1-(Hydro­xy­methyl)-3,5-di­methyl­pyrazole

Radosavljević Evans, I.; Mészáros Szécsényi, K.; Leovac, V.M.

doi:10.1107/S1600536805003971

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o625-o626

https://doi.org/10.1107/S1600536805003971

1-(Hydroxymethyl)-3,5-dimethylpyrazole

Ivana Radosavljević Evans,^a ^* Katalin Mészáros Szécsényi ^b and Vukadin M. Leovac ^b

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and ^bFaculty of Sciences, University of Novi Sad, Trg Dositeja Obradovica 3, 21000 Novi Sad, Serbia and Montenegro
^*Correspondence e-mail: ivana.radosavljevic@durham.ac.uk

(Received 31 January 2005; accepted 4 February 2005; online 12 February 2005)

The structure of the title compound, C₆H₁₀N₂O, has been determined from single crystals obtained by recrystallization from acetone. Intermolecular O—H⋯N hydrogen bonding gives rise to R₂²(10) dimers.

Comment

1-(Hydroxymethyl)-3,5-dimethylpyrazole (HL), (I), was first synthesized by a reaction of 3,5-dimethylpyrazole with paraformaldehyde (Driessen, 1982 ). HL can act as a chelating ligand, as shown by the examples of four isomorphous cubane-type cluster coordination compounds of the formula [MXL(EtOH)₄] (M = Co^II, Ni^II, X = Cl, Br; Paap et al., 1985 ), where the deprotonated species acts as a bidentate ligand, coordinating the metals through its pyridine N atom and the methoxy O atom. With a metal with different coordination preferences, such as Pd, HL acts as a monodentate ligand through the pyrazole N atom, forming a square-planar complex (Boixassa et al., 2002 ).

The molecular structure of (I) is shown in Fig. 1. The substituted pyrazole ring is essentially planar, the largest displacement being 0.01 Å for C4. The O1—C1—N1—N2 torsion angle is 90.19 (9)°. The structure is stabilized by intermolecular O—H⋯N hydrogen bonding between adjacent molecules [H⋯N = 1.89 (2) Å, O⋯N = 2.760 (1) Å and O—H⋯N = 171.0 (2)°]. These interactions give rise to dimers with an R₂²(10) hydrogen-bonding motif (Etter et al., 1990 ) (Fig. 2).

Figure 1
The molecular structure of (I

) and the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The hydrogen bonding (dashed lines) in (I

Figure 3
Two views of the packing scheme in (I

Experimental

Needle-shaped clear single crystals of (I) were obtained by recrystallization of the commercial product (Aldrich) from acetone.

Crystal data

C₆H₁₀N₂O
M_r = 126.16
Monoclinic, P2₁/n
a = 7.2877 (2) Å
b = 11.9265 (3) Å
c = 8.1586 (2) Å
β = 107.396 (1)°
V = 676.68 (3) Å³
Z = 4
D_x = 1.238 Mg m⁻³
Mo Kα radiation
Cell parameters from 6570 reflections
θ = 3.1–34.3°
μ = 0.09 mm⁻¹
T = 120 K
Needle, white
0.80 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.92, T_max = 0.98
13356 measured reflections
2742 independent reflections
2113 reflections with I > 2σ(I)
R_int = 0.019
θ_max = 34.5°
h = −11 → 11
k = −18 → 19
l = −12 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.00
2113 reflections
122 parameters
All H-atom parameters refined
w = [1 − (F_o − F_c)/6σ(F_o)²]²/[3.44T₀(x) + 4.59T₁(x) + 1.31T₂(x)] where T are the Chebychev polynomial terms and x = F_c/F_max (Watkin, 1994 ; Prince, 1982 )
(Δ/σ)_max < 0.001
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—C1	1.4007 (10)
N1—C1	1.4530 (11)
N1—C2	1.3568 (11)
N2—N1	1.3627 (10)
N2—C4	1.3362 (10)
C2—C5	1.4918 (13)
C3—C2	1.3814 (13)
C3—C4	1.4073 (12)
C6—C4	1.4934 (12)

N1—N2—C4	105.40 (7)
N2—N1—C1	119.71 (7)
N2—N1—C2	111.90 (7)
C1—N1—C2	128.31 (7)
N1—C1—O1	112.93 (7)
C2—C3—C4	105.78 (7)
C3—C2—N1	106.36 (7)
C3—C2—C5	131.14 (8)
N1—C2—C5	122.49 (8)
C6—C4—C3	128.72 (8)
C6—C4—N2	120.72 (8)
C3—C4—N2	110.55 (7)

H atoms were found in a difference Fourier map and refined using an isotropic approximation. Refined C—H bond lengths are in the range 0.95 (2)–1.04 (2) Å and the O—H bond length is 0.88 (2) Å.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ATOMS (Dowty, 2000 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805003971/wk6045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805003971/wk6045Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS.

1-(hydroxymethyl)-3,5-dimethylpyrazole top

Crystal data top

C₆H₁₀N₂O	F(000) = 272
M_r = 126.16	D_x = 1.238 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6570 reflections
a = 7.2877 (2) Å	θ = 3.1–34.3°
b = 11.9265 (3) Å	µ = 0.09 mm⁻¹
c = 8.1586 (2) Å	T = 120 K
β = 107.396 (1)°	Prism, white
V = 676.68 (3) Å³	0.80 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2113 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 34.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.92, T_max = 0.98	k = −18→19
13356 measured reflections	l = −12→12
2742 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	All H-atom parameters refined
wR(F²) = 0.100	Chebychev polynomial, (Watkin, 1994; Prince, 1982): w = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)], where A_i are the Chebychev coefficients listed below and x = F_c/F_max; method = Robust Weighting (Prince, 1982); W = w[1-(δF/6σF)²]²; A_i are 3.44 4.59 1.31
S = 1.00	(Δ/σ)_max < 0.001
2113 reflections	Δρ_max = 0.40 e Å⁻³
122 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	−0.02535 (9)	−0.04616 (6)	0.23811 (8)	0.0220
N1	0.26298 (10)	0.04284 (6)	0.40283 (9)	0.0190
N2	0.25525 (10)	0.08755 (6)	0.55433 (9)	0.0189
C1	0.16421 (12)	−0.06190 (7)	0.34201 (12)	0.0226
C2	0.36052 (11)	0.10985 (8)	0.32329 (10)	0.0211
C3	0.42099 (11)	0.20151 (7)	0.42920 (12)	0.0218
C4	0.35202 (11)	0.18413 (7)	0.57094 (11)	0.0194
C5	0.38717 (15)	0.08069 (11)	0.15405 (13)	0.0317
C6	0.37831 (13)	0.25601 (8)	0.72617 (13)	0.0280
H1	−0.101 (2)	−0.0516 (14)	0.304 (2)	0.040 (4)*
H2	0.237 (2)	−0.0995 (12)	0.2760 (19)	0.028 (3)*
H3	0.166 (2)	−0.1056 (13)	0.446 (2)	0.033 (4)*
H4	0.362 (3)	0.3355 (17)	0.692 (2)	0.053 (5)*
H5	0.508 (3)	0.2465 (15)	0.808 (3)	0.055 (5)*
H6	0.277 (3)	0.2393 (16)	0.783 (2)	0.051 (5)*
H7	0.265 (3)	0.0639 (15)	0.071 (2)	0.047 (5)*
H8	0.496 (2)	0.2622 (12)	0.408 (2)	0.031 (3)*
H9	0.480 (3)	0.0133 (16)	0.167 (2)	0.048 (4)*
H10	0.455 (3)	0.1415 (17)	0.119 (3)	0.059 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0180 (2)	0.0279 (3)	0.0187 (3)	−0.0024 (2)	0.0034 (2)	−0.0020 (2)
N1	0.0176 (3)	0.0203 (3)	0.0181 (3)	−0.0014 (2)	0.0041 (2)	−0.0009 (2)
N2	0.0180 (3)	0.0193 (3)	0.0190 (3)	−0.0019 (2)	0.0049 (2)	−0.0013 (2)
C1	0.0191 (3)	0.0201 (3)	0.0260 (4)	0.0000 (2)	0.0028 (3)	−0.0044 (3)
C2	0.0164 (3)	0.0278 (4)	0.0183 (3)	0.0008 (3)	0.0038 (2)	0.0043 (3)
C3	0.0174 (3)	0.0225 (3)	0.0242 (3)	−0.0022 (2)	0.0042 (3)	0.0053 (3)
C4	0.0158 (3)	0.0188 (3)	0.0222 (3)	−0.0013 (2)	0.0033 (2)	−0.0003 (3)
C5	0.0273 (4)	0.0490 (6)	0.0191 (4)	0.0018 (4)	0.0075 (3)	0.0018 (4)
C6	0.0247 (4)	0.0270 (4)	0.0313 (4)	−0.0050 (3)	0.0068 (3)	−0.0095 (3)

Geometric parameters (Å, º) top

O1—C1	1.4007 (10)	C6—H6	1.000 (18)
N1—C1	1.4530 (11)	C6—H4	0.98 (2)
N1—C2	1.3568 (11)	O1—H1	0.878 (17)
N2—N1	1.3627 (10)	C1—H2	0.972 (14)
N2—C4	1.3362 (10)	C1—H3	0.995 (16)
C2—C5	1.4918 (13)	C3—H8	0.952 (15)
C3—C2	1.3814 (13)	C5—H7	0.963 (18)
C3—C4	1.4073 (12)	C5—H10	0.97 (2)
C6—C4	1.4934 (12)	C5—H9	1.038 (19)
C6—H5	0.988 (19)

C4—C6—H5	111.2 (11)	H2—C1—H3	111.2 (12)
C4—C6—H6	110.7 (11)	C2—C3—C4	105.78 (7)
H5—C6—H6	110.5 (15)	C2—C3—H8	125.3 (9)
C4—C6—H4	109.8 (11)	C4—C3—H8	128.9 (9)
H5—C6—H4	108.1 (14)	C3—C2—N1	106.36 (7)
H6—C6—H4	106.2 (15)	C3—C2—C5	131.14 (8)
C1—O1—H1	107.9 (11)	N1—C2—C5	122.49 (8)
N1—N2—C4	105.40 (7)	C6—C4—C3	128.72 (8)
N2—N1—C1	119.71 (7)	C6—C4—N2	120.72 (8)
N2—N1—C2	111.90 (7)	C3—C4—N2	110.55 (7)
C1—N1—C2	128.31 (7)	C2—C5—H7	110.6 (11)
N1—C1—O1	112.93 (7)	C2—C5—H10	108.5 (12)
N1—C1—H2	106.8 (9)	H7—C5—H10	113.3 (16)
O1—C1—H2	109.3 (9)	C2—C5—H9	110.3 (11)
N1—C1—H3	106.2 (9)	H7—C5—H9	110.4 (15)
O1—C1—H3	110.4 (8)	H10—C5—H9	103.5 (14)

Acknowledgements

This work was financed in part by the Ministry of Science and Environmental Protection of the Republic of Serbia (project No. 1318 – Physicochemical, structural and biological investigation of complex compounds). IRE thanks the EPSRC for an Academic Fellowship.

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