Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038809/sj2324sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038809/sj2324Isup2.hkl |
CCDC reference: 660255
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.003 Å
- R factor = 0.054
- wR factor = 0.167
- Data-to-parameter ratio = 13.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT480_ALERT_4_C Long H...A H-Bond Reported H7 .. O2 .. 2.70 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For information on the pharmaceutical properties of the title compound, see: Shin et al. (2005).
To a stirred solution of NaOH (300 ml, 20%) at 350 K was added 5- phenyl-2H-pyrazole-3-carboxylic acid ethyl ester (21.6 g, 0.1 mol), and the solution was stirred for 8 h. The reaction mixture was cooled to 293 K, filtered. A white flocculent precipitate appeared when the filtrate was adjusted to pH = 3–5 using dilute HCl. The title compound (yield 16.90 g, 89.90%) was obtained by filtering this precipitate and crystals appropriate for data collection were obtained by recrystallization from acetone/methanol (1:1).
All H atoms bound to C were included in calculated positions and refined as riding with C—H= 0.93 Å, and Uiso(H)= 1.2 Ueq(C). Other hydrogen atoms were located in a difference Fourier map and refined freely with Uiso(H) = 1.5 Ueq(O) and Uiso(H) = 1.2 Ueq(N) respectively.
Pyrazole carboxylic acid and ester derivatives exhibit useful pharmaceutical properties, for example as agonists for the nicotinic acid receptor, refered to as RUP25 herein (Shin et al., 2005).
The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the phenyl plane and the pyrazole plane is 21.27 (6) Å. The carboxylate C4—O1—O2 plane, is twisted slightly with respect to the pyrazole ring plane, the dihedral angle between them is 9.0 (1) °.
In the crystal structure, intermolecular O1—H1···O2i [symmetry code: (i) 1 - x, 2 - y, 1 - z] and N2—H2···N1ii [symmetry code: (ii) 1 - x, y - 1/2, -z + 3/2] hydrogen bonds link the molecules into chains, which are further connected by intermolecular C7—H7···O2iii [symmetry code: (iii) -x, y + 3/2, -z + 3/2] hydrogen bonds (C—O =3.531 (3) Å), resulting in a two-dimensional-dimensional framework.
For information on the pharmaceutical properties of the title compound, see: Shin et al. (2005).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 2005); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).
C10H8N2O2 | F(000) = 392 |
Mr = 188.18 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 1971 reflections |
a = 10.2391 (12) Å | θ = 2.7–25.0° |
b = 5.3647 (6) Å | µ = 0.10 mm−1 |
c = 17.5907 (17) Å | T = 291 K |
β = 106.581 (8)° | Block, colorless |
V = 926.07 (17) Å3 | 0.32 × 0.30 × 0.18 mm |
Z = 4 |
Rigaku Saturn diffractometer | 1817 independent reflections |
Radiation source: rotating anode | 1377 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.046 |
Detector resolution: 7.31 pixels mm-1 | θmax = 26.0°, θmin = 2.1° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −6→6 |
Tmin = 0.970, Tmax = 0.983 | l = −21→21 |
9603 measured reflections |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1024P)2] where P = (Fo2 + 2Fc2)/3 |
1817 reflections | (Δ/σ)max < 0.001 |
135 parameters | Δρmax = 0.19 e Å−3 |
1 restraint | Δρmin = −0.16 e Å−3 |
C10H8N2O2 | V = 926.07 (17) Å3 |
Mr = 188.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.2391 (12) Å | µ = 0.10 mm−1 |
b = 5.3647 (6) Å | T = 291 K |
c = 17.5907 (17) Å | 0.32 × 0.30 × 0.18 mm |
β = 106.581 (8)° |
Rigaku Saturn diffractometer | 1817 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1377 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.983 | Rint = 0.046 |
9603 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 1 restraint |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.19 e Å−3 |
1817 reflections | Δρmin = −0.16 e Å−3 |
135 parameters |
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 | ||
O1 | 0.54576 (15) | 0.8690 (3) | 0.59886 (8) | 0.0705 (5) | |
H1 | 0.571 (2) | 0.983 (4) | 0.5702 (13) | 0.106* | |
O2 | 0.38316 (15) | 0.7806 (3) | 0.48748 (7) | 0.0705 (5) | |
N1 | 0.45958 (15) | 0.4857 (3) | 0.67529 (8) | 0.0535 (5) | |
N2 | 0.38121 (16) | 0.3093 (3) | 0.69483 (9) | 0.0529 (5) | |
H2 | 0.4141 (19) | 0.226 (4) | 0.7415 (12) | 0.063* | |
C1 | 0.39024 (17) | 0.5507 (3) | 0.60188 (9) | 0.0486 (5) | |
C2 | 0.26909 (17) | 0.4153 (3) | 0.57510 (10) | 0.0510 (5) | |
H2A | 0.2045 | 0.4275 | 0.5259 | 0.061* | |
C3 | 0.26539 (18) | 0.2603 (3) | 0.63673 (10) | 0.0476 (5) | |
C4 | 0.44173 (19) | 0.7448 (3) | 0.55878 (11) | 0.0526 (5) | |
C5 | 0.16279 (18) | 0.0802 (3) | 0.64533 (10) | 0.0494 (5) | |
C6 | 0.0304 (2) | 0.0999 (4) | 0.59687 (12) | 0.0617 (6) | |
H6 | 0.0071 | 0.2280 | 0.5599 | 0.074* | |
C7 | −0.0674 (2) | −0.0702 (5) | 0.60325 (14) | 0.0744 (7) | |
H7 | −0.1560 | −0.0552 | 0.5704 | 0.089* | |
C8 | −0.0356 (3) | −0.2601 (4) | 0.65715 (15) | 0.0775 (7) | |
H8 | −0.1018 | −0.3747 | 0.6607 | 0.093* | |
C9 | 0.0940 (3) | −0.2798 (4) | 0.70570 (14) | 0.0748 (7) | |
H9 | 0.1157 | −0.4083 | 0.7427 | 0.090* | |
C10 | 0.1939 (2) | −0.1121 (3) | 0.70098 (12) | 0.0606 (6) | |
H10 | 0.2818 | −0.1275 | 0.7349 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0759 (10) | 0.0725 (10) | 0.0537 (9) | −0.0270 (7) | 0.0033 (7) | 0.0068 (7) |
O2 | 0.0755 (10) | 0.0812 (10) | 0.0451 (8) | −0.0211 (8) | 0.0018 (7) | 0.0123 (7) |
N1 | 0.0577 (9) | 0.0554 (9) | 0.0418 (9) | −0.0068 (7) | 0.0053 (7) | 0.0030 (7) |
N2 | 0.0602 (10) | 0.0535 (9) | 0.0394 (9) | −0.0042 (7) | 0.0053 (7) | 0.0062 (7) |
C1 | 0.0568 (11) | 0.0479 (10) | 0.0386 (9) | −0.0023 (8) | 0.0096 (8) | 0.0000 (7) |
C2 | 0.0549 (11) | 0.0528 (10) | 0.0381 (10) | −0.0035 (8) | 0.0016 (8) | 0.0014 (7) |
C3 | 0.0552 (11) | 0.0441 (10) | 0.0402 (9) | 0.0009 (7) | 0.0083 (8) | 0.0003 (7) |
C4 | 0.0560 (11) | 0.0533 (11) | 0.0448 (11) | −0.0049 (8) | 0.0083 (9) | −0.0010 (8) |
C5 | 0.0588 (11) | 0.0454 (10) | 0.0461 (10) | −0.0029 (8) | 0.0181 (9) | −0.0055 (8) |
C6 | 0.0646 (12) | 0.0622 (12) | 0.0561 (12) | −0.0084 (9) | 0.0136 (10) | −0.0043 (9) |
C7 | 0.0669 (14) | 0.0816 (16) | 0.0772 (16) | −0.0174 (11) | 0.0244 (11) | −0.0203 (12) |
C8 | 0.0873 (17) | 0.0698 (15) | 0.0907 (18) | −0.0229 (13) | 0.0502 (15) | −0.0199 (13) |
C9 | 0.106 (2) | 0.0524 (12) | 0.0796 (16) | −0.0020 (12) | 0.0487 (16) | 0.0045 (11) |
C10 | 0.0739 (13) | 0.0519 (11) | 0.0594 (13) | 0.0036 (9) | 0.0246 (10) | 0.0050 (9) |
O1—C4 | 1.283 (2) | C5—C6 | 1.384 (3) |
O1—H1 | 0.876 (10) | C5—C10 | 1.395 (3) |
O2—C4 | 1.241 (2) | C6—C7 | 1.383 (3) |
N1—C1 | 1.330 (2) | C6—H6 | 0.9300 |
N1—N2 | 1.347 (2) | C7—C8 | 1.366 (3) |
N2—C3 | 1.352 (2) | C7—H7 | 0.9300 |
N2—H2 | 0.91 (2) | C8—C9 | 1.362 (3) |
C1—C2 | 1.398 (2) | C8—H8 | 0.9300 |
C1—C4 | 1.472 (3) | C9—C10 | 1.382 (3) |
C2—C3 | 1.375 (2) | C9—H9 | 0.9300 |
C2—H2A | 0.9300 | C10—H10 | 0.9300 |
C3—C5 | 1.467 (2) | ||
C4—O1—H1 | 112.4 (16) | C6—C5—C3 | 119.40 (16) |
C1—N1—N2 | 103.88 (14) | C10—C5—C3 | 122.18 (17) |
N1—N2—C3 | 113.67 (14) | C7—C6—C5 | 120.3 (2) |
N1—N2—H2 | 118.8 (12) | C7—C6—H6 | 119.9 |
C3—N2—H2 | 127.2 (13) | C5—C6—H6 | 119.9 |
N1—C1—C2 | 111.56 (16) | C8—C7—C6 | 120.9 (2) |
N1—C1—C4 | 121.00 (16) | C8—C7—H7 | 119.5 |
C2—C1—C4 | 127.44 (15) | C6—C7—H7 | 119.5 |
C3—C2—C1 | 105.65 (15) | C9—C8—C7 | 119.3 (2) |
C3—C2—H2A | 127.2 | C9—C8—H8 | 120.4 |
C1—C2—H2A | 127.2 | C7—C8—H8 | 120.4 |
N2—C3—C2 | 105.24 (15) | C8—C9—C10 | 121.2 (2) |
N2—C3—C5 | 123.34 (15) | C8—C9—H9 | 119.4 |
C2—C3—C5 | 131.40 (17) | C10—C9—H9 | 119.4 |
O2—C4—O1 | 124.12 (18) | C9—C10—C5 | 119.9 (2) |
O2—C4—C1 | 119.29 (16) | C9—C10—H10 | 120.0 |
O1—C4—C1 | 116.59 (16) | C5—C10—H10 | 120.0 |
C6—C5—C10 | 118.42 (17) | ||
C1—N1—N2—C3 | 0.0 (2) | N2—C3—C5—C6 | 157.93 (18) |
N2—N1—C1—C2 | −0.3 (2) | C2—C3—C5—C6 | −20.1 (3) |
N2—N1—C1—C4 | 179.23 (16) | N2—C3—C5—C10 | −22.1 (3) |
N1—C1—C2—C3 | 0.4 (2) | C2—C3—C5—C10 | 159.78 (19) |
C4—C1—C2—C3 | −179.07 (18) | C10—C5—C6—C7 | −0.9 (3) |
N1—N2—C3—C2 | 0.2 (2) | C3—C5—C6—C7 | 179.05 (18) |
N1—N2—C3—C5 | −178.32 (16) | C5—C6—C7—C8 | 0.0 (3) |
C1—C2—C3—N2 | −0.33 (19) | C6—C7—C8—C9 | 0.7 (3) |
C1—C2—C3—C5 | 178.01 (17) | C7—C8—C9—C10 | −0.4 (3) |
N1—C1—C4—O2 | 171.64 (19) | C8—C9—C10—C5 | −0.5 (3) |
C2—C1—C4—O2 | −9.0 (3) | C6—C5—C10—C9 | 1.1 (3) |
N1—C1—C4—O1 | −8.9 (3) | C3—C5—C10—C9 | −178.80 (18) |
C2—C1—C4—O1 | 170.48 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.91 (2) | 2.10 (2) | 2.961 (2) | 158.0 (17) |
O1—H1···O2ii | 0.88 (1) | 1.77 (1) | 2.6462 (19) | 178 (2) |
C7—H7···O2iii | 0.93 | 2.70 | 3.531 (3) | 150 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H8N2O2 |
Mr | 188.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 10.2391 (12), 5.3647 (6), 17.5907 (17) |
β (°) | 106.581 (8) |
V (Å3) | 926.07 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.32 × 0.30 × 0.18 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.970, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9603, 1817, 1377 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.167, 1.07 |
No. of reflections | 1817 |
No. of parameters | 135 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.16 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Berndt, 2005), CrystalStructure (Rigaku/MSC, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.91 (2) | 2.10 (2) | 2.961 (2) | 158.0 (17) |
O1—H1···O2ii | 0.876 (10) | 1.771 (10) | 2.6462 (19) | 178 (2) |
C7—H7···O2iii | 0.930 | 2.70 | 3.5311 (25) | 150 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
Pyrazole carboxylic acid and ester derivatives exhibit useful pharmaceutical properties, for example as agonists for the nicotinic acid receptor, refered to as RUP25 herein (Shin et al., 2005).
The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the phenyl plane and the pyrazole plane is 21.27 (6) Å. The carboxylate C4—O1—O2 plane, is twisted slightly with respect to the pyrazole ring plane, the dihedral angle between them is 9.0 (1) °.
In the crystal structure, intermolecular O1—H1···O2i [symmetry code: (i) 1 - x, 2 - y, 1 - z] and N2—H2···N1ii [symmetry code: (ii) 1 - x, y - 1/2, -z + 3/2] hydrogen bonds link the molecules into chains, which are further connected by intermolecular C7—H7···O2iii [symmetry code: (iii) -x, y + 3/2, -z + 3/2] hydrogen bonds (C—O =3.531 (3) Å), resulting in a two-dimensional-dimensional framework.