A second ortho­rhom­bic polymorph of 2-(pyridin-4-ylmeth­oxy)phenol

Abstract

The crystal structure of the title compound, C₁₂H₁₁NO₂, represents a new ortho­rhom­bic polymorph II of the previously reported ortho­rhom­bic form I [Zhang et al. (2009 ▶) Acta Cryst. E65, o3160]. In polymorph II, the six-membered rings form a dihedral angle of 13.8 (1)° [71.6 (1)° in I], and O—H⋯N hydrogen bonds link mol­ecules into chains along [100], whereas the crystal structure of I features hydrogen-bonded centrosymmetric dimers.

Related literature  

For details of the synthesis, see: Gao et al. (2004 ▶). For the crystal structure of polymorph I, see: Zhang et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₂H₁₁NO₂

• M _r = 201.22

• Orthorhombic,

• a = 23.398 (5) Å

• b = 5.8343 (12) Å

• c = 7.3934 (15) Å

• V = 1009.3 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 293 K

• 0.50 × 0.37 × 0.11 mm

Data collection  

• Rigaku R-AXIS RAPID diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.956, T _max = 0.990

• 8907 measured reflections

• 2285 independent reflections

• 1298 reflections with I > 2σ(I)

• R _int = 0.066

Refinement  

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.077

• S = 1.01

• 2285 reflections

• 138 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.14 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812014067/cv5271Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1i	0.82	1.95	2.763 (2)	173

Symmetry code: (i) .

supplementary crystallographic information

Comment

The reported here crystal structure of the title compound, C₁₂H₁₁NO₂, represents a new orthorhombic polymorph (II)of the previously reported orthorhombic form (I) (Zhang et al. 2009). It was crystalized from a methanol solution of the title compound and (R)-2-(4-(carboxymethoxy)phenoxy)propanoic acid mixture.

In polymorph II (Figure 1), two six-membered rings form a dihedral angle of 13.8 (1)° [71.6 (1)° in I], and intermolecular O—H···N hydrogen bonds link molecules into chains along [100] (Figure 2, Table 1), in spite of hydrogen-bonded centrosymmetric dimers in polymorph I.

Experimental

The 2-(pyridin-4-ylmethoxy)phenol was synthesized by the reaction of o-benzenediol and 4-chloromethylpyridine hydrochloride under nitrogen atmosphere and alkaline condition (Gao et al., 2004). Colourless block crystals were obtained by slow evaporation of a methanol solution (10 mL) containing title compound (0.402 g, 2 mmol) and (R)-2-(4-(carboxymethoxy)phenoxy)propanoic acid (0.48 g, 2 mmol) which only contained the molecules of title compound.

Refinement

H atoms bound to C atoms and the H atoms of the hydroxyl groups were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), O—H = 0.82 Å and with U_iso(H) = 1.2U_eq(C), U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms.

Fig. 2.

A partial packing view, showing hydrogen-bonded (dashed lines) chain structure along [100].

Crystal data

C12H11NO2	F(000) = 424
Mr = 201.22	Dx = 1.324 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 5894 reflections
a = 23.398 (5) Å	θ = 3.3–27.5°
b = 5.8343 (12) Å	µ = 0.09 mm−1
c = 7.3934 (15) Å	T = 293 K
V = 1009.3 (4) Å3	Block, colourless
Z = 4	0.50 × 0.37 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	2285 independent reflections
Radiation source: fine-focus sealed tube	1298 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scan	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −30→30
Tmin = 0.956, Tmax = 0.990	k = −7→7
8907 measured reflections	l = −9→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.0218P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2285 reflections	Δρmax = 0.15 e Å−3
138 parameters	Δρmin = −0.14 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (6)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.68990 (6)	0.4700 (3)	0.0425 (3)	0.0567 (5)
H1	0.7109	0.3578	0.0381	0.085*
O2	0.46554 (6)	0.1873 (3)	−0.0201 (2)	0.0566 (5)
N1	0.26917 (7)	−0.1195 (3)	0.0264 (3)	0.0488 (5)
C2	0.59170 (9)	0.5453 (4)	0.0842 (3)	0.0442 (6)
H2	0.6014	0.6865	0.1339	0.053*
C8	0.36646 (8)	0.1609 (4)	0.0395 (3)	0.0390 (5)
C7	0.41925 (8)	0.3104 (4)	0.0562 (3)	0.0429 (6)
H7A	0.4137	0.4538	−0.0078	0.052*
H7B	0.4269	0.3444	0.1824	0.052*
C12	0.36737 (9)	−0.0462 (4)	−0.0507 (3)	0.0448 (6)
H12	0.4003	−0.0958	−0.1091	0.054*
C3	0.53418 (9)	0.4830 (4)	0.0713 (3)	0.0461 (6)
H3	0.5057	0.5825	0.1107	0.055*
C4	0.52013 (8)	0.2740 (4)	0.0000 (3)	0.0410 (6)
C1	0.63411 (8)	0.4011 (4)	0.0247 (3)	0.0403 (5)
C6	0.61922 (9)	0.1936 (4)	−0.0516 (4)	0.0518 (6)
H6	0.6475	0.0958	−0.0948	0.062*
C9	0.31568 (9)	0.2274 (4)	0.1199 (3)	0.0463 (6)
H9	0.3132	0.3668	0.1804	0.056*
C10	0.26894 (9)	0.0849 (4)	0.1093 (3)	0.0499 (7)
H10	0.2351	0.1333	0.1629	0.060*
C5	0.56238 (9)	0.1309 (4)	−0.0638 (4)	0.0541 (7)
H5	0.5526	−0.0089	−0.1156	0.065*
C11	0.31825 (8)	−0.1789 (4)	−0.0526 (3)	0.0485 (6)
H11	0.3196	−0.3186	−0.1131	0.058*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0343 (8)	0.0535 (11)	0.0821 (13)	−0.0041 (7)	−0.0031 (10)	0.0010 (11)
O2	0.0315 (8)	0.0521 (10)	0.0861 (14)	−0.0023 (7)	0.0054 (9)	−0.0184 (11)
N1	0.0361 (10)	0.0534 (13)	0.0569 (12)	0.0003 (10)	0.0028 (10)	0.0084 (12)
C2	0.0414 (13)	0.0342 (13)	0.0569 (17)	−0.0032 (10)	−0.0020 (12)	−0.0076 (12)
C8	0.0350 (11)	0.0406 (13)	0.0416 (13)	0.0046 (10)	−0.0013 (11)	0.0052 (12)
C7	0.0378 (12)	0.0438 (13)	0.0472 (15)	0.0026 (10)	0.0045 (12)	−0.0016 (14)
C12	0.0333 (12)	0.0500 (15)	0.0510 (14)	0.0030 (11)	0.0049 (12)	0.0009 (14)
C3	0.0413 (13)	0.0392 (14)	0.0577 (16)	0.0057 (11)	0.0009 (13)	−0.0070 (13)
C4	0.0313 (11)	0.0430 (13)	0.0487 (14)	0.0001 (10)	0.0011 (10)	−0.0034 (12)
C1	0.0329 (11)	0.0421 (13)	0.0460 (14)	−0.0004 (10)	0.0000 (12)	0.0045 (13)
C6	0.0375 (12)	0.0489 (15)	0.0690 (17)	0.0089 (11)	0.0008 (14)	−0.0165 (15)
C9	0.0425 (13)	0.0437 (15)	0.0528 (15)	0.0036 (12)	0.0052 (11)	0.0025 (13)
C10	0.0367 (13)	0.0554 (17)	0.0577 (16)	0.0096 (12)	0.0054 (12)	0.0097 (15)
C5	0.0424 (13)	0.0429 (14)	0.0771 (18)	−0.0008 (11)	−0.0026 (14)	−0.0206 (16)
C11	0.0432 (12)	0.0516 (16)	0.0506 (14)	−0.0007 (12)	0.0004 (12)	−0.0006 (14)

Geometric parameters (Å, º)

O1—C1	1.372 (2)	C12—C11	1.386 (3)
O1—H1	0.8200	C12—H12	0.9300
O2—C4	1.382 (2)	C3—C4	1.368 (3)
O2—C7	1.417 (2)	C3—H3	0.9300
N1—C11	1.334 (3)	C4—C5	1.377 (3)
N1—C10	1.340 (3)	C1—C6	1.380 (3)
C2—C1	1.373 (3)	C6—C5	1.382 (3)
C2—C3	1.397 (3)	C6—H6	0.9300
C2—H2	0.9300	C9—C10	1.376 (3)
C8—C12	1.381 (3)	C9—H9	0.9300
C8—C9	1.384 (3)	C10—H10	0.9300
C8—C7	1.517 (3)	C5—H5	0.9300
C7—H7A	0.9700	C11—H11	0.9300
C7—H7B	0.9700
C1—O1—H1	109.5	C3—C4—C5	119.98 (18)
C4—O2—C7	118.54 (17)	C3—C4—O2	126.16 (19)
C11—N1—C10	115.8 (2)	C5—C4—O2	113.8 (2)
C1—C2—C3	121.0 (2)	O1—C1—C2	118.5 (2)
C1—C2—H2	119.5	O1—C1—C6	122.45 (19)
C3—C2—H2	119.5	C2—C1—C6	119.08 (19)
C12—C8—C9	117.8 (2)	C1—C6—C5	120.1 (2)
C12—C8—C7	122.01 (19)	C1—C6—H6	119.9
C9—C8—C7	120.2 (2)	C5—C6—H6	119.9
O2—C7—C8	107.36 (18)	C10—C9—C8	119.2 (2)
O2—C7—H7A	110.2	C10—C9—H9	120.4
C8—C7—H7A	110.2	C8—C9—H9	120.4
O2—C7—H7B	110.2	N1—C10—C9	124.1 (2)
C8—C7—H7B	110.2	N1—C10—H10	118.0
H7A—C7—H7B	108.5	C9—C10—H10	118.0
C8—C12—C11	118.8 (2)	C4—C5—C6	120.5 (2)
C8—C12—H12	120.6	C4—C5—H5	119.7
C11—C12—H12	120.6	C6—C5—H5	119.7
C4—C3—C2	119.3 (2)	N1—C11—C12	124.4 (2)
C4—C3—H3	120.3	N1—C11—H11	117.8
C2—C3—H3	120.3	C12—C11—H11	117.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1i	0.82	1.95	2.763 (2)	173

Symmetry code: (i) x+1/2, −y, z.