4-Hydr­oxy-3,5-dimethoxy­benzonitrile at 125 K

In the title compound, C₉H₉NO₃, all non-H atoms are coplanar. An O—H...O hydrogen bond is observed in the mol­ecular structure and inter­molecular O—H...N hydrogen bonds link the mol­ecules into a chain along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 123 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.113
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.10
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C9      ..       5.05 su
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C9     ...       1.44 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      1.099
            Tmax scaled      0.960 Tmin scaled      0.932

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Nitriles, important reagents for organic synthesis, have been known to chemists for a long time. Nitriles are used in the synthesis of thiazole derivatives which act as inhibitors of superoxide produced by neutrophils (Chihiro et al., 1995). They are also used in the preparation of antipicornavirus tetrazole anologues (Diana et al., 1993). The title compound is an important intermediate leading to bis-amidine which exhibits antimicrobial activity against a widespread range of microorganisms (Zabinski et al., 2007). We report here the crystal structure of the title compound.

The non-hydrogen atoms in the molecule of the title compound are coplanar, with atoms N1, C7 and C8 deviating by 0.025 (2), 0.066 (2) and 0.042 (2) Å, respectively. The C≡N distance (1.1373 (17) Å) shows normal value (1.136 (2) Å; Zabinski et al., 2007).

An intramolecular O—H···N hydrogen bond is observed. Intermolecular O—H···O hydrogen bonds link the molecules into chains along the a axis (Fig.2 and Table 1).

Related literature

For synthesis, see: Van Es (1965). For general background, see: Chihiro et al. (1995); Diana et al. (1993). For a related structure, see: Zabinski et al. (2007).

S2. Experimental

The title compound was prepared according to the literature method of Van Es (1965). Single crystals suitable for X-ray analysis were obtained by slow evaporation of an isoproanol solution at 295 K (m.p. 459–461 K).

S3. Refinement

H atoms were positioned geometrically (O—H = 0.84 Å and C—H = 0.95 or 0.98 Å) and refined using a riding model, with U_iso(H) = 1.5U_eq(O or C_methyl) or 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal packing of the title compound, viewed approximately down the b axis. Dashed lines indicate intermolecular hydrogen bonds.

4-Hydroxy-3,5-dimethoxybenzonitrile

Crystal data

C9H9NO3	F(000) = 752
Mr = 179.17	Dx = 1.333 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2036 reflections
a = 8.9624 (12) Å	θ = 2.6–27.5°
b = 12.5413 (16) Å	µ = 0.10 mm^−1
c = 15.881 (2) Å	T = 123 K
V = 1785.1 (4) Å^3	Block, colourless
Z = 8	0.50 × 0.50 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2036 independent reflections
Radiation source: fine-focus sealed tube	1469 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
Tmin = 0.848, Tmax = 0.874	k = −15→16
17694 measured reflections	l = −19→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 0.2676P] where P = (Fo^2 + 2Fc^2)/3
2036 reflections	(Δ/σ)max = 0.001
118 parameters	Δρmax = 0.12 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O2	0.31350 (10)	0.37213 (8)	0.04912 (7)	0.0553 (3)
O1	0.20865 (11)	0.07072 (9)	0.20812 (7)	0.0630 (3)
O3	0.39718 (10)	0.19656 (9)	0.13177 (7)	0.0603 (3)
H3	0.4478	0.2415	0.1049	0.090*
C4	−0.00241 (15)	0.17879 (11)	0.16337 (8)	0.0464 (3)
H4	−0.0729	0.1337	0.1904	0.056*
C5	0.14822 (15)	0.15641 (11)	0.16763 (8)	0.0450 (3)
C6	0.25106 (14)	0.22342 (11)	0.12798 (8)	0.0429 (3)
N1	−0.33080 (14)	0.30710 (12)	0.10859 (10)	0.0687 (4)
C3	−0.04928 (14)	0.26813 (11)	0.11906 (8)	0.0451 (3)
C2	0.05144 (15)	0.33650 (11)	0.07979 (9)	0.0462 (3)
H2	0.0174	0.3976	0.0501	0.055*
C1	0.20164 (14)	0.31359 (10)	0.08489 (9)	0.0427 (3)
C9	−0.20643 (15)	0.28999 (12)	0.11296 (10)	0.0520 (4)
C8	0.27231 (18)	0.46331 (13)	0.00121 (11)	0.0626 (4)
H8A	0.3623	0.4980	−0.0207	0.094*
H8B	0.2177	0.5134	0.0372	0.094*
H8C	0.2085	0.4414	−0.0458	0.094*
C7	0.1083 (2)	−0.00458 (15)	0.24377 (13)	0.0779 (5)
H7A	0.1651	−0.0620	0.2707	0.117*
H7B	0.0450	−0.0345	0.1993	0.117*
H7C	0.0456	0.0308	0.2859	0.117*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2	0.0366 (5)	0.0562 (6)	0.0730 (7)	−0.0017 (4)	0.0037 (4)	0.0177 (5)
O1	0.0479 (6)	0.0646 (7)	0.0765 (7)	−0.0023 (5)	−0.0043 (5)	0.0267 (5)
O3	0.0323 (5)	0.0663 (7)	0.0823 (8)	0.0024 (4)	−0.0006 (5)	0.0222 (5)
C4	0.0360 (7)	0.0545 (8)	0.0486 (7)	−0.0071 (6)	0.0021 (6)	0.0001 (6)
C5	0.0399 (7)	0.0495 (8)	0.0457 (7)	−0.0016 (6)	−0.0029 (6)	0.0047 (6)
C6	0.0301 (6)	0.0507 (8)	0.0477 (7)	−0.0009 (5)	−0.0022 (5)	0.0019 (6)
N1	0.0345 (7)	0.0733 (10)	0.0982 (11)	−0.0005 (6)	0.0002 (7)	0.0032 (8)
C3	0.0312 (6)	0.0511 (8)	0.0530 (8)	−0.0004 (6)	0.0002 (6)	−0.0065 (6)
C2	0.0361 (7)	0.0470 (7)	0.0554 (8)	0.0031 (6)	−0.0024 (6)	0.0023 (6)
C1	0.0351 (7)	0.0452 (7)	0.0477 (7)	−0.0027 (5)	0.0014 (5)	0.0008 (6)
C9	0.0360 (8)	0.0532 (8)	0.0668 (9)	−0.0028 (6)	0.0003 (6)	−0.0027 (7)
C8	0.0546 (9)	0.0538 (9)	0.0793 (11)	−0.0029 (7)	0.0051 (8)	0.0182 (8)
C7	0.0715 (11)	0.0710 (11)	0.0914 (13)	−0.0040 (9)	0.0082 (10)	0.0354 (10)

Geometric parameters (Å, º)

O2—C1	1.3663 (15)	N1—C9	1.1373 (17)
O2—C8	1.4223 (18)	C3—C2	1.3924 (19)
O1—C5	1.3645 (17)	C3—C9	1.4381 (18)
O1—C7	1.4217 (19)	C2—C1	1.3788 (18)
O3—C6	1.3536 (16)	C2—H2	0.95
O3—H3	0.84	C8—H8A	0.98
C4—C5	1.3806 (19)	C8—H8B	0.98
C4—C3	1.3883 (19)	C8—H8C	0.98
C4—H4	0.95	C7—H7A	0.98
C5—C6	1.3972 (19)	C7—H7B	0.98
C6—C1	1.3941 (19)	C7—H7C	0.98
C1—O2—C8	117.64 (11)	C3—C2—H2	120.7
C5—O1—C7	117.37 (12)	O2—C1—C2	125.45 (12)
C6—O3—H3	109.5	O2—C1—C6	114.01 (11)
C5—C4—C3	119.00 (13)	C2—C1—C6	120.53 (12)
C5—C4—H4	120.5	N1—C9—C3	179.62 (19)
C3—C4—H4	120.5	O2—C8—H8A	109.5
O1—C5—C4	124.84 (12)	O2—C8—H8B	109.5
O1—C5—C6	115.10 (12)	H8A—C8—H8B	109.5
C4—C5—C6	120.05 (13)	O2—C8—H8C	109.5
O3—C6—C1	122.08 (12)	H8A—C8—H8C	109.5
O3—C6—C5	117.94 (12)	H8B—C8—H8C	109.5
C1—C6—C5	119.97 (12)	O1—C7—H7A	109.5
C4—C3—C2	121.86 (12)	O1—C7—H7B	109.5
C4—C3—C9	118.96 (13)	H7A—C7—H7B	109.5
C2—C3—C9	119.17 (13)	O1—C7—H7C	109.5
C1—C2—C3	118.58 (13)	H7A—C7—H7C	109.5
C1—C2—H2	120.7	H7B—C7—H7C	109.5
C7—O1—C5—C4	4.3 (2)	C4—C3—C2—C1	0.5 (2)
C7—O1—C5—C6	−175.11 (14)	C9—C3—C2—C1	−178.88 (13)
C3—C4—C5—O1	−179.15 (12)	C8—O2—C1—C2	−1.2 (2)
C3—C4—C5—C6	0.2 (2)	C8—O2—C1—C6	177.66 (13)
O1—C5—C6—O3	1.36 (18)	C3—C2—C1—O2	179.30 (13)
C4—C5—C6—O3	−178.10 (13)	C3—C2—C1—C6	0.5 (2)
O1—C5—C6—C1	−179.83 (12)	O3—C6—C1—O2	−1.29 (19)
C4—C5—C6—C1	0.7 (2)	C5—C6—C1—O2	179.95 (12)
C5—C4—C3—C2	−0.9 (2)	O3—C6—C1—C2	177.69 (13)
C5—C4—C3—C9	178.54 (13)	C5—C6—C1—C2	−1.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.84	2.22	2.6710 (14)	114
O3—H3···N1^i	0.84	2.15	2.8286 (17)	138

Symmetry code: (i) x+1, y, z.