Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048854/fj2048sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048854/fj2048Isup2.hkl |
CCDC reference: 667326
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C)= 0.002 Å
- R factor = 0.043
- wR factor = 0.115
- Data-to-parameter ratio = 14.5
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
For background, see: Haisa et al. (1980); Nichols & Frampton (1998); Oswald et al. (2002); Hansen et al. (2006). For reference structural data, see: Allen et al. (1995).
Paracetamol was treated with K2CO3 and 1-iodopropane in acetone to yield the crude pruduct. Recrystallization from acetone yielded colourless prisms of (I).
The N-bound hydrogen atom was located in a difference map and its position was freely refined with Uiso(H) = 1.2Ueq(N). The C-bound hydrogen atoms were geometrically placed (C—H = 0.95–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not tip, to best fit the electron density.
The title compound, (I), with R = n-Pr, complements the series of molecules with R = H [N-(4-hydroxyphenyl)acetamide or acetaminophen or paracetamol], R = Me [N-(4-methoxyphenyl)acetamide; Haisa et al. (1980)] and R = Et [N-(4-ethoxyphenyl)acetamide or phenacetin; Hansen et al. (2006)]. Crystallographically, paracetamol is notable for its polymorphism, adopting at least four crystalline forms (Nichols & Frampton, 1998), as well as its participation in a variety of distinctive supramolecular networks (Oswald et al., 2002).
The molecule of (I) is approximately planar, with an r.m.s. deviation from the mean plane of 0.084 Å for the non-hydrogen atoms. The short C6—N1 bond length of 1.4145 (17) Å and the bond-angle sum of 360° for N1 suggest some electronic interaction between the π cloud of the benzene ring and the p electrons of N1, C7 and O1. Otherwise, the geometry of (I) may be regarded as normal (Allen et al., 1995).
In the crystal of (I), an N—H···O hydrogen bond (Table 1) links the molecules into C(4) chains propagating in [010] (Fig. 2). The unit-cell packing for (I) results in distinctive zigzag (100) sheets (Fig. 3). There are no aromatic π-π stacking interactions in (I) as the closest benzene ring centroid-centroid separation is greater than 4.51 Å.
Supramolecular C(4) hydrogen bonded chains containing the characteristic ···O=C—N—H··· amide unit are also observed in the crystals of N-(4-methoxyphenyl)acetamide (Haisa et al., 1980) and phenacetin (Hansen et al., 2006). However, paracetamol adopts different hydrogen bonding patterns: either –N—H···OH or –O—H···O—H··· hydrogen bonds are seen, depending on the polymorph (Nichols & Frampton, 1998)
For background, see: Haisa et al. (1980); Nichols & Frampton (1998); Oswald et al. (2002); Hansen et al. (2006). For reference structural data, see: Allen et al. (1995).
Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C11H15NO2 | F(000) = 832 |
Mr = 193.24 | Dx = 1.222 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 6098 reflections |
a = 11.7776 (11) Å | θ = 2.4–28.7° |
b = 9.4779 (8) Å | µ = 0.08 mm−1 |
c = 18.8180 (18) Å | T = 93 K |
V = 2100.6 (3) Å3 | Prism, colourless |
Z = 8 | 0.20 × 0.10 × 0.10 mm |
Rigaku Mercury CCD diffractometer | 1702 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 25.3°, θmin = 2.8° |
ω and φ scans | h = −14→14 |
12750 measured reflections | k = −10→11 |
1916 independent reflections | l = −22→16 |
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)] = 0.043 | Hydrogen site location: difmap and geom |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0648P)2 + 0.5326P] where P = (Fo2 + 2Fc2)/3 |
1916 reflections | (Δ/σ)max < 0.001 |
132 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C11H15NO2 | V = 2100.6 (3) Å3 |
Mr = 193.24 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 11.7776 (11) Å | µ = 0.08 mm−1 |
b = 9.4779 (8) Å | T = 93 K |
c = 18.8180 (18) Å | 0.20 × 0.10 × 0.10 mm |
Rigaku Mercury CCD diffractometer | 1702 reflections with I > 2σ(I) |
12750 measured reflections | Rint = 0.027 |
1916 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.17 e Å−3 |
1916 reflections | Δρmin = −0.17 e Å−3 |
132 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 | 0.54255 (11) | 0.29534 (13) | 0.34000 (7) | 0.0215 (3) | |
H1A | 0.5712 | 0.2107 | 0.3197 | 0.026* | |
C2 | 0.45492 (11) | 0.29033 (14) | 0.38907 (7) | 0.0226 (3) | |
H2 | 0.4242 | 0.2015 | 0.4023 | 0.027* | |
C3 | 0.41105 (11) | 0.41241 (14) | 0.41933 (7) | 0.0207 (3) | |
C4 | 0.45639 (11) | 0.54225 (14) | 0.39988 (7) | 0.0219 (3) | |
H4 | 0.4274 | 0.6268 | 0.4200 | 0.026* | |
C5 | 0.54437 (11) | 0.54724 (13) | 0.35089 (7) | 0.0210 (3) | |
H5 | 0.5752 | 0.6361 | 0.3378 | 0.025* | |
C6 | 0.58849 (10) | 0.42529 (13) | 0.32056 (7) | 0.0182 (3) | |
C7 | 0.74534 (11) | 0.34160 (14) | 0.24285 (7) | 0.0211 (3) | |
C8 | 0.83580 (12) | 0.39449 (15) | 0.19276 (8) | 0.0281 (4) | |
H8A | 0.8423 | 0.4972 | 0.1971 | 0.042* | |
H8B | 0.8152 | 0.3700 | 0.1438 | 0.042* | |
H8C | 0.9087 | 0.3506 | 0.2048 | 0.042* | |
C9 | 0.27433 (12) | 0.51676 (14) | 0.49810 (7) | 0.0245 (3) | |
H9A | 0.2452 | 0.5813 | 0.4610 | 0.029* | |
H9B | 0.3321 | 0.5676 | 0.5265 | 0.029* | |
C10 | 0.17881 (12) | 0.46751 (16) | 0.54514 (8) | 0.0316 (4) | |
H10A | 0.2092 | 0.4020 | 0.5814 | 0.038* | |
H10B | 0.1227 | 0.4153 | 0.5161 | 0.038* | |
C11 | 0.12012 (14) | 0.59032 (16) | 0.58193 (8) | 0.0351 (4) | |
H11A | 0.0586 | 0.5544 | 0.6120 | 0.053* | |
H11B | 0.0887 | 0.6545 | 0.5461 | 0.053* | |
H11C | 0.1752 | 0.6412 | 0.6114 | 0.053* | |
N1 | 0.67758 (9) | 0.44174 (12) | 0.27083 (6) | 0.0193 (3) | |
H1 | 0.6928 (14) | 0.5298 (18) | 0.2586 (7) | 0.023* | |
O1 | 0.73594 (9) | 0.21529 (10) | 0.25639 (5) | 0.0298 (3) | |
O2 | 0.32328 (8) | 0.39351 (10) | 0.46613 (5) | 0.0257 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0241 (7) | 0.0167 (7) | 0.0237 (7) | 0.0015 (5) | −0.0002 (5) | −0.0011 (5) |
C2 | 0.0252 (7) | 0.0182 (7) | 0.0246 (7) | −0.0031 (5) | 0.0005 (5) | 0.0019 (5) |
C3 | 0.0199 (7) | 0.0236 (7) | 0.0187 (6) | 0.0002 (5) | −0.0009 (5) | 0.0020 (5) |
C4 | 0.0247 (7) | 0.0183 (7) | 0.0228 (7) | 0.0025 (5) | 0.0002 (5) | −0.0023 (5) |
C5 | 0.0222 (7) | 0.0173 (7) | 0.0235 (7) | −0.0014 (5) | −0.0007 (5) | 0.0015 (5) |
C6 | 0.0183 (6) | 0.0191 (7) | 0.0174 (6) | 0.0009 (5) | −0.0039 (5) | 0.0009 (5) |
C7 | 0.0201 (7) | 0.0211 (8) | 0.0220 (7) | 0.0022 (5) | −0.0027 (5) | −0.0005 (5) |
C8 | 0.0259 (7) | 0.0272 (8) | 0.0313 (8) | 0.0028 (6) | 0.0045 (6) | −0.0004 (6) |
C9 | 0.0247 (7) | 0.0245 (7) | 0.0243 (7) | 0.0029 (6) | 0.0012 (6) | 0.0001 (6) |
C10 | 0.0279 (8) | 0.0344 (9) | 0.0326 (8) | 0.0007 (6) | 0.0083 (6) | −0.0021 (6) |
C11 | 0.0326 (8) | 0.0397 (9) | 0.0329 (8) | 0.0064 (7) | 0.0087 (7) | 0.0012 (7) |
N1 | 0.0209 (6) | 0.0151 (6) | 0.0218 (6) | −0.0007 (4) | 0.0015 (4) | 0.0008 (4) |
O1 | 0.0313 (6) | 0.0180 (6) | 0.0401 (6) | 0.0052 (4) | 0.0057 (4) | 0.0021 (4) |
O2 | 0.0262 (5) | 0.0238 (5) | 0.0270 (5) | 0.0000 (4) | 0.0080 (4) | 0.0000 (4) |
C1—C2 | 1.3856 (19) | C8—H8A | 0.9800 |
C1—C6 | 1.3941 (18) | C8—H8B | 0.9800 |
C1—H1A | 0.9500 | C8—H8C | 0.9800 |
C2—C3 | 1.3894 (18) | C9—O2 | 1.4349 (16) |
C2—H2 | 0.9500 | C9—C10 | 1.506 (2) |
C3—O2 | 1.3697 (16) | C9—H9A | 0.9900 |
C3—C4 | 1.3905 (18) | C9—H9B | 0.9900 |
C4—C5 | 1.3877 (19) | C10—C11 | 1.521 (2) |
C4—H4 | 0.9500 | C10—H10A | 0.9900 |
C5—C6 | 1.3899 (17) | C10—H10B | 0.9900 |
C5—H5 | 0.9500 | C11—H11A | 0.9800 |
C6—N1 | 1.4145 (17) | C11—H11B | 0.9800 |
C7—O1 | 1.2289 (17) | C11—H11C | 0.9800 |
C7—N1 | 1.3471 (17) | N1—H1 | 0.884 (17) |
C7—C8 | 1.5083 (19) | ||
C2—C1—C6 | 119.62 (12) | H8A—C8—H8C | 109.5 |
C2—C1—H1A | 120.2 | H8B—C8—H8C | 109.5 |
C6—C1—H1A | 120.2 | O2—C9—C10 | 107.12 (11) |
C1—C2—C3 | 121.44 (12) | O2—C9—H9A | 110.3 |
C1—C2—H2 | 119.3 | C10—C9—H9A | 110.3 |
C3—C2—H2 | 119.3 | O2—C9—H9B | 110.3 |
O2—C3—C2 | 115.80 (11) | C10—C9—H9B | 110.3 |
O2—C3—C4 | 125.09 (12) | H9A—C9—H9B | 108.5 |
C2—C3—C4 | 119.10 (12) | C9—C10—C11 | 111.72 (12) |
C5—C4—C3 | 119.46 (11) | C9—C10—H10A | 109.3 |
C5—C4—H4 | 120.3 | C11—C10—H10A | 109.3 |
C3—C4—H4 | 120.3 | C9—C10—H10B | 109.3 |
C4—C5—C6 | 121.58 (11) | C11—C10—H10B | 109.3 |
C4—C5—H5 | 119.2 | H10A—C10—H10B | 107.9 |
C6—C5—H5 | 119.2 | C10—C11—H11A | 109.5 |
C5—C6—C1 | 118.80 (12) | C10—C11—H11B | 109.5 |
C5—C6—N1 | 117.21 (11) | H11A—C11—H11B | 109.5 |
C1—C6—N1 | 123.98 (11) | C10—C11—H11C | 109.5 |
O1—C7—N1 | 123.50 (12) | H11A—C11—H11C | 109.5 |
O1—C7—C8 | 121.12 (12) | H11B—C11—H11C | 109.5 |
N1—C7—C8 | 115.38 (12) | C7—N1—C6 | 128.33 (11) |
C7—C8—H8A | 109.5 | C7—N1—H1 | 116.3 (10) |
C7—C8—H8B | 109.5 | C6—N1—H1 | 115.3 (10) |
H8A—C8—H8B | 109.5 | C3—O2—C9 | 117.79 (10) |
C7—C8—H8C | 109.5 | ||
C6—C1—C2—C3 | 0.3 (2) | C2—C1—C6—N1 | −179.72 (11) |
C1—C2—C3—O2 | 178.89 (11) | O2—C9—C10—C11 | −179.87 (12) |
C1—C2—C3—C4 | −0.1 (2) | O1—C7—N1—C6 | 2.0 (2) |
O2—C3—C4—C5 | −178.96 (12) | C8—C7—N1—C6 | −177.89 (12) |
C2—C3—C4—C5 | −0.1 (2) | C5—C6—N1—C7 | 168.77 (12) |
C3—C4—C5—C6 | 0.1 (2) | C1—C6—N1—C7 | −11.8 (2) |
C4—C5—C6—C1 | 0.17 (19) | C2—C3—O2—C9 | −179.29 (11) |
C4—C5—C6—N1 | 179.59 (11) | C4—C3—O2—C9 | −0.40 (18) |
C2—C1—C6—C5 | −0.34 (19) | C10—C9—O2—C3 | 178.51 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.884 (17) | 1.949 (17) | 2.7988 (15) | 160.8 (14) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C11H15NO2 |
Mr | 193.24 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 93 |
a, b, c (Å) | 11.7776 (11), 9.4779 (8), 18.8180 (18) |
V (Å3) | 2100.6 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.20 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12750, 1916, 1702 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.115, 1.06 |
No. of reflections | 1916 |
No. of parameters | 132 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.884 (17) | 1.949 (17) | 2.7988 (15) | 160.8 (14) |
Symmetry code: (i) −x+3/2, y+1/2, z. |
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
The title compound, (I), with R = n-Pr, complements the series of molecules with R = H [N-(4-hydroxyphenyl)acetamide or acetaminophen or paracetamol], R = Me [N-(4-methoxyphenyl)acetamide; Haisa et al. (1980)] and R = Et [N-(4-ethoxyphenyl)acetamide or phenacetin; Hansen et al. (2006)]. Crystallographically, paracetamol is notable for its polymorphism, adopting at least four crystalline forms (Nichols & Frampton, 1998), as well as its participation in a variety of distinctive supramolecular networks (Oswald et al., 2002).
The molecule of (I) is approximately planar, with an r.m.s. deviation from the mean plane of 0.084 Å for the non-hydrogen atoms. The short C6—N1 bond length of 1.4145 (17) Å and the bond-angle sum of 360° for N1 suggest some electronic interaction between the π cloud of the benzene ring and the p electrons of N1, C7 and O1. Otherwise, the geometry of (I) may be regarded as normal (Allen et al., 1995).
In the crystal of (I), an N—H···O hydrogen bond (Table 1) links the molecules into C(4) chains propagating in [010] (Fig. 2). The unit-cell packing for (I) results in distinctive zigzag (100) sheets (Fig. 3). There are no aromatic π-π stacking interactions in (I) as the closest benzene ring centroid-centroid separation is greater than 4.51 Å.
Supramolecular C(4) hydrogen bonded chains containing the characteristic ···O=C—N—H··· amide unit are also observed in the crystals of N-(4-methoxyphenyl)acetamide (Haisa et al., 1980) and phenacetin (Hansen et al., 2006). However, paracetamol adopts different hydrogen bonding patterns: either –N—H···OH or –O—H···O—H··· hydrogen bonds are seen, depending on the polymorph (Nichols & Frampton, 1998)