Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103025824/gd1280sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025824/gd1280Isup2.hkl |
CCDC reference: 235336
Compound (I) was synthesized according to the method of Meyers et al. (1974) with crystals grown by slow evaporation of a methylene chloride solution.
H atom were treated as riding atoms, with C—H = 0.93–0.97 Å, N—H = 0.86 Å and O—H = 0.82 Å.
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C11H14BrNO2 | Z = 2 |
Mr = 272.14 | F(000) = 276 |
Triclinic, P1 | Dx = 1.558 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2713 (10) Å | Cell parameters from 34 reflections |
b = 8.5860 (9) Å | θ = 4.9–16.8° |
c = 9.8424 (14) Å | µ = 3.52 mm−1 |
α = 77.123 (11)° | T = 293 K |
β = 77.785 (12)° | Prism, colorless |
γ = 79.825 (10)° | 0.4 × 0.4 × 0.3 mm |
V = 580.03 (13) Å3 |
Bruker P4 diffractometer | 1748 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω scans | h = −1→8 |
Absorption correction: ψ scan (North et al., 1968) | k = −9→9 |
Tmin = 0.242, Tmax = 0.350 | l = −11→11 |
2551 measured reflections | 3 standard reflections every 100 reflections |
2034 independent reflections | intensity decay: none |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.001P)2 + 1.5P] where P = (Fo2 + 2Fc2)/3 |
2034 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.71 e Å−3 |
C11H14BrNO2 | γ = 79.825 (10)° |
Mr = 272.14 | V = 580.03 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2713 (10) Å | Mo Kα radiation |
b = 8.5860 (9) Å | µ = 3.52 mm−1 |
c = 9.8424 (14) Å | T = 293 K |
α = 77.123 (11)° | 0.4 × 0.4 × 0.3 mm |
β = 77.785 (12)° |
Bruker P4 diffractometer | 1748 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
Tmin = 0.242, Tmax = 0.350 | 3 standard reflections every 100 reflections |
2551 measured reflections | intensity decay: none |
2034 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.62 e Å−3 |
2034 reflections | Δρmin = −0.71 e Å−3 |
136 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 | 1.28291 (7) | 0.12781 (7) | 0.59471 (6) | 0.0686 (2) | |
O1 | 0.5476 (4) | 0.6258 (4) | 0.7915 (3) | 0.0561 (8) | |
O2 | 0.7493 (4) | 0.5503 (4) | 1.1278 (3) | 0.0518 (7) | |
H2B | 0.6706 | 0.4874 | 1.1568 | 0.078* | |
N1 | 0.8426 (4) | 0.6318 (4) | 0.8265 (3) | 0.0429 (8) | |
H1A | 0.9604 | 0.5927 | 0.8076 | 0.051* | |
C1 | 0.7960 (5) | 0.4455 (5) | 0.6864 (4) | 0.0409 (9) | |
C2 | 0.9795 (5) | 0.3619 (5) | 0.6807 (4) | 0.0438 (9) | |
H2A | 1.0616 | 0.3824 | 0.7334 | 0.053* | |
C3 | 1.0367 (5) | 0.2489 (5) | 0.5961 (4) | 0.0447 (9) | |
C4 | 0.9226 (6) | 0.2183 (5) | 0.5123 (4) | 0.0481 (10) | |
H4A | 0.9662 | 0.1443 | 0.4527 | 0.058* | |
C5 | 0.7407 (6) | 0.3018 (5) | 0.5200 (5) | 0.0533 (11) | |
H5A | 0.6600 | 0.2827 | 0.4655 | 0.064* | |
C6 | 0.6781 (6) | 0.4115 (5) | 0.6060 (5) | 0.0499 (10) | |
H6A | 0.5544 | 0.4645 | 0.6110 | 0.060* | |
C7 | 0.7194 (5) | 0.5740 (5) | 0.7734 (4) | 0.0438 (9) | |
C8 | 0.7938 (6) | 0.7563 (5) | 0.9142 (4) | 0.0466 (9) | |
C9 | 0.6649 (6) | 0.6969 (5) | 1.0544 (5) | 0.0513 (10) | |
H9A | 0.6403 | 0.7778 | 1.1132 | 0.062* | |
H9B | 0.5443 | 0.6817 | 1.0355 | 0.062* | |
C10 | 0.9824 (7) | 0.7873 (6) | 0.9423 (5) | 0.0598 (12) | |
H10A | 1.0622 | 0.8238 | 0.8538 | 0.090* | |
H10B | 1.0448 | 0.6893 | 0.9910 | 0.090* | |
H10C | 0.9583 | 0.8683 | 0.9996 | 0.090* | |
C11 | 0.6925 (8) | 0.9129 (6) | 0.8360 (5) | 0.0659 (13) | |
H11A | 0.5752 | 0.8924 | 0.8179 | 0.099* | |
H11B | 0.7723 | 0.9502 | 0.7478 | 0.099* | |
H11C | 0.6667 | 0.9937 | 0.8936 | 0.099* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0435 (3) | 0.0747 (4) | 0.0942 (4) | 0.0070 (2) | −0.0152 (2) | −0.0390 (3) |
O1 | 0.0346 (15) | 0.0580 (19) | 0.078 (2) | −0.0006 (13) | −0.0085 (14) | −0.0241 (16) |
O2 | 0.0381 (15) | 0.0584 (18) | 0.0578 (18) | −0.0105 (13) | −0.0104 (13) | −0.0042 (14) |
N1 | 0.0322 (16) | 0.0492 (19) | 0.0479 (19) | −0.0037 (14) | −0.0022 (14) | −0.0165 (15) |
C1 | 0.036 (2) | 0.044 (2) | 0.044 (2) | −0.0096 (16) | −0.0062 (16) | −0.0069 (17) |
C2 | 0.036 (2) | 0.052 (2) | 0.048 (2) | −0.0079 (17) | −0.0090 (17) | −0.0148 (19) |
C3 | 0.036 (2) | 0.048 (2) | 0.051 (2) | −0.0089 (17) | −0.0046 (17) | −0.0131 (19) |
C4 | 0.050 (2) | 0.051 (2) | 0.047 (2) | −0.0118 (19) | −0.0074 (19) | −0.0144 (19) |
C5 | 0.050 (2) | 0.060 (3) | 0.057 (3) | −0.013 (2) | −0.019 (2) | −0.015 (2) |
C6 | 0.039 (2) | 0.058 (3) | 0.057 (3) | −0.0047 (18) | −0.0153 (19) | −0.013 (2) |
C7 | 0.035 (2) | 0.047 (2) | 0.048 (2) | −0.0064 (17) | −0.0051 (17) | −0.0073 (18) |
C8 | 0.046 (2) | 0.043 (2) | 0.051 (2) | −0.0045 (17) | −0.0026 (18) | −0.0162 (18) |
C9 | 0.046 (2) | 0.053 (3) | 0.053 (3) | 0.0008 (19) | −0.0044 (19) | −0.017 (2) |
C10 | 0.057 (3) | 0.057 (3) | 0.074 (3) | −0.020 (2) | −0.007 (2) | −0.025 (2) |
C11 | 0.077 (3) | 0.046 (3) | 0.070 (3) | 0.001 (2) | −0.009 (3) | −0.011 (2) |
Br1—C3 | 1.904 (4) | C5—C6 | 1.361 (6) |
O1—C7 | 1.239 (5) | C5—H5A | 0.9300 |
O2—C9 | 1.411 (5) | C6—H6A | 0.9300 |
O2—H2B | 0.8200 | C8—C10 | 1.533 (6) |
N1—C7 | 1.338 (5) | C8—C9 | 1.534 (6) |
N1—C8 | 1.471 (5) | C8—C11 | 1.540 (6) |
N1—H1A | 0.8600 | C9—H9A | 0.9700 |
C1—C6 | 1.387 (5) | C9—H9B | 0.9700 |
C1—C2 | 1.395 (5) | C10—H10A | 0.9600 |
C1—C7 | 1.505 (6) | C10—H10B | 0.9600 |
C2—C3 | 1.371 (6) | C10—H10C | 0.9600 |
C2—H2A | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.378 (5) | C11—H11B | 0.9600 |
C4—C5 | 1.384 (6) | C11—H11C | 0.9600 |
C4—H4A | 0.9300 | ||
C9—O2—H2B | 109.5 | N1—C8—C10 | 106.1 (3) |
C7—N1—C8 | 125.6 (3) | N1—C8—C9 | 110.5 (3) |
C7—N1—H1A | 117.2 | C10—C8—C9 | 110.2 (4) |
C8—N1—H1A | 117.2 | N1—C8—C11 | 111.0 (4) |
C6—C1—C2 | 118.8 (4) | C10—C8—C11 | 109.9 (4) |
C6—C1—C7 | 117.8 (4) | C9—C8—C11 | 109.2 (4) |
C2—C1—C7 | 123.4 (3) | O2—C9—C8 | 111.2 (3) |
C3—C2—C1 | 118.8 (4) | O2—C9—H9A | 109.4 |
C3—C2—H2A | 120.6 | C8—C9—H9A | 109.4 |
C1—C2—H2A | 120.6 | O2—C9—H9B | 109.4 |
C2—C3—C4 | 122.7 (4) | C8—C9—H9B | 109.4 |
C2—C3—Br1 | 118.9 (3) | H9A—C9—H9B | 108.0 |
C4—C3—Br1 | 118.5 (3) | C8—C10—H10A | 109.5 |
C3—C4—C5 | 117.6 (4) | C8—C10—H10B | 109.5 |
C3—C4—H4A | 121.2 | H10A—C10—H10B | 109.5 |
C5—C4—H4A | 121.2 | C8—C10—H10C | 109.5 |
C6—C5—C4 | 121.0 (4) | H10A—C10—H10C | 109.5 |
C6—C5—H5A | 119.5 | H10B—C10—H10C | 109.5 |
C4—C5—H5A | 119.5 | C8—C11—H11A | 109.5 |
C5—C6—C1 | 121.0 (4) | C8—C11—H11B | 109.5 |
C5—C6—H6A | 119.5 | H11A—C11—H11B | 109.5 |
C1—C6—H6A | 119.5 | C8—C11—H11C | 109.5 |
O1—C7—N1 | 122.0 (4) | H11A—C11—H11C | 109.5 |
O1—C7—C1 | 120.1 (4) | H11B—C11—H11C | 109.5 |
N1—C7—C1 | 118.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O1i | 0.82 | 1.92 | 2.734 (4) | 169 |
N1—H1A···O2ii | 0.86 | 2.38 | 3.173 (4) | 153 |
C2—H2A···O2ii | 0.93 | 2.35 | 3.277 (5) | 176 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C11H14BrNO2 |
Mr | 272.14 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.2713 (10), 8.5860 (9), 9.8424 (14) |
α, β, γ (°) | 77.123 (11), 77.785 (12), 79.825 (10) |
V (Å3) | 580.03 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.52 |
Crystal size (mm) | 0.4 × 0.4 × 0.3 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.242, 0.350 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2551, 2034, 1748 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.097, 1.03 |
No. of reflections | 2034 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.71 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2B···O1i | 0.82 | 1.92 | 2.734 (4) | 169 |
N1—H1A···O2ii | 0.86 | 2.38 | 3.173 (4) | 153 |
C2—H2A···O2ii | 0.93 | 2.35 | 3.277 (5) | 176 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+2, −y+1, −z+2. |
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Synthetic N-(2-hydroxy-1,1-dimethylethyl)amides are commonly used as intermediates in the synthesis of oxazoline compounds which have various uses in modern organic synthesis (Boyd & Hansen, 1953; Grant & Meyers, 1994). Gerkin (2000) reported the crystal structure of N-(2-hydroxy-1,1-dimethylethyl)benzamide, (II), as one of a series of reports on hydrogen bonding and C—H···O interactions in aromatic compounds. In the present paper, we report the structure of 2-bromo-N-(2-hydroxy-1,1-dimethylethyl)benzamide, (I), which differs from (II) in that it contains an additional Br substituent.
In the structure of (I) (Fig. 1), both hard and soft hydrogen bonds and parallel-displaced π–π stacking interactions (Hobza et al., 1994; Müller-Dethlefs & Hobza, 2000) are present. As shown in Fig. 2, the molecules are assembled in (010) sheets by a combination of stacking interactions and intermolecular hydrogen bonds.
Each aliphatic amide residue in (I) is involved in two hydrogen bonds and one weak but significant C—H···O interaction. An O—H···O hydrogen bond links the molecules at (x, y, z) and (1 − x, 1 − y, 2 − z), while an N—H···O hydrogen bond reinforced by a C—H···O interaction (Steiner & Desiraju, 1998) links the molecules at (x, y, z) and (2 − x, 1 − y, 2 − z). In combination, these hydrogen bonds generate a chain of centrosymmetric rings along [100] (Fig. 2), and the chains are further linked by the π-stacking interactions.
The distance between the phenyl planes of the molecules at (x, y, z) and (2 − x, 1 − y, 1 − z) is 3.54 Å, and the distance between the ring centroids is 3.79 Å, which may lead to lower quadrupole–quadrupole energy and hence a more stable structure, according to ab initio calculations (Hobza et al., 1994). The phenyl rings stack along [001] via displaced π–π interactions, forming a lipophilic layer on either side of the central polar layer.
The hydrogen-bonded aliphatic amide residues aligned along the [100] direction form a hydrophilic layer. The two oppositely polar moieties are extensively interconnected through stacking interactions and multiple hydrogen bonds (Table 2) that stabilize the structure (Fig. 2).
Compared with the structure of (II), the introduction of a bromine substituent at the 3-position of the phenyl ring alters the whole crystal structure. In (II), there is one intramolecular O—H···O hydrogen bond, one intermolecular N—H···O hydrogen bond and four significant C—H···O interactions, and a central molecule is linked directly to five neighboring molecules, forming a two-dimensional network, so the two oppositely polar-assembled layers and stacking interactions observed in (I) are not present in (II).
It is interesting to compare the dihedral angles between the best-fit phenyl plane and the amide plane (C7/O1/N1) of (I) [13.7 (7)°] and (II) [25.77 (12)°] (with the same atom-numbering scheme as in Fig. 1). Presumably, the twist between the phenyl plane and amide plane serves to minimize steric repulsion between the lone pair on atom O1 and the adjacent phenyl H atom (H6). This assumption is supported by a comparison with the structure of 4,6-dimethyl-3(−4,4-dimethyl-2-oxazolinyl)-N-(2-hydroxy- 1,1-dimethylethyl)salicylamide (Inamoto et al., 1996), which contains a methyl group at the 6-position of the phenyl ring that is markedly twisted out of the amide plane, viz. by 88.4 (9)°. In (II), atom O1 as the acceptor is involved in three hydrogen bonds [an intramolecular O—H···O bond with D···A = 2.628 (11) Å and two short C—H···O interactions], while atom O1 in (I) as acceptor is only involved in one intermolecular O—H···O hydrogen bond [D···A = 2.734 (4) Å] that is obviously weaker than those in (II). This seems to mean that the more electrons atom O1 accepts, the more twist there is between the two planes in order to minimize steric repulsion with the adjacent phenyl-ring H atom. Therefore, the torsion to make the amide plane non-coplanar with the phenyl plane is ddue to the steric repulsion between the lone pair on atom O1 and the adjacent atom or group at the 6-position of the phenyl ring.