Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052452/lx2019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052452/lx2019Isup2.hkl |
CCDC reference: 630270
CuCl2 (40.0 mg, 0.21 mmol) was added into the methanol (10 ml) gently, the suspension was kept stirring at room temperature until the solution turned clear green, after which, 5-phenyl-1H-pyrazole-3-carboxylic acid (36.3 mg, 0.21 mmol) was added, then HCl (6.0M, 1.0 ml) was dropped in and stirred for 7 h continuously. Precipitate was filtered off and the filtrate was kept in conical flask for about one month and some pretty colorless rhombic crystals were obtained from the solution, dried in vacuum. Yield: 31.2%. Crystal of the title compound suitable for single-crystal X-ray diffraction was selected directly from the sample as prepared.
All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aromatic H atoms, 0.96 Å for methyl H atoms and 0.86 Å for Nitrogen H atoms, respectively, and with Uiso(H) = 1.2Ueq(C) for aromatic and methylene H atoms, Uiso(H) = 1.5Ueq(C) for methyl H atoms and Uiso(H) = 1.2Ueq(N) for Nitrogen H atoms.
The coordination chemistry of pyrazole and its derivatives has been received great attention since poly(pyrazolyl)borate was found (Trofimenko, 1972). The electron donor (nitrogen) of non-substituted pyrazole unit can coordinate to many metal ions such as copper and vanadium, etc. (Otieno et al., 2002; Xing et al., 2007). When the carboxyl group as the substitutent at three or five position on the pyrazole ring is present, this will enhance the coordination capability of the pyrazole ring, and the substituted carboxyl group and the pyrazole ring with the metal ion can form a steady five-member cycle (Roussel et al., 2006). Herein we report the molecular and crystal structure of the title compound, methyl 5-phenyl-1H-pyrazole-3-carboxylic acid (Fig. 1).
The crystal structure of the title compound (Fig. 1) indicates that the phenyl plane was not coplanar with the pyrazole plane, with their dihedron angle of 6.4 (1)°. All the bond lengths of the pyrazole ring are close to the corresponding bond lengths of ethyl 5-phenyl-1H-pyrazole-3-carboxylate as reported previously (Infantes et al., 1999). The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between the pyrazole ring and the benzene ring of adjacent molecule, with the Cg1···Cg2 distance of 3.862 (3) Å (Cg1 and Cg2 are the centorids of the C7—C9/N2—N1 pyrazole ring and the C1—C6 benzene ring, respectively; symmetry code as in Fig. 2). The molecular packing is further stabilized by three different hydrogen bonds (Fig. 2 and Table 1).
For the coordination chemistry of similar pyrazol derivatives, see: Trofimenko (1972); Xing et al. (2007); Infantes et al. (1999). For related literature, see: Otieno et al. (2002); Roussel et al. (2006).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 1997a) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1997a).
C11H10N2O2 | F(000) = 848 |
Mr = 202.21 | Dx = 1.331 Mg m−3 |
Monoclinic, C2/c | Melting point = 185.5–185.9 K |
Hall symbol: -c 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 24.540 (6) Å | Cell parameters from 2416 reflections |
b = 5.980 (1) Å | θ = 2.5–29.0° |
c = 16.387 (4) Å | µ = 0.09 mm−1 |
β = 122.933 (2)° | T = 293 K |
V = 2018.3 (8) Å3 | Rhombic, colorless |
Z = 8 | 0.20 × 0.15 × 0.05 mm |
Bruker P4 diffractometer | 1612 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Graphite monochromator | θmax = 27.0°, θmin = 2.5° |
Detector resolution: 10.0 pixels mm-1 | h = −31→31 |
ω scans | k = −7→5 |
5591 measured reflections | l = −20→20 |
2185 independent 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.752P] where P = (Fo2 + 2Fc2)/3 |
2185 reflections | (Δ/σ)max < 0.001 |
136 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C11H10N2O2 | V = 2018.3 (8) Å3 |
Mr = 202.21 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.540 (6) Å | µ = 0.09 mm−1 |
b = 5.980 (1) Å | T = 293 K |
c = 16.387 (4) Å | 0.20 × 0.15 × 0.05 mm |
β = 122.933 (2)° |
Bruker P4 diffractometer | 1612 reflections with I > 2σ(I) |
5591 measured reflections | Rint = 0.022 |
2185 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2185 reflections | Δρmin = −0.22 e Å−3 |
136 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 | ||
C1 | 0.17604 (8) | −0.1789 (3) | 0.03661 (12) | 0.0476 (4) | |
H1 | 0.2185 | −0.1488 | 0.0870 | 0.057* | |
C2 | 0.16326 (10) | −0.3570 (3) | −0.02517 (13) | 0.0580 (5) | |
H2 | 0.1973 | −0.4456 | −0.0162 | 0.070* | |
C3 | 0.10077 (10) | −0.4042 (3) | −0.09971 (14) | 0.0594 (5) | |
H3 | 0.0924 | −0.5242 | −0.1410 | 0.071* | |
C4 | 0.05089 (9) | −0.2733 (3) | −0.11276 (13) | 0.0563 (5) | |
H4 | 0.0085 | −0.3054 | −0.1631 | 0.068* | |
C5 | 0.06269 (8) | −0.0947 (3) | −0.05225 (11) | 0.0471 (4) | |
H5 | 0.0283 | −0.0069 | −0.0623 | 0.057* | |
C6 | 0.12571 (7) | −0.0444 (3) | 0.02380 (10) | 0.0365 (4) | |
C7 | 0.13661 (7) | 0.1465 (3) | 0.08722 (10) | 0.0349 (3) | |
C8 | 0.09485 (7) | 0.3081 (3) | 0.08165 (10) | 0.0373 (4) | |
H8 | 0.0508 | 0.3221 | 0.0345 | 0.045* | |
C9 | 0.13253 (7) | 0.4464 (3) | 0.16157 (10) | 0.0358 (4) | |
C10 | 0.11091 (8) | 0.6429 (3) | 0.19061 (11) | 0.0398 (4) | |
C11 | 0.14358 (11) | 0.9382 (3) | 0.30373 (15) | 0.0663 (6) | |
H11A | 0.1821 | 0.9962 | 0.3604 | 0.099* | |
H11B | 0.1126 | 0.8983 | 0.3198 | 0.099* | |
H11C | 0.1252 | 1.0502 | 0.2537 | 0.099* | |
N1 | 0.19519 (6) | 0.1955 (2) | 0.16806 (9) | 0.0405 (3) | |
H1N | 0.2296 | 0.1177 | 0.1872 | 0.049* | |
N2 | 0.19433 (6) | 0.3774 (2) | 0.21536 (9) | 0.0413 (3) | |
O1 | 0.05575 (6) | 0.7053 (2) | 0.14871 (10) | 0.0640 (4) | |
O2 | 0.15988 (6) | 0.7429 (2) | 0.26949 (8) | 0.0522 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0431 (9) | 0.0528 (11) | 0.0442 (9) | 0.0067 (8) | 0.0219 (8) | −0.0001 (8) |
C2 | 0.0669 (13) | 0.0531 (11) | 0.0609 (11) | 0.0143 (9) | 0.0392 (10) | 0.0002 (9) |
C3 | 0.0805 (14) | 0.0510 (11) | 0.0535 (11) | −0.0026 (10) | 0.0409 (11) | −0.0100 (9) |
C4 | 0.0554 (11) | 0.0605 (12) | 0.0454 (9) | −0.0107 (9) | 0.0225 (8) | −0.0135 (9) |
C5 | 0.0383 (9) | 0.0530 (10) | 0.0430 (9) | −0.0004 (8) | 0.0176 (7) | −0.0066 (8) |
C6 | 0.0374 (8) | 0.0391 (8) | 0.0326 (7) | 0.0008 (6) | 0.0188 (7) | 0.0036 (6) |
C7 | 0.0292 (7) | 0.0378 (8) | 0.0328 (7) | −0.0017 (6) | 0.0138 (6) | 0.0023 (6) |
C8 | 0.0254 (7) | 0.0401 (9) | 0.0361 (8) | 0.0004 (6) | 0.0100 (6) | 0.0011 (6) |
C9 | 0.0296 (8) | 0.0363 (8) | 0.0371 (8) | −0.0011 (6) | 0.0152 (6) | 0.0030 (6) |
C10 | 0.0383 (9) | 0.0364 (9) | 0.0426 (8) | −0.0022 (7) | 0.0207 (7) | 0.0010 (7) |
C11 | 0.0917 (16) | 0.0487 (12) | 0.0713 (13) | −0.0093 (10) | 0.0526 (12) | −0.0182 (10) |
N1 | 0.0269 (7) | 0.0431 (8) | 0.0414 (7) | 0.0048 (5) | 0.0121 (6) | −0.0022 (6) |
N2 | 0.0322 (7) | 0.0402 (7) | 0.0412 (7) | 0.0002 (6) | 0.0132 (6) | −0.0041 (6) |
O1 | 0.0428 (7) | 0.0590 (8) | 0.0755 (9) | 0.0109 (6) | 0.0227 (7) | −0.0104 (7) |
O2 | 0.0491 (7) | 0.0479 (7) | 0.0538 (7) | −0.0055 (5) | 0.0242 (6) | −0.0153 (6) |
C1—C2 | 1.383 (2) | C7—C8 | 1.375 (2) |
C1—C6 | 1.391 (2) | C8—C9 | 1.392 (2) |
C1—H1 | 0.9300 | C8—H8 | 0.9300 |
C2—C3 | 1.374 (3) | C9—N2 | 1.339 (2) |
C2—H2 | 0.9300 | C9—C10 | 1.471 (2) |
C3—C4 | 1.368 (3) | C10—O1 | 1.197 (2) |
C3—H3 | 0.9300 | C10—O2 | 1.336 (2) |
C4—C5 | 1.377 (2) | C11—O2 | 1.443 (2) |
C4—H4 | 0.9300 | C11—H11A | 0.9600 |
C5—C6 | 1.393 (2) | C11—H11B | 0.9600 |
C5—H5 | 0.9300 | C11—H11C | 0.9600 |
C6—C7 | 1.467 (2) | N1—N2 | 1.342 (2) |
C7—N1 | 1.355 (2) | N1—H1N | 0.8600 |
C2—C1—C6 | 120.36 (16) | C7—C8—C9 | 105.38 (13) |
C2—C1—H1 | 119.8 | C7—C8—H8 | 127.3 |
C6—C1—H1 | 119.8 | C9—C8—H8 | 127.3 |
C3—C2—C1 | 120.56 (17) | N2—C9—C8 | 111.80 (13) |
C3—C2—H2 | 119.7 | N2—C9—C10 | 120.80 (13) |
C1—C2—H2 | 119.7 | C8—C9—C10 | 127.38 (14) |
C4—C3—C2 | 119.54 (17) | O1—C10—O2 | 123.87 (15) |
C4—C3—H3 | 120.2 | O1—C10—C9 | 123.93 (14) |
C2—C3—H3 | 120.2 | O2—C10—C9 | 112.21 (13) |
C3—C4—C5 | 120.74 (17) | O2—C11—H11A | 109.5 |
C3—C4—H4 | 119.6 | O2—C11—H11B | 109.5 |
C5—C4—H4 | 119.6 | H11A—C11—H11B | 109.5 |
C4—C5—C6 | 120.56 (16) | O2—C11—H11C | 109.5 |
C4—C5—H5 | 119.7 | H11A—C11—H11C | 109.5 |
C6—C5—H5 | 119.7 | H11B—C11—H11C | 109.5 |
C1—C6—C5 | 118.25 (15) | N2—N1—C7 | 113.48 (12) |
C1—C6—C7 | 122.54 (14) | N2—N1—H1N | 123.3 |
C5—C6—C7 | 119.21 (14) | C7—N1—H1N | 123.3 |
N1—C7—C8 | 105.59 (13) | C9—N2—N1 | 103.74 (12) |
N1—C7—C6 | 123.29 (13) | C10—O2—C11 | 116.42 (14) |
C8—C7—C6 | 131.11 (13) | ||
C6—C1—C2—C3 | −0.3 (3) | C7—C8—C9—N2 | −0.41 (18) |
C1—C2—C3—C4 | 0.1 (3) | C7—C8—C9—C10 | −178.60 (15) |
C2—C3—C4—C5 | 0.2 (3) | N2—C9—C10—O1 | −175.69 (16) |
C3—C4—C5—C6 | −0.3 (3) | C8—C9—C10—O1 | 2.4 (3) |
C2—C1—C6—C5 | 0.2 (2) | N2—C9—C10—O2 | 4.0 (2) |
C2—C1—C6—C7 | −179.99 (15) | C8—C9—C10—O2 | −178.00 (14) |
C4—C5—C6—C1 | 0.1 (2) | C8—C7—N1—N2 | 0.08 (17) |
C4—C5—C6—C7 | −179.73 (15) | C6—C7—N1—N2 | 179.93 (13) |
C1—C6—C7—N1 | −6.1 (2) | C8—C9—N2—N1 | 0.45 (17) |
C5—C6—C7—N1 | 173.74 (14) | C10—C9—N2—N1 | 178.78 (13) |
C1—C6—C7—C8 | 173.71 (16) | C7—N1—N2—C9 | −0.33 (17) |
C5—C6—C7—C8 | −6.5 (2) | O1—C10—O2—C11 | −0.4 (2) |
N1—C7—C8—C9 | 0.19 (16) | C9—C10—O2—C11 | 179.90 (14) |
C6—C7—C8—C9 | −179.64 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2i | 0.86 | 2.20 | 2.998 (2) | 153 |
N1—H1N···O2i | 0.86 | 2.52 | 3.134 (2) | 130 |
C5—H5···O1ii | 0.93 | 2.52 | 3.372 (2) | 153 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C11H10N2O2 |
Mr | 202.21 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.540 (6), 5.980 (1), 16.387 (4) |
β (°) | 122.933 (2) |
V (Å3) | 2018.3 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Bruker P4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5591, 2185, 1612 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.120, 1.05 |
No. of reflections | 2185 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL (Sheldrick, 1997a) and DIAMOND (Brandenburg, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···N2i | 0.86 | 2.20 | 2.998 (2) | 153.4 |
N1—H1N···O2i | 0.86 | 2.52 | 3.134 (2) | 129.5 |
C5—H5···O1ii | 0.93 | 2.52 | 3.372 (2) | 153.0 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y+1, −z. |
The coordination chemistry of pyrazole and its derivatives has been received great attention since poly(pyrazolyl)borate was found (Trofimenko, 1972). The electron donor (nitrogen) of non-substituted pyrazole unit can coordinate to many metal ions such as copper and vanadium, etc. (Otieno et al., 2002; Xing et al., 2007). When the carboxyl group as the substitutent at three or five position on the pyrazole ring is present, this will enhance the coordination capability of the pyrazole ring, and the substituted carboxyl group and the pyrazole ring with the metal ion can form a steady five-member cycle (Roussel et al., 2006). Herein we report the molecular and crystal structure of the title compound, methyl 5-phenyl-1H-pyrazole-3-carboxylic acid (Fig. 1).
The crystal structure of the title compound (Fig. 1) indicates that the phenyl plane was not coplanar with the pyrazole plane, with their dihedron angle of 6.4 (1)°. All the bond lengths of the pyrazole ring are close to the corresponding bond lengths of ethyl 5-phenyl-1H-pyrazole-3-carboxylate as reported previously (Infantes et al., 1999). The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between the pyrazole ring and the benzene ring of adjacent molecule, with the Cg1···Cg2 distance of 3.862 (3) Å (Cg1 and Cg2 are the centorids of the C7—C9/N2—N1 pyrazole ring and the C1—C6 benzene ring, respectively; symmetry code as in Fig. 2). The molecular packing is further stabilized by three different hydrogen bonds (Fig. 2 and Table 1).