organic compounds
2-[(5-Amino-3-methyl-1-phenyl-1H-pyrazol-4-yl)(4-chlorophenyl)methyl]malononitrile
aSchool of Chemical and Environmental Sciences, Henan Key Laboratory for Environmental Pollution Control, Henan Normal University, Xinxiang, Henan 453007, People's Republic of China
*Correspondence e-mail: xyzh518@sohu.com, xuesen.fan@sohu.com
In the 20H16ClN5, the dihedral angle between the pyrazole ring and the phenyl ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The methyl H atoms are disordered over two positions with site occupancy factors of ca 0.7 and 0.3. One amino H is disordered equally over two positions. In the the molecules are linked via intermolecular N—H⋯N hydrogen bonding.
of the title compound, CExperimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808011562/nc2101sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011562/nc2101Isup2.hkl
To 1 ml of 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 4-chloroaldehyde (1 mmol), malononitrile (1 mmol) and 5-amino-3-methyl-1-phenylpyrazole (1 mmol) were added. The reaction mixture was stirred at room temperature for 4 h and afterwards extracted five times with 2 ml of diethylether. The ether extracts were combined and concentrated. The obtained residue was recrystallized with 95% ethanol to give the product in a yield of 95% as white solid. Single crystals of the title compound were obtained by slow evaporation of the solvent from a petroleum ether-ethyl ether (1:1 v/v) solution.
All H atoms were placed in geometrically idealized positions (methyl H atoms are disordered in two orientations) and constrained to ride on their parent atoms, with C—H distances of 0.93 - 0.98 Å and with Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms). The N-H H atoms were located in difference map, their bond lengths were set to ideal values and afterwards they were refined using a riding model with Uiso(H) = 1.2Ueq(C). One of the N-H H atoms is disordered and was refined using a split model.
Data collection: SMART (Bruker, 1997); cell
SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C20H16ClN5 | Dx = 1.286 Mg m−3 |
Mr = 361.83 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8329 reflections |
a = 10.4700 (11) Å | θ = 2.5–25.8° |
b = 14.0482 (15) Å | µ = 0.22 mm−1 |
c = 25.409 (3) Å | T = 294 K |
V = 3737.3 (7) Å3 | Block, colourless |
Z = 8 | 0.49 × 0.48 × 0.45 mm |
F(000) = 1504 |
Bruker SMART CCD area-detector diffractometer | 4661 independent reflections |
Radiation source: fine-focus sealed tube | 3055 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 28.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −14→13 |
Tmin = 0.901, Tmax = 0.909 | k = −18→18 |
32456 measured reflections | l = −33→33 |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0404P)2 + 1.3457P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
4661 reflections | Δρmax = 0.18 e Å−3 |
237 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0012 (3) |
C20H16ClN5 | V = 3737.3 (7) Å3 |
Mr = 361.83 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.4700 (11) Å | µ = 0.22 mm−1 |
b = 14.0482 (15) Å | T = 294 K |
c = 25.409 (3) Å | 0.49 × 0.48 × 0.45 mm |
Bruker SMART CCD area-detector diffractometer | 4661 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 3055 reflections with I > 2σ(I) |
Tmin = 0.901, Tmax = 0.909 | Rint = 0.033 |
32456 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.18 e Å−3 |
4661 reflections | Δρmin = −0.32 e Å−3 |
237 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 | Occ. (<1) | |
Cl1 | 0.34596 (7) | 1.04230 (4) | 0.53076 (2) | 0.0837 (2) | |
N1 | 0.27144 (14) | 0.71251 (10) | 0.78626 (5) | 0.0509 (4) | |
N2 | 0.17726 (15) | 0.64522 (12) | 0.77803 (6) | 0.0605 (4) | |
N3 | 0.43568 (16) | 0.79533 (11) | 0.74011 (5) | 0.0623 (4) | |
N4 | 0.4155 (2) | 0.44105 (12) | 0.68772 (7) | 0.0751 (5) | |
N5 | 0.52582 (19) | 0.58634 (13) | 0.54493 (7) | 0.0748 (5) | |
C1 | 0.18531 (16) | 0.62494 (13) | 0.72710 (6) | 0.0512 (4) | |
C2 | 0.28333 (15) | 0.67629 (11) | 0.70228 (5) | 0.0414 (3) | |
C3 | 0.33723 (15) | 0.73171 (11) | 0.74145 (6) | 0.0429 (4) | |
C4 | 0.0940 (2) | 0.55545 (17) | 0.70288 (8) | 0.0772 (7) | |
H4A | 0.0613 | 0.5811 | 0.6706 | 0.116* | 0.73 |
H4B | 0.0245 | 0.5440 | 0.7267 | 0.116* | 0.73 |
H4C | 0.1376 | 0.4967 | 0.6958 | 0.116* | 0.73 |
H4D | 0.0876 | 0.5001 | 0.7249 | 0.116* | 0.27 |
H4E | 0.1244 | 0.5372 | 0.6687 | 0.116* | 0.27 |
H4F | 0.0114 | 0.5845 | 0.6996 | 0.116* | 0.27 |
C5 | 0.29537 (17) | 0.74496 (15) | 0.83845 (6) | 0.0579 (5) | |
C6 | 0.2963 (2) | 0.84064 (18) | 0.84956 (9) | 0.0847 (7) | |
H6 | 0.2812 | 0.8854 | 0.8233 | 0.102* | |
C7 | 0.3206 (3) | 0.8691 (3) | 0.90156 (14) | 0.1220 (14) | |
H7 | 0.3232 | 0.9335 | 0.9099 | 0.146* | |
C8 | 0.3407 (3) | 0.8023 (4) | 0.94005 (12) | 0.1401 (18) | |
H8 | 0.3567 | 0.8218 | 0.9744 | 0.168* | |
C9 | 0.3375 (3) | 0.7080 (3) | 0.92837 (10) | 0.1239 (13) | |
H9 | 0.3504 | 0.6632 | 0.9548 | 0.149* | |
C10 | 0.3151 (2) | 0.6782 (2) | 0.87746 (8) | 0.0846 (7) | |
H10 | 0.3133 | 0.6136 | 0.8695 | 0.102* | |
C11 | 0.33508 (15) | 0.76013 (11) | 0.61584 (5) | 0.0415 (3) | |
C12 | 0.22572 (17) | 0.79784 (13) | 0.59298 (6) | 0.0516 (4) | |
H12 | 0.1491 | 0.7647 | 0.5956 | 0.062* | |
C13 | 0.2283 (2) | 0.88387 (14) | 0.56630 (6) | 0.0588 (5) | |
H13 | 0.1545 | 0.9082 | 0.5510 | 0.071* | |
C14 | 0.3417 (2) | 0.93244 (12) | 0.56298 (6) | 0.0550 (5) | |
C15 | 0.45228 (19) | 0.89664 (13) | 0.58425 (7) | 0.0569 (5) | |
H15 | 0.5287 | 0.9299 | 0.5811 | 0.068* | |
C16 | 0.44836 (17) | 0.81010 (12) | 0.61058 (6) | 0.0510 (4) | |
H16 | 0.5230 | 0.7853 | 0.6249 | 0.061* | |
C17 | 0.32395 (14) | 0.66623 (11) | 0.64546 (5) | 0.0401 (3) | |
H17 | 0.2568 | 0.6296 | 0.6278 | 0.048* | |
C18 | 0.44800 (16) | 0.60557 (11) | 0.64192 (6) | 0.0444 (4) | |
H18 | 0.5153 | 0.6391 | 0.6613 | 0.053* | |
C19 | 0.42937 (18) | 0.51193 (13) | 0.66700 (6) | 0.0525 (4) | |
C20 | 0.49158 (17) | 0.59315 (12) | 0.58707 (7) | 0.0511 (4) | |
H1N3 | 0.4639 | 0.8173 | 0.7695 | 0.061* | |
H2N3 | 0.5027 | 0.7693 | 0.7270 | 0.061* | 0.50 |
H3N3 | 0.4647 | 0.8134 | 0.7101 | 0.061* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1235 (5) | 0.0600 (3) | 0.0677 (3) | 0.0238 (3) | 0.0273 (3) | 0.0234 (2) |
N1 | 0.0586 (9) | 0.0588 (8) | 0.0354 (7) | −0.0138 (7) | 0.0064 (6) | −0.0075 (6) |
N2 | 0.0636 (9) | 0.0760 (11) | 0.0418 (8) | −0.0252 (8) | 0.0098 (7) | −0.0067 (7) |
N3 | 0.0761 (11) | 0.0659 (9) | 0.0448 (8) | −0.0308 (8) | 0.0096 (7) | −0.0120 (7) |
N4 | 0.1013 (14) | 0.0569 (10) | 0.0669 (11) | 0.0076 (9) | −0.0131 (10) | 0.0121 (8) |
N5 | 0.0918 (13) | 0.0807 (12) | 0.0518 (9) | 0.0059 (10) | 0.0158 (9) | −0.0074 (8) |
C1 | 0.0543 (10) | 0.0587 (10) | 0.0405 (8) | −0.0137 (8) | 0.0015 (7) | −0.0033 (7) |
C2 | 0.0474 (8) | 0.0430 (8) | 0.0338 (7) | −0.0020 (7) | 0.0003 (6) | −0.0009 (6) |
C3 | 0.0505 (9) | 0.0416 (8) | 0.0365 (7) | −0.0045 (7) | 0.0040 (6) | −0.0021 (6) |
C4 | 0.0765 (14) | 0.0976 (16) | 0.0575 (11) | −0.0416 (12) | 0.0044 (10) | −0.0101 (11) |
C5 | 0.0542 (10) | 0.0810 (13) | 0.0384 (8) | −0.0124 (9) | 0.0110 (7) | −0.0155 (8) |
C6 | 0.0862 (16) | 0.0897 (16) | 0.0782 (14) | −0.0306 (13) | 0.0300 (12) | −0.0365 (12) |
C7 | 0.102 (2) | 0.157 (3) | 0.107 (2) | −0.063 (2) | 0.0500 (18) | −0.088 (2) |
C8 | 0.091 (2) | 0.268 (5) | 0.0613 (17) | −0.046 (3) | 0.0176 (15) | −0.071 (3) |
C9 | 0.112 (2) | 0.220 (4) | 0.0398 (12) | 0.002 (3) | 0.0031 (13) | −0.0061 (18) |
C10 | 0.0911 (17) | 0.120 (2) | 0.0427 (10) | 0.0025 (15) | 0.0073 (10) | −0.0001 (12) |
C11 | 0.0507 (9) | 0.0458 (8) | 0.0281 (7) | 0.0033 (7) | 0.0007 (6) | −0.0010 (6) |
C12 | 0.0513 (10) | 0.0586 (10) | 0.0449 (9) | 0.0051 (8) | −0.0033 (7) | 0.0022 (7) |
C13 | 0.0670 (12) | 0.0632 (11) | 0.0461 (9) | 0.0200 (10) | −0.0025 (8) | 0.0052 (8) |
C14 | 0.0803 (13) | 0.0494 (9) | 0.0353 (8) | 0.0139 (9) | 0.0115 (8) | 0.0056 (7) |
C15 | 0.0649 (11) | 0.0555 (10) | 0.0503 (10) | −0.0040 (9) | 0.0091 (8) | 0.0076 (8) |
C16 | 0.0514 (10) | 0.0555 (10) | 0.0462 (9) | 0.0005 (8) | −0.0012 (7) | 0.0083 (7) |
C17 | 0.0450 (8) | 0.0438 (8) | 0.0315 (7) | −0.0024 (7) | −0.0039 (6) | −0.0020 (6) |
C18 | 0.0516 (9) | 0.0471 (9) | 0.0345 (7) | 0.0018 (7) | −0.0056 (6) | −0.0022 (6) |
C19 | 0.0623 (11) | 0.0530 (10) | 0.0421 (8) | 0.0088 (8) | −0.0079 (8) | −0.0005 (7) |
C20 | 0.0560 (10) | 0.0515 (10) | 0.0457 (9) | 0.0062 (8) | 0.0001 (8) | −0.0027 (7) |
Cl1—C14 | 1.7477 (17) | C6—H6 | 0.9300 |
N1—C3 | 1.3577 (19) | C7—C8 | 1.371 (5) |
N1—N2 | 1.3819 (19) | C7—H7 | 0.9300 |
N1—C5 | 1.424 (2) | C8—C9 | 1.359 (5) |
N2—C1 | 1.328 (2) | C8—H8 | 0.9300 |
N3—C3 | 1.365 (2) | C9—C10 | 1.379 (3) |
N3—H1N3 | 0.8602 | C9—H9 | 0.9300 |
N3—H2N3 | 0.8587 | C10—H10 | 0.9300 |
N3—H3N3 | 0.8595 | C11—C16 | 1.385 (2) |
N4—C19 | 1.136 (2) | C11—C12 | 1.389 (2) |
N5—C20 | 1.133 (2) | C11—C17 | 1.523 (2) |
C1—C2 | 1.404 (2) | C12—C13 | 1.386 (2) |
C1—C4 | 1.499 (2) | C12—H12 | 0.9300 |
C2—C3 | 1.384 (2) | C13—C14 | 1.372 (3) |
C2—C17 | 1.5117 (19) | C13—H13 | 0.9300 |
C4—H4A | 0.9600 | C14—C15 | 1.373 (3) |
C4—H4B | 0.9600 | C15—C16 | 1.388 (2) |
C4—H4C | 0.9600 | C15—H15 | 0.9300 |
C4—H4D | 0.9600 | C16—H16 | 0.9300 |
C4—H4E | 0.9600 | C17—C18 | 1.556 (2) |
C4—H4F | 0.9600 | C17—H17 | 0.9800 |
C5—C6 | 1.373 (3) | C18—C19 | 1.475 (2) |
C5—C10 | 1.380 (3) | C18—C20 | 1.477 (2) |
C6—C7 | 1.404 (4) | C18—H18 | 0.9800 |
C3—N1—N2 | 111.78 (12) | C7—C6—H6 | 120.9 |
C3—N1—C5 | 128.89 (14) | C8—C7—C6 | 120.3 (3) |
N2—N1—C5 | 119.03 (13) | C8—C7—H7 | 119.8 |
C1—N2—N1 | 104.41 (13) | C6—C7—H7 | 119.8 |
C3—N3—H1N3 | 118.2 | C9—C8—C7 | 120.5 (3) |
C3—N3—H2N3 | 110.3 | C9—C8—H8 | 119.8 |
H1N3—N3—H2N3 | 102.1 | C7—C8—H8 | 119.8 |
C3—N3—H3N3 | 118.9 | C8—C9—C10 | 120.3 (3) |
H1N3—N3—H3N3 | 122.9 | C8—C9—H9 | 119.8 |
H2N3—N3—H3N3 | 59.4 | C10—C9—H9 | 119.8 |
N2—C1—C2 | 111.96 (14) | C9—C10—C5 | 119.6 (3) |
N2—C1—C4 | 119.96 (16) | C9—C10—H10 | 120.2 |
C2—C1—C4 | 128.07 (15) | C5—C10—H10 | 120.2 |
C3—C2—C1 | 105.31 (13) | C16—C11—C12 | 118.19 (15) |
C3—C2—C17 | 128.66 (14) | C16—C11—C17 | 123.53 (14) |
C1—C2—C17 | 125.92 (14) | C12—C11—C17 | 118.29 (14) |
N1—C3—N3 | 122.28 (14) | C13—C12—C11 | 121.41 (17) |
N1—C3—C2 | 106.52 (13) | C13—C12—H12 | 119.3 |
N3—C3—C2 | 131.19 (14) | C11—C12—H12 | 119.3 |
C1—C4—H4A | 109.5 | C14—C13—C12 | 118.72 (17) |
C1—C4—H4B | 109.5 | C14—C13—H13 | 120.6 |
H4A—C4—H4B | 109.5 | C12—C13—H13 | 120.6 |
C1—C4—H4C | 109.5 | C13—C14—C15 | 121.56 (16) |
H4A—C4—H4C | 109.5 | C13—C14—Cl1 | 119.35 (15) |
H4B—C4—H4C | 109.5 | C15—C14—Cl1 | 119.09 (16) |
C1—C4—H4D | 109.5 | C14—C15—C16 | 119.04 (18) |
H4A—C4—H4D | 141.1 | C14—C15—H15 | 120.5 |
H4B—C4—H4D | 56.3 | C16—C15—H15 | 120.5 |
H4C—C4—H4D | 56.3 | C11—C16—C15 | 121.05 (16) |
C1—C4—H4E | 109.5 | C11—C16—H16 | 119.5 |
H4A—C4—H4E | 56.3 | C15—C16—H16 | 119.5 |
H4B—C4—H4E | 141.1 | C2—C17—C11 | 114.36 (12) |
H4C—C4—H4E | 56.3 | C2—C17—C18 | 109.95 (12) |
H4D—C4—H4E | 109.5 | C11—C17—C18 | 112.45 (12) |
C1—C4—H4F | 109.5 | C2—C17—H17 | 106.5 |
H4A—C4—H4F | 56.3 | C11—C17—H17 | 106.5 |
H4B—C4—H4F | 56.3 | C18—C17—H17 | 106.5 |
H4C—C4—H4F | 141.1 | C19—C18—C20 | 110.08 (14) |
H4D—C4—H4F | 109.5 | C19—C18—C17 | 110.68 (14) |
H4E—C4—H4F | 109.5 | C20—C18—C17 | 112.15 (13) |
C6—C5—C10 | 121.1 (2) | C19—C18—H18 | 107.9 |
C6—C5—N1 | 120.4 (2) | C20—C18—H18 | 107.9 |
C10—C5—N1 | 118.53 (19) | C17—C18—H18 | 107.9 |
C5—C6—C7 | 118.2 (3) | N4—C19—C18 | 177.99 (18) |
C5—C6—H6 | 120.9 | N5—C20—C18 | 178.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···N4i | 0.86 | 2.41 | 3.159 (2) | 146 |
N3—H2N3···N2ii | 0.86 | 2.53 | 3.325 (2) | 155 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C20H16ClN5 |
Mr | 361.83 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 10.4700 (11), 14.0482 (15), 25.409 (3) |
V (Å3) | 3737.3 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.49 × 0.48 × 0.45 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.901, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32456, 4661, 3055 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.118, 1.03 |
No. of reflections | 4661 |
No. of parameters | 237 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.32 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H1N3···N4i | 0.86 | 2.41 | 3.159 (2) | 146.2 |
N3—H2N3···N2ii | 0.86 | 2.53 | 3.325 (2) | 154.6 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x+1/2, y, −z+3/2. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (No. 20772025), the Program for Science & Technology Innovation Talents in Universities of Henan Province (No. 2008HASTIT006) and the Department of Education of Henan Province (No. 2008 A150013).
References
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The structure determination was undertaken as a part of a project on the synthesis of new pyrazole derivatives. In the title compound the dihedral angle between the pyrazole ring and the non-substituted phenyl ring which is directly connected to the pyrazole ring is 54.7 (1)° and that between the pyrazole ring and the chloro-substituted phenyl ring is 72.4 (1)°. The dihedral angle between the non-substituted and the chloro-substituted phenyl ring amount to 69.7 (1)° (Fig. 1).
In the crystal structure the molecules are connected via intermolecular N—H···N hydrogen bonding between the amino group at N3 and the N atoms N2 and N4 (Fig. 2 and Table 1).