organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Pseudopolymorphs of 2,6-di­amino­pyrimidin-4-one and 2-amino-6-methyl­pyrimidin-4-one: one or two tautomers present in the same crystal

aInstitut für Organische Chemie und Chemische Biologie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany, and bInstitut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany
*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 6 April 2011; accepted 7 April 2011; online 14 April 2011)

The derivatives of pyrimidin-4-one can adopt either a 1H- or a 3H-tautomeric form, which affects the hydrogen-bonding inter­actions in cocrystals with compounds containing complementary functional groups. In order to study their tautomeric preferences, we crystallized 2,6-diamino­pyrimidin-4-one and 2-amino-6-methyl­pyrimidin-4-one. During various crystallization attempts, four structures of 2,6-diamino­pyrimidin-4-one were obtained, namely solvent-free 2,6-diamino­pyrimidin-4-one, C4H6N4O, (I)[link], 2,6-diamino­pyrimidin-4-one–dimethyl­formamide–water (3/4/1), C4H6N4O·1.33C3H7NO·0.33H2O, (Ia)[link], 2,6-diamino­pyrimidin-4-one dimethyl­acetamide monosolvate, C4H6N4O·C4H9NO, (Ib)[link], and 2,6-diamino­pyrimidin-4-one–N-methylpyrrolidin-2-one (3/2), C4H6N4O·1.5C5H9NO, (Ic)[link]. The 2,6-diamino­pyrimidin-4-one mol­ecules exist only as 3H-tautomers. They form ribbons characterized by R22(8) hydrogen-bonding inter­actions, which are further connected to form three-dimensional networks. An inter­molecular N—H⋯N inter­action between amine groups is observed only in (I)[link]. This might be the reason for the pyramidalization of the amine group. Crystallization experiments on 2-amino-6-methyl­pyrimidin-4-one yielded two isostructural pseudopolymorphs, namely 2-amino-6-methylpyrimidin-4(3H)-one–2-am­ino-6-methyl­pyrimidin-4(1H)-one–dimethyl­acetamide (1/1/1), C5H7N3O·C5H7N3O·C4H9NO, (IIa)[link], and 2-amino-6-methyl­pyrimidin-4(3H)-one–2-amino-6-methyl­pyrimidin-4(1H)-one–N-methylpyrrolidin-2-one (1/1/1), C5H7N3O·C5H7N3O·C5H9NO, (IIb)[link]. In both structures, a 1:1 mixture of 1H- and 3H-tautomers is present, which are linked by three hydrogen bonds similar to a Watson–Crick C–G base pair.

Comment

Pyrimidin-4-one derivatives are of particular inter­est in pharmacology and mol­ecular biology. They include nucleobases and many important pharmaceutical drugs, e.g. anti-inflammatory (Kawade et al., 2011[Kawade, D. P., Khedekar, P. B. & Bhusari, K. P. (2011). Int. J. Pharm. Biomed. Res. 2, 13-16.]), anti­cancer (Lu et al., 2007[Lu, S., Wang, A., Lu, S. & Dong, Z. (2007). Mol. Cancer Ther. 6, 2057-2064.]), anti­histaminic and bronchorelaxant agents (Youssouf et al., 2008[Youssouf, M. S., Kaiser, P., Singh, G. D., Singh, S., Bani, S., Gupta, V. K., Satti, N. K., Suri, K. A. & Johri, R. K. (2008). Int. Immunopharmacol. 8, 1049-1055.]). Pyrimidin-4-one can exist in three tautomeric forms: as a 1H- or 3H-tautomer or as a hy­droxy­pyrimidine. An NMR study revealed that the preference of each tautomeric form depends on its state, although no hy­droxy­pyrimidine form has ever been observed. In the solid state, only the 3H-tautomer has been found, while in polar solvents, a mixture of 1H-and 3H-tautomers is observed (López et al., 2000[López, C., Claramunt, R. M., Alkorta, I. & Elguero, J. (2000). Spectroscopy, 14, 121-126.]). These results agree with the two crystal structures containing pyrimidin-4-one in the Cambridge Structural Database (CSD, Version 5.31 of November 2009, plus four updates; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), which confirmed that the 3H-tautomer is preferred [CSD refcodes BAGQUV (Vaillancourt et al., 1998[Vaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem. 63, 9746-9752.]) and XOLHOW (Bhogala et al., 2008[Bhogala, B. R., Chandran, S. K., Reddy, L. S., Thakuria, R. & Nangia, A. (2008). CrystEngComm, 10, 1735-1738.])].

We are inter­ested in the hydrogen-bonding inter­action between pyrimidin-4-one derivatives and compounds con­taining complementary functional groups. Since the occurrence of tautomers results in different synthon combinations (Bhogala et al., 2008[Bhogala, B. R., Chandran, S. K., Reddy, L. S., Thakuria, R. & Nangia, A. (2008). CrystEngComm, 10, 1735-1738.]), we crystallized 2,6-diamino­pyrimidin-4-one and 2-amino-6-methyl­pyrimidin-4-one to study their tautomeric preferences. Four structures of 2,6-di­am­ino­pyrimidin-4-one were obtained during various crystallization experiments, namely solvent-free 2,6-di­­am­ino­pyrimidin-4-one, (I)[link], a dimethyl­formamide–water solvate (3/4/1), (Ia)[link], a dimethyl­acetamide monosolvate, (Ib)[link], and an N-methylpyrrolidin-2-one (3/2) solvate, (Ic)[link]. Another N-methylpyrrolidin-2-one solvate of minor crystal quality was also obtained (Gerhardt et al., 2011[Gerhardt, V., Tutughamiarso, M. & Bolte, M. (2011). Private communication (refcode 820449). CCDC, Union Road, Cambridge, England.]). All 2,6-diamino­py­rimi­din-4-one mol­ecules exist as 3H-tautomers. Crystallization attempts on 2-amino-6-methyl­pyrimidin-4-one yielded two pseudopolymorphs, namely dimethyl­acetamide monosolvate, (IIa)[link], and N-methylpyrrolidin-2-one monosolvate, (IIb)[link]. In both structures, a 1:1 mixture of 1H- and 3H-tautomers is present.

2,6-Diamino­pyrimidin-4-one, (I)[link], crystallizes in the monoclinic space group P21/c with one mol­ecule in the asymmetric unit (Fig. 1[link]). One amine group is planar and twisted slightly out of the plane of the ring, while the other is pyramidalized and shows a longer C—NH2 bond [sums of the C—N—H and H—N—H angles at the N atoms = 359.1 (at N21) and 347.3° (at N61); C—NH2 = 1.337 (2) (at N21) and 1.365 (2) Å (at N61)]. The 2,6-diamino­pyrimidin-4-one mol­ecules form ribbons characterized by three hydrogen bonds, consisting of one R22(8) inter­action (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) with N—H⋯O and N—H⋯N hydrogen bonds, and another R22(8) inter­action

[Scheme 1]
with two N—H⋯N hydrogen bonds (Fig. 2[link]). This arrangement is similar to that in the cytosine–guanine base pair. The ribbons are rippled and further connected into layers by R43(12) inter­actions. Other N—H⋯O hydrogen bonds stabilize the layers to form a three-dimensional network.

Compound (Ia)[link] formed during crystallization attempts from dimethyl­formamide (DMF). It crystallizes in the monoclinic space group P21 with three planar 2,6-diamino­pyrimidin-4-one mol­ecules (r.m.s deviations = 0.008, 0.012 and 0.013 Å for all non-H atoms) and four DMF mol­ecules. Since we used non-water-free solvent, one water mol­ecule is also present in the asymmetric unit (Fig. 3[link]). The three 2,6-diamino­pyrimidin-4-one mol­ecules show different hydrogen-bond arrangements. Mol­ecules A and B are connected by either R22(8) N—H⋯O or R22(8) N—H⋯N bonds to form planar ribbons running parallel to ([\overline{1}]01) (Fig. 4[link]). The ribbons are further stabilized by hydrogen bonds to the solvent mol­ecules. One DMF mol­ecule is N—H⋯O hydrogen bonded only to mol­ecule A, while another DMF mol­ecule links mol­ecules A and B by two N—H⋯O hydrogen bonds. Furthermore, chains running along the a axis consisting of N—H⋯O hydrogen-bonded mol­ecules C are observed (Fig. 5[link]). The chain is stabilized by N—H⋯O hydrogen bonds with the participation of solvent mol­ecules. One of the two DMF mol­ecules linked to mol­ecule C is disordered over two sites with a planar arrangement (r.m.s deviation = 0.011 Å). The packing of (Ia) shows ribbons and chains, which are connected by N—H⋯O hydrogen bonds to form a three-dimensional network. The water mol­ecule forms hydrogen bonds bridging the three 2,6-diamino­pyrimidin-4-one mol­ecules and thus additionally stabilizes the structure.

The dimethyl­acetamide (DMAC) monosolvate, (Ib)[link], crystallizes in the monoclinic space group Cc with two 2,6-diamino­pyrimidin-4-one (r.m.s deviations = 0.013 and 0.025 Å for all non-H atoms) and two DMAC mol­ecules in the asymmetric unit (Fig. 6[link]). In the packing of (Ib)[link], ribbons consisting of 2,6-diamino­pyrimidin-4-one mol­ecules run in two different directions [parallel to ([\overline{1}]11) and ([\overline{1}][\overline{1}]1)]. Similar to (Ia)[link], the mol­ecules are stabilized either by N—H⋯O or by N—H⋯N hydrogen bonds with an R22(8) pattern (Fig. 7[link]). These ribbons are further N—H⋯O hydrogen bonded to form channels, in which solvent mol­ecules are located (Fig. 8[link]). One DMAC mol­ecule is coplanar with the 2,6-diamino­pyrimidin-4-one mol­ecules and shows only van der Waals inter­actions, while the O atom of the other DMAC mol­ecule is threefold N—H⋯O hydrogen bonded to 2,6-diamino­pyrimi­din-4-one mol­ecules.

Compound (Ic)[link] crystallizes as an N-methylpyrrolidin-2-one (NMP) solvate with two 2,6-diamino­pyrimidin-4-one and three solvent mol­ecules in the asymmetric unit (Fig. 9[link]). The 2,6-diamino­pyrimidin-4-one mol­ecules are planar (r.m.s deviations = 0.005 and 0.012 Å for all non-H atoms). R22(8) inter­actions involving either two N—H⋯O or two N—H⋯N hydrogen bonds are again present. Both inter­actions connect mol­ecules A to form ribbons running parallel to (111), which are additionally stabilized by N—H⋯O bonds between mol­ecule A and one NMP mol­ecule (Fig. 10[link]). In contrast, mol­ecules B form dimers stabilized by R22(8) N—H⋯N hydrogen bonds. Two NMP mol­ecules are N—H⋯O hydrogen bonded to each mol­ecule B, and thus inversion-symmetric arrangements of two mol­ecules B and two NMP mol­ecules are formed (Fig. 11[link]). These link the ribbons to form a three-dimensional network.

The two isostructural 2-amino-6-methyl­pyrimidin-4-one solvates, (IIa)[link] and (IIb)[link], crystallize in the triclinic space group P[\overline{1}] with similar lattice parameters. A 1:1 ratio of 1H- and 3H-tautomers is present in both crystal structures. The asymmetric unit of (IIa)[link] consists of the two tautomers and one DMAC mol­ecule (Fig. 12[link]), while (IIb)[link] crystallizes with the two tautomers and one disordered NMP mol­ecule (Fig. 13[link]). In both structures, the mol­ecules are coplanar with each other, and both the hydrogen-bonding inter­actions and the crystal packings are similar (Figs. 14[link] and 15[link]). The two tautomers are linked by two R22(8) inter­actions involving N—H⋯O and N—H⋯N bonds, forming a dimer related to the cytosine–guanine base pair. Two symmetry-equivalent dimers are further connected by two N—H⋯N inter­actions with an R22(8) pattern to give a tetra­mer. The O atoms of the solvent mol­ecules, either DMAC in (IIa)[link] or NMP in (IIb)[link], adopt identical postions and are R21(6) N—H⋯O hydrogen bonded to the 3H-tautomer. The crystal structures show layers parallel to the (210) plane containing discrete arrangements of the tetra­mers.

In order to study the preference of the 1H- and 3H-tautomeric forms, a CSD substructure search for pyrimidin-4-one derivatives was undertaken. 15 entries for the 1H form, 39 entries for the 3H form and five entries with both tautomeric forms were found [refcodes ICYTIN (Sharma & McConnell, 1965[Sharma, B. D. & McConnell, J. F. (1965). Acta Cryst. 19, 797-806.]), ICYTIN01 (Portalone & Colapietro, 2007[Portalone, G. & Colapietro, M. (2007). Acta Cryst. E63, o1869-o1871.]), LEJLAN and LEJLOB (Bannister et al., 1994[Bannister, C., Burns, K., Prout, K., Watkin, D. J., Cooper, D. G., Durant, G. J., Ganellin, C. R., Ife, R. J. & Sach, G. S. (1994). Acta Cryst. B50, 221-243.]), and ZERMIS (Toledo et al., 1995[Toledo, L. M., Musa, K., Lauher, J. W. & Fowler, F. W. (1995). Chem. Mater. 7, 1639-1647.])]. Examining only entries containing 2,6-diamino­pyrimidin-4-one, no 1H-tautomer has been reported [refcodes SEYDIJ (Skoweranda et al., 1990[Skoweranda, J., Bukowska-Strzyżewska, M., Bartnik, R. & Strzyżewski, W. (1990). J. Crystallogr. Spectrosc. Res. 20, 117-121.]) and GIMZUY (Subashini et al., 2007[Subashini, A., Muthiah, P. T., Bocelli, G. & Cantoni, A. (2007). Acta Cryst. E63, o4244.])]. The preference for the 3H-tautomeric form is also shown in two recently reported polymorphs of the monohydrate (Suleiman Gwaram et al., 2011[Suleiman Gwaram, N., Khaledi, H., Mohd Ali, H. & Olmstead, M. M. (2011). Acta Cryst. C67, o6-o9.]), in the NMP solvate with minor crystal quality (Gerhardt et al., 2011[Gerhardt, V., Tutughamiarso, M. & Bolte, M. (2011). Private communication (refcode 820449). CCDC, Union Road, Cambridge, England.]) and in the four crystal structures above, viz. (I)[link] and (Ia)[link]–(Ic)[link]. A possible explanation for the absence of the 1H-tautomeric form might be the repulsion of the H atoms from the three amino groups presenting an adjacent donor–donor–donor hydrogen-bonding site. In contrast, 2-amino-6-methyl­pyrimi­din-4-one exists in both 1H- and 3H-tautomeric forms. In the solvent-free P21/n structure it exists as a 1H-tautomer (refcode FETSEC; Lowe et al., 1987[Lowe, P. R., Schwalbe, C. H. & Williams, G. J. B. (1987). Acta Cryst. C43, 330-333.]), while in the solvent-free C2/c polymorph, both 1H- and 3H-tautomers are shown as a result of disordered H atoms (refcode ZERMIS; Toledo et al., 1995[Toledo, L. M., Musa, K., Lauher, J. W. & Fowler, F. W. (1995). Chem. Mater. 7, 1639-1647.]). The 3H-tautomeric form is observed in its cocrystals with glutaric acid and adipic acid (refcodes ZUKXAE and ZUKXEI; Liao et al., 1996[Liao, R.-F., Lauher, J. W. & Fowler, F. W. (1996). Tetrahedron, 52, 3153-3162.]). Inter­estingly, only in the solvates (IIa)[link] and (IIb)[link] do both tautomers exist in a 1:1 ratio.

Almost all 2,6-diamino­pyrimidin-4-one and 2-amino-6-methyl­pyrimidin-4-one mol­ecules are planar. The pyramidal­ization of one amine group in (I)[link] is also observed in the ortho­rhom­bic polymorph of 2,6-diamino­pyrimidin-4-one monohydrate [refcode SEYDIJ (Skoweranda et al., 1990[Skoweranda, J., Bukowska-Strzyżewska, M., Bartnik, R. & Strzyżewski, W. (1990). J. Crystallogr. Spectrosc. Res. 20, 117-121.]), form I according to Suleiman Gwaram et al. (2011)[Suleiman Gwaram, N., Khaledi, H., Mohd Ali, H. & Olmstead, M. M. (2011). Acta Cryst. C67, o6-o9.]]. Similar to (I)[link], one C—NH2 bond is longer than the other [1.334 (2) and 1.359 (2) Å], and the sums of the bond angles at the N atoms are 360 and 354°. Different C—NH2 bond lengths are also observed in the monoclinic polymorph [form III according to Suleiman Gwaram et al. (2011)[Suleiman Gwaram, N., Khaledi, H., Mohd Ali, H. & Olmstead, M. M. (2011). Acta Cryst. C67, o6-o9.]; C—NH2 = 1.323 (4) and 1.354 (4) Å], but both amine groups are planar [sums of the bond angles at the N atoms = 359 (2) and 356 (2)°, respectively].

Comparing the hydrogen-bond arrangements formed by the 2,6-diamino­pyrimidin-4-one mol­ecules, ribbons characterized by R22(8) inter­actions involving either two N—H⋯O or two N—H⋯N bonds are observed in all structures. However, an inter­molecular N—H⋯N inter­action between the amine groups is only observed in (I)[link] and in the ortho­rhom­bic polymorph (form I), which may explain the pyramidalization of one amine group in these two structures. The crystal packings in the various structures show three-dimensional networks additionally stabilized by solvent mol­ecules. The 1H- and 3H-tautomers of 2-amino-6-methyl­pyrimidin-4-one are linked by three hydrogen bonds, similar to what is observed in the Watson–Crick C–G base pair. Identical arrangements are observed in the five CSD entries for pyrimidin-4-one derivatives containing both tautomeric forms. Altogether, (I)[link] and (Ia)[link]–(Ic)[link] confirm the 3H-tautomer preference of 2,6-di­amino­pyrimidin-4-one, while there is no preference for 2-amino-6-methyl­pyrimidin-4-one. It can exist as a 1H- or 3H-tautomer, or as a 1:1 mixture of both tautomers, as shown in the crystal structures of (IIa)[link] and (IIb)[link].

[Figure 1]
Figure 1
A perspective view of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
A partial packing diagram for (I)[link]. Hydrogen bonds are shown as dashed lines.
[Figure 3]
Figure 3
A perspective view of (Ia)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. One of the dimethyl­formamide mol­ecules (mol­ecule Y) is disordered and only the major occupied site is shown.
[Figure 4]
Figure 4
A partial packing diagram for (Ia)[link]. Hydrogen bonds are shown as dashed lines. Only DMF mol­ecules linked to mol­ecules A and B are shown.
[Figure 5]
Figure 5
A partial packing diagram for (Ia)[link]. Dashed lines indicate hydrogen bonds. Only DMF mol­ecules linked to mol­ecules C are shown. One of the solvent mol­ecules is disordered and its minor occupied site has been omitted.
[Figure 6]
Figure 6
A perspective view of (Ib)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 7]
Figure 7
A partial packing diagram for (Ib)[link]. Hydrogen bonds are shown as dashed lines. The solvent mol­ecules, which are only stabilized by van der Waals inter­actions, have been omitted.
[Figure 8]
Figure 8
A partial packing diagram for (Ib)[link]. Hydrogen bonds are shown as dashed lines.
[Figure 9]
Figure 9
A perspective view of (Ic)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 10]
Figure 10
A partial packing diagram for (Ic)[link]. Hydrogen bonds are shown as dashed lines. Only mol­ecules A and solvent mol­ecules connected to them are shown.
[Figure 11]
Figure 11
A partial packing diagram for (Ic)[link]. Hydrogen bonds are shown as dashed lines. Only mol­ecules B and solvent mol­ecules connected to them are shown.
[Figure 12]
Figure 12
A perspective view of (IIa)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 13]
Figure 13
A perspective view of (IIb)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. The solvent mol­ecule is disordered and only the major occupied site is shown.
[Figure 14]
Figure 14
A partial packing diagram for (IIa)[link]. Hydrogen bonds are shown as dashed lines.
[Figure 15]
Figure 15
A partial packing diagram for (IIb)[link]. Hydrogen bonds are shown as dashed lines. The minor occupied sites of the solvent mol­ecules have been omitted.

Experimental

Solvent evaporation experiments with commercially available 2,6-diamino­pyrimidin-4-one under different conditions yielded (I)[link] and (Ia)–(Ic) (Table 7[link]). Single crystals of (IIa) and (IIb) were obtained by crystallization of commercially available 2-amino-6-methyl­pyrimidin-4-one (Table 8[link]). None of the solvents used in the experiments was water-free.

Compound (I)[link]

Crystal data
  • C4H6N4O

  • Mr = 126.13

  • Monoclinic, P 21 /c

  • a = 7.7150 (9) Å

  • b = 9.7229 (7) Å

  • c = 7.4514 (8) Å

  • β = 114.453 (8)°

  • V = 508.81 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.13 mm−1

  • T = 173 K

  • 0.45 × 0.35 × 0.30 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 7117 measured reflections

  • 953 independent reflections

  • 737 reflections with I > 2σ(I)

  • Rint = 0.128

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.092

  • S = 0.97

  • 953 reflections

  • 103 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21—H21A⋯O41i 0.90 (2) 1.98 (2) 2.8678 (17) 165.9 (19)
N21—H21B⋯N61ii 0.89 (2) 2.34 (2) 3.1304 (19) 147.9 (18)
N3—H3⋯N1ii 0.92 (2) 2.15 (2) 3.0370 (17) 163.2 (17)
N61—H61B⋯N1iii 0.89 (2) 2.34 (2) 3.2131 (18) 166.8 (16)
N61—H61A⋯O41iv 0.89 (2) 2.05 (2) 2.9296 (18) 172.5 (17)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+1, -y+1, -z+1; (iv) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Compound (Ia)[link]

Crystal data
  • C4H6N4O·4/3C3H7NO·1/3H2O

  • Mr = 229.59

  • Monoclinic, P 21

  • a = 7.4417 (6) Å

  • b = 25.3217 (18) Å

  • c = 9.8578 (7) Å

  • β = 108.476 (6)°

  • V = 1761.8 (2) Å3

  • Z = 6

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.50 × 0.30 × 0.20 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 28505 measured reflections

  • 3380 independent reflections

  • 2636 reflections with I > 2σ(I)

  • Rint = 0.170

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.085

  • S = 0.91

  • 3380 reflections

  • 459 parameters

  • 4 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.19 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (Ia)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21A—H21A⋯N1Bi 0.88 2.11 2.985 (4) 170
N21A—H21B⋯O1Xi 0.88 2.12 2.820 (4) 136
N3A—H3A⋯O41B 0.88 1.86 2.734 (3) 175
N61A—H61B⋯O1W 0.88 2.05 2.872 (4) 155
N21B—H21C⋯N1Aii 0.88 2.05 2.931 (4) 175
N21B—H21D⋯O1V 0.88 2.07 2.920 (4) 161
N3B—H3B⋯O41A 0.88 1.95 2.812 (3) 167
N61B—H61C⋯O1X 0.88 2.16 3.028 (4) 168
N61B—H61D⋯O41C 0.88 2.02 2.886 (4) 169
N21C—H21E⋯O41Aiii 0.88 2.11 2.945 (4) 158
N21C—H21F⋯O1Z 0.88 2.10 2.874 (4) 146
N3C—H3C⋯O1Viv 0.88 2.03 2.890 (3) 166
N61C—H61E⋯O41Cv 0.88 1.97 2.744 (3) 147
N61C—H61F⋯O1Y 0.88 2.07 2.949 (4) 173
O1V—H1V⋯N1Cvi 0.84 (1) 2.06 (2) 2.856 (3) 157 (3)
O1V—H2V⋯O41A 0.84 (1) 1.96 (2) 2.751 (3) 156 (4)
Symmetry codes: (i) x+1, y, z+1; (ii) x-1, y, z-1; (iii) [-x+1, y+{\script{1\over 2}}, -z+1]; (iv) [-x, y+{\script{1\over 2}}, -z+1]; (v) x+1, y, z; (vi) [-x+1, y-{\script{1\over 2}}, -z+1].

Compound (Ib)[link]

Crystal data
  • C4H6N4O·C4H9NO

  • Mr = 213.25

  • Monoclinic, C c

  • a = 19.1494 (13) Å

  • b = 7.8704 (4) Å

  • c = 14.9104 (11) Å

  • β = 104.868 (6)°

  • V = 2172.0 (2) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.50 × 0.35 × 0.30 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 12494 measured reflections

  • 2054 independent reflections

  • 1922 reflections with I > 2σ(I)

  • Rint = 0.096

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.126

  • S = 1.04

  • 2054 reflections

  • 277 parameters

  • 22 restraints

  • H-atom parameters constrained

  • Δρmax = 0.47 e Å−3

  • Δρmin = −0.31 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (Ib)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21A—H21A⋯N1B 0.88 2.07 2.946 (4) 171
N21A—H21B⋯O2X 0.88 2.46 3.176 (4) 139
N3A—H3A⋯O41Bi 0.88 1.89 2.765 (3) 174
N61A—H61A⋯O2Xii 0.88 2.15 2.939 (4) 150
N61A—H61B⋯O41Biii 0.88 2.22 2.975 (4) 144
N21B—H21C⋯N1A 0.88 2.16 3.029 (4) 172
N3B—H3B⋯O41Aiv 0.88 1.84 2.700 (4) 166
N61B—H61C⋯O2X 0.88 2.17 2.960 (4) 149
N61B—H61D⋯O41Av 0.88 1.95 2.813 (4) 165
Symmetry codes: (i) [x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]; (ii) [x, -y+1, z+{\script{1\over 2}}]; (iii) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iv) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (v) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].

Compound (Ic)[link]

Crystal data
  • C4H6N4O·3/2C5H9NO

  • Mr = 274.83

  • Triclinic, [P \overline 1]

  • a = 8.4550 (9) Å

  • b = 10.0803 (9) Å

  • c = 17.0735 (15) Å

  • α = 75.558 (7)°

  • β = 78.222 (8)°

  • γ = 81.363 (8)°

  • V = 1371.9 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.25 × 0.20 × 0.20 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 18821 measured reflections

  • 5116 independent reflections

  • 2940 reflections with I > 2σ(I)

  • Rint = 0.091

Refinement
  • R[F2 > 2σ(F2)] = 0.056

  • wR(F2) = 0.127

  • S = 0.91

  • 5116 reflections

  • 355 parameters

  • H-atom parameters constrained

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.29 e Å−3

Table 4
Hydrogen-bond geometry (Å, °) for (Ic)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21A—H21A⋯O2Xi 0.88 2.22 3.092 (3) 169
N21A—H21B⋯O41B 0.88 2.00 2.756 (3) 143
N3A—H3A⋯O41Aii 0.88 1.87 2.750 (3) 177
N61A—H61A⋯N1Ai 0.88 2.15 3.023 (3) 169
N61A—H61B⋯O2X 0.88 2.14 2.891 (3) 142
N21B—H21C⋯O2Ziii 0.88 2.12 2.989 (3) 170
N21B—H21D⋯O2Y 0.88 2.06 2.832 (3) 146
N3B—H3B⋯O2Y 0.88 2.15 2.904 (3) 143
N61B—H61C⋯N1Biii 0.88 2.13 3.001 (3) 170
N61B—H61D⋯O2Z 0.88 2.11 2.840 (3) 139
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+1, -z.

Compound (IIa)[link]

Crystal data
  • C5H7N3O·C5H7N3O·C4H9NO

  • Mr = 337.39

  • Triclinic, [P \overline 1]

  • a = 7.8763 (13) Å

  • b = 9.6078 (17) Å

  • c = 12.3115 (19) Å

  • α = 108.780 (13)°

  • β = 95.194 (13)°

  • γ = 99.959 (13)°

  • V = 858.0 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.40 × 0.25 × 0.10 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 7199 measured reflections

  • 3208 independent reflections

  • 1427 reflections with I > 2σ(I)

  • Rint = 0.131

Refinement
  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.204

  • S = 0.82

  • 3208 reflections

  • 223 parameters

  • H-atom parameters constrained

  • Δρmax = 0.45 e Å−3

  • Δρmin = −0.47 e Å−3

Table 5
Hydrogen-bond geometry (Å, °) for (IIa)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21A—H21A⋯O41B 0.88 1.92 2.803 (4) 178
N21A—H21B⋯O2X 0.88 2.06 2.843 (4) 147
N1A—H1A⋯O2X 0.88 2.02 2.807 (4) 149
N3B—H3B⋯N3A 0.88 1.97 2.844 (4) 177
N21B—H21C⋯N1Bi 0.88 2.10 2.969 (4) 172
N21B—H21D⋯O41A 0.88 2.00 2.877 (4) 173
Symmetry code: (i) -x+1, -y, -z.

Compound (IIb)[link]

Crystal data
  • C5H7N3O·C5H7N3O·C5H9NO

  • Mr = 349.40

  • Triclinic, [P \overline 1]

  • a = 7.3321 (7) Å

  • b = 9.8805 (9) Å

  • c = 12.5860 (12) Å

  • α = 102.835 (7)°

  • β = 98.830 (8)°

  • γ = 91.555 (8)°

  • V = 876.70 (14) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 173 K

  • 0.45 × 0.35 × 0.25 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • 13229 measured reflections

  • 3267 independent reflections

  • 1883 reflections with I > 2σ(I)

  • Rint = 0.149

Refinement
  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.176

  • S = 0.82

  • 3267 reflections

  • 242 parameters

  • 16 restraints

  • H-atom parameters constrained

  • Δρmax = 0.34 e Å−3

  • Δρmin = −0.35 e Å−3

Table 6
Hydrogen-bond geometry (Å, °) for (IIb)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1A—H1A⋯O2X 0.88 2.00 2.800 (3) 151
N21A—H21A⋯O41B 0.88 1.92 2.794 (3) 173
N21A—H21B⋯O2X 0.88 2.09 2.869 (3) 146
N3B—H3B⋯N3A 0.88 1.97 2.838 (3) 171
N21B—H21D⋯O41A 0.88 2.01 2.888 (3) 179
N21B—H21C⋯N1Bi 0.88 2.09 2.962 (3) 172
Symmetry code: (i) -x+1, -y+2, -z+2.

Table 7
Crystallization of 2,6-diamino­pyrimidin-4-one

Crystal 2,6-Diamino­pyrimidin-4-one (mg, mmol) Solvent Temperature
(I)[link] 4.2, 0.033 Methanol (500 µl) 323 K
(Ia)[link] 1.9, 0.015 DMF (100 µl) Room temperature
(Ib)[link] 2.1, 0.017 DMAC (200 µl) 323 K
(Ic)[link] 3.0, 0.024 NMP (50 µl) Room temperature

Table 8
Crystallization of 2-amino-6-methyl­pyrimidin-4-one

Crystal 2-Amino-6-methyl­pyrimidin-4-one (mg, mmol) Solvent Temperature
(IIa)[link] 2.3, 0.018 DMAC (150 µl) 277 K
(IIb)[link] 1.9, 0.015 NMP (50 µl) 323 K

The H atoms, except those bonded to disordered solvent atoms and to solvent water, were initially located by difference Fourier synthesis. Subsequently, 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 and aromatic C—H = 0.95 Å, and with Uiso(H) = 1.5Ueq(C) for methyl or 1.2Ueq(C) for secondary and aromatic H atoms. In (I)[link], H atoms bonded to N atoms were refined isotropically, while in the other structures, they were refined using a riding model, with amide and terminal N—H = 0.88 Å and with Uiso(H) = 1.2Ueq(N). For the water mol­ecule in (Ia)[link], the following restraints were applied during refinement: O—H = 0.84 (1) Å and H⋯H = 1.40 (1) Å, with Uiso(H) = 1.2Ueq(O). Similarity restraints were applied for the 1,2 and 1,3 distances of both DMAC mol­ecules in (Ib), and for the minor occupied orientation of the NMP mol­ecule in (IIb)[link].

In (Ia)[link], all C atoms of one DMF mol­ecule are disordered over two positions, with a site-occupation factor of 0.67 (1) for the major occupied orientation. In (IIb)[link], the NMP mol­ecule is disordered over a pseudo-mirror plane along atoms O2X and C5Y. The site-occupation factor for the major occupied orientation is 0.78 (1). The disordered atoms in (Ia)[link] and (IIb)[link] were refined isotropically.

The E-value distribution of (Ib)[link] could not be used as a hint for or against a centrosymmetric space group (mean value of |E2 − 1| = 0.874). A refinement attempt for (Ib)[link] in the centrosymmetric space group C2/c showed difference electron densities higher than 0.50 e Å−3 within the nonsolvent mol­ecule, and both solvent mol­ecules are highly disordered. In spite of a possible higher symmetry, tested by ADDSYM (Le Page, 1987[Le Page, Y. (1987). J. Appl. Cryst. 20, 264-269.], 1988[Le Page, Y. (1988). J. Appl. Cryst. 21, 983-984.]; Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]), (Ib)[link] was refined in the noncentrosymmetric space group Cc, which led to ordered solvent mol­ecules. For (Ia)[link] and (Ib)[link], Friedel pairs were merged prior to refinement, due to the absence of anomalous scatterers. The absolute structure was arbitrarily assigned.

For all compounds, data collection: X-AREA (Stoe & Cie, 2001[Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Version 2.2; Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and XP (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Pyrimidin-4-one derivatives are of particular interest in pharmacology and molecular biology. They include nucleobases and many important pharmaceutical drugs, e.g. anti-inflammatory (Kawade et al., 2011), anticancer (Lu et al., 2007), antihistaminic and bronchorelaxant agents (Youssouf et al., 2008). Pyrimidin-4-one can exist in three tautomeric forms: a (1H) or a (3H) tautomer or as a hydroxypyrimidine. An NMR study revealed that the preference of each tautomeric form depends on its state, although no hydroxypyrimidine form has ever been observed. In the solid state, only the (3H) tautomer has been found, while in polar solvents, a mixture of (1H) and (3H) tautomers is observed (López et al., 2000). These results agree with the two crystal structures containing pyrimidin-4-one in the Cambridge Structural Database (CSD, Version 5.31 of November 2009, plus four updates; Allen, 2002), which confirmed that the (3H) tautomer is preferred [CSD refcodes BAGQUV (Vaillancourt et al., 1998) and XOLHOW (Bhogala et al., 2008)].

We are interested in the hydrogen-bonding interaction between pyrimidin-4-one derivatives and compounds containing complementary functional groups. Since the occurrence of tautomers results in different synthon combinations (Bhogala et al., 2008), we crystallized 2,6-diaminopyrimidin-4-one and 2-amino-6-methylpyrimidin-4-one to study their tautomeric preferences. Four structures of 2,6-diaminopyrimidin-4-one were obtained during various crystallization experiments, namely solvent-free 2,6-diaminopyrimidin-4-one, (I), a dimethylformamide–water solvate (3/4/1), (Ia), a dimethylacetamide monosolvate, (Ib), and an N-methyl-2-pyrrolidone (3/2) solvate, (Ic). Another N-methyl-2-pyrrolidone solvate of minor crystal quality was also obtained (Gerhardt et al., 2011). All 2,6-diaminopyrimidin-4-one molecules exist as (3H) tautomers. Crystallization attempts on 2-amino-6-methylpyrimidin-4-one yielded two pseudopolymorphs, namely dimethylacetamide monosolvate, (IIa), and N-methyl-2-pyrrolidone monosolvate, (IIb). In both structures, a 1:1 mixture of (1H) and (3H) tautomers is present.

2,6-Diaminopyrimidin-4-one, (I), crystallizes in the monoclinic space group P21/c with one molecule in the asymmetric unit (Fig. 1). One amine group is planar and twisted slightly out of the plane of the ring, while the other is pyramidalized and shows a longer C—NH2 bond than the planar one [sums of the C—N—H and H—N—H angles at the N atoms = 359.1 (N21) and 347.3° (N61); C—NH2 = 1.337 (2) (N21) and 1.365 (2) Å (N61)]. The 2,6-diaminopyrimidin-4-one molecules form ribbons characterized by three hydrogen bonds, consisting of one R22(8) interaction (Bernstein et al., 1995) with N—H···O and N—H···N hydrogen bonds, and another R22(8) interaction with two N—H···N hydrogen bonds (Fig. 2). This arrangement is similar to that in the cytosine–guanine base pair. The ribbons are rippled and further connected into layers by R34(12) interactions. Other N—H···O hydrogen bonds stabilize the layers to form a three-dimensional network.

Compound (Ia) formed during crystallization attempts from dimethylformamide (DMF). It crystallizes in the monoclinic space group P21 with three planar 2,6-diaminopyrimidin-4-one molecules (r.m.s deviations = 0.008, 0.012 and 0.013 Å for all non-H atoms) and four DMF molecules. Since we used non-water-free solvent, one water molecule is also present in the asymmetric unit (Fig. 3). The three 2,6-diaminopyrimidin-4-one molecules show different hydrogen-bond arrangements. Molecules A and B are connected by either R22(8) N—H···O or R22(8) N—H···N bonds to form planar ribbons running parallel to (101) (Fig. 4). The ribbons are further stabilized by hydrogen bonds to the solvent molecules. One DMF molecule is N—H···O hydrogen-bonded only to molecule A, while another DMF molecule links molecules A and B by two N—H···O hydrogen bonds. Furthermore, chains running along the a axis consisting of N—H···O hydrogen-bonded molecules C are observed (Fig. 5). The chain is stabilized by N—H···O hydrogen bonds with the participation of solvent molecules. One of the two DMF molecules linked to molecule C is disordered over two sites with a planar arrangement (r.m.s deviation = 0.011 Å). The packing of (Ia) shows ribbons and chains, which are connected by N—H···O hydrogen bonds to form a three-dimensional network. The water molecule forms hydrogen bonds bridging the three 2,6-diaminopyrimidin-4-one molecules and thus additionally stabilizes the structure.

The dimethylacetamide (DMAC) monosolvate, (Ib), crystallizes in the monoclinic space group Cc with two 2,6-diaminopyrimidin-4-one (r.m.s deviations 0.013 and 0.025 Å for all non-H atoms) and two DMAC molecules in the asymmetric unit (Fig. 6). In the packing of (Ib), ribbons consisting of 2,6-diaminopyrimidin-4-one molecules run in two different directions [parallel to (111) and (111)]. Similar to (Ia), the molecules are stabilized either by N—H···O or by N—H···N hydrogen bonds with an R22(8) pattern (Fig. 7). These ribbons are further N—H···O hydrogen-bonded to form channels, in which solvent molecules are located (Fig. 8). One DMAC molecule is coplanar with the 2,6-diaminopyrimidin-4-one molecules and shows only van der Waals interactions, while the O atom of the other DMAC molecule is threefold N—H···O hydrogen-bonded to 2,6-diaminopyrimidin-4-one molecules.

Compound (Ic) crystallizes as an N-methyl-2-pyrrolidinone (NMP) solvate with two 2,6-diaminopyrimidin-4-one and three solvent molecules in the asymmetric unit (Fig. 9). The 2,6-diaminopyrimidin-4-one molecules are planar (r.m.s deviations 0.005 and 0.012 Å for all non-H atoms). R22(8) interactions involving either two N—H···O or two N—H···N hydrogen bonds are again present. Both interactions connect molecules A to form ribbons running parallel to (111), which are additionally stabilized by N—H···O bonds between molecule A and one NMP molecule (Fig. 10). In contrast, molecules B form dimers stabilized by R22(8) N—H···N hydrogen bonds. Two NMP molecules are N—H···O hydrogen-bonded to each molecule B, thus inversion-symmetric arrangements of two molecules B and two NMP molecules are formed (Fig. 11). These link the ribbons to form a three-dimensional network.

The two isostructural 2-amino-6-methylpyrimidin-4-one solvates, (IIa) and (IIb), crystallize in the triclinic space group P1 with similar lattice parameters. A 1:1 ratio of (1H) and (3H) tautomers is present in both crystals. The asymmetric unit of (IIa) consists of the two tautomers and one disordered DMAC molecule (Fig. 12), while (IIb) crystallizes with the two tautomers and one NMP molecule (Fig. 13). In both structures, the molecules are coplanar with each other, and both the hydrogen-bonding interactions and the crystal packings are similar (Figs. 14 and 15). The two tautomers are linked by two R22(8) interactions involving N—H···O and N—H···N bonds, forming a dimer related to the cytosine–guanine base pair. Two symmetry-equivalent dimers are further connected by two N—H···N interactions with an R22(8) pattern to give a tetramer. The O atoms of the solvent molecules, either DMAC in (IIa) or NMP in (IIb), adopt identical postions and are R12(6) N—H···O hydrogen-bonded to the (3H) tautomer. The crystal structures show layers parallel to the (210) plane containing discrete arrangements of the tetramers.

In order to study the preference of the (1H) and (3H) tautomeric forms, a CSD substructure search for pyrimidin-4-one derivatives was undertaken. 15 entries for the (1H), 39 entries for the (3H) and five entries with both tautomeric forms were found [refcodes ICYTIN (Sharma & McConnell, 1965), ICYTIN01 (Portalone & Colapietro, 2007), LEJLAN and LEJLOB (Bannister et al., 1994), and ZERMIS (Toledo et al., 1995)]. Examining only entries containing 2,6-diaminopyrimidin-4-one, no (1H) tautomer has been reported [refcodes SEYDIJ (Skoweranda et al., 1990) and GIMZUY (Subashini et al., 2007)]. The preference for the (3H) tautomeric form is also shown in two recently reported polymorphs of the monohydrate (Suleiman Gwaram et al., 2011), in the NMP solvate with minor crystal quality (Gerhardt et al., 2011) and in the four crystal structures above, (I) and (Ia)–(Ic). A possible explanation for the absence of the (1H) tautomeric form might be the repulsion of the H atoms from the three amino groups presenting an adjacent donor–donor–donor hydrogen-bonding site. In contrast, 2-amino-6-methylpyrimidin-4-one exists in both (1H) and (3H) tautomeric forms. In the solvent-free P21/n structure it exists as a (1H) tautomer [refcode FETSEC (Lowe et al., 1987)], while in the solvent-free C2/c polymorph, both (1H) and (3H) tautomers are shown as a result of disordered H atoms [refcode ZERMIS (Toledo et al., 1995)]. The (3H) tautomeric form is observed in its cocrystals with glutaric acid and adipic acid [refcodes ZUKXAE and ZUKXEI (Liao et al., 1996)]. Interestingly, only in the solvates (IIa) and (IIb) do both tautomers exist in a 1:1 ratio.

Almost all 2,6-diaminopyrimidin-4-one and 2-amino-6-methylpyrimidin-4-one molecules are planar. The pyramidalization of one amine group in (I) is also observed in the orthorhombic polymorph of 2,6-diaminopyrimidin-4-one monohydrate [refcode SEYDIJ (Skoweranda et al., 1990), form I according to Suleiman Gwaram et al., 2011]. Similar to (I), one C—NH2 bond is longer than the other [1.334 (2) and 1.359 (2) Å], and the sums of the bond angles at the N atoms are 360 and 354°. Different C—NH2 bond lengths are also observed in the monoclinic polymorph [form III according to Suleiman Gwaram et al., 2011; C—NH2 = 1.323 (4) and 1.354 (4) Å], but both amine groups are planar [sums of the bond angles at the N atoms = 359 (2) and 356 (2)°, respectively].

Comparing the hydrogen-bond arrangements formed by the 2,6-diaminopyrimidin-4-one molecules, ribbons characterized by R22(8) interactions involving either two N—H···O or two N—H···N bonds are observed in all structures. However, an intermolecular N—H···N interaction between the amine groups is only observed in (I) and in the orthorhombic polymorph (form I), which may explain the pyramidalization of one amine group in these two structures. The crystal packings in the various structures show three-dimensional networks additionally stabilized by solvent molecules. The (1H) and (3H) tautomers of 2-amino-6-methylpyrimidin-4-one are linked by three hydrogen bonds, similar to what is observed in the Watson–Crick C–G base pair. Identical arrangements are observed in the five CSD entries for pyrimidin-4-one derivatives containing both tautomeric forms. Altogether, (I) and (Ia)–(Ic) confirm the (3H) tautomer preference of 2,6-diaminopyrimidin-4-one, while there is no preference for 2-amino-6-methylpyrimidin-4-one. It can exist as a (1H), a (3H) or a 1:1 mixture of both tautomers, as shown in the crystal structures of (IIa) and (IIb).

Related literature top

For related literature, see: Allen (2002); Bannister et al. (1994); Bernstein et al. (1995); Bhogala et al. (2008); Gerhardt et al. (2011); Kawade et al. (2011); López et al. (2000); Le Page (1987, 1988); Liao et al. (1996); Lowe et al. (1987); Lu et al. (2007); Portalone & Colapietro (2007); Sharma & McConnell (1965); Skoweranda et al. (1990); Spek (2009); Subashini et al. (2007); Suleiman Gwaram, Khaledi, Mohd Ali & Olmstead (2011); Toledo et al. (1995); Vaillancourt et al. (1998); Youssouf et al. (2008).

Experimental top

Solvent evaporation experiments with commercially available 2,6-diaminopyrimidin-4-one under different conditions yielded (I) and (Ia)–(Ic) (Table 7). Single crystals of (IIa) and (IIb) were obtained by crystallization of commercially available 2-amino-6-methylpyrimidin-4-one (Table 8). None of the solvents used in the experiments were water-free.

Refinement top

The H atoms, except those bonded to disordered solvent atoms and to solvent water, were initially located by difference Fourier synthesis. Subsequently, 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 and aromatic C—H = 0.95 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H or 1.2Ueq(C) for secondary and aromatic H. In (I), H atoms bonded to N atoms were refined isotropically, while in the other structures, they were refined using a riding model, with amide and terminal N—H = 0.88 Å and with Uiso(H) = 1.2Ueq(N). For the water molecule in (Ia), the following restraints were applied during refinement: O—H = 0.84 (1) Å and H···H = 1.40 (1) Å, with Uiso(H) = 1.2Ueq(O). Similarity restraints were applied for the 1,2 and 1,3 distances of both DMAC molecules in (Ib), and for the minor occupied orientation of the NMP molecule in (IIb).

In (Ia), all C atoms of one DMF molecule are disordered over two positions, with a site-occupation factor of 0.67 (1) for the major occupied orientation. In (IIb), the NMP molecule is disordered over a pseudo-mirror plane along atoms O2X and C5Y. The site-occupation factor for the major occupied orientation is 0.78 (1). The disordered atoms in (Ia) and (IIb) were refined isotropically.

The E-value distribution of (Ib) could not be used as a hint for or against a centrosymmetric space group (mean value of |E2 - 1| = 0.874). A refinement attempt for (Ib) in the centrosymmetric space group C2/c showed difference electron densities higher than 0.50 e Å-3 within the non-solvent molecule, and both solvent molecules are highly disordered. In spite of a possible higher symmetry, tested by ADDSYM (Le Page, 1987, 1988; Spek, 2009), (Ib) was refined in the non-centrosymmetric space group Cc, which led to ordered solvent molecules. For both structures, Friedel pairs were merged prior to refinement, due to the absence of anomalous scatterers. The absolute structure was arbitrarily assigned.

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). Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. A perspective view of (Ia), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. One of the dimethylformamide molecules (molecule Y) is disordered; only the major occupied site is shown.
[Figure 4] Fig. 4. A partial packing diagram for (Ia). Hydrogen bonds are shown as dashed lines. Only DMF molecules linked to molecules A and B are shown.
[Figure 5] Fig. 5. A partial packing diagram for (Ia). Dashed lines indicate hydrogen bonds. Only DMF molecules linked to molecules C are shown. One of the solvent molecules is disordered and its minor occupied site has been omitted.
[Figure 6] Fig. 6. A perspective view of (Ib), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 7] Fig. 7. A partial packing diagram for (Ib). Hydrogen bonds are shown as dashed lines. The solvent molecules, which are only stabilized by van der Waals interactions, have been omitted.
[Figure 8] Fig. 8. A partial packing diagram for (Ib). Hydrogen bonds are shown as dashed lines.
[Figure 9] Fig. 9. A perspective view of (Ic), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 10] Fig. 10. A partial packing diagram for (Ic). Hydrogen bonds are shown as dashed lines. Only molecules A and solvent molecules connected to them are shown.
[Figure 11] Fig. 11. A partial packing diagram for (Ic). Hydrogen bonds are shown as dashed lines. Only molecules B and solvent molecules connected to them are shown.
[Figure 12] Fig. 12. A perspective view of (IIa), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 13] Fig. 13. A perspective view of (IIb), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. The solvent molecule is disordered and only the major occupied site is shown.
[Figure 14] Fig. 14. A partial packing diagram for (IIa). Hydrogen bonds are shown as dashed lines.
[Figure 15] Fig. 15. A partial packing diagram for (IIb). Hydrogen bonds are shown as dashed lines. The minor occupied sites of the solvent molecules have been omitted.
(I) 2,6-diaminopyrimidin-4-one top
Crystal data top
C4H6N4OF(000) = 264
Mr = 126.13Dx = 1.647 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3967 reflections
a = 7.7150 (9) Åθ = 3.6–25.9°
b = 9.7229 (7) ŵ = 0.13 mm1
c = 7.4514 (8) ÅT = 173 K
β = 114.453 (8)°Plate, colourless
V = 508.81 (9) Å30.45 × 0.35 × 0.30 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
737 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.128
Graphite monochromatorθmax = 25.6°, θmin = 3.6°
ω scansh = 99
7117 measured reflectionsk = 1110
953 independent reflectionsl = 99
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)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092 w = 1/[σ2(Fo2) + (0.0533P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
953 reflectionsΔρmax = 0.19 e Å3
103 parametersΔρmin = 0.29 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: 0.050 (9)
Crystal data top
C4H6N4OV = 508.81 (9) Å3
Mr = 126.13Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.7150 (9) ŵ = 0.13 mm1
b = 9.7229 (7) ÅT = 173 K
c = 7.4514 (8) Å0.45 × 0.35 × 0.30 mm
β = 114.453 (8)°
Data collection top
Stoe IPDS II two-circle
diffractometer
737 reflections with I > 2σ(I)
7117 measured reflectionsRint = 0.128
953 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.19 e Å3
953 reflectionsΔρmin = 0.29 e Å3
103 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*/Ueq
N10.44747 (17)0.35695 (12)0.61684 (17)0.0152 (3)
C20.5269 (2)0.23804 (14)0.6958 (2)0.0142 (3)
N210.7024 (2)0.23796 (14)0.8406 (2)0.0185 (3)
H21A0.747 (3)0.320 (2)0.897 (3)0.037 (5)*
H21B0.761 (3)0.159 (2)0.890 (3)0.036 (5)*
N30.43741 (18)0.11555 (13)0.63261 (17)0.0154 (3)
H30.490 (3)0.036 (2)0.698 (3)0.035 (5)*
C40.2545 (2)0.10530 (15)0.4819 (2)0.0149 (4)
O410.18451 (15)0.01289 (11)0.43465 (15)0.0208 (3)
C50.1700 (2)0.23046 (14)0.3980 (2)0.0155 (4)
H50.04550.23210.29480.019*
C60.2692 (2)0.35141 (14)0.4666 (2)0.0144 (4)
N610.1955 (2)0.47663 (13)0.38987 (19)0.0176 (4)
H61B0.286 (3)0.535 (2)0.393 (3)0.029 (5)*
H61A0.084 (3)0.4742 (18)0.286 (3)0.023 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0150 (7)0.0127 (6)0.0150 (6)0.0001 (5)0.0033 (5)0.0014 (5)
C20.0147 (7)0.0141 (7)0.0141 (7)0.0020 (5)0.0065 (6)0.0010 (5)
N210.0151 (7)0.0135 (7)0.0197 (7)0.0001 (5)0.0000 (5)0.0002 (5)
N30.0154 (7)0.0106 (6)0.0168 (7)0.0005 (5)0.0034 (5)0.0018 (5)
C40.0145 (8)0.0156 (7)0.0139 (7)0.0022 (6)0.0050 (6)0.0014 (6)
O410.0194 (6)0.0128 (6)0.0225 (6)0.0018 (4)0.0010 (4)0.0013 (4)
C50.0132 (7)0.0156 (8)0.0144 (7)0.0013 (5)0.0024 (6)0.0006 (5)
C60.0158 (7)0.0152 (7)0.0135 (7)0.0016 (6)0.0073 (6)0.0008 (6)
N610.0162 (7)0.0129 (7)0.0178 (7)0.0003 (5)0.0013 (6)0.0012 (5)
Geometric parameters (Å, º) top
N1—C21.3266 (18)C4—O411.2565 (18)
N1—C61.369 (2)C4—C51.400 (2)
C2—N211.337 (2)C5—C61.381 (2)
C2—N31.3592 (18)C5—H50.9500
N21—H21A0.90 (2)C6—N611.3651 (18)
N21—H21B0.89 (2)N61—H61B0.89 (2)
N3—C41.396 (2)N61—H61A0.89 (2)
N3—H30.92 (2)
C2—N1—C6116.85 (12)O41—C4—C5127.08 (13)
N1—C2—N21119.07 (13)N3—C4—C5115.22 (13)
N1—C2—N3122.34 (14)C6—C5—C4119.38 (14)
N21—C2—N3118.58 (13)C6—C5—H5120.3
C2—N21—H21A116.1 (13)C4—C5—H5120.3
C2—N21—H21B120.4 (13)N61—C6—N1114.26 (13)
H21A—N21—H21B122.6 (19)N61—C6—C5122.25 (14)
C2—N3—C4122.71 (13)N1—C6—C5123.49 (13)
C2—N3—H3120.4 (12)C6—N61—H61B111.7 (12)
C4—N3—H3116.5 (12)C6—N61—H61A115.3 (12)
O41—C4—N3117.70 (13)H61B—N61—H61A120.3 (17)
C6—N1—C2—N21178.82 (13)O41—C4—C5—C6179.04 (13)
C6—N1—C2—N30.1 (2)N3—C4—C5—C60.14 (19)
N1—C2—N3—C40.8 (2)C2—N1—C6—N61179.36 (12)
N21—C2—N3—C4179.79 (13)C2—N1—C6—C51.1 (2)
C2—N3—C4—O41179.95 (12)C4—C5—C6—N61179.39 (13)
C2—N3—C4—C50.8 (2)C4—C5—C6—N11.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21A···O41i0.90 (2)1.98 (2)2.8678 (17)165.9 (19)
N21—H21B···N61ii0.89 (2)2.34 (2)3.1304 (19)147.9 (18)
N3—H3···N1ii0.92 (2)2.15 (2)3.0370 (17)163.2 (17)
N61—H61B···N1iii0.89 (2)2.34 (2)3.2131 (18)166.8 (16)
N61—H61A···O41iv0.89 (2)2.05 (2)2.9296 (18)172.5 (17)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1; (iv) x, y+1/2, z+1/2.
(Ia) 2,6-diaminopyrimidin-4-one dimethylformamide solvate hydrate (3/4/1) top
Crystal data top
C4H6N4O·4/3C3H7NO·1/3H2OF(000) = 736
Mr = 229.59Dx = 1.298 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 12963 reflections
a = 7.4417 (6) Åθ = 3.3–25.8°
b = 25.3217 (18) ŵ = 0.10 mm1
c = 9.8578 (7) ÅT = 173 K
β = 108.476 (6)°Block, colourless
V = 1761.8 (2) Å30.50 × 0.30 × 0.20 mm
Z = 6
Data collection top
Stoe IPDS II two-circle
diffractometer
2636 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.170
Graphite monochromatorθmax = 25.7°, θmin = 3.3°
ω scansh = 99
28505 measured reflectionsk = 3030
3380 independent reflectionsl = 1111
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)] = 0.040H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.0331P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max < 0.001
3380 reflectionsΔρmax = 0.19 e Å3
459 parametersΔρmin = 0.19 e Å3
4 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0121 (15)
Crystal data top
C4H6N4O·4/3C3H7NO·1/3H2OV = 1761.8 (2) Å3
Mr = 229.59Z = 6
Monoclinic, P21Mo Kα radiation
a = 7.4417 (6) ŵ = 0.10 mm1
b = 25.3217 (18) ÅT = 173 K
c = 9.8578 (7) Å0.50 × 0.30 × 0.20 mm
β = 108.476 (6)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2636 reflections with I > 2σ(I)
28505 measured reflectionsRint = 0.170
3380 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0404 restraints
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 0.91Δρmax = 0.19 e Å3
3380 reflectionsΔρmin = 0.19 e Å3
459 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)
N1A0.8108 (4)0.30056 (11)1.2152 (3)0.0259 (6)
C2A0.7168 (5)0.34081 (12)1.1395 (3)0.0230 (7)
N21A0.7359 (4)0.38915 (11)1.1972 (3)0.0309 (7)
H21A0.81080.39411.28540.037*
H21B0.67350.41591.14710.037*
N3A0.5984 (4)0.33572 (10)1.0033 (3)0.0234 (6)
H3A0.53750.36370.95840.028*
C4A0.5718 (4)0.28787 (13)0.9342 (3)0.0225 (7)
O41A0.4577 (3)0.28704 (9)0.8053 (2)0.0271 (5)
C5A0.6701 (5)0.24490 (13)1.0084 (3)0.0258 (7)
H5A0.65840.21110.96480.031*
C6A0.7865 (5)0.25253 (13)1.1483 (3)0.0244 (7)
N61A0.8847 (5)0.21230 (11)1.2270 (3)0.0343 (7)
H61A0.95830.21801.31520.041*
H61B0.87540.18041.19020.041*
N1B0.0210 (4)0.41264 (10)0.4808 (3)0.0244 (6)
C2B0.1126 (5)0.37170 (13)0.5545 (4)0.0247 (7)
N21B0.0823 (4)0.32310 (11)0.4976 (3)0.0355 (8)
H21C0.00150.31840.41130.043*
H21D0.14310.29590.54650.043*
N3B0.2387 (4)0.37622 (11)0.6873 (3)0.0251 (6)
H3B0.29390.34750.73150.030*
C4B0.2846 (4)0.42482 (13)0.7568 (3)0.0239 (7)
O41B0.4079 (3)0.42458 (9)0.8790 (2)0.0294 (5)
C5B0.1879 (5)0.46809 (12)0.6809 (3)0.0254 (7)
H5B0.20920.50240.72180.030*
C6B0.0601 (4)0.46080 (12)0.5451 (3)0.0243 (7)
N61B0.0332 (4)0.50164 (11)0.4664 (3)0.0308 (7)
H61C0.11260.49610.38010.037*
H61D0.01490.53390.50130.037*
N1C0.4907 (4)0.67315 (10)0.4594 (3)0.0249 (6)
C2C0.3199 (5)0.69608 (12)0.4176 (3)0.0240 (7)
N21C0.2941 (4)0.74136 (11)0.3448 (3)0.0321 (7)
H21E0.38940.75610.32420.038*
H21F0.18180.75650.31730.038*
N3C0.1680 (4)0.67483 (10)0.4451 (3)0.0230 (6)
H3C0.05880.69150.41410.028*
C4C0.1772 (4)0.62771 (12)0.5203 (3)0.0219 (7)
O41C0.0290 (3)0.61173 (9)0.5426 (2)0.0296 (5)
C5C0.3521 (4)0.60245 (13)0.5609 (3)0.0241 (7)
H5C0.36760.56930.60830.029*
C6C0.5052 (4)0.62643 (13)0.5312 (3)0.0244 (7)
N61C0.6760 (4)0.60401 (12)0.5731 (3)0.0384 (8)
H61E0.77130.61940.55400.046*
H61F0.69350.57390.61980.046*
O1V0.2076 (3)0.21935 (9)0.6207 (3)0.0271 (5)
H1V0.271 (4)0.2005 (12)0.582 (3)0.033*
H2V0.278 (4)0.2343 (13)0.695 (2)0.033*
C1W0.9054 (6)0.07825 (17)1.0454 (4)0.0463 (10)
H1W0.96860.06431.13770.056*
O1W0.8781 (5)0.12587 (12)1.0368 (3)0.0677 (10)
N2W0.8550 (5)0.04439 (12)0.9379 (3)0.0374 (7)
C3W0.7545 (8)0.0628 (2)0.7942 (5)0.0633 (13)
H3W10.62520.04870.76380.095*
H3W20.82050.05060.72830.095*
H3W30.74990.10150.79340.095*
C4W0.8889 (7)0.01146 (16)0.9573 (5)0.0553 (12)
H4W10.96360.01861.05700.083*
H4W20.95880.02370.89410.083*
H4W30.76760.03010.93410.083*
C1X0.3644 (5)0.52639 (15)0.0612 (4)0.0369 (9)
H1X0.41600.50850.02740.044*
O1X0.3195 (4)0.49928 (10)0.1693 (3)0.0489 (7)
N2X0.3477 (5)0.57831 (12)0.0562 (3)0.0354 (7)
C3X0.2729 (8)0.60950 (18)0.1845 (5)0.0715 (16)
H3X10.24820.58660.26850.107*
H3X20.36520.63670.18780.107*
H3X30.15460.62640.18420.107*
C4X0.4038 (7)0.60669 (19)0.0786 (4)0.0546 (11)
H4X10.44220.58140.15790.082*
H4X20.29670.62770.08600.082*
H4X30.51020.63010.08280.082*
O1Y0.7001 (4)0.50147 (10)0.7197 (3)0.0422 (6)
N2Y0.6245 (5)0.42567 (14)0.5915 (4)0.0449 (9)
C1Y0.7052 (8)0.4531 (2)0.7037 (6)0.0360 (16)0.672 (7)
H1Y0.77850.43380.78500.043*0.672 (7)
C3Y0.6374 (10)0.3704 (2)0.5740 (8)0.0472 (19)0.672 (7)
H3YA0.55870.36030.47750.071*0.672 (7)
H3YB0.59290.35200.64480.071*0.672 (7)
H3YC0.76950.36080.58770.071*0.672 (7)
C4Y0.5013 (8)0.4555 (2)0.4568 (6)0.0419 (16)0.672 (7)
H4YA0.44690.43020.37950.063*0.672 (7)
H4YB0.58000.48100.42650.063*0.672 (7)
H4YC0.39890.47420.47920.063*0.672 (7)
C1Y'0.620 (2)0.4736 (6)0.6093 (17)0.055 (4)*0.328 (7)
H1Y'0.54440.49280.52850.067*0.328 (7)
C3Y'0.557 (3)0.3896 (8)0.493 (2)0.079 (6)*0.328 (7)
H3YD0.59320.35440.53410.118*0.328 (7)
H3YE0.60840.39510.41400.118*0.328 (7)
H3YF0.41840.39220.45670.118*0.328 (7)
C4Y'0.757 (2)0.3919 (6)0.7360 (14)0.054 (4)*0.328 (7)
H4YD0.74880.35400.71450.081*0.328 (7)
H4YE0.71010.39870.81670.081*0.328 (7)
H4YF0.88940.40330.76090.081*0.328 (7)
C1Z0.1313 (6)0.7652 (2)0.0294 (5)0.0517 (11)
H1Z0.14600.72800.02780.062*
O1Z0.0400 (5)0.78640 (15)0.1449 (4)0.0672 (10)
N2Z0.2084 (5)0.79134 (14)0.0904 (4)0.0443 (8)
C3Z0.1892 (7)0.84789 (19)0.0986 (6)0.0606 (13)
H3Z10.12020.86180.00350.091*
H3Z20.31520.86410.13280.091*
H3Z30.11920.85620.16500.091*
C4Z0.3169 (7)0.7644 (2)0.2203 (5)0.0634 (14)
H4Z10.31560.72630.20240.095*
H4Z20.26070.77140.29590.095*
H4Z30.44790.77720.25040.095*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0312 (16)0.0217 (15)0.0244 (15)0.0002 (12)0.0082 (12)0.0012 (12)
C2A0.0279 (17)0.0205 (17)0.0204 (17)0.0017 (14)0.0073 (14)0.0010 (13)
N21A0.0394 (17)0.0223 (16)0.0238 (15)0.0036 (12)0.0002 (13)0.0015 (12)
N3A0.0242 (14)0.0208 (14)0.0230 (15)0.0037 (11)0.0042 (11)0.0009 (11)
C4A0.0224 (17)0.0231 (17)0.0227 (17)0.0037 (13)0.0083 (14)0.0055 (14)
O41A0.0250 (12)0.0289 (13)0.0245 (13)0.0019 (10)0.0035 (10)0.0067 (10)
C5A0.0284 (18)0.0219 (17)0.0275 (18)0.0026 (14)0.0095 (14)0.0054 (14)
C6A0.0263 (18)0.0223 (17)0.0258 (17)0.0008 (14)0.0098 (14)0.0036 (14)
N61A0.0452 (19)0.0227 (15)0.0285 (16)0.0016 (13)0.0025 (14)0.0015 (12)
N1B0.0270 (15)0.0212 (15)0.0219 (14)0.0014 (11)0.0030 (11)0.0003 (11)
C2B0.0248 (18)0.0229 (17)0.0257 (18)0.0014 (14)0.0069 (14)0.0015 (14)
N21B0.0461 (19)0.0232 (16)0.0243 (16)0.0063 (13)0.0073 (14)0.0026 (12)
N3B0.0274 (15)0.0221 (14)0.0210 (15)0.0050 (11)0.0008 (12)0.0008 (11)
C4B0.0231 (16)0.0233 (17)0.0259 (18)0.0012 (14)0.0084 (15)0.0040 (14)
O41B0.0324 (13)0.0273 (13)0.0223 (12)0.0010 (10)0.0000 (11)0.0019 (9)
C5B0.0291 (18)0.0205 (17)0.0253 (18)0.0026 (14)0.0068 (15)0.0049 (13)
C6B0.0236 (18)0.0235 (18)0.0267 (18)0.0010 (14)0.0092 (15)0.0035 (14)
N61B0.0372 (18)0.0202 (15)0.0294 (15)0.0023 (12)0.0026 (13)0.0001 (12)
N1C0.0235 (15)0.0244 (15)0.0291 (15)0.0015 (11)0.0115 (12)0.0045 (12)
C2C0.0277 (18)0.0212 (17)0.0245 (17)0.0022 (14)0.0100 (14)0.0018 (14)
N21C0.0280 (16)0.0261 (16)0.0466 (18)0.0045 (12)0.0183 (14)0.0114 (13)
N3C0.0168 (13)0.0233 (14)0.0305 (15)0.0023 (10)0.0097 (11)0.0025 (11)
C4C0.0222 (16)0.0205 (16)0.0247 (16)0.0017 (13)0.0100 (13)0.0029 (13)
O41C0.0202 (12)0.0252 (12)0.0479 (14)0.0029 (9)0.0172 (11)0.0027 (11)
C5C0.0202 (16)0.0248 (17)0.0297 (17)0.0002 (13)0.0112 (13)0.0024 (14)
C6C0.0225 (16)0.0272 (17)0.0261 (17)0.0007 (14)0.0114 (13)0.0022 (14)
N61C0.0222 (15)0.0405 (18)0.057 (2)0.0059 (13)0.0185 (14)0.0213 (16)
O1V0.0241 (12)0.0223 (12)0.0364 (14)0.0002 (9)0.0117 (10)0.0084 (10)
C1W0.058 (3)0.042 (3)0.039 (2)0.006 (2)0.015 (2)0.0015 (19)
O1W0.104 (3)0.0365 (19)0.0548 (19)0.0162 (18)0.0140 (18)0.0074 (14)
N2W0.0467 (19)0.0311 (17)0.0369 (17)0.0042 (14)0.0165 (15)0.0044 (14)
C3W0.093 (4)0.054 (3)0.039 (2)0.003 (3)0.016 (3)0.003 (2)
C4W0.074 (3)0.029 (2)0.072 (3)0.002 (2)0.036 (3)0.001 (2)
C1X0.039 (2)0.034 (2)0.032 (2)0.0044 (16)0.0032 (17)0.0073 (17)
O1X0.071 (2)0.0271 (14)0.0358 (15)0.0066 (13)0.0007 (13)0.0029 (13)
N2X0.0474 (19)0.0259 (16)0.0268 (16)0.0000 (13)0.0030 (14)0.0027 (13)
C3X0.114 (4)0.032 (2)0.045 (3)0.008 (3)0.007 (3)0.013 (2)
C4X0.076 (3)0.048 (3)0.038 (2)0.007 (2)0.017 (2)0.008 (2)
O1Y0.0476 (16)0.0308 (16)0.0495 (16)0.0011 (12)0.0174 (13)0.0018 (13)
N2Y0.047 (2)0.037 (2)0.061 (2)0.0071 (16)0.0316 (18)0.0101 (18)
C1Y0.038 (3)0.032 (3)0.041 (4)0.001 (2)0.017 (3)0.008 (3)
C3Y0.056 (4)0.026 (3)0.072 (5)0.006 (3)0.039 (4)0.009 (3)
C4Y0.038 (3)0.049 (4)0.039 (3)0.002 (3)0.013 (3)0.004 (3)
C1Z0.045 (3)0.058 (3)0.060 (3)0.015 (2)0.028 (2)0.014 (2)
O1Z0.055 (2)0.092 (3)0.055 (2)0.0329 (19)0.0173 (17)0.0070 (19)
N2Z0.0366 (19)0.048 (2)0.053 (2)0.0067 (15)0.0205 (17)0.0080 (17)
C3Z0.059 (3)0.048 (3)0.087 (4)0.012 (2)0.040 (3)0.015 (3)
C4Z0.053 (3)0.086 (4)0.053 (3)0.005 (3)0.021 (2)0.003 (3)
Geometric parameters (Å, º) top
N1A—C2A1.325 (4)N2W—C3W1.454 (5)
N1A—C6A1.368 (4)C3W—H3W10.9800
C2A—N21A1.338 (4)C3W—H3W20.9800
C2A—N3A1.359 (4)C3W—H3W30.9800
N21A—H21A0.8800C4W—H4W10.9800
N21A—H21B0.8800C4W—H4W20.9800
N3A—C4A1.373 (4)C4W—H4W30.9800
N3A—H3A0.8800C1X—O1X1.221 (4)
C4A—O41A1.285 (4)C1X—N2X1.323 (5)
C4A—C5A1.384 (5)C1X—H1X0.9500
C5A—C6A1.390 (4)N2X—C3X1.445 (5)
C5A—H5A0.9500N2X—C4X1.450 (5)
C6A—N61A1.347 (4)C3X—H3X10.9800
N61A—H61A0.8800C3X—H3X20.9800
N61A—H61B0.8800C3X—H3X30.9800
N1B—C2B1.324 (4)C4X—H4X10.9800
N1B—C6B1.363 (4)C4X—H4X20.9800
C2B—N21B1.341 (4)C4X—H4X30.9800
C2B—N3B1.352 (4)O1Y—C1Y1.237 (6)
N21B—H21C0.8800O1Y—C1Y'1.276 (15)
N21B—H21D0.8800N2Y—C1Y'1.227 (16)
N3B—C4B1.397 (4)N2Y—C1Y1.283 (7)
N3B—H3B0.8800N2Y—C3Y'1.313 (19)
C4B—O41B1.262 (4)N2Y—C3Y1.416 (7)
C4B—C5B1.392 (5)N2Y—C4Y1.550 (7)
C5B—C6B1.387 (5)N2Y—C4Y'1.687 (14)
C5B—H5B0.9500C1Y—H1Y0.9500
C6B—N61B1.346 (4)C3Y—H3YA0.9800
N61B—H61C0.8800C3Y—H3YB0.9800
N61B—H61D0.8800C3Y—H3YC0.9800
N1C—C2C1.338 (4)C4Y—H4YA0.9800
N1C—C6C1.365 (4)C4Y—H4YB0.9800
C2C—N21C1.334 (4)C4Y—H4YC0.9800
C2C—N3C1.354 (4)C1Y'—H1Y'0.9500
N21C—H21E0.8800C3Y'—H3YD0.9800
N21C—H21F0.8800C3Y'—H3YE0.9800
N3C—C4C1.395 (4)C3Y'—H3YF0.9800
N3C—H3C0.8800C4Y'—H4YD0.9800
C4C—O41C1.258 (4)C4Y'—H4YE0.9800
C4C—C5C1.390 (4)C4Y'—H4YF0.9800
C5C—C6C1.402 (4)C1Z—O1Z1.247 (6)
C5C—H5C0.9500C1Z—N2Z1.316 (6)
C6C—N61C1.333 (4)C1Z—H1Z0.9500
N61C—H61E0.8800N2Z—C3Z1.444 (6)
N61C—H61F0.8800N2Z—C4Z1.450 (6)
O1V—H1V0.844 (10)C3Z—H3Z10.9800
O1V—H2V0.844 (10)C3Z—H3Z20.9800
C1W—O1W1.222 (5)C3Z—H3Z30.9800
C1W—N2W1.321 (5)C4Z—H4Z10.9800
C1W—H1W0.9500C4Z—H4Z20.9800
N2W—C4W1.439 (5)C4Z—H4Z30.9800
C2A—N1A—C6A116.5 (3)H4W1—C4W—H4W3109.5
N1A—C2A—N21A119.9 (3)H4W2—C4W—H4W3109.5
N1A—C2A—N3A123.0 (3)O1X—C1X—N2X126.1 (3)
N21A—C2A—N3A117.1 (3)O1X—C1X—H1X117.0
C2A—N21A—H21A120.0N2X—C1X—H1X117.0
C2A—N21A—H21B120.0C1X—N2X—C3X121.7 (3)
H21A—N21A—H21B120.0C1X—N2X—C4X121.6 (3)
C2A—N3A—C4A121.3 (3)C3X—N2X—C4X116.7 (3)
C2A—N3A—H3A119.3N2X—C3X—H3X1109.5
C4A—N3A—H3A119.3N2X—C3X—H3X2109.5
O41A—C4A—N3A116.8 (3)H3X1—C3X—H3X2109.5
O41A—C4A—C5A125.6 (3)N2X—C3X—H3X3109.5
N3A—C4A—C5A117.6 (3)H3X1—C3X—H3X3109.5
C4A—C5A—C6A118.3 (3)H3X2—C3X—H3X3109.5
C4A—C5A—H5A120.9N2X—C4X—H4X1109.5
C6A—C5A—H5A120.9N2X—C4X—H4X2109.5
N61A—C6A—N1A115.4 (3)H4X1—C4X—H4X2109.5
N61A—C6A—C5A121.3 (3)N2X—C4X—H4X3109.5
N1A—C6A—C5A123.2 (3)H4X1—C4X—H4X3109.5
C6A—N61A—H61A120.0H4X2—C4X—H4X3109.5
C6A—N61A—H61B120.0C1Y—O1Y—C1Y'50.8 (7)
H61A—N61A—H61B120.0C1Y'—N2Y—C1Y50.9 (8)
C2B—N1B—C6B116.7 (3)C1Y'—N2Y—C3Y'140.5 (13)
N1B—C2B—N21B120.0 (3)C1Y—N2Y—C3Y'168.6 (10)
N1B—C2B—N3B122.9 (3)C1Y'—N2Y—C3Y177.9 (9)
N21B—C2B—N3B117.1 (3)C1Y—N2Y—C3Y127.5 (5)
C2B—N21B—H21C120.0C1Y'—N2Y—C4Y66.7 (8)
C2B—N21B—H21D120.0C1Y—N2Y—C4Y117.6 (4)
H21C—N21B—H21D120.0C3Y'—N2Y—C4Y73.8 (10)
C2B—N3B—C4B122.4 (3)C3Y—N2Y—C4Y114.9 (5)
C2B—N3B—H3B118.8C1Y'—N2Y—C4Y'114.6 (9)
C4B—N3B—H3B118.8C1Y—N2Y—C4Y'63.7 (6)
O41B—C4B—C5B127.8 (3)C3Y'—N2Y—C4Y'104.9 (11)
O41B—C4B—N3B117.1 (3)C3Y—N2Y—C4Y'63.7 (6)
C5B—C4B—N3B115.2 (3)C4Y—N2Y—C4Y'178.7 (6)
C6B—C5B—C4B119.6 (3)O1Y—C1Y—N2Y128.4 (5)
C6B—C5B—H5B120.2O1Y—C1Y—H1Y115.8
C4B—C5B—H5B120.2N2Y—C1Y—H1Y115.8
N61B—C6B—N1B115.1 (3)N2Y—C3Y—H3YA109.5
N61B—C6B—C5B121.6 (3)N2Y—C3Y—H3YB109.5
N1B—C6B—C5B123.2 (3)H3YA—C3Y—H3YB109.5
C6B—N61B—H61C120.0N2Y—C3Y—H3YC109.5
C6B—N61B—H61D120.0H3YA—C3Y—H3YC109.5
H61C—N61B—H61D120.0H3YB—C3Y—H3YC109.5
C2C—N1C—C6C116.5 (3)N2Y—C4Y—H4YA109.5
N21C—C2C—N1C119.9 (3)N2Y—C4Y—H4YB109.5
N21C—C2C—N3C117.5 (3)H4YA—C4Y—H4YB109.5
N1C—C2C—N3C122.5 (3)N2Y—C4Y—H4YC109.5
C2C—N21C—H21E120.0H4YA—C4Y—H4YC109.5
C2C—N21C—H21F120.0H4YB—C4Y—H4YC109.5
H21E—N21C—H21F120.0N2Y—C1Y'—O1Y130.0 (14)
C2C—N3C—C4C122.9 (3)N2Y—C1Y'—H1Y'115.0
C2C—N3C—H3C118.6O1Y—C1Y'—H1Y'115.0
C4C—N3C—H3C118.6N2Y—C3Y'—H3YD109.5
O41C—C4C—C5C126.4 (3)N2Y—C3Y'—H3YE109.5
O41C—C4C—N3C118.1 (3)H3YD—C3Y'—H3YE109.5
C5C—C4C—N3C115.5 (3)N2Y—C3Y'—H3YF109.5
C4C—C5C—C6C119.3 (3)H3YD—C3Y'—H3YF109.5
C4C—C5C—H5C120.3H3YE—C3Y'—H3YF109.5
C6C—C5C—H5C120.3N2Y—C4Y'—H4YD109.5
N61C—C6C—N1C116.1 (3)N2Y—C4Y'—H4YE109.5
N61C—C6C—C5C120.6 (3)H4YD—C4Y'—H4YE109.5
N1C—C6C—C5C123.2 (3)N2Y—C4Y'—H4YF109.5
C6C—N61C—H61E120.0H4YD—C4Y'—H4YF109.5
C6C—N61C—H61F120.0H4YE—C4Y'—H4YF109.5
H61E—N61C—H61F120.0O1Z—C1Z—N2Z124.1 (5)
H1V—O1V—H2V111.3 (17)O1Z—C1Z—H1Z117.9
O1W—C1W—N2W125.9 (4)N2Z—C1Z—H1Z117.9
O1W—C1W—H1W117.1C1Z—N2Z—C3Z121.7 (4)
N2W—C1W—H1W117.1C1Z—N2Z—C4Z121.2 (4)
C1W—N2W—C4W122.5 (4)C3Z—N2Z—C4Z117.1 (4)
C1W—N2W—C3W120.1 (4)N2Z—C3Z—H3Z1109.5
C4W—N2W—C3W117.3 (4)N2Z—C3Z—H3Z2109.5
N2W—C3W—H3W1109.5H3Z1—C3Z—H3Z2109.5
N2W—C3W—H3W2109.5N2Z—C3Z—H3Z3109.5
H3W1—C3W—H3W2109.5H3Z1—C3Z—H3Z3109.5
N2W—C3W—H3W3109.5H3Z2—C3Z—H3Z3109.5
H3W1—C3W—H3W3109.5N2Z—C4Z—H4Z1109.5
H3W2—C3W—H3W3109.5N2Z—C4Z—H4Z2109.5
N2W—C4W—H4W1109.5H4Z1—C4Z—H4Z2109.5
N2W—C4W—H4W2109.5N2Z—C4Z—H4Z3109.5
H4W1—C4W—H4W2109.5H4Z1—C4Z—H4Z3109.5
N2W—C4W—H4W3109.5H4Z2—C4Z—H4Z3109.5
C6A—N1A—C2A—N21A179.0 (3)N1C—C2C—N3C—C4C0.7 (5)
C6A—N1A—C2A—N3A1.3 (5)C2C—N3C—C4C—O41C178.7 (3)
N1A—C2A—N3A—C4A1.3 (5)C2C—N3C—C4C—C5C2.5 (4)
N21A—C2A—N3A—C4A179.0 (3)O41C—C4C—C5C—C6C178.2 (3)
C2A—N3A—C4A—O41A179.7 (3)N3C—C4C—C5C—C6C3.1 (4)
C2A—N3A—C4A—C5A0.0 (4)C2C—N1C—C6C—N61C179.6 (3)
O41A—C4A—C5A—C6A179.2 (3)C2C—N1C—C6C—C5C0.3 (4)
N3A—C4A—C5A—C6A1.1 (4)C4C—C5C—C6C—N61C177.8 (3)
C2A—N1A—C6A—N61A179.5 (3)C4C—C5C—C6C—N1C2.2 (5)
C2A—N1A—C6A—C5A0.1 (5)O1W—C1W—N2W—C4W178.7 (5)
C4A—C5A—C6A—N61A179.3 (3)O1W—C1W—N2W—C3W1.2 (7)
C4A—C5A—C6A—N1A1.1 (5)O1X—C1X—N2X—C3X0.7 (7)
C6B—N1B—C2B—N21B179.6 (3)O1X—C1X—N2X—C4X179.3 (4)
C6B—N1B—C2B—N3B0.3 (5)C1Y'—O1Y—C1Y—N2Y0.6 (9)
N1B—C2B—N3B—C4B0.9 (5)C1Y'—N2Y—C1Y—O1Y0.6 (10)
N21B—C2B—N3B—C4B178.9 (3)C3Y'—N2Y—C1Y—O1Y178 (5)
C2B—N3B—C4B—O41B178.2 (3)C3Y—N2Y—C1Y—O1Y177.7 (5)
C2B—N3B—C4B—C5B1.4 (4)C4Y—N2Y—C1Y—O1Y0.8 (8)
O41B—C4B—C5B—C6B178.2 (3)C4Y'—N2Y—C1Y—O1Y179.3 (9)
N3B—C4B—C5B—C6B1.3 (4)C1Y—N2Y—C1Y'—O1Y0.6 (10)
C2B—N1B—C6B—N61B179.0 (3)C3Y'—N2Y—C1Y'—O1Y179.8 (15)
C2B—N1B—C6B—C5B0.2 (5)C4Y—N2Y—C1Y'—O1Y179.6 (18)
C4B—C5B—C6B—N61B178.4 (3)C4Y'—N2Y—C1Y'—O1Y0.5 (19)
C4B—C5B—C6B—N1B0.8 (5)C1Y—O1Y—C1Y'—N2Y0.6 (10)
C6C—N1C—C2C—N21C178.9 (3)O1Z—C1Z—N2Z—C3Z1.5 (6)
C6C—N1C—C2C—N3C0.4 (4)O1Z—C1Z—N2Z—C4Z178.4 (4)
N21C—C2C—N3C—C4C180.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···N1Bi0.882.112.985 (4)170
N21A—H21B···O1Xi0.882.122.820 (4)136
N3A—H3A···O41B0.881.862.734 (3)175
N61A—H61B···O1W0.882.052.872 (4)155
N21B—H21C···N1Aii0.882.052.931 (4)175
N21B—H21D···O1V0.882.072.920 (4)161
N3B—H3B···O41A0.881.952.812 (3)167
N61B—H61C···O1X0.882.163.028 (4)168
N61B—H61D···O41C0.882.022.886 (4)169
N21C—H21E···O41Aiii0.882.112.945 (4)158
N21C—H21F···O1Z0.882.102.874 (4)146
N3C—H3C···O1Viv0.882.032.890 (3)166
N61C—H61E···O41Cv0.881.972.744 (3)147
N61C—H61F···O1Y0.882.072.949 (4)173
O1V—H1V···N1Cvi0.84 (1)2.06 (2)2.856 (3)157 (3)
O1V—H2V···O41A0.84 (1)1.96 (2)2.751 (3)156 (4)
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y, z1; (iii) x+1, y+1/2, z+1; (iv) x, y+1/2, z+1; (v) x+1, y, z; (vi) x+1, y1/2, z+1.
(Ib) 2,6-diaminopyrimidin-4-one dimethylacetamide solvate (1/1) top
Crystal data top
C4H6N4O·C4H9NOF(000) = 912
Mr = 213.25Dx = 1.304 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 10399 reflections
a = 19.1494 (13) Åθ = 3.3–26°
b = 7.8704 (4) ŵ = 0.10 mm1
c = 14.9104 (11) ÅT = 173 K
β = 104.868 (6)°Block, colourless
V = 2172.0 (2) Å30.50 × 0.35 × 0.30 mm
Z = 8
Data collection top
Stoe IPDS II two-circle
diffractometer
1922 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.096
Graphite monochromatorθmax = 25.6°, θmin = 3.3°
ω scansh = 2323
12494 measured reflectionsk = 99
2054 independent reflectionsl = 1818
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0831P)2 + 1.0447P]
where P = (Fo2 + 2Fc2)/3
2054 reflections(Δ/σ)max < 0.001
277 parametersΔρmax = 0.47 e Å3
22 restraintsΔρmin = 0.31 e Å3
Crystal data top
C4H6N4O·C4H9NOV = 2172.0 (2) Å3
Mr = 213.25Z = 8
Monoclinic, CcMo Kα radiation
a = 19.1494 (13) ŵ = 0.10 mm1
b = 7.8704 (4) ÅT = 173 K
c = 14.9104 (11) Å0.50 × 0.35 × 0.30 mm
β = 104.868 (6)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1922 reflections with I > 2σ(I)
12494 measured reflectionsRint = 0.096
2054 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04722 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.04Δρmax = 0.47 e Å3
2054 reflectionsΔρmin = 0.31 e Å3
277 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*/Ueq
N1A0.61616 (13)0.5230 (3)0.58590 (17)0.0210 (6)
C2A0.63414 (16)0.6155 (4)0.5207 (2)0.0201 (6)
N21A0.58328 (15)0.6543 (4)0.44317 (19)0.0285 (7)
H21A0.53860.61860.43600.034*
H21B0.59460.71540.39950.034*
N3A0.70167 (14)0.6750 (3)0.52842 (18)0.0212 (5)
H3A0.71040.73330.48210.025*
C4A0.75747 (16)0.6473 (4)0.6067 (2)0.0217 (6)
O41A0.81938 (12)0.7060 (3)0.60727 (15)0.0282 (5)
C5A0.74048 (17)0.5564 (4)0.6787 (2)0.0232 (7)
H5A0.77560.53900.73590.028*
C6A0.67048 (17)0.4916 (4)0.6645 (2)0.0206 (6)
N61A0.65267 (15)0.3953 (4)0.7290 (2)0.0292 (6)
H61A0.60830.35620.71980.035*
H61B0.68530.37100.78080.035*
N1B0.43760 (14)0.5051 (3)0.40727 (17)0.0202 (6)
C2B0.41736 (15)0.4106 (4)0.4692 (2)0.0197 (6)
N21B0.46672 (15)0.3675 (4)0.5479 (2)0.0313 (7)
H21C0.51170.40240.55740.038*
H21D0.45400.30450.58990.038*
N3B0.34909 (15)0.3540 (3)0.45794 (19)0.0221 (6)
H3B0.33930.29030.50160.026*
C4B0.29359 (16)0.3925 (4)0.3799 (2)0.0211 (6)
O41B0.23111 (12)0.3381 (3)0.37796 (16)0.0281 (5)
C5B0.31392 (17)0.4896 (4)0.3126 (2)0.0237 (7)
H5B0.27940.51800.25650.028*
C6B0.38518 (17)0.5448 (4)0.3282 (2)0.0215 (6)
N61B0.40751 (15)0.6384 (4)0.2662 (2)0.0266 (6)
H61C0.45300.67010.27760.032*
H61D0.37670.66840.21400.032*
C1X0.5954 (3)1.0338 (6)0.1704 (4)0.0489 (11)
H1X10.63841.09230.20760.073*
H1X20.56911.10960.12120.073*
H1X30.61020.93140.14270.073*
C2X0.54723 (18)0.9847 (4)0.2318 (3)0.0316 (7)
O2X0.53495 (14)0.8322 (3)0.2457 (2)0.0343 (6)
N3X0.51898 (18)1.1078 (4)0.2722 (2)0.0378 (7)
C4X0.4720 (3)1.0644 (6)0.3330 (4)0.0617 (14)
H4X10.42171.05820.29610.093*
H4X20.47641.15200.38090.093*
H4X30.48650.95420.36250.093*
C5X0.5291 (3)1.2891 (5)0.2569 (4)0.0534 (12)
H5X10.56351.30290.21880.080*
H5X20.54781.34580.31680.080*
H5X30.48261.33980.22480.080*
C1Y0.8991 (3)0.3714 (9)0.5421 (4)0.0775 (17)
H1Y10.92390.26320.53990.116*
H1Y20.89370.39000.60500.116*
H1Y30.92760.46420.52550.116*
C2Y0.8241 (3)0.3665 (7)0.4731 (3)0.0741 (18)
O2Y0.8107 (3)0.4576 (5)0.4029 (2)0.0796 (13)
N3Y0.7765 (3)0.2683 (6)0.4930 (3)0.0740 (14)
C4Y0.7040 (3)0.2654 (8)0.4267 (5)0.0778 (18)
H4Y10.70250.34870.37730.117*
H4Y20.66720.29390.45940.117*
H4Y30.69450.15180.39950.117*
C5Y0.7886 (5)0.1671 (7)0.5786 (4)0.085 (2)
H5Y10.84060.15850.60730.127*
H5Y20.76840.05310.56360.127*
H5Y30.76500.22230.62180.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0178 (13)0.0237 (13)0.0208 (13)0.0006 (10)0.0040 (11)0.0042 (10)
C2A0.0179 (15)0.0207 (14)0.0213 (15)0.0042 (12)0.0044 (12)0.0015 (12)
N21A0.0176 (13)0.0415 (16)0.0236 (14)0.0072 (12)0.0000 (11)0.0121 (12)
N3A0.0186 (12)0.0261 (13)0.0180 (12)0.0051 (10)0.0034 (10)0.0030 (10)
C4A0.0179 (14)0.0281 (16)0.0189 (14)0.0030 (12)0.0043 (11)0.0051 (12)
O41A0.0208 (11)0.0413 (14)0.0213 (11)0.0122 (10)0.0034 (8)0.0022 (10)
C5A0.0174 (14)0.0310 (16)0.0184 (15)0.0005 (12)0.0004 (11)0.0016 (12)
C6A0.0204 (15)0.0248 (15)0.0173 (15)0.0033 (12)0.0062 (12)0.0010 (11)
N61A0.0212 (14)0.0380 (16)0.0267 (14)0.0002 (12)0.0031 (11)0.0117 (12)
N1B0.0160 (12)0.0249 (13)0.0186 (13)0.0017 (10)0.0023 (10)0.0037 (10)
C2B0.0175 (15)0.0207 (14)0.0203 (15)0.0012 (12)0.0036 (12)0.0005 (12)
N21B0.0200 (14)0.0450 (17)0.0245 (15)0.0091 (12)0.0019 (12)0.0142 (12)
N3B0.0201 (13)0.0247 (13)0.0211 (13)0.0063 (11)0.0047 (11)0.0020 (11)
C4B0.0179 (15)0.0234 (15)0.0206 (15)0.0024 (12)0.0025 (12)0.0028 (12)
O41B0.0187 (11)0.0387 (14)0.0255 (12)0.0079 (10)0.0032 (9)0.0010 (10)
C5B0.0196 (16)0.0308 (17)0.0186 (15)0.0018 (13)0.0012 (12)0.0000 (12)
C6B0.0208 (15)0.0239 (15)0.0190 (15)0.0017 (12)0.0037 (12)0.0015 (12)
N61B0.0155 (12)0.0393 (16)0.0233 (13)0.0002 (11)0.0020 (10)0.0143 (12)
C1X0.048 (2)0.040 (2)0.069 (3)0.0004 (19)0.035 (2)0.010 (2)
C2X0.0283 (17)0.0281 (17)0.0398 (18)0.0034 (14)0.0111 (14)0.0003 (14)
O2X0.0330 (14)0.0219 (11)0.0531 (14)0.0003 (11)0.0203 (11)0.0023 (11)
N3X0.0439 (17)0.0233 (15)0.0495 (19)0.0013 (13)0.0180 (14)0.0019 (13)
C4X0.082 (4)0.041 (2)0.082 (4)0.006 (2)0.057 (3)0.001 (2)
C5X0.063 (3)0.0232 (18)0.079 (3)0.0035 (19)0.027 (2)0.007 (2)
C1Y0.082 (4)0.073 (4)0.070 (4)0.011 (3)0.006 (3)0.025 (3)
C2Y0.126 (6)0.047 (3)0.056 (3)0.009 (3)0.038 (3)0.014 (2)
O2Y0.143 (4)0.058 (2)0.0332 (16)0.018 (2)0.0134 (19)0.0036 (16)
N3Y0.134 (4)0.045 (2)0.054 (2)0.012 (3)0.045 (2)0.0016 (19)
C4Y0.065 (3)0.065 (4)0.099 (5)0.005 (3)0.013 (3)0.032 (3)
C5Y0.166 (7)0.043 (3)0.062 (3)0.023 (4)0.058 (4)0.010 (2)
Geometric parameters (Å, º) top
N1A—C2A1.329 (4)N61B—H61D0.8800
N1A—C6A1.375 (4)C1X—C2X1.507 (5)
C2A—N21A1.341 (4)C1X—H1X10.9800
C2A—N3A1.352 (4)C1X—H1X20.9800
N21A—H21A0.8800C1X—H1X30.9800
N21A—H21B0.8800C2X—O2X1.250 (4)
N3A—C4A1.382 (4)C2X—N3X1.327 (4)
N3A—H3A0.8800N3X—C5X1.466 (4)
C4A—O41A1.270 (4)N3X—C4X1.472 (5)
C4A—C5A1.397 (5)C4X—H4X10.9800
C5A—C6A1.399 (5)C4X—H4X20.9800
C5A—H5A0.9500C4X—H4X30.9800
C6A—N61A1.336 (4)C5X—H5X10.9800
N61A—H61A0.8800C5X—H5X20.9800
N61A—H61B0.8800C5X—H5X30.9800
N1B—C2B1.319 (4)C1Y—C2Y1.538 (7)
N1B—C6B1.374 (4)C1Y—H1Y10.9800
C2B—N21B1.348 (4)C1Y—H1Y20.9800
C2B—N3B1.350 (4)C1Y—H1Y30.9800
N21B—H21C0.8800C2Y—O2Y1.241 (6)
N21B—H21D0.8800C2Y—N3Y1.287 (6)
N3B—C4B1.393 (4)N3Y—C5Y1.471 (6)
N3B—H3B0.8800N3Y—C4Y1.483 (7)
C4B—O41B1.264 (4)C4Y—H4Y10.9800
C4B—C5B1.395 (5)C4Y—H4Y20.9800
C5B—C6B1.393 (5)C4Y—H4Y30.9800
C5B—H5B0.9500C5Y—H5Y10.9800
C6B—N61B1.335 (4)C5Y—H5Y20.9800
N61B—H61C0.8800C5Y—H5Y30.9800
C2A—N1A—C6A116.2 (3)H1X1—C1X—H1X2109.5
N1A—C2A—N21A119.2 (3)C2X—C1X—H1X3109.5
N1A—C2A—N3A123.3 (3)H1X1—C1X—H1X3109.5
N21A—C2A—N3A117.5 (3)H1X2—C1X—H1X3109.5
C2A—N21A—H21A120.0O2X—C2X—N3X120.6 (3)
C2A—N21A—H21B120.0O2X—C2X—C1X121.2 (3)
H21A—N21A—H21B120.0N3X—C2X—C1X118.2 (3)
C2A—N3A—C4A122.2 (3)C2X—N3X—C5X123.7 (3)
C2A—N3A—H3A118.9C2X—N3X—C4X119.7 (3)
C4A—N3A—H3A118.9C5X—N3X—C4X116.6 (3)
O41A—C4A—N3A117.8 (3)N3X—C4X—H4X1109.5
O41A—C4A—C5A125.6 (3)N3X—C4X—H4X2109.5
N3A—C4A—C5A116.6 (3)H4X1—C4X—H4X2109.5
C4A—C5A—C6A118.3 (3)N3X—C4X—H4X3109.5
C4A—C5A—H5A120.9H4X1—C4X—H4X3109.5
C6A—C5A—H5A120.9H4X2—C4X—H4X3109.5
N61A—C6A—N1A116.0 (3)N3X—C5X—H5X1109.5
N61A—C6A—C5A120.6 (3)N3X—C5X—H5X2109.5
N1A—C6A—C5A123.3 (3)H5X1—C5X—H5X2109.5
C6A—N61A—H61A120.0N3X—C5X—H5X3109.5
C6A—N61A—H61B120.0H5X1—C5X—H5X3109.5
H61A—N61A—H61B120.0H5X2—C5X—H5X3109.5
C2B—N1B—C6B116.6 (3)C2Y—C1Y—H1Y1109.5
N1B—C2B—N21B119.0 (3)C2Y—C1Y—H1Y2109.5
N1B—C2B—N3B123.2 (3)H1Y1—C1Y—H1Y2109.5
N21B—C2B—N3B117.7 (3)C2Y—C1Y—H1Y3109.5
C2B—N21B—H21C120.0H1Y1—C1Y—H1Y3109.5
C2B—N21B—H21D120.0H1Y2—C1Y—H1Y3109.5
H21C—N21B—H21D120.0O2Y—C2Y—N3Y122.4 (6)
C2B—N3B—C4B122.6 (3)O2Y—C2Y—C1Y120.4 (6)
C2B—N3B—H3B118.7N3Y—C2Y—C1Y117.2 (5)
C4B—N3B—H3B118.7C2Y—N3Y—C5Y124.1 (6)
O41B—C4B—N3B117.4 (3)C2Y—N3Y—C4Y116.9 (5)
O41B—C4B—C5B127.3 (3)C5Y—N3Y—C4Y118.9 (6)
N3B—C4B—C5B115.2 (3)N3Y—C4Y—H4Y1109.5
C6B—C5B—C4B119.5 (3)N3Y—C4Y—H4Y2109.5
C6B—C5B—H5B120.2H4Y1—C4Y—H4Y2109.5
C4B—C5B—H5B120.2N3Y—C4Y—H4Y3109.5
N61B—C6B—N1B115.2 (3)H4Y1—C4Y—H4Y3109.5
N61B—C6B—C5B122.0 (3)H4Y2—C4Y—H4Y3109.5
N1B—C6B—C5B122.8 (3)N3Y—C5Y—H5Y1109.5
C6B—N61B—H61C120.0N3Y—C5Y—H5Y2109.5
C6B—N61B—H61D120.0H5Y1—C5Y—H5Y2109.5
H61C—N61B—H61D120.0N3Y—C5Y—H5Y3109.5
C2X—C1X—H1X1109.5H5Y1—C5Y—H5Y3109.5
C2X—C1X—H1X2109.5H5Y2—C5Y—H5Y3109.5
C6A—N1A—C2A—N21A178.4 (3)C2B—N3B—C4B—O41B177.5 (3)
C6A—N1A—C2A—N3A0.9 (4)C2B—N3B—C4B—C5B1.9 (4)
N1A—C2A—N3A—C4A1.6 (5)O41B—C4B—C5B—C6B177.3 (3)
N21A—C2A—N3A—C4A177.8 (3)N3B—C4B—C5B—C6B2.0 (4)
C2A—N3A—C4A—O41A179.0 (3)C2B—N1B—C6B—N61B179.1 (3)
C2A—N3A—C4A—C5A1.0 (4)C2B—N1B—C6B—C5B0.0 (5)
O41A—C4A—C5A—C6A176.1 (3)C4B—C5B—C6B—N61B179.8 (3)
N3A—C4A—C5A—C6A3.9 (4)C4B—C5B—C6B—N1B1.2 (5)
C2A—N1A—C6A—N61A178.5 (3)O2X—C2X—N3X—C5X178.0 (4)
C2A—N1A—C6A—C5A2.3 (4)C1X—C2X—N3X—C5X3.2 (6)
C4A—C5A—C6A—N61A176.0 (3)O2X—C2X—N3X—C4X0.8 (6)
C4A—C5A—C6A—N1A4.8 (5)C1X—C2X—N3X—C4X179.7 (5)
C6B—N1B—C2B—N21B179.8 (3)O2Y—C2Y—N3Y—C5Y175.7 (5)
C6B—N1B—C2B—N3B0.2 (4)C1Y—C2Y—N3Y—C5Y2.5 (7)
N1B—C2B—N3B—C4B0.8 (5)O2Y—C2Y—N3Y—C4Y1.2 (7)
N21B—C2B—N3B—C4B179.2 (3)C1Y—C2Y—N3Y—C4Y179.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···N1B0.882.072.946 (4)171
N21A—H21B···O2X0.882.463.176 (4)139
N3A—H3A···O41Bi0.881.892.765 (3)174
N61A—H61A···O2Xii0.882.152.939 (4)150
N61A—H61B···O41Biii0.882.222.975 (4)144
N21B—H21C···N1A0.882.163.029 (4)172
N3B—H3B···O41Aiv0.881.842.700 (4)166
N61B—H61C···O2X0.882.172.960 (4)149
N61B—H61D···O41Av0.881.952.813 (4)165
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y+1, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x1/2, y1/2, z; (v) x1/2, y+3/2, z1/2.
(Ic) 2,6-diaminopyrimidin-4-one N-methyl-2-pyrrolidone solvate (3/2) top
Crystal data top
C4H6N4O·3/2C5H9NOZ = 4
Mr = 274.83F(000) = 588
Triclinic, P1Dx = 1.331 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4550 (9) ÅCell parameters from 6878 reflections
b = 10.0803 (9) Åθ = 3.4–25.9°
c = 17.0735 (15) ŵ = 0.10 mm1
α = 75.558 (7)°T = 173 K
β = 78.222 (8)°Block, colourless
γ = 81.363 (8)°0.25 × 0.20 × 0.20 mm
V = 1371.9 (2) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
2940 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.091
Graphite monochromatorθmax = 25.7°, θmin = 3.3°
ω scansh = 108
18821 measured reflectionsk = 1212
5116 independent 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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 0.91 w = 1/[σ2(Fo2) + (0.0536P)2]
where P = (Fo2 + 2Fc2)/3
5116 reflections(Δ/σ)max < 0.001
355 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C4H6N4O·3/2C5H9NOγ = 81.363 (8)°
Mr = 274.83V = 1371.9 (2) Å3
Triclinic, P1Z = 4
a = 8.4550 (9) ÅMo Kα radiation
b = 10.0803 (9) ŵ = 0.10 mm1
c = 17.0735 (15) ÅT = 173 K
α = 75.558 (7)°0.25 × 0.20 × 0.20 mm
β = 78.222 (8)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2940 reflections with I > 2σ(I)
18821 measured reflectionsRint = 0.091
5116 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 0.91Δρmax = 0.48 e Å3
5116 reflectionsΔρmin = 0.29 e Å3
355 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*/Ueq
N1A0.1749 (2)0.8568 (2)0.48510 (12)0.0198 (5)
C2A0.2934 (3)0.7826 (2)0.44640 (14)0.0188 (5)
N21A0.3474 (3)0.8264 (2)0.36598 (12)0.0261 (5)
H21A0.30410.90480.33870.031*
H21B0.42620.77680.34040.031*
N3A0.3652 (3)0.6599 (2)0.48510 (12)0.0211 (5)
H3A0.44390.61480.45650.025*
C4A0.3175 (3)0.6034 (3)0.56900 (15)0.0214 (6)
O41A0.3903 (2)0.49007 (18)0.59931 (10)0.0299 (5)
C5A0.1925 (3)0.6811 (3)0.61010 (15)0.0217 (6)
H5A0.15340.64900.66700.026*
C6A0.1254 (3)0.8057 (3)0.56730 (14)0.0196 (6)
N61A0.0057 (3)0.8861 (2)0.60364 (13)0.0286 (6)
H61A0.03390.96440.57460.034*
H61B0.03280.86040.65640.034*
N1B0.8413 (3)0.4999 (2)0.09722 (12)0.0214 (5)
C2B0.7368 (3)0.4523 (3)0.16360 (14)0.0216 (6)
N21B0.7296 (3)0.3163 (2)0.19107 (13)0.0284 (6)
H21C0.79460.25860.16480.034*
H21D0.65990.28470.23530.034*
N3B0.6354 (3)0.5359 (2)0.20754 (13)0.0296 (6)
H3B0.57010.49790.25200.036*
C4B0.6298 (4)0.6790 (3)0.18566 (15)0.0309 (7)
O41B0.5284 (3)0.7464 (2)0.22870 (12)0.0513 (7)
C5B0.7414 (4)0.7304 (3)0.11565 (15)0.0290 (7)
H5B0.74670.82690.09670.035*
C6B0.8436 (3)0.6400 (3)0.07435 (14)0.0223 (6)
N61B0.9542 (3)0.6831 (2)0.00733 (14)0.0336 (6)
H61C1.01710.62280.01770.040*
H61D0.96370.77170.01150.040*
N1X0.4023 (3)0.8017 (2)0.86524 (14)0.0320 (6)
C1X0.5096 (4)0.9227 (3)0.8771 (2)0.0413 (8)
H1X10.47971.00070.83160.062*
H1X20.50040.94350.92900.062*
H1X30.62170.90640.87880.062*
C2X0.2725 (3)0.8037 (3)0.80486 (16)0.0295 (7)
O2X0.2312 (2)0.9042 (2)0.74986 (11)0.0348 (5)
C3X0.1808 (4)0.6596 (3)0.81699 (18)0.0366 (7)
H3X10.07820.65830.83670.044*
H3X20.15530.62780.76500.044*
C4X0.2959 (4)0.5697 (3)0.8809 (2)0.0468 (9)
H4X10.23630.50350.92110.056*
H4X20.35220.51780.85470.056*
C5X0.4181 (4)0.6705 (3)0.92335 (17)0.0344 (7)
H5X10.53000.64450.93310.041*
H5X20.39000.67310.97640.041*
N1Y0.2529 (3)0.3622 (3)0.41759 (15)0.0362 (6)
C1Y0.1838 (4)0.4928 (3)0.3782 (2)0.0450 (8)
H1Y10.25720.52900.32740.068*
H1Y20.16750.55650.41490.068*
H1Y30.07900.48320.36520.068*
C2Y0.3710 (3)0.2859 (3)0.37989 (18)0.0329 (7)
O2Y0.4378 (2)0.3217 (2)0.30683 (11)0.0385 (5)
C3Y0.4087 (4)0.1507 (3)0.43819 (18)0.0376 (7)
H3Y10.52500.13610.44320.045*
H3Y20.38210.07290.41930.045*
C4Y0.3000 (4)0.1646 (3)0.52061 (18)0.0423 (8)
H4Y10.36720.16510.56170.051*
H4Y20.23230.08700.54210.051*
C5Y0.1932 (4)0.3011 (3)0.50258 (17)0.0404 (8)
H5Y10.07750.28550.51060.048*
H5Y20.20430.36100.53870.048*
N1Z0.9171 (3)1.1175 (3)0.15175 (17)0.0447 (7)
C1Z0.8019 (5)1.1020 (5)0.0758 (2)0.0622 (11)
H1Z10.79251.00390.05180.093*
H1Z20.69561.14860.08670.093*
H1Z30.83921.14300.03740.093*
C2Z1.0342 (4)1.0210 (3)0.1650 (2)0.0403 (8)
O2Z1.0661 (3)0.90783 (19)0.11935 (12)0.0362 (5)
C3Z1.1344 (4)1.0737 (3)0.25077 (19)0.0453 (8)
H3Z11.24491.08880.24620.054*
H3Z21.14361.00700.28570.054*
C4Z1.0418 (5)1.2071 (4)0.2859 (2)0.0623 (11)
H4Z10.99081.19710.33110.075*
H4Z21.11491.28090.30740.075*
C5Z0.9099 (5)1.2417 (3)0.2140 (2)0.0508 (10)
H5Z10.93571.32010.19530.061*
H5Z20.80131.26390.23010.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0181 (11)0.0213 (11)0.0183 (10)0.0032 (9)0.0011 (8)0.0064 (8)
C2A0.0211 (13)0.0168 (13)0.0190 (12)0.0006 (10)0.0033 (10)0.0062 (10)
N21A0.0306 (13)0.0227 (12)0.0180 (10)0.0066 (10)0.0025 (9)0.0028 (9)
N3A0.0211 (11)0.0208 (11)0.0193 (10)0.0052 (9)0.0008 (8)0.0070 (8)
C4A0.0224 (14)0.0206 (13)0.0224 (12)0.0011 (10)0.0061 (11)0.0063 (10)
O41A0.0360 (11)0.0243 (10)0.0234 (9)0.0111 (8)0.0050 (8)0.0030 (8)
C5A0.0202 (13)0.0259 (14)0.0173 (12)0.0009 (11)0.0010 (10)0.0045 (10)
C6A0.0166 (13)0.0221 (13)0.0200 (12)0.0001 (10)0.0018 (10)0.0068 (10)
N61A0.0299 (13)0.0278 (12)0.0192 (11)0.0083 (10)0.0038 (9)0.0021 (9)
N1B0.0239 (12)0.0210 (11)0.0170 (10)0.0012 (9)0.0014 (9)0.0048 (8)
C2B0.0184 (13)0.0273 (14)0.0164 (12)0.0017 (11)0.0020 (10)0.0034 (10)
N21B0.0287 (13)0.0224 (12)0.0281 (12)0.0025 (10)0.0057 (10)0.0033 (9)
N3B0.0306 (13)0.0283 (12)0.0196 (11)0.0035 (10)0.0091 (9)0.0012 (9)
C4B0.0370 (17)0.0295 (15)0.0191 (13)0.0094 (13)0.0010 (12)0.0033 (11)
O41B0.0666 (16)0.0360 (12)0.0299 (11)0.0207 (11)0.0186 (11)0.0055 (9)
C5B0.0372 (17)0.0238 (14)0.0209 (13)0.0036 (12)0.0024 (12)0.0057 (11)
C6B0.0218 (14)0.0263 (14)0.0172 (12)0.0005 (11)0.0011 (10)0.0051 (10)
N61B0.0411 (15)0.0184 (11)0.0328 (13)0.0028 (10)0.0137 (11)0.0065 (10)
N1X0.0280 (13)0.0342 (14)0.0308 (13)0.0012 (11)0.0015 (10)0.0061 (10)
C1X0.0308 (17)0.0410 (18)0.0509 (19)0.0003 (14)0.0011 (14)0.0154 (15)
C2X0.0237 (15)0.0446 (18)0.0235 (14)0.0019 (12)0.0054 (12)0.0137 (13)
O2X0.0317 (11)0.0370 (11)0.0266 (10)0.0026 (9)0.0054 (9)0.0000 (9)
C3X0.0334 (17)0.0405 (17)0.0353 (16)0.0064 (13)0.0108 (13)0.0097 (13)
C4X0.050 (2)0.0358 (18)0.052 (2)0.0011 (15)0.0156 (16)0.0027 (15)
C5X0.0310 (16)0.0387 (17)0.0288 (15)0.0064 (13)0.0066 (12)0.0039 (12)
N1Y0.0349 (14)0.0348 (14)0.0364 (14)0.0067 (11)0.0010 (11)0.0057 (11)
C1Y0.0393 (19)0.0405 (19)0.057 (2)0.0020 (15)0.0098 (16)0.0152 (15)
C2Y0.0225 (15)0.0433 (18)0.0400 (17)0.0134 (13)0.0009 (13)0.0206 (14)
O2Y0.0334 (12)0.0540 (13)0.0257 (10)0.0173 (10)0.0091 (9)0.0086 (9)
C3Y0.0374 (18)0.0368 (17)0.0393 (17)0.0135 (13)0.0080 (14)0.0036 (13)
C4Y0.0399 (19)0.049 (2)0.0341 (16)0.0193 (15)0.0017 (14)0.0010 (14)
C5Y0.0391 (18)0.059 (2)0.0270 (15)0.0246 (15)0.0049 (13)0.0149 (14)
N1Z0.0434 (17)0.0421 (16)0.0483 (16)0.0022 (13)0.0110 (13)0.0085 (13)
C1Z0.048 (2)0.097 (3)0.0421 (19)0.021 (2)0.0120 (17)0.026 (2)
C2Z0.0429 (19)0.0347 (18)0.0505 (19)0.0043 (14)0.0192 (15)0.0137 (15)
O2Z0.0420 (13)0.0237 (10)0.0335 (11)0.0015 (9)0.0025 (9)0.0026 (8)
C3Z0.053 (2)0.050 (2)0.0326 (16)0.0086 (16)0.0062 (15)0.0074 (14)
C4Z0.066 (3)0.064 (3)0.046 (2)0.005 (2)0.0079 (19)0.0057 (18)
C5Z0.060 (2)0.0388 (19)0.050 (2)0.0135 (17)0.0253 (17)0.0014 (15)
Geometric parameters (Å, º) top
N1A—C2A1.323 (3)C3X—H3X10.9900
N1A—C6A1.369 (3)C3X—H3X20.9900
C2A—N21A1.338 (3)C4X—C5X1.539 (4)
C2A—N3A1.366 (3)C4X—H4X10.9900
N21A—H21A0.8800C4X—H4X20.9900
N21A—H21B0.8800C5X—H5X10.9900
N3A—C4A1.402 (3)C5X—H5X20.9900
N3A—H3A0.8800N1Y—C2Y1.325 (4)
C4A—O41A1.255 (3)N1Y—C1Y1.420 (4)
C4A—C5A1.395 (3)N1Y—C5Y1.445 (4)
C5A—C6A1.389 (3)C1Y—H1Y10.9800
C5A—H5A0.9500C1Y—H1Y20.9800
C6A—N61A1.347 (3)C1Y—H1Y30.9800
N61A—H61A0.8800C2Y—O2Y1.247 (3)
N61A—H61B0.8800C2Y—C3Y1.507 (4)
N1B—C2B1.320 (3)C3Y—C4Y1.542 (4)
N1B—C6B1.371 (3)C3Y—H3Y10.9900
C2B—N3B1.358 (3)C3Y—H3Y20.9900
C2B—N21B1.340 (3)C4Y—C5Y1.527 (5)
N21B—H21C0.8800C4Y—H4Y10.9900
N21B—H21D0.8800C4Y—H4Y20.9900
N3B—C4B1.392 (4)C5Y—H5Y10.9900
N3B—H3B0.8800C5Y—H5Y20.9900
C4B—O41B1.247 (3)N1Z—C2Z1.307 (4)
C4B—C5B1.402 (4)N1Z—C5Z1.428 (4)
C5B—C6B1.381 (4)N1Z—C1Z1.443 (4)
C5B—H5B0.9500C1Z—H1Z10.9800
C6B—N61B1.345 (3)C1Z—H1Z20.9800
N61B—H61C0.8800C1Z—H1Z30.9800
N61B—H61D0.8800C2Z—O2Z1.238 (3)
N1X—C2X1.342 (4)C2Z—C3Z1.544 (5)
N1X—C1X1.438 (4)C3Z—C4Z1.501 (5)
N1X—C5X1.448 (4)C3Z—H3Z10.9900
C1X—H1X10.9800C3Z—H3Z20.9900
C1X—H1X20.9800C4Z—C5Z1.552 (5)
C1X—H1X30.9800C4Z—H4Z10.9900
C2X—O2X1.236 (3)C4Z—H4Z20.9900
C2X—C3X1.527 (4)C5Z—H5Z10.9900
C3X—C4X1.516 (5)C5Z—H5Z20.9900
C2A—N1A—C6A117.09 (19)H4X1—C4X—H4X2108.8
N1A—C2A—N21A120.2 (2)N1X—C5X—C4X103.5 (2)
N1A—C2A—N3A122.7 (2)N1X—C5X—H5X1111.1
N21A—C2A—N3A117.1 (2)C4X—C5X—H5X1111.1
C2A—N21A—H21A120.0N1X—C5X—H5X2111.1
C2A—N21A—H21B120.0C4X—C5X—H5X2111.1
H21A—N21A—H21B120.0H5X1—C5X—H5X2109.0
C2A—N3A—C4A122.0 (2)C2Y—N1Y—C1Y123.6 (3)
C2A—N3A—H3A119.0C2Y—N1Y—C5Y115.2 (3)
C4A—N3A—H3A119.0C1Y—N1Y—C5Y121.1 (3)
O41A—C4A—C5A126.9 (2)N1Y—C1Y—H1Y1109.5
O41A—C4A—N3A117.6 (2)N1Y—C1Y—H1Y2109.5
C5A—C4A—N3A115.5 (2)H1Y1—C1Y—H1Y2109.5
C6A—C5A—C4A119.6 (2)N1Y—C1Y—H1Y3109.5
C6A—C5A—H5A120.2H1Y1—C1Y—H1Y3109.5
C4A—C5A—H5A120.2H1Y2—C1Y—H1Y3109.5
N1A—C6A—N61A114.5 (2)O2Y—C2Y—N1Y124.3 (3)
N1A—C6A—C5A123.0 (2)O2Y—C2Y—C3Y126.0 (3)
N61A—C6A—C5A122.5 (2)N1Y—C2Y—C3Y109.7 (3)
C6A—N61A—H61A120.0C2Y—C3Y—C4Y104.3 (2)
C6A—N61A—H61B120.0C2Y—C3Y—H3Y1110.9
H61A—N61A—H61B120.0C4Y—C3Y—H3Y1110.9
C2B—N1B—C6B116.4 (2)C2Y—C3Y—H3Y2110.9
N1B—C2B—N3B122.7 (2)C4Y—C3Y—H3Y2110.9
N1B—C2B—N21B120.1 (2)H3Y1—C3Y—H3Y2108.9
N3B—C2B—N21B117.2 (2)C3Y—C4Y—C5Y106.1 (2)
C2B—N21B—H21C120.0C3Y—C4Y—H4Y1110.5
C2B—N21B—H21D120.0C5Y—C4Y—H4Y1110.5
H21C—N21B—H21D120.0C3Y—C4Y—H4Y2110.5
C2B—N3B—C4B123.1 (2)C5Y—C4Y—H4Y2110.5
C2B—N3B—H3B118.4H4Y1—C4Y—H4Y2108.7
C4B—N3B—H3B118.4N1Y—C5Y—C4Y104.4 (2)
O41B—C4B—C5B127.4 (3)N1Y—C5Y—H5Y1110.9
O41B—C4B—N3B118.0 (2)C4Y—C5Y—H5Y1110.9
C5B—C4B—N3B114.6 (2)N1Y—C5Y—H5Y2110.9
C6B—C5B—C4B119.6 (2)C4Y—C5Y—H5Y2110.9
C6B—C5B—H5B120.2H5Y1—C5Y—H5Y2108.9
C4B—C5B—H5B120.2C2Z—N1Z—C5Z117.7 (3)
N61B—C6B—N1B114.1 (2)C2Z—N1Z—C1Z121.5 (3)
N61B—C6B—C5B122.4 (2)C5Z—N1Z—C1Z120.8 (3)
N1B—C6B—C5B123.5 (2)N1Z—C1Z—H1Z1109.5
C6B—N61B—H61C120.0N1Z—C1Z—H1Z2109.5
C6B—N61B—H61D120.0H1Z1—C1Z—H1Z2109.5
H61C—N61B—H61D120.0N1Z—C1Z—H1Z3109.5
C2X—N1X—C1X123.2 (2)H1Z1—C1Z—H1Z3109.5
C2X—N1X—C5X114.9 (2)H1Z2—C1Z—H1Z3109.5
C1X—N1X—C5X121.6 (2)O2Z—C2Z—N1Z128.7 (3)
N1X—C1X—H1X1109.5O2Z—C2Z—C3Z124.0 (3)
N1X—C1X—H1X2109.5N1Z—C2Z—C3Z107.3 (3)
H1X1—C1X—H1X2109.5C4Z—C3Z—C2Z104.9 (3)
N1X—C1X—H1X3109.5C4Z—C3Z—H3Z1110.8
H1X1—C1X—H1X3109.5C2Z—C3Z—H3Z1110.8
H1X2—C1X—H1X3109.5C4Z—C3Z—H3Z2110.8
O2X—C2X—N1X126.6 (3)C2Z—C3Z—H3Z2110.8
O2X—C2X—C3X125.5 (2)H3Z1—C3Z—H3Z2108.8
N1X—C2X—C3X107.9 (2)C3Z—C4Z—C5Z105.9 (3)
C2X—C3X—C4X104.6 (2)C3Z—C4Z—H4Z1110.6
C2X—C3X—H3X1110.8C5Z—C4Z—H4Z1110.6
C4X—C3X—H3X1110.8C3Z—C4Z—H4Z2110.6
C2X—C3X—H3X2110.8C5Z—C4Z—H4Z2110.6
C4X—C3X—H3X2110.8H4Z1—C4Z—H4Z2108.7
H3X1—C3X—H3X2108.9N1Z—C5Z—C4Z102.9 (3)
C3X—C4X—C5X105.1 (3)N1Z—C5Z—H5Z1111.2
C3X—C4X—H4X1110.7C4Z—C5Z—H5Z1111.2
C5X—C4X—H4X1110.7N1Z—C5Z—H5Z2111.2
C3X—C4X—H4X2110.7C4Z—C5Z—H5Z2111.2
C5X—C4X—H4X2110.7H5Z1—C5Z—H5Z2109.1
C6A—N1A—C2A—N21A179.8 (2)C5X—N1X—C2X—C3X0.8 (4)
C6A—N1A—C2A—N3A0.1 (4)O2X—C2X—C3X—C4X169.5 (3)
N1A—C2A—N3A—C4A0.3 (4)N1X—C2X—C3X—C4X11.9 (3)
N21A—C2A—N3A—C4A179.4 (3)C2X—C3X—C4X—C5X19.0 (3)
C2A—N3A—C4A—O41A180.0 (3)C2X—N1X—C5X—C4X12.9 (4)
C2A—N3A—C4A—C5A0.2 (4)C1X—N1X—C5X—C4X172.9 (3)
O41A—C4A—C5A—C6A179.5 (3)C3X—C4X—C5X—N1X19.3 (3)
N3A—C4A—C5A—C6A0.3 (4)C1Y—N1Y—C2Y—O2Y2.3 (5)
C2A—N1A—C6A—N61A179.4 (3)C5Y—N1Y—C2Y—O2Y179.8 (3)
C2A—N1A—C6A—C5A0.6 (4)C1Y—N1Y—C2Y—C3Y176.9 (3)
C4A—C5A—C6A—N1A0.8 (4)C5Y—N1Y—C2Y—C3Y1.1 (4)
C4A—C5A—C6A—N61A179.3 (3)O2Y—C2Y—C3Y—C4Y176.5 (3)
C6B—N1B—C2B—N3B0.3 (4)N1Y—C2Y—C3Y—C4Y4.4 (4)
C6B—N1B—C2B—N21B178.5 (2)C2Y—C3Y—C4Y—C5Y5.8 (3)
N1B—C2B—N3B—C4B1.5 (4)C2Y—N1Y—C5Y—C4Y2.7 (4)
N21B—C2B—N3B—C4B179.7 (3)C1Y—N1Y—C5Y—C4Y179.3 (3)
C2B—N3B—C4B—O41B177.6 (3)C3Y—C4Y—C5Y—N1Y5.2 (3)
C2B—N3B—C4B—C5B1.9 (4)C5Z—N1Z—C2Z—O2Z177.9 (3)
O41B—C4B—C5B—C6B178.8 (3)C1Z—N1Z—C2Z—O2Z0.1 (6)
N3B—C4B—C5B—C6B0.7 (4)C5Z—N1Z—C2Z—C3Z1.0 (4)
C2B—N1B—C6B—N61B178.7 (3)C1Z—N1Z—C2Z—C3Z178.9 (3)
C2B—N1B—C6B—C5B1.6 (4)O2Z—C2Z—C3Z—C4Z174.6 (3)
C4B—C5B—C6B—N61B179.3 (3)N1Z—C2Z—C3Z—C4Z6.4 (4)
C4B—C5B—C6B—N1B1.0 (4)C2Z—C3Z—C4Z—C5Z10.5 (4)
C1X—N1X—C2X—O2X3.8 (5)C2Z—N1Z—C5Z—C4Z7.7 (4)
C5X—N1X—C2X—O2X177.8 (3)C1Z—N1Z—C5Z—C4Z174.5 (3)
C1X—N1X—C2X—C3X174.8 (3)C3Z—C4Z—C5Z—N1Z10.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O2Xi0.882.223.092 (3)169
N21A—H21B···O41B0.882.002.756 (3)143
N3A—H3A···O41Aii0.881.872.750 (3)177
N61A—H61A···N1Ai0.882.153.023 (3)169
N61A—H61B···O2X0.882.142.891 (3)142
N21B—H21C···O2Ziii0.882.122.989 (3)170
N21B—H21D···O2Y0.882.062.832 (3)146
N3B—H3B···O2Y0.882.152.904 (3)143
N61B—H61C···N1Biii0.882.133.001 (3)170
N61B—H61D···O2Z0.882.112.840 (3)139
Symmetry codes: (i) x, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z.
(IIa) 2-amino-6-methylpyrimidin-4(3H)-one–2-amino-6-methylpyrimidin-4(1H)-one–dimethylacetamide (1/1/1) top
Crystal data top
C5H7N3O·C5H7N3O·C4H9NOZ = 2
Mr = 337.39F(000) = 360
Triclinic, P1Dx = 1.306 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8763 (13) ÅCell parameters from 2325 reflections
b = 9.6078 (17) Åθ = 3.4–25.9°
c = 12.3115 (19) ŵ = 0.10 mm1
α = 108.780 (13)°T = 173 K
β = 95.194 (13)°Block, colourless
γ = 99.959 (13)°0.40 × 0.25 × 0.10 mm
V = 858.0 (2) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
1427 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.131
Graphite monochromatorθmax = 25.6°, θmin = 3.4°
ω scansh = 99
7199 measured reflectionsk = 1111
3208 independent reflectionsl = 1414
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)] = 0.068H-atom parameters constrained
wR(F2) = 0.204 w = 1/[σ2(Fo2) + (0.1094P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max < 0.001
3208 reflectionsΔρmax = 0.45 e Å3
223 parametersΔρmin = 0.47 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: 0.018 (6)
Crystal data top
C5H7N3O·C5H7N3O·C4H9NOγ = 99.959 (13)°
Mr = 337.39V = 858.0 (2) Å3
Triclinic, P1Z = 2
a = 7.8763 (13) ÅMo Kα radiation
b = 9.6078 (17) ŵ = 0.10 mm1
c = 12.3115 (19) ÅT = 173 K
α = 108.780 (13)°0.40 × 0.25 × 0.10 mm
β = 95.194 (13)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1427 reflections with I > 2σ(I)
7199 measured reflectionsRint = 0.131
3208 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.204H-atom parameters constrained
S = 0.82Δρmax = 0.45 e Å3
3208 reflectionsΔρmin = 0.47 e Å3
223 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*/Ueq
N1A0.1822 (4)0.6323 (4)0.4673 (3)0.0313 (8)
H1A0.15660.66990.53750.038*
C2A0.2487 (5)0.5060 (4)0.4397 (3)0.0297 (9)
N21A0.2741 (4)0.4471 (4)0.5222 (3)0.0398 (9)
H21A0.31600.36490.50730.048*
H21B0.24910.49030.59180.048*
N3A0.2863 (4)0.4411 (4)0.3346 (3)0.0295 (8)
C4A0.2594 (5)0.5053 (4)0.2508 (3)0.0264 (8)
O41A0.2933 (4)0.4439 (3)0.1509 (2)0.0359 (7)
C5A0.1922 (5)0.6414 (5)0.2810 (3)0.0350 (10)
H5A0.17480.68800.22480.042*
C6A0.1541 (5)0.7026 (4)0.3887 (3)0.0317 (9)
C61A0.0839 (6)0.8407 (5)0.4293 (4)0.0438 (11)
H61A0.17330.92160.48600.066*
H61B0.01890.82080.46580.066*
H61C0.05070.87100.36300.066*
N1B0.5073 (4)0.0211 (3)0.1427 (2)0.0274 (7)
C2B0.4440 (4)0.1017 (4)0.1717 (3)0.0241 (8)
N21B0.4036 (4)0.1620 (4)0.0915 (2)0.0308 (8)
H21C0.41940.11960.01940.037*
H21D0.36130.24410.11080.037*
N3B0.4118 (4)0.1701 (4)0.2808 (2)0.0254 (7)
H3B0.37010.25240.29470.030*
C4B0.4413 (5)0.1168 (5)0.3705 (3)0.0306 (9)
O41B0.4064 (4)0.1843 (3)0.4680 (2)0.0408 (8)
C5B0.5096 (5)0.0174 (4)0.3406 (3)0.0303 (9)
H5B0.53340.06250.39700.036*
C6B0.5399 (5)0.0791 (4)0.2293 (3)0.0282 (9)
C61B0.6104 (6)0.2198 (5)0.1948 (3)0.0381 (10)
H61D0.51810.30440.14490.057*
H61E0.65120.24030.26460.057*
H61F0.70790.20650.15240.057*
C1X0.0469 (6)0.8732 (5)0.8135 (4)0.0471 (12)
H1X10.03200.89230.74010.071*
H1X20.12350.96110.87310.071*
H1X30.06720.85410.83820.071*
C2X0.1269 (5)0.7381 (5)0.7971 (3)0.0367 (10)
O2X0.1735 (4)0.6728 (4)0.7028 (2)0.0436 (8)
N3X0.1524 (5)0.6883 (4)0.8854 (3)0.0418 (9)
C4X0.2320 (7)0.5590 (6)0.8719 (5)0.0606 (15)
H4X10.15070.46770.81980.091*
H4X20.25930.54890.94790.091*
H4X30.33970.57340.83890.091*
C5X0.0938 (7)0.7573 (7)0.9971 (4)0.0661 (17)
H5X10.02950.83370.99090.099*
H5X20.19560.80451.05830.099*
H5X30.01760.67951.01640.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0372 (18)0.0277 (18)0.0274 (17)0.0105 (15)0.0101 (13)0.0040 (14)
C2A0.031 (2)0.027 (2)0.029 (2)0.0074 (17)0.0035 (15)0.0065 (16)
N21A0.052 (2)0.046 (2)0.0283 (17)0.0251 (18)0.0163 (15)0.0130 (16)
N3A0.0329 (18)0.0283 (18)0.0286 (16)0.0097 (14)0.0104 (13)0.0085 (14)
C4A0.0276 (19)0.024 (2)0.0287 (19)0.0080 (16)0.0048 (15)0.0090 (16)
O41A0.0500 (17)0.0338 (16)0.0282 (14)0.0157 (14)0.0112 (12)0.0116 (12)
C5A0.035 (2)0.034 (2)0.039 (2)0.0115 (19)0.0043 (17)0.0137 (19)
C6A0.029 (2)0.024 (2)0.037 (2)0.0049 (17)0.0028 (16)0.0039 (17)
C61A0.054 (3)0.030 (2)0.048 (2)0.016 (2)0.012 (2)0.0084 (19)
N1B0.0366 (18)0.0255 (17)0.0229 (15)0.0111 (15)0.0067 (12)0.0093 (13)
C2B0.0245 (19)0.028 (2)0.0184 (17)0.0063 (17)0.0054 (14)0.0050 (16)
N21B0.0427 (19)0.0327 (19)0.0245 (16)0.0207 (15)0.0118 (13)0.0117 (14)
N3B0.0317 (17)0.0254 (17)0.0233 (15)0.0121 (14)0.0080 (12)0.0100 (13)
C4B0.039 (2)0.031 (2)0.0233 (19)0.0091 (18)0.0061 (15)0.0109 (16)
O41B0.068 (2)0.0397 (17)0.0234 (13)0.0267 (15)0.0155 (12)0.0122 (12)
C5B0.041 (2)0.030 (2)0.0268 (19)0.0142 (18)0.0080 (16)0.0150 (17)
C6B0.0297 (19)0.024 (2)0.0323 (19)0.0080 (16)0.0048 (15)0.0100 (16)
C61B0.048 (2)0.036 (2)0.038 (2)0.019 (2)0.0131 (18)0.0168 (19)
C1X0.040 (2)0.034 (2)0.061 (3)0.011 (2)0.012 (2)0.005 (2)
C2X0.030 (2)0.039 (3)0.038 (2)0.0034 (19)0.0078 (17)0.0108 (19)
O2X0.0459 (17)0.0487 (19)0.0328 (15)0.0125 (14)0.0173 (12)0.0053 (13)
N3X0.041 (2)0.046 (2)0.0386 (19)0.0078 (18)0.0066 (15)0.0158 (17)
C4X0.055 (3)0.057 (3)0.071 (3)0.002 (3)0.010 (3)0.034 (3)
C5X0.061 (3)0.093 (5)0.032 (2)0.007 (3)0.007 (2)0.016 (3)
Geometric parameters (Å, º) top
N1A—C2A1.360 (5)N3B—H3B0.8800
N1A—C6A1.370 (5)C4B—O41B1.247 (4)
N1A—H1A0.8800C4B—C5B1.435 (5)
C2A—N3A1.329 (5)C5B—C6B1.368 (5)
C2A—N21A1.328 (5)C5B—H5B0.9500
N21A—H21A0.8800C6B—C61B1.499 (5)
N21A—H21B0.8800C61B—H61D0.9800
N3A—C4A1.380 (5)C61B—H61E0.9800
C4A—O41A1.256 (4)C61B—H61F0.9800
C4A—C5A1.446 (5)C1X—C2X1.503 (6)
C5A—C6A1.351 (5)C1X—H1X10.9800
C5A—H5A0.9500C1X—H1X20.9800
C6A—C61A1.481 (6)C1X—H1X30.9800
C61A—H61A0.9800C2X—O2X1.250 (5)
C61A—H61B0.9800C2X—N3X1.334 (5)
C61A—H61C0.9800N3X—C4X1.456 (6)
N1B—C2B1.317 (5)N3X—C5X1.476 (6)
N1B—C6B1.377 (5)C4X—H4X10.9800
C2B—N21B1.336 (4)C4X—H4X20.9800
C2B—N3B1.361 (4)C4X—H4X30.9800
N21B—H21C0.8800C5X—H5X10.9800
N21B—H21D0.8800C5X—H5X20.9800
N3B—C4B1.377 (5)C5X—H5X30.9800
C2A—N1A—C6A121.7 (3)N3B—C4B—C5B114.9 (3)
C2A—N1A—H1A119.1C6B—C5B—C4B118.6 (4)
C6A—N1A—H1A119.1C6B—C5B—H5B120.7
N3A—C2A—N21A120.2 (4)C4B—C5B—H5B120.7
N3A—C2A—N1A122.4 (4)N1B—C6B—C5B124.1 (4)
N21A—C2A—N1A117.4 (3)N1B—C6B—C61B115.8 (3)
C2A—N21A—H21A120.0C5B—C6B—C61B120.1 (4)
C2A—N21A—H21B120.0C6B—C61B—H61D109.5
H21A—N21A—H21B120.0C6B—C61B—H61E109.5
C2A—N3A—C4A118.9 (3)H61D—C61B—H61E109.5
O41A—C4A—N3A119.3 (3)C6B—C61B—H61F109.5
O41A—C4A—C5A122.1 (4)H61D—C61B—H61F109.5
N3A—C4A—C5A118.7 (3)H61E—C61B—H61F109.5
C6A—C5A—C4A120.4 (4)C2X—C1X—H1X1109.5
C6A—C5A—H5A119.8C2X—C1X—H1X2109.5
C4A—C5A—H5A119.8H1X1—C1X—H1X2109.5
C5A—C6A—N1A117.9 (4)C2X—C1X—H1X3109.5
C5A—C6A—C61A125.2 (4)H1X1—C1X—H1X3109.5
N1A—C6A—C61A116.9 (3)H1X2—C1X—H1X3109.5
C6A—C61A—H61A109.5O2X—C2X—N3X119.1 (4)
C6A—C61A—H61B109.5O2X—C2X—C1X121.4 (4)
H61A—C61A—H61B109.5N3X—C2X—C1X119.5 (4)
C6A—C61A—H61C109.5C2X—N3X—C4X120.5 (4)
H61A—C61A—H61C109.5C2X—N3X—C5X121.4 (4)
H61B—C61A—H61C109.5C4X—N3X—C5X118.1 (4)
C2B—N1B—C6B116.4 (3)N3X—C4X—H4X1109.5
N1B—C2B—N21B119.9 (3)N3X—C4X—H4X2109.5
N1B—C2B—N3B122.9 (3)H4X1—C4X—H4X2109.5
N21B—C2B—N3B117.1 (3)N3X—C4X—H4X3109.5
C2B—N21B—H21C120.0H4X1—C4X—H4X3109.5
C2B—N21B—H21D120.0H4X2—C4X—H4X3109.5
H21C—N21B—H21D120.0N3X—C5X—H5X1109.5
C2B—N3B—C4B123.1 (3)N3X—C5X—H5X2109.5
C2B—N3B—H3B118.4H5X1—C5X—H5X2109.5
C4B—N3B—H3B118.4N3X—C5X—H5X3109.5
O41B—C4B—N3B119.6 (4)H5X1—C5X—H5X3109.5
O41B—C4B—C5B125.5 (4)H5X2—C5X—H5X3109.5
C6A—N1A—C2A—N3A1.7 (6)N1B—C2B—N3B—C4B0.4 (5)
C6A—N1A—C2A—N21A178.9 (3)N21B—C2B—N3B—C4B177.6 (3)
N21A—C2A—N3A—C4A179.7 (3)C2B—N3B—C4B—O41B179.0 (4)
N1A—C2A—N3A—C4A1.0 (5)C2B—N3B—C4B—C5B0.1 (5)
C2A—N3A—C4A—O41A179.4 (4)O41B—C4B—C5B—C6B179.4 (4)
C2A—N3A—C4A—C5A0.4 (5)N3B—C4B—C5B—C6B0.3 (5)
O41A—C4A—C5A—C6A178.7 (4)C2B—N1B—C6B—C5B0.3 (5)
N3A—C4A—C5A—C6A1.1 (5)C2B—N1B—C6B—C61B179.5 (3)
C4A—C5A—C6A—N1A0.4 (5)C4B—C5B—C6B—N1B0.6 (6)
C4A—C5A—C6A—C61A179.6 (4)C4B—C5B—C6B—C61B179.7 (4)
C2A—N1A—C6A—C5A0.9 (5)O2X—C2X—N3X—C4X0.5 (6)
C2A—N1A—C6A—C61A179.0 (4)C1X—C2X—N3X—C4X179.1 (4)
C6B—N1B—C2B—N21B177.8 (3)O2X—C2X—N3X—C5X177.6 (4)
C6B—N1B—C2B—N3B0.2 (5)C1X—C2X—N3X—C5X3.8 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O41B0.881.922.803 (4)178
N21A—H21B···O2X0.882.062.843 (4)147
N1A—H1A···O2X0.882.022.807 (4)149
N3B—H3B···N3A0.881.972.844 (4)177
N21B—H21C···N1Bi0.882.102.969 (4)172
N21B—H21D···O41A0.882.002.877 (4)173
Symmetry code: (i) x+1, y, z.
(IIb) 2-amino-6-methylpyrimidin-4(3H)-one–2-amino-6-methylpyrimidin-4(1H)-one–N-methyl-2-pyrrolidone (1/1/1) top
Crystal data top
C5H7N3O·C5H7N3O·C5H9NOZ = 2
Mr = 349.40F(000) = 372
Triclinic, P1Dx = 1.324 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3321 (7) ÅCell parameters from 4837 reflections
b = 9.8805 (9) Åθ = 2.4–25.9°
c = 12.5860 (12) ŵ = 0.10 mm1
α = 102.835 (7)°T = 173 K
β = 98.830 (8)°Block, colourless
γ = 91.555 (8)°0.45 × 0.35 × 0.25 mm
V = 876.70 (14) Å3
Data collection top
Stoe IPDS II two-circle
diffractometer
1883 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.149
Graphite monochromatorθmax = 25.6°, θmin = 3.4°
ω scansh = 88
13229 measured reflectionsk = 1211
3267 independent reflectionsl = 1515
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)] = 0.068H-atom parameters constrained
wR(F2) = 0.176 w = 1/[σ2(Fo2) + (0.1156P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max < 0.001
3267 reflectionsΔρmax = 0.34 e Å3
242 parametersΔρmin = 0.35 e Å3
16 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.136 (17)
Crystal data top
C5H7N3O·C5H7N3O·C5H9NOγ = 91.555 (8)°
Mr = 349.40V = 876.70 (14) Å3
Triclinic, P1Z = 2
a = 7.3321 (7) ÅMo Kα radiation
b = 9.8805 (9) ŵ = 0.10 mm1
c = 12.5860 (12) ÅT = 173 K
α = 102.835 (7)°0.45 × 0.35 × 0.25 mm
β = 98.830 (8)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1883 reflections with I > 2σ(I)
13229 measured reflectionsRint = 0.149
3267 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06816 restraints
wR(F2) = 0.176H-atom parameters constrained
S = 0.82Δρmax = 0.34 e Å3
3267 reflectionsΔρmin = 0.35 e Å3
242 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)
N1A0.8058 (3)0.3882 (2)0.55332 (19)0.0376 (6)
H1A0.82910.35550.48620.045*
C2A0.7408 (4)0.5164 (3)0.5792 (2)0.0327 (6)
N21A0.7152 (4)0.5868 (2)0.49943 (18)0.0408 (6)
H21A0.67450.67090.51310.049*
H21B0.73910.54910.43320.049*
N3A0.7048 (3)0.5734 (2)0.67908 (17)0.0326 (6)
C4A0.7343 (4)0.4989 (3)0.7608 (2)0.0341 (7)
O41A0.7026 (3)0.5522 (2)0.85511 (15)0.0424 (6)
C5A0.8032 (4)0.3617 (3)0.7333 (2)0.0394 (7)
H5A0.82540.30920.78830.047*
C6A0.8360 (4)0.3078 (3)0.6304 (2)0.0383 (7)
C61A0.9049 (5)0.1678 (3)0.5920 (3)0.0504 (9)
H61A0.93780.12550.65520.076*
H61B1.01420.17720.55750.076*
H61C0.80800.10880.53800.076*
N1B0.4878 (3)1.0314 (2)0.86287 (16)0.0292 (5)
C2B0.5426 (3)0.9037 (3)0.83649 (19)0.0271 (6)
N21B0.5804 (3)0.8304 (2)0.91387 (16)0.0334 (6)
H21C0.56880.86720.98270.040*
H21D0.61680.74540.89590.040*
N3B0.5646 (3)0.8408 (2)0.73180 (16)0.0294 (5)
H3B0.59850.75470.71870.035*
C4B0.5356 (4)0.9074 (3)0.6450 (2)0.0338 (7)
O41B0.5629 (4)0.8447 (2)0.55216 (14)0.0504 (7)
C5B0.4729 (4)1.0435 (3)0.6727 (2)0.0364 (7)
H5B0.44591.09520.61750.044*
C6B0.4517 (4)1.0993 (3)0.7788 (2)0.0307 (6)
C61B0.3855 (5)1.2424 (3)0.8115 (2)0.0416 (7)
H61D0.36041.28200.74630.062*
H61E0.48091.30160.86660.062*
H61F0.27201.23740.84300.062*
C1X0.7899 (5)0.4190 (4)0.1193 (3)0.0623 (10)
H1XA0.79010.40920.04010.093*0.778 (6)
H1XB0.87020.50040.16110.093*0.778 (6)
H1XC0.66360.43110.13470.093*0.778 (6)
H3XC0.65510.42490.09860.075*0.222 (6)
H3XD0.85350.51250.13350.075*0.222 (6)
O2X0.8257 (3)0.3738 (2)0.33072 (16)0.0499 (6)
C3X0.9511 (5)0.1439 (3)0.2625 (3)0.0521 (9)
H3XA1.07490.15770.30900.063*0.778 (6)
H3XB0.86840.08760.29360.063*0.778 (6)
H1XD0.99200.05430.22610.078*0.222 (6)
H1XE0.84300.12810.29640.078*0.222 (6)
H1XF1.05130.19350.31980.078*0.222 (6)
C5X0.9164 (5)0.1836 (4)0.0748 (3)0.0557 (10)
H5XA1.02700.21200.04680.067*0.778 (6)
H5XB0.81740.14590.01120.067*0.778 (6)
H5XC0.82700.10500.03540.067*0.222 (6)
H5XD1.04250.15830.06260.067*0.222 (6)
N1X0.8546 (5)0.3012 (4)0.1504 (2)0.0434 (11)0.778 (6)
C2X0.8683 (5)0.2880 (4)0.2534 (3)0.0343 (10)0.778 (6)
C4X0.9623 (6)0.0757 (4)0.1432 (4)0.0513 (14)0.778 (6)
H4XA1.08820.04460.13690.062*0.778 (6)
H4XB0.87300.00630.11650.062*0.778 (6)
N1X'0.9069 (16)0.2184 (11)0.1895 (8)0.040 (4)*0.222 (6)
C2X'0.841 (3)0.3440 (16)0.2253 (11)0.058 (6)*0.222 (6)
C4X'0.866 (3)0.3160 (15)0.0363 (13)0.071 (6)*0.222 (6)
H4XC0.97860.35890.01890.086*0.222 (6)
H4XD0.77460.29120.03240.086*0.222 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0438 (15)0.0331 (13)0.0325 (12)0.0033 (11)0.0099 (10)0.0026 (10)
C2A0.0328 (15)0.0280 (13)0.0339 (14)0.0003 (11)0.0075 (11)0.0015 (11)
N21A0.0582 (17)0.0379 (14)0.0263 (12)0.0115 (12)0.0134 (11)0.0024 (10)
N3A0.0387 (14)0.0308 (12)0.0283 (12)0.0053 (10)0.0094 (10)0.0035 (9)
C4A0.0366 (16)0.0321 (15)0.0327 (14)0.0027 (12)0.0094 (12)0.0028 (11)
O41A0.0589 (14)0.0392 (12)0.0317 (10)0.0116 (10)0.0147 (9)0.0072 (8)
C5A0.0457 (17)0.0332 (15)0.0393 (15)0.0064 (13)0.0061 (13)0.0083 (12)
C6A0.0415 (17)0.0303 (14)0.0398 (16)0.0033 (12)0.0073 (13)0.0008 (12)
C61A0.061 (2)0.0361 (17)0.0511 (19)0.0146 (15)0.0098 (16)0.0010 (14)
N1B0.0360 (13)0.0276 (12)0.0229 (10)0.0039 (10)0.0041 (9)0.0037 (8)
C2B0.0268 (14)0.0328 (14)0.0202 (12)0.0010 (11)0.0035 (10)0.0030 (10)
N21B0.0484 (15)0.0331 (12)0.0204 (10)0.0101 (11)0.0095 (10)0.0066 (9)
N3B0.0387 (13)0.0273 (11)0.0222 (11)0.0068 (10)0.0058 (9)0.0042 (8)
C4B0.0449 (17)0.0369 (15)0.0198 (13)0.0038 (13)0.0062 (11)0.0065 (11)
O41B0.0925 (19)0.0416 (12)0.0206 (10)0.0231 (12)0.0176 (10)0.0065 (8)
C5B0.0528 (19)0.0310 (15)0.0268 (13)0.0058 (13)0.0065 (12)0.0090 (11)
C6B0.0350 (15)0.0295 (14)0.0276 (13)0.0007 (11)0.0067 (11)0.0053 (10)
C61B0.058 (2)0.0327 (15)0.0355 (15)0.0113 (14)0.0110 (13)0.0074 (12)
C1X0.056 (2)0.062 (2)0.063 (2)0.0006 (19)0.0014 (18)0.0104 (18)
O2X0.0551 (14)0.0523 (13)0.0358 (11)0.0085 (11)0.0142 (10)0.0087 (9)
C3X0.0425 (18)0.0505 (19)0.058 (2)0.0014 (15)0.0118 (15)0.0015 (15)
C5X0.0462 (19)0.068 (2)0.0384 (17)0.0008 (17)0.0120 (14)0.0209 (16)
N1X0.042 (2)0.051 (2)0.0306 (18)0.0049 (16)0.0066 (14)0.0043 (15)
C2X0.028 (2)0.040 (2)0.0277 (18)0.0011 (17)0.0076 (14)0.0094 (17)
C4X0.036 (2)0.040 (2)0.066 (3)0.0021 (18)0.016 (2)0.018 (2)
Geometric parameters (Å, º) top
N1A—C2A1.355 (4)C1X—N1X1.381 (5)
N1A—C6A1.381 (4)C1X—C4X'1.476 (13)
N1A—H1A0.8800C1X—C2X'1.664 (13)
C2A—N3A1.327 (3)C1X—H1XA0.9800
C2A—N21A1.337 (4)C1X—H1XB0.9800
N21A—H21A0.8800C1X—H1XC0.9800
N21A—H21B0.8800C1X—H3XC0.9900
N3A—C4A1.386 (4)C1X—H3XD0.9900
C4A—O41A1.247 (3)O2X—C2X1.227 (4)
C4A—C5A1.448 (4)O2X—C2X'1.316 (12)
C5A—C6A1.347 (4)C3X—N1X'1.310 (10)
C5A—H5A0.9500C3X—C4X1.519 (5)
C6A—C61A1.489 (4)C3X—C2X1.584 (5)
C61A—H61A0.9800C3X—H3XA0.9900
C61A—H61B0.9800C3X—H3XB0.9900
C61A—H61C0.9800C3X—H1XD0.9800
N1B—C2B1.321 (3)C3X—H1XE0.9800
N1B—C6B1.371 (3)C3X—H1XF0.9800
C2B—N21B1.339 (3)C5X—N1X'1.421 (10)
C2B—N3B1.362 (3)C5X—N1X1.459 (4)
N21B—H21C0.8800C5X—C4X1.526 (6)
N21B—H21D0.8800C5X—C4X'1.527 (13)
N3B—C4B1.388 (3)C5X—H5XA0.9900
N3B—H3B0.8800C5X—H5XB0.9900
C4B—O41B1.244 (3)C5X—H5XC0.9900
C4B—C5B1.419 (4)C5X—H5XD0.9900
C5B—C6B1.362 (4)N1X—C2X1.320 (5)
C5B—H5B0.9500C4X—H4XA0.9900
C6B—C61B1.498 (4)C4X—H4XB0.9900
C61B—H61D0.9800N1X'—C2X'1.353 (15)
C61B—H61E0.9800C4X'—H4XC0.9900
C61B—H61F0.9800C4X'—H4XD0.9900
C2A—N1A—C6A121.2 (2)N1X'—C3X—C4X63.2 (5)
C2A—N1A—H1A119.4C4X—C3X—C2X102.7 (3)
C6A—N1A—H1A119.4N1X'—C3X—H3XA120.5
N3A—C2A—N21A120.0 (2)C4X—C3X—H3XA111.2
N3A—C2A—N1A122.8 (3)C2X—C3X—H3XA111.2
N21A—C2A—N1A117.2 (2)N1X'—C3X—H3XB128.6
C2A—N21A—H21A120.0C4X—C3X—H3XB111.2
C2A—N21A—H21B120.0C2X—C3X—H3XB111.2
H21A—N21A—H21B120.0H3XA—C3X—H3XB109.1
C2A—N3A—C4A118.9 (2)N1X'—C3X—H1XD109.5
O41A—C4A—N3A119.3 (2)C4X—C3X—H1XD46.3
O41A—C4A—C5A122.2 (3)C2X—C3X—H1XD149.1
N3A—C4A—C5A118.4 (2)H3XA—C3X—H1XD85.8
C6A—C5A—C4A120.5 (3)H3XB—C3X—H1XD85.2
C6A—C5A—H5A119.8N1X'—C3X—H1XE109.5
C4A—C5A—H5A119.8C4X—C3X—H1XE122.1
C5A—C6A—N1A118.1 (2)C2X—C3X—H1XE85.4
C5A—C6A—C61A125.5 (3)H3XA—C3X—H1XE118.7
N1A—C6A—C61A116.4 (2)H1XD—C3X—H1XE109.5
C6A—C61A—H61A109.5N1X'—C3X—H1XF109.5
C6A—C61A—H61B109.5C4X—C3X—H1XF127.6
H61A—C61A—H61B109.5C2X—C3X—H1XF89.5
C6A—C61A—H61C109.5H3XB—C3X—H1XF111.0
H61A—C61A—H61C109.5H1XD—C3X—H1XF109.5
H61B—C61A—H61C109.5H1XE—C3X—H1XF109.5
C2B—N1B—C6B116.7 (2)N1X'—C5X—C4X60.8 (5)
N1B—C2B—N21B120.3 (2)N1X—C5X—C4X105.1 (3)
N1B—C2B—N3B122.8 (2)N1X'—C5X—C4X'104.0 (7)
N21B—C2B—N3B116.9 (2)N1X—C5X—C4X'59.8 (6)
C2B—N21B—H21C120.0C4X—C5X—C4X'164.7 (6)
C2B—N21B—H21D120.0N1X'—C5X—H5XA120.9
H21C—N21B—H21D120.0N1X—C5X—H5XA110.7
C2B—N3B—C4B122.5 (2)C4X—C5X—H5XA110.7
C2B—N3B—H3B118.8C4X'—C5X—H5XA75.2
C4B—N3B—H3B118.8N1X'—C5X—H5XB129.4
O41B—C4B—N3B118.9 (2)N1X—C5X—H5XB110.7
O41B—C4B—C5B126.2 (2)C4X—C5X—H5XB110.7
N3B—C4B—C5B114.9 (2)C4X'—C5X—H5XB79.3
C6B—C5B—C4B119.5 (2)H5XA—C5X—H5XB108.8
C6B—C5B—H5B120.3N1X'—C5X—H5XC111.1
C4B—C5B—H5B120.3N1X—C5X—H5XC119.5
C5B—C6B—N1B123.7 (2)C4X—C5X—H5XC78.1
C5B—C6B—C61B121.2 (2)C4X'—C5X—H5XC110.8
N1B—C6B—C61B115.1 (2)H5XA—C5X—H5XC124.5
C6B—C61B—H61D109.5N1X'—C5X—H5XD110.6
C6B—C61B—H61E109.5N1X—C5X—H5XD130.6
H61D—C61B—H61E109.5C4X—C5X—H5XD75.8
C6B—C61B—H61F109.5C4X'—C5X—H5XD111.3
H61D—C61B—H61F109.5H5XB—C5X—H5XD114.8
H61E—C61B—H61F109.5H5XC—C5X—H5XD109.0
N1X—C1X—C4X'62.8 (6)C2X—N1X—C1X121.6 (3)
C4X'—C1X—C2X'97.8 (8)C2X—N1X—C5X114.5 (3)
N1X—C1X—H1XA109.5C1X—N1X—C5X123.8 (3)
C4X'—C1X—H1XA47.3O2X—C2X—N1X125.9 (4)
C2X'—C1X—H1XA144.9O2X—C2X—C3X124.8 (4)
N1X—C1X—H1XB109.5N1X—C2X—C3X109.3 (3)
C4X'—C1X—H1XB118.0C5X—C4X—C3X107.6 (3)
C2X'—C1X—H1XB89.1C5X—C4X—H4XA110.2
H1XA—C1X—H1XB109.5C3X—C4X—H4XA110.2
N1X—C1X—H1XC109.5C5X—C4X—H4XB110.2
C4X'—C1X—H1XC131.8C3X—C4X—H4XB110.2
C2X'—C1X—H1XC90.7H4XA—C4X—H4XB108.5
H1XA—C1X—H1XC109.5C2X'—N1X'—C3X117.2 (9)
H1XB—C1X—H1XC109.5C2X'—N1X'—C5X114.5 (9)
N1X—C1X—H3XC119.1C3X—N1X'—C5X128.2 (8)
C4X'—C1X—H3XC112.2O2X—C2X'—N1X'114.4 (11)
C2X'—C1X—H3XC112.2O2X—C2X'—C1X136.3 (10)
H1XA—C1X—H3XC83.7N1X'—C2X'—C1X109.2 (9)
H1XB—C1X—H3XC121.6C1X—C4X'—C5X113.1 (9)
N1X—C1X—H3XD128.8C1X—C4X'—H4XC109.0
C4X'—C1X—H3XD112.2C5X—C4X'—H4XC109.0
C2X'—C1X—H3XD112.2C1X—C4X'—H4XD109.0
H1XA—C1X—H3XD89.2C5X—C4X'—H4XD109.0
H1XC—C1X—H3XD107.9H4XC—C4X'—H4XD107.8
H3XC—C1X—H3XD109.8
C6A—N1A—C2A—N3A0.9 (4)C5X—N1X—C2X—O2X179.6 (3)
C6A—N1A—C2A—N21A179.8 (3)C1X—N1X—C2X—C3X178.6 (3)
N21A—C2A—N3A—C4A179.3 (3)C5X—N1X—C2X—C3X0.2 (4)
N1A—C2A—N3A—C4A0.1 (4)N1X'—C3X—C2X—O2X178.2 (9)
C2A—N3A—C4A—O41A179.3 (3)C4X—C3X—C2X—O2X175.4 (3)
C2A—N3A—C4A—C5A0.1 (4)N1X'—C3X—C2X—N1X1.2 (8)
O41A—C4A—C5A—C6A179.9 (3)C4X—C3X—C2X—N1X5.2 (4)
N3A—C4A—C5A—C6A0.6 (4)N1X'—C5X—C4X—C3X3.1 (6)
C4A—C5A—C6A—N1A1.3 (5)N1X—C5X—C4X—C3X8.0 (4)
C4A—C5A—C6A—C61A179.4 (3)C4X'—C5X—C4X—C3X1 (3)
C2A—N1A—C6A—C5A1.5 (4)N1X'—C3X—C4X—C5X3.3 (6)
C2A—N1A—C6A—C61A179.1 (3)C2X—C3X—C4X—C5X7.9 (4)
C6B—N1B—C2B—N21B179.9 (3)C4X—C3X—N1X'—C2X'174.6 (15)
C6B—N1B—C2B—N3B0.5 (4)C2X—C3X—N1X'—C2X'1.5 (11)
N1B—C2B—N3B—C4B1.7 (4)C4X—C3X—N1X'—C5X4.3 (8)
N21B—C2B—N3B—C4B177.9 (3)C2X—C3X—N1X'—C5X177.3 (16)
C2B—N3B—C4B—O41B178.2 (3)N1X—C5X—N1X'—C2X'1.3 (10)
C2B—N3B—C4B—C5B2.9 (4)C4X—C5X—N1X'—C2X'174.5 (14)
O41B—C4B—C5B—C6B179.2 (3)C4X'—C5X—N1X'—C2X'6.7 (16)
N3B—C4B—C5B—C6B2.0 (4)N1X—C5X—N1X'—C3X177.6 (15)
C4B—C5B—C6B—N1B0.0 (5)C4X—C5X—N1X'—C3X4.4 (8)
C4B—C5B—C6B—C61B179.9 (3)C4X'—C5X—N1X'—C3X174.4 (12)
C2B—N1B—C6B—C5B1.4 (4)C2X—O2X—C2X'—N1X'1.2 (6)
C2B—N1B—C6B—C61B178.6 (3)C2X—O2X—C2X'—C1X175 (3)
C4X'—C1X—N1X—C2X172.1 (10)C3X—N1X'—C2X'—O2X1 (2)
C2X'—C1X—N1X—C2X1.6 (13)C5X—N1X'—C2X'—O2X177.6 (11)
C4X'—C1X—N1X—C5X6.6 (10)C3X—N1X'—C2X'—C1X178.9 (9)
C2X'—C1X—N1X—C5X177.1 (13)C5X—N1X'—C2X'—C1X0.1 (17)
N1X'—C5X—N1X—C2X1.2 (7)N1X—C1X—C2X'—O2X175 (3)
C4X—C5X—N1X—C2X4.9 (4)C4X'—C1X—C2X'—O2X176 (2)
C4X'—C5X—N1X—C2X172.2 (10)N1X—C1X—C2X'—N1X'1.5 (6)
N1X'—C5X—N1X—C1X177.5 (8)C4X'—C1X—C2X'—N1X'7.0 (16)
C4X—C5X—N1X—C1X176.3 (4)N1X—C1X—C4X'—C5X5.7 (9)
C4X'—C5X—N1X—C1X6.5 (10)C2X'—C1X—C4X'—C5X11.2 (15)
C2X'—O2X—C2X—N1X2.7 (16)N1X'—C5X—C4X'—C1X12.0 (16)
C2X'—O2X—C2X—C3X176.7 (19)N1X—C5X—C4X'—C1X5.5 (8)
C1X—N1X—C2X—O2X0.8 (6)C4X—C5X—C4X'—C1X16 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O2X0.882.002.800 (3)151
N21A—H21A···O41B0.881.922.794 (3)173
N21A—H21B···O2X0.882.092.869 (3)146
N3B—H3B···N3A0.881.972.838 (3)171
N21B—H21D···O41A0.882.012.888 (3)179
N21B—H21C···N1Bi0.882.092.962 (3)172
Symmetry code: (i) x+1, y+2, z+2.

Experimental details

(I)(Ia)(Ib)(Ic)
Crystal data
Chemical formulaC4H6N4OC4H6N4O·4/3C3H7NO·1/3H2OC4H6N4O·C4H9NOC4H6N4O·3/2C5H9NO
Mr126.13229.59213.25274.83
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21Monoclinic, CcTriclinic, P1
Temperature (K)173173173173
a, b, c (Å)7.7150 (9), 9.7229 (7), 7.4514 (8)7.4417 (6), 25.3217 (18), 9.8578 (7)19.1494 (13), 7.8704 (4), 14.9104 (11)8.4550 (9), 10.0803 (9), 17.0735 (15)
α, β, γ (°)90, 114.453 (8), 9090, 108.476 (6), 9090, 104.868 (6), 9075.558 (7), 78.222 (8), 81.363 (8)
V3)508.81 (9)1761.8 (2)2172.0 (2)1371.9 (2)
Z4684
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.130.100.100.10
Crystal size (mm)0.45 × 0.35 × 0.300.50 × 0.30 × 0.200.50 × 0.35 × 0.300.25 × 0.20 × 0.20
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 correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7117, 953, 737 28505, 3380, 2636 12494, 2054, 1922 18821, 5116, 2940
Rint0.1280.1700.0960.091
(sin θ/λ)max1)0.6080.6100.6090.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.092, 0.97 0.040, 0.085, 0.91 0.047, 0.126, 1.04 0.056, 0.127, 0.91
No. of reflections953338020545116
No. of parameters103459277355
No. of restraints04220
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.290.19, 0.190.47, 0.310.48, 0.29


(IIa)(IIb)
Crystal data
Chemical formulaC5H7N3O·C5H7N3O·C4H9NOC5H7N3O·C5H7N3O·C5H9NO
Mr337.39349.40
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)173173
a, b, c (Å)7.8763 (13), 9.6078 (17), 12.3115 (19)7.3321 (7), 9.8805 (9), 12.5860 (12)
α, β, γ (°)108.780 (13), 95.194 (13), 99.959 (13)102.835 (7), 98.830 (8), 91.555 (8)
V3)858.0 (2)876.70 (14)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.100.10
Crystal size (mm)0.40 × 0.25 × 0.100.45 × 0.35 × 0.25
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7199, 3208, 1427 13229, 3267, 1883
Rint0.1310.149
(sin θ/λ)max1)0.6090.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.204, 0.82 0.068, 0.176, 0.82
No. of reflections32083267
No. of parameters223242
No. of restraints016
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.470.34, 0.35

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—H21A···O41i0.90 (2)1.98 (2)2.8678 (17)165.9 (19)
N21—H21B···N61ii0.89 (2)2.34 (2)3.1304 (19)147.9 (18)
N3—H3···N1ii0.92 (2)2.15 (2)3.0370 (17)163.2 (17)
N61—H61B···N1iii0.89 (2)2.34 (2)3.2131 (18)166.8 (16)
N61—H61A···O41iv0.89 (2)2.05 (2)2.9296 (18)172.5 (17)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x+1, y+1, z+1; (iv) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···N1Bi0.882.112.985 (4)170
N21A—H21B···O1Xi0.882.122.820 (4)136
N3A—H3A···O41B0.881.862.734 (3)175
N61A—H61B···O1W0.882.052.872 (4)155
N21B—H21C···N1Aii0.882.052.931 (4)175
N21B—H21D···O1V0.882.072.920 (4)161
N3B—H3B···O41A0.881.952.812 (3)167
N61B—H61C···O1X0.882.163.028 (4)168
N61B—H61D···O41C0.882.022.886 (4)169
N21C—H21E···O41Aiii0.882.112.945 (4)158
N21C—H21F···O1Z0.882.102.874 (4)146
N3C—H3C···O1Viv0.882.032.890 (3)166
N61C—H61E···O41Cv0.881.972.744 (3)147
N61C—H61F···O1Y0.882.072.949 (4)173
O1V—H1V···N1Cvi0.844 (10)2.060 (17)2.856 (3)157 (3)
O1V—H2V···O41A0.844 (10)1.957 (18)2.751 (3)156 (4)
Symmetry codes: (i) x+1, y, z+1; (ii) x1, y, z1; (iii) x+1, y+1/2, z+1; (iv) x, y+1/2, z+1; (v) x+1, y, z; (vi) x+1, y1/2, z+1.
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···N1B0.882.072.946 (4)171
N21A—H21B···O2X0.882.463.176 (4)139
N3A—H3A···O41Bi0.881.892.765 (3)174
N61A—H61A···O2Xii0.882.152.939 (4)150
N61A—H61B···O41Biii0.882.222.975 (4)144
N21B—H21C···N1A0.882.163.029 (4)172
N3B—H3B···O41Aiv0.881.842.700 (4)166
N61B—H61C···O2X0.882.172.960 (4)149
N61B—H61D···O41Av0.881.952.813 (4)165
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x, y+1, z+1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x1/2, y1/2, z; (v) x1/2, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) for (Ic) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O2Xi0.882.223.092 (3)169
N21A—H21B···O41B0.882.002.756 (3)143
N3A—H3A···O41Aii0.881.872.750 (3)177
N61A—H61A···N1Ai0.882.153.023 (3)169
N61A—H61B···O2X0.882.142.891 (3)142
N21B—H21C···O2Ziii0.882.122.989 (3)170
N21B—H21D···O2Y0.882.062.832 (3)146
N3B—H3B···O2Y0.882.152.904 (3)143
N61B—H61C···N1Biii0.882.133.001 (3)170
N61B—H61D···O2Z0.882.112.840 (3)139
Symmetry codes: (i) x, y+2, z+1; (ii) x+1, y+1, z+1; (iii) x+2, y+1, z.
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O41B0.881.922.803 (4)178
N21A—H21B···O2X0.882.062.843 (4)147
N1A—H1A···O2X0.882.022.807 (4)149
N3B—H3B···N3A0.881.972.844 (4)177
N21B—H21C···N1Bi0.882.102.969 (4)172
N21B—H21D···O41A0.882.002.877 (4)173
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (IIb) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O2X0.882.002.800 (3)151
N21A—H21A···O41B0.881.922.794 (3)173
N21A—H21B···O2X0.882.092.869 (3)146
N3B—H3B···N3A0.881.972.838 (3)171
N21B—H21D···O41A0.882.012.888 (3)179
N21B—H21C···N1Bi0.882.092.962 (3)172
Symmetry code: (i) x+1, y+2, z+2.
Crystallization of 2,6-diaminopyrimidin-4-one top
Crystal2,6-Diaminopyrimidin-4-one (mg; mmol)SolventTemperature
(I)4.2; 0.033Methanol (500 µl)323 K
(Ia)1.9; 0.015DMF (100 µl)Room temperature
(Ib)2.1; 0.017DMAC (200 µl)323 K
(Ic)3.0; 0.024NMP (50 µl)Room temperature
Crystallization of 2-amino-6-methylpyrimidin-4-one top
Crystal2-Amino-6-methylpyrimidin-4-one (mg; mmol)SolventTemperature
(IIa)2.3; 0.018DMAC (150 µl)277 K
(IIb)1.9; 0.015NMP (50 µl)323 K
 

Acknowledgements

The authors thank Professor Dr Ernst Egert for helpful discussions.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals
First citationBannister, C., Burns, K., Prout, K., Watkin, D. J., Cooper, D. G., Durant, G. J., Ganellin, C. R., Ife, R. J. & Sach, G. S. (1994). Acta Cryst. B50, 221–243.  CSD CrossRef CAS Web of Science IUCr Journals
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science
First citationBhogala, B. R., Chandran, S. K., Reddy, L. S., Thakuria, R. & Nangia, A. (2008). CrystEngComm, 10, 1735–1738.  CrossRef CAS
First citationGerhardt, V., Tutughamiarso, M. & Bolte, M. (2011). Private communication (refcode 820449). CCDC, Union Road, Cambridge, England.
First citationKawade, D. P., Khedekar, P. B. & Bhusari, K. P. (2011). Int. J. Pharm. Biomed. Res. 2, 13–16.  CAS
First citationLe Page, Y. (1987). J. Appl. Cryst. 20, 264–269.  CrossRef CAS Web of Science IUCr Journals
First citationLe Page, Y. (1988). J. Appl. Cryst. 21, 983–984.  CrossRef Web of Science IUCr Journals
First citationLiao, R.-F., Lauher, J. W. & Fowler, F. W. (1996). Tetrahedron, 52, 3153–3162.  CrossRef CAS
First citationLópez, C., Claramunt, R. M., Alkorta, I. & Elguero, J. (2000). Spectroscopy, 14, 121–126.
First citationLowe, P. R., Schwalbe, C. H. & Williams, G. J. B. (1987). Acta Cryst. C43, 330–333.  CSD CrossRef CAS Web of Science IUCr Journals
First citationLu, S., Wang, A., Lu, S. & Dong, Z. (2007). Mol. Cancer Ther. 6, 2057–2064.  Web of Science CrossRef PubMed CAS
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals
First citationPortalone, G. & Colapietro, M. (2007). Acta Cryst. E63, o1869–o1871.  Web of Science CSD CrossRef IUCr Journals
First citationSharma, B. D. & McConnell, J. F. (1965). Acta Cryst. 19, 797–806.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSkoweranda, J., Bukowska-Strzyżewska, M., Bartnik, R. & Strzyżewski, W. (1990). J. Crystallogr. Spectrosc. Res. 20, 117–121.  CrossRef CAS
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals
First citationStoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.
First citationSubashini, A., Muthiah, P. T., Bocelli, G. & Cantoni, A. (2007). Acta Cryst. E63, o4244.  Web of Science CSD CrossRef IUCr Journals
First citationSuleiman Gwaram, N., Khaledi, H., Mohd Ali, H. & Olmstead, M. M. (2011). Acta Cryst. C67, o6–o9.  Web of Science CSD CrossRef IUCr Journals
First citationToledo, L. M., Musa, K., Lauher, J. W. & Fowler, F. W. (1995). Chem. Mater. 7, 1639–1647.  CrossRef CAS
First citationVaillancourt, L., Simard, M. & Wuest, J. D. (1998). J. Org. Chem. 63, 9746–9752.  Web of Science CSD CrossRef CAS
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals
First citationYoussouf, M. S., Kaiser, P., Singh, G. D., Singh, S., Bani, S., Gupta, V. K., Satti, N. K., Suri, K. A. & Johri, R. K. (2008). Int. Immunopharmacol. 8, 1049–1055.  Web of Science CrossRef PubMed CAS

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds