Ethyl 5-amino-1-(4-chloro-2-nitro-phen-yl)-1H-pyrazole-4-carboxyl-ate.

In the mol-ecule of the title compound, C(12)H(11)ClN(4)O(4), the pyrazole ring is coplanar with the amino and ethoxy-carbonyl groups within 0.026 (2) and 0.105 (2) Å, respectively. The C(6) ring of the 4-chloro-2-nitro-phenyl group is twisted by 53.58 (4)° relative to the plane of the pyrazole ring. The planar structure of the pyrazole ring is stabilized by an intra-molecular N-H⋯O hydrogen bond between its substituents. Neighbouring mol-ecules are linked through inter-molecular N-H⋯N and N-H⋯O hydrogen bonds, giving rise to one-dimensional tapes along the b axis. Mol-ecules in the chain are linked to those of an adjacent chain through weak C-H⋯O inter-actions, forming a three-dimensional network.

Related literature

For the biological activity of pyrazole and its derivatives, see: Iovu et al. (2003 ▶); Mahajan et al. (1991 ▶); related literature, see: Akhtar et al. (2008 ▶); Baraldi et al. (1998 ▶); Bruno et al. (1990 ▶); Cottineau et al. (2002 ▶); Smith et al. (2001 ▶). For the use of pyrazole-based ligands in investigating the structure–activity relationship of the active site of metalloproteins, see: Dardari et al. (2006 ▶), and in the preparation of commercially important dyestuffs, see: Baroni & Kovyrzina (1961 ▶); Neunhoeffer et al. (1959 ▶). For the synthesis and biological evaluation of heterocyclic compounds, see: Akhtar et al. (2008 ▶); Zia-ur-Rehman et al. (2006 ▶, 2008 ▶).

Experimental

Crystal data

C12H11ClN4O4

M = 310.70

Monoclinic,

a = 8.5899 (8) Å

b = 10.2413 (9) Å

c = 15.6633 (14) Å

β = 96.5415 (13)°

V = 1369.0 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 150 (2) K

0.79 × 0.27 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.797, T max = 0.973

15944 measured reflections

4189 independent reflections

3588 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.096

S = 1.04

4189 reflections

197 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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 and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000488/bt2841sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000488/bt2841Isup2.hkl

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

C12H11ClN4O4	F(000) = 640
Mr = 310.70	Dx = 1.508 Mg m−3
Monoclinic, P21/n	Melting point: 435 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.5899 (8) Å	Cell parameters from 6502 reflections
b = 10.2413 (9) Å	θ = 2.6–30.6°
c = 15.6633 (14) Å	µ = 0.30 mm−1
β = 96.5415 (13)°	T = 150 K
V = 1369.0 (2) Å3	Lath, colourless
Z = 4	0.79 × 0.27 × 0.09 mm

Bruker APEXII CCD diffractometer	4189 independent reflections
Radiation source: fine-focus sealed tube	3588 reflections with I > 2σ(I)
graphite	Rint = 0.022
ω rotation with narrow frames scans	θmax = 30.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −12→12
Tmin = 0.797, Tmax = 0.973	k = −14→14
15944 measured reflections	l = −22→22

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: all non-H atoms found by direct methods
R[F2 > 2σ(F2)] = 0.034	Hydrogen site location: geom except NH coords freely refined
wR(F2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0507P)2 + 0.3692P] where P = (Fo2 + 2Fc2)/3
4189 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.27 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
C1	0.16661 (12)	0.37722 (10)	0.87165 (6)	0.01863 (19)
N1	0.00154 (11)	0.39144 (9)	0.83571 (6)	0.02209 (18)
O1	−0.04727 (11)	0.32020 (9)	0.77617 (6)	0.0316 (2)
O2	−0.07682 (10)	0.47313 (9)	0.86871 (6)	0.03110 (19)
C2	0.19621 (13)	0.36020 (11)	0.95971 (7)	0.0216 (2)
H2	0.1135	0.3609	0.9951	0.026*
C3	0.35046 (14)	0.34216 (10)	0.99458 (7)	0.0224 (2)
Cl1	0.39123 (4)	0.31052 (3)	1.103127 (17)	0.03302 (9)
C4	0.47238 (13)	0.34677 (11)	0.94341 (7)	0.0229 (2)
H4	0.5777	0.3370	0.9685	0.028*
C5	0.43941 (13)	0.36565 (10)	0.85546 (7)	0.0218 (2)
H5	0.5227	0.3691	0.8205	0.026*
C6	0.28554 (12)	0.37949 (10)	0.81810 (6)	0.01836 (19)
N2	0.25381 (11)	0.40263 (9)	0.72882 (5)	0.01940 (17)
N3	0.16947 (11)	0.51311 (9)	0.69958 (6)	0.02197 (19)
C7	0.17042 (12)	0.51027 (10)	0.61560 (7)	0.0206 (2)
H7	0.1215	0.5744	0.5778	0.025*
C8	0.25215 (12)	0.40156 (10)	0.58811 (6)	0.01772 (19)
C9	0.30396 (12)	0.33322 (10)	0.66310 (6)	0.01755 (19)
N4	0.39081 (12)	0.22356 (9)	0.67437 (6)	0.0241 (2)
H4A	0.4077 (18)	0.1853 (14)	0.6270 (11)	0.029*
H4B	0.3806 (18)	0.1713 (14)	0.7173 (10)	0.029*
C10	0.28074 (12)	0.36124 (10)	0.50279 (6)	0.01900 (19)
O3	0.35936 (10)	0.26670 (8)	0.48774 (5)	0.02577 (17)
O4	0.20696 (9)	0.43861 (8)	0.44194 (5)	0.02405 (17)
C11	0.23017 (13)	0.40996 (12)	0.35329 (7)	0.0250 (2)
H11A	0.1377	0.4396	0.3146	0.030*
H11B	0.2407	0.3145	0.3460	0.030*
C12	0.37412 (17)	0.47691 (14)	0.32935 (9)	0.0355 (3)
H12A	0.3655	0.5711	0.3389	0.053*
H12B	0.3845	0.4605	0.2686	0.053*
H12C	0.4665	0.4429	0.3649	0.053*

	U11	U22	U33	U12	U13	U23
C1	0.0220 (5)	0.0179 (4)	0.0160 (4)	0.0002 (4)	0.0023 (4)	−0.0002 (3)
N1	0.0232 (4)	0.0248 (4)	0.0183 (4)	−0.0023 (3)	0.0024 (3)	0.0032 (3)
O1	0.0339 (5)	0.0367 (5)	0.0230 (4)	−0.0084 (4)	−0.0021 (3)	−0.0042 (3)
O2	0.0271 (4)	0.0339 (5)	0.0330 (5)	0.0062 (3)	0.0063 (3)	−0.0003 (4)
C2	0.0273 (5)	0.0227 (5)	0.0153 (4)	−0.0007 (4)	0.0047 (4)	−0.0004 (4)
C3	0.0319 (5)	0.0202 (5)	0.0146 (4)	0.0005 (4)	0.0007 (4)	−0.0002 (4)
Cl1	0.04426 (18)	0.03893 (17)	0.01462 (13)	0.00482 (13)	−0.00204 (11)	0.00275 (10)
C4	0.0253 (5)	0.0213 (5)	0.0213 (5)	0.0024 (4)	−0.0011 (4)	0.0009 (4)
C5	0.0243 (5)	0.0208 (5)	0.0209 (5)	0.0029 (4)	0.0054 (4)	0.0020 (4)
C6	0.0256 (5)	0.0164 (4)	0.0134 (4)	0.0016 (4)	0.0035 (4)	0.0008 (3)
N2	0.0258 (4)	0.0188 (4)	0.0142 (4)	0.0057 (3)	0.0046 (3)	0.0019 (3)
N3	0.0291 (4)	0.0192 (4)	0.0179 (4)	0.0085 (3)	0.0044 (3)	0.0019 (3)
C7	0.0237 (5)	0.0207 (5)	0.0174 (4)	0.0043 (4)	0.0030 (4)	0.0022 (4)
C8	0.0202 (4)	0.0185 (4)	0.0149 (4)	0.0013 (3)	0.0038 (3)	0.0015 (3)
C9	0.0205 (4)	0.0171 (4)	0.0156 (4)	0.0007 (3)	0.0048 (3)	0.0004 (3)
N4	0.0361 (5)	0.0188 (4)	0.0187 (4)	0.0091 (4)	0.0090 (4)	0.0037 (3)
C10	0.0193 (4)	0.0223 (5)	0.0157 (4)	−0.0012 (4)	0.0028 (3)	0.0010 (4)
O3	0.0318 (4)	0.0266 (4)	0.0196 (4)	0.0076 (3)	0.0058 (3)	−0.0015 (3)
O4	0.0266 (4)	0.0313 (4)	0.0145 (3)	0.0064 (3)	0.0031 (3)	0.0029 (3)
C11	0.0238 (5)	0.0369 (6)	0.0141 (4)	−0.0005 (4)	0.0019 (4)	0.0012 (4)
C12	0.0395 (7)	0.0374 (7)	0.0321 (6)	−0.0095 (6)	0.0150 (5)	0.0001 (5)

C1—C2	1.3848 (14)	C7—C8	1.4096 (14)
C1—C6	1.3940 (14)	C7—H7	0.9500
C1—N1	1.4719 (14)	C8—C9	1.3958 (14)
N1—O1	1.2202 (13)	C8—C10	1.4462 (14)
N1—O2	1.2245 (13)	C9—N4	1.3487 (13)
C2—C3	1.3868 (16)	N4—H4A	0.866 (16)
C2—H2	0.9500	N4—H4B	0.871 (15)
C3—C4	1.3902 (16)	C10—O3	1.2188 (13)
C3—Cl1	1.7271 (11)	C10—O4	1.3418 (12)
C4—C5	1.3881 (15)	O4—C11	1.4549 (13)
C4—H4	0.9500	C11—C12	1.4985 (17)
C5—C6	1.3904 (15)	C11—H11A	0.9900
C5—H5	0.9500	C11—H11B	0.9900
C6—N2	1.4140 (12)	C12—H12A	0.9800
N2—C9	1.3607 (13)	C12—H12B	0.9800
N2—N3	1.3925 (12)	C12—H12C	0.9800
N3—C7	1.3166 (13)
C2—C1—C6	122.51 (10)	C8—C7—H7	123.8
C2—C1—N1	116.93 (9)	C9—C8—C7	105.13 (9)
C6—C1—N1	120.55 (9)	C9—C8—C10	124.27 (9)
O1—N1—O2	125.00 (10)	C7—C8—C10	130.60 (9)
O1—N1—C1	117.73 (9)	N4—C9—N2	123.64 (9)
O2—N1—C1	117.26 (9)	N4—C9—C8	130.26 (9)
C1—C2—C3	117.89 (10)	N2—C9—C8	106.06 (9)
C1—C2—H2	121.1	C9—N4—H4A	114.1 (10)
C3—C2—H2	121.1	C9—N4—H4B	120.7 (10)
C2—C3—C4	121.15 (10)	H4A—N4—H4B	115.1 (14)
C2—C3—Cl1	119.35 (9)	O3—C10—O4	123.99 (9)
C4—C3—Cl1	119.49 (9)	O3—C10—C8	124.18 (9)
C5—C4—C3	119.67 (10)	O4—C10—C8	111.82 (9)
C5—C4—H4	120.2	C10—O4—C11	116.99 (9)
C3—C4—H4	120.2	O4—C11—C12	110.69 (10)
C4—C5—C6	120.57 (10)	O4—C11—H11A	109.5
C4—C5—H5	119.7	C12—C11—H11A	109.5
C6—C5—H5	119.7	O4—C11—H11B	109.5
C5—C6—C1	118.15 (9)	C12—C11—H11B	109.5
C5—C6—N2	120.01 (9)	H11A—C11—H11B	108.1
C1—C6—N2	121.74 (9)	C11—C12—H12A	109.5
C9—N2—N3	111.92 (8)	C11—C12—H12B	109.5
C9—N2—C6	128.23 (9)	H12A—C12—H12B	109.5
N3—N2—C6	119.72 (8)	C11—C12—H12C	109.5
C7—N3—N2	104.38 (8)	H12A—C12—H12C	109.5
N3—C7—C8	112.50 (9)	H12B—C12—H12C	109.5
N3—C7—H7	123.8
C2—C1—N1—O1	−127.78 (11)	C9—N2—N3—C7	−0.53 (12)
C6—C1—N1—O1	51.47 (14)	C6—N2—N3—C7	175.66 (9)
C2—C1—N1—O2	51.39 (13)	N2—N3—C7—C8	0.14 (12)
C6—C1—N1—O2	−129.37 (11)	N3—C7—C8—C9	0.27 (12)
C6—C1—C2—C3	−1.37 (16)	N3—C7—C8—C10	179.76 (10)
N1—C1—C2—C3	177.85 (9)	N3—N2—C9—N4	178.62 (10)
C1—C2—C3—C4	2.81 (16)	C6—N2—C9—N4	2.83 (17)
C1—C2—C3—Cl1	−176.02 (8)	N3—N2—C9—C8	0.70 (12)
C2—C3—C4—C5	−2.04 (17)	C6—N2—C9—C8	−175.09 (10)
Cl1—C3—C4—C5	176.78 (8)	C7—C8—C9—N4	−178.30 (11)
C3—C4—C5—C6	−0.24 (16)	C10—C8—C9—N4	2.17 (18)
C4—C5—C6—C1	1.62 (16)	C7—C8—C9—N2	−0.57 (11)
C4—C5—C6—N2	178.08 (10)	C10—C8—C9—N2	179.90 (10)
C2—C1—C6—C5	−0.81 (16)	C9—C8—C10—O3	−3.61 (17)
N1—C1—C6—C5	179.99 (9)	C7—C8—C10—O3	176.99 (11)
C2—C1—C6—N2	−177.21 (10)	C9—C8—C10—O4	174.82 (10)
N1—C1—C6—N2	3.59 (15)	C7—C8—C10—O4	−4.59 (16)
C5—C6—N2—C9	52.72 (15)	O3—C10—O4—C11	−3.17 (15)
C1—C6—N2—C9	−130.95 (11)	C8—C10—O4—C11	178.40 (9)
C5—C6—N2—N3	−122.79 (11)	C10—O4—C11—C12	−86.64 (13)
C1—C6—N2—N3	53.54 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O3	0.866 (16)	2.328 (16)	2.9383 (13)	127.7 (12)
N4—H4A···O2i	0.866 (16)	2.610 (15)	3.1356 (13)	120.1 (12)
N4—H4B···N3i	0.871 (15)	2.153 (16)	3.0074 (13)	166.8 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O3	0.866 (16)	2.328 (16)	2.9383 (13)	127.7 (12)
N4—H4A⋯O2i	0.866 (16)	2.610 (15)	3.1356 (13)	120.1 (12)
N4—H4B⋯N3i	0.871 (15)	2.153 (16)	3.0074 (13)	166.8 (14)

Symmetry code: (i) .