Dimethyl 1-cyano-methyl-1H-pyrazole-3,5-dicarboxyl-ate.

The title mol-ecule, C(9)H(9)N(3)O(4), syhthesized from 1H-pyrazole-3,5-dicarboxylic acid and 2-bromo-acetonitrile, is approximately planar; the inter-planar angles between the pyrazole ring and the mean planes of the two carboxylate units and the cyanomethyl unit are 4.49 (10), 5.56 (9) and 5.03 (19)°, respectively. In the crystal, inversion dimers linked by pairs of weak C-H ⋯O bonds occur, and the packing is further stabilized by aromatic π-π stacking [centroid-centroid separation = 3.793 (4) Å].

Related literature

For details of the preparation of nitrile compounds, see: Lee et al.(1989 ▶); Chambers et al. (1985 ▶). For the chemistry of pyrazole-related compounds, see: Radl et al. (2000 ▶); Dai et al. (2008 ▶); Fu et al. (2007 ▶); Xiao et al. (2008 ▶).

Experimental

Crystal data

C9H9N3O4

M = 223.19

Triclinic,

a = 6.865 (6) Å

b = 7.779 (7) Å

c = 11.133 (11) Å

α = 71.633 (8)°

β = 80.625 (10)°

γ = 68.195 (6)°

V = 523.2 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.25 × 0.17 × 0.15 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.977, T max = 0.983

5303 measured reflections

2356 independent reflections

1363 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.177

S = 1.07

2356 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.25 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 (Sheldrick, 2008 ▶); software used to prepare material for publication: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902306X/kp2222sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902306X/kp2222Isup2.hkl

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

C9H9N3O4	V = 523.2 (8) Å3
Mr = 223.19	Z = 2
Triclinic, P1	F(000) = 232
a = 6.865 (6) Å	Dx = 1.417 Mg m−3
b = 7.779 (7) Å	Mo Kα radiation, λ = 0.71073 Å
c = 11.133 (11) Å	µ = 0.11 mm−1
α = 71.633 (8)°	T = 293 K
β = 80.625 (10)°	Prism, colourless
γ = 68.195 (6)°	0.25 × 0.17 × 0.15 mm

Rigaku SCXmini diffractometer	2356 independent reflections
Radiation source: fine-focus sealed tube	1363 reflections with I > 2σ(I)
graphite	Rint = 0.042
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −8→8
Tmin = 0.977, Tmax = 0.983	k = −10→10
5303 measured reflections	l = −14→14

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0798P)2 + 0.0028P] where P = (Fo2 + 2Fc2)/3
2356 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.25 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	0.3907 (4)	0.3854 (3)	0.8442 (2)	0.0532 (6)
C2	0.3416 (4)	0.3412 (3)	0.9739 (2)	0.0526 (6)
H2	0.3711	0.2192	1.0311	0.063*
C3	0.2401 (4)	0.5159 (3)	1.0001 (2)	0.0499 (6)
C4	0.1549 (4)	0.5643 (4)	1.1201 (2)	0.0546 (6)
C5	0.1088 (6)	0.4259 (5)	1.3408 (3)	0.0854 (10)
H5A	0.2016	0.4738	1.3658	0.128*
H5B	0.1149	0.3033	1.3989	0.128*
H5C	−0.0322	0.5153	1.3414	0.128*
C6	0.5019 (4)	0.2473 (4)	0.7684 (3)	0.0598 (7)
C7	0.6214 (6)	0.2060 (4)	0.5643 (3)	0.0843 (10)
H7A	0.7659	0.1417	0.5851	0.126*
H7B	0.6136	0.2814	0.4773	0.126*
H7C	0.5551	0.1121	0.5772	0.126*
C8	0.1385 (5)	0.8634 (3)	0.8624 (3)	0.0684 (8)
H8A	−0.0104	0.8971	0.8865	0.082*
H8B	0.2023	0.9057	0.9142	0.082*
C9	0.1666 (5)	0.9611 (4)	0.7305 (3)	0.0727 (8)
N1	0.2333 (3)	0.6541 (3)	0.88623 (19)	0.0519 (5)
N2	0.3246 (3)	0.5768 (3)	0.7904 (2)	0.0554 (6)
N3	0.1808 (6)	1.0496 (4)	0.6284 (3)	0.1128 (12)
O1	0.0817 (3)	0.7247 (3)	1.13202 (17)	0.0727 (6)
O2	0.1727 (3)	0.4040 (3)	1.21396 (18)	0.0693 (6)
O3	0.5740 (4)	0.0765 (3)	0.8165 (2)	0.0895 (8)
O4	0.5140 (3)	0.3323 (2)	0.64578 (17)	0.0697 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0572 (15)	0.0334 (12)	0.0590 (16)	−0.0092 (11)	−0.0024 (12)	−0.0072 (11)
C2	0.0561 (15)	0.0386 (13)	0.0536 (16)	−0.0145 (12)	−0.0002 (12)	−0.0036 (11)
C3	0.0509 (14)	0.0420 (14)	0.0503 (15)	−0.0140 (11)	−0.0028 (11)	−0.0062 (11)
C4	0.0588 (16)	0.0464 (15)	0.0551 (16)	−0.0175 (12)	−0.0031 (12)	−0.0099 (12)
C5	0.114 (3)	0.086 (2)	0.0453 (17)	−0.033 (2)	0.0022 (16)	−0.0077 (15)
C6	0.0692 (18)	0.0396 (14)	0.0589 (17)	−0.0130 (13)	−0.0013 (13)	−0.0057 (12)
C7	0.110 (3)	0.0609 (19)	0.0632 (19)	−0.0110 (17)	0.0130 (17)	−0.0222 (15)
C8	0.090 (2)	0.0368 (13)	0.0594 (18)	−0.0099 (14)	−0.0006 (15)	−0.0041 (12)
C9	0.093 (2)	0.0416 (14)	0.066 (2)	−0.0115 (14)	0.0034 (16)	−0.0100 (13)
N1	0.0597 (12)	0.0375 (11)	0.0487 (12)	−0.0110 (9)	−0.0022 (9)	−0.0058 (9)
N2	0.0631 (13)	0.0401 (12)	0.0516 (13)	−0.0097 (10)	0.0019 (10)	−0.0092 (9)
N3	0.167 (3)	0.0614 (17)	0.073 (2)	−0.0194 (18)	0.0156 (19)	−0.0031 (15)
O1	0.0984 (15)	0.0522 (12)	0.0589 (12)	−0.0172 (11)	0.0024 (10)	−0.0174 (9)
O2	0.0928 (14)	0.0542 (11)	0.0506 (11)	−0.0238 (10)	0.0010 (9)	−0.0047 (8)
O3	0.136 (2)	0.0370 (11)	0.0682 (14)	−0.0105 (11)	0.0055 (13)	−0.0070 (9)
O4	0.0914 (14)	0.0451 (10)	0.0536 (12)	−0.0108 (10)	0.0064 (10)	−0.0083 (8)

C1—N2	1.344 (3)	C6—O3	1.203 (3)
C1—C2	1.390 (4)	C6—O4	1.320 (3)
C1—C6	1.483 (4)	C7—O4	1.461 (3)
C2—C3	1.378 (3)	C7—H7A	0.9600
C2—H2	0.9300	C7—H7B	0.9600
C3—N1	1.374 (3)	C7—H7C	0.9600
C3—C4	1.472 (4)	C8—C9	1.444 (4)
C4—O1	1.201 (3)	C8—N1	1.464 (3)
C4—O2	1.330 (3)	C8—H8A	0.9700
C5—O2	1.453 (4)	C8—H8B	0.9700
C5—H5A	0.9600	C9—N3	1.139 (4)
C5—H5B	0.9600	N1—N2	1.342 (3)
C5—H5C	0.9600
N2—C1—C2	111.5 (2)	O4—C6—C1	113.0 (2)
N2—C1—C6	121.5 (2)	O4—C7—H7A	109.5
C2—C1—C6	127.0 (2)	O4—C7—H7B	109.5
C3—C2—C1	105.6 (2)	H7A—C7—H7B	109.5
C3—C2—H2	127.2	O4—C7—H7C	109.5
C1—C2—H2	127.2	H7A—C7—H7C	109.5
N1—C3—C2	105.9 (2)	H7B—C7—H7C	109.5
N1—C3—C4	122.6 (2)	C9—C8—N1	111.2 (2)
C2—C3—C4	131.5 (2)	C9—C8—H8A	109.4
O1—C4—O2	124.9 (3)	N1—C8—H8A	109.4
O1—C4—C3	125.2 (2)	C9—C8—H8B	109.4
O2—C4—C3	110.0 (2)	N1—C8—H8B	109.4
O2—C5—H5A	109.5	H8A—C8—H8B	108.0
O2—C5—H5B	109.5	N3—C9—C8	175.4 (3)
H5A—C5—H5B	109.5	N2—N1—C3	112.2 (2)
O2—C5—H5C	109.5	N2—N1—C8	120.3 (2)
H5A—C5—H5C	109.5	C3—N1—C8	127.5 (2)
H5B—C5—H5C	109.5	N1—N2—C1	104.8 (2)
O3—C6—O4	124.8 (3)	C4—O2—C5	116.9 (2)
O3—C6—C1	122.2 (3)	C6—O4—C7	116.4 (2)
N2—C1—C2—C3	−0.1 (3)	C4—C3—N1—N2	178.5 (2)
C6—C1—C2—C3	179.7 (3)	C2—C3—N1—C8	178.9 (2)
C1—C2—C3—N1	0.1 (3)	C4—C3—N1—C8	−2.5 (4)
C1—C2—C3—C4	−178.3 (3)	C9—C8—N1—N2	−2.1 (4)
N1—C3—C4—O1	−3.7 (4)	C9—C8—N1—C3	178.9 (3)
C2—C3—C4—O1	174.5 (3)	C3—N1—N2—C1	0.1 (3)
N1—C3—C4—O2	176.9 (2)	C8—N1—N2—C1	−179.0 (2)
C2—C3—C4—O2	−4.8 (4)	C2—C1—N2—N1	0.0 (3)
N2—C1—C6—O3	175.0 (3)	C6—C1—N2—N1	−179.8 (2)
C2—C1—C6—O3	−4.7 (4)	O1—C4—O2—C5	−3.5 (4)
N2—C1—C6—O4	−4.3 (4)	C3—C4—O2—C5	175.9 (2)
C2—C1—C6—O4	176.0 (2)	O3—C6—O4—C7	0.8 (4)
N1—C8—C9—N3	176 (5)	C1—C6—O4—C7	−180.0 (2)
C2—C3—N1—N2	−0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3i	0.93	2.33	3.256 (4)	176

Group 1	Group 2	α	Cg–Cg	τ
Cg1	Cg1i	0.03	3.793 (4)	26.14

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3i	0.93	2.33	3.256 (4)	176

Symmetry code: (i) .