3-Bromo-1-(3-chloro-pyridin-2-yl)-N-(4-eth-oxy-phen-yl)-1H-pyrazole-5-carbox-amide.

In the title compound, C(17)H(14)BrClN(4)O(2), the pyrazole ring is almost coplanar with the benzene ring [dihedral angle = 0.5 (2)°], whereas the pyrazole ring is close to perpendicular to the 3-chloro-pyridine ring [dihedral angle = 73.7 (2)°]. An intra-molecular C-H⋯O hydrogen bond occurs. The dominant inter-action in the crystal packing is an N-H⋯N hydrogen bond, which generates a chain along the c axis. Weak inter-molecular C-H⋯O and C-H⋯N contacts are also observed.

Related literature

For details of the synthesis, see: Dong et al. (2009 ▶). For the biological activity of related compounds, see: Gewehr et al. (2007 ▶); Dong et al. (2008a ▶,b ▶); Liu et al. (2007 ▶); Liu et al. (2009a ▶,b ▶,c ▶).

Experimental

Crystal data

C17H14BrClN4O2

M = 421.68

Monoclinic,

a = 16.821 (3) Å

b = 10.195 (2) Å

c = 10.064 (2) Å

β = 101.09 (3)°

V = 1693.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 2.60 mm−1

T = 113 K

0.16 × 0.12 × 0.08 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2002 ▶) T min = 0.681, T max = 0.819

11217 measured reflections

2967 independent reflections

2459 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.064

S = 0.99

2967 reflections

231 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2002 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040158/kp2276sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040158/kp2276Isup2.hkl

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

C17H14BrClN4O2	F(000) = 848
Mr = 421.68	Dx = 1.654 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4811 reflections
a = 16.821 (3) Å	θ = 2.0–27.1°
b = 10.195 (2) Å	µ = 2.60 mm−1
c = 10.064 (2) Å	T = 113 K
β = 101.09 (3)°	Ractangle, colourless
V = 1693.7 (6) Å3	0.16 × 0.12 × 0.08 mm
Z = 4

Rigaku Saturn diffractometer	2967 independent reflections
Radiation source: rotating anode	2459 reflections with I > 2σ(I)
confocal	Rint = 0.049
ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2002)	h = −14→20
Tmin = 0.681, Tmax = 0.819	k = −11→12
11217 measured reflections	l = −11→11

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0325P)2] where P = (Fo2 + 2Fc2)/3
2967 reflections	(Δ/σ)max = 0.002
231 parameters	Δρmax = 0.44 e Å−3
1 restraint	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq
Br1	0.023579 (14)	0.06344 (2)	0.32526 (2)	0.02098 (9)
Cl1	0.07553 (4)	0.63129 (7)	0.54321 (6)	0.02706 (17)
O1	0.49241 (10)	0.39661 (16)	1.23908 (18)	0.0251 (4)
O2	0.25436 (9)	0.48804 (16)	0.66299 (16)	0.0182 (4)
N1	0.26429 (11)	0.29027 (19)	0.77115 (19)	0.0143 (5)
N2	0.09269 (10)	0.31241 (18)	0.35049 (19)	0.0148 (5)
N3	0.14508 (10)	0.38461 (18)	0.44293 (18)	0.0125 (4)
N4	0.21996 (11)	0.49665 (19)	0.3078 (2)	0.0171 (5)
C1	0.32339 (13)	0.3197 (2)	0.8882 (2)	0.0147 (5)
C2	0.34708 (16)	0.4465 (2)	0.9280 (3)	0.0292 (7)
H2	0.3250	0.5177	0.8759	0.035*
C3	0.40344 (16)	0.4662 (3)	1.0450 (3)	0.0318 (8)
H3	0.4189	0.5514	1.0712	0.038*
C4	0.43755 (13)	0.3629 (2)	1.1245 (2)	0.0181 (6)
C5	0.41491 (13)	0.2361 (2)	1.0851 (2)	0.0162 (6)
H5	0.4372	0.1650	1.1372	0.019*
C6	0.35841 (13)	0.2165 (2)	0.9668 (2)	0.0165 (6)
H6	0.3437	0.1313	0.9398	0.020*
C7	0.53387 (14)	0.2914 (2)	1.3173 (2)	0.0204 (6)
H7A	0.5647	0.2407	1.2631	0.024*
H7B	0.4954	0.2336	1.3481	0.024*
C8	0.58986 (14)	0.3521 (3)	1.4367 (3)	0.0257 (7)
H8A	0.6282	0.4079	1.4048	0.039*
H8B	0.6182	0.2841	1.4925	0.039*
H8C	0.5588	0.4031	1.4886	0.039*
C9	0.23427 (13)	0.3734 (2)	0.6695 (2)	0.0128 (5)
C10	0.17324 (13)	0.3141 (2)	0.5591 (2)	0.0133 (5)
C11	0.13590 (13)	0.1945 (2)	0.5421 (2)	0.0141 (5)
H11	0.1412	0.1253	0.6033	0.017*
C12	0.08813 (13)	0.1993 (2)	0.4129 (2)	0.0143 (5)
C13	0.17110 (13)	0.5071 (2)	0.3970 (2)	0.0144 (5)
C14	0.14284 (13)	0.6260 (2)	0.4354 (2)	0.0173 (6)
C15	0.16840 (15)	0.7398 (2)	0.3811 (3)	0.0247 (7)
H15	0.1510	0.8214	0.4056	0.030*
C16	0.21971 (15)	0.7303 (2)	0.2907 (3)	0.0257 (7)
H16	0.2381	0.8052	0.2532	0.031*
C17	0.24346 (14)	0.6071 (3)	0.2566 (2)	0.0226 (6)
H17	0.2777	0.6011	0.1945	0.027*
H1	0.2473 (12)	0.2088 (11)	0.765 (2)	0.013 (6)*

	U11	U22	U33	U12	U13	U23
Br1	0.02471 (15)	0.01863 (15)	0.01646 (15)	−0.00563 (10)	−0.00392 (10)	−0.00200 (11)
Cl1	0.0241 (3)	0.0302 (4)	0.0266 (4)	0.0044 (3)	0.0042 (3)	−0.0100 (3)
O1	0.0317 (10)	0.0178 (10)	0.0183 (10)	−0.0035 (7)	−0.0142 (8)	0.0027 (8)
O2	0.0232 (9)	0.0126 (9)	0.0163 (9)	−0.0023 (7)	−0.0023 (7)	0.0005 (7)
N1	0.0168 (10)	0.0128 (11)	0.0113 (11)	−0.0031 (8)	−0.0022 (8)	−0.0001 (9)
N2	0.0165 (10)	0.0159 (11)	0.0107 (11)	−0.0010 (8)	−0.0011 (8)	−0.0029 (9)
N3	0.0162 (10)	0.0103 (10)	0.0101 (10)	−0.0011 (8)	0.0000 (8)	−0.0013 (8)
N4	0.0183 (11)	0.0175 (12)	0.0133 (11)	0.0002 (9)	−0.0025 (8)	−0.0013 (9)
C1	0.0139 (12)	0.0157 (13)	0.0136 (13)	−0.0017 (10)	0.0000 (10)	0.0007 (10)
C2	0.0378 (16)	0.0161 (15)	0.0250 (16)	0.0011 (11)	−0.0154 (12)	0.0036 (12)
C3	0.0452 (18)	0.0155 (14)	0.0260 (16)	−0.0053 (12)	−0.0145 (13)	−0.0015 (12)
C4	0.0191 (13)	0.0200 (14)	0.0127 (13)	−0.0019 (10)	−0.0034 (10)	−0.0002 (11)
C5	0.0185 (13)	0.0163 (13)	0.0124 (14)	0.0016 (10)	0.0000 (10)	0.0036 (10)
C6	0.0160 (12)	0.0133 (13)	0.0191 (15)	−0.0016 (9)	0.0006 (10)	−0.0003 (10)
C7	0.0213 (13)	0.0219 (14)	0.0153 (14)	0.0016 (10)	−0.0031 (11)	0.0036 (11)
C8	0.0240 (14)	0.0275 (16)	0.0209 (15)	−0.0052 (11)	−0.0078 (11)	0.0032 (12)
C9	0.0127 (12)	0.0136 (13)	0.0121 (13)	0.0016 (10)	0.0027 (9)	−0.0021 (10)
C10	0.0148 (12)	0.0129 (13)	0.0113 (13)	0.0029 (9)	0.0004 (10)	0.0025 (10)
C11	0.0173 (13)	0.0142 (13)	0.0109 (13)	0.0000 (10)	0.0025 (10)	0.0028 (10)
C12	0.0151 (12)	0.0155 (14)	0.0124 (13)	−0.0011 (10)	0.0029 (10)	−0.0013 (10)
C13	0.0153 (12)	0.0144 (13)	0.0104 (13)	−0.0012 (10)	−0.0050 (10)	0.0017 (10)
C14	0.0180 (13)	0.0170 (13)	0.0142 (13)	0.0026 (10)	−0.0035 (10)	−0.0030 (11)
C15	0.0277 (15)	0.0130 (13)	0.0275 (17)	0.0024 (11)	−0.0097 (12)	0.0010 (12)
C16	0.0294 (15)	0.0179 (15)	0.0241 (16)	−0.0075 (11)	−0.0090 (12)	0.0058 (12)
C17	0.0225 (14)	0.0299 (16)	0.0145 (14)	−0.0085 (11)	0.0008 (10)	0.0059 (12)

Br1—C12	1.873 (2)	C5—C6	1.387 (3)
Cl1—C14	1.713 (3)	C5—H5	0.9300
O1—C4	1.375 (3)	C6—H6	0.9300
O1—C7	1.430 (3)	C7—C8	1.510 (3)
O2—C9	1.222 (3)	C7—H7A	0.9700
N1—C9	1.350 (3)	C7—H7B	0.9700
N1—C1	1.419 (3)	C8—H8A	0.9600
N1—H1	0.877 (9)	C8—H8B	0.9600
N2—C12	1.322 (3)	C8—H8C	0.9600
N2—N3	1.367 (2)	C9—C10	1.488 (3)
N3—C10	1.376 (3)	C10—C11	1.367 (3)
N3—C13	1.429 (3)	C11—C12	1.391 (3)
N4—C17	1.330 (3)	C11—H11	0.9300
N4—C13	1.333 (3)	C13—C14	1.384 (3)
C1—C6	1.379 (3)	C14—C15	1.386 (4)
C1—C2	1.389 (3)	C15—C16	1.373 (4)
C2—C3	1.378 (3)	C15—H15	0.9300
C2—H2	0.9300	C16—C17	1.381 (4)
C3—C4	1.379 (3)	C16—H16	0.9300
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.384 (3)
C4—O1—C7	116.83 (18)	C7—C8—H8A	109.5
C9—N1—C1	126.63 (19)	C7—C8—H8B	109.5
C9—N1—H1	117.9 (14)	H8A—C8—H8B	109.5
C1—N1—H1	115.4 (14)	C7—C8—H8C	109.5
C12—N2—N3	103.58 (17)	H8A—C8—H8C	109.5
N2—N3—C10	111.61 (18)	H8B—C8—H8C	109.5
N2—N3—C13	116.61 (17)	O2—C9—N1	125.03 (19)
C10—N3—C13	130.86 (17)	O2—C9—C10	120.47 (19)
C17—N4—C13	117.5 (2)	N1—C9—C10	114.5 (2)
C6—C1—C2	118.5 (2)	C11—C10—N3	106.54 (18)
C6—C1—N1	118.0 (2)	C11—C10—C9	133.6 (2)
C2—C1—N1	123.5 (2)	N3—C10—C9	119.8 (2)
C3—C2—C1	119.7 (2)	C10—C11—C12	104.7 (2)
C3—C2—H2	120.2	C10—C11—H11	127.6
C1—C2—H2	120.2	C12—C11—H11	127.6
C2—C3—C4	121.7 (2)	N2—C12—C11	113.5 (2)
C2—C3—H3	119.2	N2—C12—Br1	120.16 (16)
C4—C3—H3	119.2	C11—C12—Br1	126.31 (18)
O1—C4—C3	115.6 (2)	N4—C13—C14	123.2 (2)
O1—C4—C5	125.3 (2)	N4—C13—N3	114.5 (2)
C3—C4—C5	119.1 (2)	C14—C13—N3	122.1 (2)
C4—C5—C6	119.0 (2)	C13—C14—C15	118.3 (2)
C4—C5—H5	120.5	C13—C14—Cl1	120.6 (2)
C6—C5—H5	120.5	C15—C14—Cl1	121.1 (2)
C1—C6—C5	122.0 (2)	C16—C15—C14	119.0 (2)
C1—C6—H6	119.0	C16—C15—H15	120.5
C5—C6—H6	119.0	C14—C15—H15	120.5
O1—C7—C8	107.1 (2)	C15—C16—C17	118.5 (2)
O1—C7—H7A	110.3	C15—C16—H16	120.7
C8—C7—H7A	110.3	C17—C16—H16	120.7
O1—C7—H7B	110.3	N4—C17—C16	123.5 (3)
C8—C7—H7B	110.3	N4—C17—H17	118.2
H7A—C7—H7B	108.6	C16—C17—H17	118.2
C12—N2—N3—C10	1.4 (3)	N1—C9—C10—C11	5.7 (4)
C12—N2—N3—C13	171.6 (2)	O2—C9—C10—N3	6.4 (4)
C9—N1—C1—C6	−167.1 (2)	N1—C9—C10—N3	−172.7 (2)
C9—N1—C1—C2	13.5 (4)	N3—C10—C11—C12	1.4 (3)
C6—C1—C2—C3	−1.0 (4)	C9—C10—C11—C12	−177.1 (3)
N1—C1—C2—C3	178.3 (3)	N3—N2—C12—C11	−0.4 (3)
C1—C2—C3—C4	0.2 (5)	N3—N2—C12—Br1	−179.10 (15)
C7—O1—C4—C3	−174.8 (2)	C10—C11—C12—N2	−0.6 (3)
C7—O1—C4—C5	5.3 (4)	C10—C11—C12—Br1	177.93 (18)
C2—C3—C4—O1	−179.5 (3)	C17—N4—C13—C14	1.5 (3)
C2—C3—C4—C5	0.4 (5)	C17—N4—C13—N3	177.11 (17)
O1—C4—C5—C6	179.7 (2)	N2—N3—C13—N4	−69.3 (2)
C3—C4—C5—C6	−0.1 (4)	C10—N3—C13—N4	98.6 (3)
C2—C1—C6—C5	1.4 (4)	N2—N3—C13—C14	106.3 (2)
N1—C1—C6—C5	−178.0 (2)	C10—N3—C13—C14	−85.8 (3)
C4—C5—C6—C1	−0.8 (4)	N4—C13—C14—C15	−1.8 (3)
C4—O1—C7—C8	−179.8 (2)	N3—C13—C14—C15	−177.04 (19)
C1—N1—C9—O2	0.4 (4)	N4—C13—C14—Cl1	176.20 (16)
C1—N1—C9—C10	179.5 (2)	N3—C13—C14—Cl1	0.9 (3)
N2—N3—C10—C11	−1.8 (3)	C13—C14—C15—C16	0.7 (3)
C13—N3—C10—C11	−170.2 (2)	Cl1—C14—C15—C16	−177.25 (17)
N2—N3—C10—C9	176.95 (19)	C14—C15—C16—C17	0.5 (3)
C13—N3—C10—C9	8.6 (4)	C13—N4—C17—C16	−0.2 (3)
O2—C9—C10—C11	−175.3 (3)	C15—C16—C17—N4	−0.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4i	0.88 (1)	2.21 (1)	3.059 (3)	165 (2)
C2—H2···O2	0.93	2.26	2.850 (3)	121
C6—H6···N4i	0.93	2.60	3.358 (3)	140
C8—H8A···O2ii	0.96	2.45	3.397 (3)	168
C11—H11···N4i	0.93	2.55	3.390 (3)	151
C16—H16···O2iii	0.93	2.33	3.244 (3)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4i	0.88 (1)	2.21 (1)	3.059 (3)	165 (2)
C2—H2⋯O2	0.93	2.26	2.850 (3)	121
C6—H6⋯N4i	0.93	2.60	3.358 (3)	140
C8—H8A⋯O2ii	0.96	2.45	3.397 (3)	168
C11—H11⋯N4i	0.93	2.55	3.390 (3)	151
C16—H16⋯O2iii	0.93	2.33	3.244 (3)	167

Symmetry codes: (i) ; (ii) ; (iii) .