Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021836/dn2170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021836/dn2170Isup2.hkl |
CCDC reference: 651426
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C)= 0.002 Å
- R factor = 0.048
- wR factor = 0.148
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
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.
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 Uiso(H) = 1.2Ueq(C, N) for aromatic ring and methylene, Uiso(H) = 1.5Ueq(C, O) for methyl and hydroxyl groups.
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.
For related literature, see: Kozlevcar et al. (2006); Moncol et al. (2006).
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.
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. |
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) Å3 | 0.38 × 0.30 × 0.22 mm |
Z = 4 |
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 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0866P)2 + 0.1946P] where P = (Fo2 + 2Fc2)/3 |
1284 reflections | (Δ/σ)max = 0.001 |
85 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C6H10N2O | V = 690.34 (17) Å3 |
Mr = 126.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2608 (12) Å | µ = 0.09 mm−1 |
b = 8.3865 (12) Å | T = 298 K |
c = 9.9672 (14) Å | 0.38 × 0.30 × 0.22 mm |
β = 91.311 (2)° |
Bruker APEXII area-detector diffractometer | 1284 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1106 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.977 | Rint = 0.016 |
5091 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.30 e Å−3 |
1284 reflections | Δρmin = −0.27 e Å−3 |
85 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 1.98 | 2.7965 (18) | 177 |
N2—H2···O1ii | 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. |
Experimental details
Crystal data | |
Chemical formula | C6H10N2O |
Mr | 126.16 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.2608 (12), 8.3865 (12), 9.9672 (14) |
β (°) | 91.311 (2) |
V (Å3) | 690.34 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.38 × 0.30 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.955, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5091, 1284, 1106 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.148, 1.06 |
No. of reflections | 1284 |
No. of parameters | 85 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.27 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 1.98 | 2.7965 (18) | 176.9 |
N2—H2···O1ii | 0.86 | 1.98 | 2.842 (2) | 179.2 |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+3/2, y−1/2, −z+3/2. |
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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.