Dimethyl 1-(3-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 ring planes is 67.7 (1)°. The crystal structure is stabilized by an intra-molecular C-H⋯O hydrogen bond and two weak inter-molecular C-H⋯O inter-actions.

Related literature

For the biological activity of pyrazoles, see: Lee et al. (1989 ▶); Chambers et al. (1985 ▶). For the importance of nitrile derivatives in the synthesis of some heterocyclic mol­ecules, see: Radl et al. (2000 ▶). For related structures, see: Fu & Zhao (2007 ▶); Xiao & Zhao (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

C15H13N3O4

M = 299.28

Triclinic,

a = 8.783 (3) Å

b = 9.538 (4) Å

c = 9.999 (4) Å

α = 68.42 (3)°

β = 71.79 (4)°

γ = 82.13 (4)°

V = 739.7 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 292 K

0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.968, T max = 0.979

7555 measured reflections

3338 independent reflections

2093 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.147

S = 1.05

3338 reflections

201 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014895/bx2204sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014895/bx2204Isup2.hkl

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

C15H13N3O4	Z = 2
Mr = 299.28	F(000) = 312
Triclinic, P1	Dx = 1.344 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.783 (3) Å	Cell parameters from 1442 reflections
b = 9.538 (4) Å	θ = 2.4–27.3°
c = 9.999 (4) Å	µ = 0.10 mm−1
α = 68.42 (3)°	T = 292 K
β = 71.79 (4)°	Block, colorless
γ = 82.13 (4)°	0.40 × 0.30 × 0.20 mm
V = 739.7 (5) Å3

Rigaku SCXmini diffractometer	3338 independent reflections
Radiation source: fine-focus sealed tube	2093 reflections with I > 2σ(I)
graphite	Rint = 0.031
Detector resolution: 13.6612 pixels mm-1	θmax = 27.4°, θmin = 2.3°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.968, Tmax = 0.979	l = −12→12
7555 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0636P)2 + 0.0696P] where P = (Fo2 + 2Fc2)/3
3338 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.16 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	0.2466 (2)	0.1608 (2)	0.4437 (2)	0.0473 (5)
C2	0.2324 (2)	0.0151 (2)	0.4487 (2)	0.0485 (5)
H2	0.2544	−0.0753	0.5185	0.058*
C3	0.1787 (2)	0.0343 (2)	0.3276 (2)	0.0453 (5)
C4	0.2972 (2)	0.2120 (3)	0.5461 (2)	0.0530 (5)
C5	0.1399 (2)	−0.0794 (2)	0.2763 (2)	0.0516 (5)
C6	0.1126 (2)	0.2702 (2)	0.1210 (2)	0.0513 (5)
H6A	0.1388	0.2105	0.0561	0.062*
H6B	0.1713	0.3630	0.0669	0.062*
C7	−0.0655 (2)	0.3076 (2)	0.1568 (2)	0.0441 (5)
C8	−0.1362 (3)	0.3905 (2)	0.2511 (2)	0.0548 (5)
H8	−0.0735	0.4208	0.2948	0.066*
C9	−0.2976 (3)	0.4282 (3)	0.2806 (3)	0.0618 (6)
H9	−0.3429	0.4818	0.3453	0.074*
C10	−0.3928 (3)	0.3868 (2)	0.2143 (2)	0.0564 (6)
H10	−0.5012	0.4135	0.2327	0.068*
C11	−0.3234 (2)	0.3050 (2)	0.1206 (2)	0.0501 (5)
C12	−0.1607 (2)	0.2639 (2)	0.0923 (2)	0.0476 (5)
H12	−0.1163	0.2074	0.0303	0.057*
C13	−0.4218 (3)	0.2621 (3)	0.0498 (3)	0.0625 (6)
C14	0.3840 (4)	0.1361 (3)	0.7627 (3)	0.0947 (10)
H14A	0.4685	0.2077	0.7128	0.142*
H14B	0.4199	0.0470	0.8309	0.142*
H14C	0.2922	0.1797	0.8174	0.142*
C15	0.1386 (3)	−0.3432 (3)	0.3310 (3)	0.0756 (7)
H15A	0.0277	−0.3388	0.3343	0.113*
H15B	0.1612	−0.4358	0.4042	0.113*
H15C	0.2046	−0.3388	0.2329	0.113*
N1	0.2055 (2)	0.26560 (19)	0.32636 (19)	0.0517 (4)
N2	0.16398 (19)	0.18644 (18)	0.25641 (17)	0.0460 (4)
N3	−0.4990 (3)	0.2293 (3)	−0.0067 (3)	0.0878 (7)
O1	0.2979 (2)	0.34090 (19)	0.5354 (2)	0.0816 (6)
O2	0.3407 (2)	0.09684 (17)	0.65206 (18)	0.0724 (5)
O3	0.1723 (2)	−0.21721 (16)	0.36374 (17)	0.0659 (5)
O4	0.0863 (2)	−0.05489 (18)	0.1728 (2)	0.0769 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0473 (12)	0.0513 (12)	0.0480 (12)	−0.0011 (9)	−0.0202 (9)	−0.0170 (9)
C2	0.0510 (12)	0.0492 (12)	0.0461 (12)	−0.0012 (9)	−0.0194 (9)	−0.0126 (9)
C3	0.0429 (11)	0.0480 (11)	0.0461 (11)	−0.0024 (8)	−0.0145 (9)	−0.0153 (9)
C4	0.0528 (13)	0.0599 (14)	0.0562 (13)	0.0044 (10)	−0.0243 (10)	−0.0258 (11)
C5	0.0471 (12)	0.0576 (13)	0.0532 (13)	−0.0022 (9)	−0.0164 (10)	−0.0206 (10)
C6	0.0494 (12)	0.0601 (13)	0.0435 (12)	−0.0053 (9)	−0.0207 (9)	−0.0094 (9)
C7	0.0505 (12)	0.0415 (11)	0.0400 (11)	−0.0054 (8)	−0.0182 (9)	−0.0078 (8)
C8	0.0627 (14)	0.0541 (13)	0.0594 (13)	−0.0035 (10)	−0.0279 (11)	−0.0232 (10)
C9	0.0677 (15)	0.0597 (14)	0.0658 (15)	0.0024 (11)	−0.0194 (12)	−0.0314 (12)
C10	0.0512 (13)	0.0570 (13)	0.0634 (14)	0.0023 (10)	−0.0194 (11)	−0.0219 (11)
C11	0.0499 (12)	0.0522 (12)	0.0526 (12)	−0.0029 (9)	−0.0233 (10)	−0.0151 (9)
C12	0.0529 (12)	0.0511 (12)	0.0459 (11)	−0.0005 (9)	−0.0206 (9)	−0.0195 (9)
C13	0.0509 (13)	0.0758 (16)	0.0698 (16)	0.0021 (11)	−0.0254 (12)	−0.0295 (12)
C14	0.140 (3)	0.098 (2)	0.0809 (19)	0.0188 (18)	−0.075 (2)	−0.0427 (16)
C15	0.097 (2)	0.0552 (15)	0.0804 (18)	−0.0088 (13)	−0.0245 (15)	−0.0280 (13)
N1	0.0544 (10)	0.0532 (10)	0.0552 (11)	−0.0020 (8)	−0.0259 (8)	−0.0185 (8)
N2	0.0464 (9)	0.0503 (10)	0.0446 (9)	−0.0034 (7)	−0.0205 (7)	−0.0131 (7)
N3	0.0656 (14)	0.124 (2)	0.1012 (18)	0.0028 (13)	−0.0437 (13)	−0.0557 (16)
O1	0.1237 (16)	0.0589 (11)	0.0919 (13)	0.0097 (10)	−0.0644 (12)	−0.0358 (9)
O2	0.1047 (14)	0.0650 (10)	0.0687 (11)	0.0110 (9)	−0.0542 (10)	−0.0268 (8)
O3	0.0894 (12)	0.0511 (9)	0.0636 (10)	−0.0076 (8)	−0.0321 (9)	−0.0164 (7)
O4	0.1025 (14)	0.0705 (11)	0.0837 (12)	0.0033 (9)	−0.0579 (11)	−0.0317 (9)

C1—N1	1.345 (2)	C8—H8	0.9300
C1—C2	1.393 (3)	C9—C10	1.387 (3)
C1—C4	1.482 (3)	C9—H9	0.9300
C2—C3	1.375 (2)	C10—C11	1.381 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—N2	1.369 (2)	C11—C12	1.397 (3)
C3—C5	1.475 (3)	C11—C13	1.452 (3)
C4—O1	1.195 (2)	C12—H12	0.9300
C4—O2	1.325 (2)	C13—N3	1.143 (3)
C5—O4	1.201 (2)	C14—O2	1.455 (3)
C5—O3	1.334 (3)	C14—H14A	0.9600
C6—N2	1.471 (2)	C14—H14B	0.9600
C6—C7	1.514 (3)	C14—H14C	0.9600
C6—H6A	0.9700	C15—O3	1.444 (3)
C6—H6B	0.9700	C15—H15A	0.9600
C7—C12	1.385 (2)	C15—H15B	0.9600
C7—C8	1.395 (3)	C15—H15C	0.9600
C8—C9	1.380 (3)	N1—N2	1.347 (2)
N1—C1—C2	111.68 (17)	C10—C9—H9	119.8
N1—C1—C4	118.44 (18)	C11—C10—C9	118.7 (2)
C2—C1—C4	129.88 (18)	C11—C10—H10	120.6
C3—C2—C1	104.90 (17)	C9—C10—H10	120.6
C3—C2—H2	127.6	C10—C11—C12	121.23 (18)
C1—C2—H2	127.6	C10—C11—C13	119.1 (2)
N2—C3—C2	107.05 (17)	C12—C11—C13	119.63 (19)
N2—C3—C5	123.21 (17)	C7—C12—C11	119.83 (19)
C2—C3—C5	129.74 (18)	C7—C12—H12	120.1
O1—C4—O2	124.09 (19)	C11—C12—H12	120.1
O1—C4—C1	124.3 (2)	N3—C13—C11	179.5 (3)
O2—C4—C1	111.57 (19)	O2—C14—H14A	109.5
O4—C5—O3	124.0 (2)	O2—C14—H14B	109.5
O4—C5—C3	126.4 (2)	H14A—C14—H14B	109.5
O3—C5—C3	109.59 (18)	O2—C14—H14C	109.5
N2—C6—C7	112.47 (16)	H14A—C14—H14C	109.5
N2—C6—H6A	109.1	H14B—C14—H14C	109.5
C7—C6—H6A	109.1	O3—C15—H15A	109.5
N2—C6—H6B	109.1	O3—C15—H15B	109.5
C7—C6—H6B	109.1	H15A—C15—H15B	109.5
H6A—C6—H6B	107.8	O3—C15—H15C	109.5
C12—C7—C8	118.64 (19)	H15A—C15—H15C	109.5
C12—C7—C6	120.28 (18)	H15B—C15—H15C	109.5
C8—C7—C6	121.05 (17)	C1—N1—N2	104.90 (16)
C9—C8—C7	121.12 (19)	N1—N2—C3	111.47 (15)
C9—C8—H8	119.4	N1—N2—C6	118.28 (16)
C7—C8—H8	119.4	C3—N2—C6	130.24 (16)
C8—C9—C10	120.4 (2)	C4—O2—C14	115.33 (19)
C8—C9—H9	119.8	C5—O3—C15	117.10 (18)
N1—C1—C2—C3	−0.4 (2)	C9—C10—C11—C13	−179.5 (2)
C4—C1—C2—C3	179.1 (2)	C8—C7—C12—C11	0.9 (3)
C1—C2—C3—N2	0.3 (2)	C6—C7—C12—C11	−177.04 (18)
C1—C2—C3—C5	−179.23 (19)	C10—C11—C12—C7	−1.1 (3)
N1—C1—C4—O1	3.2 (3)	C13—C11—C12—C7	178.51 (18)
C2—C1—C4—O1	−176.3 (2)	C2—C1—N1—N2	0.3 (2)
N1—C1—C4—O2	−177.21 (18)	C4—C1—N1—N2	−179.24 (16)
C2—C1—C4—O2	3.3 (3)	C1—N1—N2—C3	−0.1 (2)
N2—C3—C5—O4	−3.1 (3)	C1—N1—N2—C6	−179.84 (16)
C2—C3—C5—O4	176.4 (2)	C2—C3—N2—N1	−0.1 (2)
N2—C3—C5—O3	177.39 (18)	C5—C3—N2—N1	179.45 (17)
C2—C3—C5—O3	−3.1 (3)	C2—C3—N2—C6	179.55 (18)
N2—C6—C7—C12	−124.57 (19)	C5—C3—N2—C6	−0.9 (3)
N2—C6—C7—C8	57.5 (2)	C7—C6—N2—N1	−87.7 (2)
C12—C7—C8—C9	0.2 (3)	C7—C6—N2—C3	92.6 (2)
C6—C7—C8—C9	178.21 (19)	O1—C4—O2—C14	2.8 (4)
C7—C8—C9—C10	−1.3 (3)	C1—C4—O2—C14	−176.8 (2)
C8—C9—C10—C11	1.1 (3)	O4—C5—O3—C15	−0.6 (3)
C9—C10—C11—C12	0.1 (3)	C3—C5—O3—C15	178.93 (18)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···O1i	0.96	2.43	3.363 (3)	163
C9—H9···O1ii	0.93	2.53	3.348 (3)	147
C6—H6A···O4	0.97	2.41	2.979 (3)	117

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15B⋯O1i	0.96	2.43	3.363 (3)	163
C9—H9⋯O1ii	0.93	2.53	3.348 (3)	147
C6—H6A⋯O4	0.97	2.41	2.979 (3)	117

Symmetry codes: (i) ; (ii) .