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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019642/dn2164sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019642/dn2164Isup2.hkl
Contains datablock I

CCDC reference: 651369

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.044
  • wR factor = 0.106
  • Data-to-parameter ratio = 10.0

checkCIF/PLATON results

No syntax errors found



Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.116 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.12 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 9.96 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.59 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.18 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C1 - C4 .. 5.01 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.18 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.13
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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.

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.

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.116
φ and ω scansθmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1311
Tmin = 0.943, Tmax = 0.985k = 77
8106 measured reflectionsl = 2628
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 Å3
162 parametersΔρmin = 0.24 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0445 restraints
wR(F2) = 0.106H-atom parameters constrained
S = 0.97Δρmax = 0.17 e Å3
1614 reflectionsΔρmin = 0.24 e Å3
162 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. 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)0.0000.0037 (7)0.000
O30.0294 (10)0.0929 (14)0.0440 (10)0.0000.0048 (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)0.0000.0066 (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)0.0000.0066 (7)0.000
N10.0261 (10)0.0509 (12)0.0402 (11)0.0000.0041 (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)0.0000.0027 (9)0.000
C10.0273 (12)0.0474 (14)0.0384 (13)0.0000.0028 (10)0.000
C20.0257 (12)0.0530 (15)0.0387 (13)0.0000.0004 (10)0.000
C30.0285 (12)0.0452 (14)0.0421 (13)0.0000.0005 (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)0.0000.0143 (13)0.000
C60.0289 (13)0.0527 (15)0.0396 (13)0.0000.0010 (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)0.0000.0016 (10)0.000
C90.0267 (12)0.0448 (13)0.0384 (13)0.0000.0040 (10)0.000
C100.0278 (12)0.0459 (14)0.0418 (13)0.0000.0034 (11)0.000
C110.0370 (15)0.0541 (15)0.0406 (14)0.0000.0031 (11)0.000
C120.086 (3)0.161 (3)0.0332 (16)0.0000.0088 (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)0.0000.0151 (14)0.000
Geometric parameters (Å, º) 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, º) 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) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H8N2O4
Mr184.15
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)293
a, b, c (Å)10.9563 (14), 6.4983 (8), 23.589 (3)
V3)1679.5 (4)
Z8
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.49 × 0.34 × 0.13
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.943, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
8106, 1614, 1196
Rint0.116
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.106, 0.97
No. of reflections1614
No. of parameters162
No. of restraints5
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.17, 0.24

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O30.862.132.796 (2)133.9
N1—H1···N40.862.062.919 (2)176.4
C2—H2···O5i0.932.553.467 (3)167.4
C7—H7A···O8i0.962.543.431 (3)155.0
C5—H5C···O1ii0.962.563.243 (3)128.0
C14—H14C···O7iii0.962.563.424 (3)150.4
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z+3/2; (iii) x1/2, y+1/2, z+1/2.
 

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