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Five distinct strong hydrogen-bonding inter­actions of four kinds (N-H...Cl, N-H...O, O-H...N, and O-H...Cl) connect mol­ecules of the title compound, C9H18N3+·Cl-·H2O, in the crystal structure into corrugated sheets stacked along the a axis. The inter­molecular inter­actions are efficiently described in terms of the first- through fifth-level graph sets. A two-dimensional constructor graph helps visualize the supra­molecular assembly.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107031952/sf3043sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107031952/sf3043Isup2.hkl
Contains datablock I

CCDC reference: 659140

Comment top

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 ae (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 acbd R43(9), giving a quaternary system N4, and a ring formed by six hydrogen bonds aedb ec 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 aeb along [010], a tertiary C32(10) motif d e c along [001], a binary C21(8) motif ac, a binary C22(8) motif bd and their quaternary combination acdb with the additive representation C43(16) along [011], and a tertiary C32(7) motif ade, a tertiary C32(6) motif bec 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.

Related literature top

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).

Experimental top

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 (CN).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A molecular drawing of (I), shown with 50% probability displacement ellipsoids. All H atoms bonded to C atoms have been omitted for clarity. Hydrogen bonds are shown as dashed lines. [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].
[Figure 2] Fig. 2. A packing diagram for (I), shown along the a axis (Mercury; Macrae et al., 2006). All H atoms bonded to C atoms have been omitted for clarity. [Symmetry codes: (i) ?; (ii) ? Please complete]
[Figure 3] Fig. 3. A packing diagram for (I), shown along the b axis (Mercury; Macrae et al. 2006). All H atoms bonded to C atoms have been omitted for clarity.
[Figure 4] Fig. 4. Constructor graph of compound (I), viewed along the a axis. The arrows denote the five types of hydrogen bonds, labeled according to Table 1. Arrows originate at the donor molecules and point to acceptor molecules. Squares represent cations, triangles Cl- anions and circles water molecules. Solid symbols are translated mirror images of the open symbols.
(3,5-dimethyl-1H-pyrazol-4-ylmethyl)isopropylammonium chloride monohydrate top
Crystal data top
C9H18N3+·Cl·H2OF(000) = 480
Mr = 221.73Dx = 1.228 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 5373 reflections
a = 12.7944 (9) Åθ = 2.7–26.4°
b = 9.3494 (7) ŵ = 0.30 mm1
c = 10.0269 (7) ÅT = 100 K
V = 1199.42 (15) Å3Block, colourless
Z = 40.49 × 0.37 × 0.25 mm
Data collection top
Bruker SMART CCD-1000 area-detector
diffractometer
2446 independent reflections
Radiation source: fine-focus sealed tube2305 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
0.30° ω scansθmax = 26.4°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1515
Tmin = 0.869, Tmax = 0.930k = 1111
9296 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023All 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 reflectionsΔρmax = 0.26 e Å3
208 parametersΔρmin = 0.13 e Å3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.05 (4)
Crystal data top
C9H18N3+·Cl·H2OV = 1199.42 (15) Å3
Mr = 221.73Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 12.7944 (9) ŵ = 0.30 mm1
b = 9.3494 (7) ÅT = 100 K
c = 10.0269 (7) Å0.49 × 0.37 × 0.25 mm
Data collection top
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 = 0.930Rint = 0.023
9296 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023All H-atom parameters refined
wR(F2) = 0.059Δρmax = 0.26 e Å3
S = 1.04Δρmin = 0.13 e Å3
2446 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs?
208 parametersAbsolute structure parameter: 0.05 (4)
1 restraint
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
xyzUiso*/Ueq
Cl10.32941 (2)0.40622 (3)0.04588 (3)0.01824 (10)
O10.18064 (9)0.55564 (14)0.83667 (13)0.0267 (3)
H1W0.2067 (15)0.533 (2)0.765 (2)0.028 (5)*
H2W0.2218 (18)0.527 (2)0.890 (3)0.044 (6)*
N10.28910 (10)0.60977 (14)0.49639 (13)0.0182 (3)
H10.2529 (14)0.6870 (19)0.5031 (16)0.016 (4)*
N20.26978 (10)0.50390 (13)0.58606 (12)0.0191 (3)
N30.46303 (9)0.26535 (13)0.28239 (12)0.0146 (2)
H3A0.4179 (13)0.2033 (18)0.3114 (19)0.017 (4)*
H3B0.4280 (15)0.317 (2)0.218 (2)0.027 (5)*
C10.40797 (14)0.67902 (17)0.31000 (16)0.0245 (3)
H1A0.3719 (16)0.774 (2)0.317 (2)0.041 (5)*
H1B0.3904 (15)0.6443 (19)0.223 (2)0.028 (5)*
H1C0.4844 (16)0.687 (2)0.315 (2)0.029 (5)*
C20.36886 (11)0.57901 (15)0.41389 (15)0.0178 (3)
C30.40342 (11)0.44410 (15)0.44989 (15)0.0181 (3)
C40.33915 (10)0.40197 (14)0.55701 (19)0.0178 (3)
C50.34046 (14)0.26431 (17)0.63350 (18)0.0236 (3)
H5A0.3282 (14)0.281 (2)0.725 (2)0.029 (5)*
H5B0.2889 (15)0.200 (2)0.597 (2)0.031 (5)*
H5C0.4069 (14)0.2199 (19)0.6295 (18)0.022 (4)*
C60.49447 (12)0.36645 (17)0.39168 (16)0.0201 (3)
H6A0.5437 (14)0.434 (2)0.3539 (19)0.025 (5)*
H6B0.5318 (13)0.3099 (18)0.4550 (18)0.018 (4)*
C70.55434 (11)0.19055 (16)0.21634 (14)0.0174 (3)
H70.6009 (14)0.2645 (19)0.186 (2)0.027 (5)*
C80.51322 (13)0.10621 (16)0.09817 (17)0.0211 (3)
H8A0.4770 (14)0.1669 (19)0.040 (2)0.027 (4)*
H8B0.5722 (13)0.0670 (18)0.054 (2)0.022 (4)*
H8C0.4665 (15)0.032 (2)0.131 (2)0.034 (5)*
C90.61188 (14)0.09658 (19)0.31428 (18)0.0275 (4)
H9A0.6458 (16)0.154 (2)0.388 (2)0.032 (5)*
H9B0.5659 (17)0.022 (2)0.345 (2)0.044 (6)*
H9C0.6661 (14)0.051 (2)0.275 (2)0.028 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02094 (16)0.01524 (15)0.01854 (16)0.00169 (12)0.00411 (17)0.00253 (14)
O10.0315 (7)0.0326 (6)0.0161 (6)0.0149 (5)0.0021 (5)0.0018 (5)
N10.0203 (6)0.0164 (6)0.0177 (6)0.0035 (5)0.0019 (5)0.0035 (5)
N20.0204 (6)0.0195 (6)0.0174 (6)0.0010 (5)0.0012 (4)0.0025 (5)
N30.0149 (6)0.0134 (5)0.0153 (6)0.0006 (5)0.0007 (5)0.0007 (5)
C10.0308 (9)0.0205 (7)0.0222 (8)0.0046 (6)0.0005 (7)0.0019 (7)
C20.0172 (7)0.0197 (7)0.0166 (7)0.0010 (6)0.0027 (6)0.0054 (6)
C30.0176 (7)0.0180 (7)0.0187 (7)0.0019 (6)0.0029 (6)0.0055 (6)
C40.0184 (6)0.0175 (6)0.0174 (7)0.0000 (5)0.0037 (6)0.0047 (6)
C50.0276 (9)0.0205 (8)0.0225 (8)0.0026 (7)0.0030 (7)0.0006 (6)
C60.0172 (7)0.0211 (8)0.0221 (8)0.0002 (6)0.0022 (6)0.0078 (6)
C70.0166 (7)0.0180 (7)0.0174 (7)0.0006 (6)0.0047 (5)0.0016 (6)
C80.0244 (8)0.0212 (8)0.0178 (7)0.0064 (7)0.0010 (6)0.0025 (6)
C90.0272 (8)0.0337 (9)0.0217 (8)0.0138 (7)0.0002 (7)0.0019 (7)
Geometric parameters (Å, º) top
O1—H1W0.82 (2)C3—C61.492 (2)
O1—H2W0.80 (3)C4—C51.498 (2)
N1—C21.345 (2)C5—H5A0.94 (2)
N1—N21.3599 (18)C5—H5B0.97 (2)
N1—H10.860 (18)C5—H5C0.948 (17)
N2—C41.3346 (19)C6—H6A0.972 (19)
N3—C61.5020 (18)C6—H6B0.954 (18)
N3—C71.5141 (17)C7—C91.509 (2)
N3—H3A0.868 (18)C7—C81.517 (2)
N3—H3B0.92 (2)C7—H70.961 (19)
C1—C21.487 (2)C8—H8A0.94 (2)
C1—H1A1.00 (2)C8—H8B0.946 (19)
C1—H1B0.96 (2)C8—H8C0.97 (2)
C1—H1C0.98 (2)C9—H9A1.01 (2)
C2—C31.384 (2)C9—H9B0.96 (2)
C3—C41.409 (2)C9—H9C0.90 (2)
H1W—O1—H2W103 (2)H5A—C5—H5B111.0 (17)
C2—N1—N2112.89 (13)C4—C5—H5C111.4 (11)
C2—N1—H1129.5 (11)H5A—C5—H5C105.3 (16)
N2—N1—H1117.5 (11)H5B—C5—H5C108.7 (15)
C4—N2—N1104.75 (12)C3—C6—N3112.50 (12)
C6—N3—C7113.77 (11)C3—C6—H6A109.9 (11)
C6—N3—H3A110.7 (12)N3—C6—H6A107.5 (11)
C7—N3—H3A110.6 (11)C3—C6—H6B113.6 (10)
C6—N3—H3B108.3 (11)N3—C6—H6B105.7 (10)
C7—N3—H3B108.1 (12)H6A—C6—H6B107.3 (15)
H3A—N3—H3B104.9 (16)C9—C7—N3111.14 (12)
C2—C1—H1A110.4 (13)C9—C7—C8112.00 (13)
C2—C1—H1B110.2 (11)N3—C7—C8108.30 (12)
H1A—C1—H1B105.1 (18)C9—C7—H7108.7 (11)
C2—C1—H1C110.1 (11)N3—C7—H7106.5 (10)
H1A—C1—H1C112.9 (16)C8—C7—H7110.1 (12)
H1B—C1—H1C108.0 (16)C7—C8—H8A110.0 (11)
N1—C2—C3106.07 (13)C7—C8—H8B106.7 (11)
N1—C2—C1123.50 (13)H8A—C8—H8B110.0 (16)
C3—C2—C1130.41 (14)C7—C8—H8C108.9 (12)
C2—C3—C4105.49 (12)H8A—C8—H8C109.7 (15)
C2—C3—C6126.21 (14)H8B—C8—H8C111.5 (15)
C4—C3—C6128.18 (14)C7—C9—H9A112.0 (12)
N2—C4—C3110.79 (13)C7—C9—H9B109.2 (13)
N2—C4—C5120.60 (15)H9A—C9—H9B114.6 (18)
C3—C4—C5128.60 (13)C7—C9—H9C111.5 (12)
C4—C5—H5A110.7 (12)H9A—C9—H9C103.9 (17)
C4—C5—H5B109.6 (11)H9B—C9—H9C105.4 (18)
C2—N1—N2—C41.01 (16)C2—C3—C4—N20.29 (17)
N2—N1—C2—C30.84 (16)C6—C3—C4—N2175.92 (14)
N2—N1—C2—C1177.81 (13)C2—C3—C4—C5178.86 (15)
N1—C2—C3—C40.32 (15)C6—C3—C4—C54.9 (3)
C1—C2—C3—C4178.20 (15)C2—C3—C6—N395.51 (17)
N1—C2—C3—C6176.63 (14)C4—C3—C6—N389.01 (19)
C1—C2—C3—C61.9 (2)C7—N3—C6—C3176.99 (13)
N1—N2—C4—C30.77 (16)C6—N3—C7—C963.24 (17)
N1—N2—C4—C5178.46 (14)C6—N3—C7—C8173.33 (13)

Experimental details

Crystal data
Chemical formulaC9H18N3+·Cl·H2O
Mr221.73
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)100
a, b, c (Å)12.7944 (9), 9.3494 (7), 10.0269 (7)
V3)1199.42 (15)
Z4
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.49 × 0.37 × 0.25
Data collection
DiffractometerBruker SMART CCD-1000 area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.869, 0.930
No. of measured, independent and
observed [I > 2σ(I)] reflections
9296, 2446, 2305
Rint0.023
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.059, 1.04
No. of reflections2446
No. of parameters208
No. of restraints1
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.26, 0.13
Absolute structureFlack (1983), with how many Friedel pairs?
Absolute structure parameter0.05 (4)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXTL (Bruker, 2003), SHELXTL and Mercury (Macrae et al., 2006).

The interionic hydrogen-bonding interactions in (I) and their comparison with the relevant CSD data. [No comparisons given. Do you wish to add further data?] top
bondD—HH···AD—H···AD—H···A
aN1—H1···Cl1i0.860 (18)2.344 (18)3.1980 (14)171.9 (15)
bN3—H3A···O1ii0.868 (18)1.887 (18)2.7421 (17)167.9 (18)
cN3—H3B···Cl10.92 (2)2.30 (2)3.2064 (13)170.0 (16)
dO1—H1W···N20.82 (2)1.99 (2)2.8016 (17)173 (2)
eO1—H2W···Cl1iii0.80 (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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