Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The mol­ecules of the title compound, C11H14BrNO2, are assembled into a two-dimensional network by a combination of hydrogen bonds and stacking interactions. The phenyl rings are stacked along the c direction by displaced π–π interactions, forming a lipophilic layer. The aliphatic amide residues are interconnected along [100] by O—H...O, N—H...O and C—H...O hydrogen bonds, forming hydro­philic layers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103025824/gd1280sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103025824/gd1280Isup2.hkl
Contains datablock I

CCDC reference: 235336

Comment top

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 ππ 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 ππ 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.

Experimental top

Compound (I) was synthesized according to the method of Meyers et al. (1974) with crystals grown by slow evaporation of a methylene chloride solution.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1]
[Figure 2]
Fig. 1. View of the molecule of (I), showing ellipsoids at the 35% probability level and the atomic numbering scheme. H atoms are included as spheres of arbitrary size.

Fig. 2. A packing view along the b direction, double-shaded circles for Br, single-shaded circles for O, open circles for N and H and shaded at right-top for C. The atoms are of arbitrary. [Symmetry codes: (i) 1 − x, 1 − y, 2 − z; (ii) 2 − x, 1 − y, 2 − z; (iii) −1 + x, y, z; (iv) 1 + x, y, z; (v) −x, 1 − y, 2 − z; (vi) x, y, −1 + z; (vii) 1 − x, 1 − y, 1 − z; (viii) 2 − x, 1 − y, 1 − z; (ix) −1 + x, y, −1 + z; (x) 1 + x, y, −1 + z; (xi) −x, 1 − y, 1 − z.]

Fig. 3. Displaced benzene dimer of (I). Atoms marked with an asterisk are at the symmetry position (2 − x, 1 − y, 1 − z).
2-bromo-N-(2-hydroxy-1,1-dimethylethyl)benzamide top
Crystal data top
C11H14BrNO2Z = 2
Mr = 272.14F(000) = 276
Triclinic, P1Dx = 1.558 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2713 (10) ÅCell parameters from 34 reflections
b = 8.5860 (9) Åθ = 4.9–16.8°
c = 9.8424 (14) ŵ = 3.52 mm1
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
Data collection top
Bruker P4
diffractometer
1748 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 25.0°, θmin = 2.2°
ω scansh = 18
Absorption correction: ψ scan
(North et al., 1968)
k = 99
Tmin = 0.242, Tmax = 0.350l = 1111
2551 measured reflections3 standard reflections every 100 reflections
2034 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-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 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.71 e Å3
Crystal data top
C11H14BrNO2γ = 79.825 (10)°
Mr = 272.14V = 580.03 (13) Å3
Triclinic, P1Z = 2
a = 7.2713 (10) ÅMo Kα radiation
b = 8.5860 (9) ŵ = 3.52 mm1
c = 9.8424 (14) ÅT = 293 K
α = 77.123 (11)°0.4 × 0.4 × 0.3 mm
β = 77.785 (12)°
Data collection top
Bruker P4
diffractometer
1748 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.050
Tmin = 0.242, Tmax = 0.3503 standard reflections every 100 reflections
2551 measured reflections intensity decay: none
2034 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.03Δρmax = 0.62 e Å3
2034 reflectionsΔρmin = 0.71 e Å3
136 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.28291 (7)0.12781 (7)0.59471 (6)0.0686 (2)
O10.5476 (4)0.6258 (4)0.7915 (3)0.0561 (8)
O20.7493 (4)0.5503 (4)1.1278 (3)0.0518 (7)
H2B0.67060.48741.15680.078*
N10.8426 (4)0.6318 (4)0.8265 (3)0.0429 (8)
H1A0.96040.59270.80760.051*
C10.7960 (5)0.4455 (5)0.6864 (4)0.0409 (9)
C20.9795 (5)0.3619 (5)0.6807 (4)0.0438 (9)
H2A1.06160.38240.73340.053*
C31.0367 (5)0.2489 (5)0.5961 (4)0.0447 (9)
C40.9226 (6)0.2183 (5)0.5123 (4)0.0481 (10)
H4A0.96620.14430.45270.058*
C50.7407 (6)0.3018 (5)0.5200 (5)0.0533 (11)
H5A0.66000.28270.46550.064*
C60.6781 (6)0.4115 (5)0.6060 (5)0.0499 (10)
H6A0.55440.46450.61100.060*
C70.7194 (5)0.5740 (5)0.7734 (4)0.0438 (9)
C80.7938 (6)0.7563 (5)0.9142 (4)0.0466 (9)
C90.6649 (6)0.6969 (5)1.0544 (5)0.0513 (10)
H9A0.64030.77781.11320.062*
H9B0.54430.68171.03550.062*
C100.9824 (7)0.7873 (6)0.9423 (5)0.0598 (12)
H10A1.06220.82380.85380.090*
H10B1.04480.68930.99100.090*
H10C0.95830.86830.99960.090*
C110.6925 (8)0.9129 (6)0.8360 (5)0.0659 (13)
H11A0.57520.89240.81790.099*
H11B0.77230.95020.74780.099*
H11C0.66670.99370.89360.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0435 (3)0.0747 (4)0.0942 (4)0.0070 (2)0.0152 (2)0.0390 (3)
O10.0346 (15)0.0580 (19)0.078 (2)0.0006 (13)0.0085 (14)0.0241 (16)
O20.0381 (15)0.0584 (18)0.0578 (18)0.0105 (13)0.0104 (13)0.0042 (14)
N10.0322 (16)0.0492 (19)0.0479 (19)0.0037 (14)0.0022 (14)0.0165 (15)
C10.036 (2)0.044 (2)0.044 (2)0.0096 (16)0.0062 (16)0.0069 (17)
C20.036 (2)0.052 (2)0.048 (2)0.0079 (17)0.0090 (17)0.0148 (19)
C30.036 (2)0.048 (2)0.051 (2)0.0089 (17)0.0046 (17)0.0131 (19)
C40.050 (2)0.051 (2)0.047 (2)0.0118 (19)0.0074 (19)0.0144 (19)
C50.050 (2)0.060 (3)0.057 (3)0.013 (2)0.019 (2)0.015 (2)
C60.039 (2)0.058 (3)0.057 (3)0.0047 (18)0.0153 (19)0.013 (2)
C70.035 (2)0.047 (2)0.048 (2)0.0064 (17)0.0051 (17)0.0073 (18)
C80.046 (2)0.043 (2)0.051 (2)0.0045 (17)0.0026 (18)0.0162 (18)
C90.046 (2)0.053 (3)0.053 (3)0.0008 (19)0.0044 (19)0.017 (2)
C100.057 (3)0.057 (3)0.074 (3)0.020 (2)0.007 (2)0.025 (2)
C110.077 (3)0.046 (3)0.070 (3)0.001 (2)0.009 (3)0.011 (2)
Geometric parameters (Å, º) top
Br1—C31.904 (4)C5—C61.361 (6)
O1—C71.239 (5)C5—H5A0.9300
O2—C91.411 (5)C6—H6A0.9300
O2—H2B0.8200C8—C101.533 (6)
N1—C71.338 (5)C8—C91.534 (6)
N1—C81.471 (5)C8—C111.540 (6)
N1—H1A0.8600C9—H9A0.9700
C1—C61.387 (5)C9—H9B0.9700
C1—C21.395 (5)C10—H10A0.9600
C1—C71.505 (6)C10—H10B0.9600
C2—C31.371 (6)C10—H10C0.9600
C2—H2A0.9300C11—H11A0.9600
C3—C41.378 (5)C11—H11B0.9600
C4—C51.384 (6)C11—H11C0.9600
C4—H4A0.9300
C9—O2—H2B109.5N1—C8—C10106.1 (3)
C7—N1—C8125.6 (3)N1—C8—C9110.5 (3)
C7—N1—H1A117.2C10—C8—C9110.2 (4)
C8—N1—H1A117.2N1—C8—C11111.0 (4)
C6—C1—C2118.8 (4)C10—C8—C11109.9 (4)
C6—C1—C7117.8 (4)C9—C8—C11109.2 (4)
C2—C1—C7123.4 (3)O2—C9—C8111.2 (3)
C3—C2—C1118.8 (4)O2—C9—H9A109.4
C3—C2—H2A120.6C8—C9—H9A109.4
C1—C2—H2A120.6O2—C9—H9B109.4
C2—C3—C4122.7 (4)C8—C9—H9B109.4
C2—C3—Br1118.9 (3)H9A—C9—H9B108.0
C4—C3—Br1118.5 (3)C8—C10—H10A109.5
C3—C4—C5117.6 (4)C8—C10—H10B109.5
C3—C4—H4A121.2H10A—C10—H10B109.5
C5—C4—H4A121.2C8—C10—H10C109.5
C6—C5—C4121.0 (4)H10A—C10—H10C109.5
C6—C5—H5A119.5H10B—C10—H10C109.5
C4—C5—H5A119.5C8—C11—H11A109.5
C5—C6—C1121.0 (4)C8—C11—H11B109.5
C5—C6—H6A119.5H11A—C11—H11B109.5
C1—C6—H6A119.5C8—C11—H11C109.5
O1—C7—N1122.0 (4)H11A—C11—H11C109.5
O1—C7—C1120.1 (4)H11B—C11—H11C109.5
N1—C7—C1118.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···O1i0.821.922.734 (4)169
N1—H1A···O2ii0.862.383.173 (4)153
C2—H2A···O2ii0.932.353.277 (5)176
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+2, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC11H14BrNO2
Mr272.14
Crystal system, space groupTriclinic, 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)
V3)580.03 (13)
Z2
Radiation typeMo Kα
µ (mm1)3.52
Crystal size (mm)0.4 × 0.4 × 0.3
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.242, 0.350
No. of measured, independent and
observed [I > 2σ(I)] reflections
2551, 2034, 1748
Rint0.050
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.097, 1.03
No. of reflections2034
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.71

Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···O1i0.821.922.734 (4)169
N1—H1A···O2ii0.862.383.173 (4)153
C2—H2A···O2ii0.932.353.277 (5)176
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+2, y+1, z+2.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds