Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057339/om2172sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057339/om2172Isup2.hkl |
CCDC reference: 672932
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.002 Å
- R factor = 0.044
- wR factor = 0.126
- Data-to-parameter ratio = 18.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3
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 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 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 2 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
For related literature, see: Brough et al. (2005); Cheng et al. (2006); Sehon et al. (2006); Wei et al. (2006); Xia et al. (2007). For bond-length data, see: Allen et al. (1987).
A mixture of ethyl 3-phenyl-1H-pyrazole-5-carboxylate (0.01 mol), ethyl chloroacetate (0.015 mol) and potassium carbonate (0.02 mol) in acetonitrile (50 ml) was heated to reflux for 15 h. The solvent was removed under reduced pressure, and the residue was dissolved in the mixture of water (50 ml) and ethyl acetate (50 ml). After separation, the water phase was extracted with ethyl acetate (25 ml), and then the organic phase was combined, dried over anhydrous magnesium sulfate and filtered. The solvent was removed under reduced pressure. The solid product was recrystallized from ethyl acetate (yield 62%). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in ethyl acetate at room temperature for 5 d.
All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97 Å for CH groups, 0.93 Å (for CH2 groups) and 0.96 Å (for CH3 groups). Their isotropic displacement parameters were set to 1.2 times (1.5 times for CH3 groups) the equivalent displacement parameter of their parent atoms. The anisotropic thermal parameters of C3 and C4 atoms were restrained with DELU in the final cycles of refinement.
Data collection: APEX2 Software Suite (Bruker, 2005); cell refinement: APEX2 Software Suite (Bruker, 2005); data reduction: APEX2 Software Suite (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C16H18N2O4 | F(000) = 640 |
Mr = 302.32 | Dx = 1.278 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3570 reflections |
a = 8.3898 (1) Å | θ = 2.7–24.9° |
b = 22.1418 (4) Å | µ = 0.09 mm−1 |
c = 8.6374 (1) Å | T = 296 K |
β = 101.756 (1)° | Prism, colourless |
V = 1570.87 (4) Å3 | 0.49 × 0.47 × 0.34 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 3613 independent reflections |
Radiation source: fine-focus sealed tube | 2467 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (APEX2 Software Suite; Bruker, 2005) | h = −10→10 |
Tmin = 0.87, Tmax = 0.97 | k = −28→26 |
12410 measured reflections | l = −10→11 |
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) = 0.126 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0596P)2 + 0.2035P] where P = (Fo2 + 2Fc2)/3 |
3613 reflections | (Δ/σ)max = 0.001 |
201 parameters | Δρmax = 0.15 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C16H18N2O4 | V = 1570.87 (4) Å3 |
Mr = 302.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3898 (1) Å | µ = 0.09 mm−1 |
b = 22.1418 (4) Å | T = 296 K |
c = 8.6374 (1) Å | 0.49 × 0.47 × 0.34 mm |
β = 101.756 (1)° |
Bruker APEXII CCD diffractometer | 3613 independent reflections |
Absorption correction: multi-scan (APEX2 Software Suite; Bruker, 2005) | 2467 reflections with I > 2σ(I) |
Tmin = 0.87, Tmax = 0.97 | Rint = 0.022 |
12410 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.126 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.15 e Å−3 |
3613 reflections | Δρmin = −0.21 e Å−3 |
201 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 | 0.5549 (2) | 1.14929 (7) | 0.8148 (2) | 0.0617 (4) | |
H1 | 0.4771 | 1.1463 | 0.7215 | 0.074* | |
C2 | 0.6001 (2) | 1.20574 (8) | 0.8781 (3) | 0.0764 (5) | |
H2 | 0.5530 | 1.2402 | 0.8268 | 0.092* | |
C3 | 0.7135 (3) | 1.21097 (9) | 1.0154 (3) | 0.0820 (5) | |
H3 | 0.7427 | 1.2489 | 1.0584 | 0.098* | |
C4 | 0.7840 (3) | 1.15978 (10) | 1.0895 (2) | 0.0806 (5) | |
H4 | 0.8620 | 1.1633 | 1.1825 | 0.097* | |
C5 | 0.7407 (2) | 1.10325 (8) | 1.0276 (2) | 0.0648 (4) | |
H5 | 0.7897 | 1.0690 | 1.0789 | 0.078* | |
C6 | 0.62402 (17) | 1.09726 (7) | 0.88887 (17) | 0.0498 (3) | |
C7 | 0.57432 (17) | 1.03747 (6) | 0.82124 (16) | 0.0464 (3) | |
C8 | 0.44394 (16) | 1.02254 (6) | 0.69906 (17) | 0.0471 (3) | |
H8 | 0.3682 | 1.0488 | 0.6409 | 0.057* | |
C9 | 0.45055 (17) | 0.96123 (6) | 0.68258 (17) | 0.0487 (3) | |
C10 | 0.34296 (19) | 0.91989 (7) | 0.57674 (18) | 0.0557 (4) | |
C11 | 0.0989 (2) | 0.91559 (9) | 0.3812 (2) | 0.0718 (5) | |
H11A | 0.0317 | 0.8928 | 0.4395 | 0.086* | |
H11B | 0.1512 | 0.8875 | 0.3212 | 0.086* | |
C12 | −0.0026 (2) | 0.95940 (10) | 0.2730 (3) | 0.0865 (6) | |
H12A | −0.0511 | 0.9877 | 0.3339 | 0.130* | |
H12B | −0.0867 | 0.9381 | 0.2018 | 0.130* | |
H12C | 0.0645 | 0.9807 | 0.2135 | 0.130* | |
C13 | 0.6433 (2) | 0.88134 (7) | 0.82480 (19) | 0.0614 (4) | |
H13A | 0.5545 | 0.8548 | 0.8366 | 0.074* | |
H13B | 0.7222 | 0.8813 | 0.9240 | 0.074* | |
C14 | 0.72291 (19) | 0.85706 (7) | 0.69551 (18) | 0.0550 (4) | |
C15 | 0.8330 (3) | 0.76827 (8) | 0.6072 (2) | 0.0732 (5) | |
H15A | 0.9203 | 0.7925 | 0.5811 | 0.088* | |
H15B | 0.7519 | 0.7617 | 0.5113 | 0.088* | |
C16 | 0.8972 (2) | 0.71005 (8) | 0.6745 (2) | 0.0787 (5) | |
H16A | 0.9800 | 0.7170 | 0.7673 | 0.118* | |
H16B | 0.9430 | 0.6883 | 0.5979 | 0.118* | |
H16C | 0.8106 | 0.6868 | 0.7022 | 0.118* | |
N1 | 0.65788 (15) | 0.98781 (6) | 0.87805 (15) | 0.0539 (3) | |
N2 | 0.58104 (15) | 0.94193 (5) | 0.79247 (14) | 0.0537 (3) | |
O1 | 0.22050 (13) | 0.95017 (5) | 0.48930 (14) | 0.0636 (3) | |
O2 | 0.36269 (18) | 0.86606 (5) | 0.57036 (15) | 0.0820 (4) | |
O3 | 0.75104 (17) | 0.88472 (6) | 0.58571 (16) | 0.0822 (4) | |
O4 | 0.76022 (14) | 0.79933 (5) | 0.72446 (12) | 0.0623 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0662 (10) | 0.0530 (9) | 0.0665 (10) | 0.0059 (7) | 0.0148 (8) | −0.0020 (7) |
C2 | 0.0865 (13) | 0.0517 (10) | 0.0951 (14) | 0.0013 (9) | 0.0279 (11) | −0.0036 (9) |
C3 | 0.0875 (13) | 0.0659 (11) | 0.0973 (15) | −0.0191 (9) | 0.0296 (12) | −0.0195 (10) |
C4 | 0.0762 (12) | 0.0895 (13) | 0.0738 (12) | −0.0223 (10) | 0.0097 (10) | −0.0167 (10) |
C5 | 0.0616 (9) | 0.0700 (11) | 0.0618 (10) | −0.0035 (8) | 0.0103 (8) | −0.0001 (8) |
C6 | 0.0482 (7) | 0.0529 (9) | 0.0517 (8) | 0.0004 (6) | 0.0182 (6) | −0.0011 (6) |
C7 | 0.0487 (7) | 0.0469 (8) | 0.0463 (8) | 0.0068 (6) | 0.0160 (6) | 0.0043 (6) |
C8 | 0.0461 (7) | 0.0456 (8) | 0.0511 (8) | 0.0060 (6) | 0.0137 (6) | 0.0048 (6) |
C9 | 0.0534 (8) | 0.0462 (8) | 0.0488 (8) | 0.0053 (6) | 0.0154 (6) | 0.0038 (6) |
C10 | 0.0675 (10) | 0.0487 (9) | 0.0548 (9) | −0.0018 (7) | 0.0215 (8) | −0.0008 (7) |
C11 | 0.0622 (10) | 0.0781 (12) | 0.0759 (11) | −0.0222 (9) | 0.0160 (9) | −0.0213 (10) |
C12 | 0.0546 (10) | 0.1118 (17) | 0.0885 (14) | −0.0013 (10) | 0.0038 (10) | −0.0248 (12) |
C13 | 0.0820 (11) | 0.0473 (9) | 0.0563 (9) | 0.0178 (8) | 0.0173 (8) | 0.0105 (7) |
C14 | 0.0611 (9) | 0.0485 (9) | 0.0544 (9) | 0.0111 (7) | 0.0093 (7) | 0.0088 (7) |
C15 | 0.0983 (13) | 0.0651 (11) | 0.0597 (10) | 0.0174 (10) | 0.0240 (9) | −0.0052 (8) |
C16 | 0.0852 (13) | 0.0645 (11) | 0.0877 (13) | 0.0173 (9) | 0.0209 (10) | −0.0100 (10) |
N1 | 0.0593 (7) | 0.0531 (7) | 0.0494 (7) | 0.0097 (6) | 0.0112 (6) | 0.0022 (6) |
N2 | 0.0661 (8) | 0.0433 (7) | 0.0519 (7) | 0.0117 (6) | 0.0128 (6) | 0.0051 (5) |
O1 | 0.0533 (6) | 0.0584 (7) | 0.0757 (7) | −0.0044 (5) | 0.0055 (5) | −0.0126 (5) |
O2 | 0.1163 (11) | 0.0464 (7) | 0.0798 (9) | 0.0013 (7) | 0.0116 (8) | −0.0051 (6) |
O3 | 0.1095 (10) | 0.0694 (8) | 0.0780 (9) | 0.0284 (7) | 0.0433 (8) | 0.0283 (7) |
O4 | 0.0876 (8) | 0.0459 (6) | 0.0560 (6) | 0.0150 (5) | 0.0210 (6) | 0.0039 (5) |
C1—C2 | 1.386 (2) | C11—C12 | 1.488 (3) |
C1—C6 | 1.386 (2) | C11—H11A | 0.9700 |
C1—H1 | 0.9300 | C11—H11B | 0.9700 |
C2—C3 | 1.366 (3) | C12—H12A | 0.9600 |
C2—H2 | 0.9300 | C12—H12B | 0.9600 |
C3—C4 | 1.375 (3) | C12—H12C | 0.9600 |
C3—H3 | 0.9300 | C13—N2 | 1.4460 (18) |
C4—C5 | 1.380 (2) | C13—C14 | 1.512 (2) |
C4—H4 | 0.9300 | C13—H13A | 0.9700 |
C5—C6 | 1.391 (2) | C13—H13B | 0.9700 |
C5—H5 | 0.9300 | C14—O3 | 1.1921 (18) |
C6—C7 | 1.472 (2) | C14—O4 | 1.3276 (17) |
C7—N1 | 1.3422 (17) | C15—O4 | 1.4576 (19) |
C7—C8 | 1.396 (2) | C15—C16 | 1.471 (2) |
C8—C9 | 1.3673 (19) | C15—H15A | 0.9700 |
C8—H8 | 0.9300 | C15—H15B | 0.9700 |
C9—N2 | 1.3633 (19) | C16—H16A | 0.9600 |
C9—C10 | 1.467 (2) | C16—H16B | 0.9600 |
C10—O2 | 1.2061 (19) | C16—H16C | 0.9600 |
C10—O1 | 1.3263 (19) | N1—N2 | 1.3415 (18) |
C11—O1 | 1.4530 (19) | ||
C2—C1—C6 | 120.81 (17) | H11A—C11—H11B | 108.5 |
C2—C1—H1 | 119.6 | C11—C12—H12A | 109.5 |
C6—C1—H1 | 119.6 | C11—C12—H12B | 109.5 |
C3—C2—C1 | 120.35 (19) | H12A—C12—H12B | 109.5 |
C3—C2—H2 | 119.8 | C11—C12—H12C | 109.5 |
C1—C2—H2 | 119.8 | H12A—C12—H12C | 109.5 |
C2—C3—C4 | 119.48 (18) | H12B—C12—H12C | 109.5 |
C2—C3—H3 | 120.3 | N2—C13—C14 | 112.57 (12) |
C4—C3—H3 | 120.3 | N2—C13—H13A | 109.1 |
C3—C4—C5 | 120.83 (19) | C14—C13—H13A | 109.1 |
C3—C4—H4 | 119.6 | N2—C13—H13B | 109.1 |
C5—C4—H4 | 119.6 | C14—C13—H13B | 109.1 |
C4—C5—C6 | 120.27 (17) | H13A—C13—H13B | 107.8 |
C4—C5—H5 | 119.9 | O3—C14—O4 | 124.55 (15) |
C6—C5—H5 | 119.9 | O3—C14—C13 | 126.43 (14) |
C1—C6—C5 | 118.25 (15) | O4—C14—C13 | 109.02 (12) |
C1—C6—C7 | 120.39 (14) | O4—C15—C16 | 108.09 (14) |
C5—C6—C7 | 121.36 (14) | O4—C15—H15A | 110.1 |
N1—C7—C8 | 110.65 (13) | C16—C15—H15A | 110.1 |
N1—C7—C6 | 120.46 (13) | O4—C15—H15B | 110.1 |
C8—C7—C6 | 128.88 (13) | C16—C15—H15B | 110.1 |
C9—C8—C7 | 105.76 (12) | H15A—C15—H15B | 108.4 |
C9—C8—H8 | 127.1 | C15—C16—H16A | 109.5 |
C7—C8—H8 | 127.1 | C15—C16—H16B | 109.5 |
N2—C9—C8 | 106.42 (13) | H16A—C16—H16B | 109.5 |
N2—C9—C10 | 122.90 (13) | C15—C16—H16C | 109.5 |
C8—C9—C10 | 130.65 (14) | H16A—C16—H16C | 109.5 |
O2—C10—O1 | 124.82 (15) | H16B—C16—H16C | 109.5 |
O2—C10—C9 | 124.91 (15) | N2—N1—C7 | 105.21 (12) |
O1—C10—C9 | 110.27 (13) | N1—N2—C9 | 111.95 (11) |
O1—C11—C12 | 107.29 (15) | N1—N2—C13 | 118.81 (13) |
O1—C11—H11A | 110.3 | C9—N2—C13 | 129.23 (13) |
C12—C11—H11A | 110.3 | C10—O1—C11 | 117.43 (13) |
O1—C11—H11B | 110.3 | C14—O4—C15 | 116.07 (12) |
C12—C11—H11B | 110.3 | ||
C6—C1—C2—C3 | −0.3 (3) | C8—C9—C10—O1 | −1.7 (2) |
C1—C2—C3—C4 | 0.8 (3) | N2—C13—C14—O3 | 8.0 (3) |
C2—C3—C4—C5 | −0.6 (3) | N2—C13—C14—O4 | −173.03 (14) |
C3—C4—C5—C6 | −0.2 (3) | C8—C7—N1—N2 | 0.04 (15) |
C2—C1—C6—C5 | −0.4 (2) | C6—C7—N1—N2 | 179.59 (12) |
C2—C1—C6—C7 | 179.60 (14) | C7—N1—N2—C9 | −0.01 (15) |
C4—C5—C6—C1 | 0.7 (2) | C7—N1—N2—C13 | 179.56 (12) |
C4—C5—C6—C7 | −179.34 (15) | C8—C9—N2—N1 | −0.02 (15) |
C1—C6—C7—N1 | 169.66 (13) | C10—C9—N2—N1 | −178.18 (12) |
C5—C6—C7—N1 | −10.3 (2) | C8—C9—N2—C13 | −179.53 (14) |
C1—C6—C7—C8 | −10.9 (2) | C10—C9—N2—C13 | 2.3 (2) |
C5—C6—C7—C8 | 169.16 (14) | C14—C13—N2—N1 | −108.46 (16) |
N1—C7—C8—C9 | −0.05 (15) | C14—C13—N2—C9 | 71.0 (2) |
C6—C7—C8—C9 | −179.56 (13) | O2—C10—O1—C11 | 1.8 (2) |
C7—C8—C9—N2 | 0.04 (15) | C9—C10—O1—C11 | −177.99 (12) |
C7—C8—C9—C10 | 178.01 (13) | C12—C11—O1—C10 | −167.62 (14) |
N2—C9—C10—O2 | −3.8 (2) | O3—C14—O4—C15 | −3.2 (2) |
C8—C9—C10—O2 | 178.49 (15) | C13—C14—O4—C15 | 177.84 (15) |
N2—C9—C10—O1 | 175.99 (12) | C16—C15—O4—C14 | 168.07 (15) |
Experimental details
Crystal data | |
Chemical formula | C16H18N2O4 |
Mr | 302.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.3898 (1), 22.1418 (4), 8.6374 (1) |
β (°) | 101.756 (1) |
V (Å3) | 1570.87 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.49 × 0.47 × 0.34 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (APEX2 Software Suite; Bruker, 2005) |
Tmin, Tmax | 0.87, 0.97 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12410, 3613, 2467 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.126, 1.03 |
No. of reflections | 3613 |
No. of parameters | 201 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.21 |
Computer programs: APEX2 Software Suite (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), WinGX (Farrugia, 1999).
X—H···Cg | X—H | H···Cg | X···Cg | D—H···Cg |
C13—H13A···Cg1i | 0.97 | 2.88 | 3.6436 (19) | 136 |
Symmetry code: (i) 1-x,-y,-z. |
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Pyrazole derivatives are an important class of heteroaromatic ring systems that have found extensive use in the pharmaceutical industry. Many pyrazole derivatives are known to exhibit a wide range of biological properties such as antagonists (Sehon et al., 2006), anti-inflammatory (Cheng et al., 2006), inhibitors of the Hsp90 (Brough et al., 2005), and antitumor (Wei et al., 2006, Xia et al.., 2007).
In the title compound (Fig. 1), all bond lengths and angles are normal (Allen et al., 1987). The dihedral angles between the rings of the pyrazole and the benzene ring is 10.64 (9)°. The two ethyl carboxylate group are inclined to the attached pyrazole ring by 3.34 (7)° and 74.15 (9)°, respectively. The molecules are linked into a parallel network by C—H···π interactions (Table 1) involving the benzene ring (centroid Cg1).