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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 67| Part 9| September 2011| Page o2445
doi:10.1107/S1600536811033368

1-Benzoyl-3-(pyridin-2-yl)-1H-pyrazole

Alexander H. Shelton,a Andrew Stephenson,a Michael D. Warda and Mohammad B. Kassimb,c*

aDepartment of Chemistry, University of Sheffield, Sheffield S3 7HF, England, bSchool of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia, and cFuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Selangor, Malaysia
*Correspondence e-mail: mbkassim@ukm.my

(Received 16 August 2011; accepted 16 August 2011; online 27 August 2011)

In the title compound, C15H11N3O, the dihedral angle betwen the heterocyclic rings is 9.23 (5)° and the dihedral angle between the benzoyl and pyrazole rings is 58.64 (5)°. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R22(10) loops. The dimers stack into a column running parallel to the b-axis direction.

Related literature

For related structures and background, see: Jones et al. (1997[Jones, P. L., Amoroso, A. J., Jeffery, J. C., McCleverty, J. A., Psillakis, E., Rees, L. H. & Ward, M. D. (1997). Inorg. Chem. 36, 10-18.]); Adams et al. (2006[Adams, H., Alsindi, W. Z., Davies, G. M., Duriska, M. B., Easun, T. L., Fenton, H. E., Herrera, J.-M., George, M. W., Ronayne, K. L., Sun, X.-Z., Towrie, M. & Ward, M. D. (2006). Dalton Trans. pp. 39-50.]); Al-abbasi & Kassim (2011[Al-abbasi, A. A. & Kassim, M. B. (2011). Acta Cryst. E67, o611.]). For reference bond lengths, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data

  • C15H11N3O

  • Mr = 249.27

  • Monoclinic, P 21 /n

  • a = 10.6325 (11) Å

  • b = 5.7775 (6) Å

  • c = 19.572 (2) Å

  • β = 98.426 (6)°

  • V = 1189.3 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 296 K

  • 0.20 × 0.15 × 0.10 mm
Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.982, Tmax = 0.991

  • 10450 measured reflections

  • 2735 independent reflections

  • 2532 reflections with I > 2σ(I)

  • Rint = 0.023
Refinement

  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.097

  • S = 1.00

  • 2735 reflections

  • 173 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C8—H8⋯O1i 0.93 2.44 3.3720 (13) 175
Symmetry code: (i) -x, -y+3, -z.

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. 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: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995[Nardelli, M. (1995). J. Appl. Cryst. 28, 659.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811033368/hb6370sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033368/hb6370Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033368/hb6370Isup3.cml

checkCIF report


Comment top

The starting material, 3-(2-pyridyl)pyrazole, is a bidentate ligand which is commonly used in coordination chemistry (Jones et al. 1997 & Adams et al. 2006). The title compound is made up of a 3-(2-pyridyl)pyrazole and benzoyl fragments. This new compound has a potential to be applied as a tridentate ligand (ONN) involving the O atom on the carbonyl group and the N atom on the pyrazole and pyridine rings.

In the crystal structure, the mean planes of acetamide (O1/N1/C1/C7) and the benzene (C1/C2/C3/C4/C5/C6) fragments make a dihedral angle of 49.54 (5)° with each other. The mean planes of the pyrazole and pyridyl rings are slightly twisted and make a dihedral 9.23 (5)°. The C7—O1 bond length 1.2117 (12) is slightly longer that of the C=O found in another benzoyl derivative, 1-ethyl-1-methyl-3-(2-nitrobenzoyl)thiourea (Al-abbasi & Kassim, 2011). Other bond lengths and angles within the compounds are in the normal ranges (Allen et al. 1987).

A C—H···O intermolecular hydrogen bond links adjacent molecules into centrosymmetric dimers forming a one dimensional column parallel to the b-axis.

Related literature top

For related structures and background, see: Jones et al. (1997); Adams et al. (2006); Al-abbasi & Kassim (2011). For reference bond lengths, see: Allen et al. (1987).

Experimental top

3-(2-pyridyl)pyrazole (0.728 g, 5.0 mmol) was deprotonated by reacting with NaH (60% in mineral oil) in 30 ml of dry THF under N2 at room temperature for 2 h. Then, benzoyl chloride (0.702 g, 5.0 mmol) was added slowly to the mixture and the temperature was brought to reflux and left stirring for 4 hrs. The solvent was removed and the residue was re-dissolved in a minimum volume of DCM, washed 3 times with 30 ml of distilled water. The organic fraction was collected and dried with MgSO4, filtered and the solvent was removed in vacuo. Slow evaporation of acetone/DCM solution of the residue afforded colourless blocks of (I). Yield 78%.

Refinement top

All H atoms were positioned geometrically with C—H bond lengths in the range of 0.93 - 0.97 Å and refined in the riding model approximation with Uiso(H)=1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram of the title compound viewing down the b-axis showing the intermolecular hydrogen bonds C—H···O (-x, 3 - y, -z).
1-Benzoyl-3-(pyridin-2-yl)-1H-pyrazole top
Crystal data top
C15H11N3OF(000) = 520
Mr = 249.27Dx = 1.392 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7032 reflections
a = 10.6325 (11) Åθ = 4.7–55.0°
b = 5.7775 (6) ŵ = 0.09 mm−1
c = 19.572 (2) ÅT = 296 K
β = 98.426 (6)°Block, colourless
V = 1189.3 (2) Å30.20 × 0.15 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2735 independent reflections
Radiation source: fine-focus sealed tube2532 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −13→13
Tmin = 0.982, Tmax = 0.991k = −7→7
10450 measured reflectionsl = −25→25
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)] = 0.035H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0577P)2 + 0.430P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2735 reflectionsΔρmax = 0.35 e Å−3
173 parametersΔρmin = −0.22 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.025 (3)
Crystal data top
C15H11N3OV = 1189.3 (2) Å3
Mr = 249.27Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.6325 (11) ŵ = 0.09 mm−1
b = 5.7775 (6) ÅT = 296 K
c = 19.572 (2) Å0.20 × 0.15 × 0.10 mm
β = 98.426 (6)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2735 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2532 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.991Rint = 0.023
10450 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.00Δρmax = 0.35 e Å−3
2735 reflectionsΔρmin = −0.22 e Å−3
173 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
xyzUiso*/Ueq
O10.13720 (7)1.43117 (13)0.06519 (4)0.02310 (19)
N10.16990 (8)1.10288 (14)0.00732 (4)0.01636 (19)
N20.24411 (8)0.91307 (15)−0.00018 (4)0.01622 (19)
N30.22475 (8)0.59436 (16)−0.15957 (4)0.0200 (2)
C40.43069 (10)1.04513 (19)0.25014 (5)0.0206 (2)
H40.47991.00720.29190.025*
C30.34100 (10)0.88896 (18)0.21845 (5)0.0187 (2)
H30.33040.74680.23920.022*
C20.26702 (9)0.94408 (18)0.15592 (5)0.0172 (2)
H20.20960.83710.13380.021*
C10.27989 (9)1.16160 (17)0.12676 (5)0.0162 (2)
C70.19083 (9)1.24595 (17)0.06590 (5)0.0169 (2)
C100.20214 (9)0.83729 (17)−0.06333 (5)0.0158 (2)
C110.26054 (9)0.63418 (17)−0.09172 (5)0.0163 (2)
C150.27577 (11)0.4098 (2)−0.18654 (5)0.0231 (2)
H150.25190.3799−0.23330.028*
C140.36167 (10)0.26093 (19)−0.14932 (6)0.0231 (2)
H140.39380.1344−0.17050.028*
C50.44676 (10)1.25791 (19)0.21942 (5)0.0209 (2)
H50.50911.35970.23970.025*
C60.36981 (10)1.31859 (18)0.15852 (5)0.0189 (2)
H60.37811.46340.13890.023*
C130.39894 (10)0.30481 (19)−0.07940 (6)0.0216 (2)
H130.45700.2089−0.05290.026*
C120.34759 (9)0.49456 (18)−0.05019 (5)0.0186 (2)
H120.37080.5284−0.00360.022*
C90.10122 (9)0.97734 (18)−0.09703 (5)0.0187 (2)
H90.05690.9577−0.14130.022*
C80.08350 (9)1.14563 (18)−0.05088 (5)0.0185 (2)
H80.02471.2657−0.05730.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0271 (4)0.0165 (4)0.0252 (4)0.0037 (3)0.0025 (3)−0.0009 (3)
N10.0175 (4)0.0150 (4)0.0165 (4)0.0007 (3)0.0020 (3)0.0007 (3)
N20.0181 (4)0.0141 (4)0.0167 (4)0.0002 (3)0.0031 (3)−0.0001 (3)
N30.0232 (4)0.0211 (5)0.0159 (4)−0.0032 (3)0.0029 (3)−0.0016 (3)
C40.0183 (5)0.0258 (5)0.0175 (5)0.0038 (4)0.0021 (4)−0.0022 (4)
C30.0211 (5)0.0173 (5)0.0184 (5)0.0032 (4)0.0055 (4)0.0011 (4)
C20.0183 (5)0.0155 (5)0.0181 (5)−0.0010 (4)0.0039 (4)−0.0024 (4)
C10.0181 (4)0.0162 (5)0.0150 (4)0.0003 (4)0.0047 (3)−0.0022 (4)
C70.0187 (5)0.0151 (5)0.0177 (4)−0.0018 (4)0.0050 (4)−0.0003 (4)
C100.0167 (4)0.0161 (5)0.0148 (4)−0.0027 (4)0.0025 (3)0.0014 (4)
C110.0162 (4)0.0168 (5)0.0162 (4)−0.0035 (4)0.0035 (3)−0.0005 (4)
C150.0265 (5)0.0248 (5)0.0189 (5)−0.0055 (4)0.0066 (4)−0.0049 (4)
C140.0217 (5)0.0205 (5)0.0290 (5)−0.0035 (4)0.0105 (4)−0.0065 (4)
C50.0181 (5)0.0233 (5)0.0216 (5)−0.0034 (4)0.0038 (4)−0.0062 (4)
C60.0218 (5)0.0161 (5)0.0198 (5)−0.0024 (4)0.0066 (4)−0.0022 (4)
C130.0170 (5)0.0200 (5)0.0281 (5)−0.0009 (4)0.0039 (4)0.0006 (4)
C120.0179 (4)0.0198 (5)0.0178 (5)−0.0027 (4)0.0020 (3)−0.0006 (4)
C90.0179 (5)0.0209 (5)0.0168 (4)−0.0008 (4)0.0010 (4)0.0019 (4)
C80.0169 (4)0.0190 (5)0.0192 (5)0.0000 (4)0.0010 (4)0.0033 (4)
Geometric parameters (Å, º) top
O1—C71.2116 (12)C10—C91.4260 (14)
N1—N21.3713 (12)C10—C111.4740 (14)
N1—C81.3768 (12)C11—C121.3955 (14)
N1—C71.4045 (13)C15—C141.3819 (16)
N2—C101.3255 (12)C15—H150.9300
N3—C151.3393 (14)C14—C131.3910 (15)
N3—C111.3465 (12)C14—H140.9300
C4—C51.3900 (15)C5—C61.3883 (14)
C4—C31.3910 (15)C5—H50.9300
C4—H40.9300C6—H60.9300
C3—C21.3913 (14)C13—C121.3850 (15)
C3—H30.9300C13—H130.9300
C2—C11.3952 (14)C12—H120.9300
C2—H20.9300C9—C81.3589 (15)
C1—C61.3961 (14)C9—H90.9300
C1—C71.4908 (13)C8—H80.9300
N2—N1—C8112.31 (8)C12—C11—C10121.39 (9)
N2—N1—C7122.22 (8)N3—C15—C14124.21 (10)
C8—N1—C7125.20 (9)N3—C15—H15117.9
C10—N2—N1104.10 (8)C14—C15—H15117.9
C15—N3—C11116.90 (9)C15—C14—C13118.44 (10)
C5—C4—C3120.04 (9)C15—C14—H14120.8
C5—C4—H4120.0C13—C14—H14120.8
C3—C4—H4120.0C6—C5—C4120.02 (10)
C4—C3—C2120.40 (10)C6—C5—H5120.0
C4—C3—H3119.8C4—C5—H5120.0
C2—C3—H3119.8C5—C6—C1119.82 (10)
C3—C2—C1119.29 (9)C5—C6—H6120.1
C3—C2—H2120.4C1—C6—H6120.1
C1—C2—H2120.4C12—C13—C14118.53 (10)
C2—C1—C6120.32 (9)C12—C13—H13120.7
C2—C1—C7122.17 (9)C14—C13—H13120.7
C6—C1—C7117.18 (9)C13—C12—C11119.02 (9)
O1—C7—N1119.50 (9)C13—C12—H12120.5
O1—C7—C1122.72 (9)C11—C12—H12120.5
N1—C7—C1117.77 (9)C8—C9—C10105.47 (9)
N2—C10—C9111.81 (9)C8—C9—H9127.3
N2—C10—C11120.77 (9)C10—C9—H9127.3
C9—C10—C11127.41 (9)C9—C8—N1106.31 (9)
N3—C11—C12122.90 (9)C9—C8—H8126.8
N3—C11—C10115.72 (9)N1—C8—H8126.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O1i0.932.443.3720 (13)175
Symmetry code: (i) −x, −y+3, −z.

Experimental details

Crystal data
Chemical formulaC15H11N3O
Mr249.27
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)10.6325 (11), 5.7775 (6), 19.572 (2)
β (°) 98.426 (6)
V (Å3)1189.3 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.20 × 0.15 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.982, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections		10450, 2735, 2532
Rint0.023
(sin θ/λ)max (Å−1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.097, 1.00
No. of reflections2735
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.35, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···O1i0.932.443.3720 (13)175
Symmetry code: (i) −x, −y+3, −z.
 

Acknowledgements

The authors gratefully acknowledge Universiti Kebangsaan Malaysia for the UKM-GUP-BTT-07–30–190 and UKM-OUP-TK-16–73/2010 & 2011 grants and sabbatical leave for MBK at the University of Sheffield. They also thank the RSC, UK, for financial support from the Leverhulme trust.

References

First citationAdams, H., Alsindi, W. Z., Davies, G. M., Duriska, M. B., Easun, T. L., Fenton, H. E., Herrera, J.-M., George, M. W., Ronayne, K. L., Sun, X.-Z., Towrie, M. & Ward, M. D. (2006). Dalton Trans. pp. 39–50.  CrossRef Google Scholar
 First citationAl-abbasi, A. A. & Kassim, M. B. (2011). Acta Cryst. E67, o611.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
 First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationJones, P. L., Amoroso, A. J., Jeffery, J. C., McCleverty, J. A., Psillakis, E., Rees, L. H. & Ward, M. D. (1997). Inorg. Chem. 36, 10–18.  CSD CrossRef CAS Web of Science Google Scholar
 First citationNardelli, M. (1995). J. Appl. Cryst. 28, 659.  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 citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 9| September 2011| Page o2445
doi:10.1107/S1600536811033368
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