2-Amino-6-(1-imidazolyl­methyl)-4-(3,5,5-tri­methyl-2-pyrazolin-1-yl)-1,3,5-triazine and 2-amino-6-(1-benzimidazolyl­methyl)-4-(3,5,5-tri­methyl-2-pyrazolin-1-yl)-1,3,5-triazine hemihydrate

The two title compounds, C₁₃H₁₈N₈ and C₁₇H₂₀N₈·0.5H₂O, possess similar molecular shapes, with the pyrazoline moiety and s-triazine ring located approximately in one plane, and the imidazole or benz­imidazole ring nearly perpendicular to the s-triazine nucleus. In both crystal structures, despite there being a large number of accessible hydrogen-bond acceptor sites, only one H atom from the NH₂ group is involved in hydrogen bonding; the mol­ecules are assembled into discrete centrosymmetric dimers via a pair of nearly linear N—H...N hydrogen bonds.

S1. Comment

Molecules with 2,4-diamino-1,3,5-triazine skeletons are known to possess diverse biological activities. Recently, it has been demonstrated that some 2-amino-4-(3,5,5-trimethyl-2-pyrazolino) −1,3,5-triazine derivatives caused considerable growth inhibition in distinct tumor cell lines, showing that these compounds may be useful in the development of new chemotherapeutic agents (Brzozowski et al., 2000; Brzozowski & S\,aczewski, 2002).

The present structure determinations of 2-amino-6-(1-imidazolylmethyl)-4-(3,5,5- trimethyl-2-pyrazolino)-1,3,5-triazine, (I), and 2-amino-6-(1-benzimidazolylmethyl)-4-(3,5,5- trimethyl-2-pyrazolino)-1,3,5-triazine hemihydrate, (II), are part of our research program on structure–activity relationships for this series of compounds. So far, only the crystal structure of one derivative, 2-amino-4-(3,5,5-trimethyl-2-pyrazolino)-6-chloromethyl-1,3,5-triazine, has been reported (Brzozowski et al., 2000).

The molecular structures of (I) and (II) are shown in Fig. 1. Bond lengths and bond angles for (I) and (II) (Tables 1 and 3) show good agreement. The s-triazine moiety exhibits a typical pattern of bond angles with N—C—N angles greater than 125° and C—N—C angles less than 115°. In both compounds, the C11—N12 and C11—N16 bonds are the shortest in the s-triazine ring, and the C15—N16 and C13—N12 bonds are the longest. The s-triazine ring geometry compares well with some other 2,4-diamino-1,3,5-triazine derivatives (Perrakis et al., 1993; Brzozowski et al., 2000; Gidaspov et al., 2002). The triazine rings, including atoms N22, C10 and N17 of the substituents, are virtually flat, the maximum deviation from planarity being 0.0041 (7) and 0.0252 (16) Å in (I) and (II), respectively, when all these atoms are included in the calculation of the best plane.

The conformational features of (I) and (II) are generally very similar (Tables 1 and 3). As in 2-amino-4-(3,5,5-trimethyl-2-pyrazolino)-6-chloromethyl-1,3,5-triazine (Brzozowski et al., 2000), the molecules show a Z configuration at the partially double C13—N17 bond. The pyrazoline moiety and s-triazine ring lie approximately in one plane, whereas the benzimidazole and imidazole rings are nearly perpendicular to the s-triazine nucleus [the dihedral angles are 87.10 (4) and 80.09 (5)° for (I) and (II), respectively]. Interaction of these heteroaromatic substituents with the two methyl groups bound to atom C21 of the pyrazoline fragment results, most probably, in a characteristic bent shape of the molecules, with the dihedral angle between the pyrazoline and the imidazolyl planes equal to 76.71 (5) and 77.87 (8)°, and N12—C11—C10—N1 torsion angles of 17.25 (14) and 13.1 (3)°, in (I) and (II), respectively. The bonds to pyrazoline atom N17 are not strictly coplanar, and atom N17 deviates 0.1582 (11) Å from the plane defined by atoms C13, N18 and C21 in (I), whereas this deviation is 0.106 (2) Å in (II). The endocyclic torsion angles of the 3,5,5-trimethylpyrazoline moiety indicate an envelope conformation of the five-membered ring in (I) (Table 1) and a strongly flattened envelope in (II) (Table 3).

Compounds (I) and (II) have practically identical abilities to form classical hydrogen bonds. Each molecule contains one NH₂ group, which may act as a twofold hydrogen-bond donor, and five potentially good hydrogen-bond acceptors (atoms N3, N12, N14, N16 and N18; however, atom N12 can be excluded from this list, as access to the lone pair in its sp² orbital is hindered by the bulky substituents on atoms C11 and C13 of the s-triazine ring). The number of hydrogen-bond acceptors in these molecules strongly exceeds that of donors. In the crystal structure of the analogue of (I) and (II), 2-amino-4-(3,5,5-trimethyl-2-pyrazolino)- 6-chloromethyl-1,3,5-triazine, which lacks one N-acceptor site when compared with the title compounds, the molecules are assembled into tapes via R₂²(8) hydrogen-bond motifs generated by N—H···N interactions between the NH₂ group and the triazine atoms N14 and N16 (Brzozowski et al., 2000). Such one-dimensional assemblies are a characteristic supramolecular feature of many 2-aminopyrimidines (Aäkeroy et al., 1998; Krische et al., 1998; Krische et al., 2000). However, no such tapes were found in the crystal structures of (I) and (II). The molecules of (I) form centrosymmetric dimers via a pair of nearly linear N22—H22A···N14ⁱ hydrogen bonds (Fig. 2 and Table 2, symmetry codes defined in Table 2), and this is the only conventional hydrogen bond in this structure. The amine group interacts only very weakly with pyrazoline atom N18 in the same dimer. C20—H20A···N3ⁱⁱⁱ interactions join the dimers into one-dimensional networks, which are further organized into closely packed layers, parallel to the (211) plane, via π-π stacking interactions between the imidazole moieties [interplanar distance 3.305 (5) Å; Fig. 2]. Neighbouring layers are further connected via weak C2—H2···N18ⁱⁱ interactions between the imidazole and pyrazoline moieties. Interestingly, the C2···N18ⁱⁱ vector is oriented nearly perpendicular to the pyrazoline ring plane, indicating that this weak hydrogen bond is accepted by the lone pair in the p orbital and not by that of the sp² orbital of the atom N18.

We were unable to obtain (II) in the anhydrous form. When recrystallized from a hot saturated toluene solution, (II) formed a hemihydrate. The water molecules lie in special positions of twofold symmetry and act as double proton donors in O—H···N hydrogen bonds and as double proton acceptors in C—H···O hydrogen bonds (Table 4). It is interesting that, despite the presence of water molecules and differences in the overall molecular packing, the molecules of (II) are joined together by a set of weak and strong interactions that are similar to those observed in (I). Molecules of (II) are connected into centrosymetric dimers via pairs of nearly linear N22—H22A···N14ⁱ hydrogen bonds (Fig. 3 and Table 4, symmetry codes defined in Table 4). Furthermore, π-π stacking interactions between the benzimidazole rings [interplanar distance 3.323 (2) Å] and weak C2—H2···N18ⁱⁱⁱ interactions between benzimidazole and pyrazoline rings can be observed. When compared with (I), the missing C20—H20A···N3 interaction is replaced in (II) by two hydrogen bonds involving the water molecule, viz. C20—H20A···O1Wⁱⁱ and O1W—H1W···N3. Thus, as in (I), despite there being a large number of potential hydrogen-bonding sites, only one amine H atom is involved in hydrogen bonding.

S2. Experimental

Compound (I) was prepared according to the procedure described by Brzozowski & S\,aczewski (2002). For the preparation of (II), to a solution of benzimidazole (2.36 g, 0.02 mol) in dimethyl sulfoxide (10 ml) were added successively finely powdered NaOH (1.6 g, 0.04 mol) and 4-bromomethyl-6-(3,5,5-trimethyl-4,5-dihydro-1H-pyrazolyl)-1,3,5-triazin- 2-amine [6] (3.0 g, 0.01 mol). The reaction mixture was stirred vigorously at 308–313 K for 2 h and then poured into cold water (50 ml). The crude product that precipitated was separated by suction and purified by crystallization from methanol/water to give (II) in 76% yield (m.p. 402–404 K). IR (cm⁻¹): 3424, 1664, 1544, 1472, 1440, 1376, 1196. ¹H-NMR (DMSO-d₆): δ 0.92 (s, 6H, CH₃), 1.87 (s, 3H, CH₃), 2.62 (s, 2H, CH₂), 5.26 (s, 2H, CH₂), 6.9 (s, 2H, NH₂), 7.1–7.25 (m, 2H, aromat.), 7.4–7.5 (m, 1H, aromat.), 7.6–7.7 (m, 1H, aromat.), 8.24 (s, 1H, CH). The single-crystal used for X-ray analysis was obtained by slow evaporation of a toluene solution of (II).

S3. Refinement

In both (I) and (II), all H atoms were located from difference Fourier maps. In (I), they were refined freely, with isotropic displacement parameters. In (II), they were placed in positions calculated from the standarization of C—H, N—H and O—H bond lengths (0.96, 0.90 and 0.85 Å, respectively) and during refinement were constrained to ride on their parent atoms. The U_iso value of the unique H atom of the water molecule was set equal to 1.2U_eq(O1W); isotropic displacement parameters of the remaining H atoms were refined.

Computing details

For both compounds, data collection: CrysAlis (Oxford Diffraction, 2000); cell refinement: CrysAlis; data reduction: CrysAlis; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : The molecular structure of (a) (I) and (b) (II), with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. : A closely packed layer of hydrogen-bonded molecules in (I).
	Fig. 3. : The hydrogen-bonding network in (II).

(I) 2-Amino-6-(1-imidazolylmethyl)-4-(3,5,5-trimethyl-2-pyrazolin-1-yl)- 1,3,5-triazine

Crystal data

C13H18N8	Z = 2
Mr = 286.35	F(000) = 304
Triclinic, P1	Dx = 1.370 Mg m^−3
Hall symbol: -P1	Melting point = 239–241 K
a = 8.2493 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4564 (7) Å	Cell parameters from 3986 reflections
c = 9.7050 (8) Å	θ = 4–25°
α = 93.221 (5)°	µ = 0.09 mm^−1
β = 105.342 (5)°	T = 110 K
γ = 106.191 (6)°	Block, colorless
V = 694.20 (10) Å^3	0.40 × 0.40 × 0.30 mm

Data collection

Kuma CCD diffractometer	2275 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scan	h = −9→6
5098 measured reflections	k = −11→11
2448 independent reflections	l = −10→11

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)] = 0.037	Hydrogen site location: difference Fourier map
wR(F^2) = 0.096	All H-atom parameters refined
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 0.2587P] where P = (Fo^2 + 2Fc^2)/3
2834 reflections	(Δ/σ)max = 0.015
262 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. The following instruments and parameters were used: Melting points, Būchi 535 apparatus; IR spectra (KBr pellets, 400–4000 cm⁻¹) were taken on a Perkin-Elmer 1600 FTIR spectrometer; ¹H-NMR spectra were run on a Varian Gemini 200 apparatus at 200 MHz (chemical shifts are expressed as δ values relative to Me₄Si as standard). Analyses of C, H, N were within ±0.4% of the theoretical values.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	−0.26991 (12)	0.56010 (10)	0.10088 (10)	0.0158 (2)
C2	−0.34077 (15)	0.67102 (13)	0.11629 (13)	0.0195 (2)
H2	−0.3715 (19)	0.6915 (16)	0.2021 (16)	0.024 (4)*
N3	−0.36353 (14)	0.73997 (11)	0.00153 (11)	0.0234 (2)
C8	−0.24288 (15)	0.55953 (13)	−0.03304 (12)	0.0196 (2)
H8	−0.192 (2)	0.4899 (17)	−0.0665 (16)	0.025 (4)*
C9	−0.30161 (16)	0.66924 (13)	−0.09244 (13)	0.0216 (3)
H9	−0.308 (2)	0.6976 (17)	−0.1889 (17)	0.029 (4)*
C10	−0.21857 (14)	0.46810 (12)	0.20834 (12)	0.0166 (2)
H10A	−0.2778 (18)	0.4747 (15)	0.2816 (15)	0.019 (3)*
H10B	−0.258 (2)	0.3644 (17)	0.1640 (16)	0.025 (4)*
C11	−0.02085 (14)	0.51495 (12)	0.27983 (11)	0.0147 (2)
N12	0.07247 (12)	0.64972 (10)	0.26682 (10)	0.0158 (2)
C13	0.24811 (14)	0.68346 (12)	0.33291 (11)	0.0141 (2)
N14	0.32704 (12)	0.59229 (10)	0.40704 (10)	0.0157 (2)
C15	0.21596 (15)	0.45886 (12)	0.41085 (12)	0.0160 (2)
N16	0.03863 (12)	0.41319 (10)	0.34899 (10)	0.0175 (2)
N17	0.34780 (12)	0.82098 (10)	0.32232 (10)	0.0150 (2)
N18	0.53309 (12)	0.85415 (10)	0.36745 (10)	0.0154 (2)
C19	0.59850 (14)	0.98209 (12)	0.33292 (11)	0.0158 (2)
C20	0.46406 (14)	1.05579 (12)	0.26466 (12)	0.0173 (2)
H20B	0.4640 (19)	1.1338 (17)	0.3380 (16)	0.025 (4)*
H20A	0.486 (2)	1.1052 (17)	0.1814 (16)	0.026 (4)*
C21	0.29122 (14)	0.92608 (12)	0.22165 (12)	0.0151 (2)
N22	0.28486 (14)	0.36140 (12)	0.48171 (11)	0.0207 (2)
H22A	0.402 (2)	0.3760 (17)	0.5164 (17)	0.029 (4)*
H22B	0.213 (2)	0.272 (2)	0.4791 (17)	0.031 (4)*
C23	0.24984 (16)	0.85702 (14)	0.06468 (12)	0.0209 (3)
H23C	0.143 (2)	0.7707 (17)	0.0389 (16)	0.022 (3)*
H23A	0.350 (2)	0.8280 (17)	0.0501 (17)	0.030 (4)*
H23B	0.231 (2)	0.9330 (17)	0.0028 (17)	0.028 (4)*
C24	0.13763 (15)	0.97313 (13)	0.24606 (13)	0.0197 (2)
H24C	0.1624 (19)	1.0129 (17)	0.3484 (17)	0.027 (4)*
H24B	0.029 (2)	0.8896 (18)	0.2166 (17)	0.031 (4)*
H24A	0.1239 (19)	1.0538 (16)	0.1864 (15)	0.022 (3)*
C25	0.79186 (15)	1.05026 (14)	0.36078 (14)	0.0227 (3)
H25C	0.835 (2)	1.1468 (19)	0.4246 (18)	0.034 (4)*
H25B	0.855 (2)	0.9820 (18)	0.4030 (17)	0.029 (4)*
H25A	0.819 (2)	1.0740 (18)	0.2710 (18)	0.032 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0135 (4)	0.0161 (5)	0.0164 (4)	0.0042 (4)	0.0023 (3)	0.0032 (4)
C2	0.0183 (5)	0.0205 (6)	0.0209 (6)	0.0085 (4)	0.0051 (4)	0.0031 (4)
N3	0.0234 (5)	0.0228 (5)	0.0257 (5)	0.0105 (4)	0.0055 (4)	0.0069 (4)
C8	0.0203 (5)	0.0208 (6)	0.0182 (5)	0.0069 (5)	0.0056 (4)	0.0030 (4)
C9	0.0212 (6)	0.0227 (6)	0.0202 (6)	0.0054 (5)	0.0052 (5)	0.0068 (5)
C10	0.0155 (5)	0.0158 (5)	0.0178 (5)	0.0046 (4)	0.0036 (4)	0.0048 (4)
C11	0.0160 (5)	0.0155 (5)	0.0131 (5)	0.0057 (4)	0.0040 (4)	0.0020 (4)
N12	0.0147 (4)	0.0157 (5)	0.0166 (4)	0.0052 (4)	0.0034 (4)	0.0034 (3)
C13	0.0155 (5)	0.0151 (5)	0.0126 (5)	0.0063 (4)	0.0041 (4)	0.0021 (4)
N14	0.0161 (4)	0.0152 (5)	0.0162 (4)	0.0056 (4)	0.0036 (4)	0.0043 (4)
C15	0.0187 (5)	0.0159 (5)	0.0145 (5)	0.0063 (4)	0.0051 (4)	0.0030 (4)
N16	0.0160 (5)	0.0160 (5)	0.0198 (5)	0.0051 (4)	0.0033 (4)	0.0052 (4)
N17	0.0121 (4)	0.0146 (5)	0.0181 (4)	0.0053 (3)	0.0023 (3)	0.0057 (3)
N18	0.0118 (4)	0.0183 (5)	0.0162 (4)	0.0056 (4)	0.0030 (3)	0.0026 (4)
C19	0.0162 (5)	0.0168 (5)	0.0148 (5)	0.0057 (4)	0.0045 (4)	0.0028 (4)
C20	0.0165 (5)	0.0157 (5)	0.0201 (5)	0.0054 (4)	0.0046 (4)	0.0055 (4)
C21	0.0156 (5)	0.0139 (5)	0.0168 (5)	0.0060 (4)	0.0040 (4)	0.0062 (4)
N22	0.0179 (5)	0.0172 (5)	0.0263 (5)	0.0061 (4)	0.0033 (4)	0.0087 (4)
C23	0.0232 (6)	0.0211 (6)	0.0176 (6)	0.0072 (5)	0.0039 (5)	0.0041 (4)
C24	0.0168 (5)	0.0174 (5)	0.0274 (6)	0.0079 (4)	0.0072 (5)	0.0064 (5)
C25	0.0159 (6)	0.0246 (6)	0.0279 (6)	0.0054 (5)	0.0068 (5)	0.0093 (5)

Geometric parameters (Å, º)

N1—C2	1.3545 (15)	N17—C21	1.5121 (13)
N1—C8	1.3756 (15)	N18—C19	1.2823 (15)
N1—C10	1.4484 (14)	C19—C25	1.4872 (15)
C2—N3	1.3191 (16)	C19—C20	1.4996 (15)
C2—H2	0.957 (15)	C20—C21	1.5375 (15)
N3—C9	1.3815 (16)	C20—H20B	0.996 (15)
C8—C9	1.3577 (17)	C20—H20A	0.988 (15)
C8—H8	0.959 (15)	C21—C24	1.5234 (15)
C9—H9	0.980 (16)	C21—C23	1.5337 (16)
C10—C11	1.5171 (15)	N22—H22A	0.905 (17)
C10—H10A	0.971 (14)	N22—H22B	0.881 (18)
C10—H10B	0.976 (15)	C23—H23C	0.980 (15)
C11—N12	1.3248 (14)	C23—H23A	0.984 (16)
C11—N16	1.3338 (14)	C23—H23B	0.980 (16)
N12—C13	1.3565 (14)	C24—H24C	0.988 (15)
C13—N14	1.3489 (14)	C24—H24B	0.974 (17)
C13—N17	1.3570 (14)	C24—H24A	0.997 (15)
N14—C15	1.3459 (14)	C25—H25C	0.991 (17)
C15—N22	1.3424 (15)	C25—H25B	0.982 (16)
C15—N16	1.3567 (15)	C25—H25A	0.977 (17)
N17—N18	1.4105 (12)
C2—N1—C8	106.52 (9)	N18—C19—C20	114.27 (10)
C2—N1—C10	126.95 (10)	C25—C19—C20	123.69 (10)
C8—N1—C10	126.34 (9)	C19—C20—C21	102.50 (9)
N3—C2—N1	112.49 (10)	C19—C20—H20B	108.7 (8)
N3—C2—H2	126.4 (9)	C21—C20—H20B	112.0 (9)
N1—C2—H2	121.1 (9)	C19—C20—H20A	114.4 (9)
C2—N3—C9	104.38 (10)	C21—C20—H20A	112.3 (9)
C9—C8—N1	105.95 (10)	H20B—C20—H20A	107.0 (12)
C9—C8—H8	133.2 (9)	N17—C21—C24	113.65 (9)
N1—C8—H8	120.9 (9)	N17—C21—C23	109.68 (9)
C8—C9—N3	110.64 (10)	C24—C21—C23	111.33 (9)
C8—C9—H9	128.5 (9)	N17—C21—C20	99.27 (8)
N3—C9—H9	120.9 (9)	C24—C21—C20	112.11 (9)
N1—C10—C11	112.83 (9)	C23—C21—C20	110.21 (9)
N1—C10—H10A	108.2 (8)	C15—N22—H22A	123.3 (10)
C11—C10—H10A	109.1 (8)	C15—N22—H22B	117.6 (10)
N1—C10—H10B	109.8 (9)	H22A—N22—H22B	117.9 (14)
C11—C10—H10B	109.0 (9)	C21—C23—H23C	110.3 (8)
H10A—C10—H10B	107.8 (12)	C21—C23—H23A	110.5 (9)
N12—C11—N16	127.53 (10)	H23C—C23—H23A	110.4 (13)
N12—C11—C10	117.39 (9)	C21—C23—H23B	107.9 (9)
N16—C11—C10	115.08 (9)	H23C—C23—H23B	110.0 (12)
C11—N12—C13	114.03 (9)	H23A—C23—H23B	107.7 (13)
N14—C13—N17	119.25 (10)	C21—C24—H24C	111.1 (9)
N14—C13—N12	125.10 (10)	C21—C24—H24B	110.6 (9)
N17—C13—N12	115.65 (9)	H24C—C24—H24B	109.6 (13)
C15—N14—C13	114.31 (9)	C21—C24—H24A	107.1 (8)
N22—C15—N14	117.84 (10)	H24C—C24—H24A	108.5 (12)
N22—C15—N16	116.46 (10)	H24B—C24—H24A	109.9 (12)
N14—C15—N16	125.69 (10)	C19—C25—H25C	111.1 (10)
C11—N16—C15	113.34 (9)	C19—C25—H25B	110.4 (9)
C13—N17—N18	118.38 (9)	H25C—C25—H25B	110.5 (13)
C13—N17—C21	126.74 (9)	C19—C25—H25A	110.3 (10)
N18—N17—C21	111.18 (8)	H25C—C25—H25A	105.1 (13)
C19—N18—N17	107.50 (9)	H25B—C25—H25A	109.4 (13)
N18—C19—C25	122.03 (10)
N16—C11—C10—N1	−162.58 (9)	N18—C19—C20—C21	−16.22 (13)
N12—C11—C10—N1	17.25 (14)	C19—C20—C21—N17	20.89 (10)
C11—C10—N1—C2	−101.91 (12)	C20—C21—N17—N18	−21.73 (11)
C11—C10—N1—C8	72.46 (14)	C21—N17—N18—C19	13.10 (12)
N17—N18—C19—C20	2.52 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N22—H22A···N14^i	0.905 (17)	2.085 (17)	2.9906 (14)	179.0 (15)
N22—H22A···N18^i	0.905 (17)	2.626 (16)	3.0712 (14)	111.2 (12)
C2—H2···N18^ii	0.957 (15)	2.574 (15)	3.4491 (15)	152.1 (12)
C20—H20A···N3^iii	0.988 (15)	2.547 (15)	3.3782 (15)	141.6 (11)

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

(II) 2-Amino-6-(1-benzimidazolylmethyl)-4-(3,5,5-trimethyl-2-pyrazolin-1-yl)- 1,3,5-triazine hemihydrate

Crystal data

C17H20N8·0.5H2O	F(000) = 1464
Mr = 345.42	Dx = 1.334 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 4283 reflections
a = 22.5030 (14) Å	θ = 4–50°
b = 8.3217 (6) Å	µ = 0.09 mm^−1
c = 18.4269 (12) Å	T = 100 K
β = 94.667 (5)°	Needle, colorless
V = 3439.2 (4) Å^3	0.35 × 0.10 × 0.05 mm
Z = 8

Data collection

Kuma CCD diffractometer	1805 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 25.1°, θmin = 1.8°
ω scan	h = −26→26
8348 measured reflections	k = −9→9
3035 independent reflections	l = −20→21

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0337P)^2] where P = (Fo^2 + 2Fc^2)/3
3035 reflections	(Δ/σ)max < 0.001
251 parameters	Δρmax = 0.27 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.08659 (8)	0.5875 (2)	0.03456 (10)	0.0194 (5)
C2	0.09610 (11)	0.4873 (3)	0.09316 (12)	0.0234 (6)
H2	0.1320	0.4246	0.0995	0.022 (6)*
N3	0.05246 (8)	0.4842 (2)	0.13650 (10)	0.0242 (5)
C4	−0.04410 (10)	0.6411 (3)	0.12707 (14)	0.0272 (6)
H4	−0.0563	0.5902	0.1702	0.033 (7)*
C5	−0.07615 (11)	0.7543 (3)	0.08465 (14)	0.0300 (6)
H5	−0.1144	0.7880	0.0987	0.042 (8)*
C6	−0.05419 (11)	0.8198 (3)	0.02229 (14)	0.0287 (6)
H6	−0.0772	0.8989	−0.0055	0.031 (7)*
C7	0.00023 (10)	0.7739 (3)	−0.00065 (13)	0.0236 (6)
H7	0.0148	0.8161	−0.0443	0.022 (6)*
C8	0.03180 (10)	0.6596 (3)	0.04147 (12)	0.0206 (6)
C9	0.01079 (10)	0.5934 (3)	0.10454 (12)	0.0216 (6)
C10	0.12992 (10)	0.6372 (3)	−0.01543 (12)	0.0211 (6)
H10A	0.1600	0.5555	−0.0158	0.030 (7)*
H10B	0.1110	0.6456	−0.0639	0.015 (6)*
C11	0.15971 (9)	0.7951 (3)	0.00663 (12)	0.0172 (5)
N12	0.15224 (8)	0.8482 (2)	0.07301 (10)	0.0193 (5)
C13	0.17822 (10)	0.9925 (3)	0.08882 (12)	0.0181 (5)
N14	0.21043 (8)	1.0774 (2)	0.04389 (10)	0.0187 (5)
C15	0.21467 (10)	1.0078 (3)	−0.02164 (12)	0.0192 (6)
N16	0.18992 (8)	0.8655 (2)	−0.04408 (10)	0.0196 (5)
N17	0.16971 (8)	1.0520 (2)	0.15563 (10)	0.0191 (5)
N18	0.19151 (8)	1.2062 (2)	0.17559 (10)	0.0195 (5)
C19	0.17251 (10)	1.2412 (3)	0.23716 (13)	0.0225 (6)
C20	0.13471 (11)	1.1149 (3)	0.26857 (13)	0.0281 (6)
H20A	0.0971	1.1568	0.2808	0.042 (8)*
H20B	0.1556	1.0734	0.3121	0.031 (7)*
C21	0.12614 (11)	0.9891 (3)	0.20701 (13)	0.0234 (6)
N22	0.24601 (8)	1.0862 (2)	−0.06972 (10)	0.0235 (5)
H22B	0.2462	1.0466	−0.1151	0.035 (8)*
H22A	0.2587	1.1877	−0.0617	0.048 (9)*
C23	0.06302 (11)	0.9985 (3)	0.17062 (14)	0.0329 (7)
H23A	0.0526	1.1079	0.1590	0.050 (9)*
H23B	0.0364	0.9682	0.2064	0.049 (8)*
H23C	0.0583	0.9295	0.1288	0.041 (8)*
C24	0.14255 (13)	0.8205 (3)	0.23364 (14)	0.0359 (7)
H24A	0.1829	0.8136	0.2548	0.043 (8)*
H24B	0.1158	0.7984	0.2704	0.048 (8)*
H24C	0.1362	0.7474	0.1935	0.045 (8)*
C25	0.18686 (12)	1.3969 (3)	0.27468 (15)	0.0322 (7)
H25A	0.2060	1.3773	0.3224	0.056 (9)*
H25B	0.2129	1.4576	0.2463	0.054 (9)*
H25C	0.1509	1.4562	0.2799	0.053 (9)*
O1W	0.0000	0.3058 (3)	0.2500	0.0894 (12)
H1W	0.0156	0.3618	0.2180	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0178 (11)	0.0190 (11)	0.0219 (12)	−0.0020 (9)	0.0038 (9)	−0.0004 (9)
C2	0.0223 (14)	0.0221 (14)	0.0262 (15)	−0.0024 (13)	0.0038 (12)	0.0014 (12)
N3	0.0230 (12)	0.0257 (12)	0.0245 (12)	−0.0028 (10)	0.0062 (10)	0.0007 (10)
C4	0.0228 (14)	0.0311 (15)	0.0291 (16)	−0.0066 (12)	0.0099 (13)	−0.0048 (13)
C5	0.0186 (14)	0.0368 (16)	0.0348 (17)	0.0015 (12)	0.0026 (13)	−0.0103 (13)
C6	0.0265 (15)	0.0307 (16)	0.0287 (16)	0.0009 (13)	0.0002 (13)	−0.0030 (13)
C7	0.0240 (14)	0.0232 (14)	0.0234 (14)	−0.0032 (12)	0.0017 (12)	−0.0012 (12)
C8	0.0207 (14)	0.0187 (13)	0.0222 (14)	−0.0030 (11)	0.0008 (11)	−0.0061 (11)
C9	0.0214 (14)	0.0223 (14)	0.0217 (14)	−0.0049 (12)	0.0042 (12)	−0.0018 (11)
C10	0.0192 (13)	0.0241 (14)	0.0203 (15)	−0.0031 (12)	0.0032 (11)	0.0000 (11)
C11	0.0125 (12)	0.0184 (13)	0.0206 (14)	0.0011 (10)	0.0014 (11)	0.0012 (11)
N12	0.0185 (11)	0.0196 (11)	0.0199 (11)	−0.0031 (9)	0.0021 (9)	−0.0008 (9)
C13	0.0155 (13)	0.0204 (13)	0.0182 (14)	0.0024 (11)	−0.0007 (11)	0.0029 (11)
N14	0.0186 (11)	0.0237 (11)	0.0141 (11)	−0.0043 (9)	0.0041 (9)	0.0027 (9)
C15	0.0148 (12)	0.0228 (14)	0.0201 (14)	0.0003 (11)	0.0028 (11)	0.0065 (12)
N16	0.0179 (10)	0.0227 (11)	0.0188 (11)	−0.0038 (9)	0.0045 (9)	0.0007 (9)
N17	0.0218 (11)	0.0201 (11)	0.0158 (11)	−0.0069 (9)	0.0044 (10)	0.0003 (9)
N18	0.0189 (11)	0.0174 (11)	0.0222 (12)	−0.0012 (9)	0.0024 (9)	0.0001 (9)
C19	0.0213 (13)	0.0254 (14)	0.0207 (14)	−0.0014 (11)	0.0006 (12)	−0.0010 (11)
C20	0.0284 (16)	0.0379 (16)	0.0182 (15)	−0.0080 (13)	0.0026 (13)	−0.0014 (12)
C21	0.0251 (14)	0.0292 (15)	0.0168 (14)	−0.0060 (12)	0.0076 (12)	−0.0013 (12)
N22	0.0263 (12)	0.0256 (13)	0.0197 (13)	−0.0087 (10)	0.0088 (10)	−0.0003 (10)
C23	0.0279 (16)	0.046 (2)	0.0260 (16)	−0.0086 (14)	0.0079 (13)	−0.0143 (14)
C24	0.051 (2)	0.0336 (17)	0.0240 (16)	−0.0140 (14)	0.0083 (15)	0.0048 (14)
C25	0.0323 (16)	0.0307 (15)	0.0347 (18)	−0.0071 (14)	0.0102 (14)	−0.0076 (13)
O1W	0.152 (3)	0.0356 (18)	0.094 (3)	0.000	0.088 (3)	0.000

Geometric parameters (Å, º)

N1—C2	1.367 (3)	C15—N22	1.345 (3)
N1—C8	1.386 (3)	C15—N16	1.359 (3)
N1—C10	1.455 (3)	N17—N18	1.412 (2)
C2—N3	1.316 (3)	N17—C21	1.511 (3)
C2—H2	0.96	N18—C19	1.278 (3)
N3—C9	1.401 (3)	C19—C25	1.491 (3)
C4—C5	1.388 (3)	C19—C20	1.498 (3)
C4—C9	1.392 (3)	C20—C21	1.544 (3)
C4—H4	0.96	C20—H20A	0.96
C5—C6	1.398 (3)	C20—H20B	0.96
C5—H5	0.96	C21—C24	1.522 (3)
C6—C7	1.381 (3)	C21—C23	1.523 (3)
C6—H6	0.96	N22—H22B	0.90
C7—C8	1.386 (3)	N22—H22A	0.90
C7—H7	0.96	C23—H23A	0.96
C8—C9	1.403 (3)	C23—H23B	0.96
C10—C11	1.515 (3)	C23—H23C	0.96
C10—H10A	0.96	C24—H24A	0.96
C10—H10B	0.96	C24—H24B	0.96
C11—N12	1.324 (3)	C24—H24C	0.96
C11—N16	1.335 (3)	C25—H25A	0.96
N12—C13	1.357 (3)	C25—H25B	0.96
C13—N14	1.344 (3)	C25—H25C	0.96
C13—N17	1.355 (3)	O1W—H1W	0.85
N14—C15	1.349 (3)
C2—N1—C8	105.94 (19)	C11—N16—C15	112.91 (19)
C2—N1—C10	127.14 (19)	C13—N17—N18	119.80 (18)
C8—N1—C10	125.57 (19)	C13—N17—C21	126.15 (19)
N3—C2—N1	114.5 (2)	N18—N17—C21	112.39 (17)
N3—C2—H2	125.2	C19—N18—N17	107.71 (18)
N1—C2—H2	120.3	N18—C19—C25	122.3 (2)
C2—N3—C9	103.82 (19)	N18—C19—C20	115.1 (2)
C5—C4—C9	117.3 (2)	C25—C19—C20	122.6 (2)
C5—C4—H4	126.5	C19—C20—C21	103.47 (19)
C9—C4—H4	116.2	C19—C20—H20A	112.1
C4—C5—C6	121.7 (2)	C21—C20—H20A	111.1
C4—C5—H5	118.8	C19—C20—H20B	108.7
C6—C5—H5	119.5	C21—C20—H20B	113.2
C7—C6—C5	121.7 (3)	H20A—C20—H20B	108.4
C7—C6—H6	118.7	N17—C21—C24	111.6 (2)
C5—C6—H6	119.6	N17—C21—C23	109.63 (19)
C6—C7—C8	116.4 (2)	C24—C21—C23	112.5 (2)
C6—C7—H7	121.8	N17—C21—C20	100.19 (18)
C8—C7—H7	121.7	C24—C21—C20	112.1 (2)
C7—C8—N1	131.7 (2)	C23—C21—C20	110.2 (2)
C7—C8—C9	122.8 (2)	C15—N22—H22B	118.5
N1—C8—C9	105.6 (2)	C15—N22—H22A	121.5
C4—C9—N3	129.7 (2)	H22B—N22—H22A	118.1
C4—C9—C8	120.1 (2)	C21—C23—H23A	110.4
N3—C9—C8	110.1 (2)	C21—C23—H23B	107.2
N1—C10—C11	112.42 (18)	H23A—C23—H23B	104.3
N1—C10—H10A	108.2	C21—C23—H23C	111.2
C11—C10—H10A	108.6	H23A—C23—H23C	112.3
N1—C10—H10B	109.8	H23B—C23—H23C	111.1
C11—C10—H10B	109.9	C21—C24—H24A	112.5
H10A—C10—H10B	107.8	C21—C24—H24B	104.7
N12—C11—N16	127.6 (2)	H24A—C24—H24B	109.2
N12—C11—C10	116.8 (2)	C21—C24—H24C	108.5
N16—C11—C10	115.6 (2)	H24A—C24—H24C	110.6
C11—N12—C13	114.1 (2)	H24B—C24—H24C	111.1
N14—C13—N17	119.4 (2)	C19—C25—H25A	109.9
N14—C13—N12	125.2 (2)	C19—C25—H25B	108.9
N17—C13—N12	115.4 (2)	H25A—C25—H25B	109.9
C13—N14—C15	114.01 (19)	C19—C25—H25C	110.0
N22—C15—N14	117.4 (2)	H25A—C25—H25C	108.3
N22—C15—N16	116.5 (2)	H25B—C25—H25C	109.9
N14—C15—N16	126.1 (2)
N16—C11—C10—N1	−166.01 (19)	N18—C19—C20—C21	−6.6 (3)
N12—C11—C10—N1	13.1 (3)	C19—C20—C21—N17	9.4 (2)
C11—C10—N1—C2	−93.8 (3)	C20—C21—N17—N18	−10.4 (2)
C11—C10—N1—C8	71.0 (3)	C21—N17—N18—C19	7.0 (2)
N17—N18—C19—C20	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N3	0.85	2.04	2.894 (2)	176
N22—H22A···N14^i	0.90	2.09	2.991 (3)	179
N22—H22A···N18^i	0.90	2.61	3.035 (3)	110
C20—H20A···O1W^ii	0.96	2.54	3.415 (3)	152
C2—H2···N18^iii	0.96	2.60	3.443 (3)	147

Symmetry codes: (i) −x+1/2, −y+5/2, −z; (ii) x, y+1, z; (iii) x, y−1, z.