supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers buy article online

Acta Cryst. (2007). E63, o2785    [ doi:10.1107/S1600536807019642 ]

Dimethyl 1H-pyrazole-3,5-dicarboxylate

J.-P. Xiao, Q.-X. Zhou and J.-H. Tu

Abstract top

The title compound, C7H8N2O4, is an important precursor of bi- or multidentate ligands. The structure contains two molecules linked together via intermolecular N-H...O and N-H...N hydrogen bonds and intermolecular C-H...O contacts, resulting in a two-dimensional network. All atoms except for methyl H atoms lie on crystallographic mirror planes.

Comment top

Recently, there has been much interest in the study of crystal engineering of supramolecular architectures using N-donor ligands (Zheng et al., 2003; Peng et al., 2006). The title compound, C7H8N2O4, is an important organic intermediate and precursor of bi- or polydentate ligands which have been reported (Schenck et al., 1985; Ardizzoia et al., 2002).

The asymmetric unit contains two molecules linked together via intermolecular N—H··· O(2.80 Å) and N—H··· N (2.92 Å) hydrogen bonds and forming a pseudo dimer(Fig. 1). Futhermore intermolecular C—H··· O contacts (3.24–3.47 Å) satisfy the definition of weak hydrogen bonds as proposed by Taylor et al. (1982) and Desiraju et al. (1999), and resulted in a two dimensional network (Fig. 2). Interestingly, all of the nonH atoms are coplanar. Although the interpalanar distances, 3.25 Å, between stacked pyrazole molecules might indicate π···π stacking, the centroid to centroid distance between pyrazlole rings, 3.70 Å, corresponds to a large offset angle of 28.6 ° which prevents such π···π stacking.

Related literature top

For general background, see: Zheng et al., 2003; Peng et al., 2006; Schenck et al., 1985; Ardizzoia et al., 2002. For structure analysis tools used, see: Taylor et al., 1982; Desiraju et al.,1999.

Experimental top

All reagents were of analytical grade and used without further purification. Dimethyl-1H-pyrazole-3,5-dicarboxylate was prepared by the general procedure of Schenck et al. (1985). Colorless single crystals were grown from slow evaporation of the saturated MeOH solution of the compound. Analysis found: C 45.64, H 4.40, N 15.25%.; calculated for C7H8N2O4: C 45.66, H 4.38, N 15.21%.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93Å (aromatic) or 0.96Å (methyl) and N—H = 0.86Å with Uiso(H) = 1.2Ueq(CH or NH) or Uiso(H) = 1.5Ueq(CH3).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radii and H bonds are represented as dashed lines.
[Figure 2] Fig. 2. Partial packing view showing the hydrogen bonding interactions. H atoms are represented as small spheres of arbitrary radii and H bonds are shown as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry codes: (i) 1 + x, y, z; (ii) 1/2 + x, 1/2 - y, 3/2 - z; (iii) x - 1/2, 1/2 - y, 1/2 - z].
Dimethyl 1H-pyrazole-3,5-dicarboxylate top
Crystal data top
C7H8N2O4F(000) = 768
Mr = 184.15Dx = 1.457 Mg m−3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 2089 reflections
a = 10.9563 (14) Åθ = 5.1–51.9°
b = 6.4983 (8) ŵ = 0.12 mm−1
c = 23.589 (3) ÅT = 293 K
V = 1679.5 (4) Å3Prismatic, colorless
Z = 80.49 × 0.34 × 0.13 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1614 independent reflections
Radiation source: fine-focus sealed tube1196 reflections with I > 2σ(I)
graphiteRint = 0.116
φ and ω scansθmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→11
Tmin = 0.943, Tmax = 0.985k = −7→7
8106 measured reflectionsl = −26→28
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.106 w = 1/[σ2(Fo2) + (0.0538P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
1614 reflectionsΔρmax = 0.17 e Å−3
162 parametersΔρmin = −0.24 e Å−3
5 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.020 (3)
Crystal data top
C7H8N2O4V = 1679.5 (4) Å3
Mr = 184.15Z = 8
Orthorhombic, PnmaMo Kα radiation
a = 10.9563 (14) ŵ = 0.12 mm−1
b = 6.4983 (8) ÅT = 293 K
c = 23.589 (3) Å0.49 × 0.34 × 0.13 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1614 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1196 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.985Rint = 0.116
8106 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.106Δρmax = 0.17 e Å−3
S = 0.97Δρmin = −0.24 e Å−3
1614 reflectionsAbsolute structure: ?
162 parametersFlack parameter: ?
5 restraintsRogers parameter: ?
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. Highest peak 0.17 at 0.6417 0.2500 0.6281 [0.90 A from N2] Deepest hole -0.24 at 0.3595 0.2500 0.4390 [0.95 A from C10]

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.80198 (16)0.25000.71010 (7)0.0603 (5)
O20.98429 (15)0.25000.66789 (6)0.0566 (5)
O30.71755 (15)0.25000.42420 (7)0.0554 (5)
O40.91928 (14)0.25000.43727 (7)0.0509 (5)
O50.19936 (16)0.25000.56690 (7)0.0651 (6)
O60.40030 (16)0.25000.58550 (7)0.0633 (6)
O70.42515 (16)0.25000.30600 (7)0.0669 (6)
O80.22351 (14)0.25000.32051 (6)0.0489 (5)
N10.68713 (16)0.25000.54353 (8)0.0391 (5)
H10.61860.25000.52580.047*
N20.69628 (17)0.25000.59972 (8)0.0405 (5)
N30.46241 (17)0.25000.42244 (8)0.0437 (5)
H30.52870.25000.40290.052*
N40.46048 (16)0.25000.47848 (8)0.0426 (5)
C10.8175 (2)0.25000.60908 (9)0.0377 (6)
C20.8834 (2)0.25000.55897 (9)0.0391 (6)
H20.96780.25000.55480.047*
C30.79727 (19)0.25000.51709 (10)0.0386 (6)
C40.8624 (2)0.25000.66784 (10)0.0418 (6)
C51.0440 (3)0.25000.72248 (10)0.0685 (9)
H5A1.03810.11550.73910.103*0.50
H5B1.00520.34860.74680.103*0.50
H5C1.12840.28590.71780.103*0.50
C60.8042 (2)0.25000.45525 (10)0.0404 (6)
C70.9345 (2)0.25000.37656 (11)0.0694 (9)
H7A1.01650.20970.36730.104*0.50
H7B0.91920.38560.36210.104*0.50
H7C0.87810.15470.35980.104*0.50
C80.3416 (2)0.25000.49172 (9)0.0361 (5)
C90.2694 (2)0.25000.44305 (9)0.0366 (5)
H90.18460.25000.44110.044*
C100.3500 (2)0.25000.39891 (10)0.0385 (6)
C110.3041 (2)0.25000.55114 (10)0.0439 (6)
C120.3778 (3)0.25000.64513 (11)0.0934 (12)
H12A0.35610.11370.65710.140*0.50
H12B0.31220.34290.65360.140*0.50
H12C0.45010.29340.66480.140*0.50
C130.3392 (2)0.25000.33725 (10)0.0439 (6)
C140.2036 (3)0.25000.25984 (11)0.0634 (8)
H14A0.25850.15410.24220.095*0.50
H14B0.21830.38540.24510.095*0.50
H14C0.12090.21040.25200.095*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0492 (11)0.0942 (14)0.0374 (10)0.0000.0117 (9)0.000
O20.0354 (10)0.1019 (14)0.0326 (9)0.000−0.0037 (7)0.000
O30.0294 (10)0.0929 (14)0.0440 (10)0.000−0.0048 (8)0.000
O40.0277 (9)0.0867 (13)0.0382 (9)0.0000.0004 (7)0.000
O50.0399 (12)0.1052 (16)0.0502 (11)0.0000.0107 (9)0.000
O60.0440 (11)0.1088 (15)0.0371 (10)0.000−0.0066 (9)0.000
O70.0404 (11)0.1171 (17)0.0433 (11)0.0000.0096 (9)0.000
O80.0360 (10)0.0784 (12)0.0325 (9)0.000−0.0066 (7)0.000
N10.0261 (10)0.0509 (12)0.0402 (11)0.000−0.0041 (8)0.000
N20.0329 (12)0.0504 (12)0.0384 (11)0.0000.0005 (9)0.000
N30.0260 (11)0.0687 (14)0.0365 (11)0.0000.0016 (8)0.000
N40.0284 (11)0.0613 (13)0.0380 (11)0.000−0.0027 (9)0.000
C10.0273 (12)0.0474 (14)0.0384 (13)0.000−0.0028 (10)0.000
C20.0257 (12)0.0530 (15)0.0387 (13)0.000−0.0004 (10)0.000
C30.0285 (12)0.0452 (14)0.0421 (13)0.000−0.0005 (10)0.000
C40.0334 (13)0.0479 (15)0.0441 (14)0.0000.0032 (11)0.000
C50.0526 (18)0.115 (3)0.0380 (15)0.000−0.0143 (13)0.000
C60.0289 (13)0.0527 (15)0.0396 (13)0.000−0.0010 (11)0.000
C70.0432 (17)0.121 (3)0.0442 (16)0.0000.0064 (13)0.000
C80.0279 (12)0.0412 (13)0.0391 (13)0.000−0.0016 (10)0.000
C90.0267 (12)0.0448 (13)0.0384 (13)0.000−0.0040 (10)0.000
C100.0278 (12)0.0459 (14)0.0418 (13)0.000−0.0034 (11)0.000
C110.0370 (15)0.0541 (15)0.0406 (14)0.000−0.0031 (11)0.000
C120.086 (3)0.161 (3)0.0332 (16)0.000−0.0088 (17)0.000
C130.0353 (14)0.0579 (16)0.0384 (14)0.0000.0014 (11)0.000
C140.0646 (19)0.088 (2)0.0374 (14)0.000−0.0151 (14)0.000
Geometric parameters (Å, °) top
O1—C41.197 (3)C1—C41.471 (3)
O2—C41.335 (3)C2—C31.366 (3)
O2—C51.444 (3)C2—H20.9300
O3—C61.199 (3)C3—C61.461 (3)
O4—C61.330 (3)C5—H5A0.9600
O4—C71.442 (3)C5—H5B0.9600
O5—C111.206 (3)C5—H5C0.9600
O6—C111.330 (3)C7—H7A0.9600
O6—C121.428 (3)C7—H7B0.9600
O7—C131.196 (3)C7—H7C0.9600
O8—C131.327 (3)C8—C91.394 (3)
O8—C141.448 (3)C8—C111.461 (3)
N1—N21.329 (3)C9—C101.366 (3)
N1—C31.358 (3)C9—H90.9300
N1—H10.8600C10—C131.459 (3)
N2—C11.347 (3)C12—H12A0.9600
N3—N41.322 (3)C12—H12B0.9600
N3—C101.351 (3)C12—H12C0.9600
N3—H30.8600C14—H14A0.9600
N4—C81.340 (3)C14—H14B0.9600
C1—C21.385 (3)C14—H14C0.9600
C4—O2—C5116.98 (19)O4—C7—H7A109.5
C6—O4—C7115.25 (18)O4—C7—H7B109.5
C11—O6—C12117.6 (2)H7A—C7—H7B109.5
C13—O8—C14115.95 (19)O4—C7—H7C109.5
N2—N1—C3113.02 (18)H7A—C7—H7C109.5
N2—N1—H1123.5H7B—C7—H7C109.5
C3—N1—H1123.5N4—C8—C9111.1 (2)
N1—N2—C1103.76 (18)N4—C8—C11119.8 (2)
N4—N3—C10113.34 (19)C9—C8—C11129.1 (2)
N4—N3—H3123.3C10—C9—C8105.1 (2)
C10—N3—H3123.3C10—C9—H9127.4
N3—N4—C8104.40 (18)C8—C9—H9127.4
N2—C1—C2111.97 (19)N3—C10—C9106.1 (2)
N2—C1—C4119.0 (2)N3—C10—C13118.9 (2)
C2—C1—C4129.1 (2)C9—C10—C13135.0 (2)
C3—C2—C1104.9 (2)O5—C11—O6124.5 (2)
C3—C2—H2127.5O5—C11—C8124.3 (2)
C1—C2—H2127.5O6—C11—C8111.2 (2)
N1—C3—C2106.34 (19)O6—C12—H12A109.5
N1—C3—C6120.33 (19)O6—C12—H12B109.5
C2—C3—C6133.3 (2)H12A—C12—H12B109.5
O1—C4—O2123.5 (2)O6—C12—H12C109.5
O1—C4—C1126.9 (2)H12A—C12—H12C109.5
O2—C4—C1109.6 (2)H12B—C12—H12C109.5
O2—C5—H5A109.5O7—C13—O8124.7 (2)
O2—C5—H5B109.5O7—C13—C10123.4 (2)
H5A—C5—H5B109.5O8—C13—C10112.0 (2)
O2—C5—H5C109.5O8—C14—H14A109.5
H5A—C5—H5C109.5O8—C14—H14B109.5
H5B—C5—H5C109.5H14A—C14—H14B109.5
O3—C6—O4123.8 (2)O8—C14—H14C109.5
O3—C6—C3124.7 (2)H14A—C14—H14C109.5
O4—C6—C3111.58 (19)H14B—C14—H14C109.5
C3—N1—N2—C10.0C2—C3—C6—O40.0
C10—N3—N4—C80.0N3—N4—C8—C90.0
N1—N2—C1—C20.0N3—N4—C8—C11180.0
N1—N2—C1—C4180.0N4—C8—C9—C100.0
N2—C1—C2—C30.0C11—C8—C9—C10180.0
C4—C1—C2—C3180.0N4—N3—C10—C90.0
N2—N1—C3—C20.0N4—N3—C10—C13180.0
N2—N1—C3—C6180.0C8—C9—C10—N30.0
C1—C2—C3—N10.0C8—C9—C10—C13180.0
C1—C2—C3—C6180.0C12—O6—C11—O50.0
C5—O2—C4—O10.0C12—O6—C11—C8180.0
C5—O2—C4—C1180.0N4—C8—C11—O5180.0
N2—C1—C4—O10.000 (1)C9—C8—C11—O50.0
C2—C1—C4—O1180.0N4—C8—C11—O60.0
N2—C1—C4—O2180.0C9—C8—C11—O6180.0
C2—C1—C4—O20.0C14—O8—C13—O70.0
C7—O4—C6—O30.0C14—O8—C13—C10180.0
C7—O4—C6—C3180.0N3—C10—C13—O70.0
N1—C3—C6—O30.0C9—C10—C13—O7180.0
C2—C3—C6—O3180.0N3—C10—C13—O8180.0
N1—C3—C6—O4180.0C9—C10—C13—O80.0
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O30.862.132.796 (2)134
N1—H1···N40.862.062.919 (2)176
C2—H2···O5i0.932.553.467 (3)167
C7—H7A···O8i0.962.543.431 (3)155
C5—H5C···O1ii0.962.563.243 (3)128
C14—H14C···O7iii0.962.563.424 (3)150
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O30.862.132.796 (2)134
N1—H1···N40.862.062.919 (2)176
C2—H2···O5i0.932.553.467 (3)167
C7—H7A···O8i0.962.543.431 (3)155
C5—H5C···O1ii0.962.563.243 (3)128
C14—H14C···O7iii0.962.563.424 (3)150
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z+3/2; (iii) x−1/2, −y+1/2, −z+1/2.
Acknowledgements top

The authors thank the Natural Science Foundation of Henan Province (051105300) and the Creative Talented Person's Fund of Henan Province (Teach high [2005]-126) for financial support.

references
References top

Ardizzoia, G. A., Brenna, S., LaMonica, G., Maspero, A., Masciocchi, N. & Moret, M. (2002). Inorg. Chem. 41, 610–614.

Bruker (1998). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond, p. 13. Oxford University Press.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Peng, Y. F., Ge, H. Y., Li, B. Z., Li, B. L. & Zhang, Y. (2006). Cryst. Growth Des. 6, 994–998.

Schenck, T. G., Downes, J. M., Milne, C. R. C., Mackenzie, P. B., Boucher, H., Whelan, J. & Bosnich, B. (1985). Inorg. Chem. 24, 2334–2337.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Taylor, R. & Kennard, O. (1982). J. Am. Chem. Soc. 104, 5063–5070.

Zheng, S. L., Tong, M. L. & Chen, X. M. (2003). Coord. Chem. Rev. 246, 185–202.