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The structures of
N-ethyl-3-(4-fluorophenyl)-5-(4-methoxyphenyl)-2-pyrazoline-1-thiocarboxamide, C
19H
20FN
3OS, (I), and 3-(4-fluorophenyl)-
N-methyl-5-(4-methylphenyl)-2-pyrazoline-1-thiocarboxamide, C
18H
18FN
3S, (II), have similar geometric parameters. The methoxy/methyl-substituted phenyl groups are almost perpendicular to the pyrazoline (pyraz) ring [interplanar angles of 89.29 (8) and 80.39 (10)° for (I) and (II), respectively], which is coplanar with the fluorophenyl ring [interplanar angles of 5.72 (9) and 10.48 (10)°]. The pyrazoline ring approximates an envelope conformation in both structures, with the two-coordinate N atom involved in an intramolecular N—H
N
pyraz interaction. In (I), N—H
O and C—H
S intermolecular hydrogen bonds are the primary interactions, whereas in (II), there are no intermolecular hydrogen bonds.
Supporting information
CCDC references: 285794; 285795
Hydrazine hydrate (0.02 mol) was added to an ethanol solution of 1-(4-fluorophenyl)-3-aryl-2-propenones [please specify] (0.01 mol) and refluxed for 2 h. The reaction mixture was cooled to 255 K, and the solid mass that separated out was filtered and dissolved in dry diethyl ether. Substituted isothiocyanates [please specify] (0.01 mol) and three drops of Et3N were added and stirred for 4 h. The reaction mixture was evaporated to dryness and the solid mass was crystallized from alcoholic solvents [please specify]. Compound (I) was crystallized from ethanol. Yield 50.4%, m.p. 412 K. IR (KBr, cm−1): 3342 (N—H), 1606 (C═N), 1440 (C═C), 1387 (C4—H), 1320 (C═S), 1033 (C5—N1). 1H NMR (CDCl3, p.p.m.): 1.28 (t, 3H, CH2—CH3), 3.11 (dd, 1H, pyrazoline H4), 3.72 (m, 2H, CH2—CH3), 3.75 (m, 4H, –OCH3, pyrazoline H4), 6.03 (dd, 1H, pyrazoline H5), 6.83–7.74 (m, 8H, aromatic). Compound (II) was crystallized from methanol. Yield 45.8%, m.p. 422 K. IR (KBr, cm−1): 3362 (N—H), 1602 (C═N), 1419 (C═C), 1320 (C═ S), 1004 (C5—N1). 1H NMR (CDCl3, p.p.m.): 2.30 (s, 3H, Ar—CH3), 3.19 (s, 3H, NH—CH3), 3.12 (dd, 1H, pyrazoline H4), 3.76 (dd, 1H, pyrazoline H4), 6.05 (dd, 1H, pyrazoline H5), 7.09–7.73 (m, 8H, aromatic).
Atoms H8 and H2O atoms for (I) and atom H18 for (II) were located in a difference Fourier map and refined independently, with isotropic displacement parameters [C8—H8 = 1.001 (16) Å, N3—H2O = 0.865 (16) Å and C8—H18 = 0.94 (2) Å]. The remaining H atoms were positioned geometrically and refined using a riding model, fixing the aromatic C—H distances at 0.93 Å, the CH2 distances at 0.97 Å and the CH3 distances at 0.96 Å [Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(C)].
For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).
(I)
N-ethyl-3-(4-fluorophenyl)-5-(4-methoxyphenyl)-2-pyrazoline-1-thiocarboxamide
top
Crystal data top
C19H20FN3OS | F(000) = 752 |
Mr = 357.44 | Dx = 1.315 Mg m−3 |
Monoclinic, P21/c | Melting point: 412 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 9.706 (5) Å | Cell parameters from 46195 reflections |
b = 12.141 (5) Å | θ = 1.3–26.7° |
c = 17.753 (5) Å | µ = 0.20 mm−1 |
β = 120.372 (17)° | T = 293 K |
V = 1804.9 (13) Å3 | Prism, yellow |
Z = 4 | 0.60 × 0.54 × 0.30 mm |
Data collection top
Stoe IPDS-II diffractometer | 2785 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 26.3°, θmin = 2.1° |
Detector resolution: 6.67 pixels mm-1 | h = −12→12 |
ω scan | k = −15→15 |
12891 measured reflections | l = −22→22 |
3622 independent reflections | |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0499P)2 + 0.0998P] where P = (Fo2 + 2Fc2)/3 |
3622 reflections | (Δ/σ)max = 0.001 |
234 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C19H20FN3OS | V = 1804.9 (13) Å3 |
Mr = 357.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.706 (5) Å | µ = 0.20 mm−1 |
b = 12.141 (5) Å | T = 293 K |
c = 17.753 (5) Å | 0.60 × 0.54 × 0.30 mm |
β = 120.372 (17)° | |
Data collection top
Stoe IPDS-II diffractometer | 2785 reflections with I > 2σ(I) |
12891 measured reflections | Rint = 0.043 |
3622 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.14 e Å−3 |
3622 reflections | Δρmin = −0.15 e Å−3 |
234 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 | |
C1 | 0.9806 (3) | 0.72994 (18) | 0.20341 (14) | 0.0839 (6) | |
C2 | 0.91737 (15) | 0.86849 (11) | 0.27695 (9) | 0.0455 (3) | |
C3 | 0.97484 (15) | 0.93586 (12) | 0.34925 (9) | 0.0489 (3) | |
C4 | 0.87103 (15) | 0.99298 (11) | 0.36604 (9) | 0.0457 (3) | |
C5 | 0.70652 (15) | 0.98556 (10) | 0.31049 (9) | 0.0430 (3) | |
C6 | 0.65160 (16) | 0.91931 (12) | 0.23769 (9) | 0.0513 (3) | |
C7 | 0.75442 (16) | 0.86029 (13) | 0.22029 (9) | 0.0524 (4) | |
C8 | 0.59425 (16) | 1.04925 (12) | 0.32998 (10) | 0.0484 (3) | |
C9 | 0.47674 (17) | 1.12380 (12) | 0.25474 (12) | 0.0581 (4) | |
C10 | 0.31872 (16) | 1.06658 (11) | 0.22181 (9) | 0.0453 (3) | |
C11 | 0.16867 (16) | 1.09685 (11) | 0.14357 (9) | 0.0457 (3) | |
C12 | 0.16151 (19) | 1.18543 (12) | 0.09248 (10) | 0.0534 (4) | |
C13 | 0.0200 (2) | 1.21216 (13) | 0.01723 (10) | 0.0604 (4) | |
C14 | −0.11108 (19) | 1.14910 (14) | −0.00541 (10) | 0.0586 (4) | |
C15 | −0.11049 (18) | 1.06157 (14) | 0.04359 (11) | 0.0597 (4) | |
C16 | 0.03008 (17) | 1.03551 (13) | 0.11859 (10) | 0.0525 (3) | |
C17 | 0.51387 (15) | 0.90727 (11) | 0.40617 (9) | 0.0435 (3) | |
C18 | 0.39898 (19) | 0.77132 (14) | 0.46138 (11) | 0.0600 (4) | |
C19 | 0.4651 (2) | 0.65993 (15) | 0.46169 (14) | 0.0757 (5) | |
N1 | 0.48105 (12) | 0.97533 (10) | 0.33845 (8) | 0.0491 (3) | |
N2 | 0.32498 (12) | 0.98592 (10) | 0.26989 (7) | 0.0468 (3) | |
N3 | 0.39258 (14) | 0.84378 (11) | 0.39485 (8) | 0.0510 (3) | |
O1 | 1.03063 (12) | 0.81323 (10) | 0.26744 (8) | 0.0635 (3) | |
F1 | −0.24975 (12) | 1.17383 (10) | −0.08014 (6) | 0.0842 (3) | |
S1 | 0.69494 (4) | 0.90641 (4) | 0.49604 (2) | 0.05958 (14) | |
H1A | 0.9259 | 0.6733 | 0.2158 | 0.126* | |
H1B | 1.0720 | 0.6990 | 0.2039 | 0.126* | |
H1C | 0.9098 | 0.7609 | 0.1470 | 0.126* | |
H3 | 1.0844 | 0.9427 | 0.3868 | 0.059* | |
H4 | 0.9114 | 1.0374 | 0.4154 | 0.055* | |
H6 | 0.7144 | 0.8157 | 0.1711 | 0.063* | |
H7 | 0.5422 | 0.9142 | 0.1991 | 0.062* | |
H8 | 0.6546 (18) | 1.0908 (13) | 0.3862 (10) | 0.055 (4)* | |
H9A | 0.4748 | 1.1974 | 0.2755 | 0.070* | |
H9B | 0.5045 | 1.1286 | 0.2095 | 0.070* | |
H12 | 0.2526 | 1.2274 | 0.1088 | 0.064* | |
H13 | 0.0148 | 1.2718 | −0.0170 | 0.072* | |
H15 | −0.2028 | 1.0208 | 0.0266 | 0.072* | |
H16 | 0.0329 | 0.9767 | 0.1529 | 0.063* | |
H18A | 0.2921 | 0.7628 | 0.4521 | 0.072* | |
H18B | 0.4645 | 0.8052 | 0.5181 | 0.072* | |
H19A | 0.5718 | 0.6675 | 0.4722 | 0.113* | |
H19B | 0.3993 | 0.6251 | 0.4062 | 0.113* | |
H19C | 0.4665 | 0.6157 | 0.5069 | 0.113* | |
H20 | 0.301 (2) | 0.8533 (15) | 0.3479 (12) | 0.066 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0880 (14) | 0.0866 (13) | 0.0905 (14) | −0.0103 (10) | 0.0551 (12) | −0.0354 (11) |
C2 | 0.0413 (7) | 0.0470 (7) | 0.0484 (8) | −0.0046 (5) | 0.0228 (6) | −0.0026 (6) |
C3 | 0.0330 (6) | 0.0509 (8) | 0.0528 (8) | −0.0075 (5) | 0.0144 (6) | −0.0077 (6) |
C4 | 0.0393 (7) | 0.0427 (7) | 0.0461 (7) | −0.0086 (5) | 0.0150 (6) | −0.0080 (6) |
C5 | 0.0360 (6) | 0.0392 (6) | 0.0485 (7) | −0.0055 (5) | 0.0175 (6) | 0.0014 (6) |
C6 | 0.0340 (6) | 0.0574 (8) | 0.0477 (8) | −0.0061 (6) | 0.0098 (6) | −0.0048 (7) |
C7 | 0.0460 (7) | 0.0599 (9) | 0.0424 (7) | −0.0091 (6) | 0.0159 (6) | −0.0112 (6) |
C8 | 0.0410 (7) | 0.0428 (7) | 0.0585 (9) | −0.0039 (6) | 0.0229 (6) | −0.0004 (7) |
C9 | 0.0487 (8) | 0.0442 (7) | 0.0791 (11) | 0.0032 (6) | 0.0306 (8) | 0.0102 (7) |
C10 | 0.0434 (7) | 0.0420 (7) | 0.0515 (8) | 0.0035 (5) | 0.0246 (6) | 0.0025 (6) |
C11 | 0.0480 (7) | 0.0423 (7) | 0.0485 (7) | 0.0077 (6) | 0.0257 (6) | 0.0026 (6) |
C12 | 0.0592 (9) | 0.0463 (8) | 0.0550 (8) | 0.0064 (6) | 0.0290 (7) | 0.0038 (7) |
C13 | 0.0777 (11) | 0.0515 (8) | 0.0516 (9) | 0.0189 (8) | 0.0325 (8) | 0.0089 (7) |
C14 | 0.0549 (9) | 0.0672 (10) | 0.0446 (8) | 0.0209 (8) | 0.0183 (7) | 0.0005 (7) |
C15 | 0.0473 (8) | 0.0663 (10) | 0.0598 (9) | 0.0059 (7) | 0.0229 (7) | −0.0043 (8) |
C16 | 0.0474 (8) | 0.0536 (8) | 0.0559 (8) | 0.0068 (6) | 0.0256 (7) | 0.0053 (7) |
C17 | 0.0404 (7) | 0.0457 (7) | 0.0439 (7) | 0.0035 (5) | 0.0210 (6) | −0.0026 (6) |
C18 | 0.0577 (9) | 0.0698 (10) | 0.0582 (9) | 0.0039 (7) | 0.0336 (8) | 0.0143 (8) |
C19 | 0.0807 (12) | 0.0660 (11) | 0.0860 (13) | 0.0064 (9) | 0.0464 (11) | 0.0170 (10) |
N1 | 0.0338 (5) | 0.0549 (7) | 0.0513 (7) | −0.0010 (5) | 0.0161 (5) | 0.0087 (5) |
N2 | 0.0360 (6) | 0.0539 (7) | 0.0454 (6) | 0.0011 (5) | 0.0168 (5) | 0.0056 (5) |
N3 | 0.0415 (6) | 0.0598 (7) | 0.0468 (7) | 0.0003 (5) | 0.0188 (6) | 0.0109 (6) |
O1 | 0.0502 (6) | 0.0706 (7) | 0.0714 (7) | −0.0039 (5) | 0.0319 (5) | −0.0204 (6) |
F1 | 0.0702 (6) | 0.1027 (8) | 0.0531 (6) | 0.0288 (6) | 0.0115 (5) | 0.0067 (5) |
S1 | 0.0444 (2) | 0.0675 (3) | 0.0479 (2) | 0.00061 (17) | 0.00936 (16) | −0.00324 (18) |
Geometric parameters (Å, º) top
C1—O1 | 1.411 (2) | C11—C12 | 1.386 (2) |
C1—H1A | 0.9600 | C11—C16 | 1.399 (2) |
C1—H1B | 0.9600 | C12—C13 | 1.386 (2) |
C1—H1C | 0.9600 | C12—H12 | 0.9300 |
C2—O1 | 1.3692 (17) | C13—C14 | 1.360 (3) |
C2—C3 | 1.380 (2) | C13—H13 | 0.9300 |
C2—C7 | 1.384 (2) | C14—F1 | 1.3624 (18) |
C3—C4 | 1.374 (2) | C14—C15 | 1.372 (2) |
C3—H3 | 0.9300 | C15—C16 | 1.377 (2) |
C4—C5 | 1.3921 (19) | C15—H15 | 0.9300 |
C4—H4 | 0.9300 | C16—H16 | 0.9300 |
C5—C6 | 1.380 (2) | C17—N3 | 1.3345 (18) |
C5—C8 | 1.512 (2) | C17—N1 | 1.3574 (18) |
C6—C7 | 1.384 (2) | C17—S1 | 1.6729 (15) |
C6—H7 | 0.9300 | C18—N3 | 1.449 (2) |
C7—H6 | 0.9300 | C18—C19 | 1.496 (2) |
C8—N1 | 1.4840 (18) | C18—H18A | 0.9700 |
C8—C9 | 1.537 (2) | C18—H18B | 0.9700 |
C8—H8 | 1.001 (16) | C19—H19A | 0.9600 |
C9—C10 | 1.507 (2) | C19—H19B | 0.9600 |
C9—H9A | 0.9700 | C19—H19C | 0.9600 |
C9—H9B | 0.9700 | N1—N2 | 1.3886 (16) |
C10—N2 | 1.2802 (18) | N3—H20 | 0.865 (18) |
C10—C11 | 1.4627 (19) | | |
| | | |
O1—C1—H1A | 109.5 | C12—C11—C10 | 120.85 (13) |
O1—C1—H1B | 109.5 | C16—C11—C10 | 120.22 (13) |
H1A—C1—H1B | 109.5 | C11—C12—C13 | 120.65 (15) |
O1—C1—H1C | 109.5 | C11—C12—H12 | 119.7 |
H1A—C1—H1C | 109.5 | C13—C12—H12 | 119.7 |
H1B—C1—H1C | 109.5 | C14—C13—C12 | 118.45 (15) |
O1—C2—C3 | 115.66 (12) | C14—C13—H13 | 120.8 |
O1—C2—C7 | 124.68 (13) | C12—C13—H13 | 120.8 |
C3—C2—C7 | 119.66 (13) | C13—C14—F1 | 118.67 (15) |
C4—C3—C2 | 120.33 (12) | C13—C14—C15 | 123.06 (14) |
C4—C3—H3 | 119.8 | F1—C14—C15 | 118.27 (16) |
C2—C3—H3 | 119.8 | C14—C15—C16 | 118.39 (15) |
C3—C4—C5 | 121.19 (13) | C14—C15—H15 | 120.8 |
C3—C4—H4 | 119.4 | C16—C15—H15 | 120.8 |
C5—C4—H4 | 119.4 | C15—C16—C11 | 120.52 (15) |
C6—C5—C4 | 117.56 (12) | C15—C16—H16 | 119.7 |
C6—C5—C8 | 122.04 (12) | C11—C16—H16 | 119.7 |
C4—C5—C8 | 120.40 (13) | N3—C17—N1 | 115.09 (12) |
C5—C6—C7 | 122.00 (12) | N3—C17—S1 | 124.15 (11) |
C5—C6—H7 | 119.0 | N1—C17—S1 | 120.76 (10) |
C7—C6—H7 | 119.0 | N3—C18—C19 | 113.17 (14) |
C6—C7—C2 | 119.24 (13) | N3—C18—H18A | 108.9 |
C6—C7—H6 | 120.4 | C19—C18—H18A | 108.9 |
C2—C7—H6 | 120.4 | N3—C18—H18B | 108.9 |
N1—C8—C5 | 111.72 (12) | C19—C18—H18B | 108.9 |
N1—C8—C9 | 100.49 (11) | H18A—C18—H18B | 107.8 |
C5—C8—C9 | 113.96 (13) | C18—C19—H19A | 109.5 |
N1—C8—H8 | 107.1 (9) | C18—C19—H19B | 109.5 |
C5—C8—H8 | 111.0 (9) | H19A—C19—H19B | 109.5 |
C9—C8—H8 | 111.9 (9) | C18—C19—H19C | 109.5 |
C10—C9—C8 | 103.19 (12) | H19A—C19—H19C | 109.5 |
C10—C9—H9A | 111.1 | H19B—C19—H19C | 109.5 |
C8—C9—H9A | 111.1 | C17—N1—N2 | 119.75 (11) |
C10—C9—H9B | 111.1 | C17—N1—C8 | 127.13 (11) |
C8—C9—H9B | 111.1 | N2—N1—C8 | 113.00 (11) |
H9A—C9—H9B | 109.1 | C10—N2—N1 | 108.55 (11) |
N2—C10—C11 | 120.94 (12) | C17—N3—C18 | 123.85 (13) |
N2—C10—C9 | 113.46 (13) | C17—N3—H20 | 117.7 (12) |
C11—C10—C9 | 125.60 (13) | C18—N3—H20 | 117.9 (12) |
C12—C11—C16 | 118.92 (14) | C2—O1—C1 | 118.65 (12) |
| | | |
O1—C2—C3—C4 | −178.43 (13) | C12—C13—C14—F1 | −178.84 (13) |
C7—C2—C3—C4 | 1.3 (2) | C12—C13—C14—C15 | 1.3 (2) |
C2—C3—C4—C5 | −0.8 (2) | C13—C14—C15—C16 | −0.9 (2) |
C3—C4—C5—C6 | −0.4 (2) | F1—C14—C15—C16 | 179.18 (13) |
C3—C4—C5—C8 | −179.86 (13) | C14—C15—C16—C11 | −0.3 (2) |
C4—C5—C6—C7 | 1.1 (2) | C12—C11—C16—C15 | 1.1 (2) |
C8—C5—C6—C7 | −179.44 (14) | C10—C11—C16—C15 | −178.07 (13) |
C5—C6—C7—C2 | −0.6 (2) | N3—C17—N1—N2 | 8.69 (18) |
O1—C2—C7—C6 | 179.09 (14) | S1—C17—N1—N2 | −171.12 (10) |
C3—C2—C7—C6 | −0.6 (2) | N3—C17—N1—C8 | −175.64 (13) |
C6—C5—C8—N1 | 58.71 (17) | S1—C17—N1—C8 | 4.55 (19) |
C4—C5—C8—N1 | −121.86 (13) | C5—C8—N1—C17 | 73.89 (18) |
C6—C5—C8—C9 | −54.33 (18) | C9—C8—N1—C17 | −164.89 (14) |
C4—C5—C8—C9 | 125.10 (14) | C5—C8—N1—N2 | −110.20 (13) |
N1—C8—C9—C10 | −10.40 (15) | C9—C8—N1—N2 | 11.02 (15) |
C5—C8—C9—C10 | 109.21 (13) | C11—C10—N2—N1 | 179.40 (12) |
C8—C9—C10—N2 | 7.85 (17) | C9—C10—N2—N1 | −1.05 (17) |
C8—C9—C10—C11 | −172.63 (13) | C17—N1—N2—C10 | 169.43 (12) |
N2—C10—C11—C12 | 178.83 (14) | C8—N1—N2—C10 | −6.82 (16) |
C9—C10—C11—C12 | −0.7 (2) | N1—C17—N3—C18 | −175.43 (13) |
N2—C10—C11—C16 | −2.0 (2) | S1—C17—N3—C18 | 4.4 (2) |
C9—C10—C11—C16 | 178.53 (14) | C19—C18—N3—C17 | −86.88 (19) |
C16—C11—C12—C13 | −0.8 (2) | C3—C2—O1—C1 | 169.97 (16) |
C10—C11—C12—C13 | 178.41 (13) | C7—C2—O1—C1 | −9.7 (2) |
C11—C12—C13—C14 | −0.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H20···O1i | 0.865 (18) | 2.319 (18) | 3.092 (2) | 148.9 (15) |
N3—H20···N2 | 0.865 (18) | 2.211 (17) | 2.6187 (18) | 108.7 (14) |
C3—H3···S1ii | 0.93 | 2.79 | 3.5471 (18) | 140 |
C18—H18B···S1 | 0.97 | 2.75 | 3.088 (2) | 101 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+2, −z+1. |
(II) 3-(4-fluorophenyl)-
N-methyl-5-(4-methylphenyl)-2-pyrazoline-1-thiocarboxamide
top
Crystal data top
C18H18FN3S | F(000) = 688 |
Mr = 327.41 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11340 reflections |
a = 9.4191 (17) Å | θ = 1.4–26.7° |
b = 12.2032 (11) Å | µ = 0.21 mm−1 |
c = 14.673 (2) Å | T = 293 K |
β = 103.063 (14)° | Prism., yellow |
V = 1642.9 (4) Å3 | 0.60 × 0.46 × 0.25 mm |
Z = 4 | |
Data collection top
Stoe IPDS 2 diffractometer | 3429 independent reflections |
Radiation source: fine-focus sealed tube | 2655 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.6°, θmin = 2.2° |
ω scan | h = −11→11 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −14→15 |
Tmin = 0.885, Tmax = 0.954 | l = −18→18 |
10474 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0738P)2 + 0.2481P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3429 reflections | Δρmax = 0.23 e Å−3 |
214 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.041 (5) |
Crystal data top
C18H18FN3S | V = 1642.9 (4) Å3 |
Mr = 327.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4191 (17) Å | µ = 0.21 mm−1 |
b = 12.2032 (11) Å | T = 293 K |
c = 14.673 (2) Å | 0.60 × 0.46 × 0.25 mm |
β = 103.063 (14)° | |
Data collection top
Stoe IPDS 2 diffractometer | 3429 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2655 reflections with I > 2σ(I) |
Tmin = 0.885, Tmax = 0.954 | Rint = 0.051 |
10474 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.140 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.23 e Å−3 |
3429 reflections | Δρmin = −0.30 e Å−3 |
214 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 | |
C1 | −0.0791 (3) | 0.5668 (2) | 0.32224 (18) | 0.0780 (7) | |
C2 | 0.0533 (2) | 0.49507 (15) | 0.35315 (14) | 0.0549 (5) | |
C3 | 0.1489 (2) | 0.51036 (15) | 0.43928 (14) | 0.0552 (5) | |
C4 | 0.2688 (2) | 0.44391 (15) | 0.46772 (12) | 0.0510 (4) | |
C5 | 0.29738 (19) | 0.35865 (13) | 0.41191 (12) | 0.0441 (4) | |
C6 | 0.2036 (2) | 0.34376 (15) | 0.32543 (13) | 0.0532 (5) | |
C7 | 0.0841 (2) | 0.41140 (17) | 0.29727 (14) | 0.0583 (5) | |
C8 | 0.4206 (2) | 0.28008 (14) | 0.45128 (12) | 0.0469 (4) | |
C9 | 0.3754 (2) | 0.20018 (15) | 0.52082 (12) | 0.0516 (4) | |
C10 | 0.34190 (18) | 0.09779 (14) | 0.46302 (11) | 0.0446 (4) | |
C11 | 0.26411 (18) | 0.00248 (14) | 0.48697 (12) | 0.0453 (4) | |
C12 | 0.2068 (2) | 0.00285 (16) | 0.56652 (13) | 0.0539 (5) | |
C13 | 0.1255 (2) | −0.08421 (18) | 0.58586 (14) | 0.0612 (5) | |
C14 | 0.1033 (2) | −0.17167 (16) | 0.52582 (16) | 0.0595 (5) | |
C15 | 0.1599 (2) | −0.17673 (17) | 0.44849 (16) | 0.0620 (5) | |
C16 | 0.2407 (2) | −0.08890 (15) | 0.42864 (14) | 0.0537 (4) | |
C17 | 0.52724 (19) | 0.22231 (15) | 0.31508 (12) | 0.0479 (4) | |
C18 | 0.6298 (3) | 0.13239 (19) | 0.19464 (14) | 0.0662 (6) | |
N1 | 0.45171 (17) | 0.20309 (12) | 0.38164 (10) | 0.0494 (4) | |
N2 | 0.38989 (16) | 0.10033 (12) | 0.38796 (10) | 0.0480 (4) | |
N3 | 0.53707 (19) | 0.13606 (13) | 0.26064 (11) | 0.0554 (4) | |
F1 | 0.01935 (17) | −0.25571 (12) | 0.54330 (11) | 0.0881 (5) | |
S1 | 0.60120 (6) | 0.34546 (4) | 0.30441 (4) | 0.0645 (2) | |
H1A | −0.0840 | 0.6184 | 0.3708 | 0.117* | |
H1B | −0.1651 | 0.5220 | 0.3098 | 0.117* | |
H1C | −0.0724 | 0.6055 | 0.2664 | 0.117* | |
H3 | 0.4850 | 0.0793 | 0.2652 | 0.066* | |
H3A | 0.1315 | 0.5664 | 0.4784 | 0.066* | |
H4 | 0.3319 | 0.4564 | 0.5254 | 0.061* | |
H6 | 0.2212 | 0.2880 | 0.2861 | 0.064* | |
H7 | 0.0225 | 0.4002 | 0.2389 | 0.070* | |
H9A | 0.4542 | 0.1884 | 0.5752 | 0.062* | |
H9B | 0.2902 | 0.2265 | 0.5410 | 0.062* | |
H12 | 0.2236 | 0.0625 | 0.6070 | 0.065* | |
H13 | 0.0864 | −0.0837 | 0.6387 | 0.073* | |
H15 | 0.1447 | −0.2380 | 0.4098 | 0.074* | |
H16 | 0.2797 | −0.0909 | 0.3758 | 0.064* | |
H18A | 0.6190 | 0.0627 | 0.1634 | 0.099* | |
H18B | 0.7294 | 0.1421 | 0.2273 | 0.099* | |
H18C | 0.6025 | 0.1898 | 0.1494 | 0.099* | |
H18 | 0.506 (2) | 0.3208 (17) | 0.4767 (14) | 0.059 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0670 (14) | 0.0773 (15) | 0.0898 (16) | 0.0130 (12) | 0.0177 (12) | 0.0173 (13) |
C2 | 0.0523 (10) | 0.0518 (10) | 0.0631 (11) | −0.0015 (8) | 0.0184 (8) | 0.0118 (8) |
C3 | 0.0661 (12) | 0.0464 (10) | 0.0572 (10) | 0.0018 (8) | 0.0228 (9) | 0.0005 (8) |
C4 | 0.0599 (11) | 0.0485 (9) | 0.0455 (9) | −0.0033 (8) | 0.0139 (8) | −0.0016 (7) |
C5 | 0.0507 (9) | 0.0409 (8) | 0.0428 (8) | −0.0058 (7) | 0.0151 (7) | −0.0002 (6) |
C6 | 0.0595 (11) | 0.0494 (10) | 0.0492 (9) | −0.0058 (8) | 0.0091 (8) | −0.0071 (7) |
C7 | 0.0569 (11) | 0.0611 (12) | 0.0528 (10) | −0.0060 (9) | 0.0038 (8) | 0.0029 (9) |
C8 | 0.0515 (10) | 0.0452 (9) | 0.0449 (9) | −0.0062 (8) | 0.0126 (7) | −0.0028 (7) |
C9 | 0.0597 (11) | 0.0501 (10) | 0.0450 (9) | −0.0028 (8) | 0.0117 (8) | 0.0009 (7) |
C10 | 0.0427 (8) | 0.0471 (9) | 0.0429 (8) | 0.0019 (7) | 0.0075 (7) | 0.0032 (7) |
C11 | 0.0419 (9) | 0.0458 (9) | 0.0471 (9) | 0.0032 (7) | 0.0076 (7) | 0.0071 (7) |
C12 | 0.0584 (11) | 0.0560 (11) | 0.0484 (9) | −0.0009 (8) | 0.0146 (8) | 0.0042 (8) |
C13 | 0.0618 (12) | 0.0693 (13) | 0.0555 (11) | 0.0014 (10) | 0.0193 (9) | 0.0131 (9) |
C14 | 0.0533 (11) | 0.0538 (11) | 0.0741 (12) | −0.0042 (8) | 0.0198 (9) | 0.0135 (9) |
C15 | 0.0671 (12) | 0.0492 (10) | 0.0724 (13) | −0.0062 (9) | 0.0218 (10) | 0.0005 (9) |
C16 | 0.0557 (10) | 0.0486 (10) | 0.0594 (11) | 0.0005 (8) | 0.0186 (8) | 0.0026 (8) |
C17 | 0.0450 (9) | 0.0520 (10) | 0.0475 (9) | 0.0031 (7) | 0.0121 (7) | 0.0060 (7) |
C18 | 0.0740 (14) | 0.0737 (13) | 0.0571 (11) | 0.0219 (11) | 0.0277 (10) | 0.0086 (10) |
N1 | 0.0569 (9) | 0.0418 (7) | 0.0530 (8) | −0.0029 (6) | 0.0200 (7) | −0.0028 (6) |
N2 | 0.0500 (8) | 0.0410 (8) | 0.0541 (8) | −0.0013 (6) | 0.0140 (7) | −0.0007 (6) |
N3 | 0.0618 (10) | 0.0520 (9) | 0.0573 (9) | 0.0036 (7) | 0.0239 (8) | −0.0020 (7) |
F1 | 0.0904 (10) | 0.0709 (9) | 0.1129 (11) | −0.0238 (7) | 0.0436 (8) | 0.0128 (8) |
S1 | 0.0730 (4) | 0.0547 (3) | 0.0718 (4) | −0.0101 (2) | 0.0290 (3) | 0.0038 (2) |
Geometric parameters (Å, º) top
C1—C2 | 1.507 (3) | C10—C11 | 1.459 (2) |
C1—H1A | 0.9600 | C11—C12 | 1.392 (3) |
C1—H1B | 0.9600 | C11—C16 | 1.393 (3) |
C1—H1C | 0.9600 | C12—C13 | 1.376 (3) |
C2—C7 | 1.381 (3) | C12—H12 | 0.9300 |
C2—C3 | 1.388 (3) | C13—C14 | 1.370 (3) |
C3—C4 | 1.377 (3) | C13—H13 | 0.9300 |
C3—H3A | 0.9300 | C14—F1 | 1.355 (2) |
C4—C5 | 1.387 (2) | C14—C15 | 1.360 (3) |
C4—H4 | 0.9300 | C15—C16 | 1.383 (3) |
C5—C6 | 1.384 (2) | C15—H15 | 0.9300 |
C5—C8 | 1.516 (2) | C16—H16 | 0.9300 |
C6—C7 | 1.382 (3) | C17—N3 | 1.337 (2) |
C6—H6 | 0.9300 | C17—N1 | 1.352 (2) |
C7—H7 | 0.9300 | C17—S1 | 1.6786 (19) |
C8—N1 | 1.465 (2) | C18—N3 | 1.444 (3) |
C8—C9 | 1.540 (2) | C18—H18A | 0.9600 |
C8—H18 | 0.94 (2) | C18—H18B | 0.9600 |
C9—C10 | 1.503 (2) | C18—H18C | 0.9600 |
C9—H9A | 0.9700 | N1—N2 | 1.395 (2) |
C9—H9B | 0.9700 | N3—H3 | 0.8600 |
C10—N2 | 1.282 (2) | | |
| | | |
C2—C1—H1A | 109.5 | N2—C10—C9 | 113.27 (16) |
C2—C1—H1B | 109.5 | C11—C10—C9 | 125.41 (16) |
H1A—C1—H1B | 109.5 | C12—C11—C16 | 118.70 (17) |
C2—C1—H1C | 109.5 | C12—C11—C10 | 120.68 (16) |
H1A—C1—H1C | 109.5 | C16—C11—C10 | 120.57 (16) |
H1B—C1—H1C | 109.5 | C13—C12—C11 | 120.64 (19) |
C7—C2—C3 | 117.39 (18) | C13—C12—H12 | 119.7 |
C7—C2—C1 | 121.4 (2) | C11—C12—H12 | 119.7 |
C3—C2—C1 | 121.2 (2) | C14—C13—C12 | 118.69 (19) |
C4—C3—C2 | 121.02 (18) | C14—C13—H13 | 120.7 |
C4—C3—H3A | 119.5 | C12—C13—H13 | 120.7 |
C2—C3—H3A | 119.5 | F1—C14—C15 | 118.66 (19) |
C3—C4—C5 | 121.20 (17) | F1—C14—C13 | 118.61 (19) |
C3—C4—H4 | 119.4 | C15—C14—C13 | 122.72 (19) |
C5—C4—H4 | 119.4 | C14—C15—C16 | 118.6 (2) |
C6—C5—C4 | 118.10 (17) | C14—C15—H15 | 120.7 |
C6—C5—C8 | 122.76 (15) | C16—C15—H15 | 120.7 |
C4—C5—C8 | 118.90 (15) | C15—C16—C11 | 120.63 (19) |
C7—C6—C5 | 120.23 (18) | C15—C16—H16 | 119.7 |
C7—C6—H6 | 119.9 | C11—C16—H16 | 119.7 |
C5—C6—H6 | 119.9 | N3—C17—N1 | 114.43 (16) |
C2—C7—C6 | 122.04 (18) | N3—C17—S1 | 124.25 (14) |
C2—C7—H7 | 119.0 | N1—C17—S1 | 121.31 (14) |
C6—C7—H7 | 119.0 | N3—C18—H18A | 109.5 |
N1—C8—C5 | 113.34 (14) | N3—C18—H18B | 109.5 |
N1—C8—C9 | 100.66 (14) | H18A—C18—H18B | 109.5 |
C5—C8—C9 | 110.49 (15) | N3—C18—H18C | 109.5 |
N1—C8—H18 | 109.1 (13) | H18A—C18—H18C | 109.5 |
C5—C8—H18 | 109.0 (13) | H18B—C18—H18C | 109.5 |
C9—C8—H18 | 114.1 (13) | C17—N1—N2 | 119.98 (14) |
C10—C9—C8 | 101.93 (14) | C17—N1—C8 | 127.80 (15) |
C10—C9—H9A | 111.4 | N2—N1—C8 | 112.21 (14) |
C8—C9—H9A | 111.4 | C10—N2—N1 | 108.21 (14) |
C10—C9—H9B | 111.4 | C17—N3—C18 | 124.00 (18) |
C8—C9—H9B | 111.4 | C17—N3—H3 | 118.0 |
H9A—C9—H9B | 109.2 | C18—N3—H3 | 118.0 |
N2—C10—C11 | 121.33 (16) | | |
| | | |
C7—C2—C3—C4 | −0.4 (3) | C10—C11—C12—C13 | 175.83 (16) |
C1—C2—C3—C4 | 179.27 (19) | C11—C12—C13—C14 | 0.6 (3) |
C2—C3—C4—C5 | −0.8 (3) | C12—C13—C14—F1 | −177.89 (18) |
C3—C4—C5—C6 | 1.6 (3) | C12—C13—C14—C15 | 0.9 (3) |
C3—C4—C5—C8 | −172.96 (17) | F1—C14—C15—C16 | 177.41 (18) |
C4—C5—C6—C7 | −1.1 (3) | C13—C14—C15—C16 | −1.4 (3) |
C8—C5—C6—C7 | 173.21 (18) | C14—C15—C16—C11 | 0.3 (3) |
C3—C2—C7—C6 | 0.9 (3) | C12—C11—C16—C15 | 1.1 (3) |
C1—C2—C7—C6 | −178.8 (2) | C10—C11—C16—C15 | −176.32 (17) |
C5—C6—C7—C2 | −0.1 (3) | N3—C17—N1—N2 | −1.0 (2) |
C6—C5—C8—N1 | 13.3 (2) | S1—C17—N1—N2 | 179.15 (12) |
C4—C5—C8—N1 | −172.38 (15) | N3—C17—N1—C8 | −179.50 (16) |
C6—C5—C8—C9 | −98.77 (19) | S1—C17—N1—C8 | 0.7 (3) |
C4—C5—C8—C9 | 75.5 (2) | C5—C8—N1—C17 | 78.5 (2) |
N1—C8—C9—C10 | −17.86 (17) | C9—C8—N1—C17 | −163.55 (17) |
C5—C8—C9—C10 | 102.19 (16) | C5—C8—N1—N2 | −100.09 (17) |
C8—C9—C10—N2 | 14.4 (2) | C9—C8—N1—N2 | 17.89 (18) |
C8—C9—C10—C11 | −166.06 (15) | C11—C10—N2—N1 | 176.84 (14) |
N2—C10—C11—C12 | −177.04 (16) | C9—C10—N2—N1 | −3.6 (2) |
C9—C10—C11—C12 | 3.5 (3) | C17—N1—N2—C10 | 171.44 (15) |
N2—C10—C11—C16 | 0.4 (3) | C8—N1—N2—C10 | −9.87 (19) |
C9—C10—C11—C16 | −179.15 (17) | N1—C17—N3—C18 | −170.43 (17) |
C16—C11—C12—C13 | −1.6 (3) | S1—C17—N3—C18 | 9.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2 | 0.86 | 2.20 | 2.602 (2) | 108 |
C6—H6···N1 | 0.93 | 2.53 | 2.866 (3) | 102 |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C19H20FN3OS | C18H18FN3S |
Mr | 357.44 | 327.41 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 9.706 (5), 12.141 (5), 17.753 (5) | 9.4191 (17), 12.2032 (11), 14.673 (2) |
β (°) | 120.372 (17) | 103.063 (14) |
V (Å3) | 1804.9 (13) | 1642.9 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.20 | 0.21 |
Crystal size (mm) | 0.60 × 0.54 × 0.30 | 0.60 × 0.46 × 0.25 |
|
Data collection |
Diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | – | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | – | 0.885, 0.954 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12891, 3622, 2785 | 10474, 3429, 2655 |
Rint | 0.043 | 0.051 |
(sin θ/λ)max (Å−1) | 0.624 | 0.631 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.04 | 0.043, 0.140, 1.08 |
No. of reflections | 3622 | 3429 |
No. of parameters | 234 | 214 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 | 0.23, −0.30 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H20···O1i | 0.865 (18) | 2.319 (18) | 3.092 (2) | 148.9 (15) |
N3—H20···N2 | 0.865 (18) | 2.211 (17) | 2.6187 (18) | 108.7 (14) |
C3—H3···S1ii | 0.93 | 2.79 | 3.5471 (18) | 140 |
C18—H18B···S1 | 0.97 | 2.75 | 3.088 (2) | 101 |
Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2 | 0.86 | 2.20 | 2.602 (2) | 108 |
C6—H6···N1 | 0.93 | 2.53 | 2.866 (3) | 102 |
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Prodrug-based monoamine oxidase (MAO) inhibitors display important antidepressant activity. Previous studies have demonstrated the MAO inhibitory activities of 1,3,5-triphenyl-2-pyrazolines (Soni et al., 1987; Chimenti et al., 2004). We have previously synthesized several phenyl-2-pyrazoline derivatives (Bilgin et al., 1993; Palaska et al., 1996, 2001), and we report here the structures of two 1-N-substituted thiocarbamoyl-3-(4-fluorophenyl)-5-aryl-2-pyrazolines (Figs. 1–3, and Tables 1 and 2).
In (I), the five-membered pyrazoline ring has an envelope conformation, with atom C8 forming the flap, and atoms N1, N2, C9 and C10 coplanar with a maximum deviation of 0.069 (2) Å for C9; atom C8 is 0.18 (2) Å from this plane [the puckering parameters (Cremer & Pople, 1975) are q2 = 0.15 (2) Å and ϕ = 89.36 (6)°]. Compound (II) is similar, although it shows a slight envelope-like distortion; atom C8 is 0.12 (2) Å from the mean plane [q2 = 0.24 (3) Å and ϕ = 84.16 (7)°]. The bond lengths and angles in the five-membered rings in both compounds are in agreement with expected values (Allen, 2002; Krishnakumar et al., 2004). The pyrazoline ring N—N bond lengths are similar, viz. 1.3886 (16) Å in (I) and 1.395 (2) Å in (II), and influenced by the degree of conjugation within the C═N double bond of the pyrazoline ring.
The bond lengths and angles of the thiocarbamoyl groups of (I) and (II) are comparable to those of the related compound 2-[(diethylamino)carbonyl]-3- formylphenyl-N,N-diethylthiocarbamate (Castillo et al., 2003). In (I) and (II), the thiocarbamoyl S1═C7 and pyrazoline N2═C10 bonds are well defined double bonds. The N—C═S bond angles around the C atoms of the thiocarbamoyl moieties are similar, with values of 120.75 (10)° for (I) and 121.31 (14)° for (II). The N—C—N(H)—C torsion angles are −175.44 (13)° for (I) and −170.43 (17)° for (II). In each compounds, the methoxyphenyl or methylphenyl group occupies a pseudo-axial position and, as a result, is approximately perpendicular to the mean plane of the pyrazoline ring [the interplanar angle is 89.29 (8)° in (I) and 80.39 (10)° in (II)].
In (I), the carbamoyl N—H H atom forms a bifurcated hydrogen bond involving an intramolecular interaction with atom N2 of the pyrazoline group [graph set S(5) (Bernstein et al., 1995)] and an intermolecular hydrogen bond with methoxy atom O1 [N3—H20···O1i, with graph set C(11); symmetry code: (i) x − 1, y, z; Table 1]. The latter interaction links the molecules into a one-dimensional chain along (100) (Fig. 3). Intermolecular C3—H3···S1ii hydrogen bonds [symmetry code: (ii) 2 − x, 2 − y, 1 − z] further link the chains across inversion centres, forming rings with graph set R22(16) (Bernstein et al., 1995). In (II), only relatively weak intramolecular hydrogen bonds are present (Table 2).