Dimethyl 1-(2-cyano-benz-yl)-1H-pyrazole-3,5-dicarboxyl-ate.

In the mol-ecule of the title compound, C(15)H(13)N(3)O(4), the dihedral angle between the pyrazole and benzene rings is 79.89 (6)°. An intra-molecular C-H⋯O hydrogen bond is present. The crystal structure is stabilized by π-π stacking inter-actions between centrosymmetrically related pyrazole rings with a centroid-centroid distance of 3.500 (3) Å.

Related literature

For the use of pyrazoles as ligands, see: Dvorak et al. (2005 ▶). For the use of nitrile derivatives in the synthesis of heterocyclic compounds, see: Radl et al. (2000 ▶). For a related structure, see: Fu & Zhao (2007 ▶).

Experimental

Crystal data

C15H13N3O4

M = 299.28

Monoclinic,

a = 7.2416 (19) Å

b = 10.977 (3) Å

c = 18.405 (4) Å

β = 100.670 (11)°

V = 1437.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 291 K

0.35 × 0.30 × 0.25 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.968, T max = 0.980

14431 measured reflections

3287 independent reflections

2452 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.130

S = 1.09

3287 reflections

201 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); 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/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015153/rz2312sup1.cif

Structure factors: contains datablocks I, I. DOI: 10.1107/S1600536809015153/rz2312Isup2.hkl

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

C15H13N3O4	F(000) = 624
Mr = 299.28	Dx = 1.383 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3210 reflections
a = 7.2416 (19) Å	θ = 2.9–27.5°
b = 10.977 (3) Å	µ = 0.10 mm−1
c = 18.405 (4) Å	T = 291 K
β = 100.670 (11)°	Prism, colourless
V = 1437.7 (6) Å3	0.35 × 0.30 × 0.25 mm
Z = 4

Rigaku SCXmini diffractometer	3287 independent reflections
Radiation source: fine-focus sealed tube	2452 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 2.9°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
Tmin = 0.968, Tmax = 0.980	l = −23→23
14431 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0618P)2 + 0.1406P] where P = (Fo2 + 2Fc2)/3
3287 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.19 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	0.7452 (2)	−0.11741 (14)	−0.00030 (8)	0.0384 (4)
C2	0.7207 (2)	0.00398 (14)	−0.02209 (9)	0.0384 (4)
H2	0.6593	0.0337	−0.0675	0.046*
C3	0.8066 (2)	0.07034 (14)	0.03796 (9)	0.0369 (4)
C4	0.6825 (2)	−0.22943 (15)	−0.04182 (9)	0.0430 (4)
C5	0.5284 (3)	−0.3033 (2)	−0.15741 (12)	0.0698 (6)
H5A	0.6333	−0.3544	−0.1618	0.105*
H5B	0.4715	−0.2736	−0.2054	0.105*
H5C	0.4378	−0.3494	−0.1368	0.105*
C6	0.8293 (2)	0.20236 (15)	0.04805 (9)	0.0419 (4)
C7	0.7579 (3)	0.39182 (17)	−0.01060 (12)	0.0691 (6)
H7A	0.6940	0.4259	0.0259	0.104*
H7B	0.7038	0.4234	−0.0584	0.104*
H7C	0.8886	0.4132	0.0009	0.104*
C8	0.9833 (2)	0.00848 (16)	0.16631 (9)	0.0438 (4)
H8A	1.0696	0.0758	0.1655	0.053*
H8B	1.0572	−0.0635	0.1826	0.053*
C9	0.8571 (2)	0.03652 (14)	0.22102 (9)	0.0409 (4)
C10	0.9142 (2)	0.11795 (15)	0.27911 (9)	0.0455 (4)
C11	0.8042 (3)	0.13819 (17)	0.33260 (10)	0.0572 (5)
H11	0.8447	0.1919	0.3714	0.069*
C12	0.6365 (3)	0.0788 (2)	0.32785 (11)	0.0639 (5)
H12	0.5623	0.0924	0.3633	0.077*
C13	0.5775 (3)	−0.0008 (2)	0.27081 (12)	0.0636 (5)
H13	0.4631	−0.0408	0.2677	0.076*
C14	0.6869 (3)	−0.02201 (17)	0.21785 (10)	0.0519 (4)
H14	0.6452	−0.0764	0.1796	0.062*
C15	1.0869 (3)	0.18543 (18)	0.28545 (10)	0.0560 (5)
N1	0.87843 (18)	−0.01204 (12)	0.09157 (7)	0.0385 (3)
N2	0.84141 (19)	−0.12686 (12)	0.06921 (7)	0.0414 (3)
N3	1.2207 (3)	0.24250 (19)	0.29236 (11)	0.0811 (6)
O1	0.7088 (2)	−0.33067 (12)	−0.01849 (7)	0.0649 (4)
O2	0.5924 (2)	−0.20179 (11)	−0.10967 (7)	0.0574 (4)
O3	0.9169 (2)	0.25110 (12)	0.10214 (7)	0.0645 (4)
O4	0.7390 (2)	0.26063 (10)	−0.01091 (7)	0.0568 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0436 (9)	0.0354 (8)	0.0381 (9)	0.0005 (7)	0.0124 (7)	0.0002 (6)
C2	0.0426 (9)	0.0358 (8)	0.0364 (8)	0.0020 (6)	0.0068 (7)	−0.0002 (6)
C3	0.0405 (8)	0.0315 (8)	0.0404 (8)	0.0021 (6)	0.0121 (7)	0.0012 (6)
C4	0.0520 (10)	0.0354 (9)	0.0437 (9)	−0.0026 (7)	0.0140 (8)	−0.0022 (7)
C5	0.0987 (17)	0.0559 (12)	0.0525 (12)	−0.0175 (11)	0.0084 (11)	−0.0181 (9)
C6	0.0468 (9)	0.0367 (9)	0.0433 (9)	0.0000 (7)	0.0112 (7)	−0.0030 (7)
C7	0.1012 (17)	0.0315 (10)	0.0721 (14)	−0.0033 (10)	0.0092 (12)	0.0056 (9)
C8	0.0463 (9)	0.0459 (10)	0.0377 (9)	0.0035 (7)	0.0041 (7)	−0.0006 (7)
C9	0.0487 (9)	0.0368 (8)	0.0366 (8)	0.0070 (7)	0.0058 (7)	0.0040 (6)
C10	0.0579 (10)	0.0394 (9)	0.0377 (9)	0.0082 (7)	0.0050 (8)	0.0025 (7)
C11	0.0759 (13)	0.0531 (12)	0.0438 (10)	0.0114 (9)	0.0148 (10)	−0.0049 (8)
C12	0.0738 (14)	0.0707 (14)	0.0537 (11)	0.0150 (11)	0.0288 (10)	0.0053 (10)
C13	0.0589 (12)	0.0713 (14)	0.0646 (13)	−0.0013 (10)	0.0220 (10)	0.0057 (10)
C14	0.0577 (11)	0.0501 (11)	0.0484 (10)	−0.0008 (8)	0.0114 (9)	−0.0012 (8)
C15	0.0632 (12)	0.0537 (12)	0.0484 (10)	0.0007 (9)	0.0030 (9)	−0.0093 (8)
N1	0.0453 (8)	0.0350 (7)	0.0356 (7)	0.0015 (5)	0.0089 (6)	−0.0003 (5)
N2	0.0523 (8)	0.0324 (7)	0.0407 (7)	0.0006 (6)	0.0122 (6)	0.0003 (5)
N3	0.0735 (13)	0.0847 (14)	0.0806 (14)	−0.0193 (11)	0.0024 (10)	−0.0156 (11)
O1	0.0995 (11)	0.0333 (7)	0.0601 (8)	−0.0036 (7)	0.0103 (8)	0.0019 (6)
O2	0.0811 (9)	0.0403 (7)	0.0458 (7)	−0.0055 (6)	−0.0011 (6)	−0.0065 (5)
O3	0.0864 (10)	0.0431 (7)	0.0573 (8)	−0.0058 (7)	−0.0037 (7)	−0.0088 (6)
O4	0.0792 (9)	0.0307 (6)	0.0555 (8)	0.0007 (6)	−0.0005 (7)	0.0026 (5)

C1—N2	1.343 (2)	C7—H7C	0.9600
C1—C2	1.393 (2)	C8—N1	1.460 (2)
C1—C4	1.474 (2)	C8—C9	1.512 (2)
C2—C3	1.373 (2)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C3—N1	1.368 (2)	C9—C14	1.381 (3)
C3—C6	1.466 (2)	C9—C10	1.396 (2)
C4—O1	1.194 (2)	C10—C11	1.394 (3)
C4—O2	1.332 (2)	C10—C15	1.440 (3)
C5—O2	1.441 (2)	C11—C12	1.367 (3)
C5—H5A	0.9600	C11—H11	0.9300
C5—H5B	0.9600	C12—C13	1.372 (3)
C5—H5C	0.9600	C12—H12	0.9300
C6—O3	1.202 (2)	C13—C14	1.385 (3)
C6—O4	1.324 (2)	C13—H13	0.9300
C7—O4	1.446 (2)	C14—H14	0.9300
C7—H7A	0.9600	C15—N3	1.141 (3)
C7—H7B	0.9600	N1—N2	1.3376 (18)
N2—C1—C2	111.35 (14)	C9—C8—H8A	109.1
N2—C1—C4	119.02 (14)	N1—C8—H8B	109.1
C2—C1—C4	129.63 (15)	C9—C8—H8B	109.1
C3—C2—C1	105.13 (14)	H8A—C8—H8B	107.8
C3—C2—H2	127.4	C14—C9—C10	117.76 (16)
C1—C2—H2	127.4	C14—C9—C8	121.46 (15)
N1—C3—C2	106.57 (13)	C10—C9—C8	120.69 (16)
N1—C3—C6	122.89 (14)	C11—C10—C9	121.04 (18)
C2—C3—C6	130.53 (15)	C11—C10—C15	117.53 (17)
O1—C4—O2	124.53 (16)	C9—C10—C15	121.42 (16)
O1—C4—C1	125.21 (16)	C12—C11—C10	119.74 (18)
O2—C4—C1	110.25 (14)	C12—C11—H11	120.1
O2—C5—H5A	109.5	C10—C11—H11	120.1
O2—C5—H5B	109.5	C11—C12—C13	119.98 (18)
H5A—C5—H5B	109.5	C11—C12—H12	120.0
O2—C5—H5C	109.5	C13—C12—H12	120.0
H5A—C5—H5C	109.5	C12—C13—C14	120.5 (2)
H5B—C5—H5C	109.5	C12—C13—H13	119.7
O3—C6—O4	124.65 (16)	C14—C13—H13	119.7
O3—C6—C3	125.05 (16)	C9—C14—C13	120.93 (18)
O4—C6—C3	110.30 (14)	C9—C14—H14	119.5
O4—C7—H7A	109.5	C13—C14—H14	119.5
O4—C7—H7B	109.5	N3—C15—C10	177.0 (2)
H7A—C7—H7B	109.5	N2—N1—C3	111.90 (13)
O4—C7—H7C	109.5	N2—N1—C8	118.35 (13)
H7A—C7—H7C	109.5	C3—N1—C8	129.75 (14)
H7B—C7—H7C	109.5	N1—N2—C1	105.04 (12)
N1—C8—C9	112.67 (14)	C4—O2—C5	116.21 (14)
N1—C8—H8A	109.1	C6—O4—C7	116.47 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O3	0.97	2.41	2.917 (2)	112

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O3	0.97	2.41	2.917 (2)	112