organic papers
o3566
Yanget al. C15H13N3S doi:10.1107/S1600536806028467 Acta Cryst.(2006). E62, o3566–o3567
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
3-Methyl-1-phenyl-
N
-(2-thienylmethylene)-1
H
-pyrazol-5-amine
Fang Yang, Xiao-Yue Li, Hai-Ying Wang, Sai-Nan Ni and Da-Qing Shi*
Department of Chemistry, Xuzhou Normal University, Xuzhou 221116, People’s Republic of China
Correspondence e-mail: dqshi@263.net
Key indicators
Single-crystal X-ray study T= 298 K
Mean(C–C) = 0.004 A˚ Rfactor = 0.043 wRfactor = 0.131
Data-to-parameter ratio = 14.0
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 10 July 2006 Accepted 21 July 2006
#2006 International Union of Crystallography All rights reserved
The title compound, C15H13N3S, was synthesized by the reaction of 3-methyl-1-phenyl-1H-pyrazol-5-amine and thio-phene-2-carbaldehyde in boiling ethanol. The dihedral angle between the thiophene and pyrazole planes is 14.7 (1)and the
phenyl ring is twisted from the attached pyrazole ring by 32.2 (1).
Comment
Schiff bases are considered as a very important class of organic compounds which have wide applications in many biological situations (Fridovitch & Westheimer, 1962). The reaction of 2-carbaldehyde and 2,6-di2-carbaldehyde derivatives with a diamine results in open-chain and macrocyclic Schiff bases, respectively (Janusz et al., 2004). Studies performed on the synthesis and complexation behaviour of macrocyclic Schiff bases derived from 2,6-thiophene dicarbaldehyde are consid-erably more numerous compared with those of open-chain Schiff bases derived from 2-thiophene carbaldehyde (Hashemia et al., 2001). Studies on the synthesis and metal chelating properties of 2-thiophene carbaldehyde derivatives are very limited (Coakley et al., 1969; Eichhorn & Bailar, 1953). We report here the crystal structure of the title compound, (I).
In the title molecule (Fig. 1), the dihedral angle between the thiophene (S1/C5–C8) and pyrazole (N1/N2/C1–C3) planes is 14.7 (1). The C9–C14 phenyl ring is twisted from the attached
pyrazole ring by 32.2 (1). An intramolecular C14—H14 N3
hydrogen bond [H14 N3 = 2.47 A˚ , C14—N3 = 2.965 (4) A˚ and C14—H14 N3 = 114] is observed.
Experimental
X-ray diffraction were obtained by slow evaporation of an ethanol solution.
Crystal data
C15H13N3S
Mr= 267.34
Monoclinic,P21=c a= 10.035 (4) A˚
b= 8.194 (3) A˚
c= 16.671 (7) A˚
= 92.438 (5)
V= 1369.6 (9) A˚3
Z= 4
Dx= 1.296 Mg m
3
MoKradiation
= 0.23 mm 1
T= 298 (2) K Block, yellow 0.380.200.17 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.919,Tmax= 0.963
6774 measured reflections 2403 independent reflections 1499 reflections withI> 2(I)
Rint= 0.031
max= 25.0
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.043
wR(F2) = 0.131
S= 1.01 2403 reflections 172 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0542P)2
+ 0.6009P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001 max= 0.17 e A˚ 3 min= 0.26 e A˚ 3
All H atoms were positioned geometrically and treated as riding, with C—H = 0.93 or 0.96 A˚ and Uiso(H) = 1.2Ueq(C) and
1.5Ueq(methyl C).
Data collection:SMART(Bruker, 1998); cell refinement:SAINT
(Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1997); software used to prepare material for publication:SHELXTL.
The authors thank the Key Laboratory of Biotechnology for Medicinal Plants of Jiangsu Province (grant No. 02AXL13) for financial support.
References
Bruker (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1998).SMART. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (1999).SAINT. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.
Coakley, M. P., Young, L. H. & Gallagher, R. A. (1969).J. Inorg. Nucl. Chem.
31, 1449–1458.
Eichhorn, G. L. & Bailar, J. C. (1953).J. Am. Chem. Soc.75, 2905–2907. Fridovitch, I. & Westheimer, F. H. (1962).J. Am. Chem. Soc.84, 3208–3209. Hashemia, O. R., Kargarb, M. R. & Raoufia, F. (2001).Microchem. J.69, 1–6. Janusz, L., Pawel, H., Maciej, D. & Iwona, J. (2004).Inorg. Chem.43, 5789–
5791.
Sheldrick, G. M. (1996).SADABS. Version 2.05. University of Go¨ttingen, Germany.
[image:2.610.310.564.68.266.2]Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Figure 1
supporting information
sup-1 Acta Cryst. (2006). E62, o3566–o3567
supporting information
Acta Cryst. (2006). E62, o3566–o3567 [https://doi.org/10.1107/S1600536806028467]
3-Methyl-1-phenyl-
N
-(2-thienylmethylene)-1
H
-pyrazol-5-amine
Fang Yang, Xiao-Yue Li, Hai-Ying Wang, Sai-Nan Ni and Da-Qing Shi
3-Methyl-1-phenyl-N-(2-thienylmethylene)-1H-pyrazol-5-amine
Crystal data
C15H13N3S
Mr = 267.34
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 10.035 (4) Å
b = 8.194 (3) Å
c = 16.671 (7) Å
β = 92.438 (5)°
V = 1369.6 (9) Å3
Z = 4
F(000) = 560
Dx = 1.296 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1807 reflections
θ = 2.8–23.8°
µ = 0.23 mm−1
T = 298 K Block, yellow
0.38 × 0.20 × 0.17 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.919, Tmax = 0.963
6774 measured reflections 2403 independent reflections 1499 reflections with I > 2σ(I)
Rint = 0.031
θmax = 25.0°, θmin = 2.0°
h = −10→11
k = −9→9
l = −19→10
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.043
wR(F2) = 0.131
S = 1.01 2403 reflections 172 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0542P)2 + 0.6009P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.17 e Å−3
Δρmin = −0.26 e Å−3
Special details
Experimental. IR (KBr, cm-1): 3099, 1591,1518, 1492, 1433, 1406, 1142, 1041, 1024, 966, 831, 783, 762, 724, 689. 1H
NMR (DMSO-d6): 5.43 (3H, s, CH3), 6.42 (1H, s, CH), 7.25–7.35 (2H, m, ArH), 7.48 (2H, t, J = 8.0 Hz, ArH), 7.69–7.74
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)
x y z Uiso*/Ueq
N1 0.15469 (19) 0.4472 (2) 0.69549 (12) 0.0427 (5) N2 0.0735 (2) 0.4553 (3) 0.62744 (12) 0.0464 (6) N3 0.1598 (2) 0.5093 (3) 0.83491 (13) 0.0494 (6) S1 0.31109 (9) 0.48198 (12) 0.99574 (5) 0.0833 (4) C1 −0.0399 (3) 0.5191 (3) 0.65183 (16) 0.0479 (7) C2 −0.0325 (2) 0.5534 (3) 0.73340 (16) 0.0507 (7) H2 −0.0991 0.5989 0.7635 0.061* C3 0.0929 (2) 0.5069 (3) 0.76092 (15) 0.0444 (6) C4 0.1084 (3) 0.5853 (3) 0.89249 (16) 0.0495 (7)
H4 0.0282 0.6400 0.8828 0.059*
C5 0.1694 (3) 0.5896 (3) 0.97162 (16) 0.0486 (7) C6 0.1285 (3) 0.6719 (4) 1.03697 (18) 0.0639 (8)
H6 0.0523 0.7367 1.0361 0.077*
C7 0.2109 (4) 0.6502 (4) 1.10522 (18) 0.0706 (9)
H7 0.1968 0.6994 1.1544 0.085*
C8 0.3124 (4) 0.5507 (5) 1.09194 (19) 0.0839 (11)
H8 0.3770 0.5218 1.1310 0.101*
C9 0.2881 (2) 0.3894 (3) 0.68847 (15) 0.0419 (6) C10 0.3507 (3) 0.4161 (4) 0.61757 (16) 0.0530 (7) H10 0.3071 0.4730 0.5759 0.064* C11 0.4776 (3) 0.3583 (4) 0.60878 (19) 0.0674 (9) H11 0.5193 0.3754 0.5607 0.081* C12 0.5434 (3) 0.2760 (4) 0.6697 (2) 0.0701 (9) H12 0.6297 0.2382 0.6633 0.084* C13 0.4817 (3) 0.2492 (4) 0.74052 (19) 0.0624 (8) H13 0.5263 0.1930 0.7820 0.075* C14 0.3536 (3) 0.3057 (3) 0.75020 (17) 0.0523 (7) H14 0.3118 0.2874 0.7981 0.063* C15 −0.1541 (3) 0.5456 (4) 0.59229 (18) 0.0651 (8) H15A −0.1292 0.5096 0.5402 0.098* H15B −0.1760 0.6596 0.5901 0.098* H15C −0.2301 0.4846 0.6084 0.098*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2006). E62, o3566–o3567
N2 0.0439 (12) 0.0514 (13) 0.0434 (13) −0.0011 (10) −0.0037 (10) 0.0020 (11) N3 0.0477 (13) 0.0611 (14) 0.0394 (12) 0.0067 (11) 0.0019 (10) −0.0009 (11) S1 0.0893 (7) 0.1016 (7) 0.0576 (5) 0.0401 (5) −0.0150 (5) −0.0129 (5) C1 0.0433 (15) 0.0510 (16) 0.0490 (16) 0.0000 (12) −0.0026 (12) 0.0038 (14) C2 0.0433 (15) 0.0613 (18) 0.0477 (16) 0.0074 (13) 0.0050 (12) 0.0006 (14) C3 0.0436 (14) 0.0471 (15) 0.0427 (15) −0.0003 (12) 0.0032 (12) 0.0040 (13) C4 0.0476 (15) 0.0483 (15) 0.0525 (17) 0.0041 (12) 0.0013 (13) 0.0020 (14) C5 0.0538 (16) 0.0467 (15) 0.0455 (16) −0.0020 (12) 0.0047 (13) 0.0002 (13) C6 0.0688 (19) 0.064 (2) 0.059 (2) 0.0052 (15) 0.0083 (16) −0.0117 (16) C7 0.104 (3) 0.064 (2) 0.0438 (18) −0.0087 (19) 0.0057 (18) −0.0071 (16) C8 0.111 (3) 0.087 (3) 0.051 (2) 0.018 (2) −0.0242 (19) −0.0019 (19) C9 0.0409 (14) 0.0391 (14) 0.0455 (15) −0.0009 (11) −0.0001 (12) −0.0016 (12) C10 0.0487 (16) 0.0654 (18) 0.0449 (16) 0.0008 (13) 0.0016 (13) 0.0013 (15) C11 0.0516 (18) 0.090 (2) 0.062 (2) 0.0066 (16) 0.0127 (15) −0.0039 (18) C12 0.0454 (17) 0.082 (2) 0.083 (2) 0.0117 (15) 0.0031 (17) −0.012 (2) C13 0.0576 (18) 0.0626 (19) 0.066 (2) 0.0157 (15) −0.0107 (15) −0.0001 (17) C14 0.0525 (16) 0.0533 (17) 0.0511 (17) 0.0064 (13) 0.0006 (13) 0.0024 (14) C15 0.0496 (17) 0.084 (2) 0.0609 (19) 0.0078 (15) −0.0093 (14) 0.0000 (17)
Geometric parameters (Å, º)
N1—C3 1.368 (3) C7—C8 1.331 (4)
N1—N2 1.370 (3) C7—H7 0.93
N1—C9 1.430 (3) C8—H8 0.93
N2—C1 1.332 (3) C9—C10 1.379 (3)
N3—C4 1.272 (3) C9—C14 1.380 (3)
N3—C3 1.379 (3) C10—C11 1.373 (4)
S1—C8 1.699 (3) C10—H10 0.93
S1—C5 1.707 (3) C11—C12 1.366 (4)
C1—C2 1.388 (4) C11—H11 0.93
C1—C15 1.499 (4) C12—C13 1.374 (4)
C2—C3 1.375 (3) C12—H12 0.93
C2—H2 0.93 C13—C14 1.382 (4)
C4—C5 1.431 (4) C13—H13 0.93
C4—H4 0.93 C14—H14 0.93
C5—C6 1.360 (4) C15—H15A 0.96
C6—C7 1.390 (4) C15—H15B 0.96
C6—H6 0.93 C15—H15C 0.96
C3—N1—N2 111.67 (19) C7—C8—S1 112.6 (3)
C3—N1—C9 129.9 (2) C7—C8—H8 123.7
N2—N1—C9 118.3 (2) S1—C8—H8 123.7
C3—C2—C1 106.3 (2) C12—C11—C10 120.8 (3)
C3—C2—H2 126.9 C12—C11—H11 119.6
C1—C2—H2 126.9 C10—C11—H11 119.6
N1—C3—C2 105.8 (2) C11—C12—C13 119.8 (3) N1—C3—N3 119.9 (2) C11—C12—H12 120.1 C2—C3—N3 134.3 (2) C13—C12—H12 120.1 N3—C4—C5 122.5 (2) C12—C13—C14 120.2 (3)
N3—C4—H4 118.8 C12—C13—H13 119.9
C5—C4—H4 118.8 C14—C13—H13 119.9
C6—C5—C4 128.2 (3) C9—C14—C13 119.7 (3) C6—C5—S1 110.2 (2) C9—C14—H14 120.2 C4—C5—S1 121.6 (2) C13—C14—H14 120.2 C5—C6—C7 113.8 (3) C1—C15—H15A 109.5
C5—C6—H6 123.1 C1—C15—H15B 109.5
C7—C6—H6 123.1 H15A—C15—H15B 109.5 C8—C7—C6 112.1 (3) C1—C15—H15C 109.5 C8—C7—H7 124.0 H15A—C15—H15C 109.5 C6—C7—H7 124.0 H15B—C15—H15C 109.5
