Di­methyl 1-(2-cyano­benz­yl)-1H-pyrazole-3,5-di­carboxyl­ate

In the mol­ecule of the title compound, C₁₅H₁₃N₃O₄, the dihedral angle between the pyrazole and benzene rings is 79.89 (6)°. An intra­molecular C—H⋯O hydrogen bond is present. The crystal structure is stabilized by π–π stacking inter­actions 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_r = 299.28

• Monoclinic, P 2₁ /n

• a = 7.2416 (19) Å

• b = 10.977 (3) Å

• c = 18.405 (4) Å

• β = 100.670 (11)°

• V = 1437.7 (6) ų

• 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[F² > 2σ(F²)] = 0.052

• wR(F²) = 0.130

• S = 1.09

• 3287 reflections

• 201 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

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

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.

Supporting information

S1. Comment

Pyrazoles are considered as extremely versatile building blocks in organic chemistry. They constitute key fragments in active pharmaceutical and agrochemical ingredients, which have found widespread use as ligands for transition metals (Dvorak et al., 2005), In addition, nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007). As an extension of our work on the structural characterization of nitrile compounds, the structure of the title compound is reported here.

In the molecule of the title compound (Fig. 1) bond lengths and angles have normal values. The dihedral angle between the planes of the pyrazole and phenyl rings is 79.89 (6) °. The molecular conformation is stabilized by an intramolecular C—H···O hydrogen bond (Table 1). In the crystal packing, centrosymmetrically related molecules at (x, y, z) and (2-x, -y, -z) are connected by a π-π stacking interaction involving the pyrazole rings, with a centroid-centroid separation of 3.500 (3) Å, a perpendicular interplanar distance of 3.382 (3) and a centroid-centroid offset of 0.901 (2) 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).

S2. Experimental

1H-Pyrazole-3,5-dicarboxylic acid dimethyl ester (0.185 mg, 1 mmol) and 2-(bromomethyl)benzonitrile (0.196 mg, 1 mmol) were dissolved in acetone in the presence of K₂CO₃ (0.138 mg, 1 mmol) and heated under reflux for 1 day. After the mixture was cooled to room temperature, the solution was filtered and the solvents removed in vacuum to afford a white precipitate of the title compound. Colourless crystals suitable for X-ray diffraction were obtained after 9 days by slow evaporation of a diethylether solution.

S3. Refinement

All H atoms were detected in a difference Fourier map, but were placed in calculated positions and refined using a riding motion approximation, with C—H = 0.93–0.97 Å and with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Dimethyl 1-(2-cyanobenzyl)-1H-pyrazole-3,5-dicarboxylate

Crystal data

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) Å^3	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	3287 independent reflections
Radiation source: fine-focus sealed tube	2452 reflections with I > 2σ(I)
Graphite monochromator	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

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0618P)^2 + 0.1406P] where P = (Fo^2 + 2Fc^2)/3
3287 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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.

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

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

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