Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107031952/sf3043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107031952/sf3043Isup2.hkl |
CCDC reference: 659140
For related literature, see: Allen (2002); Bernstein et al. (1995); Brown & Kee (1993); Bruker (2003); Bruno et al. (2004); Elguero (1996); Esquius et al. (2000); Flack (1983); Grell et al. (1999); Guzei et al. (2007); Motherwell et al. (2000).
A mixture of 3,5-dimethylpyrazole (1.0 g, 10.4 mmol), paraformaldehyde (0.5 g, 16 mmol), KOH (0.9 g, 16 mmol) and isopropylamine (1.3 g, 20 mmol) was dissolved in water (50 ml) and refluxed for 48 h. The product was extracted from the aqueous solution using CHCl3 (180 ml) and dried over anhydrous MgSO4. The solution was concentrated in vacuo to ca 50 ml. The concentrated extract was left to stand at room temperature for ca two weeks, upon which slow evaporation of the solvent yielded X-ray quality crystals (yield 1.53 g, 87%). Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 4.80 (br, 1H, NHiPr), 3.53 (br s, 2H, CH2NHiPr), 2.81 [m, 1H, NCH(CH3)2], 2.23 (s, 6H, CH3), 1.06 [d, 3JHH = 5.8 Hz, 6H, NCH(CH3)2]; 13C{1H}NMR (CDCl3, δ, p.p.m.): 144.8 [C(3,5-pz)], 113.2 [C(4-pz], 48.3 [C(CH, iPr)], 39.2 [C(CH2NHiPr)], 20.2 [CH(CH3, iPr)], 11.1 [C(CH3, 3.5-pz)]; IR (Nujol, ν, cm-1): 3272 (N—H), 2962 (C—H), 1571 (C═N).
Compound (I) crystallizes in space group Pna21; the correctness of the chosen molecular arrangement was confirmed by the Flack parameter (Flack, 1983) value of -0.05 (4) refined with the TWIN/BASF card combination in SHELXTL (Bruker, 2003). All H atoms were located in the difference map and refined independently with isotropic displacement parameters.
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL.
C9H18N3+·Cl−·H2O | F(000) = 480 |
Mr = 221.73 | Dx = 1.228 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 5373 reflections |
a = 12.7944 (9) Å | θ = 2.7–26.4° |
b = 9.3494 (7) Å | µ = 0.30 mm−1 |
c = 10.0269 (7) Å | T = 100 K |
V = 1199.42 (15) Å3 | Block, colourless |
Z = 4 | 0.49 × 0.37 × 0.25 mm |
Bruker SMART CCD-1000 area-detector diffractometer | 2446 independent reflections |
Radiation source: fine-focus sealed tube | 2305 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
0.30° ω scans | θmax = 26.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −15→15 |
Tmin = 0.869, Tmax = 0.930 | k = −11→11 |
9296 measured reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.023 | All H-atom parameters refined |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0356P)2 + 0.1541P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2446 reflections | Δρmax = 0.26 e Å−3 |
208 parameters | Δρmin = −0.13 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (4) |
C9H18N3+·Cl−·H2O | V = 1199.42 (15) Å3 |
Mr = 221.73 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 12.7944 (9) Å | µ = 0.30 mm−1 |
b = 9.3494 (7) Å | T = 100 K |
c = 10.0269 (7) Å | 0.49 × 0.37 × 0.25 mm |
Bruker SMART CCD-1000 area-detector diffractometer | 2446 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2305 reflections with I > 2σ(I) |
Tmin = 0.869, Tmax = 0.930 | Rint = 0.023 |
9296 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | All H-atom parameters refined |
wR(F2) = 0.059 | Δρmax = 0.26 e Å−3 |
S = 1.04 | Δρmin = −0.13 e Å−3 |
2446 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
208 parameters | Absolute structure parameter: −0.05 (4) |
1 restraint |
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 | ||
Cl1 | 0.32941 (2) | 0.40622 (3) | 0.04588 (3) | 0.01824 (10) | |
O1 | 0.18064 (9) | 0.55564 (14) | 0.83667 (13) | 0.0267 (3) | |
H1W | 0.2067 (15) | 0.533 (2) | 0.765 (2) | 0.028 (5)* | |
H2W | 0.2218 (18) | 0.527 (2) | 0.890 (3) | 0.044 (6)* | |
N1 | 0.28910 (10) | 0.60977 (14) | 0.49639 (13) | 0.0182 (3) | |
H1 | 0.2529 (14) | 0.6870 (19) | 0.5031 (16) | 0.016 (4)* | |
N2 | 0.26978 (10) | 0.50390 (13) | 0.58606 (12) | 0.0191 (3) | |
N3 | 0.46303 (9) | 0.26535 (13) | 0.28239 (12) | 0.0146 (2) | |
H3A | 0.4179 (13) | 0.2033 (18) | 0.3114 (19) | 0.017 (4)* | |
H3B | 0.4280 (15) | 0.317 (2) | 0.218 (2) | 0.027 (5)* | |
C1 | 0.40797 (14) | 0.67902 (17) | 0.31000 (16) | 0.0245 (3) | |
H1A | 0.3719 (16) | 0.774 (2) | 0.317 (2) | 0.041 (5)* | |
H1B | 0.3904 (15) | 0.6443 (19) | 0.223 (2) | 0.028 (5)* | |
H1C | 0.4844 (16) | 0.687 (2) | 0.315 (2) | 0.029 (5)* | |
C2 | 0.36886 (11) | 0.57901 (15) | 0.41389 (15) | 0.0178 (3) | |
C3 | 0.40342 (11) | 0.44410 (15) | 0.44989 (15) | 0.0181 (3) | |
C4 | 0.33915 (10) | 0.40197 (14) | 0.55701 (19) | 0.0178 (3) | |
C5 | 0.34046 (14) | 0.26431 (17) | 0.63350 (18) | 0.0236 (3) | |
H5A | 0.3282 (14) | 0.281 (2) | 0.725 (2) | 0.029 (5)* | |
H5B | 0.2889 (15) | 0.200 (2) | 0.597 (2) | 0.031 (5)* | |
H5C | 0.4069 (14) | 0.2199 (19) | 0.6295 (18) | 0.022 (4)* | |
C6 | 0.49447 (12) | 0.36645 (17) | 0.39168 (16) | 0.0201 (3) | |
H6A | 0.5437 (14) | 0.434 (2) | 0.3539 (19) | 0.025 (5)* | |
H6B | 0.5318 (13) | 0.3099 (18) | 0.4550 (18) | 0.018 (4)* | |
C7 | 0.55434 (11) | 0.19055 (16) | 0.21634 (14) | 0.0174 (3) | |
H7 | 0.6009 (14) | 0.2645 (19) | 0.186 (2) | 0.027 (5)* | |
C8 | 0.51322 (13) | 0.10621 (16) | 0.09817 (17) | 0.0211 (3) | |
H8A | 0.4770 (14) | 0.1669 (19) | 0.040 (2) | 0.027 (4)* | |
H8B | 0.5722 (13) | 0.0670 (18) | 0.054 (2) | 0.022 (4)* | |
H8C | 0.4665 (15) | 0.032 (2) | 0.131 (2) | 0.034 (5)* | |
C9 | 0.61188 (14) | 0.09658 (19) | 0.31428 (18) | 0.0275 (4) | |
H9A | 0.6458 (16) | 0.154 (2) | 0.388 (2) | 0.032 (5)* | |
H9B | 0.5659 (17) | 0.022 (2) | 0.345 (2) | 0.044 (6)* | |
H9C | 0.6661 (14) | 0.051 (2) | 0.275 (2) | 0.028 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02094 (16) | 0.01524 (15) | 0.01854 (16) | −0.00169 (12) | −0.00411 (17) | 0.00253 (14) |
O1 | 0.0315 (7) | 0.0326 (6) | 0.0161 (6) | 0.0149 (5) | 0.0021 (5) | 0.0018 (5) |
N1 | 0.0203 (6) | 0.0164 (6) | 0.0177 (6) | 0.0035 (5) | −0.0019 (5) | −0.0035 (5) |
N2 | 0.0204 (6) | 0.0195 (6) | 0.0174 (6) | 0.0010 (5) | −0.0012 (4) | −0.0025 (5) |
N3 | 0.0149 (6) | 0.0134 (5) | 0.0153 (6) | −0.0006 (5) | 0.0007 (5) | −0.0007 (5) |
C1 | 0.0308 (9) | 0.0205 (7) | 0.0222 (8) | −0.0046 (6) | 0.0005 (7) | −0.0019 (7) |
C2 | 0.0172 (7) | 0.0197 (7) | 0.0166 (7) | −0.0010 (6) | −0.0027 (6) | −0.0054 (6) |
C3 | 0.0176 (7) | 0.0180 (7) | 0.0187 (7) | −0.0019 (6) | −0.0029 (6) | −0.0055 (6) |
C4 | 0.0184 (6) | 0.0175 (6) | 0.0174 (7) | 0.0000 (5) | −0.0037 (6) | −0.0047 (6) |
C5 | 0.0276 (9) | 0.0205 (8) | 0.0225 (8) | 0.0026 (7) | −0.0030 (7) | −0.0006 (6) |
C6 | 0.0172 (7) | 0.0211 (8) | 0.0221 (8) | −0.0002 (6) | −0.0022 (6) | −0.0078 (6) |
C7 | 0.0166 (7) | 0.0180 (7) | 0.0174 (7) | 0.0006 (6) | 0.0047 (5) | −0.0016 (6) |
C8 | 0.0244 (8) | 0.0212 (8) | 0.0178 (7) | 0.0064 (7) | 0.0010 (6) | −0.0025 (6) |
C9 | 0.0272 (8) | 0.0337 (9) | 0.0217 (8) | 0.0138 (7) | −0.0002 (7) | −0.0019 (7) |
O1—H1W | 0.82 (2) | C3—C6 | 1.492 (2) |
O1—H2W | 0.80 (3) | C4—C5 | 1.498 (2) |
N1—C2 | 1.345 (2) | C5—H5A | 0.94 (2) |
N1—N2 | 1.3599 (18) | C5—H5B | 0.97 (2) |
N1—H1 | 0.860 (18) | C5—H5C | 0.948 (17) |
N2—C4 | 1.3346 (19) | C6—H6A | 0.972 (19) |
N3—C6 | 1.5020 (18) | C6—H6B | 0.954 (18) |
N3—C7 | 1.5141 (17) | C7—C9 | 1.509 (2) |
N3—H3A | 0.868 (18) | C7—C8 | 1.517 (2) |
N3—H3B | 0.92 (2) | C7—H7 | 0.961 (19) |
C1—C2 | 1.487 (2) | C8—H8A | 0.94 (2) |
C1—H1A | 1.00 (2) | C8—H8B | 0.946 (19) |
C1—H1B | 0.96 (2) | C8—H8C | 0.97 (2) |
C1—H1C | 0.98 (2) | C9—H9A | 1.01 (2) |
C2—C3 | 1.384 (2) | C9—H9B | 0.96 (2) |
C3—C4 | 1.409 (2) | C9—H9C | 0.90 (2) |
H1W—O1—H2W | 103 (2) | H5A—C5—H5B | 111.0 (17) |
C2—N1—N2 | 112.89 (13) | C4—C5—H5C | 111.4 (11) |
C2—N1—H1 | 129.5 (11) | H5A—C5—H5C | 105.3 (16) |
N2—N1—H1 | 117.5 (11) | H5B—C5—H5C | 108.7 (15) |
C4—N2—N1 | 104.75 (12) | C3—C6—N3 | 112.50 (12) |
C6—N3—C7 | 113.77 (11) | C3—C6—H6A | 109.9 (11) |
C6—N3—H3A | 110.7 (12) | N3—C6—H6A | 107.5 (11) |
C7—N3—H3A | 110.6 (11) | C3—C6—H6B | 113.6 (10) |
C6—N3—H3B | 108.3 (11) | N3—C6—H6B | 105.7 (10) |
C7—N3—H3B | 108.1 (12) | H6A—C6—H6B | 107.3 (15) |
H3A—N3—H3B | 104.9 (16) | C9—C7—N3 | 111.14 (12) |
C2—C1—H1A | 110.4 (13) | C9—C7—C8 | 112.00 (13) |
C2—C1—H1B | 110.2 (11) | N3—C7—C8 | 108.30 (12) |
H1A—C1—H1B | 105.1 (18) | C9—C7—H7 | 108.7 (11) |
C2—C1—H1C | 110.1 (11) | N3—C7—H7 | 106.5 (10) |
H1A—C1—H1C | 112.9 (16) | C8—C7—H7 | 110.1 (12) |
H1B—C1—H1C | 108.0 (16) | C7—C8—H8A | 110.0 (11) |
N1—C2—C3 | 106.07 (13) | C7—C8—H8B | 106.7 (11) |
N1—C2—C1 | 123.50 (13) | H8A—C8—H8B | 110.0 (16) |
C3—C2—C1 | 130.41 (14) | C7—C8—H8C | 108.9 (12) |
C2—C3—C4 | 105.49 (12) | H8A—C8—H8C | 109.7 (15) |
C2—C3—C6 | 126.21 (14) | H8B—C8—H8C | 111.5 (15) |
C4—C3—C6 | 128.18 (14) | C7—C9—H9A | 112.0 (12) |
N2—C4—C3 | 110.79 (13) | C7—C9—H9B | 109.2 (13) |
N2—C4—C5 | 120.60 (15) | H9A—C9—H9B | 114.6 (18) |
C3—C4—C5 | 128.60 (13) | C7—C9—H9C | 111.5 (12) |
C4—C5—H5A | 110.7 (12) | H9A—C9—H9C | 103.9 (17) |
C4—C5—H5B | 109.6 (11) | H9B—C9—H9C | 105.4 (18) |
C2—N1—N2—C4 | −1.01 (16) | C2—C3—C4—N2 | −0.29 (17) |
N2—N1—C2—C3 | 0.84 (16) | C6—C3—C4—N2 | 175.92 (14) |
N2—N1—C2—C1 | −177.81 (13) | C2—C3—C4—C5 | 178.86 (15) |
N1—C2—C3—C4 | −0.32 (15) | C6—C3—C4—C5 | −4.9 (3) |
C1—C2—C3—C4 | 178.20 (15) | C2—C3—C6—N3 | −95.51 (17) |
N1—C2—C3—C6 | −176.63 (14) | C4—C3—C6—N3 | 89.01 (19) |
C1—C2—C3—C6 | 1.9 (2) | C7—N3—C6—C3 | 176.99 (13) |
N1—N2—C4—C3 | 0.77 (16) | C6—N3—C7—C9 | 63.24 (17) |
N1—N2—C4—C5 | −178.46 (14) | C6—N3—C7—C8 | −173.33 (13) |
Experimental details
Crystal data | |
Chemical formula | C9H18N3+·Cl−·H2O |
Mr | 221.73 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 100 |
a, b, c (Å) | 12.7944 (9), 9.3494 (7), 10.0269 (7) |
V (Å3) | 1199.42 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.49 × 0.37 × 0.25 |
Data collection | |
Diffractometer | Bruker SMART CCD-1000 area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.869, 0.930 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9296, 2446, 2305 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.059, 1.04 |
No. of reflections | 2446 |
No. of parameters | 208 |
No. of restraints | 1 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.13 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | −0.05 (4) |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Bruker, 2003), SHELXTL and Mercury (Macrae et al., 2006).
bond | D—H | H···A | D—H···A | D—H···A | |
a | N1—H1···Cl1i | 0.860 (18) | 2.344 (18) | 3.1980 (14) | 171.9 (15) |
b | N3—H3A···O1ii | 0.868 (18) | 1.887 (18) | 2.7421 (17) | 167.9 (18) |
c | N3—H3B···Cl1 | 0.92 (2) | 2.30 (2) | 3.2064 (13) | 170.0 (16) |
d | O1—H1W···N2 | 0.82 (2) | 1.99 (2) | 2.8016 (17) | 173 (2) |
e | O1—H2W···Cl1iii | 0.80 (3) | 2.37 (3) | 3.1583 (13) | 170 (2) |
Symmetry codes: (i) -x+1/2, y+1/2, z+1/2; (ii) -x+1/2, y-1/2, z-1/2; (iii) x, y, z+1. |
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Substituted pyrazoles constitute an important family of heterocyclic compounds that have found use in drug development and catalysis (Elguero, 1996; Brown & Kee, 1993). An important attribute of potential drug chemicals is their solubility in water, which is frequently achieved by derivatization. During our studies towards water-soluble palladium and platinum complexes with potential anticancer properties, we set out to prepare 4-alkylaminopyrazoles through the direct reaction of 3,5-dimethylpyrazole with formaldehyde and alkylamines according to Esquius et al. (2000). However, in the reaction with isopropylamine, a two-week long recrystallization of CHCl3 extracts of the final product yielded the title compound, (I), in 87% yield, and we now report the solid-state structure of this water-soluble ammonium salt.
A molecular drawing of (I) is shown in Fig. 1. The bond distances and angles within the cation are typical, as confirmed by the Mogul structural check (Bruno et al., 2004). There are five strong hydrogen-bonding interactions, denoted a–e (Table 1), of four types (N—H···Cl, N—H···O, O—H···N and O—H···Cl). These hydrogen bonds link the ions and water molecules into two-dimensional corrugated sheets (Fig. 2) stacked along the a axis, with weak intermolecular contacts between them (Fig. 3), which will be discussed below. These hydrogen bonds feature relatively short D···A distances and D—H···A angles spanning 167.9 (18)–173 (2)°, and are comparable in length to other similar hydrogen bonds in the Cambridge Structural Database (CSD; Version 5.28, January 2007 release; Allen, 2002) (Table 1).
The hydrogen-bonding interaction network in (I) generated by the n-glide plane normal to the a axis can be readily visualized with the help of the constructor graph (Grell et al., 1999; Motherwell et al., 2000). We recently used this approach for analysis of intermolecular interactions in N,N'-bis(2-hydroxy-1-methylethyl)phthalamide (Guzei et al., 2007).
A constructor graph projection of the hydrogen-bonding interactions in (I) onto the bc plane is shown in Fig. 4. The two main ring patterns are immediately identifiable, namely a ring formed by four hydrogen bonds a→c←b→d → R43(9), giving a quaternary system N4, and a ring formed by six hydrogen bonds a→e←d→b →e→c← R64(20), giving a pentary system N5 (Bernstein et al., 1995). Arrows denote the direction of the hydrogen bond; → designates a donor-to-acceptor D—H···A interaction, while ← represents an acceptor-to-donor A···H—D orientation.
The quaternary ring system links the molecules in a head-to-tail fashion, forming rows of molecules in the [011] direction. The pentary ring system (hydrogen bonds e) then links these rows of molecules together to form sheets in the bc plane. Several chain motifs propagate in four directions, namely a tertiary C32(10) motif a→e←b← along [010], a tertiary C32(10) motif d← e→ c← along [001], a binary C21(8) motif a→c←, a binary C22(8) motif b←d← and their quaternary combination a→c←d←b← with the additive representation C43(16) along [011], and a tertiary C32(7) motif a←d←e→, a tertiary C32(6) motif b→e→c← and their pentary combination C64(13) a← d← e→ c← b→ e→ along [011]. Note that in all interactions involving the chloride, the number of acceptors is fewer than the number of donors, since each acidic H atom serves as a donor in exactly one hydrogen-bonding interaction, whereas each chloride serves as the acceptor in three different interactions, a, c, and e.
There are three types of possible weaker intermolecular contacts between the hydrogen-bonded sheets, C8—H8A···Cl1 [H···A distance = 2.928 (19) Å and D—H···A angle = 140.4 (16)°], C6—H6A···Cl1(1 - x, 1 - y, z + 1/2) [2.925 (19) Å and 115.9 (13)°] and a non-classical C7—H7···N1(1 - x, 1 - y, z - 1/2) contact [2.64 (2) Å and 151.2 (15)°], which connect the sheets into a three-dimensional framework.
The current work is another illustration of the convenience of the hydrogen-bonding interaction analysis in two-dimensional networks using the constructor graph methodology.