organic compounds
1-(1-Benzyl-2,5-dimethyl-4-phenyl-1H-pyrrol-3-yl)ethanone
aEquipe de Chimie de Coordination et de Catalyse, Département de Chimie, Faculté des Sciences Semlalia, BP 2390, 40001 Marrakech, Morocco, and bLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
*Correspondence e-mail: elfirdoussi@uca.ma
In the title compound, C21H21NO, the dihedral angles between the planes of the phenyl and pyrrole rings are 47.04 (5) and 79.27 (3)°. In the crystal, centrosymmetrically related molecules are linked into dimers by pairs of C—H⋯O hydrogen bonds, forming rings of graph-set motif R22(16).
Keywords: crystal structure; natural catalyst; pyrrole derivative.
CCDC reference: 1556327
Structure description
Pyrrole derivatives, which are widespread in nature (Iwao et al., 2003), are of interest with respect to their versatility in organic synthetic procedures (Loudet & Burgess, 2007) and their biological and medicinal activities (Fan et al., 2008).
The molecular structure of 1-(1-benzyl-2,5-dimethyl-4-phenyl-1H-pyrrol-3-yl)ethanone is shown in Fig. 1. The dihedral angles between the planes of the pyrrole ring and the C8–C13 and C16–C21 phenyl rings are 47.04 (5) and 79.27 (3)°, respectively. The molecular conformation is enforced by an intramolecular hydrogen bond involving a methyl H atom and the carbonyl O atom (Table 1). In the crystal, molecules are linked through pairs of C—H⋯O hydrogen bonds to form R22(16) centrosymmetric dimers.
Synthesis and crystallization
The synthesis of the title compound was carried out by mixing acetylacetone (1.1 mmol), benzylamine (1.0 mmol), benzaldehyde (1.0 mmol) and nitroethane (1.3 mmol) in the presence of Ca5(PO4)3OH (0.05 mmol) as a catalyst. The mixture was stirred at 333 K for 24 h. After extraction with ethyl acetate (3 × 25 ml), the organic layer was dried with Na2SO4 and the solvent was removed under reduced pressure. The product was obtained in 74% yield after silica-gel using a mixture of n-hexane and ethyl acetate (94:6 v/v) as White crystals were obtained by slow evaporation of the solvent at room temperature (m.p. 364–365 K). 1H NMR (DMSO): δ 1.77 (s, 3H), 1.94 (s, 3H), 2.36 (s, 3H), 5.19 (s, 2H), 6.98–7.38 (m, 10H). 13C NMR (DMSO): δ 9.99, 11.47, 30.64, 46.25, 120.79, 121.42, 125.73, 126.41, 127.16, 128.12, 128.77, 130.29, 133.52, 136.72, 137.33, 195.04.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1556327
https://doi.org/10.1107/S2414314617008951/rz4016sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617008951/rz4016Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617008951/rz4016Isup3.cml
Data collection: APEX2 (Bruker, 2014); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C21H21NO | F(000) = 648 |
Mr = 303.39 | Dx = 1.239 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7210 (2) Å | Cell parameters from 9842 reflections |
b = 13.7039 (2) Å | θ = 2.5–30.5° |
c = 11.5761 (2) Å | µ = 0.08 mm−1 |
β = 107.0322 (6)° | T = 150 K |
V = 1626.16 (5) Å3 | Prism, colourless |
Z = 4 | 0.42 × 0.33 × 0.27 mm |
Bruker APEXII CCD diffractometer | 3926 independent reflections |
Radiation source: fine-focus sealed tube | 3484 reflections with I > 2σ(I) |
Detector resolution: 8.3333 pixels mm-1 | Rint = 0.021 |
φ and ω scans | θmax = 28.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −14→14 |
Tmin = 0.93, Tmax = 0.98 | k = −18→18 |
31011 measured reflections | l = −15→15 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.4997P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3926 reflections | Δρmax = 0.27 e Å−3 |
211 parameters | Δρmin = −0.22 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.69940 (10) | 0.00933 (7) | 0.28342 (9) | 0.0226 (2) | |
C2 | 0.77764 (9) | 0.04143 (7) | 0.21445 (9) | 0.0207 (2) | |
C3 | 0.88508 (9) | 0.09425 (7) | 0.29356 (9) | 0.0203 (2) | |
C4 | 0.86945 (10) | 0.09142 (7) | 0.40726 (9) | 0.0221 (2) | |
C5 | 0.57153 (11) | −0.04261 (8) | 0.24566 (11) | 0.0301 (2) | |
H5A | 0.5842 | −0.1110 | 0.2711 | 0.045* | |
H5B | 0.5354 | −0.0394 | 0.1576 | 0.045* | |
H5C | 0.5110 | −0.0115 | 0.2835 | 0.045* | |
C6 | 0.74045 (9) | 0.03075 (7) | 0.08261 (9) | 0.0223 (2) | |
C7 | 0.77732 (11) | 0.10944 (8) | 0.00737 (9) | 0.0271 (2) | |
H7A | 0.8575 | 0.0906 | −0.0112 | 0.041* | |
H7B | 0.7916 | 0.1710 | 0.0525 | 0.041* | |
H7C | 0.7068 | 0.1178 | −0.0680 | 0.041* | |
C8 | 0.99949 (9) | 0.13556 (7) | 0.26504 (8) | 0.0214 (2) | |
C9 | 1.06614 (10) | 0.08215 (8) | 0.19876 (9) | 0.0265 (2) | |
H9 | 1.0369 | 0.0184 | 0.1715 | 0.032* | |
C10 | 1.17418 (11) | 0.12067 (9) | 0.17224 (11) | 0.0333 (3) | |
H10 | 1.2177 | 0.0838 | 0.1263 | 0.040* | |
C11 | 1.21862 (11) | 0.21310 (10) | 0.21292 (11) | 0.0353 (3) | |
H11 | 1.2924 | 0.2397 | 0.1945 | 0.042* | |
C12 | 1.15563 (11) | 0.26646 (9) | 0.28026 (11) | 0.0322 (2) | |
H12 | 1.1871 | 0.3293 | 0.3094 | 0.039* | |
C13 | 1.04641 (10) | 0.22844 (8) | 0.30547 (10) | 0.0260 (2) | |
H13 | 1.0029 | 0.2661 | 0.3508 | 0.031* | |
C14 | 0.95716 (11) | 0.12583 (8) | 0.52522 (9) | 0.0271 (2) | |
H14A | 1.0417 | 0.1445 | 0.5154 | 0.041* | |
H14B | 0.9697 | 0.0733 | 0.5849 | 0.041* | |
H14C | 0.9178 | 0.1823 | 0.5529 | 0.041* | |
C15 | 0.70566 (11) | 0.02234 (8) | 0.50245 (9) | 0.0268 (2) | |
H15A | 0.7778 | −0.0018 | 0.5712 | 0.032* | |
H15B | 0.6384 | −0.0294 | 0.4805 | 0.032* | |
C16 | 0.64695 (10) | 0.11232 (7) | 0.54209 (9) | 0.0231 (2) | |
C17 | 0.69601 (10) | 0.14761 (8) | 0.65922 (9) | 0.0252 (2) | |
H17 | 0.7676 | 0.1155 | 0.7143 | 0.030* | |
C18 | 0.64164 (11) | 0.22944 (8) | 0.69680 (10) | 0.0274 (2) | |
H18 | 0.6760 | 0.2528 | 0.7771 | 0.033* | |
C19 | 0.53749 (11) | 0.27678 (8) | 0.61709 (10) | 0.0284 (2) | |
H19 | 0.5005 | 0.3329 | 0.6424 | 0.034* | |
C20 | 0.48743 (11) | 0.24209 (8) | 0.50021 (10) | 0.0300 (2) | |
H20 | 0.4156 | 0.2742 | 0.4455 | 0.036* | |
C21 | 0.54191 (10) | 0.16052 (8) | 0.46281 (9) | 0.0277 (2) | |
H21 | 0.5073 | 0.1373 | 0.3824 | 0.033* | |
N1 | 0.75568 (8) | 0.04036 (6) | 0.39956 (8) | 0.02273 (19) | |
O1 | 0.67584 (8) | −0.03911 (6) | 0.03179 (7) | 0.03149 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0272 (5) | 0.0185 (4) | 0.0237 (5) | 0.0001 (4) | 0.0102 (4) | −0.0007 (4) |
C2 | 0.0232 (5) | 0.0183 (4) | 0.0213 (5) | 0.0004 (3) | 0.0078 (4) | −0.0003 (3) |
C3 | 0.0220 (4) | 0.0186 (4) | 0.0207 (4) | 0.0017 (3) | 0.0068 (4) | −0.0003 (3) |
C4 | 0.0244 (5) | 0.0208 (4) | 0.0213 (5) | 0.0031 (4) | 0.0071 (4) | 0.0004 (4) |
C5 | 0.0317 (5) | 0.0280 (5) | 0.0343 (6) | −0.0083 (4) | 0.0154 (4) | −0.0046 (4) |
C6 | 0.0228 (4) | 0.0230 (5) | 0.0218 (5) | 0.0008 (4) | 0.0078 (4) | −0.0018 (4) |
C7 | 0.0318 (5) | 0.0291 (5) | 0.0211 (5) | −0.0023 (4) | 0.0088 (4) | 0.0014 (4) |
C8 | 0.0199 (4) | 0.0237 (5) | 0.0193 (4) | 0.0011 (3) | 0.0041 (3) | 0.0015 (4) |
C9 | 0.0257 (5) | 0.0281 (5) | 0.0264 (5) | 0.0007 (4) | 0.0086 (4) | −0.0028 (4) |
C10 | 0.0268 (5) | 0.0435 (6) | 0.0326 (6) | 0.0018 (5) | 0.0136 (4) | −0.0035 (5) |
C11 | 0.0236 (5) | 0.0456 (7) | 0.0378 (6) | −0.0066 (5) | 0.0109 (5) | 0.0019 (5) |
C12 | 0.0271 (5) | 0.0307 (6) | 0.0360 (6) | −0.0067 (4) | 0.0049 (4) | −0.0005 (4) |
C13 | 0.0249 (5) | 0.0252 (5) | 0.0270 (5) | −0.0001 (4) | 0.0062 (4) | −0.0023 (4) |
C14 | 0.0294 (5) | 0.0299 (5) | 0.0207 (5) | 0.0041 (4) | 0.0052 (4) | −0.0015 (4) |
C15 | 0.0365 (6) | 0.0245 (5) | 0.0240 (5) | 0.0030 (4) | 0.0162 (4) | 0.0041 (4) |
C16 | 0.0269 (5) | 0.0232 (5) | 0.0228 (5) | −0.0008 (4) | 0.0129 (4) | 0.0030 (4) |
C17 | 0.0263 (5) | 0.0282 (5) | 0.0221 (5) | −0.0001 (4) | 0.0089 (4) | 0.0035 (4) |
C18 | 0.0310 (5) | 0.0290 (5) | 0.0249 (5) | −0.0054 (4) | 0.0124 (4) | −0.0035 (4) |
C19 | 0.0296 (5) | 0.0241 (5) | 0.0358 (6) | −0.0012 (4) | 0.0163 (4) | −0.0019 (4) |
C20 | 0.0264 (5) | 0.0305 (5) | 0.0324 (5) | 0.0026 (4) | 0.0073 (4) | 0.0031 (4) |
C21 | 0.0300 (5) | 0.0297 (5) | 0.0227 (5) | −0.0008 (4) | 0.0071 (4) | 0.0001 (4) |
N1 | 0.0277 (4) | 0.0216 (4) | 0.0212 (4) | 0.0010 (3) | 0.0109 (3) | 0.0008 (3) |
O1 | 0.0374 (4) | 0.0303 (4) | 0.0272 (4) | −0.0095 (3) | 0.0100 (3) | −0.0083 (3) |
C1—N1 | 1.3701 (13) | C11—C12 | 1.3808 (17) |
C1—C2 | 1.3881 (13) | C11—H11 | 0.9500 |
C1—C5 | 1.4920 (14) | C12—C13 | 1.3885 (15) |
C2—C3 | 1.4393 (13) | C12—H12 | 0.9500 |
C2—C6 | 1.4674 (13) | C13—H13 | 0.9500 |
C3—C4 | 1.3752 (13) | C14—H14A | 0.9800 |
C3—C8 | 1.4735 (13) | C14—H14B | 0.9800 |
C4—N1 | 1.3861 (13) | C14—H14C | 0.9800 |
C4—C14 | 1.4896 (14) | C15—N1 | 1.4634 (12) |
C5—H5A | 0.9800 | C15—C16 | 1.5154 (14) |
C5—H5B | 0.9800 | C15—H15A | 0.9900 |
C5—H5C | 0.9800 | C15—H15B | 0.9900 |
C6—O1 | 1.2262 (12) | C16—C17 | 1.3897 (14) |
C6—C7 | 1.5098 (14) | C16—C21 | 1.3934 (15) |
C7—H7A | 0.9800 | C17—C18 | 1.3912 (15) |
C7—H7B | 0.9800 | C17—H17 | 0.9500 |
C7—H7C | 0.9800 | C18—C19 | 1.3840 (16) |
C8—C13 | 1.3980 (14) | C18—H18 | 0.9500 |
C8—C9 | 1.3987 (14) | C19—C20 | 1.3854 (16) |
C9—C10 | 1.3866 (15) | C19—H19 | 0.9500 |
C9—H9 | 0.9500 | C20—C21 | 1.3878 (16) |
C10—C11 | 1.3864 (18) | C20—H20 | 0.9500 |
C10—H10 | 0.9500 | C21—H21 | 0.9500 |
N1—C1—C2 | 107.42 (9) | C11—C12—C13 | 120.13 (10) |
N1—C1—C5 | 122.57 (9) | C11—C12—H12 | 119.9 |
C2—C1—C5 | 129.85 (9) | C13—C12—H12 | 119.9 |
C1—C2—C3 | 107.41 (8) | C12—C13—C8 | 120.94 (10) |
C1—C2—C6 | 122.73 (9) | C12—C13—H13 | 119.5 |
C3—C2—C6 | 129.42 (9) | C8—C13—H13 | 119.5 |
C4—C3—C2 | 107.19 (9) | C4—C14—H14A | 109.5 |
C4—C3—C8 | 124.62 (9) | C4—C14—H14B | 109.5 |
C2—C3—C8 | 127.90 (9) | H14A—C14—H14B | 109.5 |
C3—C4—N1 | 107.71 (9) | C4—C14—H14C | 109.5 |
C3—C4—C14 | 130.33 (10) | H14A—C14—H14C | 109.5 |
N1—C4—C14 | 121.74 (9) | H14B—C14—H14C | 109.5 |
C1—C5—H5A | 109.5 | N1—C15—C16 | 113.13 (8) |
C1—C5—H5B | 109.5 | N1—C15—H15A | 109.0 |
H5A—C5—H5B | 109.5 | C16—C15—H15A | 109.0 |
C1—C5—H5C | 109.5 | N1—C15—H15B | 109.0 |
H5A—C5—H5C | 109.5 | C16—C15—H15B | 109.0 |
H5B—C5—H5C | 109.5 | H15A—C15—H15B | 107.8 |
O1—C6—C2 | 121.34 (9) | C17—C16—C21 | 118.66 (10) |
O1—C6—C7 | 119.17 (9) | C17—C16—C15 | 120.43 (9) |
C2—C6—C7 | 119.44 (9) | C21—C16—C15 | 120.90 (9) |
C6—C7—H7A | 109.5 | C16—C17—C18 | 120.80 (10) |
C6—C7—H7B | 109.5 | C16—C17—H17 | 119.6 |
H7A—C7—H7B | 109.5 | C18—C17—H17 | 119.6 |
C6—C7—H7C | 109.5 | C19—C18—C17 | 119.97 (10) |
H7A—C7—H7C | 109.5 | C19—C18—H18 | 120.0 |
H7B—C7—H7C | 109.5 | C17—C18—H18 | 120.0 |
C13—C8—C9 | 117.94 (9) | C18—C19—C20 | 119.76 (10) |
C13—C8—C3 | 121.08 (9) | C18—C19—H19 | 120.1 |
C9—C8—C3 | 120.96 (9) | C20—C19—H19 | 120.1 |
C10—C9—C8 | 121.08 (10) | C19—C20—C21 | 120.20 (10) |
C10—C9—H9 | 119.5 | C19—C20—H20 | 119.9 |
C8—C9—H9 | 119.5 | C21—C20—H20 | 119.9 |
C11—C10—C9 | 119.93 (11) | C20—C21—C16 | 120.61 (10) |
C11—C10—H10 | 120.0 | C20—C21—H21 | 119.7 |
C9—C10—H10 | 120.0 | C16—C21—H21 | 119.7 |
C12—C11—C10 | 119.95 (10) | C1—N1—C4 | 110.26 (8) |
C12—C11—H11 | 120.0 | C1—N1—C15 | 125.82 (9) |
C10—C11—H11 | 120.0 | C4—N1—C15 | 123.93 (9) |
N1—C1—C2—C3 | −0.20 (11) | C10—C11—C12—C13 | −1.16 (18) |
C5—C1—C2—C3 | 175.30 (10) | C11—C12—C13—C8 | 0.93 (17) |
N1—C1—C2—C6 | −173.26 (9) | C9—C8—C13—C12 | 0.15 (15) |
C5—C1—C2—C6 | 2.24 (17) | C3—C8—C13—C12 | 178.85 (10) |
C1—C2—C3—C4 | 0.73 (11) | N1—C15—C16—C17 | −121.33 (10) |
C6—C2—C3—C4 | 173.16 (10) | N1—C15—C16—C21 | 59.56 (13) |
C1—C2—C3—C8 | 174.70 (9) | C21—C16—C17—C18 | −0.06 (15) |
C6—C2—C3—C8 | −12.87 (17) | C15—C16—C17—C18 | −179.19 (9) |
C2—C3—C4—N1 | −0.96 (11) | C16—C17—C18—C19 | −0.07 (16) |
C8—C3—C4—N1 | −175.18 (9) | C17—C18—C19—C20 | 0.30 (16) |
C2—C3—C4—C14 | 173.69 (10) | C18—C19—C20—C21 | −0.39 (16) |
C8—C3—C4—C14 | −0.53 (17) | C19—C20—C21—C16 | 0.26 (17) |
C1—C2—C6—O1 | −32.75 (15) | C17—C16—C21—C20 | −0.03 (15) |
C3—C2—C6—O1 | 155.84 (10) | C15—C16—C21—C20 | 179.09 (10) |
C1—C2—C6—C7 | 144.56 (10) | C2—C1—N1—C4 | −0.41 (11) |
C3—C2—C6—C7 | −26.86 (15) | C5—C1—N1—C4 | −176.30 (9) |
C4—C3—C8—C13 | −49.76 (14) | C2—C1—N1—C15 | −179.82 (9) |
C2—C3—C8—C13 | 137.25 (10) | C5—C1—N1—C15 | 4.28 (15) |
C4—C3—C8—C9 | 128.90 (11) | C3—C4—N1—C1 | 0.87 (11) |
C2—C3—C8—C9 | −44.10 (15) | C14—C4—N1—C1 | −174.33 (9) |
C13—C8—C9—C10 | −1.01 (15) | C3—C4—N1—C15 | −179.70 (9) |
C3—C8—C9—C10 | −179.71 (10) | C14—C4—N1—C15 | 5.09 (14) |
C8—C9—C10—C11 | 0.79 (17) | C16—C15—N1—C1 | −106.93 (11) |
C9—C10—C11—C12 | 0.31 (18) | C16—C15—N1—C4 | 73.73 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O1 | 0.98 | 2.38 | 3.0007 (17) | 121 |
C10—H10···O1i | 0.95 | 2.50 | 3.4114 (17) | 161 |
Symmetry code: (i) −x+2, −y, −z. |
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