Dimethyl 1-cyano­methyl-1H-pyrazole-3,5-dicarboxyl­ate

Qu, Z.-R.

doi:10.1107/S160053680902306X

organic compounds

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Volume 65| Part 7| July 2009| Page o1646

doi:10.1107/S160053680902306X

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Dimethyl 1-cyanomethyl-1H-pyrazole-3,5-dicarboxylate

Zhi-Rong Qu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: quzr@seu.edu.cn

(Received 2 June 2009; accepted 16 June 2009; online 20 June 2009)

The title molecule, C₉H₉N₃O₄, syhthesized from 1H-pyrazole-3,5-dicarboxylic acid and 2-bromoacetonitrile, is approximately planar; the interplanar 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_r = 223.19
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.063
wR(F²) = 0.177
S = 1.07
2356 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.25 e Å⁻³

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) -x+1, -y, -z+2.

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 ).

Supporting information

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

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

checkCIF report

Comment top

Pyrazole-related molecules have attracted considerable attention due to their biological activities (Lee et al., 1989; Chambers et al., 1985). In addition, the nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000). We have reported many nitrile compounds (Dai et al., 2008; Fu et al., 2007; Xiao et al., 2008). Here we report another nitrile compound, which was prepared from 1H-pyrazole-3,5-dicarboxylate and 2-bromoacetonitrile.

The title molecule, C₉H₉N₃O₄, syhthesized from 1H-pyrazole-3,5-dicarboxylate and 2-bromoacetonitrile, is nearly planar; the interplanar angles between the pyrazole ring and the mean planes of the carboxlate units and the acetonitrile unit are 4.49 (10), 5.56 (9) and 5.03 (19) respectively. No classical hydrogen bonds were found, but the weak hydrogen bond C2—H2 ···O3 (Table 1) connects molecule into a linear chain, and the structure is stablized by π-π stacking interactions [3.793 (4) Å] between the neighbouring pyrazole rings. (Table 2).

Related literature top

For details of the preparation of nitrile compound, 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 top

1H-pyrazole-3,5-dicarboxylic acid dimethyl ester (0.185 mg, 1 mmol) and 2-bromoacetonitrile (0.119 mg,1 mmol) were dissolved in acetone in the presence of K₂CO₃ (0.138 mg,1 mmol) and heated to 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 from a solution of 100 mg in 15 ml diethylether by slow evaporation after 7 days.

Computing details top

Data collection: CystalClear (Rigaku, 2005); cell refinement: CystalClear (Rigaku, 2005); data reduction: CystalClear (Rigaku, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with the displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound, showing the structure along the b axis. Hydrogen bonds are shown as dashed lines.

Dimethyl 1-cyanomethyl-1H-pyrazole-3,5-dicarboxylate top

Crystal data top

C₉H₉N₃O₄	V = 523.2 (8) Å³
M_r = 223.19	Z = 2
Triclinic, P1	F(000) = 232
a = 6.865 (6) Å	D_x = 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

Data collection top

Rigaku SCXmini diffractometer	2356 independent reflections
Radiation source: fine-focus sealed tube	1363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −8→8
T_min = 0.977, T_max = 0.983	k = −10→10
5303 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.0798P)² + 0.0028P] where P = (F_o² + 2F_c²)/3
2356 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₉H₉N₃O₄	γ = 68.195 (6)°
M_r = 223.19	V = 523.2 (8) Å³
Triclinic, P1	Z = 2
a = 6.865 (6) Å	Mo Kα radiation
b = 7.779 (7) Å	µ = 0.11 mm⁻¹
c = 11.133 (11) Å	T = 293 K
α = 71.633 (8)°	0.25 × 0.17 × 0.15 mm
β = 80.625 (10)°

Data collection top

Rigaku SCXmini diffractometer	2356 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1363 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.983	R_int = 0.042
5303 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.177	H-atom parameters constrained
S = 1.07	Δρ_max = 0.14 e Å⁻³
2356 reflections	Δρ_min = −0.25 e Å⁻³
147 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₄
M_r	223.19
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.865 (6), 7.779 (7), 11.133 (11)
α, β, γ (°)	71.633 (8), 80.625 (10), 68.195 (6)
V (Å³)	523.2 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.25 × 0.17 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.977, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	5303, 2356, 1363
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.177, 1.07
No. of reflections	2356
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.25

Computer programs: CystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.33	3.256 (4)	176.0

Symmetry code: (i) −x+1, −y, −z+2.

π-π interaction (Å, °) top

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

Symmetry codes: (i) 1-x, 1-y, 2-z. Cg1 is the centroid of ring N1, N2, C1, C2, C3. α is the dihedral angle between the planes τ is the angle subtended by the plane normal to the centroid–centroid vector.

Acknowledgements

This work was supported by the Technical Fund Financing Projects (No. 9207042464 and 9207041482) from Southeast University to ZRQ.

References

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