Two isomeric reaction products: hydrogen-bonded sheets in methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitro­benzoate and hydrogen-bonded chains of edge-fused rings in methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)amino]benzoate

In methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitro­benzo­ate, C₁₇H₁₄N₄O₄, the molecules are linked into complex sheets by a combination of N-H...N, N-H...O and C-H...O hydrogen bonds. In the isomeric methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)amino]­benzo­ate, mol­ecules exhibit a polarized mol­ecular-electronic structure and are linked into chains of edge-fused rings by a combination of N-H...O and C-H...O hydrogen bonds.

S1. Comment

We report here the molecular and supramolecular structures of the title compounds, (I) and (II) (Figs. 1 and 2), which are the products from the two alternative pathways for the reaction of methyl 4-fluoro-3-nitrobenzoate with 5-amino-3-phenylpyrazole. The reaction in which the atom N1 of the pyrazole ring acts as the nucleophile generates compound (I), while compound (II) is formed in the reaction in which the amino N atom of the pyrazole ring acts as the nucleophile (see first scheme below). The product mixture appears to be very sensitive to the polarity of the solvent employed; in a 1:7 v/v mixture of dimethylsulfoxide and methanol as the solvent, compounds (I) and (II) are formed in equimolar quantities, but compound (II) was the sole product isolated from the corresponding reaction in neat dimethylsulfoxide. An analogous reaction in neat dimethylsulfoxide using 5-amino-3-methylpyrazole in place of 5-amino-3-phenylpyrazole generates only compound (III), the direct analogue of compound (II) (Portilla et al., 2007). Compound (I) and its analogues should prove to be useful for the synthesis of pyrazolobenzotriazepines, which have applications as drug, agrochemical and dye intermediates (Tachibana & Kaneko, 1989).

In (I), the C—C bond distances within the aryl ring fall in the range 1.381 (3)–1.400 (3) Å, consistent with essentially unperturbed aromatic delocalization, while the remaining bond distances are all typical of their types (Allen et al., 1987). By contrast, in (II), the C53—C54 and C51—C56 bond distances are both significantly shorter than the remaining bonds in this ring (Table 2), while the C52—N52 bond is short for its type. In addition, the N52—O521 bond, which participates in an intramolecular hydrogen bond (Table 3), is long for its type. These observations, taken all together, provide evidence for the polarized forms (IIa) and (IIb) (see scheme below) as important contributors of the overall molecular–electronic structure of compound (II). A similar conclusion was drawn from the intramolecular geometry of compound (III) (Portilla et al., 2007).

The molecules of (I) are linked into sheets by a combination of N—H···N, N—H···O and C—H···O hydrogen bonds (Table 1), and the formation of the sheet is readily analysed in terms of two simple one-dimensional substructures. The atoms N5 and C16 in the molecule at (x, y, z) act as hydrogen-bond donors to pyrazole atom N2 and nitro atom O121, respectively, both in the molecule at (3/2 - x, 1/2 + y, 1/2 - z), so forming a C(5)C(6)[R²₂(13) chain of rings (Bernstein et al., 1995) running parallel to the [010] direction and generated by the 2₁ screw axis along (3/4, y, 1/4) (Fig. 3). In the second substructure, atom N5 at (x, y, z) acts as a hydrogen-bond donor to ketonic atom O141 in the molecule at (-1/2 + x, 3/2 - y, -1/2 + z), so forming a simple C(10) chain running parallel to the [101] direction and generated by the n-glide plane at y = 3/4 (Fig. 4). The combination of the chains parallel to [010] and [101] generates a sheet parallel to (101), but there are no significant direction-specific interactions between adjacent sheets.

In addition, to the intramolecular N—H···O hydrogen bond, the structure of (II) contains three significant intermolecular hydrogen bonds (Table 3), which combine to generate a one-dimensional hydrogen-bonded structure of considerable elegance. Atoms N2 and C36 in the molecule at (x, y, z) both act as hydrogen-bond donors to carbonyl atom O541 in the molecule at (1 - x, 2 - y, 1 - z), thereby generating by inversion a cyclic dimer containing concentric R²₂(22) and R²₂(26) rings, embedding two symmetry-related R¹₂(7) rings (Fig. 5). In addition atom C53 in the molecule at (x, y, z) acts as a hydrogen-bond donor to nitro atom O522 in the molecule at (1 - x, y, 1/2 - z), so forming a further cyclic motif, this time an R²₂(10) ring generated by the twofold rotation axis along (1/2, y, 1/4). Propagation of these two motifs by successive inversion and rotation then generates a complex chain of edge-fused rings running parallel to the [001] direction (Fig. 6). Two chains of this type, related to one another by the C-centring operation, pass through each unit cell, but there are no significant direction-specific interactions between adjacent chains.

By contrast with the complexity of the chain of rings formed by (II), the methyl analogue (III) forms a simpler chain of edge-fused rings containing alternating R²₂(16) and R²₂(22) rings, both generated by inversion using C—H···O and N—H···O hydrogen bonds, respectively (Portilla et al., 2007).

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Portilla et al. (2007); Tachibana & Kaneko (1989).

S2. Experimental

A solution of 5-amino-3-phenyl-1H-pyrazole (2 mmol) and methyl 4-fluoro-3-nitrobenzoate (2 mmol) in dimethylsulfoxide–methanol (8 ml of a 1:7 v/v mixture) was heated under reflux with magnetic stirring for 10 min. The mixture was cooled to ambient temperature, and the resulting solid was collected by filtration and washed with methanol (3 x 6 ml). Recrystallization of the crude reaction product from dimethylsulfoxide gave compound (II). The resulting filtrate was evaporated under reduced pressure, and the resulting solid was crystallized successively from methanol and dimethylsulfoxide to give compound (I). Compound (I): yield 46% according to the above procedure, giving yellow crystals suitable for single-crystal X-ray diffraction, m.p. 476–477 K. Analysis found: C 59.2, H 4.3, N 16.2%; C₁₇H₁₄N₄O₄ requires: C 60.3, H 4.2, N 16.6%. Compuond (II): yield 48% according to the above procedure, giving orange crystals suitable for single-crystal X-ray diffraction, m.p. 530–531 K; obtained as sole product when a similar reaction was carried out in neat dimethylsulfoxide (2 ml) at 298 K for 2 h (yield 90%). Analysis found: C 60.2, H 4.7, N 16.4%; C₁₇H₁₄N₄O₄ requires: C 60.3, H 4.2, N 16.6%.

S3. Refinement

For compound (I), the space group P2₁/n was uniquely assigned from the systematic absences. For compound (II), the systematic absences permitted Cc and C2/c as possible space groups; C2/c was selected and confirmed by the subsequent structure analysis. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were allowed to ride in geometrically idealized positions, with C—H distances of 0.95 Å (aromatic and pyrazole) or 0.98 Å (methyl), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups and 1.2 for all other H atoms bonded to C atoms. H atoms bonded to N atoms were permitted to ride at the positions deduced from difference maps, all giving N—H distances of 0.87 Å, with U_iso(H) = 1.2U_eq(N).

Computing details

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005) and WinGX (Farrugia, 1999); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded chain of rings along [010]. For the sake of clarity, H atoms bonded to C atoms that are not involved in the motif shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(10) chain along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 5. Part of the crystal structure of (II), showing the formation of a centrosymmetric hydrogen-bonded dimer. For the sake of clarity, H atoms that are not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 - x, 2 - y, 1 - z).
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded chain of edge-fused rings along [001]. For the sake of clarity, H atoms that are not involved in the motifs shown have been omitted.

(I) methyl 4-(5-amino-3-phenyl-1H-pyrazol-1-yl)-3-nitrobenzoate

Crystal data

C17H14N4O4	F(000) = 704
Mr = 338.32	Dx = 1.435 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3597 reflections
a = 12.3516 (8) Å	θ = 3.2–27.5°
b = 7.5202 (4) Å	µ = 0.11 mm^−1
c = 17.1564 (13) Å	T = 120 K
β = 100.699 (5)°	Block, yellow
V = 1565.90 (18) Å^3	0.55 × 0.35 × 0.19 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer	3597 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode	2266 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ & ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
Tmin = 0.951, Tmax = 0.980	l = −22→22
37526 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.178	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0883P)^2 + 0.9526P] where P = (Fo^2 + 2Fc^2)/3
3597 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.70074 (15)	0.6050 (3)	0.23515 (10)	0.0254 (4)
C11	0.72777 (18)	0.5683 (3)	0.31736 (13)	0.0238 (5)
C12	0.65260 (17)	0.4875 (3)	0.35802 (13)	0.0242 (5)
N12	0.54487 (16)	0.4217 (3)	0.31786 (12)	0.0298 (5)
O121	0.53573 (13)	0.3643 (2)	0.24990 (10)	0.0343 (4)
O122	0.46921 (14)	0.4242 (3)	0.35533 (11)	0.0457 (5)
C13	0.67791 (19)	0.4603 (3)	0.43961 (13)	0.0265 (5)
C141	0.81336 (19)	0.4758 (3)	0.56763 (13)	0.0268 (5)
O141	0.90419 (14)	0.5090 (2)	0.60530 (9)	0.0362 (4)
O142	0.73193 (14)	0.4072 (2)	0.59859 (9)	0.0337 (4)
C142	0.7569 (2)	0.3743 (4)	0.68303 (14)	0.0403 (6)
C14	0.78084 (18)	0.5075 (3)	0.48066 (13)	0.0240 (5)
C15	0.85666 (18)	0.5852 (3)	0.44046 (13)	0.0262 (5)
C16	0.83036 (18)	0.6158 (3)	0.35967 (13)	0.0263 (5)
N2	0.75934 (15)	0.5266 (2)	0.18323 (11)	0.0260 (4)
C3	0.70062 (18)	0.5674 (3)	0.11141 (13)	0.0256 (5)
C31	0.73660 (19)	0.5066 (3)	0.03907 (13)	0.0262 (5)
C32	0.8428 (2)	0.4419 (3)	0.04009 (14)	0.0312 (6)
C33	0.8727 (2)	0.3790 (4)	−0.02855 (14)	0.0355 (6)
C34	0.7980 (2)	0.3806 (3)	−0.09988 (14)	0.0355 (6)
C35	0.6933 (2)	0.4464 (3)	−0.10232 (14)	0.0334 (6)
C36	0.6626 (2)	0.5094 (3)	−0.03337 (13)	0.0304 (5)
C4	0.60744 (18)	0.6703 (3)	0.11715 (13)	0.0264 (5)
C5	0.61022 (18)	0.6951 (3)	0.19633 (13)	0.0256 (5)
N5	0.54292 (16)	0.7858 (3)	0.23935 (11)	0.0306 (5)
H13	0.6249	0.4098	0.4668	0.032*
H14A	0.8229	0.2996	0.6956	0.060*
H145	0.6947	0.3132	0.6993	0.060*
H1C	0.7702	0.4876	0.7114	0.060*
H15	0.9274	0.6177	0.4689	0.031*
H16	0.8829	0.6696	0.3331	0.032*
H32	0.8949	0.4410	0.0884	0.037*
H33	0.9450	0.3343	−0.0270	0.043*
H34	0.8190	0.3365	−0.1468	0.043*
H35	0.6422	0.4488	−0.1511	0.040*
H36	0.5903	0.5549	−0.0355	0.036*
H4	0.5535	0.7138	0.0746	0.032*
H5A	0.5834	0.8580	0.2721	0.037*
H5B	0.4926	0.8438	0.2069	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0251 (10)	0.0320 (10)	0.0189 (9)	0.0044 (8)	0.0034 (7)	−0.0002 (8)
C11	0.0278 (11)	0.0245 (11)	0.0183 (10)	0.0019 (9)	0.0019 (9)	−0.0004 (8)
C12	0.0212 (11)	0.0271 (12)	0.0232 (11)	0.0019 (9)	0.0009 (9)	−0.0014 (9)
N12	0.0281 (10)	0.0339 (11)	0.0267 (11)	−0.0029 (8)	0.0031 (8)	0.0021 (8)
O121	0.0330 (9)	0.0399 (10)	0.0276 (9)	−0.0025 (8)	−0.0010 (7)	−0.0057 (7)
O122	0.0264 (9)	0.0765 (15)	0.0358 (10)	−0.0069 (9)	0.0097 (8)	0.0020 (9)
C13	0.0274 (12)	0.0305 (12)	0.0222 (11)	0.0012 (9)	0.0059 (9)	0.0002 (9)
C141	0.0294 (12)	0.0286 (12)	0.0218 (11)	0.0037 (10)	0.0025 (9)	−0.0013 (9)
O141	0.0370 (10)	0.0459 (11)	0.0228 (9)	−0.0012 (8)	−0.0021 (7)	−0.0004 (7)
O142	0.0358 (9)	0.0445 (10)	0.0212 (8)	0.0021 (8)	0.0063 (7)	0.0036 (7)
C142	0.0486 (16)	0.0518 (16)	0.0207 (12)	0.0066 (13)	0.0069 (11)	0.0065 (11)
C14	0.0273 (12)	0.0236 (11)	0.0204 (11)	0.0043 (9)	0.0027 (9)	−0.0025 (8)
C15	0.0261 (11)	0.0267 (12)	0.0242 (12)	0.0005 (9)	0.0008 (9)	−0.0022 (9)
C16	0.0263 (12)	0.0271 (11)	0.0256 (12)	0.0003 (9)	0.0051 (9)	0.0003 (9)
N2	0.0277 (10)	0.0298 (10)	0.0208 (9)	0.0002 (8)	0.0053 (8)	−0.0003 (8)
C3	0.0284 (11)	0.0254 (11)	0.0223 (11)	−0.0040 (9)	0.0028 (9)	0.0013 (9)
C31	0.0312 (12)	0.0255 (11)	0.0220 (11)	−0.0048 (10)	0.0050 (9)	0.0013 (9)
C32	0.0333 (13)	0.0367 (13)	0.0234 (12)	−0.0022 (10)	0.0046 (10)	−0.0003 (10)
C33	0.0362 (14)	0.0426 (14)	0.0295 (13)	0.0026 (11)	0.0110 (11)	−0.0013 (11)
C34	0.0452 (15)	0.0389 (14)	0.0247 (12)	−0.0024 (12)	0.0124 (11)	−0.0012 (10)
C35	0.0387 (14)	0.0379 (14)	0.0222 (12)	−0.0047 (11)	0.0019 (10)	0.0003 (10)
C36	0.0327 (13)	0.0326 (13)	0.0255 (12)	−0.0003 (10)	0.0047 (10)	0.0016 (10)
C4	0.0257 (11)	0.0304 (12)	0.0209 (11)	−0.0012 (9)	−0.0015 (9)	0.0020 (9)
C5	0.0255 (11)	0.0263 (11)	0.0240 (11)	−0.0012 (9)	0.0019 (9)	0.0019 (9)
N5	0.0285 (10)	0.0353 (11)	0.0262 (10)	0.0052 (9)	0.0001 (8)	−0.0006 (8)

Geometric parameters (Å, º)

N1—C5	1.370 (3)	C16—H16	0.95
N1—N2	1.380 (3)	N2—C3	1.344 (3)
N1—C11	1.415 (3)	C3—C4	1.406 (3)
C11—C16	1.385 (3)	C3—C31	1.467 (3)
C11—C12	1.400 (3)	C31—C32	1.396 (3)
C12—C13	1.392 (3)	C31—C36	1.400 (3)
C12—N12	1.466 (3)	C32—C33	1.381 (3)
N12—O121	1.228 (2)	C32—H32	0.95
N12—O122	1.229 (3)	C33—C34	1.389 (4)
C13—C14	1.381 (3)	C33—H33	0.95
C13—H13	0.95	C34—C35	1.378 (4)
C141—O141	1.212 (3)	C34—H34	0.95
C141—O142	1.326 (3)	C35—C36	1.391 (3)
C141—C14	1.490 (3)	C35—H35	0.95
O142—C142	1.445 (3)	C36—H36	0.95
C142—H14A	0.98	C4—C5	1.365 (3)
C142—H145	0.98	C4—H4	0.95
C142—H1C	0.98	C5—N5	1.389 (3)
C14—C15	1.391 (3)	N5—H5A	0.87
C15—C16	1.383 (3)	N5—H5B	0.87
C15—H15	0.95
C5—N1—N2	112.09 (17)	C11—C16—H16	119.9
C5—N1—C11	126.98 (18)	C3—N2—N1	103.63 (17)
N2—N1—C11	120.33 (17)	N2—C3—C4	111.8 (2)
C16—C11—C12	118.5 (2)	N2—C3—C31	120.5 (2)
C16—C11—N1	119.7 (2)	C4—C3—C31	127.7 (2)
C12—C11—N1	121.72 (19)	C32—C31—C36	118.3 (2)
C13—C12—C11	121.3 (2)	C32—C31—C3	122.0 (2)
C13—C12—N12	116.0 (2)	C36—C31—C3	119.7 (2)
C11—C12—N12	122.72 (19)	C33—C32—C31	120.5 (2)
O121—N12—O122	123.9 (2)	C33—C32—H32	119.7
O121—N12—C12	118.68 (19)	C31—C32—H32	119.7
O122—N12—C12	117.45 (19)	C32—C33—C34	120.6 (2)
C14—C13—C12	119.3 (2)	C32—C33—H33	119.7
C14—C13—H13	120.4	C34—C33—H33	119.7
C12—C13—H13	120.4	C35—C34—C33	119.7 (2)
O141—C141—O142	124.2 (2)	C35—C34—H34	120.1
O141—C141—C14	123.5 (2)	C33—C34—H34	120.1
O142—C141—C14	112.31 (19)	C34—C35—C36	120.0 (2)
C141—O142—C142	115.54 (19)	C34—C35—H35	120.0
O142—C142—H14A	109.5	C36—C35—H35	120.0
O142—C142—H145	109.5	C35—C36—C31	120.9 (2)
H14A—C142—H145	109.5	C35—C36—H36	119.6
O142—C142—H1C	109.5	C31—C36—H36	119.6
H14A—C142—H1C	109.5	C5—C4—C3	105.98 (19)
H145—C142—H1C	109.5	C5—C4—H4	127.0
C13—C14—C15	119.7 (2)	C3—C4—H4	127.0
C13—C14—C141	121.4 (2)	C4—C5—N1	106.48 (19)
C15—C14—C141	118.8 (2)	C4—C5—N5	133.5 (2)
C16—C15—C14	120.8 (2)	N1—C5—N5	119.97 (19)
C16—C15—H15	119.6	C5—N5—H5A	108.7
C14—C15—H15	119.6	C5—N5—H5B	109.4
C15—C16—C11	120.3 (2)	H5A—N5—H5B	110.9
C15—C16—H16	119.9
C5—N1—C11—C16	−126.6 (2)	N1—C11—C16—C15	178.16 (19)
N2—N1—C11—C16	63.0 (3)	C5—N1—N2—C3	−1.5 (2)
C5—N1—C11—C12	52.2 (3)	C11—N1—N2—C3	170.23 (19)
N2—N1—C11—C12	−118.2 (2)	N1—N2—C3—C4	0.5 (2)
C16—C11—C12—C13	2.2 (3)	N1—N2—C3—C31	−179.92 (19)
N1—C11—C12—C13	−176.6 (2)	N2—C3—C31—C32	−15.0 (3)
C16—C11—C12—N12	−175.9 (2)	C4—C3—C31—C32	164.5 (2)
N1—C11—C12—N12	5.3 (3)	N2—C3—C31—C36	163.7 (2)
C13—C12—N12—O121	−146.4 (2)	C4—C3—C31—C36	−16.8 (4)
C11—C12—N12—O121	31.8 (3)	C36—C31—C32—C33	−1.3 (4)
C13—C12—N12—O122	32.2 (3)	C3—C31—C32—C33	177.4 (2)
C11—C12—N12—O122	−149.7 (2)	C31—C32—C33—C34	0.6 (4)
C11—C12—C13—C14	−2.7 (3)	C32—C33—C34—C35	0.4 (4)
N12—C12—C13—C14	175.54 (19)	C33—C34—C35—C36	−0.6 (4)
O141—C141—O142—C142	0.7 (3)	C34—C35—C36—C31	−0.2 (4)
C14—C141—O142—C142	−179.44 (19)	C32—C31—C36—C35	1.1 (3)
C12—C13—C14—C15	1.6 (3)	C3—C31—C36—C35	−177.6 (2)
C12—C13—C14—C141	−178.0 (2)	N2—C3—C4—C5	0.7 (3)
O141—C141—C14—C13	177.1 (2)	C31—C3—C4—C5	−178.9 (2)
O142—C141—C14—C13	−2.7 (3)	C3—C4—C5—N1	−1.6 (2)
O141—C141—C14—C15	−2.5 (3)	C3—C4—C5—N5	179.1 (2)
O142—C141—C14—C15	177.68 (19)	N2—N1—C5—C4	2.0 (2)
C13—C14—C15—C16	−0.1 (3)	C11—N1—C5—C4	−169.1 (2)
C141—C14—C15—C16	179.5 (2)	N2—N1—C5—N5	−178.54 (19)
C14—C15—C16—C11	−0.3 (3)	C11—N1—C5—N5	10.4 (3)
C12—C11—C16—C15	−0.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···N2^i	0.87	2.33	3.131 (3)	154
N5—H5B···O141^ii	0.87	2.18	3.024 (3)	163
C16—H16···O121^i	0.95	2.39	3.304 (3)	161

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z−1/2.

(II) methyl 3-nitro-4-[(5-phenyl-1H-pyrazol-3-yl)amino]benzoate

Crystal data

C17H14N4O4	F(000) = 1408
Mr = 338.32	Dx = 1.504 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3420 reflections
a = 31.0506 (4) Å	θ = 3.1–27.5°
b = 5.4210 (11) Å	µ = 0.11 mm^−1
c = 20.7251 (12) Å	T = 120 K
β = 121.071 (6)°	Lath, orange
V = 2988.1 (7) Å^3	0.50 × 0.29 × 0.28 mm
Z = 8

Data collection

Bruker–Nonius KappaCCD diffractometer	3420 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2488 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ & ω scans	h = −40→40
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −6→7
Tmin = 0.947, Tmax = 0.967	l = −26→26
33526 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 4.6327P] where P = (Fo^2 + 2Fc^2)/3
3420 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.59810 (6)	0.7513 (3)	0.60667 (8)	0.0228 (4)
N2	0.63253 (6)	0.7928 (3)	0.68076 (8)	0.0214 (3)
C3	0.66832 (6)	0.6152 (3)	0.71231 (9)	0.0184 (4)
C31	0.70897 (6)	0.6193 (3)	0.79170 (9)	0.0182 (4)
C32	0.74389 (7)	0.4276 (4)	0.82041 (10)	0.0219 (4)
C33	0.78193 (7)	0.4238 (4)	0.89564 (10)	0.0238 (4)
C34	0.78548 (7)	0.6121 (4)	0.94348 (10)	0.0238 (4)
C35	0.75135 (7)	0.8050 (4)	0.91523 (10)	0.0238 (4)
C36	0.71360 (7)	0.8107 (4)	0.84023 (10)	0.0216 (4)
C4	0.65743 (7)	0.4485 (3)	0.65562 (10)	0.0202 (4)
C5	0.61378 (6)	0.5413 (3)	0.59205 (9)	0.0195 (4)
C51	0.54722 (6)	0.4771 (3)	0.45658 (9)	0.0183 (4)
C52	0.52986 (6)	0.3312 (3)	0.39047 (9)	0.0178 (4)
N5	0.59048 (6)	0.4223 (3)	0.52237 (8)	0.0212 (3)
N52	0.55736 (5)	0.1186 (3)	0.38848 (8)	0.0200 (3)
O521	0.59647 (5)	0.0523 (3)	0.44756 (7)	0.0265 (3)
O522	0.54173 (5)	0.0068 (2)	0.32903 (7)	0.0259 (3)
C53	0.48594 (6)	0.3880 (3)	0.32318 (10)	0.0185 (4)
C54	0.45787 (6)	0.5917 (3)	0.31831 (9)	0.0188 (4)
C541	0.41265 (7)	0.6645 (3)	0.24683 (10)	0.0194 (4)
O541	0.38721 (5)	0.8454 (3)	0.23954 (7)	0.0258 (3)
O542	0.40194 (5)	0.5128 (2)	0.18978 (7)	0.0227 (3)
C542	0.35970 (7)	0.5849 (4)	0.11720 (10)	0.0251 (4)
C55	0.47383 (7)	0.7361 (3)	0.38303 (10)	0.0205 (4)
C56	0.51666 (7)	0.6817 (3)	0.44995 (10)	0.0203 (4)
H2	0.6277	0.9160	0.7034	0.026*
H32	0.7416	0.2977	0.7880	0.026*
H33	0.8055	0.2923	0.9144	0.029*
H34	0.8111	0.6088	0.9952	0.029*
H35	0.7539	0.9349	0.9478	0.029*
H36	0.6907	0.9451	0.8215	0.026*
H4	0.6754	0.3028	0.6588	0.024*
H5	0.6041	0.2833	0.5213	0.025*
H53	0.4752	0.2856	0.2803	0.022*
H54A	0.3296	0.6018	0.1209	0.038*
H54B	0.3538	0.4586	0.0797	0.038*
H54C	0.3671	0.7429	0.1020	0.038*
H55	0.4544	0.8754	0.3803	0.025*
H56	0.5261	0.7827	0.4927	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0213 (8)	0.0255 (9)	0.0162 (8)	0.0016 (7)	0.0058 (6)	−0.0031 (6)
N2	0.0215 (8)	0.0225 (8)	0.0152 (7)	0.0019 (6)	0.0059 (6)	−0.0038 (6)
C3	0.0164 (8)	0.0219 (9)	0.0178 (8)	0.0002 (7)	0.0094 (7)	0.0000 (7)
C31	0.0175 (8)	0.0208 (9)	0.0165 (8)	−0.0024 (7)	0.0088 (7)	0.0010 (7)
C32	0.0222 (9)	0.0220 (9)	0.0218 (9)	0.0014 (7)	0.0115 (8)	−0.0002 (7)
C33	0.0211 (9)	0.0247 (10)	0.0236 (9)	0.0034 (8)	0.0101 (8)	0.0043 (8)
C34	0.0196 (9)	0.0300 (10)	0.0179 (9)	−0.0019 (8)	0.0069 (7)	0.0000 (8)
C35	0.0230 (9)	0.0263 (10)	0.0199 (9)	−0.0021 (8)	0.0096 (8)	−0.0051 (7)
C36	0.0204 (9)	0.0231 (9)	0.0194 (9)	0.0017 (7)	0.0088 (7)	0.0006 (7)
C4	0.0204 (9)	0.0209 (9)	0.0185 (8)	0.0000 (7)	0.0094 (7)	−0.0007 (7)
C5	0.0187 (8)	0.0234 (9)	0.0151 (8)	−0.0018 (7)	0.0079 (7)	−0.0008 (7)
C51	0.0178 (8)	0.0210 (9)	0.0166 (8)	−0.0024 (7)	0.0092 (7)	−0.0004 (7)
C52	0.0182 (8)	0.0174 (9)	0.0189 (9)	0.0003 (7)	0.0103 (7)	−0.0002 (7)
N5	0.0200 (7)	0.0223 (8)	0.0176 (7)	0.0018 (6)	0.0070 (6)	−0.0034 (6)
N52	0.0194 (7)	0.0218 (8)	0.0176 (7)	−0.0011 (6)	0.0087 (6)	−0.0010 (6)
O521	0.0199 (6)	0.0297 (8)	0.0203 (7)	0.0060 (6)	0.0036 (5)	−0.0034 (5)
O522	0.0295 (7)	0.0262 (7)	0.0184 (6)	0.0033 (6)	0.0098 (6)	−0.0048 (5)
C53	0.0194 (8)	0.0196 (9)	0.0164 (8)	−0.0032 (7)	0.0091 (7)	−0.0017 (7)
C54	0.0172 (8)	0.0207 (9)	0.0178 (8)	−0.0011 (7)	0.0086 (7)	0.0010 (7)
C541	0.0198 (8)	0.0208 (9)	0.0185 (9)	−0.0017 (7)	0.0105 (7)	−0.0015 (7)
O541	0.0238 (7)	0.0282 (7)	0.0206 (7)	0.0062 (6)	0.0080 (6)	−0.0011 (5)
O542	0.0217 (6)	0.0240 (7)	0.0165 (6)	0.0009 (5)	0.0056 (5)	−0.0031 (5)
C542	0.0233 (9)	0.0301 (10)	0.0152 (9)	−0.0007 (8)	0.0052 (7)	−0.0012 (8)
C55	0.0209 (9)	0.0196 (9)	0.0202 (9)	0.0013 (7)	0.0102 (7)	−0.0001 (7)
C56	0.0198 (8)	0.0231 (9)	0.0175 (8)	−0.0031 (7)	0.0094 (7)	−0.0034 (7)

Geometric parameters (Å, º)

N1—C5	1.333 (2)	C51—C52	1.425 (2)
N1—N2	1.363 (2)	C52—C53	1.391 (2)
N2—C3	1.356 (2)	C53—C54	1.378 (3)
N2—H2	0.87	C54—C55	1.404 (2)
C3—C4	1.379 (2)	C55—C56	1.370 (3)
C3—C31	1.469 (2)	C56—C51	1.419 (3)
C31—C32	1.394 (3)	C52—N52	1.448 (2)
C31—C36	1.400 (3)	N5—H5	0.87
C32—C33	1.388 (2)	N52—O521	1.2522 (19)
C32—H32	0.95	N52—O522	1.2262 (19)
C33—C34	1.387 (3)	C53—H53	0.95
C33—H33	0.95	C54—C541	1.475 (2)
C34—C35	1.385 (3)	C541—O541	1.219 (2)
C34—H34	0.95	C541—O542	1.334 (2)
C35—C36	1.382 (3)	O542—C542	1.449 (2)
C35—H35	0.95	C542—H54A	0.98
C36—H36	0.95	C542—H54B	0.98
C4—C5	1.408 (2)	C542—H54C	0.98
C4—H4	0.95	C55—H55	0.95
C5—N5	1.395 (2)	C56—H56	0.95
C51—N5	1.364 (2)
C5—N1—N2	103.36 (14)	C56—C51—C52	116.00 (16)
C3—N2—N1	113.40 (15)	C53—C52—C51	121.99 (16)
C3—N2—H2	127.5	C53—C52—N52	115.77 (15)
N1—N2—H2	118.7	C51—C52—N52	122.23 (15)
N2—C3—C4	105.95 (15)	C51—N5—C5	130.60 (16)
N2—C3—C31	123.09 (16)	C51—N5—H5	113.8
C4—C3—C31	130.96 (16)	C5—N5—H5	115.3
C32—C31—C36	118.49 (16)	O522—N52—O521	121.46 (15)
C32—C31—C3	119.75 (16)	O522—N52—C52	119.26 (14)
C36—C31—C3	121.76 (16)	O521—N52—C52	119.28 (14)
C33—C32—C31	120.94 (17)	C54—C53—C52	120.40 (16)
C33—C32—H32	119.5	C54—C53—H53	119.8
C31—C32—H32	119.5	C52—C53—H53	119.8
C34—C33—C32	119.98 (17)	C53—C54—C55	118.61 (16)
C34—C33—H33	120.0	C53—C54—C541	121.75 (16)
C32—C33—H33	120.0	C55—C54—C541	119.61 (16)
C35—C34—C33	119.47 (17)	O541—C541—O542	122.48 (16)
C35—C34—H34	120.3	O541—C541—C54	124.05 (16)
C33—C34—H34	120.3	O542—C541—C54	113.46 (15)
C36—C35—C34	120.81 (18)	C541—O542—C542	115.60 (14)
C36—C35—H35	119.6	O542—C542—H54A	109.5
C34—C35—H35	119.6	O542—C542—H54B	109.5
C35—C36—C31	120.29 (17)	H54A—C542—H54B	109.5
C35—C36—H36	119.9	O542—C542—H54C	109.5
C31—C36—H36	119.9	H54A—C542—H54C	109.5
C3—C4—C5	104.91 (16)	H54B—C542—H54C	109.5
C3—C4—H4	127.5	C56—C55—C54	121.78 (17)
C5—C4—H4	127.5	C56—C55—H55	119.1
N1—C5—N5	125.10 (16)	C54—C55—H55	119.1
N1—C5—C4	112.37 (16)	C55—C56—C51	121.18 (17)
N5—C5—C4	122.53 (17)	C55—C56—H56	119.4
N5—C51—C56	122.09 (16)	C51—C56—H56	119.4
N5—C51—C52	121.92 (16)
C5—N1—N2—C3	−0.7 (2)	C56—C51—C52—N52	179.27 (15)
N1—N2—C3—C4	0.9 (2)	C56—C51—N5—C5	−1.0 (3)
N1—N2—C3—C31	−179.26 (15)	C52—C51—N5—C5	179.37 (17)
N2—C3—C31—C32	178.86 (17)	N1—C5—N5—C51	−3.7 (3)
C4—C3—C31—C32	−1.4 (3)	C4—C5—N5—C51	176.24 (18)
N2—C3—C31—C36	−0.6 (3)	C53—C52—N52—O522	1.8 (2)
C4—C3—C31—C36	179.14 (18)	C51—C52—N52—O522	−176.73 (16)
C36—C31—C32—C33	1.1 (3)	C53—C52—N52—O521	−177.92 (15)
C3—C31—C32—C33	−178.41 (16)	C51—C52—N52—O521	3.6 (2)
C31—C32—C33—C34	0.2 (3)	C51—C52—C53—C54	0.7 (3)
C32—C33—C34—C35	−1.1 (3)	N52—C52—C53—C54	−177.77 (15)
C33—C34—C35—C36	0.6 (3)	C52—C53—C54—C55	−1.7 (3)
C34—C35—C36—C31	0.7 (3)	C52—C53—C54—C541	176.70 (16)
C32—C31—C36—C35	−1.5 (3)	C53—C54—C541—O541	−178.65 (17)
C3—C31—C36—C35	177.94 (17)	C55—C54—C541—O541	−0.3 (3)
N2—C3—C4—C5	−0.71 (19)	C53—C54—C541—O542	1.1 (2)
C31—C3—C4—C5	179.51 (18)	C55—C54—C541—O542	179.46 (15)
N2—N1—C5—N5	−179.79 (16)	O541—C541—O542—C542	3.5 (2)
N2—N1—C5—C4	0.2 (2)	C54—C541—O542—C542	−176.23 (15)
C3—C4—C5—N1	0.3 (2)	C53—C54—C55—C56	1.0 (3)
C3—C4—C5—N5	−179.67 (16)	C541—C54—C55—C56	−177.40 (17)
N5—C51—C52—C53	−179.51 (16)	C54—C55—C56—C51	0.6 (3)
C56—C51—C52—C53	0.8 (3)	N5—C51—C56—C55	178.84 (17)
N5—C51—C52—N52	−1.1 (3)	C52—C51—C56—C55	−1.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···O521	0.87	1.89	2.600 (2)	137
N2—H2···O541^i	0.87	1.96	2.828 (2)	171
C36—H36···O541^i	0.95	2.36	3.266 (3)	159
C53—H53···O522^ii	0.95	2.54	3.487 (2)	173

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