Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040950/sj2337sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040950/sj2337Isup2.hkl |
CCDC reference: 660346
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.093
- Data-to-parameter ratio = 14.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H9A .. BR1 .. 2.99 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 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 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was prepared by slowly adding concentrated sulfuric acid (2.0 ml) dropwise to a mixture of N-phenylpropionamide (3.7 g, 0.025 mol), sodium bromide (2.6 g, 0.025 mol), 30% hydrogen peroxide (5.0 ml, 0.05 mol) and ethanol (20 ml). The mixture was stirred in air at room temperature for 30 min. The resulting product was separated by filtration (yield 5.3 g, 93%). Single crystals were obtained from a solution of 0.2 g of the product in 25 ml of distilled water by slow concentration over a period of 1 week at room temperature.
All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, Uiso=1.2Ueq (C) for aromatic, 0.97 Å, Uiso = 1.2Ueq (C) for CH2, 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms and 0.86 Å, Uiso = 1.2Ueq (N) for the NH atom.
The amide moiety is an important constituent of many biologically significant compounds. Structural studies of amides are therefore of interest (Knopfel et al., 2005; Guo, 2004; Parvez et al., 2004). As part of a study of possible drugs, the crystal structure of the title compound (I) is reported herein, Fig. 1. Bond distances and angles are normal, within experimental error (Allen et al., 1987).
In the structure of (I), the molecular skeleton is essentially planar with atoms O1, C7, C8 and C9 lying 0.6630, 0.2724, 0.0990 and 0.1530 Å, respectively, out of the N1/C1—C6/Br1 mean plane. Intermolecular N1—H1A···O1i hydrogen bonds (see Table 1 for symmetry code) link the molecules into chains (Fig. 2). Further, short C—H···Br contacts (distance = 3.555 (3) Å) stabilize the packing in the structure.
For structural studies on other amides, see: Knopfel et al. (2005); Guo (2004); Parvez et al. (2004).
For bond-length data, see: Allen et al. (1987).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
C9H10BrNO | F(000) = 912 |
Mr = 228.09 | Dx = 1.676 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3850 reflections |
a = 9.3879 (19) Å | θ = 2.0–27.9° |
b = 9.2952 (19) Å | µ = 4.50 mm−1 |
c = 20.721 (4) Å | T = 294 K |
V = 1808.2 (6) Å3 | Plate, colorless |
Z = 8 | 0.08 × 0.08 × 0.04 mm |
Rigaku Saturn diffractometer | 1587 independent reflections |
Radiation source: rotating anode | 1375 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.064 |
Detector resolution: 28.788 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −11→7 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −10→11 |
Tmin = 0.712, Tmax = 0.835 | l = −24→24 |
10043 measured 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0501P)2] where P = (Fo2 + 2Fc2)/3 |
1587 reflections | (Δ/σ)max = 0.001 |
110 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.76 e Å−3 |
C9H10BrNO | V = 1808.2 (6) Å3 |
Mr = 228.09 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.3879 (19) Å | µ = 4.50 mm−1 |
b = 9.2952 (19) Å | T = 294 K |
c = 20.721 (4) Å | 0.08 × 0.08 × 0.04 mm |
Rigaku Saturn diffractometer | 1587 independent reflections |
Absorption correction: multi-scan (Jacobson, 1998) | 1375 reflections with I > 2σ(I) |
Tmin = 0.712, Tmax = 0.835 | Rint = 0.064 |
10043 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.59 e Å−3 |
1587 reflections | Δρmin = −0.76 e Å−3 |
110 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 | ||
Br1 | 0.23826 (4) | 0.03223 (3) | 0.528300 (15) | 0.03307 (18) | |
N1 | 0.3167 (3) | 0.4370 (2) | 0.30106 (11) | 0.0211 (5) | |
H1A | 0.4042 | 0.4501 | 0.2932 | 0.025* | |
O1 | 0.0960 (2) | 0.45235 (19) | 0.25674 (9) | 0.0275 (5) | |
C1 | 0.2921 (3) | 0.3403 (3) | 0.35205 (13) | 0.0195 (6) | |
C2 | 0.1577 (3) | 0.3134 (3) | 0.37778 (14) | 0.0245 (7) | |
H2 | 0.0780 | 0.3580 | 0.3602 | 0.029* | |
C3 | 0.1428 (3) | 0.2203 (3) | 0.42943 (14) | 0.0248 (7) | |
H3 | 0.0530 | 0.2016 | 0.4464 | 0.030* | |
C4 | 0.2612 (3) | 0.1554 (3) | 0.45556 (15) | 0.0238 (7) | |
C5 | 0.3955 (3) | 0.1803 (3) | 0.43096 (14) | 0.0280 (7) | |
H5 | 0.4746 | 0.1353 | 0.4489 | 0.034* | |
C6 | 0.4107 (3) | 0.2730 (3) | 0.37931 (14) | 0.0251 (7) | |
H6 | 0.5009 | 0.2908 | 0.3625 | 0.030* | |
C7 | 0.2219 (3) | 0.4876 (3) | 0.25727 (16) | 0.0209 (7) | |
C8 | 0.2844 (3) | 0.5911 (3) | 0.20894 (15) | 0.0238 (7) | |
H8A | 0.3453 | 0.5384 | 0.1794 | 0.029* | |
H8B | 0.3432 | 0.6607 | 0.2315 | 0.029* | |
C9 | 0.1713 (3) | 0.6702 (3) | 0.17065 (15) | 0.0294 (7) | |
H9A | 0.1148 | 0.6021 | 0.1471 | 0.044* | |
H9B | 0.2162 | 0.7353 | 0.1410 | 0.044* | |
H9C | 0.1113 | 0.7234 | 0.1996 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0451 (3) | 0.0296 (3) | 0.0246 (3) | 0.00330 (13) | 0.00111 (13) | 0.00321 (12) |
N1 | 0.0113 (12) | 0.0276 (12) | 0.0244 (13) | −0.0007 (10) | 0.0004 (11) | 0.0004 (10) |
O1 | 0.0147 (11) | 0.0365 (11) | 0.0314 (12) | −0.0016 (9) | −0.0024 (9) | 0.0040 (9) |
C1 | 0.0200 (15) | 0.0187 (14) | 0.0200 (15) | 0.0013 (12) | −0.0006 (12) | −0.0058 (12) |
C2 | 0.0153 (15) | 0.0315 (15) | 0.0267 (17) | −0.0013 (12) | −0.0021 (13) | −0.0026 (13) |
C3 | 0.0210 (16) | 0.0309 (15) | 0.0224 (17) | −0.0044 (13) | −0.0007 (13) | −0.0025 (12) |
C4 | 0.0333 (18) | 0.0202 (15) | 0.0177 (15) | 0.0001 (12) | −0.0009 (13) | −0.0006 (14) |
C5 | 0.0245 (17) | 0.0319 (15) | 0.0276 (17) | 0.0077 (14) | −0.0042 (14) | −0.0024 (14) |
C6 | 0.0180 (15) | 0.0304 (15) | 0.0269 (17) | 0.0034 (12) | 0.0007 (13) | −0.0014 (13) |
C7 | 0.0168 (16) | 0.0246 (14) | 0.0212 (17) | 0.0019 (12) | 0.0012 (12) | −0.0060 (12) |
C8 | 0.0202 (16) | 0.0249 (15) | 0.0263 (17) | −0.0023 (12) | 0.0014 (12) | 0.0032 (14) |
C9 | 0.0282 (17) | 0.0292 (15) | 0.0308 (18) | 0.0024 (14) | 0.0007 (15) | 0.0041 (14) |
Br1—C4 | 1.905 (3) | C4—C5 | 1.380 (4) |
N1—C7 | 1.355 (4) | C5—C6 | 1.382 (4) |
N1—C1 | 1.406 (4) | C5—H5 | 0.9300 |
N1—H1A | 0.8457 | C6—H6 | 0.9300 |
O1—C7 | 1.226 (3) | C7—C8 | 1.508 (4) |
C1—C2 | 1.392 (4) | C8—C9 | 1.516 (4) |
C1—C6 | 1.397 (4) | C8—H8A | 0.9700 |
C2—C3 | 1.383 (4) | C8—H8B | 0.9700 |
C2—H2 | 0.9300 | C9—H9A | 0.9600 |
C3—C4 | 1.376 (4) | C9—H9B | 0.9600 |
C3—H3 | 0.9300 | C9—H9C | 0.9600 |
C7—N1—C1 | 128.1 (3) | C5—C6—C1 | 120.7 (3) |
C7—N1—H1A | 117.3 | C5—C6—H6 | 119.7 |
C1—N1—H1A | 113.3 | C1—C6—H6 | 119.7 |
C2—C1—C6 | 119.1 (3) | O1—C7—N1 | 123.1 (3) |
C2—C1—N1 | 123.5 (3) | O1—C7—C8 | 122.6 (3) |
C6—C1—N1 | 117.3 (3) | N1—C7—C8 | 114.2 (3) |
C3—C2—C1 | 120.1 (3) | C7—C8—C9 | 112.6 (3) |
C3—C2—H2 | 120.0 | C7—C8—H8A | 109.1 |
C1—C2—H2 | 120.0 | C9—C8—H8A | 109.1 |
C4—C3—C2 | 119.8 (3) | C7—C8—H8B | 109.1 |
C4—C3—H3 | 120.1 | C9—C8—H8B | 109.1 |
C2—C3—H3 | 120.1 | H8A—C8—H8B | 107.8 |
C3—C4—C5 | 121.3 (3) | C8—C9—H9A | 109.5 |
C3—C4—Br1 | 118.9 (2) | C8—C9—H9B | 109.5 |
C5—C4—Br1 | 119.8 (2) | H9A—C9—H9B | 109.5 |
C4—C5—C6 | 119.0 (3) | C8—C9—H9C | 109.5 |
C4—C5—H5 | 120.5 | H9A—C9—H9C | 109.5 |
C6—C5—H5 | 120.5 | H9B—C9—H9C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···Br1i | 0.96 | 2.99 | 3.555 (3) | 119 |
C2—H2···O1 | 0.93 | 2.32 | 2.880 (4) | 118 |
N1—H1A···O1ii | 0.85 | 2.08 | 2.886 (3) | 160 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H10BrNO |
Mr | 228.09 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 9.3879 (19), 9.2952 (19), 20.721 (4) |
V (Å3) | 1808.2 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 4.50 |
Crystal size (mm) | 0.08 × 0.08 × 0.04 |
Data collection | |
Diffractometer | Rigaku Saturn |
Absorption correction | Multi-scan (Jacobson, 1998) |
Tmin, Tmax | 0.712, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10043, 1587, 1375 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.093, 1.10 |
No. of reflections | 1587 |
No. of parameters | 110 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.76 |
Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXTL (Bruker, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···Br1i | 0.96 | 2.99 | 3.555 (3) | 118.6 |
C2—H2···O1 | 0.93 | 2.32 | 2.880 (4) | 118.1 |
N1—H1A···O1ii | 0.85 | 2.08 | 2.886 (3) | 159.8 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1/2, y, −z+1/2. |
The amide moiety is an important constituent of many biologically significant compounds. Structural studies of amides are therefore of interest (Knopfel et al., 2005; Guo, 2004; Parvez et al., 2004). As part of a study of possible drugs, the crystal structure of the title compound (I) is reported herein, Fig. 1. Bond distances and angles are normal, within experimental error (Allen et al., 1987).
In the structure of (I), the molecular skeleton is essentially planar with atoms O1, C7, C8 and C9 lying 0.6630, 0.2724, 0.0990 and 0.1530 Å, respectively, out of the N1/C1—C6/Br1 mean plane. Intermolecular N1—H1A···O1i hydrogen bonds (see Table 1 for symmetry code) link the molecules into chains (Fig. 2). Further, short C—H···Br contacts (distance = 3.555 (3) Å) stabilize the packing in the structure.