4,8-Di­methoxy-1-naphthalene­methanol

The title compound, C₁₃H₁₄O₃, crystallized in the centrosymmetric space group C2/c with one mol­ecule as the asymmetric unit. Each hydroxyl O atom is involved in hydrogen bonds with two other hydroxyl O atoms. The resulting chains of interactions propagate along [001]. In these interactions, the hydroxyl H atoms are disordered and the O...O distances are 2.648 (2) and 2.698 (2) Å. Two leading intermolecular C—H...O interactions have H...O distances of 2.80 and 2.84 Å and C—H...O angles of 136 and 144°; these interactions form chain and ring patterns. Taken together with the hydrogen bonds, they result in a three-dimensional network.

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 C2/c with one molecule as the asymmetric unit. The refined molecule and the labelling scheme are given in Fig. 1. Two hydrogen bonds and two 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. The results of basic first- and second-level graph-set analysis (Bernstein et al., 1995) involving these interactions, labelled a-d for this purpose in the order of their appearance in Table 2, are given in Table 3. (For this analysis, the hydroxyl H atoms were assigned in turn to ordered positions with unit occupancy, so that each hydroxyl O atom was associated with a single unit-occupancy hydroxyl H atom.) At the first level, finite patterns and rings appear. The second-level patterns are all chains, propagating variously along [001], [101], [112] and [103]. Each molecule is linked by these four interactions directly to four other molecules, and a three-dimensional network results. \sch

In the naphthalene ring of (I), the maximum deviation of any of its atoms from the best-fit plane describing them is 0.025 (1) Å, while the average deviation is 0.010 (13) Å. These values are quite similar to the corresponding values for 1,8-dimethoxynaphthalene (Cosmo et al., 1990, corrected by Fitzgerald et al., 1991), but are much smaller than those for, e.g., 1,8-bis(dimethylamino)naphthalene (Einspahr et al., 1973) or naphthalene-1,8-dicarboxylic acid (Fitzgerald et al., 1991), in which the maximum deviations are approximately 0.150 and 0.100 Å, respectively. Further, as also in 1,8-dimethoxynaphthalene, all the non-H atoms in (I) lie roughly in a plane: the maximum deviation of any non-H atom from the best-fit plane describing them is 0.062 (1) Å. In (I), the dihedral angle between naphthalene-ring planes not required by symmetry to be parallel is 71.9 (1)°. Thus, the best-fit planes of the molecules are either strictly parallel or roughly perpendicular. These features are apparent in the packing diagram, Fig. 2.

Selected bond distances and angles of (I) are given in Table 1. A l l distances and angles fall within normal limits. The methoxy group C—O distances agree well with those in 1,8-dimethoxynaphthalene: 1.372 (1) and 1.365 (1) versus 1.359 (2) Å, and 1.423 (1) and 1.414 (1) versus 1.425 (2) Å. The exterior ring angles C1—C9—C8 and C4—C10—C5 show a consistent pattern in all four of the 1,8-disubstituted molecules discussed above, with C1—C9—C8 values 124.4 (1) for (I) and 125.7, 125.8 and 126.7° for the remaining three and with C4—C10—C5 values 120.1 (1) for (I) and 119.9, 119.6 and 120.1° for the other three. Further, a consistent pattern of C1—C8 and C4—C5 distances in which the former are \sim 0.1 Å greater than the latter is shown by all four of these molecules. These patterns document a distortion of the naphthalene cores associated with the 1,8- disubstitution. In (I), the closest intermolecular approaches, excluding pairs of atoms involved in the hydrogen bonding or the tabulated C—H···O interactions, are between C8 and H13C^v (v = x, 1 − y, −1/2 + z) and fall short of the corresponding Bondi (1964) van der Waals radius sum by 0.04 Å.

S2. Experimental

(I) was obtained as pale ecru, thin plates from a sample in Dr D. J. Hart's chemical collection. A solution of this material in a mixed solvent (ether/acetone/ethanol/ethyl acetate) produced suitable, virtually colorless crystals upon slow evaporation at room temperature. A synthesis is described by Young (1994).

S3. Refinement

Difference Fourier maps gave initial locations of the H atoms except for the hydroxyl group. Since two hydroxyl O atoms were found to occur within (short) hydrogen-bonding distances, 2.647 (2) and 2.699 (2) Å, of a given hydroxyl O atom, a model involving a disordered hydroxyl H atom was adopted. Half-occupancy H atoms were fixed 0.77 Å from the hydroxyl O atom along the line of centers to the two hydrogen-bonded hydroxyl O atoms, and with B = 1.2 × B_eq of the hydroxyl O atom. The distance, 0.77 Å, was chosen on the basis that it is the mean of two refined values for similarly disordered half-occupancy H atoms in the hydrogen bonds of naphthalene-1,8-dicarboxylic acid (Fitzgerald et al., 1991).

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, 1995); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN and PLATON (Spek, 1990).

Figures

	Fig. 1. ORTEPII (Johnson, 1976) drawing of (I), showing the labelling scheme. Displacement ellipsoids are drawn for 50% probability for all non-H atoms; spheres of arbitrary small radius depict H atoms. Half-occupancy H atoms are shaded.
	Fig. 2. ORTEPII (Johnson, 1976) packing diagram of (I) showing a central molecule and its neighbors. Displacement ellipsoids are drawn for 20% probability for all non-H atoms; spheres of arbitrary small radius depict H atoms. Hydrogen bonds and C—H···O interactions are depicted by the finer interatomic lines.

(I)

Crystal data

C13H14O3	F(000) = 928
Mr = 218.25	Dx = 1.331 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 32.1141 (6) Å	Cell parameters from 30,322 reflections
b = 10.3464 (2) Å	θ = 1.3–27.5°
c = 6.5790 (1) Å	µ = 0.09 mm^−1
β = 94.679 (1)°	T = 291 K
V = 2178.69 (6) Å^3	Irregular polyhedron, colorless
Z = 8	0.38 × 0.23 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer	1950 reflections with I > 2.00σI
Radiation source: X-ray tube	Rint = 0.035
Graphite monochromator	θmax = 27.5°
ω scans with κ offsets	h = −41→41
30322 measured reflections	k = −13→13
2506 independent reflections	l = −8→8

Refinement

Refinement on F^2	145 parameters
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.048	Weighting scheme based on measured s.u.'s 1/[σ^2cs + (0.037 I)^2]
wR(F^2) = 0.126	(Δ/σ)max = 0.0004
S = 1.98	Δρmax = 0.24 e Å^−3
2506 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 as C2/c (No. 15); since refinement proceeded well, it was adopted. Fourier difference methods were used to locate initial H atom positions, excepting the hydroxyl H atom, and these H atoms were refined. Refined C—H distances ranged from 0.91 (1) to 1.07 (2) Å, with mean value 0.98 (4) Å; their U_iso values ranged from 1.0 to 1.5 times the U_eq values of the attached C atoms. The H atoms, excepting the hydroxyl H atom, were then made canonical, with C—H = 0.98 Å and U_iso = 1.2 × U_eq of the attached C atom. In the later stages of refinement the extinction coefficient was predicted to be negligibly small, so was not included in the model. The maximum peak in the final difference map occurs ~0.4 Å from O1, the maximum negative peak ~1.0 Å from O1 also.

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

————– Plane number 1 —————

Atoms Defining Plane Distance e.s.d. C1 (1) 0.0199 0.0011 C2 (1) −0.0039 0.0012 C3 (1) −0.0246 0.0013 C4 (1) −0.0005 0.0011 C5 (1) 0.0100 0.0012 C6 (1) 0.0052 0.0013 C7 (1) −0.0075 0.0012 C8 (1) −0.0193 0.0011 C9 (1) 0.0035 0.0010 C10 (1) 0.0054 0.0010

Additional Atoms Distance O1 (1) 0.1360 O2 (1) −0.0055 O3 (1) −0.0320 C11 (1) 0.0837 C12 (1) −0.0563 C13 (1) −0.0135

Mean deviation from plane is 0.0100 angstroms Chi-squared: 1502.1

————– Plane number 2 —————

Atoms Defining Plane Distance e.s.d. C1 (2) −0.0199 0.0011 C2 (2) 0.0039 0.0012 C3 (2) 0.0246 0.0013 C4 (2) 0.0005 0.0011 C5 (2) −0.0100 0.0012 C6 (2) −0.0052 0.0013 C7 (2) 0.0075 0.0012 C8 (2) 0.0193 0.0011 C9 (2) −0.0035 0.0010 C10 (2) −0.0054 0.0010

Mean deviation from plane is 0.0100 angstroms Chi-squared: 1502.1

Dihedral angles between least-squares planes plane plane angle 2 1 108.08

————– Plane number 3 —————

Atoms Defining Plane Distance e.s.d. O1 (1) 0.0613 0.0012 O2 (1) 0.0191 0.0009 O3 (1) −0.0503 0.0009 C1 (1) −0.0117 0.0011 C2 (1) −0.0396 0.0012 C3 (1) −0.0421 0.0013 C4 (1) 0.0049 0.0011 C5 (1) 0.0453 0.0012 C6 (1) 0.0462 0.0013 C7 (1) 0.0157 0.0013 C8 (1) −0.0195 0.0011 C9 (1) −0.0038 0.0010 C10 (1) 0.0167 0.0010 C11 (1) 0.0312 0.0012 C12 (1) −0.0362 0.0015 C13 (1) −0.0262 0.0015

Mean deviation from plane is 0.0294 angstroms Chi-squared: 13699.3

Dihedral angles between least-squares planes plane plane angle 3 1 1.01 3 2 108.71

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.48905 (3)	0.8792 (1)	0.4397 (1)	0.0743 (4)
O2	0.29494 (2)	0.82580 (9)	0.1602 (1)	0.0532 (3)
O3	0.42438 (2)	0.67134 (9)	0.8219 (1)	0.0518 (3)
C1	0.41575 (3)	0.8149 (1)	0.4542 (2)	0.0349 (3)
C2	0.40739 (4)	0.8847 (1)	0.2794 (2)	0.0418 (3)
C3	0.36724 (4)	0.8926 (1)	0.1752 (2)	0.0445 (3)
C4	0.33515 (4)	0.8268 (1)	0.2483 (2)	0.0389 (3)
C5	0.30705 (3)	0.6864 (1)	0.5075 (2)	0.0428 (3)
C6	0.31266 (4)	0.6170 (1)	0.6830 (2)	0.0486 (4)
C7	0.35207 (4)	0.6102 (1)	0.7922 (2)	0.0454 (3)
C8	0.38535 (4)	0.6742 (1)	0.7228 (2)	0.0376 (3)
C9	0.38166 (3)	0.7477 (1)	0.5372 (1)	0.0334 (3)
C10	0.34112 (3)	0.7529 (1)	0.4320 (2)	0.0353 (3)
C11	0.46028 (3)	0.8095 (1)	0.5505 (2)	0.0431 (3)
C12	0.28629 (4)	0.9008 (1)	−0.0197 (2)	0.0579 (4)
C13	0.43090 (5)	0.5977 (1)	1.0029 (2)	0.0586 (4)
H1O1	0.4955	0.8793	0.3289	0.090*	0.500
H2O1	0.4953	0.9482	0.4739	0.090*	0.500
H2	0.4304	0.9316	0.2235	0.050*
H3	0.3626	0.9450	0.0514	0.053*
H5	0.2794	0.6903	0.4329	0.051*
H6	0.2889	0.5713	0.7342	0.058*
H7	0.3557	0.5594	0.9181	0.054*
H11A	0.4691	0.7189	0.5590	0.052*
H11B	0.4608	0.8460	0.6882	0.052*
H12A	0.2906	0.9926	0.0126	0.070*
H12B	0.3051	0.8748	−0.1224	0.070*
H12C	0.2573	0.8869	−0.0732	0.070*
H13A	0.4598	0.6080	1.0598	0.070*
H13B	0.4119	0.6279	1.1023	0.070*
H13C	0.4253	0.5063	0.9722	0.070*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0443 (5)	0.1062 (9)	0.0723 (7)	−0.0262 (5)	0.0041 (4)	0.0318 (6)
O2	0.0417 (5)	0.0620 (6)	0.0537 (5)	−0.0036 (4)	−0.0093 (4)	0.0103 (4)
O3	0.0460 (5)	0.0611 (6)	0.0469 (5)	−0.0095 (4)	−0.0057 (4)	0.0183 (4)
C1	0.0342 (6)	0.0337 (6)	0.0371 (6)	−0.0022 (5)	0.0046 (4)	−0.0026 (5)
C2	0.0389 (6)	0.0432 (7)	0.0437 (7)	−0.0067 (5)	0.0065 (5)	0.0058 (5)
C3	0.0466 (7)	0.0461 (7)	0.0405 (6)	−0.0019 (6)	0.0014 (5)	0.0095 (5)
C4	0.0364 (6)	0.0395 (6)	0.0400 (6)	0.0004 (5)	−0.0019 (5)	−0.0019 (5)
C5	0.0346 (6)	0.0453 (7)	0.0489 (7)	−0.0035 (5)	0.0068 (5)	−0.0036 (6)
C6	0.0431 (7)	0.0521 (8)	0.0520 (7)	−0.0108 (6)	0.0133 (5)	0.0021 (6)
C7	0.0490 (7)	0.0462 (7)	0.0417 (6)	−0.0053 (6)	0.0088 (5)	0.0052 (5)
C8	0.0395 (6)	0.0362 (6)	0.0374 (6)	−0.0019 (5)	0.0042 (5)	−0.0017 (5)
C9	0.0356 (6)	0.0295 (6)	0.0353 (6)	−0.0006 (4)	0.0049 (4)	−0.0023 (5)
C10	0.0351 (6)	0.0330 (6)	0.0381 (6)	−0.0007 (4)	0.0051 (5)	−0.0049 (5)
C11	0.0352 (6)	0.0464 (7)	0.0476 (7)	−0.0080 (5)	0.0037 (5)	0.0050 (6)
C12	0.0528 (8)	0.0642 (9)	0.0536 (8)	0.0037 (7)	−0.0142 (6)	0.0092 (7)
C13	0.0628 (8)	0.0615 (9)	0.0493 (8)	−0.0049 (7)	−0.0081 (6)	0.0159 (6)

Geometric parameters (Å, º)

O1—C11	1.420 (1)	C5—C10	1.416 (2)
O1—H1O1	0.77	C5—H5	0.98
O1—H2O1	0.77	C6—C7	1.405 (2)
O2—C4	1.372 (1)	C6—H6	0.98
O2—C12	1.423 (1)	C7—C8	1.367 (2)
O3—C8	1.365 (1)	C7—H7	0.98
O3—C13	1.414 (1)	C8—C9	1.435 (2)
C1—C2	1.366 (2)	C9—C10	1.425 (2)
C1—C9	1.441 (2)	C11—H11A	0.98
C1—C11	1.517 (2)	C11—H11B	0.98
C2—C3	1.412 (2)	C12—H12A	0.98
C2—H2	0.98	C12—H12B	0.98
C3—C4	1.356 (2)	C12—H12C	0.98
C3—H3	0.98	C13—H13A	0.98
C4—C10	1.429 (2)	C13—H13B	0.98
C5—C6	1.359 (2)	C13—H13C	0.98
C11—O1—H1O1	136.0	O3—C8—C9	115.25 (9)
C11—O1—H2O1	119.1	C7—C8—C9	121.9 (1)
H1O1—O1—H2O1	101.0	C1—C9—C8	124.4 (1)
C4—O2—C12	117.43 (9)	C1—C9—C10	119.3 (1)
C8—O3—C13	118.74 (9)	C8—C9—C10	116.2 (1)
C2—C1—C9	118.1 (1)	C4—C10—C5	120.1 (1)
C2—C1—C11	119.0 (1)	C4—C10—C9	119.0 (1)
C9—C1—C11	122.9 (1)	C5—C10—C9	120.8 (1)
C1—C2—C3	123.2 (1)	O1—C11—C1	113.42 (9)
C1—C2—H2	118.4	O1—C11—H11A	108.5
C3—C2—H2	118.4	O1—C11—H11B	108.4
C2—C3—C4	119.3 (1)	C1—C11—H11A	108.5
C2—C3—H3	120.4	C1—C11—H11B	108.5
C4—C3—H3	120.3	H11A—C11—H11B	109.5
O2—C4—C3	124.8 (1)	O2—C12—H12A	109.5
O2—C4—C10	114.2 (1)	O2—C12—H12B	109.5
C3—C4—C10	121.0 (1)	O2—C12—H12C	109.5
C6—C5—C10	120.1 (1)	H12A—C12—H12B	109.4
C6—C5—H5	119.9	H12A—C12—H12C	109.4
C10—C5—H5	120.0	H12B—C12—H12C	109.5
C5—C6—C7	120.8 (1)	O3—C13—H13A	109.5
C5—C6—H6	119.6	O3—C13—H13B	109.4
C7—C6—H6	119.6	O3—C13—H13C	109.5
C6—C7—C8	120.0 (1)	H13A—C13—H13B	109.4
C6—C7—H7	120.0	H13A—C13—H13C	109.6
C8—C7—H7	120.0	H13B—C13—H13C	109.4
O3—C8—C7	122.8 (1)
O1—C11—C1—C2	−1.1 (2)	C3—C4—O2—C12	−0.8 (2)
O1—C11—C1—C9	178.0 (1)	C3—C4—C10—C5	179.0 (1)
O2—C4—C3—C2	−179.4 (1)	C3—C4—C10—C9	−0.8 (2)
O2—C4—C10—C5	0.2 (1)	C4—C10—C5—C6	−179.5 (1)
O2—C4—C10—C9	−179.65 (9)	C4—C10—C9—C8	178.71 (9)
O3—C8—C7—C6	180.0 (1)	C5—C6—C7—C8	0.2 (2)
O3—C8—C9—C1	0.3 (2)	C5—C10—C9—C8	−1.2 (2)
O3—C8—C9—C10	−179.48 (9)	C6—C5—C10—C9	0.4 (2)
C1—C2—C3—C4	−1.0 (2)	C6—C7—C8—C9	−1.1 (2)
C1—C9—C8—C7	−178.7 (1)	C7—C6—C5—C10	0.2 (2)
C1—C9—C10—C4	−1.1 (2)	C7—C8—O3—C13	0.9 (2)
C1—C9—C10—C5	179.04 (9)	C7—C8—C9—C10	1.5 (2)
C2—C1—C9—C8	−177.9 (1)	C8—C9—C1—C11	3.1 (2)
C2—C1—C9—C10	1.9 (2)	C9—C8—O3—C13	−178.1 (1)
C2—C3—C4—C10	1.9 (2)	C10—C4—O2—C12	178.0 (1)
C3—C2—C1—C9	−0.9 (2)	C10—C9—C1—C11	−177.1 (1)
C3—C2—C1—C11	178.1 (1)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O1^i	0.77	1.87	2.648 (2)	180
O1—H2O1···O1^ii	0.77	1.93	2.698 (2)	180
C12—H12C···O2^iii	0.98	2.80	3.572 (2)	136
C11—H11B···O1^iv	0.98	2.84	3.678 (2)	144

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