(1H-Imidazol-4-yl)methanol

Sanders, M.B.; Farrokh, J.C.; Hardie, J.; Chan, B.C.

doi:10.1107/S160053681301636X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1151

https://doi.org/10.1107/S160053681301636X

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(1H-Imidazol-4-yl)methanol

Marisa B. Sanders,^a John C. Farrokh,^a Joseph Hardie ^a and Benny C. Chan ^a ^*

^aDepartment of Chemistry, The College of New Jersey, 2000 Pennington Rd, Ewing, NJ 08628, USA
^*Correspondence e-mail: chan@tcnj.edu

(Received 5 March 2013; accepted 12 June 2013; online 26 June 2013)

The title compound, C₄H₆N₂O, displays two predominant hydrogen-bonding interactions in the crystal structure. The first is between the unprotonated imidazole N atom of one molecule and the hydroxy H atom of an adjacent molecule. The second is between the hydroxy O atom of one molecule and the imidazole N—H group of a corresponding molecule. These interactions lead to the formation of a two-dimnensional network parallel to (10-1). C—H⋯O interactions also occur.

Related literature

For background information on imidazole complex formation, see: Bauman & Wang (1964 ); Fan et al. (2000 ). For related structures, see: Nyamori et al. (2010 ); Albov et al. (2006 ). For the use of imidazole-containing compounds in coordination chemistry, see: Huff et al. (1993 ); Fujita et al. (1994 ). For the use of the title compound in the synthesis of biological compounds, see: Darby et al. (1942 ).

Experimental

Crystal data

C₄H₆N₂O
M_r = 98.11
Monoclinic, C 2/c
a = 13.9180 (9) Å
b = 7.1980 (5) Å
c = 11.6509 (12) Å
β = 125.249 (1)°
V = 953.20 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.52 × 0.37 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.688, T_max = 0.746
5389 measured reflections
1158 independent reflections
1086 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.07
1158 reflections
65 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.84	1.92	2.7563 (13)	172
N2—H2⋯O1ⁱⁱ	0.88	1.99	2.8315 (11)	161
C4—H4⋯O1ⁱⁱⁱ	0.95	2.57	3.4574 (17)	155
Symmetry codes: (i) -x+1, -y, -z+2; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (CrystalMaker Software, 2009 ); software used to prepare material for publication: enCIFer (Allen et al. 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681301636X/fj2622sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681301636X/fj2622Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681301636X/fj2622Isup3.cml

checkCIF report

Comment top

Imidazole ligands have been used in coordination chemistry with great success over the last twenty years (Huff et al., 1993). These successes can be attributed to how the nitrogen in imidazole assists in the formation of metal complexes (Fujita et al., 1994). Imidazole-containing metal complexes have a variety of applications, such as redox mediators in enzyme-based electrochemical sensors (Fan et al., 2000). A few examples of imidazole complex compounds with biological applications have been reported (Bauman and Wang, 1964). Histidine, an essential amino acid, and histamine, a bioorganic compound that acts as neurotransmitter, both involve (1H-imidazol-5-yl)methanol in their respective synthesizes (Darby et al., 1942). Here we report on a new imidazole compound, the hydroxymethyl-substituted imidazole, the title compound, C₄H₆N₂O. The bond lengths and bond angles are within normal ranges in the molecular structure of this compound (Fig. 1). The compound forms hydrogen bonds of 1.985 (8) Å between the nitrogen (N1) on the imidazole ring of one molecule and the hydrogen (H1') of the hydroxyl on an adjacent molecule (Fig. 2). Hydrogen bonding also takes place between the oxygen (O1") on the hydroxyl group of one molecule and the hydrogen (H2) bonded to a nitrogen (N2) on the imidazole ring of a corresponding molecule. This bond measures 1.921 (1) Å (Fig. 3).

Related literature top

For background information on imidazole complex formation, see: Bauman & Wang (1964); Fan et al. (2000). For related structures, see: Nyamori et al. (2010); Albov et al. (2006). For the use of imidazole-containing compounds in coordination chemistry, see: Huff et al. (1993); Fujita et al. (1994). For the use of the title compound in the synthesis of biological compounds, see: Darby et al. (1942).

Experimental top

Approximately 100 mg of the target compound was dissolved in 2 ml of a 50% methanol: 50% toluene solution. The solution was allowed to evaporate slowly for two weeks until clear, colorless crystals formed. A crystal was isolated and analyzed on a Bruker APEX II CCD single-crystal X-ray diffractometer.

Structure description top

For background information on imidazole complex formation, see: Bauman & Wang (1964); Fan et al. (2000). For related structures, see: Nyamori et al. (2010); Albov et al. (2006). For the use of imidazole-containing compounds in coordination chemistry, see: Huff et al. (1993); Fujita et al. (1994). For the use of the title compound in the synthesis of biological compounds, see: Darby et al. (1942).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (CrystalMaker Software, 2009); software used to prepare material for publication: enCIFer (Allen et al. 2004).

Figures top

	Fig. 1. Thermal ellipsoid plot at 50% probability.
	Fig. 2. The title structure is stabilized by hydrogen bonds between N1' and H1, which each measure 1.985 (8) Å. Oxygen atoms are shown in red, carbon atoms in black, hydrogen atoms in pink, and nitrogen atoms in blue.
	Fig. 3. Hydrogen bonding between the oxygen (O1") on the hydroxyl group of one molecule and the hydrogen (H2) bonded to a nitrogen (N2) on the imidazole ring of a corresponding molecule measures 1.921 (1) Å.

(1H-Imidazol-4-yl)methanol top

Crystal data top

C₄H₆N₂O	F(000) = 416
M_r = 98.11	D_x = 1.367 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9180 (9) Å	Cell parameters from 189 reflections
b = 7.1980 (5) Å	θ = 3.6–28.2°
c = 11.6509 (12) Å	µ = 0.10 mm⁻¹
β = 125.249 (1)°	T = 100 K
V = 953.20 (13) Å³	Blocks, colourless
Z = 8	0.52 × 0.37 × 0.29 mm

Data collection top

Bruker APEXII CCD diffractometer	1158 independent reflections
Radiation source: fine-focus sealed tube	1086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.6°, θ_min = 3.4°
ω and φ scans	h = −18→18
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −9→9
T_min = 0.688, T_max = 0.746	l = −15→15
5389 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0511P)² + 0.6749P] where P = (F_o² + 2F_c²)/3
1158 reflections	(Δ/σ)_max = 0.002
65 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₄H₆N₂O	V = 953.20 (13) Å³
M_r = 98.11	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.9180 (9) Å	µ = 0.10 mm⁻¹
b = 7.1980 (5) Å	T = 100 K
c = 11.6509 (12) Å	0.52 × 0.37 × 0.29 mm
β = 125.249 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1158 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	1086 reflections with I > 2σ(I)
T_min = 0.688, T_max = 0.746	R_int = 0.015
5389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.07	Δρ_max = 0.35 e Å⁻³
1158 reflections	Δρ_min = −0.27 e Å⁻³
65 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

	x	y	z	U_iso*/U_eq
O1	0.39678 (6)	0.03753 (10)	1.06291 (7)	0.0178 (2)
H1	0.4528	−0.0374	1.093	0.027*
N1	0.43471 (7)	0.23365 (12)	0.85046 (9)	0.0176 (2)
N2	0.27914 (7)	0.41114 (12)	0.71171 (9)	0.0178 (2)
H2	0.2243	0.4731	0.6368	0.021*
C1	0.43706 (9)	0.22305 (14)	1.06767 (10)	0.0189 (2)
H1A	0.5241	0.2245	1.1246	0.023*
H1B	0.4118	0.3067	1.113	0.023*
C2	0.38850 (8)	0.29121 (13)	0.92295 (10)	0.0160 (2)
C3	0.36594 (9)	0.30971 (14)	0.72413 (11)	0.0178 (2)
H3	0.3766	0.2945	0.6512	0.021*
C4	0.29183 (9)	0.40012 (14)	0.83752 (11)	0.0179 (2)
H4	0.2433	0.4567	0.8605	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0161 (4)	0.0178 (4)	0.0184 (4)	0.0035 (3)	0.0093 (3)	0.0032 (3)
N1	0.0164 (4)	0.0173 (4)	0.0191 (4)	0.0018 (3)	0.0103 (4)	0.0007 (3)
N2	0.0165 (4)	0.0164 (4)	0.0178 (4)	0.0027 (3)	0.0083 (3)	0.0024 (3)
C1	0.0197 (5)	0.0181 (5)	0.0154 (5)	0.0009 (4)	0.0081 (4)	−0.0012 (4)
C2	0.0159 (5)	0.0140 (4)	0.0169 (5)	−0.0009 (3)	0.0088 (4)	−0.0016 (3)
C3	0.0182 (5)	0.0168 (5)	0.0193 (5)	0.0005 (4)	0.0113 (4)	0.0005 (4)
C4	0.0184 (5)	0.0165 (5)	0.0196 (5)	0.0019 (4)	0.0114 (4)	−0.0001 (4)

Geometric parameters (Å, º) top

O1—C1	1.4369 (12)	C1—C2	1.4917 (13)
O1—H1	0.84	C1—H1A	0.99
N1—C3	1.3251 (13)	C1—H1B	0.99
N1—C2	1.3877 (12)	C2—C4	1.3674 (14)
N2—C3	1.3459 (13)	C3—H3	0.95
N2—C4	1.3738 (13)	C4—H4	0.95
N2—H2	0.88

C1—O1—H1		H1A—C1—H1B
C3—N1—C2		C4—C2—N1
C3—N2—C4		C4—C2—C1
C3—N2—H2		N1—C2—C1
C4—N2—H2		N1—C3—N2
O1—C1—C2		N1—C3—H3
O1—C1—H1A		N2—C3—H3
C2—C1—H1A		C2—C4—N2
O1—C1—H1B		C2—C4—H4
C2—C1—H1B		N2—C4—H4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.92	2.7563 (13)	172
N2—H2···O1ⁱⁱ	0.88	1.99	2.8315 (11)	161
C4—H4···O1ⁱⁱⁱ	0.95	2.57	3.4574 (17)	155

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

Experimental details

Crystal data
Chemical formula	C₄H₆N₂O
M_r	98.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	13.9180 (9), 7.1980 (5), 11.6509 (12)
β (°)	125.249 (1)
V (Å³)	953.20 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.52 × 0.37 × 0.29

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.688, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	5389, 1158, 1086
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.07
No. of reflections	1158
No. of parameters	65
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.27

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (CrystalMaker Software, 2009), enCIFer (Allen et al. 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.84	1.92	2.7563 (13)	172
N2—H2···O1ⁱⁱ	0.88	1.99	2.8315 (11)	161
C4—H4···O1ⁱⁱⁱ	0.95	2.57	3.4574 (17)	155

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

Acknowledgements

The authors gratefully acknowledge The College of New Jersey's School of Science for research funding and the National Science Foundation for major research instrumentation grant (NSF-0922931) for diffractometer acquisition.

References

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