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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 7| July 2012| Page o2203
https://doi.org/10.1107/S1600536812027298

3-(4-Bromo­phen­yl)-1-(4-chloro­benz­yl)-1H-pyrazole-5-carbaldehyde

Fu-Rong Li,a Yu-Juan Zhang,a Feng-Guang Guo,a Gui-Yun Duana and Yan-Qing Gea*

aTaishan Medical University, Tai an 271016, People's Republic of China
*Correspondence e-mail: yqge@yahoo.cn

(Received 24 May 2012; accepted 15 June 2012; online 23 June 2012)

The title compound, C17H12BrClN2O, was synthesized by oxidation of [3-(4-bromo­phen­yl)-1-(4-chloro­benz­yl)-1H-pyrazol-5-yl]methanol under mild conditions. The pyrazole ring makes dihedral angles of 3.29 (9) and 74.91 (4)°, respectively, with the bromo­phenyl and chloro­phenyl rings.

Related literature

For applications of nitro­gen-containing heterocyclic compounds in the agrochemical and pharmaceutical fields, see: Ge et al. (2007[Ge, Y.-Q., Dong, W.-L., Xia, Y., Wei, F. & Zhao, B.-X. (2007). Acta Cryst. E63, o1313-o1314.], 2009[Ge, Y. Q., Jia, J., Li, Y., Yin, L. & Wang, J. W. (2009). Heterocycles, 42, 197-206.], 2011[Ge, Y. Q., Hao, B. Q., Duan, G. Y. & Wang, J. W. (2011). J. Lumin. 131, 1070-1076.]). For the biological activity of some pyrazole derivatives belonging to this class of compounds, see: Xia et al. (2007[Xia, Y., Dong, Z. W., Zhao, B. X., Ge, X., Meng, N., Shin, D. S. & Miao, J. Y. (2007). Bioorg. Med. Chem. 15, 6893-6899.]). For a related compound, see: Hao et al. (2012[Hao, B.-Q., Xu, W.-R., Meng, F.-C. & Duan, G.-Y. (2012). Acta Cryst. E68, o877.]).

[Scheme 1]

Experimental

Crystal data

  • C17H12BrClN2O

  • Mr = 375.65

  • Triclinic, [P \overline 1]

  • a = 6.759 (5) Å

  • b = 10.061 (5) Å

  • c = 12.263 (5) Å

  • α = 109.080 (5)°

  • β = 94.521 (5)°

  • γ = 93.098 (5)°

  • V = 782.8 (8) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.80 mm−1

  • T = 293 K

  • 0.18 × 0.15 × 0.14 mm
Data collection

  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2005[Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.860, Tmax = 0.891

  • 4563 measured reflections

  • 3151 independent reflections

  • 2410 reflections with I > 2σ(I)

  • Rint = 0.013
Refinement

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.104

  • S = 1.05

  • 3151 reflections

  • 200 parameters

  • H-atom parameters constrained

  • Δρmax = 0.50 e Å−3

  • Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2005[Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812027298/bh2439sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027298/bh2439Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027298/bh2439Isup3.cml

checkCIF report


Comment top

Synthesis of nitrogen-containing heterocyclic compounds has been a subject of great interest due to the wide application in agrochemical and pharmaceutical fields (Ge et al. 2007, 2009, 2011). Some pyrazole derivatives which belong to this category have been of interest for their biological activities (Xia et al., 2007). Considerable efforts have been devoted to the development of novel pyrazole compounds. The title compound (Fig. 1) is a new pyrazole derivative, which was synthesized in order to study and compare its biological properties with other related compounds (Xia et al., 2007). The title compound was screened for anticancer activities and found to be inactive. We report here the crystal structure of the title compound. The pyrazole ring makes dihedral angles of 3.29 (9) and 74.91 (4)°, respectively, with the bromophenyl and chlorophenyl rings. This conformation is close to that found in a related pyrazole derivative (Hao et al., 2012).

Related literature top

For applications of nitrogen-containing heterocyclic compounds in the agrochemical and pharmaceutical fields, see: Ge et al. (2007, 2009, 2011). For the biological activity of some pyrazole derivatives belonging to this class of compounds, see: Xia et al. (2007). For a related compound, see: Hao et al. (2012).

Experimental top

A mixture of (3-(4-bromophenyl)-1-(4-chlorobenzyl)-1H-pyrazol-5-yl)methanol (0.02 mol) and PCC (0.06 mol) in DMF (50 ml) was stirred for 3 h. After the starting material was consumed (monitored by TLC), the reaction mixture was poured into water (100 ml) and extracted with dichloromethane. The organic extracts were washed with water, dried, filtered and concentrated. The final product was isolated by column chromatography on silica gel (yield 72%). Crystals of the title compound suitable for X-ray diffraction were obtained by allowing a refluxed solution of the product in ethyl acetate (0.10 M) to cool slowly to room temperature (without temperature control) and allowing the solvent to evaporate for 3 days.

Refinement top

All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97 Å (for the CH2 group) and 0.93 Å (for aromatic CH); their isotropic displacement parameters were set to 1.2 times the equivalent displacement parameter of their parent atoms.

Structure description top

Synthesis of nitrogen-containing heterocyclic compounds has been a subject of great interest due to the wide application in agrochemical and pharmaceutical fields (Ge et al. 2007, 2009, 2011). Some pyrazole derivatives which belong to this category have been of interest for their biological activities (Xia et al., 2007). Considerable efforts have been devoted to the development of novel pyrazole compounds. The title compound (Fig. 1) is a new pyrazole derivative, which was synthesized in order to study and compare its biological properties with other related compounds (Xia et al., 2007). The title compound was screened for anticancer activities and found to be inactive. We report here the crystal structure of the title compound. The pyrazole ring makes dihedral angles of 3.29 (9) and 74.91 (4)°, respectively, with the bromophenyl and chlorophenyl rings. This conformation is close to that found in a related pyrazole derivative (Hao et al., 2012).

For applications of nitrogen-containing heterocyclic compounds in the agrochemical and pharmaceutical fields, see: Ge et al. (2007, 2009, 2011). For the biological activity of some pyrazole derivatives belonging to this class of compounds, see: Xia et al. (2007). For a related compound, see: Hao et al. (2012).

Computing details top

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms have been omitted.
3-(4-Bromophenyl)-1-(4-chlorobenzyl)-1H-pyrazole-5-carbaldehyde top
Crystal data top
C17H12BrClN2OZ = 2
Mr = 375.65F(000) = 376
Triclinic, P1Dx = 1.594 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 6.759 (5) ÅCell parameters from 5043 reflections
b = 10.061 (5) Åθ = 0.9–28.3°
c = 12.263 (5) ŵ = 2.80 mm−1
α = 109.080 (5)°T = 293 K
β = 94.521 (5)°Block, colourless
γ = 93.098 (5)°0.18 × 0.15 × 0.14 mm
V = 782.8 (8) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3151 independent reflections
Radiation source: fine-focus sealed tube2410 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
φ and ω scansθmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −8→4
Tmin = 0.860, Tmax = 0.891k = −12→11
4563 measured reflectionsl = −13→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.104 w = 1/[σ2(Fo2) + (0.0602P)2 + 0.068P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3151 reflectionsΔρmax = 0.50 e Å−3
200 parametersΔρmin = −0.43 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraintsExtinction coefficient: 0.019 (3)
Primary atom site location: structure-invariant direct methods
Crystal data top
C17H12BrClN2Oγ = 93.098 (5)°
Mr = 375.65V = 782.8 (8) Å3
Triclinic, P1Z = 2
a = 6.759 (5) ÅMo Kα radiation
b = 10.061 (5) ŵ = 2.80 mm−1
c = 12.263 (5) ÅT = 293 K
α = 109.080 (5)°0.18 × 0.15 × 0.14 mm
β = 94.521 (5)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3151 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		2410 reflections with I > 2σ(I)
Tmin = 0.860, Tmax = 0.891Rint = 0.013
4563 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.05Δρmax = 0.50 e Å−3
3151 reflectionsΔρmin = −0.43 e Å−3
200 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.33740 (5)−0.03239 (4)−0.36464 (3)0.07272 (18)
C10.2091 (4)0.4007 (3)0.0013 (3)0.0622 (7)
H10.16660.4399−0.05460.075*
C20.3841 (4)0.3206 (3)−0.0184 (2)0.0488 (6)
C30.4976 (4)0.2937 (3)−0.1103 (2)0.0486 (6)
H30.48000.3243−0.17400.058*
C40.6443 (4)0.2110 (2)−0.0884 (2)0.0439 (6)
C50.4145 (4)0.2593 (3)0.1680 (2)0.0529 (6)
H5A0.45870.17660.18370.063*
H5B0.27110.25690.16930.063*
C60.5106 (4)0.3908 (3)0.2619 (2)0.0476 (6)
C70.3960 (4)0.4906 (3)0.3274 (2)0.0533 (7)
H70.25820.47830.31100.064*
C80.4806 (5)0.6079 (3)0.4166 (2)0.0588 (7)
H80.40130.67380.46010.071*
C90.7135 (5)0.4130 (4)0.2855 (3)0.0772 (10)
H90.79400.34830.24150.093*
C100.7995 (5)0.5311 (4)0.3743 (3)0.0867 (11)
H100.93740.54590.38930.104*
C110.6828 (5)0.6255 (3)0.4398 (2)0.0606 (8)
C120.8084 (4)0.1521 (3)−0.1560 (2)0.0449 (6)
C130.9331 (4)0.0666 (3)−0.1209 (2)0.0580 (7)
H130.91100.0459−0.05410.070*
C141.0906 (5)0.0105 (3)−0.1818 (3)0.0624 (8)
H141.1735−0.0465−0.15620.075*
C150.8436 (5)0.1785 (3)−0.2571 (3)0.0591 (7)
H150.76110.2351−0.28350.071*
C160.9981 (5)0.1229 (3)−0.3193 (3)0.0616 (7)
H161.01860.1408−0.38750.074*
C171.1211 (4)0.0411 (3)−0.2803 (2)0.0497 (6)
Cl10.79191 (16)0.76908 (10)0.55587 (7)0.0864 (3)
N10.4642 (3)0.2545 (2)0.05291 (18)0.0478 (5)
N20.6237 (3)0.1883 (2)0.01222 (19)0.0482 (5)
O10.1149 (3)0.4203 (3)0.0836 (2)0.0785 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0582 (2)0.0828 (3)0.0653 (2)0.01627 (16)0.02256 (15)0.00339 (16)
C10.0485 (16)0.0687 (18)0.0609 (17)0.0207 (14)−0.0006 (14)0.0088 (14)
C20.0431 (14)0.0466 (13)0.0507 (14)0.0101 (11)0.0009 (11)0.0079 (11)
C30.0502 (15)0.0489 (14)0.0447 (14)0.0116 (12)−0.0003 (11)0.0127 (11)
C40.0457 (14)0.0406 (12)0.0438 (13)0.0081 (10)0.0052 (11)0.0110 (10)
C50.0530 (16)0.0523 (15)0.0565 (16)0.0091 (12)0.0201 (12)0.0183 (12)
C60.0464 (15)0.0530 (14)0.0476 (14)0.0083 (11)0.0178 (11)0.0186 (12)
C70.0535 (16)0.0626 (17)0.0469 (14)0.0163 (13)0.0160 (12)0.0181 (13)
C80.071 (2)0.0601 (17)0.0475 (15)0.0200 (14)0.0202 (13)0.0154 (13)
C90.0508 (18)0.079 (2)0.080 (2)0.0106 (15)0.0246 (16)−0.0071 (17)
C100.0503 (19)0.100 (3)0.088 (3)−0.0059 (18)0.0204 (17)−0.001 (2)
C110.076 (2)0.0576 (16)0.0471 (15)−0.0060 (14)0.0220 (14)0.0137 (13)
C120.0445 (14)0.0426 (13)0.0452 (13)0.0060 (11)0.0065 (11)0.0107 (11)
C130.0630 (18)0.0687 (18)0.0516 (15)0.0275 (14)0.0175 (13)0.0263 (14)
C140.0639 (18)0.0686 (18)0.0604 (17)0.0303 (15)0.0158 (14)0.0232 (15)
C150.0572 (17)0.0703 (18)0.0621 (17)0.0221 (14)0.0133 (14)0.0345 (15)
C160.0671 (19)0.0727 (19)0.0515 (16)0.0130 (15)0.0179 (14)0.0254 (14)
C170.0448 (14)0.0493 (14)0.0469 (14)0.0064 (11)0.0103 (11)0.0035 (11)
Cl10.1054 (7)0.0785 (6)0.0600 (5)−0.0247 (5)0.0211 (4)0.0047 (4)
N10.0454 (12)0.0472 (11)0.0491 (12)0.0106 (9)0.0109 (9)0.0115 (10)
N20.0470 (12)0.0473 (12)0.0527 (13)0.0162 (9)0.0148 (10)0.0156 (10)
O10.0548 (13)0.1008 (17)0.0737 (15)0.0337 (12)0.0132 (11)0.0150 (13)
Geometric parameters (Å, º) top
Br1—C171.900 (3)C8—C111.363 (4)
C1—O11.203 (4)C8—H80.9300
C1—C21.459 (4)C9—C101.384 (5)
C1—H10.9300C9—H90.9300
C2—N11.358 (3)C10—C111.361 (5)
C2—C31.376 (4)C10—H100.9300
C3—C41.393 (4)C11—Cl11.741 (3)
C3—H30.9300C12—C131.378 (4)
C4—N21.342 (3)C12—C151.385 (4)
C4—C121.471 (4)C13—C141.387 (4)
C5—N11.462 (3)C13—H130.9300
C5—C61.514 (4)C14—C171.368 (4)
C5—H5A0.9700C14—H140.9300
C5—H5B0.9700C15—C161.377 (4)
C6—C91.370 (4)C15—H150.9300
C6—C71.382 (4)C16—C171.365 (4)
C7—C81.379 (4)C16—H160.9300
C7—H70.9300N1—N21.342 (3)
O1—C1—C2125.6 (3)C10—C9—H9119.8
O1—C1—H1117.2C11—C10—C9120.2 (3)
C2—C1—H1117.2C11—C10—H10119.9
N1—C2—C3106.4 (2)C9—C10—H10119.9
N1—C2—C1125.1 (3)C10—C11—C8120.7 (3)
C3—C2—C1128.5 (3)C10—C11—Cl1119.8 (3)
C2—C3—C4105.7 (2)C8—C11—Cl1119.5 (2)
C2—C3—H3127.1C13—C12—C15117.2 (2)
C4—C3—H3127.1C13—C12—C4120.7 (2)
N2—C4—C3110.4 (2)C15—C12—C4122.1 (2)
N2—C4—C12119.5 (2)C12—C13—C14122.3 (3)
C3—C4—C12130.0 (2)C12—C13—H13118.9
N1—C5—C6111.9 (2)C14—C13—H13118.9
N1—C5—H5A109.2C17—C14—C13118.4 (3)
C6—C5—H5A109.2C17—C14—H14120.8
N1—C5—H5B109.2C13—C14—H14120.8
C6—C5—H5B109.2C16—C15—C12121.4 (3)
H5A—C5—H5B107.9C16—C15—H15119.3
C9—C6—C7118.2 (3)C12—C15—H15119.3
C9—C6—C5120.9 (2)C17—C16—C15119.6 (3)
C7—C6—C5120.9 (3)C17—C16—H16120.2
C8—C7—C6121.7 (3)C15—C16—H16120.2
C8—C7—H7119.2C16—C17—C14121.1 (3)
C6—C7—H7119.2C16—C17—Br1119.5 (2)
C11—C8—C7118.8 (3)C14—C17—Br1119.4 (2)
C11—C8—H8120.6N2—N1—C2111.8 (2)
C7—C8—H8120.6N2—N1—C5118.3 (2)
C6—C9—C10120.4 (3)C2—N1—C5129.5 (2)
C6—C9—H9119.8N1—N2—C4105.6 (2)

Experimental details

Crystal data
Chemical formulaC17H12BrClN2O
Mr375.65
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.759 (5), 10.061 (5), 12.263 (5)
α, β, γ (°)109.080 (5), 94.521 (5), 93.098 (5)
V (Å3)782.8 (8)
Z2
Radiation typeMo Kα
µ (mm−1)2.80
Crystal size (mm)0.18 × 0.15 × 0.14
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.860, 0.891
No. of measured, independent and
observed [I > 2σ(I)] reflections		4563, 3151, 2410
Rint0.013
(sin θ/λ)max (Å−1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.104, 1.05
No. of reflections3151
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.50, −0.43

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This study was supported by the Science and Technology Development Project of Shandong Province (2011GGH22112 and 2012 GSF11812).

References

First citationBruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationGe, Y.-Q., Dong, W.-L., Xia, Y., Wei, F. & Zhao, B.-X. (2007). Acta Cryst. E63, o1313–o1314.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationGe, Y. Q., Hao, B. Q., Duan, G. Y. & Wang, J. W. (2011). J. Lumin. 131, 1070–1076.  Web of Science CrossRef CAS Google Scholar
 First citationGe, Y. Q., Jia, J., Li, Y., Yin, L. & Wang, J. W. (2009). Heterocycles, 42, 197–206.  Google Scholar
 First citationHao, B.-Q., Xu, W.-R., Meng, F.-C. & Duan, G.-Y. (2012). Acta Cryst. E68, o877.  CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationXia, Y., Dong, Z. W., Zhao, B. X., Ge, X., Meng, N., Shin, D. S. & Miao, J. Y. (2007). Bioorg. Med. Chem. 15, 6893–6899.  Web of Science CrossRef PubMed CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 7| July 2012| Page o2203
https://doi.org/10.1107/S1600536812027298
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