4-Hydroxy­methyl-3,5-dimethyl-1H-pyrazole

In the title compound, C₆H₁₀N₂O, corrugated sheets parallel to the (101) plane are formed via inter­molecular O—H...N and N—H...O hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C)= 0.002 Å
• R factor = 0.048
• wR factor = 0.148
• Data-to-parameter ratio = 15.1

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S1. Comment

Hydrogen-bonding interactions between ligands are specific and directional and are, when present in metal complexes, usually not dependent on the properties of the metal ions, but they are playing a critical role in the structures and functions of the complexes. In this sense, 4-hydroxymethyl-3,5-dimethylpyrazole is an excellent candidate for the construction of supramolecular complexes, since it not only has multiple coordination modes but also can form regular hydrogen bonding by functioning as both a hydrogen-bonding donor and acceptor. (Moncol et al., 2006; Kozlevcar et al., 2006).

The molecular structure of (I) is depicted in Fig. 1. The C—O, C—C and C—N distances show no remarkable features, with C—N distances in the range of 1.336 (2)–1.343 (2) Å. The intermolecular O—H···N and N—H···O hydrogen bonds (Table 1) lead to the formation of a zigzag like layer structure developping parallel to the (1 0 1) plane.

Related literature

For related literature, see: Kozlevcar et al. (2006); Moncol et al. (2006).

S2. Experimental

4-hydroxymethyl-3,5-dimethylpyrazole was dissolved in hot methanol with stirring. The colourless single crystals suitable for X-ray diffraction were obtained at room temperature by slow evaporation of the solvent over several days.

S3. Refinement

All H atoms were placed in calculated positions (C—H = 0.96 or 0.97 /%A; O—H = 0.82 /%A; N—H = 0.86 /%A) refined using a riding model, with U_iso(H) = 1.2U_eq(C, N) for aromatic ring and methylene, U_iso(H) = 1.5U_eq(C, O) for methyl and hydroxyl groups.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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, 2004); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of (I), showing the atomic numbering scheme. Displacements ellipsoids are drawn at the 50% probability level. H atoms are depicted as spheres of arbitrary radii.

4-Hydroxymethyl-3,5-dimethyl-1H-pyrazole

Crystal data

C6H10N2O	F(000) = 272
Mr = 126.16	Dx = 1.214 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2400 reflections
a = 8.2608 (12) Å	θ = 1.4–26.0°
b = 8.3865 (12) Å	µ = 0.09 mm^−1
c = 9.9672 (14) Å	T = 298 K
β = 91.311 (2)°	Block, colourless
V = 690.34 (17) Å^3	0.38 × 0.30 × 0.22 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	1284 independent reflections
Radiation source: fine-focus sealed tube	1106 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 25.5°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.955, Tmax = 0.977	k = −10→10
5091 measured reflections	l = −12→12

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0866P)^2 + 0.1946P] where P = (Fo^2 + 2Fc^2)/3
1284 reflections	(Δ/σ)max = 0.001
85 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.27 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
N1	1.01921 (18)	0.08862 (18)	0.73825 (14)	0.0474 (4)
N2	0.86594 (19)	0.03797 (18)	0.71167 (14)	0.0482 (4)
H2	0.8369	−0.0125	0.6400	0.058*
C1	1.0139 (2)	0.16032 (19)	0.85775 (16)	0.0429 (4)
C2	0.8560 (2)	0.15464 (18)	0.90737 (16)	0.0410 (4)
C3	0.7647 (2)	0.0757 (2)	0.81028 (16)	0.0443 (4)
C4	0.7974 (2)	0.2163 (2)	1.03853 (17)	0.0497 (5)
H4A	0.7174	0.1434	1.0733	0.060*
H4B	0.8874	0.2212	1.1026	0.060*
C5	1.1609 (2)	0.2342 (3)	0.9195 (2)	0.0621 (6)
H5A	1.2546	0.2009	0.8716	0.093*
H5B	1.1717	0.2013	1.0115	0.093*
H5C	1.1516	0.3482	0.9153	0.093*
C6	0.5902 (3)	0.0310 (3)	0.8047 (2)	0.0667 (6)
H6A	0.5510	0.0342	0.7133	0.100*
H6B	0.5296	0.1048	0.8575	0.100*
H6C	0.5774	−0.0748	0.8398	0.100*
O1	0.7283 (2)	0.36867 (16)	1.02448 (13)	0.0678 (5)
H1	0.6660	0.3845	1.0860	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0503 (9)	0.0473 (8)	0.0452 (8)	−0.0004 (6)	0.0171 (6)	−0.0007 (6)
N2	0.0558 (9)	0.0515 (9)	0.0377 (8)	−0.0043 (7)	0.0111 (6)	−0.0073 (6)
C1	0.0497 (10)	0.0374 (8)	0.0419 (9)	0.0019 (7)	0.0087 (7)	0.0030 (7)
C2	0.0502 (10)	0.0376 (8)	0.0355 (8)	0.0016 (7)	0.0104 (7)	0.0013 (6)
C3	0.0476 (10)	0.0462 (9)	0.0395 (9)	−0.0011 (7)	0.0110 (7)	0.0007 (7)
C4	0.0655 (12)	0.0472 (10)	0.0369 (9)	0.0071 (8)	0.0131 (8)	0.0008 (7)
C5	0.0555 (12)	0.0620 (12)	0.0688 (13)	−0.0054 (9)	−0.0010 (9)	−0.0006 (10)
C6	0.0517 (12)	0.0837 (15)	0.0652 (13)	−0.0084 (10)	0.0092 (9)	−0.0069 (11)
O1	0.1014 (12)	0.0557 (9)	0.0479 (8)	0.0278 (7)	0.0356 (7)	0.0115 (6)

Geometric parameters (Å, º)

N1—C1	1.336 (2)	C4—H4A	0.9700
N1—N2	1.356 (2)	C4—H4B	0.9700
N2—C3	1.343 (2)	C5—H5A	0.9600
N2—H2	0.8600	C5—H5B	0.9600
C1—C2	1.406 (2)	C5—H5C	0.9600
C1—C5	1.485 (3)	C6—H6A	0.9600
C2—C3	1.382 (2)	C6—H6B	0.9600
C2—C4	1.497 (2)	C6—H6C	0.9600
C3—C6	1.490 (3)	O1—H1	0.8200
C4—O1	1.405 (2)
C1—N1—N2	105.41 (13)	O1—C4—H4B	109.3
C3—N2—N1	112.18 (14)	C2—C4—H4B	109.3
C3—N2—H2	123.9	H4A—C4—H4B	108.0
N1—N2—H2	123.9	C1—C5—H5A	109.5
N1—C1—C2	110.37 (15)	C1—C5—H5B	109.5
N1—C1—C5	120.95 (16)	H5A—C5—H5B	109.5
C2—C1—C5	128.68 (16)	C1—C5—H5C	109.5
C3—C2—C1	105.41 (14)	H5A—C5—H5C	109.5
C3—C2—C4	126.49 (16)	H5B—C5—H5C	109.5
C1—C2—C4	128.08 (16)	C3—C6—H6A	109.5
N2—C3—C2	106.63 (15)	C3—C6—H6B	109.5
N2—C3—C6	122.13 (17)	H6A—C6—H6B	109.5
C2—C3—C6	131.22 (16)	C3—C6—H6C	109.5
O1—C4—C2	111.48 (14)	H6A—C6—H6C	109.5
O1—C4—H4A	109.3	H6B—C6—H6C	109.5
C2—C4—H4A	109.3	C4—O1—H1	109.5
C1—N1—N2—C3	0.1 (2)	N1—N2—C3—C6	−179.26 (17)
N2—N1—C1—C2	0.16 (19)	C1—C2—C3—N2	0.42 (19)
N2—N1—C1—C5	−178.96 (16)	C4—C2—C3—N2	−178.21 (15)
N1—C1—C2—C3	−0.37 (19)	C1—C2—C3—C6	179.2 (2)
C5—C1—C2—C3	178.66 (18)	C4—C2—C3—C6	0.6 (3)
N1—C1—C2—C4	178.24 (15)	C3—C2—C4—O1	−84.9 (2)
C5—C1—C2—C4	−2.7 (3)	C1—C2—C4—O1	96.7 (2)
N1—N2—C3—C2	−0.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.82	1.98	2.7965 (18)	177
N2—H2···O1^ii	0.86	1.98	2.842 (2)	179

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