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Due to its donor-acceptor-donor site, the anti­malarial drug pyrimethamine [systematic name: 5-(4-chloro­phenyl)-6-ethyl­pyrimidine-2,4-diamine] is a potential component of a supra­­molecular synthon. During a cocrystallization screen, one new polymorph of solvent-free pyrimethamine, C12H13ClN4, (I), and two pseudopolymorphs, pyrimethamine dimethyl sul­fox­ide monosolvate, C12H13ClN4·C2H6OS, (Ia), and pyrimethamine N-methyl­pyrrolidin-2-one monosolvate, C12H13ClN4·C5H9NO, (Ib), were obtained. In (I), (Ia), (Ib) and the previously reported polymorph, the pyrimethamine mol­ecules exhibit similar conformations and form R22(8) dimers stabilized by a pair of N-H...N hydrogen bonds. However, the packing arrangements are completely different. In (I), the dimers are connected by two additional N-H...N hydrogen bonds to form ribbons and further connected into a two-dimensional network parallel to (100), while layers con­taining N-H...Cl hydrogen-bonded pyrimethamine ribbons are observed in the packing of the known polymorph. In the two pseudopolymorphs, two pyrimethamine mol­ecules are linked to form R22(8) dimers and the solvent mol­ecules are connected to the dimers by R23(8) inter­actions involving two N-H...O hydrogen bonds. These arrangements are connected to form zigzag chains by N-H...Cl inter­actions in (Ia) and to form ribbons by N-H...N inter­actions in (Ib). Unexpectedly, a reaction between pyrimethamine and N-methyl­pyrrolidin-2-one occurred during another cocrystallization experiment from a solvent mixture of N-methyl­pyrrolidin-2-one and dimethyl sulfoxide, yielding solvent-free 5,5'-{[5-(4-chloro­phenyl)-6-ethylpyrimidine-2,4-diyl]bis­(azane­diyl)}bis­(1-methyl­pyrrolidin-2-one), C22H27ClN6O2, (II). In the packing of (II), the pyrimethamine derivatives are N-H...O hydrogen bonded to form ribbons. A database study was carried out to compare the mol­ecular conformations and hydrogen-bonding inter­actions of pyrimethamine.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111038868/sk3416sup1.cif
Contains datablocks I, Ia, Ib, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111038868/sk3416Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111038868/sk3416Iasup3.hkl
Contains datablock Ia

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111038868/sk3416Ibsup4.hkl
Contains datablock Ib

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111038868/sk3416IIsup5.hkl
Contains datablock II

CCDC references: 855958; 855959; 855960; 855961

Comment top

Pyrimethamine is an antifolate drug used for the prevention and treatment of malaria by inhibiting the enzyme dihydrofolate reductase (Sardarian et al., 2003). Like most antifolates, pyrimethamine contains a 2,4-diaminopyrimidine group and a phenyl ring, separated by one rotatable bond (Schwalbe & Cody, 2006). Previous theoretical and structural studies revealed that the relative orientation of the two rings and the protonation state of the 2,4-diaminopyrimidine play a key role in drug binding (Sansom et al., 1989; Kongsaeree et al., 2005). Moreover, pyrimethamine exhibits a donor–acceptor–donor site, so that together with a complementary molecule it can form three hydrogen bonds, yielding a robust supramolecular synthon (Desiraju, 1995).

In order to study the molecular geometry of pyrimethamine and its hydrogen-bonded interactions, we cocrystallized pyrimethamine with several potential receptors. Various cocrystallization experiments yielded a complex of pyrimethamine and orotic acid. Unfortunately, all of these crystals were of minor quality (Tutughamiarso & Bolte, 2011). In addition to the complex, one new polymorph of solvent-free pyrimethamine, (I), and two pseudopolymorphs were obtained, the dimethyl sulfoxide monosolvate, (Ia), and the N-methylpyrrolidin-2-one monosolvate, (Ib). Furthermore, solvent-free 5,5'-(5-(4-chlorophenyl)-6-ethylpyrimidine-2,4-diyl)bis(azanediyl)bis(1-methylpyrrolidin-2-one), (II), was formed during another crystallization attempt of pyrimethamine with N(2)-9-diacetylguanine from a solvent mixture of N-methylpyrrolidin-2-one (NMP) and dimethyl sulfoxide (DMSO).

The new polymorph, (I), crystallizes in the monoclinic space group P21/c (Fig. 1), whereas the previously known modification of this compound [Cambridge Structural Database (CSD; Allen, 2002) refcode MUFMAB; Sethuraman & Thomas Muthiah (2002)] is triclinic. In (I), the pyrimidine and phenyl rings enclose a dihedral angle of 75.9 (3)°, with atom C5 anticlinal to atom C62 [torsion angle 96.9 (9)°]. The asymmetric unit of MUFMAB contains two pyrimethamine molecules, which show some similarity to (I): the dihedral angles between the two rings are 74.4 (1) and 82.4 (1)°, while the torsion angles between the methyl C atom and the pivot pyrimidine C atom are 97.3 (3) and -97.2 (3)°. In both polymorphs, the pyrimethamine molecules form ribbons stabilized by repeated R22(8) interactions (Bernstein et al., 1995) involving two N—H···N bonds [see Fig. 2 for the packing of (I)]. In (I), another R22(8) interaction with two N—H···N bonds connects adjacent ribbons to form a two-dimensional network parallel to (100), while the packing of the triclinic polymorph shows layers consisting of N—H···Cl hydrogen-bonded ribbons.

Compound (Ia) crystallizes as a DMSO solvate, with the S atom of the solvate molecule disordered over two sites (Fig. 3). A dihedral angle of 76.1 (1)° is formed between the plane through the pyrimidine and phenyl rings, while atoms C5 and C62 are in an anticlinal arrangement [torsion angle 101.5 (2)°]. In the packing, two pyrimethamine and two DMSO molecules form a centrosymmetric dimer held together by six hydrogen bonds (Fig. 4). The pyrimethamine molecules are connected by two N—H···N bonds with an R22(8) motif, while the pyrimethamine and the solvent molecules are linked by an R23(8) interaction with four additional N—H···O bonds. Within the dimer, the pyrimidine rings are coplanar but do not lie in a common plane; the planes are displaced by ca 0.6 Å with respect to each other. The dimers are N—H···Cl hydrogen-bonded to form zigzag chains running parallel to (101).

The asymmetric unit of (Ib) consists of two pyrimethamine and two NMP molecules (Fig. 5). The terminal C atom of the ethyl group of pyrimethamine molecule B is disordered over two sites. However, similar conformations of both pyrimethamine molecules are observed: dihedral angles of 62.6 (1) and 76.1 (2)° are enclosed between the pyrimidine and phenyl rings in molecules A and B, with the ethyl groups nearly perpendicular to the pyrimidine rings [dihedral angles 71.9 (4) (molecule A), and 84.0 (6) and 85.9 (8)° (molecule B)]. The pyrimidine rings are planar [r.m.s. deviations 0.014 (molecule A) and 0.006 Å (molecule B) for all non-H atoms] and are twisted by 19.1 (1)° with respect to each other. The NMP molecule (atoms labelled with the suffix X) is planar (r.m.s. deviation 0.034 Å for all non-H atoms), and although the other NMP molecule (atoms labelled with the suffix Y) is disordered over two sites, all the non-H atoms of these two sites lie essentially in a common plane (r.m.s. deviation 0.056 Å for all non-H atoms). In the packing, the solvent molecules are perpendicular to the bc plane. The hydrogen-bonded interactions between the molecules in the asymmetric unit are identical to those in the centrosymmetric dimer of (Ia): the pyrimethamine molecules are connected by an R22(8) interaction with two N—H···N bonds, while four N—H···O bonds link the pyrimethamine and the NMP molecules. Furthermore, the dimers are joined to form ribbons runing along the b axis by another R22(8) interaction involving two N—H···N bonds (Fig. 6).

Unexpectedly, crystals of (II) were obtained by cocrystallization attempts from a solvent mixture of NMP and DMSO (Fig. 7). The DMSO molecule probably reacted as a mild oxidizing agent, so that the pyrimethamine and NMP could undergo a dehydrogenation reaction, yielding compound (II). However, no such reaction has yet been reported for pyrimethamine. The dihedral angle between the planes through the pyrimidine and phenyl rings is 76.1 (1)°, with atoms C5 and C62 in an anticlinal arrangement (Table 4). Pyrimidine atom N3 is antiperiplanar to atom C5X and synperiplanar to atom C5Y, while the planes through the amide groups and the pyrimidine ring enclose dihedral angles of 17.7 (2) (N21—H) and 11.6 (5)° (N41—H). Different conformations of 1-methylpyrrolidin-2-one fragments are observed: pyrrolidine ring X is planar (r.m.s. deviation 0.018 Å for all non-H atoms), with the C5X—H5X bond pointing away from atom N3. In contrast, the Y ring adopts a twist conformation, with atoms N1Y, C2Y and C5Y in a plane and atoms C3Y and C4Y deviating from this plane by -0.14 (1) and 0.25 (1) Å, respectively. The C5Y—H5Y bond is directed to the same side as atom N3. Although atoms C1X and N21 and C1Y and N41 atoms are in a synclinal arrangement (Table 4), the two methyl groups are opposite each other. In the crystal structure, two N—H···O bonds stabilize the centrosymmetric dimers, which are further N—H···O hydrogen-bonded to form ribbons running parallel to (110) (Fig. 8).

The conformation of the pyrimethamine molecule is characterized by the dihedral angle between the plane through the two rings and the C5—C6—C61—C62 torsion angle, representing the deviation of the ethyl group from the pyrimidine ring. The latter is not essential for drug binding, since the orientation of the ethyl group does not affect the overall binding energy of the enzyme–drug complex (Sansom et al., 1989). In the four structures, (I), (Ia), (Ib) and (II), similar molecular geometries are observed: the dihedral angle between the planes through the pyrimidine ring and the substituted phenyl ring varies from 62.6 (1) to 76.1 (2)°, while the C5—C6—C61—C62 torsion angle ranges from 84.9 (8) to 108.7 (5)°. In the cocrystal of pyrimethamine and orotic acid, the protonated pyrimethamine molecules also show similar conformations: the pyrimidine and phenyl rings are twisted by 86.2 and 83.6° from each other, with atoms C5 anticlinal to atoms C62.

A search of the CSD (Version 5.32 of November 2010 plus three updates) for structures containing pyrimethamine yielded 30 entries. Since the protonation state of pyrimethamine is important for its drug binding, it is protonated in almost all entries, and in fact in one of them [refcode LAVZOY; Balasubramani et al. (2005)] both pyrimidine N atoms of the pyrimethamine molecule are protonated. Only MUFMAB revealed neutral pyrimethamine molecules. However, the values of the characteristic dihedral and torsion angles are in agreement with those in our four structures: the dihedral angle between the two rings varies from 61.4 to 89.7° and the torsion angle between the terminal C atom of the ethyl group and the pivot pyrimidine C atom varies from 67.5 to 110.9°. In the structure of pyrimethamine hydrochloride [refcode CIVDEQ01; Tanaka et al. (2004)], the terminal C atom of the ethyl group is disordered over two sites. Thus, torsion angles of 143.2 and -155.3° are formed between these disordered C atoms and the pivot pyrimidine C atom.

As observed in (I), (Ia), (Ib) and 18 CSD entries, the pyrimethamine molecule forms R22(8) dimers characterized by two N—H···O bonds. Although different solvent molecules are included in (Ia) and (Ib), similar arrangements consisting of two pyrimethamine and two solvent molecules held together by six hydrogen bonds are formed. These so-called DADA array motifs (Sethuraman et al., 2003) are also shown in 15 CSD entries; the pyrimidine molecules are bridged by O atoms of the carboxylate groups [refcodes BOJGEN (Balasubramani & Muthiah, 2008), KUQQUJ (Thanigaimani & Muthiah, 2010), LENKEV (Devi, Muthiah, Bocelli & Cantoni, 2006 or Devi, Muthiah, Rychlewska & Plutecka, 2006 ?), PARXAI, PARXEM, PARXIQ (Stanley et al., 2005), UHAYEH, UHAYIL (Stanley et al., 2002), ULAXOU, ULAXUA and ULAYAH (Sethuraman et al., 2003)], solvent molecules [refcode QOVQAU (Thanigaimani et al., 2009)] or anions [refcodes CIVDEQ01 (Tanaka et al., 2004), DUTTOC (Nirmalram & Thomas Muthiah, 2010) and YIZCOA (Balasubramani, Muthiah, Bocelli & Cantoni, 2007 or Balasubramani, Muthiah & Lynch, 2007) ?]. In the other seven [Not clear. 7 + 15 + 18 = 40, but only 30 hits mentioned in previous paragraph] CSD entries, the pyrimethamine molecules are linked to the other compounds, rather than forming R22(8) homodimers [refcodes AFESOU (Subashini et al., 2007), GINNIB (Balasubramani, Muthiah, Bocelli & Cantoni, 2007 or Balasubramani, Muthiah & Lynch, 2007 ?), KUQRAQ, KUQREU (Thanigaimani & Muthiah, 2010), LAVZOY (Balasubramani et al., 2005), ULAXIO (Sethuraman et al., 2003) and VEVNIU (Devi, Muthiah, Bocelli & Cantoni, 2006 or Devi, Muthiah, Rychlewska & Plutecka, 2006 ?)]. In the cocrystal of pyrimethamine and orotic acid (Fig. 9), both molecules exhibit the desired arrangement of donor and acceptor groups, being held together by three hydrogen bonds forming complementary complexes. No other CSD entry with pyrimethamine shows a similar hydrogen-bonding pattern. Furthermore, the N—H···Cl bond does not seem to be a favourable interaction in the solid state, therefore it is only formed in (Ia) and four other CSD entries [refcodes GAMFAC (Hemamalini et al., 2005), MUFMAB (Sethuraman & Thomas Muthiah, 2002), ULAXIO (Sethuraman et al., 2003) and VEVNIU (Devi, Muthiah, Bocelli & Cantoni, 2006 or Devi, Muthiah, Rychlewska & Plutecka, 2006) ?].

Pyrimethamine, either neutral or protonated, reveals similar conformations, which represent the molecular geometry observed in previous studies of drug–enzyme complexes. The formation of R22(8) homodimers is obviously predominant for pyrimethamine molecules in the solid state, but such homodimers are not observed in the cocrystal of pyrimethamine and orotic acid. Since both molecules exhibit complementary functional groups, the pyrimethamine molecule is hydrogen-bonded to the orotic acid molecule rather than forming the supposedly preferred R22(8) homodimer. Altogether, our study confirms the robustness of the supramolecular synthon containing molecules with a donor–acceptor–donor site and an acceptor–donor–acceptor site.

Related literature top

For related literature, see: Allen (2002); Balasubramani & Muthiah (2008); Balasubramani et al. (2005); Balasubramani, Muthiah & Lynch (2007); Balasubramani, Muthiah, Bocelli & Cantoni (2007); Bernstein et al. (1995); Desiraju (1995); Devi, Muthiah, Bocelli & Cantoni (2006); Devi, Muthiah, Rychlewska & Plutecka (2006); Hemamalini et al. (2005); Kongsaeree et al. (2005); Nirmalram & Thomas Muthiah (2010); Sansom et al. (1989); Sardarian et al. (2003); Schwalbe & Cody (2006); Sethuraman & Thomas Muthiah (2002); Sethuraman et al. (2003); Sheldrick (2008); Spek (2009); Stanley et al. (2002, 2005); Subashini et al. (2007); Tanaka et al. (2004); Thanigaimani & Muthiah (2010); Thanigaimani et al. (2009); Tutughamiarso & Bolte (2011).

Experimental top

Single crystals of (I) were obtained during attempts to cocrystallize pyrimethamine (2.5 mg, 0.010 mmol) with 2,4-dihydroxypteridine (2.0 mg, 0.012 mmol) and 2,6-diaminopurine hydrate (1.3 mg, 0.009 mmol) in dimethyl sulfoxide (DMSO; 250 µl) at room temperature. Solvent-evaporation experiments with mixtures of pyrimethamine (2.2 mg, 0.088 mmol) and 2-acetamidothiazole (1.7 mg, 0.012 mmol) from DMSO (150 µl) at room temperature yielded (Ia). Cocrystallization attempts of pyrimethamine (3.5 mg, 0.014 mmol) and N(2)-9-diacetylguanine (2.5 mg, 0.011 mmol) from N-methylpyrrolidin-2-one (NMP; 350 µl) at room temperature yielded (Ib), while crystals (II) were obtained by crystallization attempts of pyrimethamine (2.8 mg, 0.011 mmol) with N(2)-9-diacetylguanine (3.1 mg, 0.013 mmol) from a solvent mixture of NMP (150 µl) and DMSO (150 µl) at 323 K. All chemical substances are commercially available and none of the solvents used in the experiments was water-free.

Refinement top

The H atoms, except those bonded to disordered atoms, were initially located by difference Fourier synthesis. H atoms bonded to C atoms were refined using a riding model, with methyl C—H = 0.98 Å, secondary C—H = 0.99 Å, tertiary C—H = 1.00 Å and aromatic C—H = 0.95 Å, and with Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for secondary, tertiary and aromatic H atoms. The positions of all amine H atoms in the structures were refined, although a bond-length restraint of 0.88 (2) Å was applied to the N—H distances involving N41 in (I), N21A and N41B in (Ib), and N21 and N41 in (II). The displacement parameters of the amine H atoms in (Ia) were refined isotropically, while in the other structures, their isotropic displacement parameters were coupled to those of the parent N atoms, with Uiso(H) = 1.2Ueq(N).

The crystal of (I) is a nonmerohedral twin indicated by its systematically high K value for reflections with low intensity [K = mean(Fo2)/mean(Fc2)]. The twin law (1 0 0.73/0 1 0/0 0 1) and the reflection data file for refinement was prepared using PLATON (Spek, 2009). PLATON produces a file containing 1588 non-overlaps from the main domain, plus those 719 reflections that it considers would be overlaps from both domains flagged as such so that the domain ratio can be refined. For refinement, the data were read in via HKLF5 (SHELXL97; Sheldrick, 2008) and an additional variable was introduced (using the BASF command in SHELXL97) describing the fractional contributions of the two twin components; the ratio refined to 0.38 (1):0.62 (1). The approximations inherent in the PLATON method of generating a HKLF5 file may be responsible for the relatively poor final agreement factors and reduced precision of the geometric parameters for this structure.

In (Ia), the S atom of the DMSO solvent molecule is disordered over two positions, with a site-occupation factor of 0.564 (2) for the major occupied orientation. All non-H atoms were refined anisotropically.

In (Ib), the terminal C atom of the ethyl group in pyrimethamine molecule B is disordered over two sites. Furthermore, NMP molecule Y is disordered over a pseudo-mirror plane along the O2Y and C5Y atoms. The site-occupation factors for the major occupied orientations are 0.61 (1) for the methyl group and 0.72 (1) for the solvent molecule. The minor-occupied orientations of the disordered atoms were refined isotropically. Bond-length and bond-angle restraints were applied for the ethyl group of molecule B, the NMP molecule X and the major occupied orientation of the NMP molecule Y, while similarity restraints were applied for the 1,2- and 1,3-distances of the minor occupied orientation of molecule Y.

The presence of relatively high residual electron-density peaks in (Ib) and (II) indicates possible disorder of NMP molecule X [in (Ib)] and the 'X' ring [in (II)]. However, the height of these peaks are less than 1 e Å-3 and attempts to model a second component failed. The NMP molecule X [in (Ib)] and the 'X' ring [in (II)] seem to be planar (r.m.s. deviations = 0.034 and 0.018 Å for all non-H atoms, respectively), but the apparent planarity is probably merely a consequence of the untreated disorder.

Computing details top

For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Version 2.2; Macrae et al., 2008) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial packing diagram for (I), showing ribbons running along the b axis. Hydrogen bonds are shown as dashed lines. (Symmetry codes are as in Table 1.)
[Figure 3] Fig. 3. A perspective view of (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The N—H···O hydrogen bond is shown as a dashed line. The solvent molecule is disordered and its minor occupied site has been omitted.
[Figure 4] Fig. 4. A partial packing diagram for (Ia). Hydrogen bonds are shown as dashed lines. The minor occupied sites of the solvent molecules and the solvent H atoms have been omitted. (Symmetry codes are as in Table 2.)
[Figure 5] Fig. 5. A perspective view of (Ib), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. One of the methyl groups (C62B) and one of the NMP molecules (molecule Y) are disordered and their minor occupied sites have been omitted.
[Figure 6] Fig. 6. A partial packing diagram for (Ib). Hydrogen bonds are shown as dashed lines. The minor occupied site of the methyl group and that of the solvent molecule are not shown. (Symmetry codes are as in Table 3.)
[Figure 7] Fig. 7. A perspective view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 8] Fig. 8. A packing diagram for (II). Hydrogen bonds are shown as dashed lines. (Symmetry codes are as in Table 5.)
[Figure 9] Fig. 9. The complex of pyrimethamine and orotic acid, connected by three hydrogen bonds (dashed lines).
(I) 2,4-diamino-5(4-chlorophenyl)-6-ethylpyrimidine top
Crystal data top
C12H13ClN4F(000) = 520
Mr = 248.71Dx = 1.345 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6581 reflections
a = 14.4471 (18) Åθ = 3.3–25.9°
b = 7.5774 (7) ŵ = 0.29 mm1
c = 11.7526 (15) ÅT = 173 K
β = 107.279 (10)°Block, colourless
V = 1228.5 (2) Å30.50 × 0.40 × 0.20 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
1616 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.221
Graphite monochromatorθmax = 25.0°, θmin = 3.2°
ω scansh = 1716
15453 measured reflectionsk = 99
2149 independent reflectionsl = 1213
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.131Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.333H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.1194P)2 + 7.1236P]
where P = (Fo2 + 2Fc2)/3
2149 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.58 e Å3
2 restraintsΔρmin = 0.53 e Å3
Crystal data top
C12H13ClN4V = 1228.5 (2) Å3
Mr = 248.71Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.4471 (18) ŵ = 0.29 mm1
b = 7.5774 (7) ÅT = 173 K
c = 11.7526 (15) Å0.50 × 0.40 × 0.20 mm
β = 107.279 (10)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1616 reflections with I > 2σ(I)
15453 measured reflectionsRint = 0.221
2149 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.1312 restraints
wR(F2) = 0.333H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.58 e Å3
2149 reflectionsΔρmin = 0.53 e Å3
167 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N10.4011 (4)0.5347 (8)0.3027 (6)0.0267 (14)
C20.4564 (5)0.6797 (9)0.3199 (7)0.0254 (15)
N30.4490 (4)0.8227 (7)0.3846 (6)0.0244 (13)
C40.3797 (4)0.8173 (9)0.4386 (6)0.0234 (15)
C50.3162 (5)0.6699 (9)0.4276 (6)0.0244 (15)
C60.3318 (5)0.5330 (10)0.3584 (7)0.0274 (16)
N210.5293 (5)0.6840 (10)0.2681 (7)0.0343 (16)
H2110.552 (7)0.791 (14)0.254 (8)0.041*
H2120.532 (7)0.604 (14)0.218 (9)0.041*
N410.3699 (5)0.9627 (9)0.5023 (6)0.0309 (15)
H4110.343 (6)0.940 (11)0.559 (6)0.037*
H4120.417 (4)1.039 (9)0.531 (8)0.037*
C510.2367 (5)0.6733 (9)0.4851 (6)0.0253 (15)
C520.2413 (6)0.5763 (11)0.5865 (7)0.0351 (19)
H520.29720.50770.62330.042*
C530.1643 (7)0.5788 (12)0.6347 (8)0.042 (2)
H530.16770.51140.70400.051*
C540.0837 (6)0.6779 (13)0.5827 (8)0.045 (2)
C550.0776 (6)0.7758 (16)0.4837 (9)0.055 (3)
H550.02180.84550.44830.066*
C560.1543 (5)0.7718 (14)0.4354 (8)0.043 (2)
H560.14990.83910.36580.051*
C610.2660 (6)0.3727 (10)0.3314 (8)0.0364 (19)
H61A0.30520.26540.33170.044*
H61B0.23330.35920.39400.044*
C620.1906 (7)0.3919 (13)0.2110 (9)0.052 (2)
H62A0.14870.28740.19500.062*
H62B0.22300.40360.14900.062*
H62C0.15120.49720.21120.062*
Cl10.01345 (18)0.6786 (5)0.6422 (2)0.0732 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.022 (3)0.023 (3)0.041 (4)0.005 (2)0.018 (3)0.004 (3)
C20.026 (3)0.020 (3)0.029 (4)0.001 (3)0.006 (3)0.001 (3)
N30.021 (3)0.021 (3)0.033 (3)0.004 (2)0.011 (2)0.003 (3)
C40.015 (3)0.028 (4)0.026 (4)0.000 (3)0.004 (3)0.001 (3)
C50.018 (3)0.029 (4)0.027 (4)0.002 (3)0.008 (3)0.003 (3)
C60.020 (3)0.028 (4)0.035 (4)0.000 (3)0.009 (3)0.004 (3)
N210.033 (3)0.027 (3)0.052 (4)0.005 (3)0.027 (3)0.005 (3)
N410.031 (3)0.032 (3)0.037 (4)0.011 (3)0.021 (3)0.011 (3)
C510.020 (3)0.027 (4)0.026 (4)0.002 (3)0.003 (3)0.001 (3)
C520.043 (4)0.032 (4)0.036 (5)0.005 (3)0.021 (4)0.001 (3)
C530.061 (6)0.036 (5)0.040 (5)0.013 (4)0.031 (4)0.006 (4)
C540.029 (4)0.069 (6)0.046 (5)0.022 (4)0.023 (4)0.015 (5)
C550.028 (4)0.087 (8)0.050 (6)0.012 (5)0.013 (4)0.004 (5)
C560.022 (4)0.071 (6)0.034 (5)0.008 (4)0.007 (3)0.009 (4)
C610.035 (4)0.024 (4)0.058 (6)0.009 (3)0.026 (4)0.004 (4)
C620.041 (5)0.045 (5)0.065 (7)0.021 (4)0.009 (5)0.004 (5)
Cl10.0428 (13)0.128 (3)0.0618 (17)0.0371 (15)0.0361 (12)0.0388 (17)
Geometric parameters (Å, º) top
N1—C21.338 (9)C52—C531.390 (11)
N1—C61.349 (9)C52—H520.9500
C2—N31.346 (9)C53—C541.367 (14)
C2—N211.365 (10)C53—H530.9500
N3—C41.336 (9)C54—C551.360 (14)
C4—N411.363 (9)C54—Cl11.745 (8)
C4—C51.427 (10)C55—C561.388 (12)
C5—C61.378 (10)C55—H550.9500
C5—C511.496 (10)C56—H560.9500
C6—C611.517 (10)C61—C621.514 (13)
N21—H2110.91 (11)C61—H61A0.9900
N21—H2120.86 (10)C61—H61B0.9900
N41—H4110.89 (2)C62—H62A0.9800
N41—H4120.88 (2)C62—H62B0.9800
C51—C561.379 (11)C62—H62C0.9800
C51—C521.385 (11)
C2—N1—C6115.5 (6)C53—C52—H52119.9
N1—C2—N3127.1 (6)C54—C53—C52120.2 (8)
N1—C2—N21117.3 (7)C54—C53—H53119.9
N3—C2—N21115.7 (7)C52—C53—H53119.9
C4—N3—C2116.1 (6)C55—C54—C53120.8 (8)
N3—C4—N41116.8 (6)C55—C54—Cl1119.0 (8)
N3—C4—C5122.3 (6)C53—C54—Cl1120.1 (7)
N41—C4—C5120.8 (6)C54—C55—C56118.7 (9)
C6—C5—C4115.4 (6)C54—C55—H55120.6
C6—C5—C51124.2 (6)C56—C55—H55120.6
C4—C5—C51120.4 (6)C51—C56—C55122.2 (9)
N1—C6—C5123.7 (7)C51—C56—H56118.9
N1—C6—C61114.5 (7)C55—C56—H56118.9
C5—C6—C61121.6 (6)C62—C61—C6110.5 (7)
C2—N21—H211118 (6)C62—C61—H61A109.5
C2—N21—H212120 (6)C6—C61—H61A109.5
H211—N21—H212114 (9)C62—C61—H61B109.5
C4—N41—H411114 (6)C6—C61—H61B109.5
C4—N41—H412123 (6)H61A—C61—H61B108.1
H411—N41—H412108 (8)C61—C62—H62A109.5
C56—C51—C52117.8 (7)C61—C62—H62B109.5
C56—C51—C5120.0 (7)H62A—C62—H62B109.5
C52—C51—C5122.2 (7)C61—C62—H62C109.5
C51—C52—C53120.3 (8)H62A—C62—H62C109.5
C51—C52—H52119.9H62B—C62—H62C109.5
C6—N1—C2—N31.0 (11)C6—C5—C51—C56102.0 (10)
C6—N1—C2—N21178.0 (7)C4—C5—C51—C5675.5 (10)
N1—C2—N3—C41.0 (11)C6—C5—C51—C5276.4 (10)
N21—C2—N3—C4178.0 (7)C4—C5—C51—C52106.1 (9)
C2—N3—C4—N41178.6 (6)C56—C51—C52—C530.5 (12)
C2—N3—C4—C50.8 (10)C5—C51—C52—C53177.9 (8)
N3—C4—C5—C60.6 (10)C51—C52—C53—C540.4 (13)
N41—C4—C5—C6178.3 (7)C52—C53—C54—C550.2 (14)
N3—C4—C5—C51177.1 (7)C52—C53—C54—Cl1179.2 (7)
N41—C4—C5—C510.6 (10)C53—C54—C55—C560.7 (15)
C2—N1—C6—C50.7 (11)Cl1—C54—C55—C56178.7 (8)
C2—N1—C6—C61176.3 (7)C52—C51—C56—C550.0 (14)
C4—C5—C6—N10.6 (11)C5—C51—C56—C55178.4 (9)
C51—C5—C6—N1177.0 (7)C54—C55—C56—C510.6 (16)
C4—C5—C6—C61175.8 (7)N1—C6—C61—C6278.7 (9)
C51—C5—C6—C611.8 (12)C5—C6—C61—C6297.0 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H211···N1i0.91 (11)2.14 (11)3.043 (10)172 (8)
N21—H212···N3ii0.86 (10)2.50 (11)3.339 (10)166 (8)
N41—H412···N3iii0.88 (2)2.17 (3)3.032 (8)167 (8)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+2, z+1.
(Ia) 2,4-diamino-5(4-chlorophenyl)-6-ethylpyrimidine dimethyl sulfoxide monosolvate top
Crystal data top
C12H13ClN4·C2H6OSF(000) = 688
Mr = 326.84Dx = 1.369 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7272 reflections
a = 13.5596 (9) Åθ = 3.7–26.0°
b = 7.7212 (4) ŵ = 0.38 mm1
c = 16.2870 (11) ÅT = 173 K
β = 111.609 (5)°Block, colourless
V = 1585.35 (17) Å30.50 × 0.40 × 0.30 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
2939 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ω scansθmax = 25.7°, θmin = 3.6°
Absorption correction: multi-scan
[MULABS (Spek, 2009; Blessing, 1995)]
h = 1612
Tmin = 0.834, Tmax = 0.895k = 98
7296 measured reflectionsl = 1919
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)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110 w = 1/[σ2(Fo2) + (0.0627P)2 + 0.6444P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
2939 reflectionsΔρmax = 0.30 e Å3
217 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.020 (2)
Crystal data top
C12H13ClN4·C2H6OSV = 1585.35 (17) Å3
Mr = 326.84Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.5596 (9) ŵ = 0.38 mm1
b = 7.7212 (4) ÅT = 173 K
c = 16.2870 (11) Å0.50 × 0.40 × 0.30 mm
β = 111.609 (5)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2939 independent reflections
Absorption correction: multi-scan
[MULABS (Spek, 2009; Blessing, 1995)]
2615 reflections with I > 2σ(I)
Tmin = 0.834, Tmax = 0.895Rint = 0.047
7296 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.30 e Å3
2939 reflectionsΔρmin = 0.25 e Å3
217 parameters
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*/UeqOcc. (<1)
N10.59331 (12)0.96779 (19)0.27418 (9)0.0220 (3)
C20.54315 (14)1.0490 (2)0.32031 (11)0.0208 (4)
N30.54644 (12)1.00771 (19)0.40151 (9)0.0221 (3)
C40.60824 (14)0.8725 (2)0.44101 (11)0.0213 (4)
C50.66741 (14)0.7791 (2)0.39949 (10)0.0200 (4)
C60.65485 (14)0.8323 (2)0.31493 (11)0.0200 (4)
N210.48311 (15)1.1879 (2)0.28079 (11)0.0308 (4)
H2110.4759 (19)1.208 (3)0.2277 (16)0.032 (6)*
H2120.446 (2)1.241 (4)0.3051 (17)0.043 (7)*
N410.61030 (15)0.8293 (2)0.52169 (10)0.0293 (4)
H4110.567 (2)0.879 (3)0.5396 (16)0.035 (6)*
H4120.640 (2)0.732 (4)0.5461 (16)0.037 (6)*
C510.73493 (14)0.6282 (2)0.44354 (10)0.0207 (4)
C520.83494 (15)0.6519 (2)0.50927 (12)0.0263 (4)
H520.85870.76600.52840.032*
C530.90030 (15)0.5126 (3)0.54714 (12)0.0281 (4)
H530.96810.53000.59200.034*
C540.86460 (15)0.3478 (2)0.51821 (11)0.0240 (4)
C550.76576 (16)0.3188 (2)0.45428 (12)0.0254 (4)
H550.74250.20450.43530.030*
C560.70096 (15)0.4602 (2)0.41813 (11)0.0240 (4)
H560.63200.44140.37520.029*
C610.70662 (14)0.7389 (2)0.25973 (11)0.0237 (4)
H61A0.76620.66750.29860.028*
H61B0.73560.82470.22940.028*
C620.62655 (16)0.6230 (3)0.19121 (11)0.0280 (4)
H62A0.66150.56380.15610.042*
H62B0.56810.69390.15230.042*
H62C0.59870.53690.22130.042*
Cl10.94680 (4)0.17022 (6)0.56355 (3)0.03477 (18)
O1X0.65500 (15)0.5785 (2)0.66513 (11)0.0447 (4)
S2X0.60153 (7)0.40852 (12)0.66242 (6)0.0311 (3)0.564 (2)
S2X'0.70407 (9)0.41757 (14)0.70965 (7)0.0291 (4)0.436 (2)
C3X0.6318 (2)0.3388 (3)0.77096 (15)0.0428 (5)
H3XA0.59630.41390.80010.064*0.564 (2)
H3XB0.70870.34420.80300.064*0.564 (2)
H3XC0.60740.21930.77070.064*0.564 (2)
H3XD0.63980.41760.82020.064*0.436 (2)
H3XE0.65840.22400.79420.064*0.436 (2)
H3XF0.55670.33040.73290.064*0.436 (2)
C4X0.6751 (2)0.2524 (3)0.62857 (15)0.0420 (5)
H4XA0.66640.27380.56700.063*0.564 (2)
H4XB0.64930.13610.63400.063*0.564 (2)
H4XC0.75040.26130.66610.063*0.564 (2)
H4XD0.71100.27840.58760.063*0.436 (2)
H4XE0.59840.24670.59590.063*0.436 (2)
H4XF0.70030.14100.65740.063*0.436 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0230 (7)0.0230 (8)0.0221 (7)0.0006 (6)0.0109 (6)0.0004 (6)
C20.0215 (9)0.0196 (8)0.0211 (8)0.0015 (7)0.0077 (7)0.0011 (6)
N30.0258 (8)0.0211 (7)0.0216 (7)0.0026 (6)0.0114 (6)0.0001 (6)
C40.0232 (9)0.0204 (8)0.0214 (8)0.0005 (7)0.0095 (7)0.0014 (6)
C50.0198 (8)0.0203 (8)0.0207 (8)0.0002 (7)0.0084 (6)0.0026 (6)
C60.0196 (8)0.0210 (8)0.0210 (8)0.0020 (7)0.0094 (6)0.0030 (6)
N210.0393 (10)0.0307 (9)0.0243 (8)0.0125 (8)0.0139 (7)0.0064 (7)
N410.0402 (10)0.0290 (9)0.0251 (8)0.0151 (8)0.0195 (7)0.0060 (7)
C510.0235 (9)0.0230 (9)0.0193 (7)0.0026 (7)0.0123 (7)0.0003 (6)
C520.0266 (9)0.0217 (9)0.0283 (9)0.0002 (7)0.0074 (7)0.0041 (7)
C530.0249 (9)0.0294 (10)0.0258 (9)0.0018 (8)0.0043 (7)0.0020 (7)
C540.0299 (10)0.0242 (9)0.0208 (8)0.0079 (7)0.0128 (7)0.0032 (6)
C550.0322 (10)0.0208 (9)0.0253 (8)0.0016 (8)0.0130 (7)0.0020 (7)
C560.0239 (9)0.0253 (9)0.0222 (8)0.0009 (7)0.0078 (7)0.0007 (7)
C610.0261 (9)0.0259 (9)0.0238 (8)0.0025 (7)0.0146 (7)0.0009 (7)
C620.0328 (10)0.0286 (9)0.0236 (8)0.0016 (8)0.0116 (8)0.0042 (7)
Cl10.0424 (3)0.0295 (3)0.0305 (3)0.0146 (2)0.0112 (2)0.00520 (18)
O1X0.0654 (11)0.0270 (8)0.0522 (9)0.0125 (7)0.0339 (8)0.0133 (7)
S2X0.0248 (5)0.0347 (5)0.0338 (5)0.0031 (4)0.0107 (4)0.0009 (3)
S2X'0.0283 (6)0.0236 (6)0.0388 (6)0.0011 (4)0.0165 (5)0.0017 (4)
C3X0.0582 (15)0.0386 (12)0.0420 (11)0.0001 (11)0.0307 (11)0.0036 (9)
C4X0.0536 (14)0.0348 (12)0.0468 (12)0.0014 (10)0.0293 (11)0.0073 (9)
Geometric parameters (Å, º) top
N1—C21.340 (2)C61—H61A0.9900
N1—C61.350 (2)C61—H61B0.9900
C2—N31.345 (2)C62—H62A0.9800
C2—N211.357 (2)C62—H62B0.9800
N3—C41.345 (2)C62—H62C0.9800
C4—N411.346 (2)O1X—S2X'1.4689 (18)
C4—C51.422 (2)O1X—S2X1.4922 (19)
C5—C61.386 (2)S2X—C3X1.746 (2)
C5—C511.492 (2)S2X—C4X1.777 (2)
C6—C611.512 (2)S2X—H3XF1.6009
N21—H2110.85 (2)S2X—H4XE1.6447
N21—H2120.85 (3)S2X'—C3X1.746 (2)
N41—H4110.84 (3)S2X'—C4X1.773 (2)
N41—H4120.88 (3)C3X—H3XA0.9800
C51—C561.388 (3)C3X—H3XB0.9800
C51—C521.396 (3)C3X—H3XC0.9800
C52—C531.386 (3)C3X—H3XD0.9800
C52—H520.9500C3X—H3XE0.9795
C53—C541.381 (3)C3X—H3XF0.9800
C53—H530.9500C4X—H4XA0.9800
C54—C551.379 (3)C4X—H4XB0.9800
C54—Cl11.7494 (18)C4X—H4XC0.9800
C55—C561.389 (3)C4X—H4XD0.9799
C55—H550.9500C4X—H4XE0.9799
C56—H560.9500C4X—H4XF0.9796
C61—C621.527 (3)
C2—N1—C6115.85 (14)O1X—S2X—H4XE125.6
N1—C2—N3126.91 (16)C3X—S2X—H4XE111.9
N1—C2—N21116.33 (15)H3XF—S2X—H4XE105.2
N3—C2—N21116.76 (16)O1X—S2X'—C3X109.23 (12)
C2—N3—C4116.32 (14)O1X—S2X'—C4X107.77 (12)
N41—C4—N3116.42 (16)C3X—S2X'—C4X99.13 (12)
N41—C4—C5121.73 (16)S2X'—C3X—H3XA123.4
N3—C4—C5121.85 (15)S2X—C3X—H3XA109.5
C6—C5—C4115.95 (16)S2X'—C3X—H3XB65.1
C6—C5—C51122.58 (15)S2X—C3X—H3XB109.5
C4—C5—C51121.42 (14)H3XA—C3X—H3XB109.5
N1—C6—C5123.08 (15)S2X'—C3X—H3XC125.8
N1—C6—C61114.55 (14)S2X—C3X—H3XC109.5
C5—C6—C61122.35 (16)H3XA—C3X—H3XC109.5
C2—N21—H211117.0 (16)H3XB—C3X—H3XC109.5
C2—N21—H212120.8 (18)S2X'—C3X—H3XD109.6
H211—N21—H212121 (2)S2X—C3X—H3XD123.4
C4—N41—H411117.5 (17)H3XB—C3X—H3XD76.3
C4—N41—H412119.7 (16)H3XC—C3X—H3XD121.5
H411—N41—H412120 (2)S2X'—C3X—H3XE109.4
C56—C51—C52118.23 (16)S2X—C3X—H3XE125.9
C56—C51—C5120.59 (15)H3XA—C3X—H3XE121.7
C52—C51—C5121.15 (16)H3XB—C3X—H3XE70.4
C53—C52—C51121.39 (17)H3XD—C3X—H3XE109.4
C53—C52—H52119.3S2X'—C3X—H3XF109.4
C51—C52—H52119.3S2X—C3X—H3XF65.0
C54—C53—C52118.50 (17)H3XA—C3X—H3XF76.4
C54—C53—H53120.8H3XB—C3X—H3XF173.4
C52—C53—H53120.8H3XC—C3X—H3XF70.4
C55—C54—C53121.85 (17)H3XD—C3X—H3XF109.5
C55—C54—Cl1118.87 (14)H3XE—C3X—H3XF109.5
C53—C54—Cl1119.29 (14)S2X'—C4X—H4XA123.5
C54—C55—C56118.70 (17)S2X—C4X—H4XA109.5
C54—C55—H55120.7S2X'—C4X—H4XB125.5
C56—C55—H55120.7S2X—C4X—H4XB109.5
C55—C56—C51121.30 (17)H4XA—C4X—H4XB109.5
C55—C56—H56119.4S2X'—C4X—H4XC65.8
C51—C56—H56119.4S2X—C4X—H4XC109.5
C6—C61—C62110.68 (15)H4XA—C4X—H4XC109.5
C6—C61—H61A109.5H4XB—C4X—H4XC109.5
C62—C61—H61A109.5S2X'—C4X—H4XD109.3
C6—C61—H61B109.5S2X—C4X—H4XD123.2
C62—C61—H61B109.5H4XB—C4X—H4XD122.2
H61A—C61—H61B108.1H4XC—C4X—H4XD75.4
C61—C62—H62A109.5S2X'—C4X—H4XE109.7
C61—C62—H62B109.5S2X—C4X—H4XE66.1
H62A—C62—H62B109.5H4XA—C4X—H4XE75.3
C61—C62—H62C109.5H4XB—C4X—H4XE70.3
H62A—C62—H62C109.5H4XC—C4X—H4XE174.6
H62B—C62—H62C109.5H4XD—C4X—H4XE109.4
S2X'—O1X—S2X52.93 (8)S2X'—C4X—H4XF109.4
O1X—S2X—C3X108.09 (12)S2X—C4X—H4XF125.7
O1X—S2X—C4X106.47 (11)H4XA—C4X—H4XF121.9
C3X—S2X—C4X98.94 (12)H4XC—C4X—H4XF70.3
O1X—S2X—H3XF128.2H4XD—C4X—H4XF109.5
C4X—S2X—H3XF111.8H4XE—C4X—H4XF109.5
C6—N1—C2—N31.2 (3)C51—C52—C53—C540.2 (3)
C6—N1—C2—N21178.47 (16)C52—C53—C54—C551.1 (3)
N1—C2—N3—C41.3 (3)C52—C53—C54—Cl1178.77 (14)
N21—C2—N3—C4178.39 (16)C53—C54—C55—C560.2 (3)
C2—N3—C4—N41178.96 (16)Cl1—C54—C55—C56179.69 (13)
C2—N3—C4—C50.4 (3)C54—C55—C56—C511.6 (3)
N41—C4—C5—C6177.37 (17)C52—C51—C56—C552.5 (3)
N3—C4—C5—C62.0 (3)C5—C51—C56—C55175.62 (16)
N41—C4—C5—C510.1 (3)N1—C6—C61—C6276.67 (19)
N3—C4—C5—C51179.41 (16)C5—C6—C61—C62101.5 (2)
C2—N1—C6—C50.6 (2)S2X'—O1X—S2X—C3X51.88 (11)
C2—N1—C6—C61177.54 (15)S2X'—O1X—S2X—C4X53.62 (11)
C4—C5—C6—N12.1 (3)S2X—O1X—S2X'—C3X52.39 (12)
C51—C5—C6—N1179.49 (16)S2X—O1X—S2X'—C4X54.37 (11)
C4—C5—C6—C61175.92 (16)O1X—S2X'—C3X—S2X50.52 (11)
C51—C5—C6—C611.5 (3)C4X—S2X'—C3X—S2X62.03 (11)
C6—C5—C51—C5674.1 (2)O1X—S2X—C3X—S2X'49.00 (10)
C4—C5—C51—C56103.2 (2)C4X—S2X—C3X—S2X'61.70 (11)
C6—C5—C51—C52103.9 (2)O1X—S2X'—C4X—S2X52.08 (11)
C4—C5—C51—C5278.8 (2)C3X—S2X'—C4X—S2X61.61 (11)
C56—C51—C52—C531.5 (3)O1X—S2X—C4X—S2X'50.45 (10)
C5—C51—C52—C53176.56 (16)C3X—S2X—C4X—S2X'61.53 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H211···Cl1i0.85 (2)2.72 (3)3.5607 (18)170 (2)
N21—H212···O1Xii0.85 (3)2.14 (3)2.958 (2)164 (2)
N41—H411···N3ii0.84 (3)2.26 (3)3.102 (2)174 (2)
N41—H412···O1X0.88 (3)2.22 (3)2.921 (2)137 (2)
Symmetry codes: (i) x1/2, y+3/2, z1/2; (ii) x+1, y+2, z+1.
(Ib) 2,4-diamino-5(4-chlorophenyl)-6-ethylpyrimidine N-methylpyrrolidin-2-one monosolvate top
Crystal data top
C12H13ClN4·C5H9NOZ = 4
Mr = 347.85F(000) = 736
Triclinic, P1Dx = 1.269 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.5221 (14) ÅCell parameters from 5376 reflections
b = 10.8372 (15) Åθ = 3.5–25.8°
c = 18.650 (2) ŵ = 0.22 mm1
α = 101.937 (11)°T = 173 K
β = 99.555 (11)°Block, colourless
γ = 98.892 (12)°0.60 × 0.60 × 0.20 mm
V = 1820.9 (4) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
3240 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.107
Graphite monochromatorθmax = 25.6°, θmin = 3.5°
ω scansh = 1111
16150 measured reflectionsk = 1313
6800 independent reflectionsl = 2221
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.079Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 0.93 w = 1/[σ2(Fo2) + (0.1138P)2]
where P = (Fo2 + 2Fc2)/3
6800 reflections(Δ/σ)max < 0.001
486 parametersΔρmax = 0.83 e Å3
36 restraintsΔρmin = 0.46 e Å3
Crystal data top
C12H13ClN4·C5H9NOγ = 98.892 (12)°
Mr = 347.85V = 1820.9 (4) Å3
Triclinic, P1Z = 4
a = 9.5221 (14) ÅMo Kα radiation
b = 10.8372 (15) ŵ = 0.22 mm1
c = 18.650 (2) ÅT = 173 K
α = 101.937 (11)°0.60 × 0.60 × 0.20 mm
β = 99.555 (11)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3240 reflections with I > 2σ(I)
16150 measured reflectionsRint = 0.107
6800 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.07936 restraints
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.83 e Å3
6800 reflectionsΔρmin = 0.46 e Å3
486 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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*/UeqOcc. (<1)
N1A0.8422 (4)0.8000 (3)0.74349 (18)0.0318 (8)
C2A0.8248 (4)0.6952 (4)0.6866 (2)0.0273 (9)
N3A0.8144 (4)0.5720 (3)0.69285 (17)0.0306 (8)
C4A0.8135 (5)0.5518 (4)0.7614 (2)0.0285 (9)
C5A0.8248 (5)0.6551 (4)0.8251 (2)0.0294 (9)
C6A0.8409 (5)0.7778 (4)0.8122 (2)0.0300 (10)
N21A0.8202 (5)0.7161 (4)0.61758 (19)0.0373 (9)
H2110.786 (5)0.652 (3)0.5777 (18)0.045*
H2120.816 (5)0.792 (3)0.607 (2)0.045*
N41A0.8014 (5)0.4286 (4)0.7674 (2)0.0403 (10)
H4110.794 (5)0.364 (5)0.728 (3)0.048*
H4120.814 (5)0.408 (5)0.811 (3)0.048*
C51A0.8164 (5)0.6262 (4)0.8996 (2)0.0320 (10)
C52A0.6931 (6)0.5503 (5)0.9095 (3)0.0426 (12)
H52A0.61070.52210.86950.051*
C53A0.6867 (6)0.5144 (5)0.9770 (3)0.0512 (13)
H53A0.60210.46110.98260.061*
C54A0.8066 (7)0.5582 (5)1.0354 (3)0.0531 (15)
C55A0.9289 (7)0.6353 (5)1.0286 (3)0.0549 (15)
H55A1.00920.66621.06960.066*
C56A0.9342 (6)0.6680 (5)0.9603 (2)0.0430 (12)
H56A1.02000.72010.95500.052*
C61A0.8580 (6)0.8984 (4)0.8733 (2)0.0415 (12)
H61A0.83410.87410.91880.050*
H61B0.78850.95110.85690.050*
C62A1.0118 (7)0.9788 (5)0.8925 (3)0.0609 (16)
H62A1.01781.05560.93220.091*
H62B1.03531.00460.84790.091*
H62C1.08090.92760.90970.091*
ClA0.7993 (2)0.50953 (18)1.11881 (8)0.0915 (7)
N1B0.8090 (5)0.0143 (4)0.5896 (2)0.0481 (11)
C2B0.8093 (5)0.0859 (4)0.6457 (2)0.0337 (10)
N3B0.7794 (4)0.2007 (3)0.63832 (18)0.0305 (8)
C4B0.7436 (5)0.2149 (4)0.5680 (2)0.0296 (9)
C5B0.7393 (5)0.1158 (4)0.5041 (2)0.0341 (10)
C6B0.7717 (7)0.0015 (5)0.5187 (2)0.0529 (14)
N21B0.8480 (5)0.0715 (4)0.7163 (2)0.0452 (11)
H2130.823 (5)0.121 (5)0.756 (3)0.054*
H2140.844 (6)0.004 (6)0.726 (3)0.054*
N41B0.7135 (4)0.3304 (3)0.56111 (19)0.0352 (9)
H4130.745 (5)0.395 (3)0.6012 (18)0.042*
H4140.705 (5)0.349 (4)0.5172 (15)0.042*
C51B0.7018 (5)0.1346 (4)0.4265 (2)0.0347 (10)
C52B0.5585 (6)0.1304 (5)0.3934 (3)0.0523 (14)
H52B0.48430.11670.42090.063*
C53B0.5214 (6)0.1458 (6)0.3206 (3)0.0554 (14)
H53B0.42350.14480.29910.066*
C54B0.6280 (6)0.1624 (5)0.2809 (2)0.0456 (13)
C55B0.7705 (6)0.1702 (6)0.3120 (3)0.0549 (14)
H55B0.84400.18590.28430.066*
C56B0.8065 (6)0.1550 (5)0.3846 (2)0.0473 (13)
H56B0.90530.15870.40590.057*
C61B0.7714 (10)0.1100 (6)0.4582 (3)0.094 (3)
H6110.81020.07820.41790.112*0.608 (13)
H6120.83850.16200.47800.112*0.608 (13)
H6130.73240.18580.47590.112*0.392 (13)
H6140.69550.10550.41610.112*0.392 (13)
C62B0.6368 (9)0.1896 (9)0.4271 (5)0.058 (3)0.608 (13)
H6210.64720.26060.38750.087*0.608 (13)
H6220.56980.14010.40590.087*0.608 (13)
H6230.59830.22430.46600.087*0.608 (13)
C62C0.8851 (14)0.1454 (15)0.4259 (8)0.061 (5)*0.392 (13)
H6240.84880.22470.38650.092*0.392 (13)
H6250.96030.15990.46430.092*0.392 (13)
H6260.92630.07670.40420.092*0.392 (13)
ClB0.58071 (19)0.17874 (15)0.18833 (7)0.0703 (5)
O2Y0.7455 (5)0.2152 (4)0.85500 (19)0.0562 (10)
C5Y0.3915 (7)0.1569 (7)0.8901 (5)0.090 (2)
H510.35520.21600.92750.108*0.716 (13)
H520.34680.06730.88840.108*0.716 (13)
H530.32570.21930.89320.108*0.284 (13)
H540.33270.06990.86640.108*0.284 (13)
N1Y0.5493 (7)0.1759 (6)0.9093 (4)0.061 (3)0.716 (13)
C2Y0.6130 (9)0.1971 (7)0.8524 (5)0.048 (2)0.716 (13)
C3Y0.4956 (14)0.1923 (16)0.7851 (8)0.104 (8)0.716 (13)
H310.51540.27030.76570.125*0.716 (13)
H320.49020.11570.74440.125*0.716 (13)
C4Y0.3559 (12)0.1852 (12)0.8142 (6)0.104 (5)0.716 (13)
H410.32220.26790.81840.125*0.716 (13)
H420.27880.11610.78030.125*0.716 (13)
C1Y0.631 (2)0.1630 (18)0.9795 (7)0.105 (6)0.716 (13)
H110.73490.18160.97980.157*0.716 (13)
H120.60280.07500.98500.157*0.716 (13)
H130.60940.22371.02120.157*0.716 (13)
N1Y'0.503 (3)0.192 (2)0.8451 (13)0.077 (8)*0.284 (13)
C2Y'0.634 (3)0.198 (3)0.8831 (14)0.051 (9)*0.284 (13)
C3Y'0.624 (4)0.162 (4)0.958 (2)0.057 (9)*0.284 (13)
H330.64870.07700.95810.069*0.284 (13)
H340.68740.22761.00060.069*0.284 (13)
C4Y'0.465 (3)0.160 (3)0.9590 (16)0.094 (10)*0.284 (13)
H430.42410.08350.97540.113*0.284 (13)
H440.45510.23770.99500.113*0.284 (13)
C1Y'0.479 (4)0.211 (4)0.7794 (16)0.058 (10)*0.284 (13)
H140.41360.27290.77760.087*0.284 (13)
H150.43320.13010.74310.087*0.284 (13)
H160.57050.24640.76710.087*0.284 (13)
N1X0.6761 (7)0.5058 (5)0.3552 (3)0.0945 (19)
C2X0.7720 (8)0.5210 (5)0.4135 (3)0.082 (2)
C3X0.9232 (7)0.5505 (11)0.3971 (5)0.137 (4)
H3X10.97730.48100.40290.164*
H3X20.98020.63320.42960.164*
C4X0.8861 (12)0.5579 (19)0.3151 (6)0.222 (9)
H4X10.92200.64610.31050.266*
H4X20.93290.49770.28400.266*
C1X0.5221 (7)0.4818 (9)0.3482 (6)0.121 (3)
H1X10.49740.45150.39140.181*
H1X20.47680.41610.30210.181*
H1X30.48640.56140.34630.181*
C5X0.7232 (10)0.5224 (6)0.2889 (3)0.099 (3)
H5X10.68410.59200.27030.119*
H5X20.69400.44190.24900.119*
O2X0.7427 (7)0.5168 (4)0.4772 (2)0.113 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.042 (2)0.0207 (19)0.0332 (18)0.0109 (17)0.0013 (15)0.0087 (15)
C2A0.026 (2)0.025 (2)0.032 (2)0.0057 (18)0.0041 (17)0.0090 (17)
N3A0.046 (2)0.0176 (19)0.0284 (16)0.0085 (16)0.0032 (15)0.0083 (13)
C4A0.035 (2)0.018 (2)0.030 (2)0.0056 (19)0.0001 (17)0.0050 (16)
C5A0.037 (3)0.025 (2)0.0258 (19)0.0094 (19)0.0017 (17)0.0066 (16)
C6A0.039 (3)0.020 (2)0.030 (2)0.0092 (19)0.0022 (18)0.0049 (16)
N21A0.059 (3)0.024 (2)0.0299 (18)0.008 (2)0.0100 (17)0.0074 (15)
N41A0.072 (3)0.019 (2)0.0307 (18)0.0114 (19)0.0065 (19)0.0078 (16)
C51A0.050 (3)0.020 (2)0.027 (2)0.013 (2)0.0069 (19)0.0061 (16)
C52A0.049 (3)0.042 (3)0.041 (2)0.013 (2)0.013 (2)0.013 (2)
C53A0.070 (4)0.044 (3)0.051 (3)0.015 (3)0.034 (3)0.016 (2)
C54A0.098 (5)0.038 (3)0.037 (3)0.034 (3)0.028 (3)0.014 (2)
C55A0.087 (4)0.043 (3)0.034 (2)0.025 (3)0.000 (3)0.008 (2)
C56A0.059 (3)0.031 (3)0.039 (2)0.009 (2)0.004 (2)0.011 (2)
C61A0.069 (3)0.022 (2)0.030 (2)0.011 (2)0.005 (2)0.0014 (18)
C62A0.087 (4)0.031 (3)0.047 (3)0.005 (3)0.009 (3)0.001 (2)
ClA0.1643 (19)0.0935 (13)0.0467 (8)0.0556 (13)0.0504 (10)0.0379 (8)
N1B0.089 (3)0.029 (2)0.037 (2)0.027 (2)0.022 (2)0.0133 (16)
C2B0.050 (3)0.020 (2)0.033 (2)0.008 (2)0.0107 (19)0.0082 (17)
N3B0.039 (2)0.0210 (19)0.0320 (17)0.0060 (16)0.0056 (15)0.0080 (14)
C4B0.035 (3)0.019 (2)0.034 (2)0.0030 (19)0.0080 (18)0.0058 (17)
C5B0.052 (3)0.023 (2)0.031 (2)0.010 (2)0.0145 (19)0.0086 (17)
C6B0.103 (5)0.032 (3)0.037 (2)0.028 (3)0.029 (3)0.017 (2)
N21B0.082 (3)0.027 (2)0.0322 (19)0.016 (2)0.0138 (19)0.0128 (17)
N41B0.053 (3)0.021 (2)0.0316 (18)0.0122 (18)0.0043 (17)0.0060 (15)
C51B0.052 (3)0.025 (2)0.031 (2)0.012 (2)0.013 (2)0.0076 (17)
C52B0.054 (3)0.065 (4)0.051 (3)0.029 (3)0.021 (2)0.023 (3)
C53B0.054 (3)0.066 (4)0.054 (3)0.029 (3)0.008 (3)0.022 (3)
C54B0.070 (4)0.033 (3)0.031 (2)0.010 (3)0.002 (2)0.0092 (19)
C55B0.060 (4)0.065 (4)0.038 (3)0.003 (3)0.011 (2)0.019 (2)
C56B0.046 (3)0.059 (4)0.038 (2)0.002 (3)0.009 (2)0.020 (2)
C61B0.219 (10)0.044 (4)0.043 (3)0.063 (5)0.041 (5)0.028 (3)
C62B0.058 (7)0.038 (6)0.074 (6)0.018 (5)0.016 (5)0.004 (5)
ClB0.1058 (13)0.0658 (10)0.0360 (6)0.0166 (9)0.0017 (7)0.0178 (6)
O2Y0.066 (3)0.050 (2)0.055 (2)0.012 (2)0.0127 (19)0.0184 (17)
C5Y0.064 (5)0.057 (4)0.157 (8)0.017 (4)0.047 (5)0.022 (5)
N1Y0.069 (5)0.048 (4)0.070 (5)0.004 (4)0.031 (4)0.017 (3)
C2Y0.069 (8)0.023 (4)0.051 (6)0.008 (4)0.016 (5)0.005 (4)
C3Y0.072 (10)0.036 (7)0.19 (2)0.016 (6)0.004 (9)0.004 (7)
C4Y0.081 (9)0.080 (8)0.141 (11)0.014 (6)0.016 (7)0.033 (7)
C1Y0.139 (13)0.111 (11)0.067 (9)0.015 (8)0.020 (9)0.033 (9)
N1X0.131 (6)0.052 (4)0.105 (5)0.025 (4)0.032 (4)0.020 (3)
C2X0.139 (7)0.021 (3)0.066 (4)0.009 (3)0.031 (4)0.011 (3)
C3X0.036 (4)0.178 (11)0.168 (9)0.010 (5)0.019 (5)0.010 (8)
C4X0.138 (11)0.45 (3)0.161 (11)0.106 (14)0.066 (9)0.191 (15)
C1X0.045 (4)0.122 (8)0.190 (9)0.033 (5)0.028 (5)0.009 (6)
C5X0.204 (10)0.052 (4)0.039 (3)0.003 (5)0.059 (4)0.001 (3)
O2X0.258 (7)0.045 (3)0.034 (2)0.012 (3)0.036 (3)0.0170 (18)
Geometric parameters (Å, º) top
N1A—C2A1.352 (5)C61B—H6120.9900
N1A—C6A1.354 (5)C61B—H6130.9899
C2A—N21A1.347 (5)C61B—H6140.9901
C2A—N3A1.354 (5)C62B—H6131.1648
N3A—C4A1.342 (5)C62B—H6141.0701
C4A—N41A1.352 (5)C62B—H6210.9800
C4A—C5A1.431 (5)C62B—H6220.9800
C5A—C6A1.389 (6)C62B—H6230.9800
C5A—C51A1.498 (5)C62C—H6240.9800
C6A—C61A1.513 (5)C62C—H6250.9800
N21A—H2110.88 (2)C62C—H6260.9800
N21A—H2120.90 (2)O2Y—C2Y1.238 (7)
N41A—H4110.89 (5)O2Y—C2Y'1.26 (3)
N41A—H4120.87 (5)C5Y—C4Y'1.35 (3)
C51A—C52A1.389 (7)C5Y—N1Y1.457 (7)
C51A—C56A1.398 (6)C5Y—C4Y1.505 (8)
C52A—C53A1.399 (6)C5Y—N1Y'1.51 (2)
C52A—H52A0.9500C5Y—H510.9900
C53A—C54A1.386 (8)C5Y—H520.9900
C53A—H53A0.9500C5Y—H530.9900
C54A—C55A1.366 (8)C5Y—H540.9900
C54A—ClA1.751 (5)N1Y—C2Y1.349 (8)
C55A—C56A1.397 (7)N1Y—C1Y1.452 (9)
C55A—H55A0.9500C2Y—C3Y1.521 (10)
C56A—H56A0.9500C3Y—C4Y1.516 (10)
C61A—C62A1.527 (8)C3Y—H310.9900
C61A—H61A0.9900C3Y—H320.9900
C61A—H61B0.9900C4Y—H410.9900
C62A—H62A0.9800C4Y—H420.9900
C62A—H62B0.9800C1Y—H110.9800
C62A—H62C0.9800C1Y—H120.9800
N1B—C2B1.343 (5)C1Y—H130.9800
N1B—C6B1.363 (6)N1Y'—C1Y'1.28 (4)
C2B—N3B1.348 (5)N1Y'—C2Y'1.31 (4)
C2B—N21B1.353 (5)C2Y'—C3Y'1.54 (4)
N3B—C4B1.346 (5)C3Y'—C4Y'1.51 (5)
C4B—N41B1.353 (5)C3Y'—H330.9900
C4B—C5B1.420 (5)C3Y'—H340.9900
C5B—C6B1.391 (6)C4Y'—H430.9900
C5B—C51B1.496 (6)C4Y'—H440.9900
C6B—C61B1.473 (7)C1Y'—H140.9800
N21B—H2130.91 (5)C1Y'—H150.9800
N21B—H2140.87 (6)C1Y'—H160.9800
N41B—H4130.89 (2)N1X—C2X1.263 (6)
N41B—H4140.88 (2)N1X—C5X1.418 (6)
C51B—C56B1.384 (6)N1X—C1X1.428 (7)
C51B—C52B1.390 (7)C2X—O2X1.272 (6)
C52B—C53B1.397 (7)C2X—C3X1.521 (7)
C52B—H52B0.9500C3X—C4X1.533 (8)
C53B—C54B1.362 (7)C3X—H3X10.9900
C53B—H53B0.9500C3X—H3X20.9900
C54B—C55B1.367 (7)C4X—C5X1.510 (8)
C54B—ClB1.764 (4)C4X—H4X10.9900
C55B—C56B1.391 (6)C4X—H4X20.9900
C55B—H55B0.9500C1X—H1X10.9800
C56B—H56B0.9500C1X—H1X20.9800
C61B—C62B1.389 (8)C1X—H1X30.9800
C61B—C62C1.389 (9)C5X—H5X10.9900
C61B—H6110.9900C5X—H5X20.9900
C2A—N1A—C6A116.3 (3)C61B—C62B—H622109.5
N21A—C2A—N1A116.7 (4)H613—C62B—H622144.7
N21A—C2A—N3A117.2 (4)H614—C62B—H62269.4
N1A—C2A—N3A126.0 (3)H621—C62B—H622109.5
C4A—N3A—C2A116.7 (3)C61B—C62B—H623109.5
N3A—C4A—N41A116.7 (3)H613—C62B—H62370.8
N3A—C4A—C5A121.9 (4)H614—C62B—H623143.7
N41A—C4A—C5A121.4 (4)H621—C62B—H623109.5
C6A—C5A—C4A116.1 (3)H622—C62B—H623109.5
C6A—C5A—C51A124.4 (3)C61B—C62C—H624109.5
C4A—C5A—C51A119.5 (4)C61B—C62C—H625109.5
N1A—C6A—C5A122.8 (3)H624—C62C—H625109.5
N1A—C6A—C61A113.9 (4)C61B—C62C—H626109.5
C5A—C6A—C61A123.3 (4)H624—C62C—H626109.5
C2A—N21A—H211120 (3)H625—C62C—H626109.5
C2A—N21A—H212124 (3)C4Y'—C5Y—N1Y57.0 (13)
H211—N21A—H212112 (4)C4Y'—C5Y—C4Y160.4 (15)
C4A—N41A—H411121 (3)N1Y—C5Y—C4Y106.0 (6)
C4A—N41A—H412122 (3)C4Y'—C5Y—N1Y'106.8 (17)
H411—N41A—H412116 (5)N1Y—C5Y—N1Y'50.2 (10)
C52A—C51A—C56A117.4 (4)C4Y—C5Y—N1Y'55.8 (11)
C52A—C51A—C5A120.8 (4)C4Y'—C5Y—H5171.4
C56A—C51A—C5A121.7 (4)N1Y—C5Y—H51110.5
C51A—C52A—C53A121.8 (5)C4Y—C5Y—H51110.5
C51A—C52A—H52A119.1N1Y'—C5Y—H51127.6
C53A—C52A—H52A119.1C4Y'—C5Y—H5286.3
C54A—C53A—C52A118.5 (5)N1Y—C5Y—H52110.5
C54A—C53A—H53A120.7C4Y—C5Y—H52110.5
C52A—C53A—H53A120.7N1Y'—C5Y—H52123.6
C55A—C54A—C53A121.6 (5)H51—C5Y—H52108.7
C55A—C54A—ClA120.2 (4)C4Y'—C5Y—H53110.4
C53A—C54A—ClA118.2 (5)N1Y—C5Y—H53131.1
C54A—C55A—C56A119.0 (5)C4Y—C5Y—H5372.3
C54A—C55A—H55A120.5N1Y'—C5Y—H53110.4
C56A—C55A—H55A120.5H52—C5Y—H53115.7
C55A—C56A—C51A121.7 (5)C4Y'—C5Y—H54110.4
C55A—C56A—H56A119.2N1Y—C5Y—H54120.2
C51A—C56A—H56A119.2C4Y—C5Y—H5486.1
C6A—C61A—C62A112.3 (4)N1Y'—C5Y—H54110.4
C6A—C61A—H61A109.1H51—C5Y—H54119.3
C62A—C61A—H61A109.1H53—C5Y—H54108.6
C6A—C61A—H61B109.1C2Y—N1Y—C1Y122.6 (10)
C62A—C61A—H61B109.1C2Y—N1Y—C5Y112.8 (6)
H61A—C61A—H61B107.9C1Y—N1Y—C5Y124.4 (9)
C61A—C62A—H62A109.5O2Y—C2Y—N1Y124.8 (9)
C61A—C62A—H62B109.5O2Y—C2Y—C3Y126.3 (8)
H62A—C62A—H62B109.5N1Y—C2Y—C3Y108.9 (8)
C61A—C62A—H62C109.5C4Y—C3Y—C2Y104.9 (9)
H62A—C62A—H62C109.5C4Y—C3Y—H31110.8
H62B—C62A—H62C109.5C2Y—C3Y—H31110.8
C2B—N1B—C6B116.5 (4)C4Y—C3Y—H32110.8
N1B—C2B—N3B126.0 (4)C2Y—C3Y—H32110.8
N1B—C2B—N21B116.9 (4)H31—C3Y—H32108.8
N3B—C2B—N21B117.1 (4)C5Y—C4Y—C3Y105.8 (8)
C4B—N3B—C2B116.7 (3)C5Y—C4Y—H41110.6
N3B—C4B—N41B116.2 (3)C3Y—C4Y—H41110.6
N3B—C4B—C5B122.5 (4)C5Y—C4Y—H42110.6
N41B—C4B—C5B121.3 (4)C3Y—C4Y—H42110.6
C6B—C5B—C4B115.6 (4)H41—C4Y—H42108.7
C6B—C5B—C51B122.9 (4)C1Y'—N1Y'—C2Y'123 (3)
C4B—C5B—C51B121.5 (4)C1Y'—N1Y'—C5Y127 (3)
N1B—C6B—C5B122.7 (4)C2Y'—N1Y'—C5Y110 (2)
N1B—C6B—C61B115.4 (4)O2Y—C2Y'—N1Y'122 (2)
C5B—C6B—C61B121.9 (4)O2Y—C2Y'—C3Y'128 (2)
C2B—N21B—H213122 (3)N1Y'—C2Y'—C3Y'110 (3)
C2B—N21B—H214122 (3)C4Y'—C3Y'—C2Y'101 (3)
H213—N21B—H214105 (5)C4Y'—C3Y'—H33111.5
C4B—N41B—H413117 (3)C2Y'—C3Y'—H33111.5
C4B—N41B—H414120 (3)C4Y'—C3Y'—H34111.5
H413—N41B—H414117 (4)C2Y'—C3Y'—H34111.5
C56B—C51B—C52B117.6 (4)H33—C3Y'—H34109.3
C56B—C51B—C5B121.8 (4)C5Y—C4Y'—C3Y'110 (2)
C52B—C51B—C5B120.6 (4)C5Y—C4Y'—H43109.7
C51B—C52B—C53B121.2 (5)C3Y'—C4Y'—H43109.7
C51B—C52B—H52B119.4C5Y—C4Y'—H44109.7
C53B—C52B—H52B119.4C3Y'—C4Y'—H44109.7
C54B—C53B—C52B119.0 (5)H43—C4Y'—H44108.2
C54B—C53B—H53B120.5N1Y'—C1Y'—H14109.5
C52B—C53B—H53B120.5N1Y'—C1Y'—H15109.5
C53B—C54B—C55B121.5 (4)H14—C1Y'—H15109.5
C53B—C54B—ClB119.0 (4)N1Y'—C1Y'—H16109.5
C55B—C54B—ClB119.4 (4)H14—C1Y'—H16109.5
C54B—C55B—C56B119.0 (5)H15—C1Y'—H16109.5
C54B—C55B—H55B120.5C2X—N1X—C5X117.8 (6)
C56B—C55B—H55B120.5C2X—N1X—C1X127.7 (7)
C51B—C56B—C55B121.5 (5)C5X—N1X—C1X114.4 (7)
C51B—C56B—H56B119.2N1X—C2X—O2X123.3 (7)
C55B—C56B—H56B119.2N1X—C2X—C3X110.6 (6)
C62B—C61B—C62C115.1 (8)O2X—C2X—C3X126.0 (6)
C62B—C61B—C6B115.3 (7)C2X—C3X—C4X100.8 (6)
C62C—C61B—C6B129.6 (9)C2X—C3X—H3X1111.6
C62B—C61B—H611108.5C4X—C3X—H3X1111.6
C62C—C61B—H61152.4C2X—C3X—H3X2111.6
C6B—C61B—H611108.5C4X—C3X—H3X2111.6
C62B—C61B—H612108.5H3X1—C3X—H3X2109.4
C62C—C61B—H61255.8C5X—C4X—C3X108.3 (7)
C6B—C61B—H612108.5C5X—C4X—H4X1110.0
H611—C61B—H612107.5C3X—C4X—H4X1110.0
C62B—C61B—H61355.6C5X—C4X—H4X2110.0
C62C—C61B—H613104.4C3X—C4X—H4X2110.0
C6B—C61B—H613104.8H4X1—C4X—H4X2108.4
H611—C61B—H613146.7N1X—C1X—H1X1109.5
H612—C61B—H61360.3N1X—C1X—H1X2109.5
C62B—C61B—H61450.1H1X1—C1X—H1X2109.5
C62C—C61B—H614105.5N1X—C1X—H1X3109.5
C6B—C61B—H614104.8H1X1—C1X—H1X3109.5
H611—C61B—H61466.1H1X2—C1X—H1X3109.5
H612—C61B—H614146.2N1X—C5X—C4X102.2 (6)
H613—C61B—H614105.7N1X—C5X—H5X1111.3
C61B—C62B—H61445.2C4X—C5X—H5X1111.3
H613—C62B—H61489.8N1X—C5X—H5X2111.3
C61B—C62B—H621109.5C4X—C5X—H5X2111.3
H613—C62B—H621103.1H5X1—C5X—H5X2109.2
H614—C62B—H621104.5
C6A—N1A—C2A—N21A177.5 (4)C52B—C53B—C54B—ClB178.8 (4)
C6A—N1A—C2A—N3A3.9 (6)C53B—C54B—C55B—C56B3.0 (8)
N21A—C2A—N3A—C4A177.5 (4)ClB—C54B—C55B—C56B178.9 (4)
N1A—C2A—N3A—C4A3.8 (6)C52B—C51B—C56B—C55B0.3 (7)
C2A—N3A—C4A—N41A179.3 (4)C5B—C51B—C56B—C55B178.9 (5)
C2A—N3A—C4A—C5A0.7 (6)C54B—C55B—C56B—C51B1.3 (8)
N3A—C4A—C5A—C6A1.8 (6)N1B—C6B—C61B—C62B96.8 (8)
N41A—C4A—C5A—C6A178.2 (4)C5B—C6B—C61B—C62B84.7 (8)
N3A—C4A—C5A—C51A177.2 (4)N1B—C6B—C61B—C62C85.5 (10)
N41A—C4A—C5A—C51A2.8 (6)C5B—C6B—C61B—C62C93.1 (11)
C2A—N1A—C6A—C5A0.9 (6)C4Y'—C5Y—N1Y—C2Y176.4 (17)
C2A—N1A—C6A—C61A178.9 (4)C4Y—C5Y—N1Y—C2Y7.2 (9)
C4A—C5A—C6A—N1A1.8 (6)N1Y'—C5Y—N1Y—C2Y4.6 (13)
C51A—C5A—C6A—N1A177.3 (4)C4Y'—C5Y—N1Y—C1Y8.6 (19)
C4A—C5A—C6A—C61A178.5 (4)C4Y—C5Y—N1Y—C1Y177.8 (11)
C51A—C5A—C6A—C61A2.5 (7)N1Y'—C5Y—N1Y—C1Y179.6 (16)
C6A—C5A—C51A—C52A118.1 (5)C2Y'—O2Y—C2Y—N1Y5 (3)
C4A—C5A—C51A—C52A60.9 (6)C2Y'—O2Y—C2Y—C3Y176 (4)
C6A—C5A—C51A—C56A65.5 (6)C1Y—N1Y—C2Y—O2Y4.4 (14)
C4A—C5A—C51A—C56A115.6 (5)C5Y—N1Y—C2Y—O2Y179.6 (7)
C56A—C51A—C52A—C53A1.3 (6)C1Y—N1Y—C2Y—C3Y174.4 (12)
C5A—C51A—C52A—C53A175.3 (4)C5Y—N1Y—C2Y—C3Y0.7 (10)
C51A—C52A—C53A—C54A1.2 (7)O2Y—C2Y—C3Y—C4Y172.9 (9)
C52A—C53A—C54A—C55A0.3 (7)N1Y—C2Y—C3Y—C4Y8.2 (13)
C52A—C53A—C54A—ClA178.5 (4)C4Y'—C5Y—C4Y—C3Y40 (5)
C53A—C54A—C55A—C56A1.6 (7)N1Y—C5Y—C4Y—C3Y11.9 (12)
ClA—C54A—C55A—C56A177.2 (4)N1Y'—C5Y—C4Y—C3Y9.4 (14)
C54A—C55A—C56A—C51A1.4 (7)C2Y—C3Y—C4Y—C5Y12.2 (13)
C52A—C51A—C56A—C55A0.0 (6)C4Y'—C5Y—N1Y'—C1Y'173 (3)
C5A—C51A—C56A—C55A176.6 (4)N1Y—C5Y—N1Y'—C1Y'180 (4)
N1A—C6A—C61A—C62A71.5 (5)C4Y—C5Y—N1Y'—C1Y'3 (3)
C5A—C6A—C61A—C62A108.8 (5)C4Y'—C5Y—N1Y'—C2Y'8 (3)
C6B—N1B—C2B—N3B1.6 (8)N1Y—C5Y—N1Y'—C2Y'0.5 (16)
C6B—N1B—C2B—N21B179.2 (5)C4Y—C5Y—N1Y'—C2Y'177 (2)
N1B—C2B—N3B—C4B1.2 (7)C2Y—O2Y—C2Y'—N1Y'5.0 (16)
N21B—C2B—N3B—C4B178.8 (4)C2Y—O2Y—C2Y'—C3Y'165 (6)
C2B—N3B—C4B—N41B179.8 (4)C1Y'—N1Y'—C2Y'—O2Y6 (5)
C2B—N3B—C4B—C5B1.0 (6)C5Y—N1Y'—C2Y'—O2Y174 (2)
N3B—C4B—C5B—C6B1.2 (7)C1Y'—N1Y'—C2Y'—C3Y'177 (3)
N41B—C4B—C5B—C6B179.6 (5)C5Y—N1Y'—C2Y'—C3Y'3 (3)
N3B—C4B—C5B—C51B178.9 (4)O2Y—C2Y'—C3Y'—C4Y'179 (3)
N41B—C4B—C5B—C51B0.2 (7)N1Y'—C2Y'—C3Y'—C4Y'10 (3)
C2B—N1B—C6B—C5B1.8 (8)N1Y—C5Y—C4Y'—C3Y'8.0 (19)
C2B—N1B—C6B—C61B179.7 (6)C4Y—C5Y—C4Y'—C3Y'40 (6)
C4B—C5B—C6B—N1B1.7 (8)N1Y'—C5Y—C4Y'—C3Y'15 (3)
C51B—C5B—C6B—N1B178.5 (5)C2Y'—C3Y'—C4Y'—C5Y15 (3)
C4B—C5B—C6B—C61B179.9 (6)C5X—N1X—C2X—O2X175.3 (5)
C51B—C5B—C6B—C61B0.1 (9)C1X—N1X—C2X—O2X0.1 (11)
C6B—C5B—C51B—C56B75.9 (7)C5X—N1X—C2X—C3X2.0 (9)
C4B—C5B—C51B—C56B104.3 (5)C1X—N1X—C2X—C3X177.4 (8)
C6B—C5B—C51B—C52B103.1 (6)N1X—C2X—C3X—C4X4.1 (12)
C4B—C5B—C51B—C52B76.6 (6)O2X—C2X—C3X—C4X173.2 (9)
C56B—C51B—C52B—C53B0.1 (7)C2X—C3X—C4X—C5X4.6 (14)
C5B—C51B—C52B—C53B179.0 (5)C2X—N1X—C5X—C4X1.1 (11)
C51B—C52B—C53B—C54B1.5 (8)C1X—N1X—C5X—C4X174.9 (10)
C52B—C53B—C54B—C55B3.1 (8)C3X—C4X—C5X—N1X3.7 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H212···N1Bi0.90 (2)2.19 (2)3.087 (5)176 (4)
N21A—H211···O2X0.88 (2)2.06 (2)2.931 (5)168 (4)
N41A—H411···N3B0.89 (5)2.14 (5)3.025 (5)176 (4)
N41A—H412···O2Y0.87 (5)2.44 (5)3.126 (5)136 (4)
N21B—H214···N1Aii0.87 (6)2.21 (6)3.082 (5)176 (5)
N21B—H213···O2Y0.91 (5)2.21 (5)3.117 (5)172 (5)
N41B—H413···N3A0.89 (2)2.21 (2)3.097 (5)173 (4)
N41B—H414···O2X0.88 (2)2.10 (4)2.808 (5)137 (4)
Symmetry codes: (i) x, y+1, z; (ii) x, y1, z.
(II) 5,5'-(5-(4-chlorophenyl)-6-ethylpyrimidine-2,4-diyl)bis(azanediyl)bis(1- methylpyrrolidin-2-one) top
Crystal data top
C22H27ClN6O2Z = 2
Mr = 442.95F(000) = 468
Triclinic, P1Dx = 1.368 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7742 (6) ÅCell parameters from 5506 reflections
b = 9.2265 (8) Åθ = 3.3–26.0°
c = 17.3345 (15) ŵ = 0.21 mm1
α = 95.363 (7)°T = 173 K
β = 92.435 (7)°Block, yellow
γ = 93.783 (7)°0.50 × 0.20 × 0.10 mm
V = 1075.06 (16) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
3776 independent reflections
Radiation source: fine-focus sealed tube2262 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.115
ω scansθmax = 25.0°, θmin = 3.3°
Absorption correction: multi-scan
[MULABS (Spek, 2009; Blessing, 1995)]
h = 87
Tmin = 0.902, Tmax = 0.979k = 1010
15311 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H atoms treated by a mixture of independent and constrained refinement
S = 0.90 w = 1/[σ2(Fo2) + (0.0864P)2]
where P = (Fo2 + 2Fc2)/3
3776 reflections(Δ/σ)max < 0.001
288 parametersΔρmax = 0.97 e Å3
2 restraintsΔρmin = 0.34 e Å3
Crystal data top
C22H27ClN6O2γ = 93.783 (7)°
Mr = 442.95V = 1075.06 (16) Å3
Triclinic, P1Z = 2
a = 6.7742 (6) ÅMo Kα radiation
b = 9.2265 (8) ŵ = 0.21 mm1
c = 17.3345 (15) ÅT = 173 K
α = 95.363 (7)°0.50 × 0.20 × 0.10 mm
β = 92.435 (7)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3776 independent reflections
Absorption correction: multi-scan
[MULABS (Spek, 2009; Blessing, 1995)]
2262 reflections with I > 2σ(I)
Tmin = 0.902, Tmax = 0.979Rint = 0.115
15311 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0612 restraints
wR(F2) = 0.161H atoms treated by a mixture of independent and constrained refinement
S = 0.90Δρmax = 0.97 e Å3
3776 reflectionsΔρmin = 0.34 e Å3
288 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N10.8705 (4)0.4432 (3)0.80613 (16)0.0270 (7)
C20.8573 (5)0.4213 (3)0.72882 (19)0.0219 (7)
N30.7607 (4)0.5018 (3)0.67996 (15)0.0231 (6)
C40.6666 (4)0.6127 (3)0.71342 (18)0.0215 (7)
C50.6604 (5)0.6412 (3)0.79492 (19)0.0237 (7)
C60.7672 (5)0.5520 (3)0.83870 (19)0.0242 (7)
N210.9510 (4)0.3091 (3)0.69387 (17)0.0284 (7)
H210.929 (6)0.294 (4)0.6440 (12)0.034*
N410.5749 (4)0.6985 (3)0.66465 (16)0.0267 (7)
H410.524 (5)0.776 (3)0.685 (2)0.032*
C510.5361 (5)0.7563 (3)0.82962 (18)0.0236 (7)
C520.6172 (5)0.8900 (4)0.8635 (2)0.0347 (9)
H520.75660.91070.86470.042*
C530.4986 (6)0.9941 (4)0.8955 (2)0.0426 (10)
H530.55641.08510.91880.051*
C540.2981 (6)0.9652 (4)0.8935 (2)0.0329 (9)
C550.2116 (6)0.8326 (4)0.8617 (2)0.0377 (9)
H550.07220.81250.86130.045*
C560.3317 (5)0.7293 (4)0.8302 (2)0.0346 (9)
H560.27310.63740.80830.041*
C610.7733 (6)0.5649 (4)0.9255 (2)0.0342 (9)
H61A0.68300.63930.94410.041*
H61B0.90910.59890.94560.041*
C620.7138 (7)0.4217 (4)0.9580 (2)0.0447 (10)
H62A0.72030.43631.01480.067*
H62B0.80450.34800.94090.067*
H62C0.57830.38840.93940.067*
Cl10.14939 (17)1.09884 (11)0.93191 (6)0.0491 (3)
N1X1.2138 (5)0.1587 (4)0.7246 (2)0.0458 (9)
C1X1.3664 (8)0.2677 (6)0.7579 (3)0.0745 (19)
H1X11.49360.22340.76110.112*
H1X21.33130.30480.81000.112*
H1X31.37700.34840.72500.112*
C3X1.0565 (8)0.0519 (6)0.6667 (3)0.0688 (15)
H3X11.04540.07150.60950.083*
H3X21.04550.14630.68960.083*
C4X0.9096 (7)0.0348 (5)0.6922 (4)0.0669 (15)
H4X10.82990.01470.72990.080*
H4X20.82050.05300.64790.080*
C2X1.2618 (6)0.0350 (4)0.6935 (2)0.0415 (10)
O2X1.4146 (4)0.0170 (3)0.68094 (18)0.0466 (7)
C5X1.0126 (6)0.1878 (4)0.7330 (3)0.0430 (10)
H5X0.98260.20080.78910.052*
N1Y0.3334 (4)0.6563 (3)0.55957 (16)0.0263 (6)
C1Y0.1903 (6)0.5679 (4)0.5981 (2)0.0435 (10)
H1Y10.05660.58080.57720.065*
H1Y20.19940.59820.65390.065*
H1Y30.21830.46500.58920.065*
C2Y0.2861 (5)0.7304 (4)0.4997 (2)0.0272 (8)
O2Y0.1170 (4)0.7420 (3)0.47342 (15)0.0413 (7)
C3Y0.4759 (5)0.7889 (4)0.4678 (2)0.0320 (8)
H3Y10.46570.89050.45490.038*
H3Y20.50850.72770.42070.038*
C4Y0.6307 (5)0.7819 (4)0.5333 (2)0.0305 (8)
H4Y10.65190.87710.56500.037*
H4Y20.75850.75460.51260.037*
C5Y0.5433 (5)0.6633 (3)0.58196 (18)0.0246 (7)
H5Y0.59860.56780.56610.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0265 (16)0.0276 (15)0.0274 (16)0.0104 (12)0.0006 (12)0.0007 (12)
C20.0170 (16)0.0215 (16)0.0271 (18)0.0035 (13)0.0003 (13)0.0000 (13)
N30.0221 (15)0.0218 (13)0.0263 (15)0.0071 (11)0.0008 (12)0.0031 (11)
C40.0173 (16)0.0209 (16)0.0261 (17)0.0017 (13)0.0009 (13)0.0020 (13)
C50.0236 (17)0.0204 (16)0.0267 (18)0.0021 (13)0.0019 (14)0.0009 (13)
C60.0225 (17)0.0220 (16)0.0275 (18)0.0025 (13)0.0026 (14)0.0001 (14)
N210.0324 (17)0.0286 (15)0.0268 (16)0.0165 (13)0.0037 (13)0.0060 (13)
N410.0352 (17)0.0205 (14)0.0251 (15)0.0124 (12)0.0020 (13)0.0004 (12)
C510.0291 (19)0.0203 (16)0.0218 (17)0.0082 (14)0.0009 (14)0.0002 (13)
C520.0262 (19)0.0320 (19)0.043 (2)0.0056 (15)0.0108 (16)0.0073 (16)
C530.049 (3)0.0281 (19)0.047 (2)0.0105 (17)0.0133 (19)0.0143 (17)
C540.042 (2)0.035 (2)0.0240 (19)0.0190 (16)0.0008 (16)0.0012 (15)
C550.027 (2)0.032 (2)0.055 (3)0.0088 (16)0.0137 (17)0.0010 (18)
C560.029 (2)0.0250 (18)0.048 (2)0.0001 (15)0.0044 (17)0.0057 (16)
C610.039 (2)0.039 (2)0.0255 (19)0.0137 (17)0.0027 (16)0.0018 (16)
C620.056 (3)0.049 (2)0.032 (2)0.013 (2)0.0062 (19)0.0092 (18)
Cl10.0596 (7)0.0468 (6)0.0426 (6)0.0336 (5)0.0017 (5)0.0074 (4)
N1X0.048 (2)0.044 (2)0.051 (2)0.0229 (16)0.0091 (16)0.0157 (16)
C1X0.083 (4)0.073 (3)0.058 (3)0.060 (3)0.040 (3)0.025 (3)
C3X0.062 (3)0.058 (3)0.078 (4)0.015 (3)0.002 (3)0.021 (3)
C4X0.040 (3)0.045 (3)0.112 (5)0.009 (2)0.017 (3)0.010 (3)
C2X0.048 (2)0.045 (2)0.038 (2)0.028 (2)0.0097 (18)0.0150 (18)
O2X0.0376 (16)0.0360 (14)0.071 (2)0.0230 (12)0.0196 (14)0.0100 (14)
C5X0.042 (2)0.047 (2)0.047 (2)0.0289 (19)0.0147 (18)0.0176 (19)
N1Y0.0284 (16)0.0256 (14)0.0250 (15)0.0012 (12)0.0009 (12)0.0031 (12)
C1Y0.047 (3)0.044 (2)0.038 (2)0.0133 (19)0.0073 (18)0.0037 (18)
C2Y0.028 (2)0.0254 (17)0.0279 (18)0.0082 (14)0.0002 (15)0.0050 (14)
O2Y0.0291 (15)0.0609 (17)0.0333 (15)0.0156 (13)0.0054 (11)0.0046 (13)
C3Y0.039 (2)0.0303 (18)0.0281 (19)0.0055 (15)0.0021 (16)0.0054 (15)
C4Y0.0252 (19)0.0353 (19)0.0311 (19)0.0031 (15)0.0041 (15)0.0025 (15)
C5Y0.0292 (18)0.0240 (16)0.0216 (17)0.0114 (14)0.0007 (14)0.0016 (13)
Geometric parameters (Å, º) top
N1—C21.335 (4)N1X—C2X1.283 (5)
N1—C61.355 (4)N1X—C5X1.417 (5)
C2—N31.353 (4)N1X—C1X1.455 (5)
C2—N211.358 (4)C1X—H1X10.9800
N3—C41.341 (4)C1X—H1X20.9800
C4—N411.368 (4)C1X—H1X30.9800
C4—C51.415 (5)C3X—C4X1.379 (8)
C5—C61.387 (4)C3X—C2X1.588 (6)
C5—C511.497 (5)C3X—H3X10.9900
C6—C611.497 (5)C3X—H3X20.9900
N21—C5X1.437 (4)C4X—C5X1.619 (6)
N21—H210.869 (18)C4X—H4X10.9900
N41—C5Y1.443 (4)C4X—H4X20.9900
N41—H410.866 (19)C2X—O2X1.190 (5)
C51—C521.385 (5)C5X—H5X1.0000
C51—C561.391 (5)N1Y—C2Y1.334 (4)
C52—C531.384 (5)N1Y—C1Y1.450 (5)
C52—H520.9500N1Y—C5Y1.454 (4)
C53—C541.365 (6)C1Y—H1Y10.9800
C53—H530.9500C1Y—H1Y20.9800
C54—C551.377 (5)C1Y—H1Y30.9800
C54—Cl11.746 (4)C2Y—O2Y1.229 (4)
C55—C561.382 (5)C2Y—C3Y1.508 (5)
C55—H550.9500C3Y—C4Y1.522 (5)
C56—H560.9500C3Y—H3Y10.9900
C61—C621.521 (5)C3Y—H3Y20.9900
C61—H61A0.9900C4Y—C5Y1.545 (5)
C61—H61B0.9900C4Y—H4Y10.9900
C62—H62A0.9800C4Y—H4Y20.9900
C62—H62B0.9800C5Y—H5Y1.0000
C62—H62C0.9800
C2—N1—C6116.3 (3)H1X1—C1X—H1X2109.5
N1—C2—N3126.5 (3)N1X—C1X—H1X3109.5
N1—C2—N21118.3 (3)H1X1—C1X—H1X3109.5
N3—C2—N21115.1 (3)H1X2—C1X—H1X3109.5
C4—N3—C2116.0 (3)C4X—C3X—C2X106.7 (4)
N3—C4—N41116.6 (3)C4X—C3X—H3X1110.4
N3—C4—C5122.5 (3)C2X—C3X—H3X1110.4
N41—C4—C5121.0 (3)C4X—C3X—H3X2110.4
C6—C5—C4116.0 (3)C2X—C3X—H3X2110.4
C6—C5—C51123.4 (3)H3X1—C3X—H3X2108.6
C4—C5—C51120.6 (3)C3X—C4X—C5X108.5 (4)
N1—C6—C5122.6 (3)C3X—C4X—H4X1110.0
N1—C6—C61114.4 (3)C5X—C4X—H4X1110.0
C5—C6—C61123.0 (3)C3X—C4X—H4X2110.0
C2—N21—C5X123.7 (3)C5X—C4X—H4X2110.0
C2—N21—H21115 (3)H4X1—C4X—H4X2108.4
C5X—N21—H21117 (3)O2X—C2X—N1X134.5 (4)
C4—N41—C5Y124.6 (3)O2X—C2X—C3X120.9 (4)
C4—N41—H41118 (2)N1X—C2X—C3X104.5 (4)
C5Y—N41—H41117 (2)N1X—C5X—N21114.5 (3)
C52—C51—C56117.7 (3)N1X—C5X—C4X98.9 (3)
C52—C51—C5122.4 (3)N21—C5X—C4X111.3 (3)
C56—C51—C5119.9 (3)N1X—C5X—H5X110.6
C53—C52—C51121.1 (4)N21—C5X—H5X110.6
C53—C52—H52119.5C4X—C5X—H5X110.6
C51—C52—H52119.5C2Y—N1Y—C1Y123.5 (3)
C54—C53—C52119.7 (3)C2Y—N1Y—C5Y115.3 (3)
C54—C53—H53120.2C1Y—N1Y—C5Y121.1 (3)
C52—C53—H53120.2N1Y—C1Y—H1Y1109.5
C53—C54—C55121.1 (3)N1Y—C1Y—H1Y2109.5
C53—C54—Cl1119.3 (3)H1Y1—C1Y—H1Y2109.5
C55—C54—Cl1119.6 (3)N1Y—C1Y—H1Y3109.5
C54—C55—C56118.7 (3)H1Y1—C1Y—H1Y3109.5
C54—C55—H55120.7H1Y2—C1Y—H1Y3109.5
C56—C55—H55120.7O2Y—C2Y—N1Y125.4 (3)
C55—C56—C51121.8 (3)O2Y—C2Y—C3Y126.5 (3)
C55—C56—H56119.1N1Y—C2Y—C3Y108.0 (3)
C51—C56—H56119.1C2Y—C3Y—C4Y104.0 (3)
C6—C61—C62112.9 (3)C2Y—C3Y—H3Y1111.0
C6—C61—H61A109.0C4Y—C3Y—H3Y1111.0
C62—C61—H61A109.0C2Y—C3Y—H3Y2111.0
C6—C61—H61B109.0C4Y—C3Y—H3Y2111.0
C62—C61—H61B109.0H3Y1—C3Y—H3Y2109.0
H61A—C61—H61B107.8C3Y—C4Y—C5Y104.6 (3)
C61—C62—H62A109.5C3Y—C4Y—H4Y1110.8
C61—C62—H62B109.5C5Y—C4Y—H4Y1110.8
H62A—C62—H62B109.5C3Y—C4Y—H4Y2110.8
C61—C62—H62C109.5C5Y—C4Y—H4Y2110.8
H62A—C62—H62C109.5H4Y1—C4Y—H4Y2108.9
H62B—C62—H62C109.5N41—C5Y—N1Y110.6 (3)
C2X—N1X—C5X121.2 (4)N41—C5Y—C4Y113.9 (3)
C2X—N1X—C1X120.2 (4)N1Y—C5Y—C4Y102.5 (2)
C5X—N1X—C1X118.4 (4)N41—C5Y—H5Y109.8
N1X—C1X—H1X1109.5N1Y—C5Y—H5Y109.8
N1X—C1X—H1X2109.5C4Y—C5Y—H5Y109.8
C6—N1—C2—N34.0 (5)C5—C51—C56—C55180.0 (3)
C6—N1—C2—N21177.0 (3)N1—C6—C61—C6252.6 (4)
N1—C2—N3—C41.3 (5)C5—C6—C61—C62125.6 (4)
N21—C2—N3—C4179.7 (3)C2X—C3X—C4X—C5X3.2 (6)
C2—N3—C4—N41177.5 (3)C5X—N1X—C2X—O2X178.6 (4)
C2—N3—C4—C52.6 (4)C1X—N1X—C2X—O2X3.9 (7)
N3—C4—C5—C63.4 (5)C5X—N1X—C2X—C3X3.9 (5)
N41—C4—C5—C6176.7 (3)C1X—N1X—C2X—C3X178.6 (4)
N3—C4—C5—C51173.5 (3)C4X—C3X—C2X—O2X177.8 (5)
N41—C4—C5—C516.3 (5)C4X—C3X—C2X—N1X4.3 (6)
C2—N1—C6—C52.9 (5)C2X—N1X—C5X—N21120.3 (4)
C2—N1—C6—C61175.3 (3)C1X—N1X—C5X—N2164.9 (5)
C4—C5—C6—N10.5 (5)C2X—N1X—C5X—C4X1.9 (5)
C51—C5—C6—N1176.4 (3)C1X—N1X—C5X—C4X176.8 (4)
C4—C5—C6—C61178.6 (3)C2—N21—C5X—N1X128.3 (4)
C51—C5—C6—C611.8 (5)C2—N21—C5X—C4X120.7 (4)
N1—C2—N21—C5X19.2 (5)C3X—C4X—C5X—N1X1.2 (5)
N3—C2—N21—C5X161.7 (3)C3X—C4X—C5X—N21119.5 (5)
N3—C4—N41—C5Y11.4 (5)C1Y—N1Y—C2Y—O2Y5.5 (5)
C5—C4—N41—C5Y168.5 (3)C5Y—N1Y—C2Y—O2Y177.6 (3)
C6—C5—C51—C5277.8 (5)C1Y—N1Y—C2Y—C3Y171.2 (3)
C4—C5—C51—C52105.5 (4)C5Y—N1Y—C2Y—C3Y5.6 (4)
C6—C5—C51—C56100.7 (4)O2Y—C2Y—C3Y—C4Y164.7 (3)
C4—C5—C51—C5676.0 (4)N1Y—C2Y—C3Y—C4Y18.6 (4)
C56—C51—C52—C531.1 (5)C2Y—C3Y—C4Y—C5Y23.6 (4)
C5—C51—C52—C53179.6 (3)C4—N41—C5Y—N1Y121.3 (3)
C51—C52—C53—C540.4 (6)C4—N41—C5Y—C4Y123.8 (3)
C52—C53—C54—C551.6 (6)C2Y—N1Y—C5Y—N41131.4 (3)
C52—C53—C54—Cl1178.4 (3)C1Y—N1Y—C5Y—N4151.6 (4)
C53—C54—C55—C561.3 (6)C2Y—N1Y—C5Y—C4Y9.6 (4)
Cl1—C54—C55—C56178.7 (3)C1Y—N1Y—C5Y—C4Y173.5 (3)
C54—C55—C56—C510.2 (6)C3Y—C4Y—C5Y—N41139.9 (3)
C52—C51—C56—C551.4 (5)C3Y—C4Y—C5Y—N1Y20.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O2Yi0.87 (2)2.04 (2)2.906 (4)179 (4)
N41—H41···O2Xii0.87 (2)2.10 (2)2.900 (4)154 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y+1, z.

Experimental details

(I)(Ia)(Ib)(II)
Crystal data
Chemical formulaC12H13ClN4C12H13ClN4·C2H6OSC12H13ClN4·C5H9NOC22H27ClN6O2
Mr248.71326.84347.85442.95
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/nTriclinic, P1Triclinic, P1
Temperature (K)173173173173
a, b, c (Å)14.4471 (18), 7.5774 (7), 11.7526 (15)13.5596 (9), 7.7212 (4), 16.2870 (11)9.5221 (14), 10.8372 (15), 18.650 (2)6.7742 (6), 9.2265 (8), 17.3345 (15)
α, β, γ (°)90, 107.279 (10), 9090, 111.609 (5), 90101.937 (11), 99.555 (11), 98.892 (12)95.363 (7), 92.435 (7), 93.783 (7)
V3)1228.5 (2)1585.35 (17)1820.9 (4)1075.06 (16)
Z4442
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.290.380.220.21
Crystal size (mm)0.50 × 0.40 × 0.200.50 × 0.40 × 0.300.60 × 0.60 × 0.200.50 × 0.20 × 0.10
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correctionMulti-scan
[MULABS (Spek, 2009; Blessing, 1995)]
Multi-scan
[MULABS (Spek, 2009; Blessing, 1995)]
Tmin, Tmax0.834, 0.8950.902, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
15453, 2149, 1616 7296, 2939, 2615 16150, 6800, 3240 15311, 3776, 2262
Rint0.2210.0470.1070.115
(sin θ/λ)max1)0.5950.6100.6090.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.131, 0.333, 1.11 0.041, 0.110, 1.00 0.079, 0.226, 0.93 0.061, 0.161, 0.90
No. of reflections2149293968003776
No. of parameters167217486288
No. of restraints20362
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.58, 0.530.30, 0.250.83, 0.460.97, 0.34

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Version 2.2; Macrae et al., 2008) and XP (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N21—H211···N1i0.91 (11)2.14 (11)3.043 (10)172 (8)
N21—H212···N3ii0.86 (10)2.50 (11)3.339 (10)166 (8)
N41—H412···N3iii0.88 (2)2.17 (3)3.032 (8)167 (8)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N21—H211···Cl1i0.85 (2)2.72 (3)3.5607 (18)170 (2)
N21—H212···O1Xii0.85 (3)2.14 (3)2.958 (2)164 (2)
N41—H411···N3ii0.84 (3)2.26 (3)3.102 (2)174 (2)
N41—H412···O1X0.88 (3)2.22 (3)2.921 (2)137 (2)
Symmetry codes: (i) x1/2, y+3/2, z1/2; (ii) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N21A—H212···N1Bi0.90 (2)2.19 (2)3.087 (5)176 (4)
N21A—H211···O2X0.88 (2)2.06 (2)2.931 (5)168 (4)
N41A—H411···N3B0.89 (5)2.14 (5)3.025 (5)176 (4)
N41A—H412···O2Y0.87 (5)2.44 (5)3.126 (5)136 (4)
N21B—H214···N1Aii0.87 (6)2.21 (6)3.082 (5)176 (5)
N21B—H213···O2Y0.91 (5)2.21 (5)3.117 (5)172 (5)
N41B—H413···N3A0.89 (2)2.21 (2)3.097 (5)173 (4)
N41B—H414···O2X0.88 (2)2.10 (4)2.808 (5)137 (4)
Symmetry codes: (i) x, y+1, z; (ii) x, y1, z.
Selected torsion angles (º) for (II) top
N3—C2—N21—C5X161.7 (3)C1X—N1X—C5X—N2164.9 (5)
N3—C4—N41—C5Y11.4 (5)C1Y—N1Y—C5Y—N4151.6 (4)
C5—C6—C61—C62125.6 (4)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N21—H21···O2Yi0.869 (18)2.038 (19)2.906 (4)179 (4)
N41—H41···O2Xii0.866 (19)2.10 (2)2.900 (4)154 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y+1, z.
 

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