tert-Butyl 4-{[5-(4-chloro­phen­yl)-1-(4-fluoro­phen­yl)-1H-pyrazol-3-yl]carbon­yl}piperazine-1-carboxyl­ate

Ragavan, R.V.; Vijayakumar, V.; Sarveswari, S.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536810038560

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2682

doi:10.1107/S1600536810038560

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tert-Butyl 4-{[5-(4-chlorophenyl)-1-(4-fluorophenyl)-1H-pyrazol-3-yl]carbonyl}piperazine-1-carboxylate

R. Venkat Ragavan,^a V. Vijayakumar,^a ‡ S. Sarveswari,^a Seik Weng Ng ^b and Edward R. T. Tiekink ^b ^*

^aOrganic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, Tamilnadu, India, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 23 September 2010; accepted 27 September 2010; online 30 September 2010)

In the title pyrazole derivative, C₂₅H₂₆ClFN₄O₃, both benzene rings are twisted out of the plane through the pyrazole ring, with dihedral angles of 67.62 (10) and 27.63 (10)° for the fluoro- and chloro-substituted rings, respectively. The dihedral angle between the two benzene rings is 64.54 (9)°. The piperazine ring (with a chair conformation) is linked to the pyrazole ring via a carbonyl spacer and is orientated to lie to one side of the pyrazole plane. In addition to an intramolecular C—H⋯N contact, there are intermolecular C—H⋯O interactions, which generate a supramolecular chain with an undulating topology along the c axis that is sustained by alternating centrosymmetric ten-membered {⋯HCNCO}₂ and {⋯HC3O}₂ synthons.

Related literature

For the pharmacological potential of pyrazol derivatives, see: Ragavan et al. (2009 ). For the synthesis, see: Ragavan et al. (2010 ). For a related structure, see: Samshuddin et al. (2010 ).

Experimental

Crystal data

C₂₅H₂₆ClFN₄O₃
M_r = 484.95
Triclinic, $[P \overline 1]$
a = 6.0568 (5) Å
b = 12.0047 (10) Å
c = 16.2615 (13) Å
α = 88.852 (1)°
β = 81.206 (1)°
γ = 87.644 (1)°
V = 1167.37 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.35 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: analytical (FACES; Bruker, 2009 ) T_min = 0.931, T_max = 0.980
11213 measured reflections
5318 independent reflections
4351 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.145
S = 1.06
5318 reflections
310 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17a⋯N2	0.99	2.24	2.950 (2)	128
C14—H14⋯O1ⁱ	0.95	2.28	3.192 (2)	161
C18—H18a⋯O2ⁱⁱ	0.99	2.52	3.223 (2)	128
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038560/hb5646sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038560/hb5646Isup2.hkl

checkCIF report

Comment top

The anti-bacterial and anti-fungal activities of the azoles are well known and some derivatives are used clinically as anti-microbial agents. However, the emergence of azole-resistant strains of microbes requires the development of new anti-microbial compounds. Pyrazole forms an important class of heterocyclic compounds and many pyrazole derivatives are reported to display a broad spectrum of biological activities, such as anti-inflammatory, anti-fungal, herbicidal, anti-tumour, cytotoxic, and anti-viral activities. Since the high electronegativity of halogens (particularly chlorine and fluorine) in aromatic rings of drug molecules plays an important role in enhancing biological activity, we are interested to have 4-fluoro or 4-chloro substitution in the aryl rings of 1,5-diaryl pyrazoles. As part of our on-going research aimed at the synthesis of new anti-microbial compounds based on pyrazole (Ragavan et al., 2009, 2010) and reflecting our interest in pyrazole structures (Samshuddin et al., 2010), herein we report the crystallographic characterization of a novel pyrazole derivative, (I).

The pyrazole ring in (I), Fig. 1, is planar (r.m.s. deviation = 0.003 Å) and is connected to two halo-substituted benzene rings. Whereas the chloro-substituted ring is slightly twisted out of the plane of the pyrazoyl ring [dihedral angle = 27.63 (10) °], the fluoro-substituted ring is almost orthogonal [dihedral angle = 67.62 (10) °]; the dihedral angle between the two benzene rings = 64.54 (9) °. The ester derivatized piperazine ring (with a chair conformation) is linked to the pyrazoyl ring via a carbonyl spacer [the N2—C15—C16—N3 torsion angle = 13.6 (3) °] and is orientated to lie to one side of the pyrazoyl plane. Finally, the ester group is co-planar with the C18—N4—C19 plane as seen in the C18—N4—C21—O2 torsion angle of -0.3 (3) °.

In addition to an intramolecular C—H···N bond, there are two significant intermolecular C—H···O contacts of note, Table 1. The latter lead to the formation of an undulating supramolecular chain along the c axis comprising alternating centrosymmetric 10-membered {···HCNCO}₂ and {···HC₃O}₂ synthons, Fig. 2. Chains pack in the ac plane and these stack along the b axis, Fig. 3.

Related literature top

For the pharmacological potential of pyrazol derivatives, see: Ragavan et al. (2009). For the synthesis, see: Ragavan et al. (2010). For a related structure, see: Samshuddin et al. (2010).

Experimental top

The compound was synthesized by the literature method (Ragavan et al., 2010). Colourless blocks of (I) were obtained by recrystallization from absolute ethanol; m.pt. 356.1–357.2 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular chains aligned along the c axis in (I) mediated by C—H···O interactions (orange dashed lines).
	Fig. 3. Unit-cell contents shown in projection down the a axis in (I) showing the stacking of layers along the b direction. The C–H···O contacts are shown as orange dashed lines.

tert-Butyl 4-{[5-(4-chlorophenyl)-1-(4-fluorophenyl)- 1H-pyrazol-3-yl]carbonyl}piperazine-1-carboxylate top

Crystal data top

C₂₅H₂₆ClFN₄O₃	Z = 2
M_r = 484.95	F(000) = 508
Triclinic, P1	D_x = 1.380 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0568 (5) Å	Cell parameters from 3796 reflections
b = 12.0047 (10) Å	θ = 3.0–30.6°
c = 16.2615 (13) Å	µ = 0.21 mm⁻¹
α = 88.852 (1)°	T = 100 K
β = 81.206 (1)°	Block, colourless
γ = 87.644 (1)°	0.35 × 0.10 × 0.10 mm
V = 1167.37 (17) Å³

Data collection top

Bruker SMART APEX diffractometer	5318 independent reflections
Radiation source: fine-focus sealed tube	4351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scan	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: analytical (FACES; Bruker, 2009)	h = −7→7
T_min = 0.931, T_max = 0.980	k = −15→15
11213 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0829P)² + 0.4102P] where P = (F_o² + 2F_c²)/3
5318 reflections	(Δ/σ)_max = 0.001
310 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₂₅H₂₆ClFN₄O₃	γ = 87.644 (1)°
M_r = 484.95	V = 1167.37 (17) Å³
Triclinic, P1	Z = 2
a = 6.0568 (5) Å	Mo Kα radiation
b = 12.0047 (10) Å	µ = 0.21 mm⁻¹
c = 16.2615 (13) Å	T = 100 K
α = 88.852 (1)°	0.35 × 0.10 × 0.10 mm
β = 81.206 (1)°

Data collection top

Bruker SMART APEX diffractometer	5318 independent reflections
Absorption correction: analytical (FACES; Bruker, 2009)	4351 reflections with I > 2σ(I)
T_min = 0.931, T_max = 0.980	R_int = 0.030
11213 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.06	Δρ_max = 0.37 e Å⁻³
5318 reflections	Δρ_min = −0.39 e Å⁻³
310 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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

	x	y	z	U_iso*/U_eq
Cl1	−0.54699 (8)	0.35562 (4)	0.36749 (3)	0.02774 (15)
F1	−0.3361 (2)	0.60200 (11)	0.83637 (8)	0.0351 (3)
O1	0.6767 (2)	−0.00368 (11)	0.59753 (8)	0.0216 (3)
O2	0.6127 (2)	−0.13676 (12)	1.00046 (8)	0.0223 (3)
O3	0.9285 (2)	−0.21367 (11)	0.92542 (8)	0.0186 (3)
N1	0.1504 (2)	0.26137 (12)	0.66173 (9)	0.0155 (3)
N2	0.3142 (2)	0.20929 (13)	0.69823 (10)	0.0167 (3)
N3	0.6639 (2)	0.04516 (13)	0.73200 (9)	0.0150 (3)
N4	0.6836 (3)	−0.11496 (14)	0.86022 (10)	0.0202 (3)
C1	0.0220 (3)	0.35009 (14)	0.70660 (10)	0.0148 (3)
C2	0.1251 (3)	0.44859 (15)	0.71731 (11)	0.0174 (4)
H2	0.2778	0.4572	0.6948	0.021*
C3	0.0030 (3)	0.53487 (16)	0.76141 (12)	0.0225 (4)
H3	0.0699	0.6033	0.7692	0.027*
C4	−0.2166 (3)	0.51834 (17)	0.79337 (12)	0.0226 (4)
C5	−0.3210 (3)	0.42072 (17)	0.78344 (12)	0.0213 (4)
H5	−0.4732	0.4122	0.8067	0.026*
C6	−0.2004 (3)	0.33534 (16)	0.73909 (11)	0.0183 (4)
H6	−0.2690	0.2675	0.7310	0.022*
C7	−0.0359 (3)	0.25317 (15)	0.53333 (11)	0.0154 (4)
C8	−0.1139 (3)	0.36381 (15)	0.52973 (11)	0.0180 (4)
H8	−0.0618	0.4178	0.5634	0.022*
C9	−0.2670 (3)	0.39586 (16)	0.47737 (12)	0.0199 (4)
H9	−0.3181	0.4715	0.4747	0.024*
C10	−0.3444 (3)	0.31675 (16)	0.42920 (11)	0.0183 (4)
C11	−0.2662 (3)	0.20696 (16)	0.43007 (12)	0.0212 (4)
H11	−0.3183	0.1535	0.3960	0.025*
C12	−0.1106 (3)	0.17607 (16)	0.48145 (11)	0.0188 (4)
H12	−0.0536	0.1011	0.4814	0.023*
C13	0.1254 (3)	0.21355 (14)	0.58746 (11)	0.0147 (3)
C14	0.2801 (3)	0.12616 (15)	0.57692 (11)	0.0166 (4)
H14	0.3060	0.0757	0.5319	0.020*
C15	0.3920 (3)	0.12677 (14)	0.64627 (11)	0.0150 (3)
C16	0.5851 (3)	0.04965 (14)	0.65783 (11)	0.0149 (3)
C17	0.5275 (3)	0.06276 (15)	0.81360 (11)	0.0168 (4)
H17A	0.3856	0.1031	0.8066	0.020*
H17B	0.6083	0.1087	0.8482	0.020*
C18	0.4778 (3)	−0.04902 (16)	0.85671 (12)	0.0194 (4)
H18A	0.3988	−0.0365	0.9139	0.023*
H18B	0.3788	−0.0904	0.8261	0.023*
C19	0.8221 (3)	−0.13264 (16)	0.77930 (11)	0.0190 (4)
H19A	0.7429	−0.1786	0.7441	0.023*
H19B	0.9640	−0.1726	0.7869	0.023*
C20	0.8709 (3)	−0.02034 (16)	0.73720 (11)	0.0180 (4)
H20A	0.9664	0.0214	0.7690	0.022*
H20B	0.9537	−0.0320	0.6805	0.022*
C21	0.7328 (3)	−0.15410 (15)	0.93439 (11)	0.0165 (4)
C22	1.0055 (3)	−0.26720 (16)	0.99898 (11)	0.0191 (4)
C23	1.2187 (3)	−0.32815 (17)	0.96125 (13)	0.0250 (4)
H23A	1.1842	−0.3848	0.9231	0.038*
H23B	1.2900	−0.3642	1.0056	0.038*
H23C	1.3205	−0.2750	0.9306	0.038*
C24	0.8349 (3)	−0.34893 (18)	1.03985 (14)	0.0285 (5)
H24A	0.7967	−0.3989	0.9977	0.043*
H24B	0.6998	−0.3076	1.0655	0.043*
H24C	0.8984	−0.3928	1.0826	0.043*
C25	1.0532 (3)	−0.17857 (18)	1.05902 (12)	0.0236 (4)
H25A	1.1630	−0.1278	1.0301	0.035*
H25B	1.1128	−0.2146	1.1061	0.035*
H25C	0.9145	−0.1363	1.0795	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0254 (3)	0.0297 (3)	0.0319 (3)	−0.0024 (2)	−0.0172 (2)	0.0069 (2)
F1	0.0380 (7)	0.0319 (7)	0.0337 (7)	0.0169 (6)	−0.0032 (6)	−0.0137 (6)
O1	0.0250 (7)	0.0246 (7)	0.0150 (6)	0.0078 (6)	−0.0038 (5)	−0.0048 (5)
O2	0.0206 (7)	0.0289 (7)	0.0157 (7)	0.0027 (5)	0.0011 (5)	0.0025 (6)
O3	0.0179 (6)	0.0224 (7)	0.0154 (6)	0.0036 (5)	−0.0036 (5)	0.0020 (5)
N1	0.0174 (7)	0.0153 (7)	0.0146 (7)	0.0012 (6)	−0.0054 (6)	0.0004 (6)
N2	0.0159 (7)	0.0155 (7)	0.0192 (8)	0.0029 (6)	−0.0057 (6)	0.0019 (6)
N3	0.0150 (7)	0.0178 (7)	0.0117 (7)	0.0035 (6)	−0.0017 (5)	0.0005 (6)
N4	0.0211 (8)	0.0230 (8)	0.0148 (7)	0.0073 (6)	−0.0001 (6)	0.0034 (6)
C1	0.0170 (8)	0.0150 (8)	0.0123 (8)	0.0057 (6)	−0.0037 (6)	−0.0006 (6)
C2	0.0180 (8)	0.0198 (9)	0.0147 (8)	−0.0006 (7)	−0.0031 (7)	0.0003 (7)
C3	0.0299 (10)	0.0169 (9)	0.0221 (9)	0.0012 (8)	−0.0090 (8)	−0.0037 (7)
C4	0.0274 (10)	0.0216 (10)	0.0185 (9)	0.0107 (8)	−0.0049 (8)	−0.0044 (7)
C5	0.0173 (9)	0.0276 (10)	0.0182 (9)	0.0042 (7)	−0.0018 (7)	0.0011 (8)
C6	0.0197 (9)	0.0179 (9)	0.0178 (9)	0.0005 (7)	−0.0043 (7)	0.0002 (7)
C7	0.0141 (8)	0.0172 (9)	0.0145 (8)	0.0000 (6)	−0.0015 (6)	0.0024 (7)
C8	0.0202 (9)	0.0176 (9)	0.0166 (8)	−0.0001 (7)	−0.0040 (7)	−0.0003 (7)
C9	0.0211 (9)	0.0193 (9)	0.0194 (9)	0.0007 (7)	−0.0043 (7)	0.0024 (7)
C10	0.0150 (8)	0.0245 (10)	0.0157 (8)	0.0009 (7)	−0.0048 (7)	0.0044 (7)
C11	0.0236 (9)	0.0215 (10)	0.0203 (9)	−0.0035 (7)	−0.0083 (7)	−0.0007 (7)
C12	0.0226 (9)	0.0185 (9)	0.0153 (8)	0.0005 (7)	−0.0037 (7)	0.0007 (7)
C13	0.0161 (8)	0.0147 (8)	0.0134 (8)	−0.0002 (6)	−0.0023 (6)	−0.0005 (6)
C14	0.0185 (8)	0.0160 (9)	0.0155 (8)	−0.0010 (7)	−0.0033 (7)	0.0002 (7)
C15	0.0160 (8)	0.0127 (8)	0.0162 (8)	0.0017 (6)	−0.0028 (7)	0.0000 (7)
C16	0.0159 (8)	0.0139 (8)	0.0148 (8)	−0.0005 (6)	−0.0019 (6)	0.0005 (7)
C17	0.0184 (8)	0.0183 (9)	0.0126 (8)	0.0042 (7)	−0.0004 (7)	−0.0016 (7)
C18	0.0167 (8)	0.0233 (10)	0.0169 (9)	0.0040 (7)	−0.0008 (7)	0.0039 (7)
C19	0.0210 (9)	0.0204 (9)	0.0141 (8)	0.0087 (7)	−0.0006 (7)	−0.0021 (7)
C20	0.0142 (8)	0.0243 (10)	0.0152 (8)	0.0043 (7)	−0.0024 (7)	0.0013 (7)
C21	0.0160 (8)	0.0139 (8)	0.0199 (9)	0.0003 (6)	−0.0039 (7)	0.0001 (7)
C22	0.0194 (9)	0.0220 (9)	0.0167 (9)	0.0008 (7)	−0.0061 (7)	0.0041 (7)
C23	0.0226 (10)	0.0252 (10)	0.0276 (10)	0.0059 (8)	−0.0070 (8)	0.0011 (8)
C24	0.0262 (10)	0.0279 (11)	0.0319 (11)	−0.0026 (8)	−0.0070 (9)	0.0127 (9)
C25	0.0196 (9)	0.0335 (11)	0.0175 (9)	0.0018 (8)	−0.0030 (7)	−0.0020 (8)

Geometric parameters (Å, º) top

Cl1—C10	1.7439 (18)	C9—H9	0.9500
F1—C4	1.355 (2)	C10—C11	1.383 (3)
O1—C16	1.228 (2)	C11—C12	1.387 (2)
O2—C21	1.218 (2)	C11—H11	0.9500
O3—C21	1.349 (2)	C12—H12	0.9500
O3—C22	1.475 (2)	C13—C14	1.373 (2)
N1—N2	1.357 (2)	C14—C15	1.402 (2)
N1—C13	1.379 (2)	C14—H14	0.9500
N1—C1	1.436 (2)	C15—C16	1.494 (2)
N2—C15	1.338 (2)	C17—C18	1.521 (3)
N3—C16	1.363 (2)	C17—H17A	0.9900
N3—C20	1.465 (2)	C17—H17B	0.9900
N3—C17	1.466 (2)	C18—H18A	0.9900
N4—C21	1.356 (2)	C18—H18B	0.9900
N4—C18	1.457 (2)	C19—C20	1.519 (3)
N4—C19	1.463 (2)	C19—H19A	0.9900
C1—C6	1.387 (3)	C19—H19B	0.9900
C1—C2	1.386 (2)	C20—H20A	0.9900
C2—C3	1.392 (3)	C20—H20B	0.9900
C2—H2	0.9500	C22—C23	1.509 (3)
C3—C4	1.373 (3)	C22—C24	1.523 (3)
C3—H3	0.9500	C22—C25	1.524 (3)
C4—C5	1.378 (3)	C23—H23A	0.9800
C5—C6	1.382 (3)	C23—H23B	0.9800
C5—H5	0.9500	C23—H23C	0.9800
C6—H6	0.9500	C24—H24A	0.9800
C7—C8	1.394 (3)	C24—H24B	0.9800
C7—C12	1.398 (2)	C24—H24C	0.9800
C7—C13	1.471 (2)	C25—H25A	0.9800
C8—C9	1.390 (2)	C25—H25B	0.9800
C8—H8	0.9500	C25—H25C	0.9800
C9—C10	1.384 (3)

C21—O3—C22	119.64 (14)	C14—C15—C16	124.05 (16)
N2—N1—C13	112.50 (14)	O1—C16—N3	121.74 (16)
N2—N1—C1	117.44 (14)	O1—C16—C15	118.02 (15)
C13—N1—C1	129.91 (14)	N3—C16—C15	120.11 (15)
C15—N2—N1	104.23 (14)	N3—C17—C18	109.81 (14)
C16—N3—C20	118.19 (14)	N3—C17—H17A	109.7
C16—N3—C17	125.08 (14)	C18—C17—H17A	109.7
C20—N3—C17	112.72 (14)	N3—C17—H17B	109.7
C21—N4—C18	120.10 (15)	C18—C17—H17B	109.7
C21—N4—C19	125.57 (15)	H17A—C17—H17B	108.2
C18—N4—C19	114.33 (14)	N4—C18—C17	110.80 (15)
C6—C1—C2	121.44 (16)	N4—C18—H18A	109.5
C6—C1—N1	119.72 (16)	C17—C18—H18A	109.5
C2—C1—N1	118.84 (16)	N4—C18—H18B	109.5
C1—C2—C3	119.41 (17)	C17—C18—H18B	109.5
C1—C2—H2	120.3	H18A—C18—H18B	108.1
C3—C2—H2	120.3	N4—C19—C20	109.09 (15)
C4—C3—C2	118.21 (18)	N4—C19—H19A	109.9
C4—C3—H3	120.9	C20—C19—H19A	109.9
C2—C3—H3	120.9	N4—C19—H19B	109.9
F1—C4—C3	118.44 (18)	C20—C19—H19B	109.9
F1—C4—C5	118.57 (18)	H19A—C19—H19B	108.3
C3—C4—C5	122.99 (18)	N3—C20—C19	111.15 (14)
C4—C5—C6	118.84 (18)	N3—C20—H20A	109.4
C4—C5—H5	120.6	C19—C20—H20A	109.4
C6—C5—H5	120.6	N3—C20—H20B	109.4
C5—C6—C1	119.12 (17)	C19—C20—H20B	109.4
C5—C6—H6	120.4	H20A—C20—H20B	108.0
C1—C6—H6	120.4	O2—C21—O3	124.94 (16)
C8—C7—C12	118.48 (16)	O2—C21—N4	123.32 (17)
C8—C7—C13	123.44 (16)	O3—C21—N4	111.74 (15)
C12—C7—C13	118.06 (16)	O3—C22—C23	102.28 (14)
C9—C8—C7	120.63 (17)	O3—C22—C24	110.27 (15)
C9—C8—H8	119.7	C23—C22—C24	110.76 (17)
C7—C8—H8	119.7	O3—C22—C25	109.96 (15)
C10—C9—C8	119.52 (17)	C23—C22—C25	110.84 (16)
C10—C9—H9	120.2	C24—C22—C25	112.29 (17)
C8—C9—H9	120.2	C22—C23—H23A	109.5
C11—C10—C9	121.10 (16)	C22—C23—H23B	109.5
C11—C10—Cl1	119.40 (14)	H23A—C23—H23B	109.5
C9—C10—Cl1	119.49 (14)	C22—C23—H23C	109.5
C10—C11—C12	118.99 (17)	H23A—C23—H23C	109.5
C10—C11—H11	120.5	H23B—C23—H23C	109.5
C12—C11—H11	120.5	C22—C24—H24A	109.5
C11—C12—C7	121.22 (17)	C22—C24—H24B	109.5
C11—C12—H12	119.4	H24A—C24—H24B	109.5
C7—C12—H12	119.4	C22—C24—H24C	109.5
C14—C13—N1	105.62 (15)	H24A—C24—H24C	109.5
C14—C13—C7	129.58 (16)	H24B—C24—H24C	109.5
N1—C13—C7	124.79 (16)	C22—C25—H25A	109.5
C13—C14—C15	105.83 (16)	C22—C25—H25B	109.5
C13—C14—H14	127.1	H25A—C25—H25B	109.5
C15—C14—H14	127.1	C22—C25—H25C	109.5
N2—C15—C14	111.80 (15)	H25A—C25—H25C	109.5
N2—C15—C16	124.02 (15)	H25B—C25—H25C	109.5

C13—N1—N2—C15	−0.52 (19)	N1—C13—C14—C15	−0.33 (19)
C1—N1—N2—C15	175.46 (15)	C7—C13—C14—C15	179.05 (17)
N2—N1—C1—C6	−110.40 (18)	N1—N2—C15—C14	0.29 (19)
C13—N1—C1—C6	64.8 (2)	N1—N2—C15—C16	176.34 (16)
N2—N1—C1—C2	68.8 (2)	C13—C14—C15—N2	0.0 (2)
C13—N1—C1—C2	−116.1 (2)	C13—C14—C15—C16	−176.02 (16)
C6—C1—C2—C3	−0.2 (3)	C20—N3—C16—O1	3.6 (3)
N1—C1—C2—C3	−179.36 (16)	C17—N3—C16—O1	−152.18 (17)
C1—C2—C3—C4	0.5 (3)	C20—N3—C16—C15	−172.10 (15)
C2—C3—C4—F1	179.97 (16)	C17—N3—C16—C15	32.1 (2)
C2—C3—C4—C5	−0.3 (3)	N2—C15—C16—O1	−162.19 (17)
F1—C4—C5—C6	179.53 (16)	C14—C15—C16—O1	13.4 (3)
C3—C4—C5—C6	−0.3 (3)	N2—C15—C16—N3	13.6 (3)
C4—C5—C6—C1	0.5 (3)	C14—C15—C16—N3	−170.78 (16)
C2—C1—C6—C5	−0.3 (3)	C16—N3—C17—C18	101.11 (19)
N1—C1—C6—C5	178.85 (15)	C20—N3—C17—C18	−55.79 (19)
C12—C7—C8—C9	1.7 (3)	C21—N4—C18—C17	124.53 (18)
C13—C7—C8—C9	−179.81 (17)	C19—N4—C18—C17	−55.4 (2)
C7—C8—C9—C10	0.8 (3)	N3—C17—C18—N4	53.54 (19)
C8—C9—C10—C11	−2.3 (3)	C21—N4—C19—C20	−124.91 (19)
C8—C9—C10—Cl1	176.78 (14)	C18—N4—C19—C20	55.0 (2)
C9—C10—C11—C12	1.2 (3)	C16—N3—C20—C19	−101.57 (18)
Cl1—C10—C11—C12	−177.88 (14)	C17—N3—C20—C19	57.07 (19)
C10—C11—C12—C7	1.4 (3)	N4—C19—C20—N3	−54.33 (19)
C8—C7—C12—C11	−2.9 (3)	C22—O3—C21—O2	2.6 (3)
C13—C7—C12—C11	178.60 (17)	C22—O3—C21—N4	−177.38 (15)
N2—N1—C13—C14	0.5 (2)	C18—N4—C21—O2	−0.3 (3)
C1—N1—C13—C14	−174.80 (17)	C19—N4—C21—O2	179.57 (17)
N2—N1—C13—C7	−178.88 (16)	C18—N4—C21—O3	179.63 (15)
C1—N1—C13—C7	5.8 (3)	C19—N4—C21—O3	−0.5 (3)
C8—C7—C13—C14	−151.42 (19)	C21—O3—C22—C23	177.25 (15)
C12—C7—C13—C14	27.0 (3)	C21—O3—C22—C24	59.4 (2)
C8—C7—C13—N1	27.9 (3)	C21—O3—C22—C25	−64.9 (2)
C12—C7—C13—N1	−153.69 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17a···N2	0.99	2.24	2.950 (2)	128
C14—H14···O1ⁱ	0.95	2.28	3.192 (2)	161
C18—H18a···O2ⁱⁱ	0.99	2.52	3.223 (2)	128

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₆ClFN₄O₃
M_r	484.95
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.0568 (5), 12.0047 (10), 16.2615 (13)
α, β, γ (°)	88.852 (1), 81.206 (1), 87.644 (1)
V (Å³)	1167.37 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.35 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Analytical (FACES; Bruker, 2009)
T_min, T_max	0.931, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	11213, 5318, 4351
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.145, 1.06
No. of reflections	5318
No. of parameters	310
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.39

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17a···N2	0.99	2.24	2.950 (2)	128
C14—H14···O1ⁱ	0.95	2.28	3.192 (2)	161
C18—H18a···O2ⁱⁱ	0.99	2.52	3.223 (2)	128

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

Footnotes

‡Additional correspondence author, e-mail: kvpsvijayakumar@gmail.com.

Acknowledgements

VV is grateful to the DST, India, for funding through the Young Scientist Scheme (Fast Track Proposal). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). FACES, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ragavan, R. V., Vijayakumar, V. & Kumari, N. S. (2009). Eur. J. Med. Chem. 44, 3852–3857. PubMed CAS Google Scholar
Ragavan, R. V., Vijayakumar, V. & Kumari, N. S. (2010). Eur. J. Med. Chem. 45, 1173–1180. Web of Science CrossRef CAS PubMed Google Scholar
Samshuddin, S., Narayana, B., Yathirajan, H. S., Safwan, A. P. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o1279–o1280. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 10| October 2010| Page o2682

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

tert-Butyl 4-{[5-(4-chloro­phen­yl)-1-(4-fluoro­phen­yl)-1H-pyrazol-3-yl]carbon­yl}piperazine-1-carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

tert-Butyl 4-{[5-(4-chlorophenyl)-1-(4-fluorophenyl)-1H-pyrazol-3-yl]carbonyl}piperazine-1-carboxylate