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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o319.
Published online 2007 December 21. doi:  10.1107/S1600536807066391
PMCID: PMC2915363

Bis(3,5-dimethyl­pyrazol-1-yl)acetic acid

Abstract

In the title compound, C12H16N4O2, the dihedral angle between the two pyrazole rings is 78.17 (7)°. Inter­molecular O—H(...)N hydrogen bonds link the mol­ecules into one-dimensional chains along the c axis.

Related literature

For the synthesis of bis­(3,5-dimethyl­pyrazol-1-yl)acetic acid, see: Otero et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o319-scheme1.jpg

Experimental

Crystal data

  • C12H16N4O2
  • M r = 248.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o319-efi1.jpg
  • a = 8.4317 (8) Å
  • b = 18.8569 (16) Å
  • c = 8.6083 (7) Å
  • β = 114.576 (7)°
  • V = 1244.69 (19) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 (2) K
  • 0.50 × 0.40 × 0.35 mm

Data collection

  • Enraf–Nonius CAD-4 four-circle diffractometer
  • Absorption correction: none
  • 2526 measured reflections
  • 2305 independent reflections
  • 1924 reflections with I > 2σ(I)
  • R int = 0.007
  • 3 standard reflections frequency: 60 min intensity decay: 0.2%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.120
  • S = 1.08
  • 2305 reflections
  • 171 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1999 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066391/kj2077sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066391/kj2077Isup2.hkl

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

supplementary crystallographic information

Comment

The title compound, C12H16N4O2, was synthesized through the protonation of bis(3,5-dimethylpyrazol-1-yl)acetate. This compound was used to prepare 2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol, which was the reagent for the NNO monoanionic heteroscorpionate ligand (Otero et al., 2004). Intermolecular O—H···N hydrogen bonds link the molecules into one-dimensional chains along the c axis (Fig. 2 and Table 1). The dihedral angle between the two pyrazol rings is 78.17 (7)°.

Experimental

The title compound was synthesized according to the literature procedure (Otero et al., 2004). Single crystals of the compound suitable for X-ray analysis were obtained by diffusion of ether into a THF solution.

Refinement

All H-atoms except the H atom of the acid group, which was refined isotropically, were positioned geometrically and included in the refinement using a riding model with C—H = 0.98 Å, Uiso(H) = 1.2Ueq(C) for C(sp3)—H, C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C) for CH3, and C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) for C(sp2)—H.

Figures

Fig. 1.
A view of the title compound. Displacement ellipsoids are drawn at the 40% probability level.
Fig. 2.
A packing diagram of the title compound viewed approximately perpendicular to the bc plane. Hydrogen bonds are indicated by dashed lines. H atoms of the methyl groups were omitted for clarity.

Crystal data

C12H16N4O2F000 = 528
Mr = 248.29Dx = 1.325 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 8.4317 (8) Åθ = 9.3–11.6º
b = 18.8569 (16) ŵ = 0.09 mm1
c = 8.6083 (7) ÅT = 293 (2) K
β = 114.576 (7)ºBlock, colourless
V = 1244.69 (19) Å30.50 × 0.40 × 0.35 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 four-circle diffractometerRint = 0.007
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.8º
T = 293(2) Kh = 0→10
ω/2θ scansk = 0→22
Absorption correction: nonel = −10→9
2526 measured reflections3 standard reflections
2305 independent reflections every 60 min
1924 reflections with I > 2σ(I) intensity decay: 0.2%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.120  w = 1/[σ2(Fo2) + (0.0687P)2 + 0.2835P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2305 reflectionsΔρmax = 0.23 e Å3
171 parametersΔρmin = −0.26 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.01420 (18)0.19070 (8)0.40486 (18)0.0328 (3)
H1A0.03990.21150.31350.039*
N10.17999 (15)0.17643 (7)0.54704 (15)0.0337 (3)
N20.19887 (16)0.18728 (7)0.71087 (15)0.0363 (3)
C20.36285 (19)0.16958 (8)0.80788 (19)0.0342 (3)
C30.4348 (2)0.17514 (10)0.9979 (2)0.0444 (4)
H3A0.34250.18681.03130.067*
H3B0.52230.21151.03660.067*
H3C0.48580.13061.04810.067*
C40.4481 (2)0.14729 (9)0.7074 (2)0.0389 (4)
H4A0.56330.13230.74620.047*
C50.3290 (2)0.15185 (8)0.5408 (2)0.0359 (4)
C60.3447 (2)0.13593 (11)0.3783 (2)0.0521 (5)
H6A0.28770.09180.33280.078*
H6B0.46570.13260.40000.078*
H6C0.29080.17320.29750.078*
N3−0.08641 (16)0.12648 (7)0.33639 (15)0.0332 (3)
N4−0.10877 (16)0.10578 (7)0.17637 (15)0.0341 (3)
C7−0.1927 (2)0.04440 (8)0.1485 (2)0.0380 (4)
C8−0.2378 (3)0.00510 (10)−0.0153 (2)0.0554 (5)
H8A−0.19000.0296−0.08380.083*
H8B−0.36230.0023−0.07630.083*
H8C−0.1900−0.04190.00890.083*
C9−0.2243 (2)0.02556 (9)0.2895 (2)0.0435 (4)
H9A−0.2817−0.01500.30040.052*
C10−0.15508 (19)0.07794 (8)0.4088 (2)0.0379 (4)
C11−0.1488 (3)0.08317 (11)0.5835 (2)0.0524 (5)
H11A−0.03450.09810.66190.079*
H11B−0.17430.03770.61780.079*
H11C−0.23350.11710.58380.079*
C12−0.0880 (2)0.24644 (8)0.45592 (19)0.0379 (4)
O1−0.22573 (17)0.23504 (8)0.4587 (2)0.0652 (4)
O2−0.00521 (16)0.30749 (6)0.49036 (15)0.0442 (3)
H2−0.052 (3)0.3382 (14)0.551 (3)0.081 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0339 (8)0.0349 (8)0.0287 (7)−0.0003 (6)0.0123 (6)0.0000 (6)
N10.0312 (6)0.0405 (7)0.0293 (6)0.0031 (5)0.0126 (5)−0.0017 (5)
N20.0350 (7)0.0436 (7)0.0308 (6)0.0018 (5)0.0141 (5)−0.0015 (5)
C20.0332 (8)0.0334 (7)0.0345 (8)−0.0007 (6)0.0126 (6)0.0020 (6)
C30.0430 (9)0.0520 (10)0.0347 (8)0.0046 (7)0.0127 (7)0.0033 (7)
C40.0326 (8)0.0428 (8)0.0412 (8)0.0068 (6)0.0154 (6)0.0044 (7)
C50.0360 (8)0.0351 (8)0.0395 (8)0.0031 (6)0.0187 (7)0.0009 (6)
C60.0519 (10)0.0673 (12)0.0419 (9)0.0139 (9)0.0242 (8)−0.0018 (8)
N30.0350 (7)0.0345 (7)0.0312 (6)−0.0013 (5)0.0149 (5)0.0007 (5)
N40.0360 (7)0.0339 (7)0.0306 (6)−0.0017 (5)0.0121 (5)−0.0009 (5)
C70.0373 (8)0.0312 (7)0.0394 (8)−0.0002 (6)0.0100 (6)0.0009 (6)
C80.0637 (12)0.0465 (10)0.0476 (10)−0.0099 (9)0.0147 (9)−0.0102 (8)
C90.0408 (9)0.0371 (8)0.0502 (10)−0.0053 (7)0.0165 (7)0.0064 (7)
C100.0333 (8)0.0412 (9)0.0399 (8)0.0027 (6)0.0160 (6)0.0077 (6)
C110.0513 (10)0.0659 (12)0.0472 (10)−0.0005 (9)0.0277 (8)0.0084 (8)
C120.0355 (8)0.0407 (8)0.0332 (8)0.0044 (6)0.0101 (6)−0.0002 (6)
O10.0395 (7)0.0564 (8)0.1023 (12)0.0023 (6)0.0320 (7)−0.0173 (8)
O20.0562 (7)0.0363 (6)0.0463 (6)0.0003 (5)0.0276 (6)−0.0049 (5)

Geometric parameters (Å, °)

C1—N11.4496 (18)N3—C101.3644 (19)
C1—N31.4551 (19)N3—N41.3673 (17)
C1—C121.535 (2)N4—C71.325 (2)
C1—H1A0.9800C7—C91.392 (2)
N1—C51.3608 (19)C7—C81.496 (2)
N1—N21.3673 (17)C8—H8A0.9600
N2—C21.327 (2)C8—H8B0.9600
C2—C41.400 (2)C8—H8C0.9600
C2—C31.493 (2)C9—C101.369 (2)
C3—H3A0.9600C9—H9A0.9300
C3—H3B0.9600C10—C111.486 (2)
C3—H3C0.9600C11—H11A0.9600
C4—C51.369 (2)C11—H11B0.9600
C4—H4A0.9300C11—H11C0.9600
C5—C61.489 (2)C12—O11.1910 (19)
C6—H6A0.9600C12—O21.315 (2)
C6—H6B0.9600O2—H20.97 (3)
C6—H6C0.9600
N1—C1—N3112.50 (12)H6B—C6—H6C109.5
N1—C1—C12110.15 (11)C10—N3—N4111.21 (12)
N3—C1—C12112.56 (12)C10—N3—C1131.29 (12)
N1—C1—H1A107.1N4—N3—C1117.30 (11)
N3—C1—H1A107.1C7—N4—N3105.74 (12)
C12—C1—H1A107.1N4—C7—C9110.26 (14)
C5—N1—N2112.22 (12)N4—C7—C8120.71 (15)
C5—N1—C1127.72 (12)C9—C7—C8129.02 (15)
N2—N1—C1120.06 (11)C7—C8—H8A109.5
C2—N2—N1104.80 (12)C7—C8—H8B109.5
N2—C2—C4110.80 (13)H8A—C8—H8B109.5
N2—C2—C3120.94 (14)C7—C8—H8C109.5
C4—C2—C3128.26 (14)H8A—C8—H8C109.5
C2—C3—H3A109.5H8B—C8—H8C109.5
C2—C3—H3B109.5C10—C9—C7107.06 (14)
H3A—C3—H3B109.5C10—C9—H9A126.5
C2—C3—H3C109.5C7—C9—H9A126.5
H3A—C3—H3C109.5N3—C10—C9105.72 (14)
H3B—C3—H3C109.5N3—C10—C11125.07 (15)
C5—C4—C2106.67 (14)C9—C10—C11129.20 (15)
C5—C4—H4A126.7C10—C11—H11A109.5
C2—C4—H4A126.7C10—C11—H11B109.5
N1—C5—C4105.51 (13)H11A—C11—H11B109.5
N1—C5—C6123.35 (14)C10—C11—H11C109.5
C4—C5—C6131.13 (15)H11A—C11—H11C109.5
C5—C6—H6A109.5H11B—C11—H11C109.5
C5—C6—H6B109.5O1—C12—O2125.75 (15)
H6A—C6—H6B109.5O1—C12—C1123.40 (15)
C5—C6—H6C109.5O2—C12—C1110.83 (13)
H6A—C6—H6C109.5C12—O2—H2110.3 (15)
N3—C1—N1—C578.86 (18)N1—C1—N3—N4−111.63 (13)
C12—C1—N1—C5−154.68 (15)C12—C1—N3—N4123.21 (13)
N3—C1—N1—N2−100.73 (15)C10—N3—N4—C70.43 (16)
C12—C1—N1—N225.73 (18)C1—N3—N4—C7175.80 (12)
C5—N1—N2—C20.43 (17)N3—N4—C7—C9−0.02 (16)
C1—N1—N2—C2−179.92 (13)N3—N4—C7—C8−179.15 (14)
N1—N2—C2—C4−0.27 (17)N4—C7—C9—C10−0.39 (18)
N1—N2—C2—C3179.31 (14)C8—C7—C9—C10178.65 (16)
N2—C2—C4—C50.02 (19)N4—N3—C10—C9−0.66 (17)
C3—C2—C4—C5−179.52 (15)C1—N3—C10—C9−175.19 (14)
N2—N1—C5—C4−0.42 (17)N4—N3—C10—C11178.27 (14)
C1—N1—C5—C4179.97 (14)C1—N3—C10—C113.7 (3)
N2—N1—C5—C6−179.67 (15)C7—C9—C10—N30.62 (18)
C1—N1—C5—C60.7 (2)C7—C9—C10—C11−178.25 (16)
C2—C4—C5—N10.24 (17)N1—C1—C12—O1−117.82 (17)
C2—C4—C5—C6179.40 (17)N3—C1—C12—O18.6 (2)
N1—C1—N3—C1062.62 (19)N1—C1—C12—O263.93 (16)
C12—C1—N3—C10−62.5 (2)N3—C1—C12—O2−169.64 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···N4i0.97 (3)1.71 (3)2.676 (2)172 (3)

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KJ2077).

References

  • Enraf–Nonius (1989). CAD-4 Software Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • McArdle, P. (1999). XCAD National University of Ireland, Galway, Ireland.
  • Otero, A., Fernández-Baeza, J., Antiñolo, A., Tejeda, J., Lara-Sánchez, A., Sánchez-Barba, L. & Rodríguez, A. M. (2004). Eur. J. Inorg. Chem. pp. 260–266.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography