Hydro­gen bonds and C—H...O interactions in N-(2-hydroxy-1,1-dimethyl­ethyl)benzamide at 150 K

The title compound, C₁₁H₁₅NO₂, crystallized in the centrosymmetric space group P2₁/n with one mol­ecule in the asymmetric unit. There is a single intermolecular hydrogen bond, in which the N_donor...O_acceptor distance is 3.0374 (11) Å and the N—H...O angle is 171.0 (12)°. The single intramol­ecular hydrogen bond has an O_donor...O_acceptor distance of 2.6279 (11) Å and an O—H...O angle of 161.8 (14)°. The four leading intermolecular C—H...O interactions have H...O distances ranging from 2.52 to 2.65 (2) Å and C—H...O angles ranging from 125.2 (9) to 143°. Chains of interactions form two-dimensional networks.

S1. Comment

This report is one of a series on hydrogen bonding and C—H···O interactions in aromatic compounds. The title compound, (I), crystallized in the centrosymmetric space group P2₁/n with one molecule as the asymmetric unit. The refined molecule and the labelling scheme are given in Fig. 1. \sch

Two hydrogen bonds, one of them intramolecular, and four leading intermolecular C—H···O interactions (Taylor & Kennard, 1982; Steiner & Desiraju, 1998) are present in this structure. The geometric parameters of these are given in Table 2. A central molecule is linked directly to five neighbouring molecules by the tabulated interactions, as shown in the stereodiagram (Fig. 2). The results of basic first- and second-level graph-set analysis (Bernstein et al., 1995) involving these interactions, labelled a-f for this purpose in the order of their appearance in Table 2, are given in Table 3. Among the twenty-one patterns fifteen are chains, which propagate variously along [101] (8), [010] (5) and [111] (2). Since only two of three such vectors are linearly independent, however, the resulting network of interactions is two-dimensional. Of the five ring patterns, two are disposed about centres of symmetry.

The phenyl ring is nearly planar, the maximum deviation of a ring atom from the best-fit plane describing them being 0.0053 (11) Å. The dihedral angle between this plane and that of the amide group atoms C7, O1 and N1 is 25.77 (12)°. This angle is apparent in Fig. 2.

Selected bond distances and angles of (I) are given in Table 1. A l l distances and angles fall within normal limits. For structural comparisons of the aliphatic amide portion of (I), the structure of 4,6-dimethyl-3-(4,4-dimethyl-2-oxazolinyl)-N-(2-hydroxy-1,1-dimethylethyl) salicylamide [Inamoto et al., 1996; hereinafter (II)] appears to be the best available, although the s.u.s are almost ten times those of the present study. For the eight pairs of corresponding non-H interatomic distances in the aliphatic amide substructures of (I) and (II), the greatest difference is just twice the s.u. of that distance given for (II), so these results are in good agreement. The orientation of this group with respect to the attached phenyl ring, however, is quite different in the two molecules, since in (II) the dihedral angle between the best-fit phenyl plane and the amide plane as defined above is 88.4 (9)°. In view of the four additional substituents on the phenyl ring of (II), two of them capable of hydrogen bonding, this difference is not problematic. In (I) the closest intermolecular approaches, excluding pairs of atoms involved in the hydrogen-bonding groups or the tabulated C—H···O interactions, are between H2 and H9Bⁱ [symmetry code: (i) 1/2 + x, 3/2 − y, 1/2 + z] and fall short of the corresponding Bondi (1964) van der Waals radius sum by 0.04 Å.

S2. Experimental

Compound (I) was obtained as a column from a crystalline sample in Dr M. S. Newman's chemical collection. This was cut to provide the experimental sample. One synthesis, among others, is given by Boyd & Hansen (1953).

S3. Refinement

Fourier difference methods were used to locate initial H-atom positions, and these H atoms were refined. Refined C—H distances ranged from 0.96 (1) to 1.05 (1) Å, with a mean value of 0.99 (3) Å; their U_iso values ranged from 0.96 to 1.5 times the U_eq values of the attached C atoms. The ring H atoms were then made canonical, with C—H = 0.98 Å and U_iso = 1.2 × U_eq of the attached C atom.

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1992-1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN and PLATON (Spek, 1990).

Figures

	Fig. 1. The molecular view of compound (I), showing the atom-labelling scheme, with displacement ellipsoids at the 50% probability level. The dashed line depicts the intramolecular hydrogen bond. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. Stereodiagram of (I) viewed nearly down the a axis. The finer interatomic lines depict interactions given in Table 2. For clarity, only those H atoms involved in these interactions are included.

N-(2-hydroxy-1,1-dimethylethyl)benzamide

Crystal data

C11H15NO2	F(000) = 416
Mr = 193.24	Dx = 1.282 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.4286 (2) Å	Cell parameters from 22319 reflections
b = 9.1195 (2) Å	θ = 1.9–27.5°
c = 11.3748 (2) Å	µ = 0.09 mm^−1
β = 112.2995 (11)°	T = 150 K
V = 1000.88 (3) Å^3	Cut column, colourless
Z = 4	0.35 × 0.27 × 0.27 mm

Data collection

Nonius KappaCCD diffractometer	1936 reflections with I > 2σ(I)
Radiation source: X-ray tube	Rint = 0.032
Graphite monochromator	θmax = 27.5°
ω scans with κ offsets	h = −13→13
22319 measured reflections	k = −11→11
2293 independent reflections	l = −14→14

Refinement

Refinement on F^2	167 parameters
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.038	Weighting scheme based on measured s.u.'s w = 1/[σ^2cs + (0.032I)^2]
wR(F^2) = 0.098	(Δ/σ)max < 0.001
S = 1.97	Δρmax = 0.23 e Å^−3
2293 reflections	Δρmin = −0.22 e Å^−3

Special details

Experimental. The Laue group assignment, the systematic absences and the centrosymmetry indicated by the intensity statistics led to assignment of the space group uniquely as P2₁/n (No. 14); since refinement proceeded well, it was adopted. The maximum peak in the final difference map occurs ~0.7 Å from C8, the maximum negative peak ~0.8 Å from N1.

Geometry. Table of Least-Squares Planes ——————————

————– Plane number 1 —————

Atoms Defining Plane Distance e.s.d. C1 (1) 0.0004 0.0009 C2 (1) 0.0034 0.0010 C3 (1) −0.0043 0.0010 C4 (1) −0.0006 0.0010 C5 (1) 0.0053 0.0011 C6 (1) −0.0049 0.0010

Mean deviation from plane is 0.0032 angstroms Chi-squared: 82.1

————– Plane number 2 —————

Atoms Defining Plane Distance e.s.d. C7 (1) 0.0000 O1 (1) 0.0000 N1 (1) 0.0000

Additional Atoms Distance H1N1 (1) 0.0286 C8 (1) 0.2295

Mean deviation from plane is 0.0000 angstroms Chi-squared: 0.0

Dihedral angles between least-squares planes plane plane angle 2 1 25.78

————– Plane number 3 —————

Atoms Defining Plane Distance e.s.d. C1 (2) −0.0004 0.0009 C2 (2) −0.0034 0.0010 C3 (2) 0.0043 0.0010 C4 (2) 0.0006 0.0010 C5 (2) −0.0053 0.0011 C6 (2) 0.0049 0.0010

Mean deviation from plane is 0.0032 angstroms Chi-squared: 82.1

Dihedral angles between least-squares planes plane plane angle 3 1 67.22 3 2 59.80

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.38115 (7)	0.94206 (8)	0.59498 (6)	0.0300 (2)
O2	0.19580 (8)	0.73133 (9)	0.54108 (7)	0.0339 (2)
N1	0.47517 (9)	0.80918 (9)	0.77665 (8)	0.0222 (2)
C1	0.55789 (10)	1.05709 (11)	0.76738 (9)	0.0209 (3)
C2	0.61404 (10)	1.08217 (11)	0.89781 (9)	0.0251 (3)
C3	0.69892 (11)	1.20288 (12)	0.94623 (9)	0.0282 (3)
C4	0.72969 (11)	1.29820 (11)	0.86598 (10)	0.0282 (3)
C5	0.67476 (11)	1.27313 (12)	0.73615 (10)	0.0274 (3)
C6	0.58854 (10)	1.15414 (11)	0.68683 (9)	0.0246 (3)
C7	0.46428 (10)	0.93037 (11)	0.70703 (9)	0.0217 (3)
C8	0.40992 (10)	0.66479 (11)	0.72703 (9)	0.0216 (3)
C9	0.25125 (11)	0.67532 (12)	0.66639 (10)	0.0267 (3)
C10	0.46951 (12)	0.60438 (13)	0.63300 (10)	0.0280 (3)
C11	0.44665 (12)	0.56344 (13)	0.84169 (10)	0.0288 (3)
H1N1	0.5361 (13)	0.8083 (14)	0.8512 (12)	0.039 (4)*
H1O2	0.2495 (16)	0.8077 (18)	0.5421 (14)	0.070 (5)*
H2	0.5937	1.0146	0.9555	0.030*
H3	0.7374	1.2207	1.0381	0.034*
H4	0.7900	1.3829	0.9008	0.034*
H5	0.6970	1.3398	0.6790	0.033*
H6	0.5488	1.1380	0.5948	0.030*
H9A	0.2203 (11)	0.7366 (13)	0.7255 (10)	0.029 (3)*
H9B	0.2152 (11)	0.5747 (13)	0.6633 (10)	0.026 (3)*
H10A	0.4260 (12)	0.5107 (15)	0.6003 (10)	0.037 (3)*
H10B	0.4531 (12)	0.6744 (13)	0.5606 (10)	0.033 (3)*
H10C	0.5732 (13)	0.5886 (12)	0.6787 (10)	0.033 (3)*
H11A	0.4125 (12)	0.4573 (15)	0.8106 (10)	0.038 (3)*
H11B	0.5461 (14)	0.5600 (14)	0.8882 (11)	0.043 (3)*
H11C	0.4041 (13)	0.5977 (14)	0.9010 (11)	0.043 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0337 (4)	0.0274 (4)	0.0192 (4)	−0.0051 (3)	−0.0009 (3)	0.0043 (3)
O2	0.0291 (5)	0.0295 (5)	0.0275 (4)	−0.0047 (4)	−0.0068 (3)	0.0054 (3)
N1	0.0233 (5)	0.0206 (5)	0.0165 (4)	−0.0012 (4)	0.0008 (4)	0.0020 (3)
C1	0.0191 (5)	0.0195 (5)	0.0220 (5)	0.0033 (4)	0.0055 (4)	0.0005 (4)
C2	0.0275 (6)	0.0245 (6)	0.0225 (5)	0.0026 (4)	0.0085 (4)	0.0010 (4)
C3	0.0287 (6)	0.0282 (6)	0.0235 (5)	0.0030 (5)	0.0052 (5)	−0.0063 (4)
C4	0.0240 (6)	0.0204 (6)	0.0362 (6)	0.0004 (4)	0.0069 (5)	−0.0051 (5)
C5	0.0275 (6)	0.0231 (5)	0.0308 (6)	−0.0001 (4)	0.0102 (5)	0.0022 (4)
C6	0.0264 (6)	0.0230 (6)	0.0221 (5)	0.0026 (4)	0.0066 (4)	0.0018 (4)
C7	0.0231 (5)	0.0225 (5)	0.0181 (5)	0.0012 (4)	0.0064 (4)	0.0014 (4)
C8	0.0230 (5)	0.0188 (5)	0.0193 (5)	−0.0013 (4)	0.0036 (4)	0.0013 (4)
C9	0.0244 (6)	0.0274 (6)	0.0240 (5)	−0.0011 (5)	0.0043 (5)	0.0006 (5)
C10	0.0316 (6)	0.0235 (6)	0.0287 (6)	−0.0019 (5)	0.0110 (5)	−0.0023 (5)
C11	0.0322 (7)	0.0237 (6)	0.0248 (5)	−0.0013 (5)	0.0043 (5)	0.0047 (5)

Geometric parameters (Å, º)

O1—C7	1.2446 (11)	C5—C6	1.3849 (15)
O2—C9	1.4148 (13)	C5—H5	0.98
O2—H1O2	0.890 (16)	C6—H6	0.98
N1—C7	1.3391 (12)	C8—C9	1.5352 (14)
N1—C8	1.4913 (12)	C8—C10	1.5292 (14)
N1—H1N1	0.845 (13)	C8—C11	1.5241 (14)
C1—C2	1.3918 (13)	C9—H9B	0.987 (11)
C1—C6	1.3954 (14)	C9—H9A	1.017 (11)
C1—C7	1.5004 (14)	C10—H10A	0.973 (13)
C2—C3	1.3888 (15)	C10—H10B	1.004 (11)
C2—H2	0.98	C10—H10C	1.016 (12)
C3—C4	1.3835 (15)	C11—H11A	1.045 (13)
C3—H3	0.98	C11—H11B	0.969 (13)
C4—C5	1.3853 (15)	C11—H11C	0.988 (13)
C4—H4	0.98
C9—O2—H1O2	104.7 (9)	N1—C8—C9	111.97 (8)
C7—N1—C8	125.51 (8)	N1—C8—C10	109.55 (8)
C7—N1—H1N1	117.6 (9)	N1—C8—C11	106.33 (8)
C8—N1—H1N1	115.7 (9)	C9—C8—C10	111.29 (8)
C2—C1—C6	119.16 (9)	C9—C8—C11	107.49 (8)
C2—C1—C7	123.49 (9)	C10—C8—C11	110.07 (9)
C6—C1—C7	117.36 (8)	O2—C9—C8	115.73 (8)
C1—C2—C3	120.00 (9)	O2—C9—H9B	107.2 (6)
C1—C2—H2	120.0	O2—C9—H9A	110.9 (6)
C3—C2—H2	120.0	C8—C9—H9B	106.8 (6)
C2—C3—C4	120.59 (9)	C8—C9—H9A	107.2 (6)
C2—C3—H3	119.7	H9B—C9—H9A	108.8 (9)
C4—C3—H3	119.7	C8—C10—H10B	110.9 (6)
C3—C4—C5	119.61 (10)	C8—C10—H10C	109.2 (6)
C3—C4—H4	120.2	C8—C10—H10A	109.2 (6)
C5—C4—H4	120.2	H10B—C10—H10C	109.1 (9)
C4—C5—C6	120.23 (9)	H10B—C10—H10A	109.6 (9)
C4—C5—H5	119.9	H10C—C10—H10A	108.8 (9)
C6—C5—H5	119.9	C8—C11—H11B	110.8 (7)
C1—C6—C5	120.41 (9)	C8—C11—H11C	111.1 (7)
C1—C6—H6	119.8	C8—C11—H11A	109.2 (6)
C5—C6—H6	119.8	H11B—C11—H11C	107.6 (9)
O1—C7—N1	123.10 (9)	H11B—C11—H11A	108.1 (10)
O1—C7—C1	118.81 (9)	H11C—C11—H11A	109.9 (10)
N1—C7—C1	118.08 (8)
O1—C7—N1—C8	10.89 (16)	C1—C7—N1—C8	−168.61 (9)
O1—C7—C1—C2	154.49 (10)	C2—C1—C6—C5	0.60 (14)
O1—C7—C1—C6	−25.19 (13)	C2—C3—C4—C5	0.27 (15)
O2—C9—C8—N1	79.90 (11)	C3—C2—C1—C6	0.26 (15)
O2—C9—C8—C10	−43.09 (13)	C3—C2—C1—C7	−179.42 (9)
O2—C9—C8—C11	−163.68 (9)	C3—C4—C5—C6	0.59 (15)
N1—C7—C1—C2	−25.98 (14)	C5—C6—C1—C7	−179.70 (9)
N1—C7—C1—C6	154.33 (9)	C7—N1—C8—C9	−60.68 (12)
C1—C2—C3—C4	−0.70 (15)	C7—N1—C8—C10	63.28 (12)
C1—C6—C5—C4	−1.03 (15)	C7—N1—C8—C11	−177.80 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1	0.89 (2)	1.77 (2)	2.6279 (11)	162 (1)
N1—H1N1···O2^i	0.85 (2)	2.20 (2)	3.0374 (11)	171 (1)
C2—H2···O2^i	0.98	2.52	3.2407 (13)	131
C4—H4···O1^ii	0.98	2.60	3.4305 (12)	143
C6—H6···O1^iii	0.98	2.63	3.4517 (12)	141
C11—H11B···O2^i	0.97 (2)	2.65 (2)	3.3054 (14)	125 (1)

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x+1/2, −y+5/2, z+1/2; (iii) −x+1, −y+2, −z+1.