organic compounds
H-pyrazol-1-yl)methyl]benzoate
of ethyl 4-[(1aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, People's Republic of China, and bSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: fchg042@163.com
In the title molecule, C13H14N2O2, the dihedral angle between the pyrazole and benzene ring mean planes is 76.06 (11)°, and the conformation of the ethyl side chain is anti [C—O—C—C = −175.4 (3)°]. In the crystal, the only directional interactions are very weak C—H ⋯π interactions involving both the pyrazole and benzene rings, leading to the formation of a three-dimensional network.
Keywords: crystal structure; ester; pyrazole derivative.
CCDC reference: 1034364
1. Related literature
For a related structure, see: Dong et al. (2011). For background to the properties of pyrazole derivatives, see: Adnan & Tarek (2004); Ashraf et al. (2003).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: FRAMBO (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 1034364
10.1107/S1600536814025100/hb7319sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814025100/hb7319Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814025100/hb7319Isup3.cml
In a 250 ml four-necked round-bottom flask equipped with a mechanical stirrer, pyrazole (0.680 g 10 mmol), potassium carbonate (2.073 g 15 mmol) and 1-(4-(bromomethyl)phenyl)-1-hydroxypentan-2-one (2.712 g, 10 mmol) were cautiously dissolved in acetone (100 ml). The solution was heated at 65 °C for 6 h, then the mixture was filtered off was removed by rotatory evaporator at 35 °C and the crude product was obtained 1.815 g (66.1%). Colourless blocks of the title compound were obtained from ethanol by slow evaporation.
H-atoms were placed in calculated positions and refined constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å, Uiso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C) for the methylene.
Data collection: FRAMBO (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. View of the packing diagram of the title compound along the b axis. |
C13H14N2O2 | Z = 2 |
Mr = 230.26 | F(000) = 244 |
Triclinic, P1 | Dx = 1.222 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1338 (12) Å | Cell parameters from 1485 reflections |
b = 8.1961 (9) Å | θ = 4.3–28.2° |
c = 10.7933 (11) Å | µ = 0.08 mm−1 |
α = 74.013 (9)° | T = 293 K |
β = 83.308 (10)° | Block, colourless |
γ = 64.734 (13)° | 0.22 × 0.20 × 0.18 mm |
V = 625.54 (13) Å3 |
Agilent SuperNova (Single source at offset, Eos) diffractometer | 2197 independent reflections |
Radiation source: fine-focus sealed tube | 1639 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
phi and ω scans | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012) | h = −9→9 |
Tmin = 0.982, Tmax = 0.985 | k = −9→9 |
4295 measured reflections | l = −12→8 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.15 | w = 1/[σ2(Fo2) + (0.079P)2 + 0.2197P] where P = (Fo2 + 2Fc2)/3 |
2197 reflections | (Δ/σ)max < 0.001 |
155 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C13H14N2O2 | γ = 64.734 (13)° |
Mr = 230.26 | V = 625.54 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1338 (12) Å | Mo Kα radiation |
b = 8.1961 (9) Å | µ = 0.08 mm−1 |
c = 10.7933 (11) Å | T = 293 K |
α = 74.013 (9)° | 0.22 × 0.20 × 0.18 mm |
β = 83.308 (10)° |
Agilent SuperNova (Single source at offset, Eos) diffractometer | 2197 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012) | 1639 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.985 | Rint = 0.032 |
4295 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.18 e Å−3 |
2197 reflections | Δρmin = −0.23 e Å−3 |
155 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 | −0.3321 (5) | 0.2354 (4) | 0.0922 (3) | 0.0772 (9) | |
H1 | −0.4412 | 0.3219 | 0.0516 | 0.093* | |
C2 | −0.3185 (4) | 0.0903 (5) | 0.1964 (3) | 0.0787 (9) | |
H2 | −0.4119 | 0.0606 | 0.2394 | 0.094* | |
C3 | −0.1386 (4) | −0.0001 (4) | 0.2228 (3) | 0.0718 (9) | |
H3 | −0.0841 | −0.1068 | 0.2885 | 0.086* | |
C4 | 0.1384 (4) | 0.0519 (4) | 0.1369 (3) | 0.0653 (8) | |
H4A | 0.1766 | 0.0861 | 0.0486 | 0.078* | |
H4B | 0.2091 | −0.0805 | 0.1712 | 0.078* | |
C5 | 0.1753 (3) | 0.1603 (4) | 0.2163 (2) | 0.0543 (7) | |
C6 | 0.2157 (4) | 0.0834 (4) | 0.3464 (3) | 0.0610 (7) | |
H6 | 0.2269 | −0.0374 | 0.3842 | 0.073* | |
C7 | 0.2396 (4) | 0.1856 (4) | 0.4205 (2) | 0.0584 (7) | |
H7 | 0.2671 | 0.1326 | 0.5077 | 0.070* | |
C8 | 0.2227 (3) | 0.3657 (3) | 0.3656 (2) | 0.0505 (6) | |
C9 | 0.1870 (4) | 0.4413 (4) | 0.2343 (3) | 0.0573 (7) | |
H9 | 0.1784 | 0.5611 | 0.1959 | 0.069* | |
C10 | 0.1643 (4) | 0.3379 (4) | 0.1609 (3) | 0.0588 (7) | |
H10 | 0.1413 | 0.3888 | 0.0731 | 0.071* | |
C11 | 0.2393 (4) | 0.4838 (4) | 0.4420 (3) | 0.0561 (7) | |
C12 | 0.2906 (4) | 0.5017 (5) | 0.6500 (3) | 0.0726 (9) | |
H12A | 0.1747 | 0.6050 | 0.6552 | 0.087* | |
H12B | 0.3805 | 0.5512 | 0.6164 | 0.087* | |
C13 | 0.3460 (6) | 0.3720 (6) | 0.7790 (4) | 0.1028 (13) | |
H13A | 0.2574 | 0.3219 | 0.8103 | 0.154* | |
H13B | 0.3544 | 0.4378 | 0.8374 | 0.154* | |
H13C | 0.4622 | 0.2722 | 0.7729 | 0.154* | |
N1 | −0.0526 (3) | 0.0895 (3) | 0.13866 (19) | 0.0554 (6) | |
N2 | −0.1716 (4) | 0.2383 (3) | 0.0558 (2) | 0.0741 (8) | |
O1 | 0.2758 (3) | 0.3958 (3) | 0.56635 (18) | 0.0672 (6) | |
O2 | 0.2213 (3) | 0.6418 (3) | 0.3986 (2) | 0.0823 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.075 (2) | 0.072 (2) | 0.083 (2) | −0.0205 (17) | −0.0233 (17) | −0.0225 (17) |
C2 | 0.070 (2) | 0.088 (2) | 0.079 (2) | −0.0365 (18) | 0.0043 (16) | −0.0178 (18) |
C3 | 0.078 (2) | 0.075 (2) | 0.0547 (17) | −0.0352 (17) | −0.0020 (14) | 0.0029 (15) |
C4 | 0.0684 (18) | 0.083 (2) | 0.0557 (17) | −0.0358 (16) | 0.0119 (13) | −0.0318 (15) |
C5 | 0.0541 (15) | 0.0664 (17) | 0.0469 (15) | −0.0276 (13) | 0.0101 (11) | −0.0209 (12) |
C6 | 0.0804 (19) | 0.0549 (16) | 0.0506 (16) | −0.0330 (14) | 0.0032 (13) | −0.0109 (12) |
C7 | 0.0788 (19) | 0.0601 (16) | 0.0391 (14) | −0.0336 (14) | 0.0003 (12) | −0.0086 (12) |
C8 | 0.0534 (14) | 0.0530 (14) | 0.0456 (14) | −0.0235 (12) | 0.0016 (11) | −0.0114 (11) |
C9 | 0.0660 (17) | 0.0557 (15) | 0.0489 (15) | −0.0289 (13) | −0.0030 (12) | −0.0035 (12) |
C10 | 0.0630 (17) | 0.0721 (18) | 0.0404 (14) | −0.0305 (14) | 0.0011 (11) | −0.0090 (13) |
C11 | 0.0593 (16) | 0.0558 (16) | 0.0552 (16) | −0.0262 (13) | −0.0016 (12) | −0.0124 (13) |
C12 | 0.079 (2) | 0.082 (2) | 0.072 (2) | −0.0358 (17) | −0.0023 (15) | −0.0388 (17) |
C13 | 0.131 (3) | 0.105 (3) | 0.070 (2) | −0.031 (2) | −0.027 (2) | −0.039 (2) |
N1 | 0.0692 (14) | 0.0607 (13) | 0.0401 (12) | −0.0296 (11) | −0.0015 (10) | −0.0136 (10) |
N2 | 0.100 (2) | 0.0673 (16) | 0.0533 (14) | −0.0374 (14) | −0.0200 (13) | −0.0007 (12) |
O1 | 0.0917 (15) | 0.0665 (12) | 0.0502 (12) | −0.0353 (11) | −0.0060 (10) | −0.0181 (9) |
O2 | 0.1173 (19) | 0.0621 (13) | 0.0756 (15) | −0.0452 (13) | −0.0147 (13) | −0.0102 (11) |
C1—N2 | 1.327 (4) | C7—H7 | 0.9300 |
C1—C2 | 1.367 (5) | C8—C9 | 1.391 (3) |
C1—H1 | 0.9300 | C8—C11 | 1.487 (4) |
C2—C3 | 1.351 (4) | C9—C10 | 1.385 (4) |
C2—H2 | 0.9300 | C9—H9 | 0.9300 |
C3—N1 | 1.333 (4) | C10—H10 | 0.9300 |
C3—H3 | 0.9300 | C11—O2 | 1.200 (3) |
C4—N1 | 1.448 (3) | C11—O1 | 1.336 (3) |
C4—C5 | 1.524 (4) | C12—O1 | 1.460 (3) |
C4—H4A | 0.9700 | C12—C13 | 1.481 (5) |
C4—H4B | 0.9700 | C12—H12A | 0.9700 |
C5—C10 | 1.381 (4) | C12—H12B | 0.9700 |
C5—C6 | 1.385 (4) | C13—H13A | 0.9600 |
C6—C7 | 1.386 (4) | C13—H13B | 0.9600 |
C6—H6 | 0.9300 | C13—H13C | 0.9600 |
C7—C8 | 1.384 (4) | N1—N2 | 1.348 (3) |
N2—C1—C2 | 112.2 (3) | C10—C9—C8 | 119.9 (2) |
N2—C1—H1 | 123.9 | C10—C9—H9 | 120.1 |
C2—C1—H1 | 123.9 | C8—C9—H9 | 120.1 |
C3—C2—C1 | 104.4 (3) | C5—C10—C9 | 120.9 (2) |
C3—C2—H2 | 127.8 | C5—C10—H10 | 119.5 |
C1—C2—H2 | 127.8 | C9—C10—H10 | 119.5 |
N1—C3—C2 | 108.4 (3) | O2—C11—O1 | 122.7 (3) |
N1—C3—H3 | 125.8 | O2—C11—C8 | 124.4 (3) |
C2—C3—H3 | 125.8 | O1—C11—C8 | 112.9 (2) |
N1—C4—C5 | 111.3 (2) | O1—C12—C13 | 107.1 (3) |
N1—C4—H4A | 109.4 | O1—C12—H12A | 110.3 |
C5—C4—H4A | 109.4 | C13—C12—H12A | 110.3 |
N1—C4—H4B | 109.4 | O1—C12—H12B | 110.3 |
C5—C4—H4B | 109.4 | C13—C12—H12B | 110.3 |
H4A—C4—H4B | 108.0 | H12A—C12—H12B | 108.5 |
C10—C5—C6 | 119.0 (2) | C12—C13—H13A | 109.5 |
C10—C5—C4 | 120.7 (2) | C12—C13—H13B | 109.5 |
C6—C5—C4 | 120.3 (2) | H13A—C13—H13B | 109.5 |
C5—C6—C7 | 120.4 (2) | C12—C13—H13C | 109.5 |
C5—C6—H6 | 119.8 | H13A—C13—H13C | 109.5 |
C7—C6—H6 | 119.8 | H13B—C13—H13C | 109.5 |
C8—C7—C6 | 120.4 (2) | C3—N1—N2 | 110.7 (3) |
C8—C7—H7 | 119.8 | C3—N1—C4 | 127.7 (2) |
C6—C7—H7 | 119.8 | N2—N1—C4 | 121.4 (2) |
C7—C8—C9 | 119.2 (2) | C1—N2—N1 | 104.3 (2) |
C7—C8—C11 | 122.5 (2) | C11—O1—C12 | 117.0 (2) |
C9—C8—C11 | 118.3 (2) | ||
N2—C1—C2—C3 | −0.8 (4) | C7—C8—C11—O2 | −178.2 (3) |
C1—C2—C3—N1 | 0.6 (4) | C9—C8—C11—O2 | 1.1 (4) |
N1—C4—C5—C10 | −88.7 (3) | C7—C8—C11—O1 | 1.5 (4) |
N1—C4—C5—C6 | 89.5 (3) | C9—C8—C11—O1 | −179.2 (2) |
C10—C5—C6—C7 | 1.8 (4) | C2—C3—N1—N2 | −0.3 (4) |
C4—C5—C6—C7 | −176.5 (2) | C2—C3—N1—C4 | 174.4 (3) |
C5—C6—C7—C8 | 0.2 (4) | C5—C4—N1—C3 | −89.3 (4) |
C6—C7—C8—C9 | −2.0 (4) | C5—C4—N1—N2 | 84.9 (3) |
C6—C7—C8—C11 | 177.3 (2) | C2—C1—N2—N1 | 0.6 (4) |
C7—C8—C9—C10 | 1.6 (4) | C3—N1—N2—C1 | −0.2 (3) |
C11—C8—C9—C10 | −177.7 (2) | C4—N1—N2—C1 | −175.3 (2) |
C6—C5—C10—C9 | −2.1 (4) | O2—C11—O1—C12 | 1.0 (4) |
C4—C5—C10—C9 | 176.1 (2) | C8—C11—O1—C12 | −178.7 (2) |
C8—C9—C10—C5 | 0.4 (4) | C13—C12—O1—C11 | −175.4 (3) |
Cg1 and Cg2 are the centroids of the N1/N2/C1–C3 and C5–C10 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg2i | 0.93 | 2.94 | 3.670 (4) | 137 |
C4—H4A···Cg1ii | 0.97 | 3.00 | 3.600 (3) | 122 |
C12—H12A···Cg2iii | 0.97 | 2.82 | 3.689 (4) | 150 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z+1. |
Cg1 and Cg2 are the centroids of the N1/N2/C1–C3 and C5–C10 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg2i | 0.93 | 2.94 | 3.670 (4) | 137 |
C4—H4A···Cg1ii | 0.97 | 3.00 | 3.600 (3) | 122 |
C12—H12A···Cg2iii | 0.97 | 2.82 | 3.689 (4) | 150 |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z+1. |
Acknowledgements
We are grateful for financial support from the National Natural Science Foundation of China (No. 81302644) and Jiangsu Ainaji Neo Energy Science & Technology Co. Ltd (No. 8507040091).
References
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Pyrazole and its derivatives are an important class of N-heterocyclic compounds because they exhibit a broad spectrum of pharmacological activities such as antifungal (Adnan & Tarek, 2004), antitumor and antiangiogenic activities (Ashraf et al., 2003). As part of pyrazole derivatives, the crystal structure of 1, 4-bis[(1H-pyrazol-1-yl)methyl]benzene has been determined (Dong et al., 2011). As part of this ongoing search for new pyrazole compounds, the title compound was synthesized and its crystal structure is reported herein. In the title compound (Fig. 1), bond lengths and angles fall in normal ranges. The dihedral angle between the pyrazole ring (N1/N2/C1—C3) and the phenyl ring (C5—C10) is 76.06 (11) °. In the crystal, there exists weak C–H···π contacts.