PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3263.
Published online 2009 November 28. doi:  10.1107/S1600536809050685
PMCID: PMC2971773

(E)-2-[(4-Chloro-1,3-dimethyl-1H-pyrazol-5-yl)methyl­eneamino]benzamide

Abstract

In the title compound, C13H13ClN4O, the dihedral angle between the aromatic rings is 33.47 (9)° and an intra­molecular N—H(...)N hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H(...)O hydrogen bonds occur, resulting in R 2 2(8) loops.

Related literature

For catalytic studies on a related compound, see: Chen et al. (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3263-scheme1.jpg

Experimental

Crystal data

  • C13H13ClN4O
  • M r = 276.72
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3263-efi1.jpg
  • a = 22.046 (3) Å
  • b = 8.6785 (10) Å
  • c = 14.1137 (16) Å
  • β = 96.005 (2)°
  • V = 2685.5 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 296 K
  • 0.32 × 0.30 × 0.28 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.725, T max = 1.000
  • 6634 measured reflections
  • 2375 independent reflections
  • 2098 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.098
  • S = 1.06
  • 2375 reflections
  • 175 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050685/hb5252sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050685/hb5252Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

The title compound was synthesized by the reaction of 4-chloro-1,3-dimethyl-1H-pyrazole-5- carbaldehyde with 2-aminobenzamide in 1,2-dichloroethane. The crude product was purified by silica-gel column chromatography and then grown from methylene chloride to afford colourless blocks of (I).

Anal. Calcd for C13H13N4O1: C, 56.42; H, 4.74; N, 20.25; O, 5.78. Found: C, 56.57; H, 4.64; N, 20.66; O, 5.25. 1H NMR(DMSO): 2.21(s,3H, CH3), 4.12 (s,3H, N—CH3), 7.33(s, 2H, CONH2), 7.50–7.61 (m, 2H, Ph), 7.89 (t, 1H, Ph—H), 8.26 (s, 1H, Ph—H), 8.46 (s, 1H, CH=N).

Refinement

All H atoms were visible in difference maps; they were finally placed in geometrically calculated positions, with C—H = 0.93–0.96Å and N—H = 0.86 Å, and refined as riding with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), with 30% probability displacement ellipsoids.

Crystal data

C13H13ClN4OF(000) = 1152
Mr = 276.72Dx = 1.369 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4144 reflections
a = 22.046 (3) Åθ = 2.2–30.2°
b = 8.6785 (10) ŵ = 0.28 mm1
c = 14.1137 (16) ÅT = 296 K
β = 96.005 (2)°Block, colourless
V = 2685.5 (5) Å30.32 × 0.30 × 0.28 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer2375 independent reflections
Radiation source: fine-focus sealed tube2098 reflections with I > 2σ(I)
graphiteRint = 0.018
ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −25→26
Tmin = 0.725, Tmax = 1.000k = −6→10
6634 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.098w = 1/[σ2(Fo2) + (0.052P)2 + 1.4091P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2375 reflectionsΔρmax = 0.17 e Å3
175 parametersΔρmin = −0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0266 (12)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cl10.45129 (2)0.49955 (4)0.12551 (4)0.0612 (2)
N40.29251 (6)0.43146 (17)0.04310 (11)0.0531 (4)
H4A0.30060.34800.01400.064*
H4B0.32170.48990.06700.064*
O10.19254 (5)0.38809 (14)0.01737 (10)0.0600 (4)
N10.52045 (6)0.91074 (16)0.12334 (10)0.0486 (4)
N20.46079 (6)0.94242 (16)0.12143 (10)0.0445 (3)
C60.36052 (7)0.82150 (17)0.12489 (11)0.0397 (4)
H60.34170.91740.12020.048*
N30.32795 (6)0.70280 (14)0.13302 (9)0.0376 (3)
C10.46698 (7)0.69287 (17)0.12368 (11)0.0400 (4)
C20.52480 (7)0.75722 (19)0.12428 (11)0.0430 (4)
C30.58468 (8)0.6779 (2)0.12766 (15)0.0576 (5)
H3A0.61590.75180.11810.086*
H3B0.58310.60130.07840.086*
H3C0.59380.62940.18860.086*
C40.44200 (9)1.1028 (2)0.12241 (16)0.0614 (5)
H4C0.43161.12920.18470.092*
H4D0.40721.11790.07660.092*
H4E0.47491.16720.10660.092*
C50.42578 (7)0.81350 (17)0.12263 (11)0.0379 (4)
C70.26516 (7)0.72357 (17)0.14214 (10)0.0364 (3)
C80.22185 (7)0.61479 (17)0.10333 (10)0.0363 (3)
C90.16068 (7)0.6395 (2)0.11507 (12)0.0445 (4)
H90.13170.56940.08900.053*
C100.14195 (8)0.7653 (2)0.16439 (13)0.0541 (5)
H100.10070.78070.17010.065*
C110.18475 (8)0.8675 (2)0.20506 (14)0.0577 (5)
H110.17260.95090.23980.069*
C120.24531 (8)0.8468 (2)0.19446 (13)0.0504 (4)
H120.27380.91630.22270.060*
C130.23540 (7)0.46978 (18)0.05100 (11)0.0401 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0557 (3)0.0314 (3)0.0956 (4)−0.00049 (17)0.0037 (2)−0.0028 (2)
N40.0376 (7)0.0445 (8)0.0774 (10)−0.0038 (6)0.0064 (7)−0.0244 (7)
O10.0391 (6)0.0426 (7)0.0960 (10)−0.0043 (5)−0.0039 (6)−0.0204 (6)
N10.0387 (7)0.0446 (8)0.0618 (9)−0.0076 (6)0.0021 (6)0.0017 (6)
N20.0407 (7)0.0328 (7)0.0589 (8)−0.0046 (5)−0.0004 (6)0.0008 (6)
C60.0404 (8)0.0316 (8)0.0452 (8)0.0002 (6)−0.0044 (6)0.0003 (6)
N30.0356 (7)0.0345 (7)0.0418 (7)−0.0026 (5)−0.0006 (5)−0.0032 (5)
C10.0417 (8)0.0332 (8)0.0442 (8)−0.0017 (6)−0.0001 (6)−0.0015 (6)
C20.0403 (8)0.0434 (9)0.0450 (9)−0.0012 (7)0.0025 (7)−0.0004 (7)
C30.0447 (10)0.0609 (12)0.0674 (12)0.0047 (8)0.0066 (8)0.0000 (9)
C40.0561 (11)0.0322 (9)0.0946 (15)−0.0052 (8)0.0017 (10)−0.0010 (9)
C50.0389 (8)0.0322 (8)0.0414 (8)−0.0043 (6)−0.0018 (6)−0.0007 (6)
C70.0374 (8)0.0346 (8)0.0364 (7)0.0027 (6)0.0004 (6)0.0009 (6)
C80.0367 (8)0.0338 (8)0.0381 (8)−0.0006 (6)0.0018 (6)0.0023 (6)
C90.0366 (8)0.0452 (9)0.0513 (9)−0.0019 (7)0.0024 (7)0.0001 (7)
C100.0404 (9)0.0613 (11)0.0614 (11)0.0102 (8)0.0097 (8)−0.0044 (9)
C110.0547 (11)0.0574 (11)0.0608 (11)0.0142 (9)0.0046 (8)−0.0175 (9)
C120.0478 (10)0.0461 (9)0.0557 (10)0.0014 (8)−0.0012 (8)−0.0145 (8)
C130.0379 (8)0.0343 (8)0.0472 (8)−0.0027 (6)0.0009 (6)−0.0010 (6)

Geometric parameters (Å, °)

Cl1—C11.7137 (16)C3—H3B0.9600
N4—C131.318 (2)C3—H3C0.9600
N4—H4A0.8600C4—H4C0.9600
N4—H4B0.8600C4—H4D0.9600
O1—C131.2356 (18)C4—H4E0.9600
N1—C21.336 (2)C7—C121.396 (2)
N1—N21.3413 (19)C7—C81.412 (2)
N2—C51.360 (2)C8—C91.392 (2)
N2—C41.452 (2)C8—C131.505 (2)
C6—N31.2677 (19)C9—C101.381 (2)
C6—C51.444 (2)C9—H90.9300
C6—H60.9300C10—C111.376 (3)
N3—C71.4151 (19)C10—H100.9300
C1—C51.385 (2)C11—C121.371 (2)
C1—C21.391 (2)C11—H110.9300
C2—C31.485 (2)C12—H120.9300
C3—H3A0.9600
C13—N4—H4A120.0H4C—C4—H4E109.5
C13—N4—H4B120.0H4D—C4—H4E109.5
H4A—N4—H4B120.0N2—C5—C1104.45 (14)
C2—N1—N2105.89 (13)N2—C5—C6121.91 (13)
N1—N2—C5112.81 (13)C1—C5—C6133.62 (14)
N1—N2—C4118.44 (13)C12—C7—C8118.74 (14)
C5—N2—C4128.70 (14)C12—C7—N3120.63 (13)
N3—C6—C5122.55 (14)C8—C7—N3120.52 (13)
N3—C6—H6118.7C9—C8—C7118.35 (14)
C5—C6—H6118.7C9—C8—C13115.57 (13)
C6—N3—C7118.26 (13)C7—C8—C13126.07 (13)
C5—C1—C2107.22 (14)C10—C9—C8121.76 (16)
C5—C1—Cl1127.38 (12)C10—C9—H9119.1
C2—C1—Cl1125.40 (13)C8—C9—H9119.1
N1—C2—C1109.62 (14)C11—C10—C9119.45 (16)
N1—C2—C3121.67 (15)C11—C10—H10120.3
C1—C2—C3128.70 (16)C9—C10—H10120.3
C2—C3—H3A109.5C12—C11—C10120.20 (16)
C2—C3—H3B109.5C12—C11—H11119.9
H3A—C3—H3B109.5C10—C11—H11119.9
C2—C3—H3C109.5C11—C12—C7121.41 (16)
H3A—C3—H3C109.5C11—C12—H12119.3
H3B—C3—H3C109.5C7—C12—H12119.3
N2—C4—H4C109.5O1—C13—N4121.44 (15)
N2—C4—H4D109.5O1—C13—C8119.04 (14)
H4C—C4—H4D109.5N4—C13—C8119.52 (13)
N2—C4—H4E109.5
C2—N1—N2—C50.99 (18)N3—C6—C5—C13.3 (3)
C2—N1—N2—C4178.50 (16)C6—N3—C7—C12−37.2 (2)
C5—C6—N3—C7175.07 (13)C6—N3—C7—C8146.70 (15)
N2—N1—C2—C1−0.46 (18)C12—C7—C8—C93.1 (2)
N2—N1—C2—C3−179.23 (15)N3—C7—C8—C9179.31 (13)
C5—C1—C2—N1−0.19 (18)C12—C7—C8—C13−175.57 (15)
Cl1—C1—C2—N1−179.43 (12)N3—C7—C8—C130.6 (2)
C5—C1—C2—C3178.46 (17)C7—C8—C9—C10−0.9 (2)
Cl1—C1—C2—C3−0.8 (3)C13—C8—C9—C10177.86 (15)
N1—N2—C5—C1−1.09 (18)C8—C9—C10—C11−1.5 (3)
C4—N2—C5—C1−178.29 (17)C9—C10—C11—C121.7 (3)
N1—N2—C5—C6177.42 (13)C10—C11—C12—C70.5 (3)
C4—N2—C5—C60.2 (3)C8—C7—C12—C11−2.9 (3)
C2—C1—C5—N20.75 (17)N3—C7—C12—C11−179.15 (16)
Cl1—C1—C5—N2179.96 (12)C9—C8—C13—O14.2 (2)
C2—C1—C5—C6−177.51 (16)C7—C8—C13—O1−177.06 (15)
Cl1—C1—C5—C61.7 (3)C9—C8—C13—N4−174.85 (15)
N3—C6—C5—N2−174.72 (15)C7—C8—C13—N43.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4B···N30.862.072.749 (2)136
N4—H4A···O1i0.862.102.930 (2)161

Symmetry codes: (i) −x+1/2, −y+1/2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5252).

References

  • Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, J., Su, W., Wu, H., Liu, M. & Jin, C. (2008). Catal. Commun. 9, 785–788.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography