 121.5 (2) | C26—C25—H25A | 120.6 |
C1—C10—C11 | 128.7 (2) | C24—C25—H25A | 120.6 |
C10—C11—H11A | 109.5 | C25—C26—C27 | 120.9 (4) |
C10—C11—H11B | 109.5 | C25—C26—H26A | 119.6 |
H11A—C11—H11B | 109.5 | C27—C26—H26A | 119.6 |
C10—C11—H11C | 109.5 | C26—C27—C22 | 121.8 (3) |
H11A—C11—H11C | 109.5 | C26—C27—H27A | 119.1 |
H11B—C11—H11C | 109.5 | C22—C27—H27A | 119.1 |
N3—C12—C13 | 110.9 (2) | | |
| | | |
C2—N1—N2—C10 | 7.3 (3) | C1—N3—C12—C13 | −64.3 (3) |
C3—N1—N2—C10 | 164.9 (2) | C20—N3—C12—C13 | 167.4 (2) |
C2—N1—N2—C9 | 168.0 (2) | O2—N4—C13—C14 | 179.0 (2) |
C3—N1—N2—C9 | −34.5 (4) | O2—N4—C13—C12 | −2.1 (4) |
C20—N3—C1—C10 | −131.2 (3) | N3—C12—C13—N4 | 103.4 (3) |
C12—N3—C1—C10 | 100.7 (3) | N3—C12—C13—C14 | −77.7 (3) |
C20—N3—C1—C2 | 53.9 (3) | N4—C13—C14—C15 | 179.3 (3) |
C12—N3—C1—C2 | −74.2 (3) | C12—C13—C14—C15 | 0.4 (4) |
N2—N1—C2—O1 | 175.2 (2) | N4—C13—C14—C19 | −0.2 (4) |
C3—N1—C2—O1 | 19.4 (4) | C12—C13—C14—C19 | −179.2 (2) |
N2—N1—C2—C1 | −6.2 (3) | C19—C14—C15—C16 | 0.6 (5) |
C3—N1—C2—C1 | −161.9 (2) | C13—C14—C15—C16 | −178.9 (3) |
C10—C1—C2—O1 | −178.7 (3) | C14—C15—C16—C17 | 0.1 (6) |
N3—C1—C2—O1 | −3.2 (5) | C15—C16—C17—C18 | −0.6 (6) |
C10—C1—C2—N1 | 2.9 (3) | C16—C17—C18—C19 | 0.3 (5) |
N3—C1—C2—N1 | 178.4 (2) | C17—C18—C19—C14 | 0.5 (5) |
C2—N1—C3—C4 | −102.7 (3) | C15—C14—C19—C18 | −0.9 (4) |
N2—N1—C3—C4 | 103.9 (3) | C13—C14—C19—C18 | 178.6 (3) |
C2—N1—C3—C8 | 78.3 (3) | C1—N3—C20—C21 | 166.9 (2) |
N2—N1—C3—C8 | −75.1 (3) | C12—N3—C20—C21 | −65.3 (3) |
C8—C3—C4—C5 | −0.3 (4) | O3—N5—C21—C22 | 178.7 (2) |
N1—C3—C4—C5 | −179.4 (3) | O3—N5—C21—C20 | −0.7 (4) |
C3—C4—C5—C6 | 0.4 (5) | N3—C20—C21—N5 | 105.1 (3) |
C4—C5—C6—C7 | −0.3 (6) | N3—C20—C21—C22 | −74.2 (3) |
C5—C6—C7—C8 | 0.2 (6) | N5—C21—C22—C27 | 177.7 (3) |
C4—C3—C8—C7 | 0.2 (4) | C20—C21—C22—C27 | −2.9 (4) |
N1—C3—C8—C7 | 179.2 (3) | N5—C21—C22—C23 | −2.2 (4) |
C6—C7—C8—C3 | −0.1 (5) | C20—C21—C22—C23 | 177.1 (3) |
N1—N2—C10—C1 | −5.4 (3) | C27—C22—C23—C24 | 0.5 (6) |
C9—N2—C10—C1 | −163.7 (3) | C21—C22—C23—C24 | −179.5 (3) |
N1—N2—C10—C11 | 174.9 (2) | C22—C23—C24—C25 | −0.1 (7) |
C9—N2—C10—C11 | 16.6 (4) | C23—C24—C25—C26 | −0.7 (7) |
C2—C1—C10—N2 | 1.6 (3) | C24—C25—C26—C27 | 1.0 (6) |
N3—C1—C10—N2 | −174.1 (2) | C25—C26—C27—C22 | −0.6 (6) |
C2—C1—C10—C11 | −178.7 (3) | C23—C22—C27—C26 | −0.2 (5) |
N3—C1—C10—C11 | 5.5 (4) | C21—C22—C27—C26 | 179.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4i | 0.82 | 1.88 | 2.663 (3) | 159 |
O3—H3A···O1ii | 0.82 | 1.88 | 2.695 (3) | 178 |
O4—H4C···O1 | 0.86 (4) | 1.99 (4) | 2.779 (3) | 152 (4) |
O4—H4B···N5ii | 0.99 (4) | 1.87 (4) | 2.848 (4) | 170 (3) |
O4—H4B···O3ii | 0.99 (4) | 2.57 (4) | 3.372 (3) | 138 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C27H27N5O3·H2O |
Mr | 487.55 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.385 (6), 18.024 (4), 14.229 (5) |
β (°) | 102.05 (5) |
V (Å3) | 2604.6 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.46 × 0.38 × 0.12 |
|
Data collection |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4862, 4592, 2956 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.155, 1.02 |
No. of reflections | 4592 |
No. of parameters | 334 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.22 |
Selected geometric parameters (Å, º) topO1—C2 | 1.259 (3) | N2—C9 | 1.446 (3) |
O3—N5 | 1.393 (3) | N3—C20 | 1.475 (3) |
N1—C2 | 1.384 (3) | N3—C12 | 1.480 (3) |
N1—N2 | 1.403 (3) | N4—C13 | 1.285 (3) |
N1—C3 | 1.428 (3) | N5—C21 | 1.288 (3) |
| | | |
N1—N2—C9 | 119.9 (2) | C21—N5—O3 | 112.8 (2) |
C1—N3—C12 | 111.90 (19) | O1—C2—N1 | 121.5 (2) |
C13—N4—O2 | 112.4 (2) | N3—C12—C13 | 110.9 (2) |
| | | |
C1—N3—C12—C13 | −64.3 (3) | O3—N5—C21—C22 | 178.7 (2) |
O2—N4—C13—C14 | 179.0 (2) | N3—C20—C21—N5 | 105.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···O4i | 0.82 | 1.88 | 2.663 (3) | 159 |
O3—H3A···O1ii | 0.82 | 1.88 | 2.695 (3) | 178 |
O4—H4C···O1 | 0.86 (4) | 1.99 (4) | 2.779 (3) | 152 (4) |
O4—H4B···N5ii | 0.99 (4) | 1.87 (4) | 2.848 (4) | 170 (3) |
O4—H4B···O3ii | 0.99 (4) | 2.57 (4) | 3.372 (3) | 138 (3) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
In recent years, there has been considerable interest in the chemistry of antipyrine and its derivatives. These compounds exhibit a wide range of biological activities and applications (Ismail, 2000; Abd El Rehim et al., 2001; Yadav et al., 2003; Madhu et al., 2003). X-ray crystallographic studies of antipyrine Schiff base derivatives have been abundantly reported (You et al., 2002, 2003; Wang et al., 2002; Liang et al., 2002; 2004). However, the comparatively less well known oxime derivatives have not been adequately explored in crystal engineering; a recent survey of the Cambridge Structural Database (Version?; Allen, 2002) found 370 entries containing the oxime moiety (Aakeröy et al., 2001, 2002). Here, we describe the structure of the title compound, (I), which contains both oxime and pyrazolinone functionalities simultaneously. \sch
A view of the molecule of (I) is shown in Fig. 1. The C2—O1 bond distance is slightly longer than that in the 4-aminoantipyrine derivatives 4-{[(1E)-(2-hydroxyphenyl)methylidene]amino}-1,5-dimethyl-2-phenyl- 2,3-dihydro-1H-pyrazol-3-one (Hökelek et al., 2001) and 4-(antipyrin-4-yliminomethyl)benzoic acid (Zhang et al., 2002), in which the C═O double-bond distances are 1.230 (2) and 1.248 (2) Å, respectively. The bond lengths and angles in the acetophenone oxime moieties are in the normal ranges and compare well with the literature values for similar compounds (Aakeröy et al., 2001). The dihedral angle between the pyrazolinone ring and the C3—C8 phenyl ring is 87.66 (1)°, whereas the C14—C19 plane deviates from the pyrazolinone ring by 47.04 (1)°. The angle between the C22—C27 and C14—C19 rings is 69.97 (1)°.
Previous structural studies of molecules containing both oxime and carboxylic acid moieties have demonstrated that there is a pronounced preference for heteromeric (oxime-acid) interactions over homomeric motifs, in the absence of other strong hydrogen-bond donors or acceptors (Aakeröy et al., 2002; Téllez et al., 2002). The supramolecular network of (I) is built up of moderate intermolecular hydrogen bonds, involving the oxime O—H moiety and the aminoantipyrine carbonyl O atom of adjacent molecules (O3···O1 and O2···O4; Fig. 2). Neighbouring molecules are held together by water molecules of crystallization, which are hydrogen-bonded to the pyrazolinone carbonyl O atom via O4—H4C···O1 and to the oxime N atom via O4—H4B···N5ii [symmetry code: (ii) Please provide missing symmetry code]. The water molecule on each side further interacts with the oxime O atom to form a three-centre hydrogen bond, to satisfy both the donor and acceptor functionality. The hydrogen bonds between the oxime and pyrazolinone moieties can be considered strong because of the short O—H distances and the O—H···O angles, which are close to 180° (Table 2).
The structure of (I), incorporating antipyrine, acetophenone oxime and water, is a rare example among analogous reported structures of compounds incorporating mainly aminoantipyrine Schiff base and carboxylic acid derivatives. Such structures have potential applications in catalysis or separation (Aakeröy et al., 2001). Each molecule has eight lone pairs (three on each oxime and two on the carbonyl) available for accepting hydrogen bonds. Since water is a hydrogen-bond donor and acceptor, the molecules form many intermolecular hydrogen bonds to assemble the molecules in this specific manner. Of course, the size and shape of the molecule are also of key importance to the resulting structure.