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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Cocrystals of 6-propyl-2-thio­uracil: N—H⋯O versus N—H⋯S hydrogen bonds

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

(Received 26 July 2011; accepted 16 September 2011; online 11 October 2011)

In order to investigate the relative stability of N—H⋯O and N—H⋯S hydrogen bonds, we cocrystallized the anti­thyroid drug 6-propyl-2-thio­uracil with two complementary heterocycles. In the cocrystal pyrimidin-2-amine–6-propyl-2-thio­uracil (1/2), C4H5N3·2C7H10N2OS, (I), the `base pair' is connected by one N—H⋯S and one N—H⋯N hydrogen bond. Homodimers of 6-propyl-2-thio­uracil linked by two N—H⋯S hydrogen bonds are observed in the cocrystal N-(6-acetamido­pyridin-2-yl)acetamide–6-propyl-2-thio­uracil (1/2), C9H11N3O2·2C7H10N2OS, (II). The crystal structure of 6-propyl-2-thio­uracil itself, C7H10N2OS, (III), is stabilized by pairwise N—H⋯O and N—H⋯S hydrogen bonds. In all three structures, N—H⋯S hydrogen bonds occur only within R22(8) patterns, whereas N—H⋯O hydrogen bonds tend to connect the homo- and heterodimers into extended networks. In agreement with related structures, the hydrogen-bonding capability of C=O and C=S groups seems to be comparable.

Comment

Hydrogen-bond inter­actions with an S atom as an acceptor are important in biological processes. For example, sulfur-containing nucleosides are components of the anti­codon of transfer RNAs. They exhibit the same arrangement of hydrogen-donor and -acceptor groups as unmodified nucleosides, but the replacement of an O with an S atom induces changes in their properties and inter­actions. The thio residue can be selectively photoactivated, so that it is used as an intrinsic photolabel to probe the nucleic acid structure and to identify inter­actions within nucleic acids or between nucleic acids and proteins (Favre et al., 1998[Favre, A., Saintomé, C., Fourrey, J.-L., Clivio, P. & Laugâa, P. (1998). J. Photochem. Photobiol. B, 42, 109-124.]). Furthermore, the enhanced base-pairing specificity of thio­nucleosides can be utilized, for example, in the design of anti­sense oligonucleotides (Testa et al., 1999[Testa, S. M., Disney, M. D., Turner, D. H. & Kierzek, R. (1999). Biochemistry, 38, 16655-16662.]).

Because of its reduced electronegativity, an S atom should be a weaker hydrogen-bond acceptor than an O atom. Many theoretical and experimental investigations have been concerned with the stability of the N—H⋯O and the N—H⋯S hydrogen bonds, but no clear trend has emerged. Ab initio energy calculations (Šponer et al., 1997[Šponer, J., Leszczynski, J. & Hobza, P. (1997). J. Phys. Chem. A, 101, 9489-9495.]; Basilio Janke et al., 2001[Basilio Janke, E. M., Dunger, A., Limbach, H.-H. & Weisz, K. (2001). Magn. Reson. Chem. 39, 177-182.]) and a study of the thermodynamics of RNA duplexes containing thio­uridine (Testa et al., 1999[Testa, S. M., Disney, M. D., Turner, D. H. & Kierzek, R. (1999). Biochemistry, 38, 16655-16662.]) showed that a base pair connected by an N—H⋯O hydrogen bond is more stable than that connected by an N—H⋯S hydrogen bond. In the case of 2-thio­uridine, the Watson–Crick base pair with adenine, which is connected by an N—H⋯O hydrogen bond, is preferred over the wobble base pair with guanine, which is linked by an N—H⋯S hydrogen bond. In contrast, 4-thio­uridine increases the stability of the wobble base pair compared with the Watson–Crick base pairing. However, the IR spectroscopic red shift of the N—H stretching frequency indicated that N—H⋯S is comparable or even stronger than the N—H⋯O inter­action (Lautié & Novak, 1980[Lautié, A. & Novak, A. (1980). Chem. Phys. Lett. 71, 290-293.]; Biswal & Wategaonkar, 2009[Biswal, H. S. & Wategaonkar, S. (2009). J. Phys. Chem. A, 113, 12763-12773.]).

[Scheme 1]

In order to study the stability of the N—H⋯S hydrogen bond in the presence of a competitive carbonyl O atom as an acceptor, we cocrystallized pyrimidin-2-amine and N-(6-acetamido­pyridin-2-yl)acetamide, respectively, with the anti­thyroid drug 6-propyl-2-thio­uracil, also known as propyl­thio­uracil. It inhibits the synthesis of thyroid hormones and has been used for the treatment of hyperthyroidism caused by Graves' disease (Cooper, 2005[Cooper, D. S. (2005). N. Engl. J. Med. 352, 905-917.]). Because of its risk of serious liver injury, 6-propyl-2-thio­uracil is used as a second-line drug for patients who are intolerant of other therapies (Bahn et al., 2009[Bahn, R. S., Burch, H. S., Cooper, D. S., Garber, J. R., Greenlee, C. M., Klein, I. L., Laurberg, P., McDougall, I. R., Rivkees, S. A., Ross, D., Sosa, J. A. & Stan, M. N. (2009). Thyroid, 19, 673-674.]).

We chose pyrimidin-2-amine because of its adjacent amine and imine groups resembling the donor–acceptor site of adenine. Since it has a mirror plane bis­ecting the mol­ecule along the C—NH2 bond, one pyrimidin-2-amine mol­ecule may be hydrogen bonded to two 6-propyl-2-thio­uracil mol­ecules. Indeed, the asymmetric unit of cocrystal (I)[link], namely pyrimidin-2-amine–6-propyl-2-thio­uracil (1/2), contains two 6-propyl-2-thio­uracil mol­ecules and one pyrimidin-2-amine mol­ecule (Fig. 1[link]). The plane of the pyrimidin-2-amine mol­ecule forms dihedral angles of 17.1 (1) and 10.6 (1)° with those of the thio­uracil rings of mol­ecules A and B, respectively. Different propyl side-chain conformations are observed: in mol­ecule A, methyl C atom C9A and thio­uracil ring atom C6A are synclinal, with the C8A—C9A bond almost perpendicular to the plane of the ring, while in mol­ecule B they are anti­periplanar, with a dihedral angle of 32.7 (2)° between the plane of the thio­uracil ring and the plane through the side chain (Table 1[link]). Each 6-propyl-2-thio­uracil mol­ecule is hydrogen bonded to the pyrimidin-2-amine mol­ecule by an R22(8) motif (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) characterized by one N—H⋯S and one N—H⋯N hydrogen bond. The O atoms participate in N—H⋯O inter­actions (Table 2[link]) connecting the 6-propyl-2-thio­uracil mol­ecules into C(6) chains running along the b axis. The packing of (I)[link] shows layers parallel to (101) containing circular arrangements of four adjacent trimeric units with an R88(34) hydrogen-bond pattern (Fig. 2[link]).

Its participation in the `base pairing' of (I)[link] suggests that the S atom competes as an acceptor with the O atom. Hence, we were also inter­ested in whether both S and O atoms can be hydrogen bonded simultaneously to a complementary mol­ecule. Since 6-propyl-2-thio­uracil possesses an acceptor–donor–acceptor site, we cocrystallized it with N-(6-acet­am­ido­pyridin-2-yl)acetamide, which exhibits a donor–accep­tor–donor site.

Cocrystal (II)[link], namely N-(6-acetamido­pyridin-2-yl)acet­amide–6-propyl-2-thio­uracil (1/2), contains three symmetry-independent complexes, each consisting of two 6-propyl-2-thio­uracil mol­ecules and one N-(6-acetamido­pyridin-2-yl)acetamide mol­ecule (Fig. 3[link]). The mol­ecular structures of the six propyl­thio­uracil and the three N-(6-acetamido­pyridin-2-yl)acetamide mol­ecules are very similar. The r.m.s. deviation from the mean plane through the non-H atoms of each 6-pro­pyl-2-thio­uracil mol­ecule varies from 0.012 to 0.028 Å, confirming their planarity. All side chains show an extended conformation, with C8 anti­periplanar to N1 and C9 anti­periplanar to C6 (Table 3[link]). Both N—H bonds of the N-(6-acetamido­pyridin-2-yl)acetamide mol­ecules are directed to the same side of the side chains as the pyridine N atom, while the methyl groups are anti­periplanar to ring atoms C2 and C6 (Table 4[link]). Thus, dihedral angles ranging from 12.6 (1) to 15.6 (1)° are formed between the planes through one of the amide groups and the pyridine ring (Table 5[link]). The hydrogen-bond patterns within the three complexes are also identical. The 6-propyl-2-thio­uracil mol­ecules are linked into dimers by an R22(8) motif involving two N—H⋯S hydrogen bonds. In addition, an N—H⋯O interaction connects one 6-propyl-2-thio­uracil molecule to an N-(6-acetamido­pyridin-2-yl)acet­amide molecule. However, the geometric arrangements of the complexes show some flexibility. The planes through the two 6-propyl-2-thio­uracil mol­ecules of a dimer enclose a dihedral angle ranging from 4.4 (1) to 11.9 (1)°, while dihedral angles ranging from 2.0 (1) to 9.7 (1)° are observed between the planes through the pyridine ring and the neighbouring 6-propyl-2-thio­uracil mol­ecule (Table 6[link]). In the packing, all three complexes are twisted by 17° with respect to each other and are connected by N—H⋯O hydrogen bonds into chains running along [310] (Fig. 4[link]). Furthermore, a second chain is formed consisting of N—H⋯O-bonded symmetry-related complexes aligned along the b axis. Altogether, an extended three-dimensional network of hydrogen bonds is observed (Table 7[link]).

In spite of the appropriate arrangement of donor and acceptor groups, 6-propyl-2-thio­uracil does not form three hydrogen bonds to N-(6-acetamido­pyridin-2-yl)acetamide in (II)[link], but undergoes homodimerization without participation of the carbonyl O atom. In order to further investigate its preferred hydrogen-bonding inter­actions, we analysed related crystal structures. Two structures containing 6-propyl-2-thio­uracil are present in the Cambridge Structural Database (CSD, Version 5.32 of November 2010, plus two updates; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), namely a 1,4-dioxane solvate (refcode BUWYOH; Okabe et al., 1983[Okabe, N., Fujiwara, T., Yamagata, Y. & Tomita, K. (1983). Bull. Chem. Soc. Jpn, 56, 1543-1544.]) and a charge-transfer complex with diiodine (refcode HAFLAC; Antoniadis et al., 2003[Antoniadis, C. D., Corban, G. J., Hadjikakou, S. K., Hadjiliadis, N., Kubicki, M., Warner, S. & Butler, I. S. (2003). Eur. J. Inorg. Chem. pp. 1635-1640.]). The latter structure is not further considered, since the S atom is connected to the diiodine mol­ecule and hence can hardly participate as a hydrogen-bond acceptor. In the 1,4-dioxane solvate, only the carbonyl O atom takes part in the hydrogen bonding and connects the 6-propyl-2-thio­uracil mol­ecules into chains, while no N—H⋯S inter­actions are observed. In the solvent-free structure of the selenium analogue of 6-propyl-2-thio­uracil (refcode PELHEU; Antoniadis et al., 2006[Antoniadis, C. D., Blake, A. J., Hadjikakou, S. K., Hadjiliadis, N., Hubberstey, P., Schröder, M. & Wilson, C. (2006). Acta Cryst. B62, 580-591.]), the mol­ecules are hydrogen bonded into chains by R22(8) inter­actions involving either N—H⋯Se or N—H⋯O hydrogen bonds. We therefore undertook crystallization experiments with 6-propyl-2-thio­uracil alone to study whether similar inter­actions can be observed.

The crystal structure of 6-propyl-2-thio­uracil, (III)[link], is isostructural with PELHEU (Fig. 5[link]). The thio­uracil rings of the two independent mol­ecules are planar [r.m.s. deviations = 0.006 (A) and 0.016 Å (B) for all non-H atoms] and the propyl side chains are again extended but slightly twisted, with the planes through the ring and the side chain enclosing dihedral angles of 26.0 (2)° in A and 29.8 (2)° in B (Table 8[link]). The 6-propyl-2-thio­uracil mol­ecules are connected into vaulted chains running along the b axis by two kinds of hydrogen-bond inter­actions (Table 9[link]). Although both show the same R22(8) graph set, the hydrogen-bond pattern consists of either two N—H⋯O or two N—H⋯S inter­actions (Fig. 6[link]). In the crystal packing, two adjacent chains form a tubular arrangement stabilized by van der Waals inter­actions (Fig. 7[link]).

In (I)–(III), 6-propyl-2-thio­uracil exhibits different side-chain conformations. The dihedral angle between the planar thio­uracil ring and the plane through the side chain varies from 2.3 (1) to 89.4 (1)°, although an extended arrangement is preferred. Since sufficient donor groups are available both O and S atoms participate in the hydrogen bonding. The N—H⋯O hydrogen bonds have different functions: they connect hydrogen-bonded 6-propyl-2-thio­uracil mol­ecules either with themselves [in (I)] or with the other cocrystal component [in (II)], thus forming chains, or they stabilize homodimers of 6-propyl-2-thio­uracil with an R22(8) pattern [in (III)]. In contrast, the S atoms are only involved in R22(8) hydrogen-bond formation linking the 6-propyl-2-thio­uracil mol­ecules into a heterodimer [in (I)] or into a homodimer [in (II)[link] and (III)].

From the hydrogen-bond inter­actions in the three structures [(I)–(III)], it is not evident whether an N—H⋯O or an N—H⋯S hydrogen bond is stronger. A CSD search of six-membered ring compounds with hydrogen-bonding sites similar to 2-thio­uracil yielded four different types of R22(8) patterns. 19 entries showed R22(8) motifs characterized by two N—H⋯O hydrogen bonds; the S atoms take part as acceptors only in five of them [refcodes LACJIJ (Tashkhodzhaev et al., 2002[Tashkhodzhaev, B., Turgunov, K. K., Usmanova, B., Averkiev, B. B., Antipin, M. Yu. & Shakhidoyatov, Kh. M. (2002). Zh. Strukt. Khim. 43, 944-948.]), XUHJIY (Pawlowski et al., 2009[Pawlowski, M., Lendzion, A., Szawkalo, J., Leniewski, A., Maurin, J. K. & Czarnocki, Z. (2009). Phosphorus Sulfur Silicon Relat. Elem. 184, 1307-1313.]), XEXWAZ, XEXWED and XEXWIH (Balalaie et al., 2006[Balalaie, S., Bararjanian, M. & Rominger, F. (2006). J. Heterocycl. Chem. 43, 821-826.])], whereby chains stabilized by N—H⋯S hydrogen bonds are observed only in XUHJIY. Nine structures contain two different R22(8) patterns with either two N—H⋯O or two N—H⋯S hydrogen bonds [refcodes CASPUI (Hu et al., 2005[Hu, S.-L., Yin, G.-D. & Wu, A.-X. (2005). Acta Cryst. E61, o2408-o2409.]), CUKBOA (Hori et al., 2009[Hori, A., Ishida, Y., Kikuchi, T., Miyamoto, K. & Sakaguchi, H. (2009). Acta Cryst. C65, o593-o597.]), GEMCAC (Read et al., 1988[Read, G., Randal, R., Hursthouse, M. B. & Short, R. (1988). J. Chem. Soc. Perkin Trans. 2, pp. 1103-1105.]), PABPAL (Chierotti et al., 2010[Chierotti, M. R., Ferrero, L., Garino, N., Gobetto, R., Pellegrino, L., Braga, D., Grepioni, F. & Maini, L. (2010). Chem. Eur. J. 16, 4347-4358.]), RAPNAY (Long et al., 2005[Long, T., Zhou, H.-B. & Wu, A.-X. (2005). Acta Cryst. E61, o2169-o2171.]), TURCIL01 (Tiekink, 1989[Tiekink, E. R. T. (1989). Z. Kristallogr. 187, 79-84.]), TURCIL02 (Munshi & Guru Row, 2006[Munshi, P. & Guru Row, T. N. (2006). Acta Cryst. B62, 612-626.]), WIVJAM (Coxall et al., 2000[Coxall, R. A., Harris, S. G., Henderson, D. K., Parsons, S., Tasker, P. A. & Winpenny, R. E. P. (2000). J. Chem. Soc. Dalton Trans. pp. 2349-2356.]) and ZEWDOU (Ferrari et al., 1995[Ferrari, M. B., Fava, G. G., Pelosi, G., Rodriguez-Argüelles, M. C. & Tarasconi, P. (1995). J. Chem. Soc. Dalton Trans. pp. 3035-3040.])]. Furthermore, six entries showed R22(8) inter­actions consisting of two N—H⋯S hydrogen bonds [refcodes FALWOF (Orzeszko et al., 2004[Orzeszko, B., Kazimierczuk, Z., Maurin, J. K., Laudy, A. E., Starościak, B. J., Vilpo, J., Vilpo, L., Balzarini, J. & Orzeszko, A. (2004). Il Farmaco, 59, 929-937.]), JESWEK (Xue et al., 2006[Xue, S.-J., Wang, Q.-D. & Li, J.-Z. (2006). Acta Cryst. C62, o666-o668.]), MTURAC (Hawkinson, 1975[Hawkinson, S. W. (1975). Acta Cryst. B31, 2153-2156.]), PABNIR (Chierotti et al., 2010[Chierotti, M. R., Ferrero, L., Garino, N., Gobetto, R., Pellegrino, L., Braga, D., Grepioni, F. & Maini, L. (2010). Chem. Eur. J. 16, 4347-4358.]), VOKBUT (Luo et al., 2008[Luo, W., Yu, Q.-S., Tweedie, D., Deschamps, J., Parrish, D., Holloway, H. W., Li, Y., Brossi, A. & Greig, N. H. (2008). Synthesis, 21, 3415-3422.]) and ZUWMUZ (Branch et al., 1996[Branch, C. L., Eggleston, D. S., Haltiwanger, R. C., Kaura, A. C. & Tyler, J. W. (1996). Synth. Commun. 26, 2075-2084.])]. In three of these structures, the O atoms do not participate in hydrogen bonds. Finally, R22(8) motifs with one N—H⋯O and one N—H⋯S hydrogen bond are only observed in EAZTHY (Voutsas et al., 1978[Voutsas, G. P., Venetopoulos, C. C., Kálmán, A., Párkányi, L., Hornyák, G. & Lempert, K. (1978). Tetrahedron Lett. 19, 4431-4434.]).

The CSD study might suggest that an N—H⋯O is more stable than an N—H⋯S interaction, but some structures revealed hydrogen-bond inter­actions only with C=S as a supposedly weaker acceptor group. Although the R22(8) motif with two N—H⋯O hydrogen bonds is more abundant in the CSD, it is not formed in two of our three structures. A closer examination of the hydrogen-bonding inter­actions between 6-propyl-2-thio­uracil and pyrimidin-2-amine in (I)[link] revealed unusually large N⋯S distances [N21⋯S2A = 3.6234 (18) Å and N21⋯S2B = 3.5145 (17) Å]. Presumably the complex is further stabilized by a weak C—H⋯O inter­action, which leads to a slightly twisted arrangement of the mol­ecules. The hydrogen-bond pattern with the O atom as an acceptor appears to be essential for the packing in (I)[link]. If the N—H⋯O hydrogen bond was instead present in the R22(8) motif (an inter­action similar to the 2-thio­uracil–adenine Watson–Crick base pair), the heterodimer between 6-propyl-2-thio­uracil and pyrimidin-2-amine would be further stabilized by a C—H⋯S instead of a C—H⋯O interaction and the 6-propyl-2-thio­uracil chains linked by N—H⋯S instead of N—H⋯O hydrogen bonds. The C—H⋯S interaction and chains connected by N—H⋯S hydrogen bonds seem to be less stable, since they are rarely observed in crystal structures (Domagała et al., 2003[Domagała, M., Grabowski, S. J., Urbaniak, K. & Mlostón, G. (2003). J. Phys. Chem. A, 107, 2730-2736.]; Pawlowski et al., 2009[Pawlowski, M., Lendzion, A., Szawkalo, J., Leniewski, A., Maurin, J. K. & Czarnocki, Z. (2009). Phosphorus Sulfur Silicon Relat. Elem. 184, 1307-1313.]).

The hydrogen-bond inter­actions in (II)[link] can be rationalized by similar arguments. If the homodimer of 6-propyl-2-thio­uracil was linked by an R22(8) motif with two N—H⋯O hydrogen bonds, the N—H⋯S hydrogen bonds would connect the 6-propyl-2-thio­uracil and N-(6-acetamido­pyridin-2-yl)acetamide mol­ecules into chains. The desired heterodimer with three hydrogen bonds is not observed. This is probably due to the fact that the intra­molecular distances between the hydrogen donor and acceptor groups of 6-propyl-2-thio­uracil do not match with those of N-(6-acetamido­pyridin-2-yl)acetamide (pyrimidine–thio N⋯S ca 2.7 Å and pyridine–amide N⋯N ca 2.3 Å). Therefore, formation of the desired complex may result in a strained arrangement; no such cocrystal has yet been reported in the CSD. The hydrogen-bonding inter­actions in (III)[link] are similar to those of its selenium analogue and to the nine entries from the CSD study (see above). In none of the three structures, (I)–(III), is an R22(8) motif with one N—H⋯O and one N—H⋯S hydrogen bond observed.

Obviously, the relative strength of the N—H⋯O and N—H⋯S hydrogen bonds cannot be clearly judged, since there are many factors affecting hydrogen-bond formation in the crystal. All donor groups will strive to form hydrogen bonds with available acceptor groups within a favourable crystal packing. This complex situation might explain why previous theoretical and experimental studies revealed different relative stabilities for the N—H⋯O and N—H⋯S hydrogen bonds. As a result of our investigation, C=O and C=S are indeed competitive acceptor groups.

[Figure 1]
Figure 1
A perspective view of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 2]
Figure 2
A packing diagram for (I)[link]. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) −x + 2, y − [1 \over 2], −z + [1 \over 2]; (ii) −x + 1, y − [1 \over 2], −z + [3 \over 2].]
[Figure 3]
Figure 3
Perspective views of (a) the first, (b) the second and (c) the third symmetry-independent complex molecules in the asymmetric unit of (II)[link], showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 4]
Figure 4
A partial packing diagram for (II)[link]. Dashed lines indicate hydrogen bonds. The mol­ecules are designated according to the atom-numbering scheme, with 6-propyl-2-thiouracil molecules marked with primes (see Fig. 3[link]).
[Figure 5]
Figure 5
A perspective view of (III)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 6]
Figure 6
A partial packing diagram for (III)[link], showing chains of dimers running along the b axis. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, y − 1, z; (ii) x, y + 1, z.]
[Figure 7]
Figure 7
A packing diagram for (III)[link], viewed down the b axis, showing the tubular arrangement of chains. Dashed lines indicate hydrogen bonds.

Experimental

Crystals of (III)[link] were obtained by solvent evaporation from 6-propyl-2-thio­uracil (4.7 mg, 0.028 mmol) dissolved in dimethyl sulfoxide (40 µl). Cocrystallization attempts with 6-propyl-2-thio­uracil (3.3 mg, 0.019 mmol) and pyrimidin-2-amine (4.3 mg, 0.045 mmol) from n-pro­panol (350 µl) yielded (I)[link]. Single crystals of (II)[link] were obtained during attempts to cocrystallize 6-propyl-2-thio­uracil (2.5 mg, 0.015 mmol) and N-(6-acetamido­pyridin-2-yl)acetamide (2.6 mg, 0.015 mmol) from dimethyl­acetamide (90 µl). All crystallization experiments were performed at room temperature using commercially available compounds.

Compound (I)[link]

Crystal data
  • C4H5N3·2C7H10N2OS

  • Mr = 435.58

  • Monoclinic, P 21 /c

  • a = 7.6094 (5) Å

  • b = 12.9888 (6) Å

  • c = 20.8838 (14) Å

  • β = 99.179 (5)°

  • V = 2037.7 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.29 mm−1

  • T = 173 K

  • 0.60 × 0.20 × 0.15 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • Absorption correction: multi-scan (MULABS; Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.844, Tmax = 0.958

  • 25516 measured reflections

  • 3819 independent reflections

  • 3163 reflections with I > 2σ(I)

  • Rint = 0.094

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.105

  • S = 1.05

  • 3819 reflections

  • 289 parameters

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

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Selected torsion angles (°) for (I)[link]

N1A—C6A—C7A—C8A 162.10 (17)
C6A—C7A—C8A—C9A −78.4 (2)
N1B—C6B—C7B—C8B 150.28 (17)
C6B—C7B—C8B—C9B 176.90 (17)

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

D—H⋯A D—H H⋯A DA D—H⋯A
N21—H211⋯S2B 0.89 (2) 2.63 (2) 3.5145 (17) 173 (2)
N21—H212⋯S2A 0.87 (2) 2.77 (2) 3.6234 (18) 168 (2)
N1A—H1A⋯O4Ai 0.83 (2) 2.17 (2) 2.983 (2) 167 (2)
N3A—H3A⋯N3 0.87 (2) 2.06 (2) 2.926 (2) 174 (2)
N1B—H1B⋯O4Bii 0.82 (2) 2.31 (2) 3.107 (2) 166 (2)
N3B—H3B⋯N1 0.88 (2) 2.10 (2) 2.975 (2) 175 (2)
Symmetry codes: (i) [-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Compound (II)[link]

Crystal data
  • C9H11N3O2·2C7H10N2OS

  • Mr = 533.68

  • Orthorhombic, F d d 2

  • a = 37.9355 (12) Å

  • b = 76.880 (3) Å

  • c = 10.5666 (3) Å

  • V = 30817.3 (18) Å3

  • Z = 48

  • Mo Kα radiation

  • μ = 0.25 mm−1

  • T = 173 K

  • 0.50 × 0.30 × 0.20 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • Absorption correction: multi-scan (MULABS; Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.885, Tmax = 0.951

  • 108254 measured reflections

  • 14445 independent reflections

  • 10225 reflections with I > 2σ(I)

  • Rint = 0.129

Refinement
  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.097

  • S = 0.91

  • 14445 reflections

  • 985 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.25 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 6784 Friedel pairs

  • Flack parameter: 0.12 (7)

Table 7
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N21A—H21A⋯O4′Di 0.88 2.03 2.904 (5) 169
N61A—H61A⋯O4′Eii 0.88 2.05 2.921 (5) 171
N21B—H21B⋯O4′A 0.88 2.04 2.906 (5) 170
N61B—H61B⋯O4′Fiii 0.88 2.03 2.893 (5) 169
N21C—H21C⋯O4′B 0.88 2.01 2.873 (5) 168
N61C—H61C⋯O4′Civ 0.88 2.07 2.934 (5) 165
N1′A—H1′A⋯O24A 0.88 2.03 2.892 (4) 167
N3′A—H3′A⋯S2′D 0.88 2.42 3.279 (3) 166
N1′B—H1′B⋯O24B 0.88 2.00 2.859 (5) 165
N3′B—H3′B⋯S2′E 0.88 2.43 3.286 (4) 165
N1′C—H1′C⋯O24C 0.88 2.09 2.951 (4) 166
N3′C—H3′C⋯S2′F 0.88 2.45 3.313 (3) 166
N1′D—H1′D⋯O64Av 0.88 2.00 2.870 (5) 168
N3′D—H3′D⋯S2′A 0.88 2.45 3.317 (3) 168
N1′E—H1′E⋯O64Bvi 0.88 2.06 2.919 (4) 166
N3′E—H3′E⋯S2′B 0.88 2.49 3.358 (3) 168
N1′F—H1′F⋯O64Cvii 0.88 2.08 2.944 (4) 166
N3′F—H3′F⋯S2′C 0.88 2.49 3.359 (3) 168
Symmetry codes: (i) -x, -y+1, z; (ii) [-x+{\script{1\over 4}}, y-{\script{1\over 4}}, z-{\script{1\over 4}}]; (iii) [-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]; (iv) [x-{\script{1\over 4}}, -y+{\script{5\over 4}}, z-{\script{1\over 4}}]; (v) [-x+{\script{1\over 4}}, y+{\script{1\over 4}}, z+{\script{1\over 4}}]; (vi) [-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]; (vii) [-x+{\script{5\over 4}}, y+{\script{1\over 4}}, z+{\script{1\over 4}}].

Compound (III)[link]

Crystal data
  • C7H10N2OS

  • Mr = 170.23

  • Orthorhombic, P b c a

  • a = 10.4340 (6) Å

  • b = 11.1320 (6) Å

  • c = 28.7090 (17) Å

  • V = 3334.6 (3) Å3

  • Z = 16

  • Mo Kα radiation

  • μ = 0.33 mm−1

  • T = 173 K

  • 0.40 × 0.20 × 0.20 mm

Data collection
  • Stoe IPDS II two-circle diffractometer

  • Absorption correction: multi-scan (MULABS; Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.879, Tmax = 0.937

  • 29872 measured reflections

  • 3131 independent reflections

  • 1990 reflections with I > 2σ(I)

  • Rint = 0.132

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.093

  • S = 0.91

  • 3131 reflections

  • 201 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.25 e Å−3

Table 8
Selected torsion angles (°) for (III)[link]

N1A—C6A—C7A—C8A 152.9 (3)
C6A—C7A—C8A—C9A −174.9 (3)
N1B—C6B—C7B—C8B 148.6 (3)
C6B—C7B—C8B—C9B −178.8 (3)

Table 9
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N1A—H1A⋯S2Bi 0.88 2.48 3.341 (2) 165
N3A—H3A⋯O4B 0.88 1.94 2.797 (3) 163
N1B—H1B⋯S2Aii 0.88 2.50 3.361 (2) 167
N3B—H3B⋯O4A 0.88 1.98 2.826 (3) 161
Symmetry codes: (i) x, y-1, z; (ii) x, y+1, z.

Table 3
R.m.s. deviations (Å) of the non-H atoms from the mean ring planes and selected geometric parameters (°) of 6-propyl-2-thio­uracil for (II)[link]

Mol­ecule R.m.s. deviation N1′—C6′—C7′—C8′ C6′—C7′—C8′—C9′
A 0.024 178.7 (3) −178.2 (3)
B 0.028 −178.2 (3) 178.8 (3)
C 0.028 176.9 (3) 178.1 (3)
D 0.018 176.7 (3) 178.0 (3)
E 0.017 −178.4 (3) −177.4 (3)
F 0.012 −178.0 (3) 179.8 (3)

Table 4
Selected geometric parameters (°) of N-(6-acet­amido­pyridin-2-yl)acet­amide for (II)[link]

Mol­ecule 1 2 3 4
A −167.1 (4) 179.9 (3) −166.1 (4) 178.5 (4)
B 167.9 (3) 179.7 (3) 166.5 (3) 179.1 (4)
C −169.8 (4) −177.8 (4) −167.2 (3) −177.9 (3)
Torsion 1 = N1—C2—N21—C22, torsion 2 = C2—N21—C22—C23, torsion 3 = N1—C6—N61—C62 and torsion 4 = C6—N61—C62—C63.

Table 5
Dihedral angles (°) between the pyridine ring and the amide groups of N-(6-acetamido­pyridin-2-yl)acetamide [designated by α (N21) and β (N61)] for (II)[link]

Mol­ecule α β
A 13.4 (1) 15.5 (1)
B 12.6 (1) 14.6 (1)
C 12.6 (1) 15.6 (1)

Table 6
Dihedral angles (°) within the three symmetry-independent complexes for (II)[link]

γ designates the angle between two 6-propyl-2-thio­uracil mol­ecules and δ designates the angle between the pyridine ring and the central 6-propyl-2-thio­uracil mol­ecule; the molecules are designated according to Fig. 4[link].

Complex γ δ
AA′D′ 7.3 (1) 9.7 (1)
BB′E′ 11.9 (1) 2.0 (1)
CC′F′ 4.4 (1) 7.3 (1)

All H atoms 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 (II)[link] and (III)[link], H atoms bonded to N atoms were refined using a riding model, with amide N—H = 0.88 Å and Uiso(H) = 1.2Ueq(N), while in (I)[link] they were refined isotropically. The methyl groups were allowed to rotate about their local threefold axes.

Owing to the systematic absences analysed by the program XPREP (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), (II)[link] was solved and refined in the noncentrosymmetric space group Fdd2. Structure validation with PLATON/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.]) detected a pseudo-inversion centre at (0.126, 0.208, 0.466), which is not compatible with this space group. Since no correlation matrix elements larger than 0.5 are observed and the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter is consistent with a noncentrosymmetric structure, the space group was retained.

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 (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

Hydrogen-bond interactions with an S atom as an acceptor are important in biological processes. For example, sulfur-containing nucleosides are components of the anticodon of transfer RNAs. They exhibit the same arrangement of hydrogen-donor and -acceptor groups as unmodified nucleosides, but the replacement of an O with an S atom induces changes in their properties and interactions. The thio residue can be selectively photoactivated, so that it is used as an intrinsic photolabel to probe the nucleic acid structure and to identify interactions within nucleic acids or between nucleic acids and proteins (Favre et al., 1998). Furthermore, the enhanced base-pairing specificity of thionucleosides can be utilized, for example, in the design of antisense oligonucleotides (Testa et al., 1999).

Because of its reduced electronegativity, an S atom should be a weaker hydrogen-bond acceptor than an O atom. Many theoretical and experimental investigations have been concerned with the stability of the N—H···O and the N—H···S hydrogen bond, but there is no clear tendency. Ab initio energy calculations (Šponer et al., 1997; Basilio Janke et al., 2001) and a study of the thermodynamics of RNA duplexes containing thiouridine (Testa et al., 1999) showed that a base pair connected by an N—H···O bond is more stable than that with an N—H···S hydrogen bond. In the case of 2-thiouridine, the Watson–Crick base pair with adenine is preferred over the wobble base pair with guanine, while 4-thiouridine increases the stability of the wobble base pair compared with the Watson–Crick base pairing. In contrast, the infrared spectroscopic red shift of the N—H stretching frequency indicated that the N—H···S is comparable or even stronger than the N—H···O interaction (Lautié & Novak, 1980; Biswal & Wategaonkar, 2009).

In order to study the stability of the N—H···S hydrogen bond in the presence of a competitive carbonyl O atom as an acceptor, we cocrystallized 2-aminopyrimidine and N-(6-acetamidopyridin-2-yl)acetamide, respectively, with the antithyroid drug 6-propyl-2-thiouracil, also known as propylthiouracil. It inhibits the synthesis of thyroid hormones and has been used for the treatment of hyperthyroidism caused by Graves' disease (Cooper, 2005). Because of its risk of serious liver injury, 6-propyl-2-thiouracil is used as a second-line drug for patients who are intolerant of other therapies (Bahn et al., 2009).

We chose 2-aminopyrimidine because of its adjacent amine and imine groups resembling the donor–acceptor site of adenine. Since it has a mirror plane bisecting the molecule along the C—NH2 bond, one 2-aminopyrimidine molecule may be hydrogen bonded to two 6-propyl-2-thiouracil molecules. Indeed the asymmetric unit of cocrystal (I), namely 2-aminopyrimidine–6-propyl-2-thiouracil (1/2), contains two 6-propyl-2-thiouracil molecules and one 2-aminopyrimidine molecule (Fig. 1). The 2-aminopyrimidine molecule forms dihedral angles of 17.1 (1) and 10.6 (1)° with the thiouracil rings of molecules A and B, respectively. Different propyl side-chain conformations are observed: in molecule A, the methyl C atom C9A and the thiouracil ring atom C6A are synclinal with the C8A—C9A bond almost perpendicular to the ring, while in molecule B they are antiperiplanar with a dihedral angle of 32.7 (2)° between the thiouracil ring and the plane through the side chain (Table 1). Each 6-propyl-2-thiouracil molecule is hydrogen-bonded to the 2-aminopyrimidine molecule by an R22(8) motif (Bernstein et al., 1995) characterized by one N—H···S and one N—H···N bond. The O atoms participate in N—H···O interactions (Table 2) connecting the 6-propyl-2-thiouracil molecules to chains running along the b axis. The packing of (I) shows layers parallel to (101) containing circular arrangements of four adjacent trimeric units with an R88(34) hydrogen-bond pattern (Fig. 2).

Its participation in the `base pairing' of (I) suggests that the S atom is an acceptor competitive with the O atom. Hence, we were also interested in whether both S and O atoms can be hydrogen bonded simultaneously to a complementary molecule. Since 6-propyl-2-thiouracil possesses an acceptor–donor–acceptor site, we cocrystallized it with N-(6-acetamidopyridin-2-yl)acetamide, which exhibits a donor–acceptor–donor site.

Cocrystal (II), namely N-(6-acetamidopyridin-2-yl)acetamide–6-propyl-2-thiouracil (1/2), contains three symmetry-independent complexes, each consisting of two 6-propyl-2-thiouracil molecules and one N-(6-acetamidopyridin-2-yl)acetamide molecule (Fig. 3). The molecular structures of the six propylthiouracil and the three N-(6-acetamidopyridin-2-yl)acetamide molecules, respectively, are very similar. The r.m.s deviation for all non-H atoms of the 6-propyl-2-thiouracil molecules varies from 0.012 to 0.028 Å, confirming its planarity. All side chains show an extended conformation with C8 antiperiplanar to N1 and C9 antiperiplanar to C6 (Table 6). Both N—H bonds of the N-(6-acetamidopyridin-2-yl)acetamide molecules are directed to the same side as the pyridine N atom, while the methyl groups are antiperiplanar to the ring atoms C2 and C6 (Table 7). Thus a dihedral angle of 12.5 (1) to 15.6 (1)° is formed between the planes through one of the amide groups and the pyridine ring (Table 8). The hydrogen-bond patterns within the three complexes are also identical. The 6-propyl-2-thiouracil molecules are linked to dimers by an R22(8) motif with two N—H···S bonds. In addition, an N—H···O bond connects one 6-propyl-2-thiouracil to N-(6-acetamidopyridin-2-yl)acetamide. However, the geometric arrangements of the complexes show some flexibility. The planes through the two 6-propyl-2-thiouracil molecules of a dimer enclose a dihedral angle ranging from 4.4 (1) to 11.9 (1)°, while dihedral angles of 2.0 (1) to 9.7 (1)° are observed between the planes through the pyridine ring and the neighbouring 6-propyl-2-thiouracil molecule (Table 9). In the packing, all three complexes are twisted by 17° with respect to each other and are connected by N—H···O bonds to chains running along [310] (Fig. 4). Furthermore, a second chain is formed consisting of N—H···O-bonded symmetry-related complexes aligned along the b axis. Altogether, an extended three-dimensional network of hydrogen bonds is observed (Table 3).

In spite of the appropriate arrangement of donor and acceptor groups, 6-propyl-2-thiouracil does not form three hydrogen bonds to N-(6-acetamidopyridin-2-yl)acetamide in (II), but undergoes homodimerization without participation of the carbonyl O atom. In order to further investigate its preferred hydrogen-bonding interactions, we analysed related crystal structures. Two structures containing 6-propyl-2-thiouracil are present in the Cambridge Structural Database (CSD, Version 5.32 of November 2010, plus two updates; Allen, 2002), namely a 1,4-dioxane solvate [refcode BUWYOH (Okabe et al., 1983)] and a charge-transfer complex with diiodine [refcode HAFLAC (Antoniadis et al., 2003)]. The latter structure is not further considered, since the S atom is connected to the diiodine molecule and hence can hardly participate as a hydrogen-bond acceptor. In the 1,4-dioxane solvate, only the carbonyl O atom takes part in the hydrogen bonding and connects the 6-propyl-2-thiouracil molecules to chains, while no N—H···S interactions are observed. In the solvent-free structure of the selenium analogue of 6-propyl-2-thiouracil [refcode PELHEU (Antoniadis et al., 2006)], the molecules are hydrogen bonded to chains by R22(8) interactions involving either N—H···Se or N—H···O bonds. We therefore undertook crystallization experiments with 6-propyl-2-thiouracil alone to study whether similar interactions can be observed.

The crystal structure of 6-propyl-2-thiouracil, (III), is isostructural with PELHEU (Fig. 5). The thiouracil rings of the two independent molecules are planar [r.m.s deviations = 0.006 (A) and 0.016 Å (B) for all non-H atoms] and the propyl side chains are again extended but slightly twisted with the planes through the ring and the side chain enclosing dihedral angles of 26.0 (2)° in A and 29.8 (2)° in B (Table 4). The 6-propyl-2-thiouracil molecules are connected to chains running along the b axis by two kinds of hydrogen-bond interactions (Table 5). Although both show the same R22(8) graph set, the hydrogen-bond pattern consists of either two N—H···O or two N—H···S interactions (Fig. 6). In the crystal packing, two adjacent chains are stabilized by van der Waals interactions forming tubes (Fig. 7).

In (I)–(III), 6-propyl-2-thiouracil exhibits different side-chain conformations. The dihedral angle between the planar thiouracil ring and the plane through the side chain varies from 2.0 (2) to 89.4 (1)°, although an extended arrangement is preferred. Since sufficient donor groups are available both O and S atoms participate in the hydrogen bonding. The N—H···O bonds have different functions: they connect hydrogen-bonded 6-propyl-2-thiouracil molecules either with itself [in (I)] or with the other cocrystal component [in (II)] thus forming chains, or they stabilize homodimers of 6-propyl-2-thiouracil with an R22(8) pattern [in (III)]. In contrast, the S atoms are only involved in R22(8) hydrogen-bond formation linking the 6-propyl-2-thiouracil molecules to a heterodimer [in (I)] or to a homodimer [in (II) and (III)].

From the hydrogen-bond interactions in the three structures [(I)–(III)], it is not evident whether an N—H···O or an N—H···S bond is stronger. A CSD search of six-membered ring compounds with hydrogen-bonding sites similar to 2-thiouracil yielded four different types of R22(8) patterns. Nineteen entries showed R22(8) motifs characterized by two N—H···O bonds; the S atoms take part as acceptors only in five of them [refcodes LACJIJ (Tashkhodzhaev et al., 2002), XUHJIY (Pawlowski et al., 2009), XEXWAZ, XEXWED and XEXWIH (Balalaie et al., 2006)], whereby chains stabilized by N—H···S bonds are observed only in XUHJIY. Nine structures contain two different R22(8) patterns with either two N—H···O or two N—H···S bonds [refcodes CASPUI (Hu et al., 2005), CUKBOA (Hori et al., 2009), GEMCAC (Read et al., 1988), PABPAL (Chierotti et al., 2010), RAPNAY (Long et al., 2005), TURCIL01 (Tiekink, 1989), TURCIL02 (Munshi & Guru Row, 2006), WIVJAM (Coxall et al., 2000) and ZEWDOU (Ferrari et al., 1995)]. Furthermore, six entries showed R22(8) interactions consisting of two N—H···S bonds [refcodes FALWOF (Orzeszko et al., 2004), JESWEK (Xue et al., 2006), MTURAC (Hawkinson, 1975), PABNIR (Chierotti et al., 2010), VOKBUT (Luo et al., 2008) and ZUWMUZ (Branch et al., 1996)]. In three of these structures, the O atoms do not participate in hydrogen bonds. Finally, R22(8) motifs with one N—H···O and one N—H···S bond are only observed in EAZTHY (Voutsas et al., 1978).

The CSD study might suggest that an N—H···O is more stable than an N—H···S bond, but some structures revealed hydrogen-bond interactions only with C S as a supposedly weaker acceptor group. Although the R22(8) motif with two N—H···O bonds is more abundant in the CSD, it is not formed in two of our three structures. A closer examination of the hydrogen-bonding interactions between 6-propyl-2-thiouracil and 2-aminopyrimidine in (I) revealed unusually large N···S distances [N21···S2A = 3.6234 (18) Å and N21···S2B = 3.5145 (17) Å]. Assumedly the complex is further stabilized by a weak C—H···O interaction, which leads to a slightly twisted arrangement of the molecules. The hydrogen-bond pattern with the O atom as an acceptor appears to be essential for the packing in (I). If the N—H···O bond was instead present in the R22(8) motif (an interaction similar to the 2-thiouracil–adenine Watson–Crick base pair), the heterodimer between 6-propyl-2-thiouracil and 2-aminopyrimidine would be further stabilized by a C—H···S instead of a C—H···O bond and the 6-propyl-2-thiouracil chains linked by N—H···S instead of N—H···O bonds. The C—H···S bond and chains connected by N—H···S bonds seem to be less stable, since they are rarely observed in crystal structures (Domagała et al., 2003; Pawlowski et al., 2009).

The hydrogen-bond interactions in (II) can be rationalized by similar arguments. If the homodimer of 6-propyl-2-thiouracil was linked by an R22(8) motif with two N—H···O bonds, the N—H···S bonds would connect the 6-propyl-2-thiouracil and N-(6-acetamidopyridin-2-yl)acetamide molecules to chains. The desired heterodimer with three hydrogen bonds is not observed. This is probably caused by the fact that the intramolecular distances between the hydrogen donor and acceptor groups of 6-propyl-2-thiouracil do not match with those of N-(6-acetamidopyridin-2-yl)acetamide (pyrimidine–thio N···S ca 2.6 Å and pyridine–amide N···N ca 2.3 Å). Therefore, formation of the desired complex may result in a strained arrangement; no such cocrystal has yet been reported in the CSD. The hydrogen-bonding interactions in (III) are similar to those of its selenium analogue and to the nine entries of the CSD study (see above). In none of the three structures, (I)–(III), an R22(8) motif with one N—H···O and one N—H···S bond is observed.

Obviously, the relative strength of the N—H···O and N—H···S bonds cannot be clearly judged, since there are many factors affecting hydrogen-bond formation in the crystal. All donor groups will strive to form hydrogen bonds with available acceptor groups within a favourable crystal packing. This complex situation might explain why previous theoretical and experimental studies revealed different relative stabilities for the N—H···O and N—H···S hydrogen bonds. As a result of our investigation, CO and C S are indeed competitive acceptor groups.

Related literature top

For related literature, see: Allen (2002); Antoniadis et al. (2003, 2006); Bahn et al. (2009); Balalaie et al. (2006); Basilio Janke, Dunger, Limbach & Weisz (2001); Biswal & Wategaonkar (2009); Branch et al. (1996); Chierotti et al. (2010); Cooper (2005); Coxall et al. (2000); Domagała et al. (2003); Favre et al. (1998); Ferrari et al. (1995); Hawkinson (1975); Hori et al. (2009); Hu et al. (2005); Lautié & Novak (1980); Le Page (1987, 1988); Long et al. (2005); Luo et al. (2008); Munshi & Guru Row (2006); Okabe et al. (1983); Orzeszko et al. (2004); Pawlowski et al. (2009); Read et al. (1988); Sheldrick (2008); Spek (2009); Tashkhodzhaev et al. (2002); Testa et al. (1999); Tiekink (1989); Voutsas et al. (1978); Xue et al. (2006); Šponer et al. (1997).

Experimental top

Crystals of (III) were obtained by solvent evaporation from 6-propyl-2-thiouracil (4.7 mg, 0.028 mmol) dissolved in dimethyl sulfoxide (40 µl). Cocrystallization attempts with 6-propyl-2-thiouracil (3.3 mg, 0.019 mmol) and 2-aminopyrimidine (4.3 mg, 0.045 mmol) from n-propanol (350 µl) yielded (I). Single crystals of (II) were obtained during attempts to cocrystallize 6-propyl-2-thiouracil (2.5 mg, 0.015 mmol) and N-(6-acetamidopyridin-2-yl)acetamide (2.6 mg; 0.015 mmol) from dimethylacetamide (90 µl). All experiments were performed at room temperature using commercially available compounds.

Refinement top

All H atoms 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 (II) and (III), H atoms bonded to N atoms were refined using a riding model, with amide N—H = 0.88 Å and Uiso(H) = 1.2Ueq(N), while in (I) they were refined isotropically. The methyl groups were allowed to rotate about their local threefold axes.

Owing to the systematic absences analysed by the program XPREP (Sheldrick, 2008), (II) was solved and refined in the noncentrosymmetric space group Fdd2. No correlation matrix elements larger than 0.5 are observed. During structure validation with PLATON/ADDSYM (Le Page, 1987, 1988; Spek, 2009), an inversion centre at (0.126, 0.208, 0.466) was detected. However, refinement in the suggested space group C2/c was not satisfactory; the anisotropic displacement parameters of 12 atoms were nonpositive definite and the parameters of the recommended weighting scheme were unusually large (WGHT 0.0629 880.6169). Thus, the space group Fdd2 was retained.

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 (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 and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. A packing diagram for (I). Dashed lines indicate hydrogen bonds.
[Figure 3] Fig. 3. Perspective views of (a) the first, (b) the second and (c) the third symmetry-independent complex in the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 4] Fig. 4. A partial packing diagram for (II). Dashed lines indicate hydrogen bonds. The molecules are designated according to the atom numbering.
[Figure 5] Fig. 5. A perspective view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
[Figure 6] Fig. 6. A partial packing diagram for (III) showing chains of dimers running along the b axis. Dashed lines indicate hydrogen bonds.
[Figure 7] Fig. 7. A packing diagram for (III) showing the formation of tubes. Dashed lines indicate hydrogen bonds. [Please indicate the origin]
(I) 2-aminopyrimidine bis(6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one) top
Crystal data top
C4H5N3·2C7H10N2OSF(000) = 920
Mr = 435.57Dx = 1.420 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.6094 (5) ÅCell parameters from 18641 reflections
b = 12.9888 (6) Åθ = 3.5–25.8°
c = 20.8838 (14) ŵ = 0.29 mm1
β = 99.179 (5)°T = 173 K
V = 2037.7 (2) Å3Block, colourless
Z = 40.60 × 0.20 × 0.15 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
3819 independent reflections
Radiation source: fine-focus sealed tube3163 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.094
ω scansθmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 99
Tmin = 0.844, Tmax = 0.958k = 1514
25516 measured reflectionsl = 2525
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)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.2289P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
3819 reflectionsΔρmax = 0.30 e Å3
289 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: 0.0028 (6)
Crystal data top
C4H5N3·2C7H10N2OSV = 2037.7 (2) Å3
Mr = 435.57Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.6094 (5) ŵ = 0.29 mm1
b = 12.9888 (6) ÅT = 173 K
c = 20.8838 (14) Å0.60 × 0.20 × 0.15 mm
β = 99.179 (5)°
Data collection top
Stoe IPDS II two-circle
diffractometer
3819 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
3163 reflections with I > 2σ(I)
Tmin = 0.844, Tmax = 0.958Rint = 0.094
25516 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.30 e Å3
3819 reflectionsΔρmin = 0.29 e Å3
289 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
N10.70342 (19)0.49488 (12)0.54717 (7)0.0197 (3)
C20.7299 (2)0.44500 (14)0.49259 (8)0.0188 (4)
N30.7939 (2)0.48800 (12)0.44186 (7)0.0207 (3)
C40.8376 (3)0.58776 (14)0.44800 (9)0.0238 (4)
H40.88280.62050.41340.029*
C50.8201 (3)0.64541 (14)0.50220 (9)0.0249 (4)
H50.85500.71560.50610.030*
C60.7484 (2)0.59469 (14)0.55068 (9)0.0216 (4)
H60.73050.63260.58800.026*
N210.6877 (2)0.34417 (13)0.48783 (9)0.0280 (4)
H2110.664 (3)0.3122 (19)0.5234 (11)0.038 (6)*
H2120.721 (3)0.3089 (19)0.4568 (12)0.036 (6)*
N1A0.9954 (2)0.29340 (12)0.25432 (7)0.0181 (3)
H1A1.009 (3)0.2326 (18)0.2442 (11)0.029 (6)*
C2A0.9322 (2)0.31518 (13)0.31017 (8)0.0179 (4)
N3A0.9080 (2)0.41733 (11)0.32194 (7)0.0184 (3)
H3A0.873 (3)0.4340 (17)0.3584 (11)0.028 (6)*
C4A0.9442 (2)0.49830 (13)0.28190 (8)0.0187 (4)
C5A1.0058 (2)0.46774 (14)0.22268 (9)0.0215 (4)
H5A1.02780.51850.19220.026*
C6A1.0321 (2)0.36715 (14)0.21066 (8)0.0195 (4)
S2A0.88847 (6)0.22183 (4)0.36131 (2)0.02233 (15)
O4A0.92311 (18)0.58839 (9)0.29822 (6)0.0246 (3)
C7A1.1080 (3)0.32542 (15)0.15363 (10)0.0293 (5)
H7A11.04470.26070.13950.035*
H7A21.23440.30760.16850.035*
C8A1.0986 (3)0.39622 (15)0.09466 (9)0.0256 (4)
H8A11.18630.37280.06750.031*
H8A21.13140.46700.10960.031*
C9A0.9153 (3)0.3977 (2)0.05403 (12)0.0458 (6)
H9A10.88250.32780.03890.069*
H9A20.91600.44310.01660.069*
H9A30.82860.42320.08030.069*
N1B0.4997 (2)0.31722 (12)0.74197 (7)0.0176 (3)
H1B0.485 (3)0.2579 (18)0.7530 (11)0.029 (6)*
C2B0.5533 (2)0.33663 (13)0.68388 (8)0.0182 (4)
N3B0.57733 (19)0.43775 (11)0.67011 (7)0.0184 (3)
H3B0.611 (3)0.4512 (17)0.6328 (11)0.028 (6)*
C4B0.5526 (2)0.52082 (13)0.71078 (9)0.0195 (4)
C5B0.4991 (2)0.49254 (14)0.77175 (9)0.0211 (4)
H5B0.48220.54460.80210.025*
C6B0.4729 (2)0.39260 (13)0.78597 (8)0.0183 (4)
S2B0.58686 (7)0.24071 (4)0.63318 (2)0.02457 (15)
O4B0.57692 (18)0.61003 (10)0.69342 (6)0.0265 (3)
C7B0.4101 (3)0.35478 (14)0.84640 (9)0.0212 (4)
H7B10.45510.28390.85550.025*
H7B20.27840.35150.83830.025*
C8B0.4680 (3)0.42045 (16)0.90602 (9)0.0304 (5)
H8B10.42810.49230.89690.036*
H8B20.59950.42050.91650.036*
C9B0.3900 (3)0.37976 (16)0.96403 (9)0.0349 (5)
H9B10.25970.38250.95440.052*
H9B20.43180.42231.00220.052*
H9B30.42830.30840.97280.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0235 (8)0.0186 (8)0.0184 (7)0.0016 (6)0.0079 (6)0.0003 (6)
C20.0204 (9)0.0180 (9)0.0186 (9)0.0015 (7)0.0051 (7)0.0016 (7)
N30.0280 (8)0.0180 (8)0.0181 (8)0.0016 (6)0.0095 (6)0.0010 (6)
C40.0314 (10)0.0196 (10)0.0231 (9)0.0012 (8)0.0131 (8)0.0035 (7)
C50.0324 (10)0.0153 (9)0.0293 (10)0.0009 (8)0.0118 (8)0.0008 (7)
C60.0253 (9)0.0200 (9)0.0207 (9)0.0023 (7)0.0075 (7)0.0026 (7)
N210.0447 (10)0.0177 (8)0.0260 (9)0.0049 (7)0.0194 (8)0.0022 (7)
N1A0.0262 (8)0.0116 (8)0.0178 (8)0.0017 (6)0.0072 (6)0.0010 (6)
C2A0.0206 (8)0.0159 (9)0.0176 (8)0.0019 (7)0.0045 (7)0.0018 (7)
N3A0.0275 (8)0.0141 (8)0.0156 (7)0.0013 (6)0.0093 (6)0.0016 (6)
C4A0.0228 (9)0.0161 (9)0.0180 (9)0.0004 (7)0.0051 (7)0.0006 (7)
C5A0.0289 (9)0.0161 (9)0.0215 (9)0.0017 (7)0.0098 (7)0.0033 (7)
C6A0.0233 (9)0.0178 (9)0.0185 (9)0.0013 (7)0.0069 (7)0.0009 (7)
S2A0.0343 (3)0.0145 (3)0.0206 (3)0.00223 (17)0.01194 (19)0.00127 (16)
O4A0.0404 (8)0.0132 (6)0.0227 (7)0.0006 (5)0.0125 (6)0.0023 (5)
C7A0.0451 (12)0.0204 (10)0.0268 (10)0.0089 (9)0.0192 (9)0.0031 (8)
C8A0.0359 (11)0.0211 (10)0.0237 (10)0.0023 (8)0.0171 (8)0.0004 (8)
C9A0.0465 (14)0.0547 (16)0.0368 (13)0.0054 (11)0.0086 (10)0.0132 (11)
N1B0.0265 (8)0.0125 (8)0.0151 (7)0.0004 (6)0.0069 (6)0.0001 (6)
C2B0.0204 (8)0.0164 (9)0.0182 (9)0.0012 (7)0.0045 (7)0.0008 (7)
N3B0.0276 (8)0.0153 (8)0.0139 (8)0.0003 (6)0.0080 (6)0.0008 (6)
C4B0.0230 (9)0.0155 (9)0.0201 (9)0.0015 (7)0.0043 (7)0.0004 (7)
C5B0.0308 (10)0.0146 (9)0.0193 (9)0.0010 (7)0.0085 (7)0.0025 (7)
C6B0.0215 (9)0.0160 (9)0.0177 (9)0.0006 (7)0.0041 (7)0.0010 (7)
S2B0.0412 (3)0.0152 (3)0.0209 (3)0.00032 (19)0.0160 (2)0.00253 (17)
O4B0.0431 (8)0.0145 (7)0.0239 (7)0.0021 (6)0.0119 (6)0.0023 (5)
C7B0.0308 (10)0.0162 (9)0.0186 (9)0.0035 (7)0.0101 (7)0.0013 (7)
C8B0.0490 (12)0.0244 (11)0.0214 (10)0.0128 (9)0.0163 (9)0.0048 (8)
C9B0.0616 (14)0.0259 (11)0.0217 (10)0.0126 (10)0.0202 (10)0.0052 (8)
Geometric parameters (Å, º) top
N1—C61.340 (2)C8A—C9A1.513 (3)
N1—C21.354 (2)C8A—H8A10.9900
C2—N211.348 (2)C8A—H8A20.9900
C2—N31.355 (2)C9A—H9A10.9800
N3—C41.339 (2)C9A—H9A20.9800
C4—C51.381 (3)C9A—H9A30.9800
C4—H40.9500N1B—C2B1.364 (2)
C5—C61.390 (3)N1B—C6B1.380 (2)
C5—H50.9500N1B—H1B0.82 (2)
C6—H60.9500C2B—N3B1.363 (2)
N21—H2110.89 (2)C2B—S2B1.6807 (17)
N21—H2120.87 (2)N3B—C4B1.404 (2)
N1A—C2A1.361 (2)N3B—H3B0.88 (2)
N1A—C6A1.381 (2)C4B—O4B1.237 (2)
N1A—H1A0.83 (2)C4B—C5B1.445 (2)
C2A—N3A1.367 (2)C5B—C6B1.353 (2)
C2A—S2A1.6836 (18)C5B—H5B0.9500
N3A—C4A1.398 (2)C6B—C7B1.502 (2)
N3A—H3A0.87 (2)C7B—C8B1.516 (3)
C4A—O4A1.236 (2)C7B—H7B10.9900
C4A—C5A1.446 (2)C7B—H7B20.9900
C5A—C6A1.351 (2)C8B—C9B1.526 (2)
C5A—H5A0.9500C8B—H8B10.9900
C6A—C7A1.505 (2)C8B—H8B20.9900
C7A—C8A1.529 (3)C9B—H9B10.9800
C7A—H7A10.9900C9B—H9B20.9800
C7A—H7A20.9900C9B—H9B30.9800
C6—N1—C2115.98 (15)C9A—C8A—H8A2109.1
N21—C2—N1117.45 (15)H8A1—C8A—H8A2107.9
N21—C2—N3117.00 (16)C8A—C9A—H9A1109.5
N1—C2—N3125.54 (17)C8A—C9A—H9A2109.5
C4—N3—C2116.03 (15)H9A1—C9A—H9A2109.5
N3—C4—C5123.26 (17)C8A—C9A—H9A3109.5
N3—C4—H4118.4H9A1—C9A—H9A3109.5
C5—C4—H4118.4H9A2—C9A—H9A3109.5
C4—C5—C6116.12 (17)C2B—N1B—C6B123.92 (15)
C4—C5—H5121.9C2B—N1B—H1B120.0 (16)
C6—C5—H5121.9C6B—N1B—H1B116.0 (16)
N1—C6—C5123.03 (17)N1B—C2B—N3B115.80 (15)
N1—C6—H6118.5N1B—C2B—S2B121.36 (13)
C5—C6—H6118.5N3B—C2B—S2B122.85 (13)
C2—N21—H211117.9 (15)C2B—N3B—C4B125.26 (15)
C2—N21—H212118.3 (16)C2B—N3B—H3B116.6 (15)
H211—N21—H212120 (2)C4B—N3B—H3B118.2 (15)
C2A—N1A—C6A123.91 (15)O4B—C4B—N3B120.12 (16)
C2A—N1A—H1A119.5 (15)O4B—C4B—C5B124.95 (16)
C6A—N1A—H1A116.5 (15)N3B—C4B—C5B114.93 (15)
N3A—C2A—N1A115.60 (15)C6B—C5B—C4B120.62 (16)
N3A—C2A—S2A122.62 (13)C6B—C5B—H5B119.7
N1A—C2A—S2A121.78 (13)C4B—C5B—H5B119.7
C2A—N3A—C4A125.28 (15)C5B—C6B—N1B119.46 (16)
C2A—N3A—H3A117.8 (15)C5B—C6B—C7B125.16 (16)
C4A—N3A—H3A116.9 (15)N1B—C6B—C7B115.35 (15)
O4A—C4A—N3A120.03 (15)C6B—C7B—C8B114.62 (15)
O4A—C4A—C5A124.72 (16)C6B—C7B—H7B1108.6
N3A—C4A—C5A115.25 (15)C8B—C7B—H7B1108.6
C6A—C5A—C4A120.14 (16)C6B—C7B—H7B2108.6
C6A—C5A—H5A119.9C8B—C7B—H7B2108.6
C4A—C5A—H5A119.9H7B1—C7B—H7B2107.6
C5A—C6A—N1A119.76 (16)C7B—C8B—C9B111.01 (16)
C5A—C6A—C7A125.60 (17)C7B—C8B—H8B1109.4
N1A—C6A—C7A114.58 (15)C9B—C8B—H8B1109.4
C6A—C7A—C8A116.50 (16)C7B—C8B—H8B2109.4
C6A—C7A—H7A1108.2C9B—C8B—H8B2109.4
C8A—C7A—H7A1108.2H8B1—C8B—H8B2108.0
C6A—C7A—H7A2108.2C8B—C9B—H9B1109.5
C8A—C7A—H7A2108.2C8B—C9B—H9B2109.5
H7A1—C7A—H7A2107.3H9B1—C9B—H9B2109.5
C7A—C8A—C9A112.32 (17)C8B—C9B—H9B3109.5
C7A—C8A—H8A1109.1H9B1—C9B—H9B3109.5
C9A—C8A—H8A1109.1H9B2—C9B—H9B3109.5
C7A—C8A—H8A2109.1
C6—N1—C2—N21179.34 (16)C2A—N1A—C6A—C7A177.62 (17)
C6—N1—C2—N31.3 (3)C5A—C6A—C7A—C8A20.7 (3)
N21—C2—N3—C4179.01 (17)N1A—C6A—C7A—C8A162.10 (17)
N1—C2—N3—C41.6 (3)C6A—C7A—C8A—C9A78.4 (2)
C2—N3—C4—C50.1 (3)C6B—N1B—C2B—N3B1.1 (3)
N3—C4—C5—C61.8 (3)C6B—N1B—C2B—S2B178.90 (13)
C2—N1—C6—C50.7 (3)N1B—C2B—N3B—C4B0.5 (3)
C4—C5—C6—N12.2 (3)S2B—C2B—N3B—C4B179.49 (14)
C6A—N1A—C2A—N3A0.9 (3)C2B—N3B—C4B—O4B179.51 (17)
C6A—N1A—C2A—S2A179.54 (13)C2B—N3B—C4B—C5B0.6 (2)
N1A—C2A—N3A—C4A0.5 (3)O4B—C4B—C5B—C6B178.89 (18)
S2A—C2A—N3A—C4A179.04 (14)N3B—C4B—C5B—C6B1.2 (3)
C2A—N3A—C4A—O4A177.58 (16)C4B—C5B—C6B—N1B0.7 (3)
C2A—N3A—C4A—C5A2.3 (3)C4B—C5B—C6B—C7B177.31 (16)
O4A—C4A—C5A—C6A177.03 (18)C2B—N1B—C6B—C5B0.5 (3)
N3A—C4A—C5A—C6A2.9 (3)C2B—N1B—C6B—C7B178.74 (16)
C4A—C5A—C6A—N1A1.7 (3)C5B—C6B—C7B—C8B31.6 (3)
C4A—C5A—C6A—C7A175.31 (17)N1B—C6B—C7B—C8B150.28 (17)
C2A—N1A—C6A—C5A0.3 (3)C6B—C7B—C8B—C9B176.90 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H211···S2B0.89 (2)2.63 (2)3.5145 (17)173 (2)
N21—H212···S2A0.87 (2)2.77 (2)3.6234 (18)168 (2)
N1A—H1A···O4Ai0.83 (2)2.17 (2)2.983 (2)167 (2)
N3A—H3A···N30.87 (2)2.06 (2)2.926 (2)174 (2)
N1B—H1B···O4Bii0.82 (2)2.31 (2)3.107 (2)166 (2)
N3B—H3B···N10.88 (2)2.10 (2)2.975 (2)175 (2)
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x+1, y1/2, z+3/2.
(II) N-(6-acetamidopyridin-2-yl)acetamide bis(6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one) top
Crystal data top
C9H11N3O2·2C7H10N2OSDx = 1.380 Mg m3
Mr = 533.67Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2Cell parameters from 37383 reflections
a = 37.9355 (12) Åθ = 3.3–25.9°
b = 76.880 (3) ŵ = 0.25 mm1
c = 10.5666 (3) ÅT = 173 K
V = 30817.3 (18) Å3Block, colourless
Z = 480.50 × 0.30 × 0.20 mm
F(000) = 13536
Data collection top
Stoe IPDS II two-circle
diffractometer
14445 independent reflections
Radiation source: fine-focus sealed tube10225 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.129
ω scansθmax = 25.7°, θmin = 3.3°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 4546
Tmin = 0.885, Tmax = 0.951k = 9393
108254 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.097 w = 1/[σ2(Fo2) + (0.0392P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.91(Δ/σ)max = 0.002
14445 reflectionsΔρmax = 0.22 e Å3
985 parametersΔρmin = 0.25 e Å3
1 restraintAbsolute structure: Flack (1983), 6784 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.12 (7)
Crystal data top
C9H11N3O2·2C7H10N2OSV = 30817.3 (18) Å3
Mr = 533.67Z = 48
Orthorhombic, Fdd2Mo Kα radiation
a = 37.9355 (12) ŵ = 0.25 mm1
b = 76.880 (3) ÅT = 173 K
c = 10.5666 (3) Å0.50 × 0.30 × 0.20 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
14445 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
10225 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.951Rint = 0.129
108254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.097Δρmax = 0.22 e Å3
S = 0.91Δρmin = 0.25 e Å3
14445 reflectionsAbsolute structure: Flack (1983), 6784 Friedel pairs
985 parametersAbsolute structure parameter: 0.12 (7)
1 restraint
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.04637 (8)0.41911 (4)0.3404 (3)0.0205 (7)
C2A0.06441 (11)0.43341 (5)0.3765 (3)0.0210 (9)
C3A0.10109 (12)0.43423 (6)0.3785 (4)0.0293 (10)
H3A0.11310.44450.40480.035*
C4A0.11922 (11)0.41971 (6)0.3409 (5)0.0323 (10)
H4A0.14430.42000.34020.039*
C5A0.10196 (12)0.40476 (5)0.3041 (4)0.0270 (10)
H5A0.11450.39470.27850.032*
C6A0.06491 (12)0.40519 (5)0.3064 (3)0.0223 (9)
N21A0.04261 (10)0.44734 (4)0.4136 (3)0.0240 (7)
H21A0.02020.44480.42580.029*
C22A0.05194 (11)0.46425 (5)0.4327 (3)0.0235 (9)
C23A0.02307 (12)0.47639 (6)0.4719 (4)0.0354 (10)
H23A0.03270.48530.52840.053*
H23B0.00470.46980.51630.053*
H23C0.01300.48190.39670.053*
O24A0.08282 (8)0.46960 (4)0.4170 (3)0.0334 (7)
N61A0.04430 (10)0.39090 (4)0.2680 (3)0.0222 (7)
H61A0.02190.39310.25260.027*
C62A0.05486 (12)0.37402 (5)0.2519 (4)0.0249 (9)
C63A0.02653 (12)0.36131 (5)0.2129 (4)0.0315 (10)
H63A0.03210.35660.12900.047*
H63B0.00370.36730.21000.047*
H63C0.02540.35180.27440.047*
O64A0.08540 (9)0.36925 (4)0.2725 (3)0.0359 (7)
N1B0.29331 (10)0.50438 (4)0.6043 (3)0.0198 (7)
C2B0.31130 (11)0.51879 (5)0.5776 (3)0.0210 (9)
C3B0.34789 (12)0.51984 (6)0.5756 (4)0.0275 (10)
H3B0.35970.53040.55600.033*
C4B0.36629 (13)0.50483 (6)0.6033 (5)0.0348 (11)
H4B0.39130.50500.60210.042*
C5B0.34889 (12)0.48959 (6)0.6326 (4)0.0279 (10)
H5B0.36150.47930.65320.033*
C6B0.31265 (12)0.48984 (5)0.6310 (3)0.0227 (9)
N21B0.28956 (10)0.53334 (4)0.5495 (3)0.0225 (8)
H21B0.26710.53120.53670.027*
C22B0.29998 (12)0.55044 (5)0.5400 (3)0.0235 (9)
C23B0.27049 (13)0.56306 (6)0.5079 (4)0.0341 (10)
H23D0.26640.57090.57980.051*
H23E0.24890.55650.48970.051*
H23F0.27710.56990.43350.051*
O24B0.33021 (8)0.55548 (4)0.5558 (3)0.0324 (7)
N61B0.29157 (9)0.47512 (4)0.6587 (3)0.0234 (8)
H61B0.26910.47710.67350.028*
C62B0.30265 (11)0.45815 (5)0.6649 (3)0.0230 (9)
C63B0.27454 (12)0.44515 (5)0.6982 (4)0.0326 (10)
H63D0.26380.44060.62050.049*
H63E0.25640.45080.74980.049*
H63F0.28510.43550.74610.049*
O64B0.33312 (8)0.45376 (4)0.6441 (3)0.0326 (7)
N1C0.53966 (7)0.58569 (5)0.3414 (3)0.0215 (6)
C2C0.55780 (12)0.60074 (5)0.3528 (3)0.0217 (9)
C3C0.59398 (14)0.60159 (6)0.3500 (5)0.0368 (11)
H3C0.60600.61230.35960.044*
C4C0.61234 (11)0.58609 (7)0.3324 (6)0.0448 (12)
H4C0.63730.58630.32750.054*
C5C0.59504 (12)0.57067 (6)0.3221 (4)0.0336 (11)
H5C0.60760.56000.31260.040*
C6C0.55822 (11)0.57096 (5)0.3261 (3)0.0201 (8)
N21C0.53634 (10)0.61562 (4)0.3698 (3)0.0233 (8)
H21C0.51380.61370.38460.028*
C22C0.54652 (12)0.63266 (5)0.3660 (4)0.0245 (9)
C23C0.51835 (13)0.64592 (6)0.3921 (4)0.0350 (11)
H23G0.52030.64990.47990.052*
H23H0.49510.64070.37890.052*
H23I0.52130.65580.33470.052*
O24C0.57706 (8)0.63735 (4)0.3401 (3)0.0290 (7)
N61C0.53781 (10)0.55587 (4)0.3123 (3)0.0247 (8)
H61C0.51520.55750.29820.030*
C62C0.54898 (11)0.53895 (5)0.3182 (3)0.0237 (9)
C63C0.52117 (12)0.52517 (5)0.2950 (4)0.0331 (10)
H63G0.53080.51610.23950.050*
H63H0.50060.53050.25460.050*
H63I0.51420.52000.37580.050*
O64C0.57937 (8)0.53474 (3)0.3428 (2)0.0302 (7)
N1'A0.13439 (9)0.49684 (4)0.4535 (3)0.0209 (7)
H1'A0.11640.48970.44860.025*
C2'A0.12755 (11)0.51404 (5)0.4722 (3)0.0211 (8)
N3'A0.15686 (9)0.52431 (4)0.4775 (3)0.0218 (7)
H3'A0.15330.53560.48560.026*
C4'A0.19187 (11)0.51875 (5)0.4714 (3)0.0230 (9)
C5'A0.19626 (11)0.50059 (5)0.4509 (3)0.0234 (9)
H5'A0.21930.49580.44360.028*
C6'A0.16765 (11)0.48996 (5)0.4418 (3)0.0209 (8)
S2'A0.08665 (3)0.521886 (13)0.48871 (10)0.0289 (2)
O4'A0.21543 (8)0.52978 (4)0.4852 (3)0.0303 (7)
C7'A0.16891 (11)0.47065 (5)0.4192 (3)0.0223 (8)
H7'10.15500.46800.34220.027*
H7'20.15730.46470.49120.027*
C8'A0.20564 (11)0.46300 (5)0.4032 (4)0.0298 (9)
H8'10.21950.46500.48120.036*
H8'20.21780.46890.33230.036*
C9'A0.20376 (12)0.44355 (6)0.3768 (4)0.0363 (11)
H9'10.19400.43760.45080.054*
H9'20.22750.43910.35940.054*
H9'30.18860.44150.30330.054*
N1'B0.38184 (10)0.58121 (4)0.4941 (3)0.0213 (7)
H1'B0.36370.57420.50180.026*
C2'B0.37563 (12)0.59809 (5)0.4675 (3)0.0203 (9)
N3'B0.40486 (10)0.60829 (4)0.4569 (3)0.0238 (8)
H3'B0.40140.61950.44350.029*
C4'B0.43985 (12)0.60269 (5)0.4653 (4)0.0214 (9)
C5'B0.44406 (12)0.58472 (5)0.4949 (4)0.0243 (9)
H5'B0.46710.58000.50390.029*
C6'B0.41576 (12)0.57434 (5)0.5102 (3)0.0209 (9)
S2'B0.33509 (3)0.606102 (13)0.44351 (9)0.0257 (2)
O4'B0.46371 (8)0.61343 (4)0.4453 (3)0.0311 (7)
C7'B0.41645 (12)0.55538 (5)0.5413 (4)0.0242 (9)
H7'30.40510.54890.47130.029*
H7'40.40220.55340.61840.029*
C8'B0.45326 (12)0.54784 (5)0.5632 (4)0.0263 (9)
H8'30.46500.55430.63270.032*
H8'40.46760.54930.48570.032*
C9'B0.45136 (13)0.52837 (6)0.5973 (4)0.0337 (10)
H9'40.43590.52680.67070.050*
H9'50.47500.52410.61760.050*
H9'60.44190.52180.52520.050*
N1'C0.63084 (9)0.66318 (4)0.4136 (3)0.0203 (7)
H1'C0.61230.65650.40050.024*
C2'C0.62536 (11)0.68026 (5)0.4414 (3)0.0194 (8)
N3'C0.65513 (9)0.68986 (4)0.4591 (3)0.0209 (7)
H3'C0.65230.70110.47300.025*
C4'C0.68971 (11)0.68358 (5)0.4571 (3)0.0227 (9)
C5'C0.69303 (12)0.66564 (5)0.4251 (3)0.0226 (9)
H5'C0.71580.66060.41780.027*
C6'C0.66410 (11)0.65572 (5)0.4051 (3)0.0190 (8)
S2'C0.58490 (3)0.688842 (13)0.45544 (9)0.0266 (2)
O4'C0.71390 (8)0.69381 (4)0.4805 (3)0.0280 (7)
C7'C0.66410 (12)0.63658 (5)0.3752 (4)0.0230 (9)
H7'50.65050.63470.29640.028*
H7'60.65170.63030.44410.028*
C8'C0.70052 (12)0.62859 (5)0.3587 (4)0.0289 (10)
H8'50.71280.63430.28720.035*
H8'60.71460.63060.43620.035*
C9'C0.69790 (14)0.60927 (6)0.3334 (5)0.0406 (12)
H9'70.68790.60340.40760.061*
H9'80.72140.60460.31610.061*
H9'90.68260.60730.26000.061*
N1'D0.11197 (9)0.59257 (4)0.5034 (3)0.0234 (7)
H1'D0.13030.59960.50520.028*
C2'D0.11786 (10)0.57519 (5)0.4990 (3)0.0204 (8)
N3'D0.08833 (9)0.56501 (4)0.4948 (3)0.0235 (7)
H3'D0.09150.55370.49250.028*
C4'D0.05337 (11)0.57097 (5)0.4937 (4)0.0252 (9)
C5'D0.04972 (11)0.58954 (5)0.5003 (4)0.0250 (9)
H5'D0.02690.59460.50130.030*
C6'D0.07851 (10)0.59991 (5)0.5053 (3)0.0187 (8)
S2'D0.15874 (3)0.566847 (13)0.49901 (11)0.0322 (2)
O4'D0.02949 (8)0.56006 (4)0.4886 (3)0.0310 (7)
C7'D0.07832 (11)0.61952 (5)0.5136 (4)0.0242 (9)
H7'70.09000.62290.59360.029*
H7'80.09280.62410.44330.029*
C8'D0.04280 (12)0.62824 (5)0.5086 (4)0.0314 (10)
H8'70.02770.62370.57760.038*
H8'80.03120.62550.42700.038*
C9'D0.04670 (12)0.64801 (5)0.5227 (4)0.0351 (10)
H9'X0.05590.65070.60710.053*
H9'Y0.02360.65360.51160.053*
H9'Z0.06310.65240.45830.053*
N1'E0.36296 (9)0.67688 (4)0.4185 (3)0.0205 (7)
H1'E0.38170.68360.41530.025*
C2'E0.36797 (12)0.65940 (5)0.4210 (4)0.0237 (9)
N3'E0.33807 (10)0.64972 (4)0.4297 (3)0.0238 (8)
H3'E0.34080.63840.43360.029*
C4'E0.30356 (11)0.65599 (5)0.4332 (4)0.0216 (9)
C5'E0.30064 (11)0.67473 (5)0.4282 (4)0.0233 (9)
H5'E0.27800.68000.43020.028*
C6'E0.32987 (12)0.68475 (5)0.4208 (3)0.0220 (9)
S2'E0.40831 (3)0.650629 (14)0.41640 (11)0.0315 (3)
O4'E0.27904 (8)0.64556 (4)0.4411 (3)0.0315 (7)
C7'E0.33083 (11)0.70422 (5)0.4139 (3)0.0228 (8)
H7'90.34250.70770.33390.027*
H7'X0.34550.70860.48450.027*
C8'E0.29459 (11)0.71310 (5)0.4200 (4)0.0303 (10)
H8'90.28310.71040.50200.036*
H8'X0.27930.70860.35130.036*
C9'E0.29917 (13)0.73295 (6)0.4060 (5)0.0417 (12)
H9'A0.31470.73730.47300.063*
H9'B0.27610.73860.41270.063*
H9'C0.30960.73560.32320.063*
N1'F0.61587 (9)0.75861 (4)0.5395 (3)0.0213 (7)
H1'F0.63470.76510.55010.026*
C2'F0.62052 (11)0.74121 (5)0.5208 (3)0.0208 (9)
N3'F0.59025 (9)0.73191 (4)0.5054 (3)0.0211 (7)
H3'F0.59260.72060.49400.025*
C4'F0.55616 (11)0.73843 (5)0.5060 (4)0.0236 (9)
C5'F0.55347 (11)0.75687 (5)0.5256 (3)0.0224 (9)
H5'F0.53100.76230.52660.027*
C6'F0.58300 (11)0.76663 (5)0.5426 (3)0.0200 (8)
S2'F0.66055 (3)0.732086 (13)0.51839 (10)0.0279 (2)
O4'F0.53115 (8)0.72836 (3)0.4878 (3)0.0298 (7)
C7'F0.58398 (12)0.78580 (5)0.5630 (4)0.0259 (9)
H7'Y0.59750.79110.49280.031*
H7'Z0.59710.78810.64220.031*
C8'F0.54838 (12)0.79484 (5)0.5712 (4)0.0323 (10)
H8'Y0.53460.78980.64170.039*
H8'Z0.53510.79280.49180.039*
C9'F0.55272 (13)0.81434 (5)0.5925 (5)0.0425 (12)
H9'D0.56550.81630.67170.064*
H9'E0.52940.81980.59760.064*
H9'F0.56600.81940.52200.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0183 (15)0.0184 (18)0.0248 (14)0.0009 (14)0.0025 (15)0.0015 (12)
C2A0.022 (2)0.018 (2)0.0230 (18)0.0036 (16)0.0004 (15)0.0020 (14)
C3A0.020 (2)0.025 (2)0.043 (2)0.0026 (18)0.0082 (17)0.0020 (17)
C4A0.018 (2)0.024 (3)0.054 (2)0.0000 (18)0.005 (2)0.008 (2)
C5A0.018 (2)0.018 (2)0.045 (2)0.0021 (17)0.0018 (17)0.0069 (17)
C6A0.023 (2)0.020 (2)0.0244 (18)0.0025 (17)0.0037 (16)0.0007 (15)
N21A0.0175 (18)0.0208 (18)0.0337 (17)0.0009 (14)0.0039 (13)0.0044 (13)
C22A0.026 (2)0.020 (2)0.0243 (18)0.0038 (17)0.0007 (16)0.0013 (15)
C23A0.030 (2)0.026 (2)0.051 (3)0.0003 (19)0.002 (2)0.0077 (18)
O24A0.0224 (16)0.0236 (16)0.0543 (17)0.0057 (12)0.0059 (13)0.0070 (13)
N61A0.0171 (19)0.0167 (18)0.0327 (16)0.0020 (13)0.0038 (13)0.0037 (13)
C62A0.022 (2)0.022 (2)0.0309 (19)0.0036 (17)0.0022 (17)0.0025 (16)
C63A0.025 (2)0.021 (2)0.048 (2)0.0004 (18)0.0025 (19)0.0044 (18)
O64A0.0222 (18)0.0185 (16)0.0669 (19)0.0058 (13)0.0019 (14)0.0039 (13)
N1B0.0157 (18)0.0188 (17)0.0251 (15)0.0008 (14)0.0017 (13)0.0031 (12)
C2B0.018 (2)0.022 (2)0.0230 (18)0.0014 (17)0.0033 (16)0.0035 (15)
C3B0.018 (2)0.016 (2)0.049 (2)0.0023 (16)0.0010 (18)0.0007 (17)
C4B0.013 (2)0.030 (3)0.062 (3)0.0021 (19)0.002 (2)0.001 (2)
C5B0.020 (2)0.021 (2)0.042 (2)0.0032 (18)0.0031 (17)0.0024 (17)
C6B0.021 (2)0.017 (2)0.0294 (19)0.0018 (17)0.0008 (16)0.0008 (15)
N21B0.0174 (19)0.0163 (18)0.0336 (17)0.0015 (14)0.0045 (13)0.0038 (13)
C22B0.025 (2)0.019 (2)0.0261 (19)0.0021 (17)0.0020 (15)0.0018 (15)
C23B0.030 (3)0.022 (2)0.050 (2)0.0023 (18)0.014 (2)0.0028 (19)
O24B0.0217 (17)0.0247 (16)0.0508 (17)0.0074 (12)0.0031 (13)0.0021 (12)
N61B0.0113 (17)0.0197 (18)0.0391 (18)0.0025 (13)0.0070 (14)0.0040 (14)
C62B0.022 (2)0.018 (2)0.0284 (19)0.0052 (16)0.0011 (16)0.0034 (15)
C63B0.025 (2)0.018 (2)0.056 (3)0.0046 (17)0.0106 (19)0.0047 (19)
O64B0.0192 (16)0.0247 (16)0.0540 (17)0.0052 (13)0.0066 (13)0.0051 (13)
N1C0.0192 (15)0.0178 (18)0.0275 (13)0.0017 (15)0.0019 (15)0.0006 (12)
C2C0.020 (2)0.024 (2)0.0213 (18)0.0025 (18)0.0016 (15)0.0001 (15)
C3C0.028 (3)0.021 (2)0.062 (3)0.0048 (19)0.002 (2)0.005 (2)
C4C0.0122 (19)0.040 (3)0.083 (3)0.001 (2)0.001 (3)0.004 (2)
C5C0.014 (2)0.024 (2)0.062 (3)0.0028 (18)0.0038 (19)0.001 (2)
C6C0.013 (2)0.024 (2)0.0227 (17)0.0013 (16)0.0028 (15)0.0011 (15)
N21C0.0125 (18)0.0211 (19)0.0362 (18)0.0026 (14)0.0034 (13)0.0025 (13)
C22C0.020 (2)0.025 (2)0.0286 (19)0.0032 (17)0.0003 (16)0.0026 (16)
C23C0.031 (3)0.026 (2)0.048 (2)0.0017 (19)0.011 (2)0.0053 (18)
O24C0.0230 (17)0.0215 (15)0.0427 (15)0.0057 (12)0.0043 (12)0.0034 (12)
N61C0.0155 (18)0.0228 (19)0.0358 (17)0.0023 (14)0.0045 (14)0.0010 (13)
C62C0.020 (2)0.023 (2)0.0273 (19)0.0007 (16)0.0016 (16)0.0022 (16)
C63C0.029 (2)0.023 (2)0.048 (2)0.0019 (18)0.0073 (19)0.0069 (18)
O64C0.0236 (16)0.0236 (15)0.0433 (15)0.0071 (12)0.0057 (12)0.0057 (12)
N1'A0.0151 (17)0.0177 (18)0.0298 (16)0.0030 (13)0.0024 (13)0.0009 (12)
C2'A0.019 (2)0.017 (2)0.0266 (18)0.0063 (16)0.0002 (15)0.0033 (14)
N3'A0.0170 (18)0.0156 (17)0.0329 (16)0.0017 (13)0.0044 (14)0.0004 (12)
C4'A0.017 (2)0.023 (2)0.029 (2)0.0025 (17)0.0005 (15)0.0063 (16)
C5'A0.017 (2)0.025 (2)0.0290 (19)0.0013 (17)0.0011 (15)0.0018 (16)
C6'A0.022 (2)0.017 (2)0.0233 (17)0.0016 (16)0.0024 (15)0.0022 (14)
S2'A0.0172 (5)0.0218 (5)0.0478 (6)0.0001 (4)0.0004 (5)0.0026 (4)
O4'A0.0162 (16)0.0244 (16)0.0502 (17)0.0042 (12)0.0025 (13)0.0006 (13)
C7'A0.020 (2)0.017 (2)0.0296 (18)0.0018 (16)0.0017 (15)0.0022 (15)
C8'A0.025 (2)0.026 (2)0.039 (2)0.0018 (18)0.0005 (17)0.0046 (17)
C9'A0.025 (2)0.025 (2)0.058 (3)0.0035 (19)0.009 (2)0.0163 (19)
N1'B0.0165 (19)0.0191 (18)0.0285 (16)0.0020 (14)0.0004 (13)0.0017 (13)
C2'B0.024 (2)0.015 (2)0.0214 (18)0.0001 (17)0.0010 (15)0.0020 (14)
N3'B0.021 (2)0.0169 (18)0.0333 (17)0.0007 (14)0.0004 (15)0.0000 (14)
C4'B0.018 (2)0.015 (2)0.031 (2)0.0017 (16)0.0049 (16)0.0048 (15)
C5'B0.021 (3)0.020 (2)0.033 (2)0.0005 (17)0.0000 (17)0.0015 (16)
C6'B0.021 (2)0.023 (2)0.0189 (16)0.0057 (17)0.0041 (15)0.0004 (14)
S2'B0.0173 (5)0.0177 (5)0.0421 (5)0.0003 (4)0.0012 (4)0.0005 (4)
O4'B0.0211 (18)0.0221 (16)0.0503 (17)0.0074 (13)0.0069 (14)0.0003 (13)
C7'B0.022 (2)0.019 (2)0.032 (2)0.0029 (17)0.0033 (16)0.0012 (15)
C8'B0.025 (2)0.018 (2)0.035 (2)0.0009 (17)0.0016 (17)0.0031 (16)
C9'B0.028 (3)0.022 (2)0.051 (3)0.0058 (19)0.007 (2)0.0037 (19)
N1'C0.0147 (18)0.0183 (17)0.0278 (16)0.0026 (13)0.0004 (12)0.0028 (13)
C2'C0.015 (2)0.019 (2)0.0235 (17)0.0052 (15)0.0012 (15)0.0044 (14)
N3'C0.0175 (18)0.0132 (17)0.0320 (16)0.0003 (13)0.0008 (13)0.0042 (12)
C4'C0.019 (2)0.022 (2)0.0273 (18)0.0016 (17)0.0029 (16)0.0038 (15)
C5'C0.015 (2)0.020 (2)0.033 (2)0.0032 (16)0.0021 (16)0.0015 (16)
C6'C0.018 (2)0.015 (2)0.0241 (17)0.0018 (16)0.0014 (15)0.0029 (14)
S2'C0.0166 (5)0.0210 (5)0.0422 (5)0.0012 (4)0.0001 (4)0.0007 (4)
O4'C0.0198 (16)0.0219 (15)0.0424 (16)0.0028 (12)0.0044 (12)0.0007 (12)
C7'C0.022 (2)0.019 (2)0.0285 (18)0.0012 (17)0.0011 (16)0.0024 (15)
C8'C0.020 (2)0.024 (2)0.042 (2)0.0006 (18)0.0020 (17)0.0034 (18)
C9'C0.029 (3)0.029 (3)0.063 (3)0.007 (2)0.005 (2)0.006 (2)
N1'D0.0189 (19)0.0174 (18)0.0340 (16)0.0031 (14)0.0001 (14)0.0001 (13)
C2'D0.014 (2)0.020 (2)0.0278 (18)0.0008 (16)0.0022 (15)0.0002 (16)
N3'D0.0194 (19)0.0150 (17)0.0360 (16)0.0002 (14)0.0017 (15)0.0008 (13)
C4'D0.019 (2)0.028 (2)0.0283 (19)0.0009 (18)0.0015 (17)0.0045 (17)
C5'D0.018 (2)0.025 (2)0.0321 (19)0.0008 (17)0.0010 (16)0.0027 (17)
C6'D0.017 (2)0.018 (2)0.0206 (16)0.0019 (16)0.0006 (15)0.0010 (14)
S2'D0.0173 (5)0.0199 (6)0.0594 (6)0.0001 (4)0.0012 (5)0.0007 (5)
O4'D0.0209 (17)0.0254 (16)0.0468 (15)0.0086 (13)0.0031 (13)0.0048 (12)
C7'D0.023 (2)0.018 (2)0.0318 (19)0.0028 (16)0.0006 (16)0.0012 (15)
C8'D0.028 (2)0.020 (2)0.047 (2)0.0019 (18)0.0035 (19)0.0022 (19)
C9'D0.029 (3)0.020 (2)0.057 (3)0.0010 (18)0.006 (2)0.0036 (19)
N1'E0.0163 (19)0.0132 (17)0.0321 (16)0.0007 (13)0.0019 (13)0.0011 (13)
C2'E0.026 (3)0.017 (2)0.0285 (19)0.0011 (18)0.0030 (17)0.0012 (16)
N3'E0.018 (2)0.0149 (18)0.0388 (17)0.0025 (14)0.0026 (15)0.0009 (14)
C4'E0.017 (2)0.019 (2)0.0283 (19)0.0022 (17)0.0050 (17)0.0022 (16)
C5'E0.012 (2)0.021 (2)0.037 (2)0.0004 (16)0.0021 (16)0.0008 (17)
C6'E0.021 (2)0.021 (2)0.0238 (18)0.0035 (17)0.0022 (16)0.0031 (15)
S2'E0.0175 (6)0.0191 (6)0.0581 (7)0.0012 (4)0.0041 (5)0.0013 (5)
O4'E0.0189 (18)0.0213 (16)0.0543 (18)0.0036 (13)0.0064 (14)0.0058 (13)
C7'E0.017 (2)0.018 (2)0.034 (2)0.0005 (16)0.0011 (16)0.0025 (16)
C8'E0.020 (2)0.019 (2)0.052 (3)0.0023 (17)0.0013 (18)0.0052 (18)
C9'E0.027 (3)0.025 (2)0.073 (3)0.0040 (19)0.005 (2)0.004 (2)
N1'F0.0164 (18)0.0151 (17)0.0324 (16)0.0065 (13)0.0001 (13)0.0023 (12)
C2'F0.017 (2)0.019 (2)0.0258 (18)0.0025 (16)0.0024 (15)0.0003 (15)
N3'F0.0192 (19)0.0116 (16)0.0324 (16)0.0016 (13)0.0000 (14)0.0034 (13)
C4'F0.022 (2)0.024 (2)0.0250 (18)0.0008 (18)0.0010 (16)0.0021 (16)
C5'F0.015 (2)0.021 (2)0.031 (2)0.0016 (16)0.0012 (15)0.0013 (15)
C6'F0.017 (2)0.019 (2)0.0235 (17)0.0006 (16)0.0008 (14)0.0009 (14)
S2'F0.0174 (5)0.0200 (5)0.0463 (6)0.0009 (4)0.0013 (4)0.0008 (4)
O4'F0.0193 (17)0.0195 (15)0.0505 (17)0.0068 (12)0.0074 (13)0.0011 (12)
C7'F0.022 (2)0.019 (2)0.036 (2)0.0023 (16)0.0029 (17)0.0017 (15)
C8'F0.022 (2)0.023 (2)0.052 (3)0.0013 (17)0.0007 (18)0.0023 (19)
C9'F0.032 (3)0.020 (2)0.076 (3)0.0010 (19)0.011 (2)0.007 (2)
Geometric parameters (Å, º) top
N1A—C6A1.330 (5)N3'B—C4'B1.398 (6)
N1A—C2A1.350 (5)N3'B—H3'B0.8800
C2A—C3A1.393 (6)C4'B—O4'B1.243 (5)
C2A—N21A1.409 (5)C4'B—C5'B1.425 (6)
C3A—C4A1.369 (6)C5'B—C6'B1.348 (6)
C3A—H3A0.9500C5'B—H5'B0.9500
C4A—C5A1.379 (6)C6'B—C7'B1.494 (5)
C4A—H4A0.9500C7'B—C8'B1.530 (6)
C5A—C6A1.406 (6)C7'B—H7'30.9900
C5A—H5A0.9500C7'B—H7'40.9900
C6A—N61A1.408 (5)C8'B—C9'B1.541 (6)
N21A—C22A1.363 (5)C8'B—H8'30.9900
N21A—H21A0.8800C8'B—H8'40.9900
C22A—O24A1.253 (5)C9'B—H9'40.9800
C22A—C23A1.497 (6)C9'B—H9'50.9800
C23A—H23A0.9800C9'B—H9'60.9800
C23A—H23B0.9800N1'C—C2'C1.362 (5)
C23A—H23C0.9800N1'C—C6'C1.389 (5)
N61A—C62A1.369 (5)N1'C—H1'C0.8800
N61A—H61A0.8800C2'C—N3'C1.362 (5)
C62A—O64A1.235 (5)C2'C—S2'C1.677 (4)
C62A—C63A1.510 (6)N3'C—C4'C1.398 (5)
C63A—H63A0.9800N3'C—H3'C0.8800
C63A—H63B0.9800C4'C—O4'C1.233 (5)
C63A—H63C0.9800C4'C—C5'C1.426 (5)
N1B—C2B1.331 (5)C5'C—C6'C1.353 (6)
N1B—C6B1.366 (5)C5'C—H5'C0.9500
C2B—C3B1.390 (6)C6'C—C7'C1.505 (5)
C2B—N21B1.421 (5)C7'C—C8'C1.522 (6)
C3B—C4B1.380 (7)C7'C—H7'50.9900
C3B—H3B0.9500C7'C—H7'60.9900
C4B—C5B1.380 (6)C8'C—C9'C1.512 (6)
C4B—H4B0.9500C8'C—H8'50.9900
C5B—C6B1.375 (6)C8'C—H8'60.9900
C5B—H5B0.9500C9'C—H9'70.9800
C6B—N61B1.416 (5)C9'C—H9'80.9800
N21B—C22B1.376 (5)C9'C—H9'90.9800
N21B—H21B0.8800N1'D—C2'D1.355 (5)
C22B—O24B1.222 (5)N1'D—C6'D1.390 (5)
C22B—C23B1.519 (6)N1'D—H1'D0.8800
C23B—H23D0.9800C2'D—N3'D1.367 (5)
C23B—H23E0.9800C2'D—S2'D1.678 (4)
C23B—H23F0.9800N3'D—C4'D1.403 (5)
N61B—C62B1.372 (5)N3'D—H3'D0.8800
N61B—H61B0.8800C4'D—O4'D1.236 (5)
C62B—O64B1.224 (5)C4'D—C5'D1.435 (6)
C62B—C63B1.503 (6)C5'D—C6'D1.353 (6)
C63B—H63D0.9800C5'D—H5'D0.9500
C63B—H63E0.9800C6'D—C7'D1.510 (5)
C63B—H63F0.9800C7'D—C8'D1.506 (6)
N1C—C6C1.343 (5)C7'D—H7'70.9900
N1C—C2C1.351 (5)C7'D—H7'80.9900
C2C—C3C1.374 (7)C8'D—C9'D1.534 (6)
C2C—N21C1.416 (5)C8'D—H8'70.9900
C3C—C4C1.393 (7)C8'D—H8'80.9900
C3C—H3C0.9500C9'D—H9'X0.9800
C4C—C5C1.360 (7)C9'D—H9'Y0.9800
C4C—H4C0.9500C9'D—H9'Z0.9800
C5C—C6C1.398 (6)N1'E—C2'E1.357 (5)
C5C—H5C0.9500N1'E—C6'E1.394 (5)
C6C—N61C1.402 (5)N1'E—H1'E0.8800
N21C—C22C1.366 (5)C2'E—N3'E1.360 (6)
N21C—H21C0.8800C2'E—S2'E1.673 (5)
C22C—O24C1.244 (5)N3'E—C4'E1.396 (6)
C22C—C23C1.503 (6)N3'E—H3'E0.8800
C23C—H23G0.9800C4'E—O4'E1.231 (5)
C23C—H23H0.9800C4'E—C5'E1.447 (6)
C23C—H23I0.9800C5'E—C6'E1.352 (6)
N61C—C62C1.370 (5)C5'E—H5'E0.9500
N61C—H61C0.8800C6'E—C7'E1.499 (5)
C62C—O64C1.225 (5)C7'E—C8'E1.536 (6)
C62C—C63C1.515 (6)C7'E—H7'90.9900
C63C—H63G0.9800C7'E—H7'X0.9900
C63C—H63H0.9800C8'E—C9'E1.543 (6)
C63C—H63I0.9800C8'E—H8'90.9900
N1'A—C2'A1.362 (5)C8'E—H8'X0.9900
N1'A—C6'A1.374 (5)C9'E—H9'A0.9800
N1'A—H1'A0.8800C9'E—H9'B0.9800
C2'A—N3'A1.365 (5)C9'E—H9'C0.9800
C2'A—S2'A1.674 (4)N1'F—C2'F1.364 (5)
N3'A—C4'A1.397 (5)N1'F—C6'F1.392 (5)
N3'A—H3'A0.8800N1'F—H1'F0.8800
C4'A—O4'A1.240 (5)C2'F—N3'F1.362 (5)
C4'A—C5'A1.423 (6)C2'F—S2'F1.673 (4)
C5'A—C6'A1.362 (6)N3'F—C4'F1.387 (5)
C5'A—H5'A0.9500N3'F—H3'F0.8800
C6'A—C7'A1.505 (5)C4'F—O4'F1.239 (5)
C7'A—C8'A1.522 (6)C4'F—C5'F1.436 (5)
C7'A—H7'10.9900C5'F—C6'F1.360 (6)
C7'A—H7'20.9900C5'F—H5'F0.9500
C8'A—C9'A1.523 (6)C6'F—C7'F1.490 (5)
C8'A—H8'10.9900C7'F—C8'F1.521 (6)
C8'A—H8'20.9900C7'F—H7'Y0.9900
C9'A—H9'10.9800C7'F—H7'Z0.9900
C9'A—H9'20.9800C8'F—C9'F1.525 (6)
C9'A—H9'30.9800C8'F—H8'Y0.9900
N1'B—C2'B1.348 (5)C8'F—H8'Z0.9900
N1'B—C6'B1.402 (5)C9'F—H9'D0.9800
N1'B—H1'B0.8800C9'F—H9'E0.9800
C2'B—N3'B1.363 (5)C9'F—H9'F0.9800
C2'B—S2'B1.676 (4)
C6A—N1A—C2A117.6 (3)C6'B—C5'B—C4'B120.8 (4)
N1A—C2A—C3A123.2 (4)C6'B—C5'B—H5'B119.6
N1A—C2A—N21A113.6 (4)C4'B—C5'B—H5'B119.6
C3A—C2A—N21A123.2 (4)C5'B—C6'B—N1'B119.5 (4)
C4A—C3A—C2A117.4 (4)C5'B—C6'B—C7'B126.2 (4)
C4A—C3A—H3A121.3N1'B—C6'B—C7'B114.2 (4)
C2A—C3A—H3A121.3C6'B—C7'B—C8'B114.8 (4)
C3A—C4A—C5A121.5 (4)C6'B—C7'B—H7'3108.6
C3A—C4A—H4A119.2C8'B—C7'B—H7'3108.6
C5A—C4A—H4A119.2C6'B—C7'B—H7'4108.6
C4A—C5A—C6A116.8 (4)C8'B—C7'B—H7'4108.6
C4A—C5A—H5A121.6H7'3—C7'B—H7'4107.6
C6A—C5A—H5A121.6C7'B—C8'B—C9'B111.1 (4)
N1A—C6A—C5A123.5 (4)C7'B—C8'B—H8'3109.4
N1A—C6A—N61A114.3 (4)C9'B—C8'B—H8'3109.4
C5A—C6A—N61A122.1 (4)C7'B—C8'B—H8'4109.4
C22A—N21A—C2A127.9 (4)C9'B—C8'B—H8'4109.4
C22A—N21A—H21A116.1H8'3—C8'B—H8'4108.0
C2A—N21A—H21A116.1C8'B—C9'B—H9'4109.5
O24A—C22A—N21A122.4 (4)C8'B—C9'B—H9'5109.5
O24A—C22A—C23A121.1 (4)H9'4—C9'B—H9'5109.5
N21A—C22A—C23A116.5 (4)C8'B—C9'B—H9'6109.5
C22A—C23A—H23A109.5H9'4—C9'B—H9'6109.5
C22A—C23A—H23B109.5H9'5—C9'B—H9'6109.5
H23A—C23A—H23B109.5C2'C—N1'C—C6'C123.4 (3)
C22A—C23A—H23C109.5C2'C—N1'C—H1'C118.3
H23A—C23A—H23C109.5C6'C—N1'C—H1'C118.3
H23B—C23A—H23C109.5N1'C—C2'C—N3'C115.2 (4)
C62A—N61A—C6A127.8 (4)N1'C—C2'C—S2'C122.6 (3)
C62A—N61A—H61A116.1N3'C—C2'C—S2'C122.3 (3)
C6A—N61A—H61A116.1C2'C—N3'C—C4'C126.1 (3)
O64A—C62A—N61A122.3 (4)C2'C—N3'C—H3'C116.9
O64A—C62A—C63A121.6 (4)C4'C—N3'C—H3'C116.9
N61A—C62A—C63A116.1 (4)O4'C—C4'C—N3'C118.4 (4)
C62A—C63A—H63A109.5O4'C—C4'C—C5'C126.8 (4)
C62A—C63A—H63B109.5N3'C—C4'C—C5'C114.9 (4)
H63A—C63A—H63B109.5C6'C—C5'C—C4'C120.7 (4)
C62A—C63A—H63C109.5C6'C—C5'C—H5'C119.6
H63A—C63A—H63C109.5C4'C—C5'C—H5'C119.6
H63B—C63A—H63C109.5C5'C—C6'C—N1'C119.6 (3)
C2B—N1B—C6B116.7 (4)C5'C—C6'C—C7'C125.8 (4)
N1B—C2B—C3B124.2 (4)N1'C—C6'C—C7'C114.7 (4)
N1B—C2B—N21B113.7 (4)C6'C—C7'C—C8'C114.7 (4)
C3B—C2B—N21B122.1 (4)C6'C—C7'C—H7'5108.6
C4B—C3B—C2B117.0 (4)C8'C—C7'C—H7'5108.6
C4B—C3B—H3B121.5C6'C—C7'C—H7'6108.6
C2B—C3B—H3B121.5C8'C—C7'C—H7'6108.6
C5B—C4B—C3B121.0 (5)H7'5—C7'C—H7'6107.6
C5B—C4B—H4B119.5C9'C—C8'C—C7'C110.9 (4)
C3B—C4B—H4B119.5C9'C—C8'C—H8'5109.5
C6B—C5B—C4B117.6 (4)C7'C—C8'C—H8'5109.5
C6B—C5B—H5B121.2C9'C—C8'C—H8'6109.5
C4B—C5B—H5B121.2C7'C—C8'C—H8'6109.5
N1B—C6B—C5B123.4 (4)H8'5—C8'C—H8'6108.0
N1B—C6B—N61B113.2 (4)C8'C—C9'C—H9'7109.5
C5B—C6B—N61B123.4 (4)C8'C—C9'C—H9'8109.5
C22B—N21B—C2B126.9 (4)H9'7—C9'C—H9'8109.5
C22B—N21B—H21B116.6C8'C—C9'C—H9'9109.5
C2B—N21B—H21B116.6H9'7—C9'C—H9'9109.5
O24B—C22B—N21B124.2 (4)H9'8—C9'C—H9'9109.5
O24B—C22B—C23B121.3 (4)C2'D—N1'D—C6'D123.5 (3)
N21B—C22B—C23B114.5 (4)C2'D—N1'D—H1'D118.3
C22B—C23B—H23D109.5C6'D—N1'D—H1'D118.3
C22B—C23B—H23E109.5N1'D—C2'D—N3'D115.5 (3)
H23D—C23B—H23E109.5N1'D—C2'D—S2'D122.0 (3)
C22B—C23B—H23F109.5N3'D—C2'D—S2'D122.6 (3)
H23D—C23B—H23F109.5C2'D—N3'D—C4'D126.0 (3)
H23E—C23B—H23F109.5C2'D—N3'D—H3'D117.0
C62B—N61B—C6B126.6 (4)C4'D—N3'D—H3'D117.0
C62B—N61B—H61B116.7O4'D—C4'D—N3'D118.1 (4)
C6B—N61B—H61B116.7O4'D—C4'D—C5'D127.3 (4)
O64B—C62B—N61B122.9 (4)N3'D—C4'D—C5'D114.6 (4)
O64B—C62B—C63B121.9 (4)C6'D—C5'D—C4'D120.7 (4)
N61B—C62B—C63B115.2 (4)C6'D—C5'D—H5'D119.7
C62B—C63B—H63D109.5C4'D—C5'D—H5'D119.7
C62B—C63B—H63E109.5C5'D—C6'D—N1'D119.8 (4)
H63D—C63B—H63E109.5C5'D—C6'D—C7'D125.9 (4)
C62B—C63B—H63F109.5N1'D—C6'D—C7'D114.3 (3)
H63D—C63B—H63F109.5C8'D—C7'D—C6'D116.5 (4)
H63E—C63B—H63F109.5C8'D—C7'D—H7'7108.2
C6C—N1C—C2C117.8 (3)C6'D—C7'D—H7'7108.2
N1C—C2C—C3C123.2 (4)C8'D—C7'D—H7'8108.2
N1C—C2C—N21C114.2 (4)C6'D—C7'D—H7'8108.2
C3C—C2C—N21C122.6 (4)H7'7—C7'D—H7'8107.3
C2C—C3C—C4C117.5 (4)C7'D—C8'D—C9'D110.6 (4)
C2C—C3C—H3C121.3C7'D—C8'D—H8'7109.5
C4C—C3C—H3C121.3C9'D—C8'D—H8'7109.5
C5C—C4C—C3C121.0 (4)C7'D—C8'D—H8'8109.5
C5C—C4C—H4C119.5C9'D—C8'D—H8'8109.5
C3C—C4C—H4C119.5H8'7—C8'D—H8'8108.1
C4C—C5C—C6C117.8 (4)C8'D—C9'D—H9'X109.5
C4C—C5C—H5C121.1C8'D—C9'D—H9'Y109.5
C6C—C5C—H5C121.1H9'X—C9'D—H9'Y109.5
N1C—C6C—C5C122.7 (4)C8'D—C9'D—H9'Z109.5
N1C—C6C—N61C114.9 (4)H9'X—C9'D—H9'Z109.5
C5C—C6C—N61C122.4 (4)H9'Y—C9'D—H9'Z109.5
C22C—N21C—C2C127.5 (4)C2'E—N1'E—C6'E123.7 (4)
C22C—N21C—H21C116.3C2'E—N1'E—H1'E118.1
C2C—N21C—H21C116.3C6'E—N1'E—H1'E118.1
O24C—C22C—N21C123.2 (4)N1'E—C2'E—N3'E115.2 (4)
O24C—C22C—C23C120.4 (4)N1'E—C2'E—S2'E121.8 (3)
N21C—C22C—C23C116.4 (4)N3'E—C2'E—S2'E123.0 (3)
C22C—C23C—H23G109.5C2'E—N3'E—C4'E126.5 (3)
C22C—C23C—H23H109.5C2'E—N3'E—H3'E116.7
H23G—C23C—H23H109.5C4'E—N3'E—H3'E116.7
C22C—C23C—H23I109.5O4'E—C4'E—N3'E119.1 (4)
H23G—C23C—H23I109.5O4'E—C4'E—C5'E126.4 (4)
H23H—C23C—H23I109.5N3'E—C4'E—C5'E114.5 (4)
C62C—N61C—C6C127.6 (4)C6'E—C5'E—C4'E120.4 (4)
C62C—N61C—H61C116.2C6'E—C5'E—H5'E119.8
C6C—N61C—H61C116.2C4'E—C5'E—H5'E119.8
O64C—C62C—N61C123.5 (4)C5'E—C6'E—N1'E119.5 (4)
O64C—C62C—C63C120.3 (4)C5'E—C6'E—C7'E126.3 (4)
N61C—C62C—C63C116.2 (4)N1'E—C6'E—C7'E114.2 (4)
C62C—C63C—H63G109.5C6'E—C7'E—C8'E114.8 (4)
C62C—C63C—H63H109.5C6'E—C7'E—H7'9108.6
H63G—C63C—H63H109.5C8'E—C7'E—H7'9108.6
C62C—C63C—H63I109.5C6'E—C7'E—H7'X108.6
H63G—C63C—H63I109.5C8'E—C7'E—H7'X108.6
H63H—C63C—H63I109.5H7'9—C7'E—H7'X107.5
C2'A—N1'A—C6'A124.2 (3)C7'E—C8'E—C9'E109.6 (4)
C2'A—N1'A—H1'A117.9C7'E—C8'E—H8'9109.8
C6'A—N1'A—H1'A117.9C9'E—C8'E—H8'9109.8
N1'A—C2'A—N3'A114.3 (4)C7'E—C8'E—H8'X109.8
N1'A—C2'A—S2'A122.8 (3)C9'E—C8'E—H8'X109.8
N3'A—C2'A—S2'A122.9 (3)H8'9—C8'E—H8'X108.2
C2'A—N3'A—C4'A126.6 (3)C8'E—C9'E—H9'A109.5
C2'A—N3'A—H3'A116.7C8'E—C9'E—H9'B109.5
C4'A—N3'A—H3'A116.7H9'A—C9'E—H9'B109.5
O4'A—C4'A—N3'A118.1 (4)C8'E—C9'E—H9'C109.5
O4'A—C4'A—C5'A127.2 (4)H9'A—C9'E—H9'C109.5
N3'A—C4'A—C5'A114.8 (4)H9'B—C9'E—H9'C109.5
C6'A—C5'A—C4'A120.4 (4)C2'F—N1'F—C6'F123.6 (3)
C6'A—C5'A—H5'A119.8C2'F—N1'F—H1'F118.2
C4'A—C5'A—H5'A119.8C6'F—N1'F—H1'F118.2
C5'A—C6'A—N1'A119.6 (4)N3'F—C2'F—N1'F115.0 (4)
C5'A—C6'A—C7'A125.3 (4)N3'F—C2'F—S2'F122.9 (3)
N1'A—C6'A—C7'A115.1 (3)N1'F—C2'F—S2'F122.1 (3)
C6'A—C7'A—C8'A115.4 (3)C2'F—N3'F—C4'F126.6 (3)
C6'A—C7'A—H7'1108.4C2'F—N3'F—H3'F116.7
C8'A—C7'A—H7'1108.4C4'F—N3'F—H3'F116.7
C6'A—C7'A—H7'2108.4O4'F—C4'F—N3'F119.2 (4)
C8'A—C7'A—H7'2108.4O4'F—C4'F—C5'F125.8 (4)
H7'1—C7'A—H7'2107.5N3'F—C4'F—C5'F115.0 (4)
C7'A—C8'A—C9'A110.9 (3)C6'F—C5'F—C4'F120.3 (4)
C7'A—C8'A—H8'1109.5C6'F—C5'F—H5'F119.8
C9'A—C8'A—H8'1109.5C4'F—C5'F—H5'F119.8
C7'A—C8'A—H8'2109.5C5'F—C6'F—N1'F119.4 (4)
C9'A—C8'A—H8'2109.5C5'F—C6'F—C7'F125.8 (4)
H8'1—C8'A—H8'2108.0N1'F—C6'F—C7'F114.8 (4)
C8'A—C9'A—H9'1109.5C6'F—C7'F—C8'F116.0 (4)
C8'A—C9'A—H9'2109.5C6'F—C7'F—H7'Y108.3
H9'1—C9'A—H9'2109.5C8'F—C7'F—H7'Y108.3
C8'A—C9'A—H9'3109.5C6'F—C7'F—H7'Z108.3
H9'1—C9'A—H9'3109.5C8'F—C7'F—H7'Z108.3
H9'2—C9'A—H9'3109.5H7'Y—C7'F—H7'Z107.4
C2'B—N1'B—C6'B123.3 (4)C7'F—C8'F—C9'F111.2 (4)
C2'B—N1'B—H1'B118.4C7'F—C8'F—H8'Y109.4
C6'B—N1'B—H1'B118.4C9'F—C8'F—H8'Y109.4
N1'B—C2'B—N3'B115.4 (4)C7'F—C8'F—H8'Z109.4
N1'B—C2'B—S2'B123.1 (3)C9'F—C8'F—H8'Z109.4
N3'B—C2'B—S2'B121.5 (3)H8'Y—C8'F—H8'Z108.0
C2'B—N3'B—C4'B126.2 (3)C8'F—C9'F—H9'D109.5
C2'B—N3'B—H3'B116.9C8'F—C9'F—H9'E109.5
C4'B—N3'B—H3'B116.9H9'D—C9'F—H9'E109.5
O4'B—C4'B—N3'B118.4 (4)C8'F—C9'F—H9'F109.5
O4'B—C4'B—C5'B126.8 (4)H9'D—C9'F—H9'F109.5
N3'B—C4'B—C5'B114.7 (4)H9'E—C9'F—H9'F109.5
C6A—N1A—C2A—C3A0.7 (6)S2'B—C2'B—N3'B—C4'B174.8 (3)
C6A—N1A—C2A—N21A178.6 (3)C2'B—N3'B—C4'B—O4'B175.3 (3)
N1A—C2A—C3A—C4A0.3 (6)C2'B—N3'B—C4'B—C5'B3.7 (5)
N21A—C2A—C3A—C4A179.5 (4)O4'B—C4'B—C5'B—C6'B177.7 (4)
C2A—C3A—C4A—C5A0.8 (7)N3'B—C4'B—C5'B—C6'B1.3 (5)
C3A—C4A—C5A—C6A0.3 (7)C4'B—C5'B—C6'B—N1'B1.4 (6)
C2A—N1A—C6A—C5A1.2 (6)C4'B—C5'B—C6'B—C7'B180.0 (3)
C2A—N1A—C6A—N61A179.0 (3)C2'B—N1'B—C6'B—C5'B2.2 (5)
C4A—C5A—C6A—N1A0.8 (6)C2'B—N1'B—C6'B—C7'B179.1 (3)
C4A—C5A—C6A—N61A178.4 (4)C5'B—C6'B—C7'B—C8'B3.1 (6)
N1A—C2A—N21A—C22A167.1 (4)N1'B—C6'B—C7'B—C8'B178.2 (3)
C3A—C2A—N21A—C22A13.7 (6)C6'B—C7'B—C8'B—C9'B178.8 (3)
C2A—N21A—C22A—O24A0.9 (6)C6'C—N1'C—C2'C—N3'C0.8 (5)
C2A—N21A—C22A—C23A179.9 (3)C6'C—N1'C—C2'C—S2'C178.2 (3)
N1A—C6A—N61A—C62A166.1 (4)N1'C—C2'C—N3'C—C4'C3.3 (5)
C5A—C6A—N61A—C62A16.1 (6)S2'C—C2'C—N3'C—C4'C175.7 (3)
C6A—N61A—C62A—O64A1.2 (6)C2'C—N3'C—C4'C—O4'C176.8 (3)
C6A—N61A—C62A—C63A178.5 (4)C2'C—N3'C—C4'C—C5'C4.4 (5)
C6B—N1B—C2B—C3B0.2 (6)O4'C—C4'C—C5'C—C6'C178.1 (4)
C6B—N1B—C2B—N21B179.3 (3)N3'C—C4'C—C5'C—C6'C3.1 (5)
N1B—C2B—C3B—C4B0.1 (6)C4'C—C5'C—C6'C—N1'C1.1 (5)
N21B—C2B—C3B—C4B179.4 (4)C4'C—C5'C—C6'C—C7'C177.8 (3)
C2B—C3B—C4B—C5B0.6 (7)C2'C—N1'C—C6'C—C5'C0.1 (5)
C3B—C4B—C5B—C6B1.2 (7)C2'C—N1'C—C6'C—C7'C179.2 (3)
C2B—N1B—C6B—C5B0.8 (6)C5'C—C6'C—C7'C—C8'C4.2 (5)
C2B—N1B—C6B—N61B179.8 (3)N1'C—C6'C—C7'C—C8'C176.9 (3)
C4B—C5B—C6B—N1B1.3 (6)C6'C—C7'C—C8'C—C9'C178.1 (3)
C4B—C5B—C6B—N61B179.8 (4)C6'D—N1'D—C2'D—N3'D0.8 (5)
N1B—C2B—N21B—C22B167.9 (3)C6'D—N1'D—C2'D—S2'D179.1 (3)
C3B—C2B—N21B—C22B12.6 (6)N1'D—C2'D—N3'D—C4'D0.5 (5)
C2B—N21B—C22B—O24B0.5 (6)S2'D—C2'D—N3'D—C4'D179.6 (3)
C2B—N21B—C22B—C23B179.7 (3)C2'D—N3'D—C4'D—O4'D179.4 (4)
N1B—C6B—N61B—C62B166.5 (3)C2'D—N3'D—C4'D—C5'D1.3 (5)
C5B—C6B—N61B—C62B14.5 (6)O4'D—C4'D—C5'D—C6'D179.9 (4)
C6B—N61B—C62B—O64B1.3 (6)N3'D—C4'D—C5'D—C6'D0.9 (5)
C6B—N61B—C62B—C63B179.1 (4)C4'D—C5'D—C6'D—N1'D0.3 (5)
C6C—N1C—C2C—C3C0.2 (6)C4'D—C5'D—C6'D—C7'D179.5 (3)
C6C—N1C—C2C—N21C179.4 (3)C2'D—N1'D—C6'D—C5'D1.2 (5)
N1C—C2C—C3C—C4C1.0 (7)C2'D—N1'D—C6'D—C7'D178.6 (3)
N21C—C2C—C3C—C4C179.9 (4)C5'D—C6'D—C7'D—C8'D3.5 (6)
C2C—C3C—C4C—C5C1.8 (8)N1'D—C6'D—C7'D—C8'D176.7 (3)
C3C—C4C—C5C—C6C1.8 (8)C6'D—C7'D—C8'D—C9'D178.0 (3)
C2C—N1C—C6C—C5C0.2 (6)C6'E—N1'E—C2'E—N3'E1.9 (5)
C2C—N1C—C6C—N61C178.8 (3)C6'E—N1'E—C2'E—S2'E179.3 (3)
C4C—C5C—C6C—N1C1.0 (7)N1'E—C2'E—N3'E—C4'E1.6 (6)
C4C—C5C—C6C—N61C177.9 (4)S2'E—C2'E—N3'E—C4'E179.5 (3)
N1C—C2C—N21C—C22C169.8 (4)C2'E—N3'E—C4'E—O4'E179.9 (4)
C3C—C2C—N21C—C22C11.0 (6)C2'E—N3'E—C4'E—C5'E0.8 (6)
C2C—N21C—C22C—O24C3.6 (6)O4'E—C4'E—C5'E—C6'E179.3 (4)
C2C—N21C—C22C—C23C177.8 (4)N3'E—C4'E—C5'E—C6'E0.1 (6)
N1C—C6C—N61C—C62C167.2 (3)C4'E—C5'E—C6'E—N1'E0.3 (6)
C5C—C6C—N61C—C62C13.8 (6)C4'E—C5'E—C6'E—C7'E179.4 (3)
C6C—N61C—C62C—O64C3.3 (6)C2'E—N1'E—C6'E—C5'E1.3 (5)
C6C—N61C—C62C—C63C177.9 (3)C2'E—N1'E—C6'E—C7'E178.5 (3)
C6'A—N1'A—C2'A—N3'A0.6 (5)C5'E—C6'E—C7'E—C8'E1.9 (6)
C6'A—N1'A—C2'A—S2'A178.8 (3)N1'E—C6'E—C7'E—C8'E178.4 (3)
N1'A—C2'A—N3'A—C4'A3.0 (5)C6'E—C7'E—C8'E—C9'E177.4 (3)
S2'A—C2'A—N3'A—C4'A176.4 (3)C6'F—N1'F—C2'F—N3'F0.2 (5)
C2'A—N3'A—C4'A—O4'A175.8 (3)C6'F—N1'F—C2'F—S2'F179.7 (3)
C2'A—N3'A—C4'A—C5'A3.5 (5)N1'F—C2'F—N3'F—C4'F0.6 (5)
O4'A—C4'A—C5'A—C6'A177.7 (4)S2'F—C2'F—N3'F—C4'F179.9 (3)
N3'A—C4'A—C5'A—C6'A1.5 (5)C2'F—N3'F—C4'F—O4'F178.3 (4)
C4'A—C5'A—C6'A—N1'A0.5 (5)C2'F—N3'F—C4'F—C5'F0.4 (5)
C4'A—C5'A—C6'A—C7'A179.4 (3)O4'F—C4'F—C5'F—C6'F179.0 (4)
C2'A—N1'A—C6'A—C5'A1.1 (5)N3'F—C4'F—C5'F—C6'F0.3 (5)
C2'A—N1'A—C6'A—C7'A178.9 (3)C4'F—C5'F—C6'F—N1'F0.7 (5)
C5'A—C6'A—C7'A—C8'A1.3 (5)C4'F—C5'F—C6'F—C7'F179.6 (3)
N1'A—C6'A—C7'A—C8'A178.7 (3)C2'F—N1'F—C6'F—C5'F0.4 (5)
C6'A—C7'A—C8'A—C9'A178.2 (3)C2'F—N1'F—C6'F—C7'F179.4 (3)
C6'B—N1'B—C2'B—N3'B0.0 (5)C5'F—C6'F—C7'F—C8'F3.0 (5)
C6'B—N1'B—C2'B—S2'B177.9 (3)N1'F—C6'F—C7'F—C8'F178.0 (3)
N1'B—C2'B—N3'B—C4'B3.1 (5)C6'F—C7'F—C8'F—C9'F179.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O4Di0.882.032.904 (5)169
N61A—H61A···O4Eii0.882.052.921 (5)171
N21B—H21B···O4A0.882.042.906 (5)170
N61B—H61B···O4Fiii0.882.032.893 (5)169
N21C—H21C···O4B0.882.012.873 (5)168
N61C—H61C···O4Civ0.882.072.934 (5)165
N1A—H1A···O24A0.882.032.892 (4)167
N3A—H3A···S2D0.882.423.279 (3)166
N1B—H1B···O24B0.882.002.859 (5)165
N3B—H3B···S2E0.882.433.286 (4)165
N1C—H1C···O24C0.882.092.951 (4)166
N3C—H3C···S2F0.882.453.313 (3)166
N1D—H1D···O64Av0.882.002.870 (5)168
N3D—H3D···S2A0.882.453.317 (3)168
N1E—H1E···O64Bvi0.882.062.919 (4)166
N3E—H3E···S2B0.882.493.358 (3)168
N1F—H1F···O64Cvii0.882.082.944 (4)166
N3F—H3F···S2C0.882.493.359 (3)168
Symmetry codes: (i) x, y+1, z; (ii) x+1/4, y1/4, z1/4; (iii) x+3/4, y1/4, z+1/4; (iv) x1/4, y+5/4, z1/4; (v) x+1/4, y+1/4, z+1/4; (vi) x+3/4, y+1/4, z1/4; (vii) x+5/4, y+1/4, z+1/4.
(III) 6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one top
Crystal data top
C7H10N2OSDx = 1.356 Mg m3
Mr = 170.23Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 9432 reflections
a = 10.4340 (6) Åθ = 3.4–25.9°
b = 11.1320 (6) ŵ = 0.33 mm1
c = 28.7090 (17) ÅT = 173 K
V = 3334.6 (3) Å3Block, colourless
Z = 160.40 × 0.20 × 0.20 mm
F(000) = 1440
Data collection top
Stoe IPDS II two-circle
diffractometer
3131 independent reflections
Radiation source: fine-focus sealed tube1990 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.132
ω scansθmax = 25.6°, θmin = 3.4°
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
h = 1212
Tmin = 0.879, Tmax = 0.937k = 1313
29872 measured reflectionsl = 3134
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093H-atom parameters constrained
S = 0.91 w = 1/[σ2(Fo2) + (0.0362P)2]
where P = (Fo2 + 2Fc2)/3
3131 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C7H10N2OSV = 3334.6 (3) Å3
Mr = 170.23Z = 16
Orthorhombic, PbcaMo Kα radiation
a = 10.4340 (6) ŵ = 0.33 mm1
b = 11.1320 (6) ÅT = 173 K
c = 28.7090 (17) Å0.40 × 0.20 × 0.20 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
3131 independent reflections
Absorption correction: multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
1990 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.937Rint = 0.132
29872 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.093H-atom parameters constrained
S = 0.91Δρmax = 0.19 e Å3
3131 reflectionsΔρmin = 0.25 e Å3
201 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
N1A0.8859 (2)0.2776 (2)0.57732 (8)0.0214 (5)
H1A0.88380.19900.58060.026*
C2A0.9065 (3)0.3450 (2)0.61574 (9)0.0181 (6)
S2A0.92485 (8)0.28630 (6)0.66912 (2)0.02394 (17)
N3A0.9118 (2)0.46603 (19)0.60853 (8)0.0206 (5)
H3A0.92520.51200.63300.025*
C4A0.8978 (3)0.5223 (2)0.56577 (10)0.0212 (6)
O4A0.9048 (2)0.63362 (16)0.56353 (7)0.0288 (5)
C5A0.8741 (3)0.4450 (2)0.52715 (11)0.0230 (6)
H5A0.86250.47810.49690.028*
C6A0.8680 (3)0.3243 (2)0.53336 (10)0.0196 (6)
C7A0.8417 (3)0.2344 (3)0.49555 (11)0.0242 (7)
H7A10.79520.16540.50930.029*
H7A20.92460.20400.48360.029*
C8A0.7643 (3)0.2822 (3)0.45478 (13)0.0349 (8)
H8A10.68420.31890.46670.042*
H8A20.81400.34580.43890.042*
C9A0.7306 (3)0.1846 (3)0.41987 (13)0.0337 (8)
H9A10.80950.14740.40820.050*
H9A20.68330.22010.39380.050*
H9A30.67740.12360.43500.050*
N1B0.8939 (2)0.98578 (19)0.67050 (8)0.0215 (5)
H1B0.89031.06440.66750.026*
C2B0.9147 (3)0.9196 (2)0.63148 (10)0.0209 (6)
S2B0.93405 (8)0.98091 (6)0.57878 (3)0.02508 (19)
N3B0.9176 (2)0.79850 (19)0.63823 (8)0.0205 (5)
H3B0.93120.75310.61360.025*
C4B0.9008 (3)0.7404 (2)0.68095 (11)0.0239 (7)
O4B0.9026 (2)0.62950 (17)0.68242 (7)0.0300 (5)
C5B0.8849 (3)0.8183 (3)0.72011 (10)0.0244 (6)
H5B0.87910.78490.75050.029*
C6B0.8780 (3)0.9383 (3)0.71454 (10)0.0221 (6)
C7B0.8538 (3)1.0276 (3)0.75279 (12)0.0303 (7)
H7B10.81291.09960.73910.036*
H7B20.93741.05290.76590.036*
C8B0.7705 (4)0.9829 (3)0.79208 (15)0.0402 (9)
H8B10.81200.91230.80670.048*
H8B20.68710.95650.77930.048*
C9B0.7475 (3)1.0777 (3)0.82892 (14)0.0383 (8)
H9B10.82991.10750.84050.057*
H9B20.69871.04270.85470.057*
H9B30.69891.14440.81540.057*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0306 (13)0.0130 (10)0.0205 (13)0.0002 (9)0.0014 (10)0.0006 (11)
C2A0.0181 (14)0.0156 (13)0.0205 (14)0.0002 (11)0.0011 (11)0.0007 (11)
S2A0.0348 (4)0.0190 (3)0.0180 (3)0.0003 (3)0.0025 (3)0.0004 (3)
N3A0.0266 (13)0.0146 (11)0.0207 (13)0.0019 (10)0.0020 (11)0.0022 (9)
C4A0.0268 (16)0.0147 (13)0.0220 (15)0.0010 (11)0.0030 (12)0.0021 (12)
O4A0.0481 (13)0.0141 (9)0.0241 (10)0.0006 (9)0.0010 (10)0.0008 (8)
C5A0.0312 (16)0.0192 (14)0.0186 (15)0.0014 (12)0.0009 (12)0.0013 (12)
C6A0.0211 (14)0.0179 (13)0.0196 (15)0.0007 (11)0.0012 (11)0.0024 (12)
C7A0.0349 (17)0.0168 (15)0.0210 (16)0.0018 (12)0.0001 (12)0.0028 (12)
C8A0.046 (2)0.0318 (17)0.027 (2)0.0062 (16)0.0132 (14)0.0023 (16)
C9A0.0393 (18)0.0331 (17)0.029 (2)0.0054 (14)0.0051 (14)0.0012 (15)
N1B0.0322 (14)0.0135 (11)0.0189 (13)0.0006 (9)0.0005 (10)0.0008 (10)
C2B0.0204 (14)0.0195 (13)0.0227 (15)0.0000 (12)0.0027 (12)0.0031 (11)
S2B0.0378 (4)0.0177 (3)0.0197 (4)0.0041 (3)0.0017 (3)0.0002 (3)
N3B0.0289 (13)0.0130 (11)0.0196 (12)0.0017 (10)0.0007 (11)0.0027 (9)
C4B0.0224 (16)0.0222 (15)0.0270 (17)0.0005 (11)0.0027 (13)0.0007 (11)
O4B0.0490 (14)0.0135 (10)0.0275 (11)0.0024 (9)0.0004 (10)0.0021 (8)
C5B0.0343 (17)0.0211 (14)0.0178 (15)0.0033 (12)0.0037 (12)0.0010 (12)
C6B0.0249 (15)0.0219 (15)0.0195 (16)0.0028 (12)0.0043 (12)0.0035 (12)
C7B0.050 (2)0.0196 (14)0.0209 (16)0.0004 (13)0.0001 (14)0.0072 (14)
C8B0.047 (2)0.0318 (18)0.041 (2)0.0016 (16)0.0135 (17)0.0075 (17)
C9B0.049 (2)0.0366 (17)0.030 (2)0.0089 (15)0.0075 (15)0.0035 (17)
Geometric parameters (Å, º) top
N1A—C2A1.351 (4)N1B—C2B1.358 (4)
N1A—C6A1.378 (4)N1B—C6B1.380 (4)
N1A—H1A0.8800N1B—H1B0.8800
C2A—N3A1.364 (3)C2B—N3B1.363 (3)
C2A—S2A1.677 (3)C2B—S2B1.672 (3)
N3A—C4A1.386 (4)N3B—C4B1.397 (4)
N3A—H3A0.8800N3B—H3B0.8800
C4A—O4A1.243 (3)C4B—O4B1.236 (3)
C4A—C5A1.425 (4)C4B—C5B1.429 (4)
C5A—C6A1.357 (4)C5B—C6B1.348 (4)
C5A—H5A0.9500C5B—H5B0.9500
C6A—C7A1.502 (4)C6B—C7B1.503 (4)
C7A—C8A1.519 (5)C7B—C8B1.508 (5)
C7A—H7A10.9900C7B—H7B10.9900
C7A—H7A20.9900C7B—H7B20.9900
C8A—C9A1.519 (5)C8B—C9B1.514 (5)
C8A—H8A10.9900C8B—H8B10.9900
C8A—H8A20.9900C8B—H8B20.9900
C9A—H9A10.9800C9B—H9B10.9800
C9A—H9A20.9800C9B—H9B20.9800
C9A—H9A30.9800C9B—H9B30.9800
C2A—N1A—C6A124.0 (2)C2B—N1B—C6B124.6 (2)
C2A—N1A—H1A118.0C2B—N1B—H1B117.7
C6A—N1A—H1A118.0C6B—N1B—H1B117.7
N1A—C2A—N3A115.5 (2)N1B—C2B—N3B115.0 (3)
N1A—C2A—S2A123.2 (2)N1B—C2B—S2B123.0 (2)
N3A—C2A—S2A121.3 (2)N3B—C2B—S2B122.0 (2)
C2A—N3A—C4A125.2 (2)C2B—N3B—C4B125.4 (2)
C2A—N3A—H3A117.4C2B—N3B—H3B117.3
C4A—N3A—H3A117.4C4B—N3B—H3B117.3
O4A—C4A—N3A119.4 (3)O4B—C4B—N3B119.4 (3)
O4A—C4A—C5A124.9 (3)O4B—C4B—C5B125.5 (3)
N3A—C4A—C5A115.7 (2)N3B—C4B—C5B115.1 (2)
C6A—C5A—C4A120.3 (3)C6B—C5B—C4B120.9 (3)
C6A—C5A—H5A119.9C6B—C5B—H5B119.5
C4A—C5A—H5A119.9C4B—C5B—H5B119.5
C5A—C6A—N1A119.2 (3)C5B—C6B—N1B118.8 (3)
C5A—C6A—C7A125.0 (3)C5B—C6B—C7B125.3 (3)
N1A—C6A—C7A115.8 (2)N1B—C6B—C7B115.9 (2)
C6A—C7A—C8A114.9 (2)C6B—C7B—C8B115.2 (3)
C6A—C7A—H7A1108.6C6B—C7B—H7B1108.5
C8A—C7A—H7A1108.6C8B—C7B—H7B1108.5
C6A—C7A—H7A2108.6C6B—C7B—H7B2108.5
C8A—C7A—H7A2108.6C8B—C7B—H7B2108.5
H7A1—C7A—H7A2107.5H7B1—C7B—H7B2107.5
C9A—C8A—C7A112.4 (3)C7B—C8B—C9B112.6 (3)
C9A—C8A—H8A1109.1C7B—C8B—H8B1109.1
C7A—C8A—H8A1109.1C9B—C8B—H8B1109.1
C9A—C8A—H8A2109.1C7B—C8B—H8B2109.1
C7A—C8A—H8A2109.1C9B—C8B—H8B2109.1
H8A1—C8A—H8A2107.9H8B1—C8B—H8B2107.8
C8A—C9A—H9A1109.5C8B—C9B—H9B1109.5
C8A—C9A—H9A2109.5C8B—C9B—H9B2109.5
H9A1—C9A—H9A2109.5H9B1—C9B—H9B2109.5
C8A—C9A—H9A3109.5C8B—C9B—H9B3109.5
H9A1—C9A—H9A3109.5H9B1—C9B—H9B3109.5
H9A2—C9A—H9A3109.5H9B2—C9B—H9B3109.5
C6A—N1A—C2A—N3A1.5 (4)C6B—N1B—C2B—N3B0.8 (4)
C6A—N1A—C2A—S2A178.6 (2)C6B—N1B—C2B—S2B179.7 (2)
N1A—C2A—N3A—C4A0.1 (4)N1B—C2B—N3B—C4B0.2 (4)
S2A—C2A—N3A—C4A179.9 (2)S2B—C2B—N3B—C4B179.2 (2)
C2A—N3A—C4A—O4A179.9 (3)C2B—N3B—C4B—O4B178.3 (3)
C2A—N3A—C4A—C5A1.0 (4)C2B—N3B—C4B—C5B2.7 (4)
O4A—C4A—C5A—C6A179.8 (3)O4B—C4B—C5B—C6B176.7 (3)
N3A—C4A—C5A—C6A0.8 (4)N3B—C4B—C5B—C6B4.4 (4)
C4A—C5A—C6A—N1A0.5 (4)C4B—C5B—C6B—N1B3.6 (4)
C4A—C5A—C6A—C7A179.0 (3)C4B—C5B—C6B—C7B176.3 (3)
C2A—N1A—C6A—C5A1.7 (4)C2B—N1B—C6B—C5B0.9 (4)
C2A—N1A—C6A—C7A177.8 (3)C2B—N1B—C6B—C7B179.0 (3)
C5A—C6A—C7A—C8A26.6 (4)C5B—C6B—C7B—C8B31.3 (5)
N1A—C6A—C7A—C8A152.9 (3)N1B—C6B—C7B—C8B148.6 (3)
C6A—C7A—C8A—C9A174.9 (3)C6B—C7B—C8B—C9B178.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···S2Bi0.882.483.341 (2)165
N3A—H3A···O4B0.881.942.797 (3)163
N1B—H1B···S2Aii0.882.503.361 (2)167
N3B—H3B···O4A0.881.982.826 (3)161
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC4H5N3·2C7H10N2OSC9H11N3O2·2C7H10N2OSC7H10N2OS
Mr435.57533.67170.23
Crystal system, space groupMonoclinic, P21/cOrthorhombic, Fdd2Orthorhombic, Pbca
Temperature (K)173173173
a, b, c (Å)7.6094 (5), 12.9888 (6), 20.8838 (14)37.9355 (12), 76.880 (3), 10.5666 (3)10.4340 (6), 11.1320 (6), 28.7090 (17)
α, β, γ (°)90, 99.179 (5), 9090, 90, 9090, 90, 90
V3)2037.7 (2)30817.3 (18)3334.6 (3)
Z44816
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.290.250.33
Crystal size (mm)0.60 × 0.20 × 0.150.50 × 0.30 × 0.200.40 × 0.20 × 0.20
Data collection
DiffractometerStoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Stoe IPDS II two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Spek, 2009; Blessing, 1995)
Multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
Multi-scan
(MULABS; Spek, 2009; Blessing, 1995)
Tmin, Tmax0.844, 0.9580.885, 0.9510.879, 0.937
No. of measured, independent and
observed [I > 2σ(I)] reflections
25516, 3819, 3163 108254, 14445, 10225 29872, 3131, 1990
Rint0.0940.1290.132
(sin θ/λ)max1)0.6090.6090.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.105, 1.05 0.047, 0.097, 0.91 0.046, 0.093, 0.91
No. of reflections3819144453131
No. of parameters289985201
No. of restraints010
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.290.22, 0.250.19, 0.25
Absolute structure?Flack (1983), 6784 Friedel pairs?
Absolute structure parameter?0.12 (7)?

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

Selected torsion angles (º) for (I) top
N1A—C6A—C7A—C8A162.10 (17)N1B—C6B—C7B—C8B150.28 (17)
C6A—C7A—C8A—C9A78.4 (2)C6B—C7B—C8B—C9B176.90 (17)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N21—H211···S2B0.89 (2)2.63 (2)3.5145 (17)173 (2)
N21—H212···S2A0.87 (2)2.77 (2)3.6234 (18)168 (2)
N1A—H1A···O4Ai0.83 (2)2.17 (2)2.983 (2)167 (2)
N3A—H3A···N30.87 (2)2.06 (2)2.926 (2)174 (2)
N1B—H1B···O4Bii0.82 (2)2.31 (2)3.107 (2)166 (2)
N3B—H3B···N10.88 (2)2.10 (2)2.975 (2)175 (2)
Symmetry codes: (i) x+2, y1/2, z+1/2; (ii) x+1, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O4'Di0.882.032.904 (5)169
N61A—H61A···O4'Eii0.882.052.921 (5)171
N21B—H21B···O4'A0.882.042.906 (5)170
N61B—H61B···O4'Fiii0.882.032.893 (5)169
N21C—H21C···O4'B0.882.012.873 (5)168
N61C—H61C···O4'Civ0.882.072.934 (5)165
N1'A—H1'A···O24A0.882.032.892 (4)167
N3'A—H3'A···S2'D0.882.423.279 (3)166
N1'B—H1'B···O24B0.882.002.859 (5)165
N3'B—H3'B···S2'E0.882.433.286 (4)165
N1'C—H1'C···O24C0.882.092.951 (4)166
N3'C—H3'C···S2'F0.882.453.313 (3)166
N1'D—H1'D···O64Av0.882.002.870 (5)168
N3'D—H3'D···S2'A0.882.453.317 (3)168
N1'E—H1'E···O64Bvi0.882.062.919 (4)166
N3'E—H3'E···S2'B0.882.493.358 (3)168
N1'F—H1'F···O64Cvii0.882.082.944 (4)166
N3'F—H3'F···S2'C0.882.493.359 (3)168
Symmetry codes: (i) x, y+1, z; (ii) x+1/4, y1/4, z1/4; (iii) x+3/4, y1/4, z+1/4; (iv) x1/4, y+5/4, z1/4; (v) x+1/4, y+1/4, z+1/4; (vi) x+3/4, y+1/4, z1/4; (vii) x+5/4, y+1/4, z+1/4.
Selected torsion angles (º) for (III) top
N1A—C6A—C7A—C8A152.9 (3)N1B—C6B—C7B—C8B148.6 (3)
C6A—C7A—C8A—C9A174.9 (3)C6B—C7B—C8B—C9B178.8 (3)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···S2Bi0.882.483.341 (2)164.6
N3A—H3A···O4B0.881.942.797 (3)162.6
N1B—H1B···S2Aii0.882.503.361 (2)167.3
N3B—H3B···O4A0.881.982.826 (3)161.3
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.
R.m.s. deviations (Å) for all non-H atoms and selected geometric parameters (°) of 6-propyl-2-thiouracil for (II). top
MoleculeR.m.s deviationN1'—C6'—C7'—C8'C6'—C7'—C8'—C9'
A'0.024178.7 (3)-178.2 (3)
B'0.028-178.2 (3)178.8 (3)
C'0.028176.9 (3)178.1 (3)
D'0.018176.7 (3)178.0 (3)
E'0.017-178.4 (3)-177.4 (3)
F'0.012-178.0 (3)179.8 (3)
Selected geometric parameters (°) of N-(6-acetamidopyridin-2-yl)acetamide for (II). top
MoleculeN1—C2—N21—C22C2—N21—C22—C23N1—C6—N61—C62C6—N61—C62—C63
A-167.1 (4)179.9 (3)-166.1 (4)178.5 (4)
B167.9 (3)179.7 (3)166.5 (3)179.1 (4)
C-169.8 (4)-177.8 (4)-167.2 (3)-177.9 (3)
Dihedral angles (°) between the pyridine ring and the amide groups of N-(6-acetamidopyridin-2-yl)acetamide [designated by α (N21) and β (N61)] for (II). top
Moleculeαβ
A13.4 (1)15.4 (1)
B12.6 (1)14.6 (1)
C12.6 (1)15.6 (1)
Dihedral angles (°) within the three symmetry-independent complexes for (II). γ designates the angle between two 6-propyl-2-thiouracil molecules and δ designates the angle between the pyridine ring and the central 6-propyl-2-thiouracil molecule. top
Complexγδ
AA'D'7.3 (1)9.7 (1)
BB'E'11.9 (1)2.0 (1)
CC'F'4.4 (1)7.3 (1)
 

Acknowledgements

The authors thank Dr Michael Bolte for helpful discussions.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals
First citationAntoniadis, C. D., Blake, A. J., Hadjikakou, S. K., Hadjiliadis, N., Hubberstey, P., Schröder, M. & Wilson, C. (2006). Acta Cryst. B62, 580–591.  Web of Science CSD CrossRef CAS IUCr Journals
First citationAntoniadis, C. D., Corban, G. J., Hadjikakou, S. K., Hadjiliadis, N., Kubicki, M., Warner, S. & Butler, I. S. (2003). Eur. J. Inorg. Chem. pp. 1635–1640.  CSD CrossRef
First citationBahn, R. S., Burch, H. S., Cooper, D. S., Garber, J. R., Greenlee, C. M., Klein, I. L., Laurberg, P., McDougall, I. R., Rivkees, S. A., Ross, D., Sosa, J. A. & Stan, M. N. (2009). Thyroid, 19, 673–674.  CrossRef PubMed CAS
First citationBalalaie, S., Bararjanian, M. & Rominger, F. (2006). J. Heterocycl. Chem. 43, 821–826.  CrossRef CAS
First citationBasilio Janke, E. M., Dunger, A., Limbach, H.-H. & Weisz, K. (2001). Magn. Reson. Chem. 39, 177–182.  CrossRef
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 citationBiswal, H. S. & Wategaonkar, S. (2009). J. Phys. Chem. A, 113, 12763–12773.  Web of Science CrossRef PubMed CAS
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals
First citationBranch, C. L., Eggleston, D. S., Haltiwanger, R. C., Kaura, A. C. & Tyler, J. W. (1996). Synth. Commun. 26, 2075–2084.  CrossRef CAS Web of Science
First citationChierotti, M. R., Ferrero, L., Garino, N., Gobetto, R., Pellegrino, L., Braga, D., Grepioni, F. & Maini, L. (2010). Chem. Eur. J. 16, 4347–4358.  Web of Science CSD CrossRef CAS PubMed
First citationCooper, D. S. (2005). N. Engl. J. Med. 352, 905–917.  Web of Science CrossRef PubMed CAS
First citationCoxall, R. A., Harris, S. G., Henderson, D. K., Parsons, S., Tasker, P. A. & Winpenny, R. E. P. (2000). J. Chem. Soc. Dalton Trans. pp. 2349–2356.  Web of Science CSD CrossRef
First citationDomagała, M., Grabowski, S. J., Urbaniak, K. & Mlostón, G. (2003). J. Phys. Chem. A, 107, 2730–2736.
First citationFavre, A., Saintomé, C., Fourrey, J.-L., Clivio, P. & Laugâa, P. (1998). J. Photochem. Photobiol. B, 42, 109–124.  CrossRef CAS PubMed
First citationFerrari, M. B., Fava, G. G., Pelosi, G., Rodriguez-Argüelles, M. C. & Tarasconi, P. (1995). J. Chem. Soc. Dalton Trans. pp. 3035–3040.  CSD CrossRef Web of Science
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals
First citationHawkinson, S. W. (1975). Acta Cryst. B31, 2153–2156.  CSD CrossRef CAS IUCr Journals Web of Science
First citationHori, A., Ishida, Y., Kikuchi, T., Miyamoto, K. & Sakaguchi, H. (2009). Acta Cryst. C65, o593–o597.  Web of Science CSD CrossRef IUCr Journals
First citationHu, S.-L., Yin, G.-D. & Wu, A.-X. (2005). Acta Cryst. E61, o2408–o2409.  Web of Science CSD CrossRef IUCr Journals
First citationLautié, A. & Novak, A. (1980). Chem. Phys. Lett. 71, 290–293.
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 citationLong, T., Zhou, H.-B. & Wu, A.-X. (2005). Acta Cryst. E61, o2169–o2171.  Web of Science CSD CrossRef IUCr Journals
First citationLuo, W., Yu, Q.-S., Tweedie, D., Deschamps, J., Parrish, D., Holloway, H. W., Li, Y., Brossi, A. & Greig, N. H. (2008). Synthesis, 21, 3415–3422.
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 citationMunshi, P. & Guru Row, T. N. (2006). Acta Cryst. B62, 612–626.  Web of Science CSD CrossRef CAS IUCr Journals
First citationOkabe, N., Fujiwara, T., Yamagata, Y. & Tomita, K. (1983). Bull. Chem. Soc. Jpn, 56, 1543–1544.  CrossRef CAS Web of Science
First citationOrzeszko, B., Kazimierczuk, Z., Maurin, J. K., Laudy, A. E., Starościak, B. J., Vilpo, J., Vilpo, L., Balzarini, J. & Orzeszko, A. (2004). Il Farmaco, 59, 929–937.  CrossRef PubMed CAS
First citationPawlowski, M., Lendzion, A., Szawkalo, J., Leniewski, A., Maurin, J. K. & Czarnocki, Z. (2009). Phosphorus Sulfur Silicon Relat. Elem. 184, 1307–1313.  CAS
First citationRead, G., Randal, R., Hursthouse, M. B. & Short, R. (1988). J. Chem. Soc. Perkin Trans. 2, pp. 1103–1105.  CSD CrossRef Web of Science
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals
First citationŠponer, J., Leszczynski, J. & Hobza, P. (1997). J. Phys. Chem. A, 101, 9489–9495.
First citationStoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.
First citationTashkhodzhaev, B., Turgunov, K. K., Usmanova, B., Averkiev, B. B., Antipin, M. Yu. & Shakhidoyatov, Kh. M. (2002). Zh. Strukt. Khim. 43, 944–948.
First citationTesta, S. M., Disney, M. D., Turner, D. H. & Kierzek, R. (1999). Biochemistry, 38, 16655–16662.  Web of Science CrossRef PubMed CAS
First citationTiekink, E. R. T. (1989). Z. Kristallogr. 187, 79–84.  CrossRef CAS Web of Science
First citationVoutsas, G. P., Venetopoulos, C. C., Kálmán, A., Párkányi, L., Hornyák, G. & Lempert, K. (1978). Tetrahedron Lett. 19, 4431–4434.  CSD CrossRef
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals
First citationXue, S.-J., Wang, Q.-D. & Li, J.-Z. (2006). Acta Cryst. C62, o666–o668.  Web of Science CSD CrossRef CAS IUCr Journals

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