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In order to examine the preferred hydrogen-bonding pattern of various uracil derivatives, namely 5-(hy­droxy­meth­yl)uracil, 5-carb­oxy­uracil and 5-carb­oxy-2-thio­uracil, and for a conformational study, crystallization experiments yielded eight different structures: 5-(hy­droxy­meth­yl)uracil, C5H6N2O3, (I), 5-carb­oxy­ura­cil–N,N-di­methyl­formamide (1/1), C5H4N2O4·C3H7NO, (II), 5-carb­oxy­ura­cil–dimethyl sulfoxide (1/1), C5H4N2O4·C2H6OS, (III), 5-carb­oxy­uracil–N,N-di­methyl­acetamide (1/1), C5H4N2O4·C4H9NO, (IV), 5-carb­oxy-2-thio­uracil–N,N-di­methyl­formamide (1/1), C5H4N2O3S·C3H7NO, (V), 5-carb­oxy-2-thio­ura­cil–dimethyl sulfoxide (1/1), C5H4N2O3S·C2H6OS, (VI), 5-carb­oxy-2-thio­uracil–1,4-dioxane (2/3), 2C5H4N2O3S·3C6H12O3, (VII), and 5-carb­oxy-2-thio­uracil, C10H8N4O6S2, (VIII). While the six solvated structures, i.e. (II)–(VII), contain intra­molecular S(6) O—H...O hydrogen-bond motifs between the carb­oxy and carbonyl groups, the usually favoured R22(8) pattern between two carb­oxy groups is formed in the solvent-free structure, i.e. (VIII). Further R22(8) hydrogen-bond motifs involving either two N—H...O or two N—H...S hydrogen bonds were observed in three crystal structures, namely (I), (IV) and (VIII). In all eight structures, the residue at the ring 5-position shows a coplanar arrangement with respect to the pyrimidine ring which is in agreement with a search of the Cambridge Structural Database for six-membered cyclic compounds containing a carb­oxy group. The search confirmed that coplanarity between the carb­oxy group and the cyclic residue is strongly favoured.

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Supplementary material

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CCDC references: 1470144; 1470143; 1470142; 1470141; 1470140; 1470139; 1470138; 1470137

Introduction top

One of the main targets of crystal engineering is to establish reliable inter­molecular inter­action motifs, so-called synthons, which are suitable for the design of new crystal structures of molecular compounds (Desiraju, 2007). Especially hydrogen bonds are one of the most used inter­molecular inter­actions in crystal engineering due to their strength and directionality (Aakeröy, 1997). Among the hydrogen-bonded synthons, the R22(8) motif is of particular importance (Bernstein et al., 1995) as it is formed by a large number of functional groups, for example, by carb­oxy or amide groups (Blagden et al., 2007; Rodríguez-Cuamatzi et al., 2007). The three compounds 5-(hy­droxy­methyl)­uracil (5HMU), 5-carb­oxy­uracil (5CU) and 5-carb­oxy-2-thio­uracil (5CTU) show various biologically important properties: 5HMU is one of the major oxidative modifications of thymine and might be used as a biomarker in order to estimate biologically effective levels of carcinogen exposure (Bianchini et al., 1998); 5CU exhibits anti­tumour, anti-HIV and anti­epileptic activity (Ross et al., 1960; Lea et al., 1992; Nichol & Clegg, 2009); and 5CTU, as well as its derivatives, exhibits anti­cancer and anti­bacterial properties (Hueso-Urena & Moreno-Carretero, 1995). All three compounds are well suited for the formation of hydrogen-bonded networks within crystal and cocrystal structures since they all contain an ADA (A = acceptor and D = donor) and an AD site. In addition, they are capable of forming an intra­molecular S(6) motif involving an O—H···O hydrogen bond between the OH group of the hy­droxy­methyl group (5HMU) or the carb­oxy group (5CU and 5CTU) and the carbonyl group at atom C4. The formation of this intra­molecular hydrogen bond is possible only if atom C4 and the O atom of the hy­droxy group adopt a synperiplanar arrangement (defined via the torsion angle ω). In the case of 5CU and 5CTU, this is important for the formation of R22(8) carb­oxy-carb­oxy dimers since the intra­molecular hydrogen bonds would prevent the formation of inter­molecular hydrogen bonds. A search of the Cambridge Structural Database (CSD, Version 5.37, November 2015; Groom & Allen, 2014) restricted to organic and not polymeric structures yielded no match for 5HMU, two hits for 5CU, namely 5-carb­oxy­uracil monohydrate (CSD refcode AYEBIP; Law et al., 2004) and 4,4'-bipyridin-1-ium uracil-5-carboxyl­ate–4,4'-bi­pyridine–5-carb­oxy­uracil (2/1/4) (HOXHIM; Nichol & Clegg, 2009), and one hit for 5CTU, viz. 5-carb­oxy-2-thio­uracil monohydrate (QEHSEB; Tiekink, 2001). In order to gain more information about the preferred hydrogen-bonding patterns of 5HMU, 5CU and 5CTU and to point out the preferred conformation of the residue bonded to atom C5 we performed crystallization experiments from different solvents yielding two solvent free structures, (I) and (VIII), as well as the six new solvates (II)–(VII).

Experimental top

Synthesis and crystallization top

Crystals of (I)–(VIII) were obtained by isothermal solvent evaporation experiments under different conditions from commercially available uracil derivatives and various solvents (Table 1). All solvents were applied without further purification and the crystallization experiments were performed at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms, except those of the disordered solvent molecules, were located initially by difference Fourier synthesis. Carbon-bound H atoms were placed in calculated positions and 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. Free rotation about the local threefold axis was allowed for all methyl groups except those of the minor-occupied sites of the disordered DMAC molecule in (IV) and the minor-occupied conformation of the rotationally disordered methyl group of the DMF molecule in (V). H atoms bonded to O atoms or N atoms were refined isotropically with the isotropic displacement parameters coupled to the equivalent isotropic displacement parameters of the parent N atoms or O atoms, with Uiso(H) = 1.2Ueq(N,O). Tentative free refinements of their positional coordinates resulted in an unsatisfactory wide range of D—H distances; bond lengths were therefore restrained to 0.88 (2) Å for N—H and to 0.84 (2) Å for O—H.

In (IV), the DMAC molecule is disordered over a pseudo-mirror plane along atoms O21X and C12X perpendicular to the molecular plane [site-occupancy factor for the major-occupied orientation = 0.644 (9)]. For the DMAC molecule, similarity restraints for the 1,2- and 1,3-distances were applied as well as the similar-ADP and the rigid-bond (Hirshfeld, 1976) restraints (SIMU and DELU in SHELXL2014; Sheldrick, 2015).

In (IV) [(V)?], the H atoms of the C11X methyl group of the DMF molecule show a rotational disorder [site-occupancy factor for the major-occupied conformation = 0.55 (3)].

Results and discussion top

5-(Hy­droxy­methyl)­uracil, (I), crystallizes in the triclinic space group P1 with one planar molecule in the asymmetric unit (r.m.s deviation for all non-H atoms = 0.040 Å), whereby atoms C4A and O51A exhibit an anti­periplanar conformation [ω = 175.0 (2)°] (Fig. 1). In the packing, chains of 5HMU molecules are formed via R22(8) N—H···O hydrogen-bond motifs, which are extended to a two-dimensional network via R24(16) and R44(20) patterns involving further O—H···O hydrogen bonds (Fig. 2 and Table 3).

The DMF solvate of 5-carb­oxy­uracil, (II), crystallizes in the monoclinic space group P21/c. The asymmetric unit consists of one planar 5CU molecule (A) and one DMF molecule (X) connected by an N—H···O hydrogen bond and enclosing a dihedral angle of 7.75 (14)° (r.m.s deviations for all non-H atoms = 0.047 Å for A and 0.009 Å for X). Atoms C4A and O52A adopt a synperiplanar conformation [ω = -3.0 (5)°] and an S(6) motif is formed via an O—H···O hydrogen bond (Fig. 3). In the packing, additional R22(9) patterns consisting of one N—H···O and one C—H···O hydrogen bond are formed between the 5CU molecules yielding chains running along the b axis whereby the DMF molecules are located at both sides of the chains (Fig. 4 and Table 4).

The DMSO solvate of 5-carb­oxy­uracil, (III), crystallizes in the monoclinic space group P21/c with one planar 5CU molecule (A; r.m.s. deviation for all non-H atoms = 0.010 Å) and one DMSO molecule (X) in the asymmetric unit. Atoms C4A and O52A show a synperiplanar arrangement [ω = 0.4 (4)°] leading to the S(6) O—H···O motif and molecules A and X are connected via a single N—H···O hydrogen bond (Fig. 5). In the packing, R23(9) patterns are formed consisting of two N—H···O hydrogen bonds and a weak C—H···O hydrogen bond yielding chains running along the b axis incorporating the DMSO molecules into the chains (Fig. 6 and Table 5).

The DMAC solvate of 5-carb­oxy­uracil, (IV), crystallizes in the monoclinic space group P21/n. The asymmetric unit consists of one 5CU molecule (A) and one disordered DMAC molecule (X), and the two molecules are connected by an N—H···O hydrogen bond enclosing a dihedral angle of 54.34 (6)° (r.m.s deviations for all non-H atoms = 0.030 Å for A and 0.041 Å for X) (Fig. 7). Again, atoms C4A and O52A show a synperiplanar arrangement [ω = 2.1 (4)°], forming the S(6) O—H···O hydrogen-bond motif. In the crystal packing, homodimers of 5CU molecules are formed via R22(8) N—H···O hydrogen bonds and the dimers show a herring-bone like arrangement whereby atom O51A is not involved in hydrogen bonds but only in weak electrostatic inter­actions (Fig. 8 and Table 6).

5-Carb­oxy-2-thio­uracil–N,N-di­methyl­formamide (1/1), (V), crystallizes in the monoclinic space group P21/c with one 5CTU molecule (A) and one DMF molecule (X) in the asymmetric unit (Fig. 9). 5CTU molecule A exhibits an S(6) O—H···O hydrogen-bond motif [ω = 1.7 (3)°] and is linked to DMF molecule X by an N—H···O hydrogen bond enclosing a dihedral angle of 11.27 (10)° (r.m.s deviations for all non-H atoms = 0.014 Å for A and 0.014 Å for X). In the crystal packing, the 5CTU molecules form zigzag-like chains running along the b axis via R22(7) N—H···O and C—H···O hydrogen-bond motifs (Fig. 10 and Table 7).

The DMSO solvate of 5-carb­oxy-2-thio­uracil, (VI), crystallizes in the triclinic space group P1 with one planar 5CTU molecule (A; r.m.s deviation for all non-H atoms = 0.040 Å) and one DMSO molecule (X) in the asymmetric unit (Fig. 11). Once more, an intra­molecular S(6) O—H···O hydrogen-bond motif is formed [ω = 5.3 (2)°] and 5CTU molecule A is connected to DMSO molecule X via a single N—H···O hydrogen bond. In the crystal packing, molecules are connected by C21(6) inter­actions consisting of N—H···O hydrogen bonds, resulting in chains running along the a axis (Fig. 12 and Table 8).

The dioxane solvate of 5-carb­oxy-2-thio­uracil, (VII), crystallizes in the triclinic space group P1. The asymmetric unit consists of one planar 5CTU molecule (A; r.m.s deviation for all non-H atoms = 0.030 Å) and three independent halves of dioxane molecules (X, Y and Z), since the solvent molecules are located at special positions (Fig. 13). Solvent molecules X and Z are connected to 5CTU molecule A via single N—H···O hydrogen bonds and an intra­molecular S(6) O—H···O hydrogen-bond motif formed by A is present as well [ω = 0.2 (2)°]. Molecules A and X enclose a dihedral angle of 74.62 (7)°, and A and Z enclose a dihedral angle of 78.2 (7)° (with the mean planes of the dioxane molecules defined by the four C atoms of each molecule). In the packing, a two-dimensional network is formed via single N—H···O hydrogen bonds and R22(10) C—H···O hydrogen-bond motifs, whereby dioxane molecule Y does not form any hydrogen bonds and is located in the centre of a mesh characterized by an R1010(46) pattern (Fig. 14 and Table 9).

The ansolvate of 5-carb­oxy-2-thio­uracil, (VIII), crystallizes in the monoclinic space group P21/c with two planar molecules A and B in the asymmetric unit (r.m.s. deviations for all non-H atoms = 0.053 Å for A and 0.046 Å for B). Molecules A and B are linked via R22(8) N—H···S hydrogen-bond motifs and are slightly tilted against each other enclosing a dihedral angle of 5.54 (19)° (Fig. 15). No intra­molecular hydrogen bond is formed since the carb­oxy groups of adjacent 5CTU molecules form R22(8) O—H···O hydrogen-bond mofits even though atoms C4A/B and O52A/B show synperiplanar conformations, respectively [ω = 1.0 (10)° for A and -4.0 (11)° for B]. In the packing, additional R12(6) and R21(5) motifs involving N—H···O and C—H···O hydrogen bonds are formed yielding a two-dimensional network (Fig. 16 and Table 10).

Comparing the structures of (I)–(VIII), R22(8) motifs involving two N—H···O hydrogen bonds were observed in (I) and (IV), whereas in (VIII), R22(8) N—H···S hydrogen-bond motifs are formed. An intra­molecular S(6) O—H···O motif was formed in six structures [i.e. (II)–(VII)], while in (VIII), the carb­oxy group is involved in an R22(8) O—H···O motif. In all cases, the carb­oxy group shows a coplanar arrangement compared to the pyrimidine ring, with atoms C4 and O52 adopting a synperiplanar conformation. This is in agreement with the CSD search which yielded the structures of the monohydrate structures of 5CU (AYEBIP; Law et al., 2004) and 5CTU (QEHSEB; Tiekink, 2001), respectively, where atoms C4 and O52 show a synperiplanar arrangement whereby inter­molecular O—H···O hydrogen bonds with the water molecules are formed in both cases. However, the only cocrystal structure, i.e. 4,4'-bipyridin-1-ium uracil-5-carboxyl­ate–4,4'-bi­pyridine–5-carb­oxy­uracil (2/1/4) (HOXHIM; Nichol & Clegg, 2009), shows that the structural flexibility is great enough that atoms C4 and O52 can adopt an anti­periplanar arrangement if necessary. In all three structures, R22(8) motifs are formed consisting of either two N—H···O (AYEBIP and HOXHIM) or two N—H···S hydrogen bonds (QEHSEB). A more generalized CSD search for six-membered cyclic molecules containing a carb­oxy group in the β-position of a carbonyl group (Fig. 17a) (restricted to organic and not polymeric structures with determined three-dimensional coordinates and without errors) confirmed that a coplanar arrangement of the carb­oxy group is strongly preferred not only in structures of molecules with the uracil substructure (Fig. 17b). All 94 structures show a synperiplanar conformation illustrated by the torsion angle ω and the values of ω observed in the structures of (II)–(VIII) lie well within the same range. Even in structures where no S(6) inter­action is possible due to the lack of a hydrogen-bond donor, like in GIMREA (an ansolvate of 5-formyl­uracil; Portalone & Colapietro, 2007) or DOTGID (cytosinium uracil-5-carboxyl­ate monohydrate; Portalone & Colapietro, 2009), a coplanar arrangement of the residue at atom C5 with respect to the pyrimidine ring is favoured, once more illustrating the preference for coplanarity.

A substructure search of the CSD for the respective isomeric compounds 6-(hy­droxy­methyl)­uracil (6HMU), 6-carb­oxy­uracil (6CU) and 6-carb­oxy-2-thio­uracil (6CTU), restricted to organic and not polymeric structures, yielded three hits for 6HMU, namely 6-(hy­droxy­methyl)­uracil–water (1/1) (CSD refcode HIMMUM; Spek & Kooljman, 2007), 6-(hy­droxy­methyl)­uracil–melamine–water (2/1/3) (REVVAQ; Kooijman et al., 2007) and 6-(hy­droxy­methyl)­uracil–2,4-di­amino-6-hy­droxy­methyl-1,3,5-triazine (1/1) (TUHJAH; Beijer et al., 1996), eight hits for 6CU, viz. 6-carb­oxy­uracil–water (1/1) [OROTAC (Takusagawa & Shimada, 1973) and OROTAC01 (Portalone, 2008)], 6-carb­oxy­uracil–melamine–water (1/1/1) (LIDCAE, LIDCAE01 and LIDCAE02; Xu et al., 2011), 6-carb­oxy­uracil–di­methyl sulfoxide (1/1), di­methyl­ammonium uracil-6-carboxyl­ate–6-carb­oxy­uracil (1/1) and di­methyl­ammonium uracil-6-carboxyl­ate–6-carb­oxy­uracil (3/1) (XARBEZ, XARBID and XARBOJ; Gerhardt et al., 2012), and one hit for 6CTU, viz. 6-carb­oxy-2-thio­uracil–di­methyl sulfoxide (1/1) (FOFLET; Papazoglou et al., 2014). In all these structures, R22(8) hydrogen-bond motifs consisting of two N—H···O hydrogen bonds are observed. In the cocrystal structures REVVAQ and TUHJAH, triply hydrogen-bonded ADA/DAD synthons are formed with the coformers melamine and 2,4-di­amino-6-hy­droxy­methyl-1,3,5-triazine, respectively. Except for HIMMUM, where the O atom of the hy­droxy group adopts a synclinal arrangement with respect to atom N1 of the pyrimidine ring, a coplanar arrangement compared to the pyrimidine ring is preferred in all structures.

In conclusion, even though 5-(hy­droxy­methyl)­uracil, 5-carb­oxy­uracil and 5-carb­oxy-2-thio­uracil tend to form intra­molecular S(6) O—H···O hydrogen-bond motifs, the structural flexibility is great enough for the formation of inter­molecular hydrogen bonds instead if a suitable coformer is present. Synthons involving R22(8) inter­actions are favourable for the formation of doubly hydrogen-bonded complexes, but triply hydrogen-bonded ADA/DAD synthons can be taken into account for the formation of cocrystals of these compounds as well. This knowledge is helpful in order to select suitable coformers for the design of cocrystals of the title compounds and, therefore, for the development of new solid materials.

Structure description top

One of the main targets of crystal engineering is to establish reliable inter­molecular inter­action motifs, so-called synthons, which are suitable for the design of new crystal structures of molecular compounds (Desiraju, 2007). Especially hydrogen bonds are one of the most used inter­molecular inter­actions in crystal engineering due to their strength and directionality (Aakeröy, 1997). Among the hydrogen-bonded synthons, the R22(8) motif is of particular importance (Bernstein et al., 1995) as it is formed by a large number of functional groups, for example, by carb­oxy or amide groups (Blagden et al., 2007; Rodríguez-Cuamatzi et al., 2007). The three compounds 5-(hy­droxy­methyl)­uracil (5HMU), 5-carb­oxy­uracil (5CU) and 5-carb­oxy-2-thio­uracil (5CTU) show various biologically important properties: 5HMU is one of the major oxidative modifications of thymine and might be used as a biomarker in order to estimate biologically effective levels of carcinogen exposure (Bianchini et al., 1998); 5CU exhibits anti­tumour, anti-HIV and anti­epileptic activity (Ross et al., 1960; Lea et al., 1992; Nichol & Clegg, 2009); and 5CTU, as well as its derivatives, exhibits anti­cancer and anti­bacterial properties (Hueso-Urena & Moreno-Carretero, 1995). All three compounds are well suited for the formation of hydrogen-bonded networks within crystal and cocrystal structures since they all contain an ADA (A = acceptor and D = donor) and an AD site. In addition, they are capable of forming an intra­molecular S(6) motif involving an O—H···O hydrogen bond between the OH group of the hy­droxy­methyl group (5HMU) or the carb­oxy group (5CU and 5CTU) and the carbonyl group at atom C4. The formation of this intra­molecular hydrogen bond is possible only if atom C4 and the O atom of the hy­droxy group adopt a synperiplanar arrangement (defined via the torsion angle ω). In the case of 5CU and 5CTU, this is important for the formation of R22(8) carb­oxy-carb­oxy dimers since the intra­molecular hydrogen bonds would prevent the formation of inter­molecular hydrogen bonds. A search of the Cambridge Structural Database (CSD, Version 5.37, November 2015; Groom & Allen, 2014) restricted to organic and not polymeric structures yielded no match for 5HMU, two hits for 5CU, namely 5-carb­oxy­uracil monohydrate (CSD refcode AYEBIP; Law et al., 2004) and 4,4'-bipyridin-1-ium uracil-5-carboxyl­ate–4,4'-bi­pyridine–5-carb­oxy­uracil (2/1/4) (HOXHIM; Nichol & Clegg, 2009), and one hit for 5CTU, viz. 5-carb­oxy-2-thio­uracil monohydrate (QEHSEB; Tiekink, 2001). In order to gain more information about the preferred hydrogen-bonding patterns of 5HMU, 5CU and 5CTU and to point out the preferred conformation of the residue bonded to atom C5 we performed crystallization experiments from different solvents yielding two solvent free structures, (I) and (VIII), as well as the six new solvates (II)–(VII).

5-(Hy­droxy­methyl)­uracil, (I), crystallizes in the triclinic space group P1 with one planar molecule in the asymmetric unit (r.m.s deviation for all non-H atoms = 0.040 Å), whereby atoms C4A and O51A exhibit an anti­periplanar conformation [ω = 175.0 (2)°] (Fig. 1). In the packing, chains of 5HMU molecules are formed via R22(8) N—H···O hydrogen-bond motifs, which are extended to a two-dimensional network via R24(16) and R44(20) patterns involving further O—H···O hydrogen bonds (Fig. 2 and Table 3).

The DMF solvate of 5-carb­oxy­uracil, (II), crystallizes in the monoclinic space group P21/c. The asymmetric unit consists of one planar 5CU molecule (A) and one DMF molecule (X) connected by an N—H···O hydrogen bond and enclosing a dihedral angle of 7.75 (14)° (r.m.s deviations for all non-H atoms = 0.047 Å for A and 0.009 Å for X). Atoms C4A and O52A adopt a synperiplanar conformation [ω = -3.0 (5)°] and an S(6) motif is formed via an O—H···O hydrogen bond (Fig. 3). In the packing, additional R22(9) patterns consisting of one N—H···O and one C—H···O hydrogen bond are formed between the 5CU molecules yielding chains running along the b axis whereby the DMF molecules are located at both sides of the chains (Fig. 4 and Table 4).

The DMSO solvate of 5-carb­oxy­uracil, (III), crystallizes in the monoclinic space group P21/c with one planar 5CU molecule (A; r.m.s. deviation for all non-H atoms = 0.010 Å) and one DMSO molecule (X) in the asymmetric unit. Atoms C4A and O52A show a synperiplanar arrangement [ω = 0.4 (4)°] leading to the S(6) O—H···O motif and molecules A and X are connected via a single N—H···O hydrogen bond (Fig. 5). In the packing, R23(9) patterns are formed consisting of two N—H···O hydrogen bonds and a weak C—H···O hydrogen bond yielding chains running along the b axis incorporating the DMSO molecules into the chains (Fig. 6 and Table 5).

The DMAC solvate of 5-carb­oxy­uracil, (IV), crystallizes in the monoclinic space group P21/n. The asymmetric unit consists of one 5CU molecule (A) and one disordered DMAC molecule (X), and the two molecules are connected by an N—H···O hydrogen bond enclosing a dihedral angle of 54.34 (6)° (r.m.s deviations for all non-H atoms = 0.030 Å for A and 0.041 Å for X) (Fig. 7). Again, atoms C4A and O52A show a synperiplanar arrangement [ω = 2.1 (4)°], forming the S(6) O—H···O hydrogen-bond motif. In the crystal packing, homodimers of 5CU molecules are formed via R22(8) N—H···O hydrogen bonds and the dimers show a herring-bone like arrangement whereby atom O51A is not involved in hydrogen bonds but only in weak electrostatic inter­actions (Fig. 8 and Table 6).

5-Carb­oxy-2-thio­uracil–N,N-di­methyl­formamide (1/1), (V), crystallizes in the monoclinic space group P21/c with one 5CTU molecule (A) and one DMF molecule (X) in the asymmetric unit (Fig. 9). 5CTU molecule A exhibits an S(6) O—H···O hydrogen-bond motif [ω = 1.7 (3)°] and is linked to DMF molecule X by an N—H···O hydrogen bond enclosing a dihedral angle of 11.27 (10)° (r.m.s deviations for all non-H atoms = 0.014 Å for A and 0.014 Å for X). In the crystal packing, the 5CTU molecules form zigzag-like chains running along the b axis via R22(7) N—H···O and C—H···O hydrogen-bond motifs (Fig. 10 and Table 7).

The DMSO solvate of 5-carb­oxy-2-thio­uracil, (VI), crystallizes in the triclinic space group P1 with one planar 5CTU molecule (A; r.m.s deviation for all non-H atoms = 0.040 Å) and one DMSO molecule (X) in the asymmetric unit (Fig. 11). Once more, an intra­molecular S(6) O—H···O hydrogen-bond motif is formed [ω = 5.3 (2)°] and 5CTU molecule A is connected to DMSO molecule X via a single N—H···O hydrogen bond. In the crystal packing, molecules are connected by C21(6) inter­actions consisting of N—H···O hydrogen bonds, resulting in chains running along the a axis (Fig. 12 and Table 8).

The dioxane solvate of 5-carb­oxy-2-thio­uracil, (VII), crystallizes in the triclinic space group P1. The asymmetric unit consists of one planar 5CTU molecule (A; r.m.s deviation for all non-H atoms = 0.030 Å) and three independent halves of dioxane molecules (X, Y and Z), since the solvent molecules are located at special positions (Fig. 13). Solvent molecules X and Z are connected to 5CTU molecule A via single N—H···O hydrogen bonds and an intra­molecular S(6) O—H···O hydrogen-bond motif formed by A is present as well [ω = 0.2 (2)°]. Molecules A and X enclose a dihedral angle of 74.62 (7)°, and A and Z enclose a dihedral angle of 78.2 (7)° (with the mean planes of the dioxane molecules defined by the four C atoms of each molecule). In the packing, a two-dimensional network is formed via single N—H···O hydrogen bonds and R22(10) C—H···O hydrogen-bond motifs, whereby dioxane molecule Y does not form any hydrogen bonds and is located in the centre of a mesh characterized by an R1010(46) pattern (Fig. 14 and Table 9).

The ansolvate of 5-carb­oxy-2-thio­uracil, (VIII), crystallizes in the monoclinic space group P21/c with two planar molecules A and B in the asymmetric unit (r.m.s. deviations for all non-H atoms = 0.053 Å for A and 0.046 Å for B). Molecules A and B are linked via R22(8) N—H···S hydrogen-bond motifs and are slightly tilted against each other enclosing a dihedral angle of 5.54 (19)° (Fig. 15). No intra­molecular hydrogen bond is formed since the carb­oxy groups of adjacent 5CTU molecules form R22(8) O—H···O hydrogen-bond mofits even though atoms C4A/B and O52A/B show synperiplanar conformations, respectively [ω = 1.0 (10)° for A and -4.0 (11)° for B]. In the packing, additional R12(6) and R21(5) motifs involving N—H···O and C—H···O hydrogen bonds are formed yielding a two-dimensional network (Fig. 16 and Table 10).

Comparing the structures of (I)–(VIII), R22(8) motifs involving two N—H···O hydrogen bonds were observed in (I) and (IV), whereas in (VIII), R22(8) N—H···S hydrogen-bond motifs are formed. An intra­molecular S(6) O—H···O motif was formed in six structures [i.e. (II)–(VII)], while in (VIII), the carb­oxy group is involved in an R22(8) O—H···O motif. In all cases, the carb­oxy group shows a coplanar arrangement compared to the pyrimidine ring, with atoms C4 and O52 adopting a synperiplanar conformation. This is in agreement with the CSD search which yielded the structures of the monohydrate structures of 5CU (AYEBIP; Law et al., 2004) and 5CTU (QEHSEB; Tiekink, 2001), respectively, where atoms C4 and O52 show a synperiplanar arrangement whereby inter­molecular O—H···O hydrogen bonds with the water molecules are formed in both cases. However, the only cocrystal structure, i.e. 4,4'-bipyridin-1-ium uracil-5-carboxyl­ate–4,4'-bi­pyridine–5-carb­oxy­uracil (2/1/4) (HOXHIM; Nichol & Clegg, 2009), shows that the structural flexibility is great enough that atoms C4 and O52 can adopt an anti­periplanar arrangement if necessary. In all three structures, R22(8) motifs are formed consisting of either two N—H···O (AYEBIP and HOXHIM) or two N—H···S hydrogen bonds (QEHSEB). A more generalized CSD search for six-membered cyclic molecules containing a carb­oxy group in the β-position of a carbonyl group (Fig. 17a) (restricted to organic and not polymeric structures with determined three-dimensional coordinates and without errors) confirmed that a coplanar arrangement of the carb­oxy group is strongly preferred not only in structures of molecules with the uracil substructure (Fig. 17b). All 94 structures show a synperiplanar conformation illustrated by the torsion angle ω and the values of ω observed in the structures of (II)–(VIII) lie well within the same range. Even in structures where no S(6) inter­action is possible due to the lack of a hydrogen-bond donor, like in GIMREA (an ansolvate of 5-formyl­uracil; Portalone & Colapietro, 2007) or DOTGID (cytosinium uracil-5-carboxyl­ate monohydrate; Portalone & Colapietro, 2009), a coplanar arrangement of the residue at atom C5 with respect to the pyrimidine ring is favoured, once more illustrating the preference for coplanarity.

A substructure search of the CSD for the respective isomeric compounds 6-(hy­droxy­methyl)­uracil (6HMU), 6-carb­oxy­uracil (6CU) and 6-carb­oxy-2-thio­uracil (6CTU), restricted to organic and not polymeric structures, yielded three hits for 6HMU, namely 6-(hy­droxy­methyl)­uracil–water (1/1) (CSD refcode HIMMUM; Spek & Kooljman, 2007), 6-(hy­droxy­methyl)­uracil–melamine–water (2/1/3) (REVVAQ; Kooijman et al., 2007) and 6-(hy­droxy­methyl)­uracil–2,4-di­amino-6-hy­droxy­methyl-1,3,5-triazine (1/1) (TUHJAH; Beijer et al., 1996), eight hits for 6CU, viz. 6-carb­oxy­uracil–water (1/1) [OROTAC (Takusagawa & Shimada, 1973) and OROTAC01 (Portalone, 2008)], 6-carb­oxy­uracil–melamine–water (1/1/1) (LIDCAE, LIDCAE01 and LIDCAE02; Xu et al., 2011), 6-carb­oxy­uracil–di­methyl sulfoxide (1/1), di­methyl­ammonium uracil-6-carboxyl­ate–6-carb­oxy­uracil (1/1) and di­methyl­ammonium uracil-6-carboxyl­ate–6-carb­oxy­uracil (3/1) (XARBEZ, XARBID and XARBOJ; Gerhardt et al., 2012), and one hit for 6CTU, viz. 6-carb­oxy-2-thio­uracil–di­methyl sulfoxide (1/1) (FOFLET; Papazoglou et al., 2014). In all these structures, R22(8) hydrogen-bond motifs consisting of two N—H···O hydrogen bonds are observed. In the cocrystal structures REVVAQ and TUHJAH, triply hydrogen-bonded ADA/DAD synthons are formed with the coformers melamine and 2,4-di­amino-6-hy­droxy­methyl-1,3,5-triazine, respectively. Except for HIMMUM, where the O atom of the hy­droxy group adopts a synclinal arrangement with respect to atom N1 of the pyrimidine ring, a coplanar arrangement compared to the pyrimidine ring is preferred in all structures.

In conclusion, even though 5-(hy­droxy­methyl)­uracil, 5-carb­oxy­uracil and 5-carb­oxy-2-thio­uracil tend to form intra­molecular S(6) O—H···O hydrogen-bond motifs, the structural flexibility is great enough for the formation of inter­molecular hydrogen bonds instead if a suitable coformer is present. Synthons involving R22(8) inter­actions are favourable for the formation of doubly hydrogen-bonded complexes, but triply hydrogen-bonded ADA/DAD synthons can be taken into account for the formation of cocrystals of these compounds as well. This knowledge is helpful in order to select suitable coformers for the design of cocrystals of the title compounds and, therefore, for the development of new solid materials.

Synthesis and crystallization top

Crystals of (I)–(VIII) were obtained by isothermal solvent evaporation experiments under different conditions from commercially available uracil derivatives and various solvents (Table 1). All solvents were applied without further purification and the crystallization experiments were performed at room temperature.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms, except those of the disordered solvent molecules, were located initially by difference Fourier synthesis. Carbon-bound H atoms were placed in calculated positions and 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. Free rotation about the local threefold axis was allowed for all methyl groups except those of the minor-occupied sites of the disordered DMAC molecule in (IV) and the minor-occupied conformation of the rotationally disordered methyl group of the DMF molecule in (V). H atoms bonded to O atoms or N atoms were refined isotropically with the isotropic displacement parameters coupled to the equivalent isotropic displacement parameters of the parent N atoms or O atoms, with Uiso(H) = 1.2Ueq(N,O). Tentative free refinements of their positional coordinates resulted in an unsatisfactory wide range of D—H distances; bond lengths were therefore restrained to 0.88 (2) Å for N—H and to 0.84 (2) Å for O—H.

In (IV), the DMAC molecule is disordered over a pseudo-mirror plane along atoms O21X and C12X perpendicular to the molecular plane [site-occupancy factor for the major-occupied orientation = 0.644 (9)]. For the DMAC molecule, similarity restraints for the 1,2- and 1,3-distances were applied as well as the similar-ADP and the rigid-bond (Hirshfeld, 1976) restraints (SIMU and DELU in SHELXL2014; Sheldrick, 2015).

In (IV) [(V)?], the H atoms of the C11X methyl group of the DMF molecule show a rotational disorder [site-occupancy factor for the major-occupied conformation = 0.55 (3)].

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: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008) and XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A partial packing diagram for (I), showing one layer of the two-dimensional network. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x + 1, -y + 2, -z; (ii) -x, -y + 1, -z + 1; (iii) x + 1, y - 1, z.]
[Figure 3] Fig. 3. A perspective view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 4] Fig. 4. A partial packing diagram for (II), with chains running along the b axis. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x, y - 1/2, -z + 1/2; (ii) -x, y + 1/2, -z + 1/2.]
[Figure 5] Fig. 5. A perspective view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 6] Fig. 6. A partial packing diagram for (III). Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, y - 1, z; (ii) x, y + 1, z.]
[Figure 7] Fig. 7. A perspective view of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. Only the major occupied site of the disordered DMAC molecule is shown.
[Figure 8] Fig. 8. A partial packing diagram for (IV). Hydrogen bonds are shown as dashed lines. Only the major occupied sites of the disordered DMAC molecules are shown. [Symmetry code: (i) -x + 1, -y, -z + 1.]
[Figure 9] Fig. 9. A perspective view of (V), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 10] Fig. 10. A partial packing diagram for (V). Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x, y - 1/2, -z + 3/2.]
[Figure 11] Fig. 11. A perspective view of (VI), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 12] Fig. 12. A partial packing diagram for (VI). Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) x + 1, y, z..]
[Figure 13] Fig. 13. A perspective view of (VII), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds. Unlabeled atoms are not part of the asymmetric unit.
[Figure 14] Fig. 14. A partial packing diagram for (VII). Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x, -y + 1, -z..]
[Figure 15] Fig. 15. A perspective view of (VIII), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate N—H···S hydrogen bonds.
[Figure 16] Fig. 16. A partial packing diagram for (VIII). Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 1/2; (ii) -x, y - 1/2, -z - 1/2; (iii) x, y + 1, z; (iv) x, y - 1, z..]
[Figure 17] Fig. 17. (a) The substructure used for a CSD search (Groome & Allen, 2014) on the torsion angle ω in structures of six-membered cyclic compounds containing a carboxy group in the β-position of a carbonyl group. (b) A histogram showing the number of occurrences versus the value of the torsion angle ω in this CSD search. For comparison, the values of ω in (II)–(VIII) are indicated as black lines at the top.
(I) 5-(Hydroxymethyl)uracil top
Crystal data top
C5H6N2O3Z = 2
Mr = 142.12F(000) = 148
Triclinic, P1Dx = 1.652 Mg m3
a = 4.874 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.663 (2) ÅCell parameters from 3734 reflections
c = 8.325 (3) Åθ = 4.2–26.1°
α = 66.97 (2)°µ = 0.14 mm1
β = 88.09 (2)°T = 173 K
γ = 87.07 (2)°Block, colourless
V = 285.7 (2) Å30.30 × 0.30 × 0.10 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
807 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.046
ω scansθmax = 25.8°, θmin = 4.2°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 55
Tmin = 0.221, Tmax = 1.000k = 98
2369 measured reflectionsl = 1010
1091 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.145 w = 1/[σ2(Fo2) + (0.0885P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1091 reflectionsΔρmax = 0.42 e Å3
100 parametersΔρmin = 0.30 e Å3
Crystal data top
C5H6N2O3γ = 87.07 (2)°
Mr = 142.12V = 285.7 (2) Å3
Triclinic, P1Z = 2
a = 4.874 (3) ÅMo Kα radiation
b = 7.663 (2) ŵ = 0.14 mm1
c = 8.325 (3) ÅT = 173 K
α = 66.97 (2)°0.30 × 0.30 × 0.10 mm
β = 88.09 (2)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1091 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
807 reflections with I > 2σ(I)
Tmin = 0.221, Tmax = 1.000Rint = 0.046
2369 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0553 restraints
wR(F2) = 0.145H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.42 e Å3
1091 reflectionsΔρmin = 0.30 e Å3
100 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.5660 (4)0.7411 (3)0.1098 (2)0.0359 (5)
H1A0.642 (6)0.839 (3)0.031 (3)0.043*
C2A0.3415 (5)0.7754 (3)0.1960 (3)0.0326 (5)
O21A0.2416 (4)0.9366 (2)0.1639 (2)0.0412 (5)
N3A0.2324 (4)0.6186 (3)0.3222 (2)0.0341 (5)
H3A0.085 (5)0.638 (4)0.382 (3)0.041*
C4A0.3311 (5)0.4326 (3)0.3714 (3)0.0325 (6)
O41A0.2218 (3)0.3042 (2)0.49405 (19)0.0359 (5)
C5A0.5660 (5)0.4053 (3)0.2708 (3)0.0336 (6)
C51A0.6791 (5)0.2072 (3)0.3083 (3)0.0373 (6)
H51A0.75410.15050.42770.045*
H51B0.53160.12690.30040.045*
O51A0.8878 (4)0.2167 (3)0.1852 (2)0.0494 (6)
H51C0.956 (7)0.107 (5)0.205 (4)0.059*
C6A0.6701 (5)0.5607 (3)0.1439 (3)0.0339 (5)
H6A0.82160.54410.07570.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0353 (12)0.0288 (10)0.0358 (11)0.0018 (8)0.0057 (8)0.0047 (8)
C2A0.0310 (13)0.0299 (11)0.0320 (11)0.0005 (9)0.0001 (9)0.0069 (9)
O21A0.0412 (10)0.0290 (8)0.0438 (10)0.0023 (7)0.0097 (7)0.0051 (7)
N3A0.0295 (11)0.0305 (10)0.0372 (11)0.0013 (8)0.0039 (8)0.0080 (8)
C4A0.0302 (13)0.0315 (11)0.0332 (12)0.0023 (9)0.0018 (9)0.0096 (9)
O41A0.0331 (10)0.0309 (9)0.0365 (9)0.0029 (7)0.0058 (7)0.0056 (7)
C5A0.0289 (13)0.0332 (12)0.0362 (12)0.0016 (9)0.0003 (9)0.0109 (10)
C51A0.0366 (13)0.0310 (11)0.0398 (13)0.0008 (9)0.0065 (10)0.0097 (9)
O51A0.0500 (12)0.0360 (9)0.0550 (11)0.0057 (8)0.0147 (9)0.0120 (8)
C6A0.0314 (13)0.0330 (11)0.0345 (12)0.0012 (9)0.0002 (9)0.0104 (9)
Geometric parameters (Å, º) top
N1A—C2A1.359 (3)C4A—C5A1.451 (3)
N1A—C6A1.371 (3)C5A—C6A1.354 (3)
N1A—H1A0.872 (17)C5A—C51A1.503 (3)
C2A—O21A1.234 (3)C51A—O51A1.403 (3)
C2A—N3A1.368 (3)C51A—H51A0.9900
N3A—C4A1.385 (3)C51A—H51B0.9900
N3A—H3A0.899 (17)O51A—H51C0.84 (4)
C4A—O41A1.235 (3)C6A—H6A0.9500
C2A—N1A—C6A122.0 (2)C6A—C5A—C51A122.9 (2)
C2A—N1A—H1A117.0 (19)C4A—C5A—C51A119.12 (19)
C6A—N1A—H1A121.0 (19)O51A—C51A—C5A108.29 (19)
O21A—C2A—N1A122.8 (2)O51A—C51A—H51A110.0
O21A—C2A—N3A121.8 (2)C5A—C51A—H51A110.0
N1A—C2A—N3A115.5 (2)O51A—C51A—H51B110.0
C2A—N3A—C4A126.5 (2)C5A—C51A—H51B110.0
C2A—N3A—H3A117.2 (18)H51A—C51A—H51B108.4
C4A—N3A—H3A116.2 (18)C51A—O51A—H51C110 (2)
O41A—C4A—N3A120.2 (2)C5A—C6A—N1A122.7 (2)
O41A—C4A—C5A124.6 (2)C5A—C6A—H6A118.6
N3A—C4A—C5A115.17 (19)N1A—C6A—H6A118.6
C6A—C5A—C4A118.0 (2)
C6A—N1A—C2A—O21A178.2 (2)O41A—C4A—C5A—C51A3.7 (4)
C6A—N1A—C2A—N3A1.9 (3)N3A—C4A—C5A—C51A177.0 (2)
O21A—C2A—N3A—C4A178.5 (2)C6A—C5A—C51A—O51A3.7 (3)
N1A—C2A—N3A—C4A1.4 (3)C4A—C5A—C51A—O51A175.0 (2)
C2A—N3A—C4A—O41A176.2 (2)C4A—C5A—C6A—N1A1.2 (4)
C2A—N3A—C4A—C5A3.1 (3)C51A—C5A—C6A—N1A179.9 (2)
O41A—C4A—C5A—C6A177.6 (2)C2A—N1A—C6A—C5A3.3 (4)
N3A—C4A—C5A—C6A1.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21Ai0.87 (2)1.94 (2)2.804 (3)171 (3)
N3A—H3A···O41Aii0.90 (2)1.92 (2)2.817 (3)176 (3)
O51A—H51C···O21Aiii0.84 (4)1.97 (4)2.741 (3)151 (3)
Symmetry codes: (i) x+1, y+2, z; (ii) x, y+1, z+1; (iii) x+1, y1, z.
(II) 5-Carboxyuracil N,N-dimethylformamide monosolvate top
Crystal data top
C5H4N2O4·C3H7NOF(000) = 480
Mr = 229.20Dx = 1.510 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.671 (3) ÅCell parameters from 8843 reflections
b = 12.394 (2) Åθ = 3.6–25.7°
c = 9.381 (2) ŵ = 0.13 mm1
β = 90.17 (2)°T = 173 K
V = 1008.2 (4) Å3Block, colourless
Z = 40.29 × 0.21 × 0.20 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1180 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.132
ω scansθmax = 26.2°, θmin = 3.6°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 1010
Tmin = 0.415, Tmax = 1.000k = 1515
8325 measured reflectionsl = 1111
1955 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.064H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165 w = 1/[σ2(Fo2) + (0.0766P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
1955 reflectionsΔρmax = 0.22 e Å3
156 parametersΔρmin = 0.24 e Å3
Crystal data top
C5H4N2O4·C3H7NOV = 1008.2 (4) Å3
Mr = 229.20Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.671 (3) ŵ = 0.13 mm1
b = 12.394 (2) ÅT = 173 K
c = 9.381 (2) Å0.29 × 0.21 × 0.20 mm
β = 90.17 (2)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1955 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1180 reflections with I > 2σ(I)
Tmin = 0.415, Tmax = 1.000Rint = 0.132
8325 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0643 restraints
wR(F2) = 0.165H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.22 e Å3
1955 reflectionsΔρmin = 0.24 e Å3
156 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.1621 (4)0.23274 (18)0.3886 (3)0.0414 (7)
H1A0.209 (4)0.282 (2)0.445 (3)0.050*
C2A0.1779 (4)0.1250 (2)0.4290 (3)0.0417 (8)
O21A0.2561 (3)0.09750 (17)0.5296 (2)0.0507 (7)
N3A0.0959 (4)0.05409 (18)0.3449 (3)0.0427 (7)
H3A0.105 (4)0.0142 (17)0.370 (4)0.051*
C4A0.0004 (4)0.0804 (2)0.2347 (3)0.0406 (8)
O41A0.0697 (3)0.00920 (15)0.1663 (2)0.0494 (7)
C5A0.0170 (4)0.1951 (2)0.2060 (3)0.0393 (8)
C51A0.1224 (4)0.2348 (2)0.0953 (3)0.0402 (8)
O51A0.1430 (3)0.33105 (15)0.0716 (2)0.0475 (7)
O52A0.1968 (3)0.16145 (16)0.0178 (2)0.0506 (7)
H52A0.170 (5)0.100 (2)0.053 (4)0.061*
C6A0.0684 (4)0.2650 (2)0.2849 (3)0.0404 (8)
H6A0.06090.34000.26510.048*
N1X0.4824 (4)0.40624 (19)0.7310 (3)0.0476 (8)
C11X0.5839 (5)0.3583 (3)0.8373 (4)0.0589 (11)
H1XA0.53910.36780.93220.088*
H1XB0.68490.39360.83380.088*
H1XC0.59600.28110.81740.088*
C12X0.4650 (5)0.5234 (2)0.7336 (4)0.0550 (10)
H2XA0.39340.54570.65820.083*
H2XB0.56560.55740.71800.083*
H2XC0.42440.54570.82640.083*
C2X0.4080 (5)0.3468 (2)0.6357 (3)0.0481 (9)
H2X0.42590.27120.63730.058*
O21X0.3172 (3)0.38165 (17)0.5450 (2)0.0544 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.061 (2)0.0222 (12)0.0410 (15)0.0030 (11)0.0205 (14)0.0013 (10)
C2A0.060 (3)0.0296 (15)0.0353 (17)0.0020 (14)0.0167 (17)0.0002 (12)
O21A0.0737 (19)0.0336 (11)0.0446 (13)0.0036 (10)0.0286 (12)0.0028 (9)
N3A0.066 (2)0.0196 (11)0.0425 (15)0.0017 (11)0.0188 (15)0.0008 (10)
C4A0.059 (2)0.0227 (13)0.0402 (17)0.0015 (13)0.0154 (16)0.0009 (12)
O41A0.0753 (19)0.0211 (10)0.0517 (13)0.0030 (10)0.0273 (13)0.0014 (9)
C5A0.058 (2)0.0210 (13)0.0387 (17)0.0022 (13)0.0115 (16)0.0001 (11)
C51A0.060 (2)0.0261 (14)0.0341 (17)0.0022 (13)0.0163 (16)0.0009 (11)
O51A0.0696 (18)0.0230 (10)0.0499 (13)0.0013 (9)0.0248 (12)0.0011 (9)
O52A0.076 (2)0.0251 (10)0.0508 (13)0.0021 (10)0.0352 (13)0.0005 (9)
C6A0.061 (2)0.0219 (13)0.0384 (17)0.0013 (13)0.0136 (16)0.0003 (11)
N1X0.064 (2)0.0367 (13)0.0417 (15)0.0035 (13)0.0202 (14)0.0016 (11)
C11X0.072 (3)0.054 (2)0.051 (2)0.0048 (18)0.023 (2)0.0009 (16)
C12X0.075 (3)0.0338 (16)0.056 (2)0.0083 (17)0.024 (2)0.0024 (15)
C2X0.066 (3)0.0365 (16)0.0419 (18)0.0038 (15)0.0133 (19)0.0028 (14)
O21X0.077 (2)0.0385 (12)0.0474 (14)0.0101 (11)0.0266 (13)0.0014 (10)
Geometric parameters (Å, º) top
N1A—C6A1.327 (4)O52A—H52A0.859 (19)
N1A—C2A1.394 (4)C6A—H6A0.9500
N1A—H1A0.902 (18)N1X—C2X1.325 (4)
C2A—O21A1.210 (4)N1X—C11X1.455 (5)
C2A—N3A1.377 (4)N1X—C12X1.460 (4)
N3A—C4A1.366 (4)C11X—H1XA0.9800
N3A—H3A0.882 (18)C11X—H1XB0.9800
C4A—O41A1.245 (4)C11X—H1XC0.9800
C4A—C5A1.453 (4)C12X—H2XA0.9800
C5A—C6A1.358 (4)C12X—H2XB0.9800
C5A—C51A1.466 (4)C12X—H2XC0.9800
C51A—O51A1.226 (3)C2X—O21X1.236 (4)
C51A—O52A1.330 (4)C2X—H2X0.9500
C6A—N1A—C2A123.2 (3)N1A—C6A—H6A118.7
C6A—N1A—H1A120 (2)C5A—C6A—H6A118.7
C2A—N1A—H1A117 (2)C2X—N1X—C11X121.8 (3)
O21A—C2A—N3A123.6 (3)C2X—N1X—C12X121.0 (3)
O21A—C2A—N1A122.4 (3)C11X—N1X—C12X117.2 (3)
N3A—C2A—N1A113.9 (3)N1X—C11X—H1XA109.5
C4A—N3A—C2A126.4 (2)N1X—C11X—H1XB109.5
C4A—N3A—H3A119 (3)H1XA—C11X—H1XB109.5
C2A—N3A—H3A114 (3)N1X—C11X—H1XC109.5
O41A—C4A—N3A120.9 (2)H1XA—C11X—H1XC109.5
O41A—C4A—C5A123.4 (3)H1XB—C11X—H1XC109.5
N3A—C4A—C5A115.7 (3)N1X—C12X—H2XA109.5
C6A—C5A—C4A118.0 (3)N1X—C12X—H2XB109.5
C6A—C5A—C51A120.7 (2)H2XA—C12X—H2XB109.5
C4A—C5A—C51A121.4 (3)N1X—C12X—H2XC109.5
O51A—C51A—O52A119.7 (3)H2XA—C12X—H2XC109.5
O51A—C51A—C5A123.0 (3)H2XB—C12X—H2XC109.5
O52A—C51A—C5A117.3 (2)O21X—C2X—N1X125.3 (3)
C51A—O52A—H52A105 (3)O21X—C2X—H2X117.3
N1A—C6A—C5A122.6 (3)N1X—C2X—H2X117.3
C6A—N1A—C2A—O21A175.2 (3)C6A—C5A—C51A—O51A2.6 (5)
C6A—N1A—C2A—N3A4.4 (5)C4A—C5A—C51A—O51A177.5 (3)
O21A—C2A—N3A—C4A176.5 (3)C6A—C5A—C51A—O52A176.9 (3)
N1A—C2A—N3A—C4A3.1 (5)C4A—C5A—C51A—O52A3.0 (5)
C2A—N3A—C4A—O41A179.5 (3)C2A—N1A—C6A—C5A2.0 (5)
C2A—N3A—C4A—C5A0.5 (5)C4A—C5A—C6A—N1A1.9 (5)
O41A—C4A—C5A—C6A177.9 (4)C51A—C5A—C6A—N1A178.2 (3)
N3A—C4A—C5A—C6A3.1 (5)C11X—N1X—C2X—O21X178.0 (4)
O41A—C4A—C5A—C51A1.9 (5)C12X—N1X—C2X—O21X1.7 (6)
N3A—C4A—C5A—C51A177.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21X0.90 (2)1.81 (2)2.712 (3)174 (3)
N3A—H3A···O51Ai0.88 (2)2.02 (2)2.902 (3)176 (4)
O52A—H52A···O41A0.86 (2)1.78 (2)2.590 (3)158 (4)
C6A—H6A···O41Aii0.952.193.061 (3)151
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2.
(III) 5-Carboxyuracil dimethyl sulfoxide monosolvate top
Crystal data top
C5H4N2O4·C2H6OSF(000) = 488
Mr = 234.23Dx = 1.564 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.7107 Å
a = 6.9341 (9) ÅCell parameters from 5673 reflections
b = 6.9015 (5) Åθ = 3.5–26.0°
c = 20.919 (3) ŵ = 0.33 mm1
β = 96.604 (10)°T = 173 K
V = 994.5 (2) Å3Block, colourless
Z = 40.25 × 0.12 × 0.10 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1443 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.074
ω scansθmax = 25.8°, θmin = 3.5°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 87
Tmin = 0.565, Tmax = 1.000k = 88
7444 measured reflectionsl = 2525
1900 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1900 reflectionsΔρmax = 0.25 e Å3
147 parametersΔρmin = 0.44 e Å3
Crystal data top
C5H4N2O4·C2H6OSV = 994.5 (2) Å3
Mr = 234.23Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.9341 (9) ŵ = 0.33 mm1
b = 6.9015 (5) ÅT = 173 K
c = 20.919 (3) Å0.25 × 0.12 × 0.10 mm
β = 96.604 (10)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1900 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1443 reflections with I > 2σ(I)
Tmin = 0.565, Tmax = 1.000Rint = 0.074
7444 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0463 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.25 e Å3
1900 reflectionsΔρmin = 0.44 e Å3
147 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.1715 (3)0.7392 (3)0.45369 (9)0.0207 (5)
H1A0.136 (4)0.842 (3)0.4314 (12)0.025*
C2A0.1206 (4)0.5693 (3)0.42009 (11)0.0205 (5)
O21A0.0326 (3)0.5673 (2)0.36653 (8)0.0278 (4)
N3A0.1761 (3)0.4014 (3)0.45324 (9)0.0204 (4)
H3A0.144 (4)0.296 (3)0.4319 (12)0.025*
C4A0.2719 (4)0.3887 (3)0.51435 (11)0.0194 (5)
O41A0.3128 (3)0.2287 (2)0.53880 (8)0.0255 (4)
C5A0.3178 (4)0.5735 (3)0.54612 (11)0.0195 (5)
C51A0.4193 (4)0.5817 (4)0.61195 (11)0.0231 (5)
O51A0.4618 (3)0.7319 (3)0.64053 (9)0.0318 (5)
O52A0.4664 (3)0.4103 (3)0.63979 (8)0.0300 (4)
H52A0.426 (5)0.329 (4)0.6109 (12)0.036*
C6A0.2653 (4)0.7402 (3)0.51367 (11)0.0199 (5)
H6A0.29600.86100.53410.024*
S1X0.03084 (10)1.09275 (8)0.31404 (3)0.0236 (2)
O11X0.0627 (3)1.0730 (2)0.38765 (8)0.0265 (4)
C11X0.2118 (4)0.9439 (4)0.28519 (13)0.0278 (6)
H1XA0.34050.99770.29930.042*
H1XB0.19160.93970.23810.042*
H1XC0.20300.81250.30240.042*
C12X0.1787 (4)0.9502 (4)0.28980 (13)0.0273 (6)
H2XA0.16030.81950.30780.041*
H2XB0.19880.94250.24270.041*
H2XC0.29241.01010.30550.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0263 (13)0.0144 (9)0.0215 (11)0.0028 (9)0.0028 (9)0.0025 (8)
C2A0.0205 (14)0.0181 (11)0.0238 (13)0.0002 (10)0.0059 (10)0.0005 (9)
O21A0.0383 (12)0.0231 (9)0.0207 (9)0.0013 (8)0.0023 (8)0.0020 (7)
N3A0.0246 (12)0.0156 (9)0.0211 (10)0.0005 (9)0.0024 (8)0.0027 (8)
C4A0.0178 (13)0.0172 (10)0.0240 (12)0.0010 (10)0.0063 (10)0.0015 (10)
O41A0.0326 (11)0.0162 (8)0.0277 (9)0.0040 (8)0.0033 (8)0.0047 (7)
C5A0.0184 (13)0.0201 (11)0.0206 (12)0.0006 (11)0.0055 (9)0.0004 (9)
C51A0.0236 (14)0.0250 (12)0.0216 (12)0.0010 (11)0.0057 (10)0.0016 (10)
O51A0.0397 (13)0.0283 (9)0.0260 (10)0.0002 (9)0.0027 (8)0.0075 (8)
O52A0.0369 (12)0.0277 (9)0.0240 (9)0.0042 (9)0.0023 (8)0.0010 (8)
C6A0.0217 (15)0.0163 (10)0.0229 (12)0.0029 (10)0.0074 (10)0.0032 (9)
S1X0.0338 (4)0.0162 (3)0.0205 (3)0.0001 (3)0.0014 (2)0.0007 (2)
O11X0.0438 (12)0.0149 (8)0.0202 (9)0.0007 (8)0.0011 (8)0.0011 (7)
C11X0.0300 (16)0.0268 (13)0.0270 (13)0.0003 (12)0.0045 (11)0.0008 (10)
C12X0.0252 (15)0.0281 (13)0.0285 (14)0.0000 (11)0.0019 (11)0.0016 (10)
Geometric parameters (Å, º) top
N1A—C6A1.345 (3)C51A—O52A1.343 (3)
N1A—C2A1.392 (3)O52A—H52A0.847 (18)
N1A—H1A0.867 (17)C6A—H6A0.9500
C2A—O21A1.213 (3)S1X—O11X1.5364 (17)
C2A—N3A1.382 (3)S1X—C12X1.779 (3)
N3A—C4A1.374 (3)S1X—C11X1.780 (3)
N3A—H3A0.867 (17)C11X—H1XA0.9800
C4A—O41A1.236 (3)C11X—H1XB0.9800
C4A—C5A1.457 (3)C11X—H1XC0.9800
C5A—C6A1.364 (3)C12X—H2XA0.9800
C5A—C51A1.474 (3)C12X—H2XB0.9800
C51A—O51A1.216 (3)C12X—H2XC0.9800
C6A—N1A—C2A122.9 (2)N1A—C6A—C5A122.2 (2)
C6A—N1A—H1A125.1 (18)N1A—C6A—H6A118.9
C2A—N1A—H1A112.1 (18)C5A—C6A—H6A118.9
O21A—C2A—N3A122.4 (2)O11X—S1X—C12X104.76 (12)
O21A—C2A—N1A123.2 (2)O11X—S1X—C11X105.25 (12)
N3A—C2A—N1A114.4 (2)C12X—S1X—C11X99.72 (13)
C4A—N3A—C2A126.7 (2)S1X—C11X—H1XA109.5
C4A—N3A—H3A119.6 (18)S1X—C11X—H1XB109.5
C2A—N3A—H3A113.7 (18)H1XA—C11X—H1XB109.5
O41A—C4A—N3A120.4 (2)S1X—C11X—H1XC109.5
O41A—C4A—C5A124.5 (2)H1XA—C11X—H1XC109.5
N3A—C4A—C5A115.2 (2)H1XB—C11X—H1XC109.5
C6A—C5A—C4A118.7 (2)S1X—C12X—H2XA109.5
C6A—C5A—C51A120.3 (2)S1X—C12X—H2XB109.5
C4A—C5A—C51A121.1 (2)H2XA—C12X—H2XB109.5
O51A—C51A—O52A120.3 (2)S1X—C12X—H2XC109.5
O51A—C51A—C5A123.7 (2)H2XA—C12X—H2XC109.5
O52A—C51A—C5A115.9 (2)H2XB—C12X—H2XC109.5
C51A—O52A—H52A103 (2)
C6A—N1A—C2A—O21A178.5 (2)N3A—C4A—C5A—C51A179.6 (2)
C6A—N1A—C2A—N3A0.6 (4)C6A—C5A—C51A—O51A0.2 (4)
O21A—C2A—N3A—C4A178.5 (2)C4A—C5A—C51A—O51A179.6 (2)
N1A—C2A—N3A—C4A0.6 (4)C6A—C5A—C51A—O52A179.5 (2)
C2A—N3A—C4A—O41A179.7 (2)C4A—C5A—C51A—O52A0.4 (4)
C2A—N3A—C4A—C5A0.1 (4)C2A—N1A—C6A—C5A0.1 (4)
O41A—C4A—C5A—C6A179.7 (2)C4A—C5A—C6A—N1A0.5 (4)
N3A—C4A—C5A—C6A0.5 (4)C51A—C5A—C6A—N1A179.6 (2)
O41A—C4A—C5A—C51A0.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O52A—H52A···O41A0.85 (2)1.76 (2)2.579 (3)162 (3)
N1A—H1A···O11X0.87 (2)1.88 (2)2.747 (3)176 (3)
N3A—H3A···O11Xi0.87 (2)1.85 (2)2.718 (3)177 (3)
C6A—H6A···O41Aii0.952.543.422 (3)154
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.
(IV) 5-Carboxyuracil N,N-dimethylacetamide monosolvate top
Crystal data top
C5H4N2O4·C4H9NOF(000) = 512
Mr = 243.22Dx = 1.472 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 11.7707 (19) ÅCell parameters from 7500 reflections
b = 6.1053 (10) Åθ = 3.6–26.0°
c = 15.271 (3) ŵ = 0.12 mm1
β = 90.858 (13)°T = 173 K
V = 1097.3 (3) Å3Block, colourless
Z = 40.30 × 0.25 × 0.15 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1328 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.065
ω scansθmax = 25.9°, θmin = 3.6°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 1412
Tmin = 0.317, Tmax = 1.000k = 77
8148 measured reflectionsl = 1818
2119 independent reflections
Refinement top
Refinement on F2131 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.060H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.150 w = 1/[σ2(Fo2) + (0.0743P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
2119 reflectionsΔρmax = 0.17 e Å3
185 parametersΔρmin = 0.25 e Å3
Crystal data top
C5H4N2O4·C4H9NOV = 1097.3 (3) Å3
Mr = 243.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.7707 (19) ŵ = 0.12 mm1
b = 6.1053 (10) ÅT = 173 K
c = 15.271 (3) Å0.30 × 0.25 × 0.15 mm
β = 90.858 (13)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2119 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1328 reflections with I > 2σ(I)
Tmin = 0.317, Tmax = 1.000Rint = 0.065
8148 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060131 restraints
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.17 e Å3
2119 reflectionsΔρmin = 0.25 e Å3
185 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N1A0.2926 (2)0.3079 (4)0.59331 (16)0.0472 (6)
H1A0.2214 (17)0.266 (5)0.583 (2)0.057*
C2A0.3761 (3)0.1841 (4)0.55581 (17)0.0454 (7)
O21A0.35541 (17)0.0140 (3)0.51590 (13)0.0514 (5)
N3A0.4839 (2)0.2636 (4)0.56715 (15)0.0462 (6)
H3A0.538 (2)0.184 (4)0.5453 (19)0.055*
C4A0.5141 (3)0.4552 (4)0.60850 (17)0.0458 (7)
O41A0.61524 (18)0.5132 (3)0.61118 (14)0.0550 (5)
C5A0.4216 (3)0.5770 (4)0.64618 (17)0.0459 (7)
C51A0.4404 (3)0.7878 (5)0.69157 (18)0.0511 (7)
O51A0.3652 (2)0.8934 (3)0.72479 (14)0.0621 (6)
O52A0.5472 (2)0.8624 (3)0.69315 (14)0.0586 (6)
H52A0.587 (3)0.762 (5)0.666 (2)0.070*
C6A0.3158 (3)0.4958 (4)0.63678 (18)0.0473 (7)
H6A0.25460.57420.66190.057*
C11X0.0690 (4)0.1555 (6)0.6380 (3)0.0880 (13)
H1XA0.13290.06910.61640.132*0.644 (9)
H1XB0.05730.28350.60010.132*0.644 (9)
H1XC0.08570.20430.69790.132*0.644 (9)
H1A'0.00700.23720.66500.132*0.356 (9)
H1B'0.09800.23860.58810.132*0.356 (9)
H1C'0.13030.13320.68120.132*0.356 (9)
C12X0.1503 (3)0.0981 (6)0.6608 (2)0.0716 (10)
H1XD0.14080.22670.69860.107*0.644 (9)
H1XE0.19270.13950.60760.107*0.644 (9)
H1XF0.19220.01550.69210.107*0.644 (9)
H1D'0.23030.05730.66740.107*0.356 (9)
H1E'0.14510.22680.62270.107*0.356 (9)
H1F'0.11710.13240.71840.107*0.356 (9)
O21X0.07125 (19)0.2298 (4)0.56743 (14)0.0619 (6)
C3X0.1352 (3)0.3063 (6)0.5873 (3)0.0751 (10)
H1XG0.19310.22330.55460.113*0.644 (9)
H1XH0.12010.44440.55700.113*0.644 (9)
H1XI0.16260.33720.64630.113*0.644 (9)
H1G'0.21660.31430.59950.113*0.356 (9)
H1H'0.09570.42750.61680.113*0.356 (9)
H1I'0.12380.31660.52400.113*0.356 (9)
N1X0.0390 (5)0.0142 (8)0.6371 (3)0.0602 (14)0.644 (9)
C2X0.0258 (5)0.1718 (9)0.5936 (3)0.0553 (15)0.644 (9)
N1X'0.0874 (7)0.0871 (14)0.6212 (5)0.054 (2)0.356 (9)
C2X'0.0248 (8)0.0672 (15)0.6061 (6)0.048 (2)0.356 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0469 (15)0.0409 (12)0.0537 (14)0.0021 (11)0.0015 (11)0.0008 (10)
C2A0.0514 (18)0.0418 (14)0.0428 (15)0.0031 (13)0.0012 (12)0.0029 (12)
O21A0.0551 (13)0.0425 (10)0.0565 (12)0.0003 (9)0.0002 (9)0.0068 (9)
N3A0.0486 (15)0.0398 (12)0.0501 (13)0.0049 (11)0.0016 (11)0.0016 (10)
C4A0.0541 (19)0.0382 (14)0.0452 (15)0.0030 (13)0.0004 (13)0.0046 (11)
O41A0.0528 (13)0.0465 (11)0.0658 (13)0.0006 (10)0.0005 (10)0.0031 (9)
C5A0.0563 (18)0.0399 (14)0.0414 (14)0.0024 (13)0.0015 (13)0.0031 (11)
C51A0.065 (2)0.0448 (15)0.0434 (16)0.0022 (15)0.0010 (14)0.0014 (12)
O51A0.0735 (16)0.0527 (12)0.0605 (13)0.0043 (11)0.0085 (12)0.0110 (10)
O52A0.0685 (16)0.0461 (11)0.0613 (13)0.0032 (10)0.0000 (11)0.0057 (9)
C6A0.0542 (18)0.0417 (14)0.0460 (15)0.0056 (13)0.0032 (13)0.0035 (12)
C11X0.110 (3)0.059 (2)0.094 (3)0.038 (2)0.039 (2)0.0210 (18)
C12X0.076 (2)0.066 (2)0.073 (2)0.0150 (18)0.0054 (19)0.0030 (17)
O21X0.0549 (14)0.0620 (13)0.0688 (14)0.0009 (11)0.0006 (11)0.0002 (11)
C3X0.070 (2)0.063 (2)0.092 (3)0.0218 (17)0.0242 (19)0.0198 (18)
N1X0.069 (4)0.051 (3)0.061 (3)0.003 (2)0.005 (2)0.005 (2)
C2X0.068 (4)0.051 (3)0.046 (3)0.001 (3)0.006 (3)0.008 (2)
N1X'0.049 (5)0.051 (5)0.063 (5)0.003 (3)0.002 (4)0.008 (4)
C2X'0.049 (5)0.048 (5)0.047 (5)0.004 (4)0.008 (4)0.011 (4)
Geometric parameters (Å, º) top
N1A—C6A1.351 (4)C11X—H1C'0.9800
N1A—C2A1.372 (3)C12X—N1X1.458 (6)
N1A—H1A0.888 (18)C12X—N1X'1.485 (9)
C2A—O21A1.227 (3)C12X—H1XD0.9800
C2A—N3A1.367 (4)C12X—H1XE0.9800
N3A—C4A1.374 (4)C12X—H1XF0.9800
N3A—H3A0.873 (18)C12X—H1D'0.9800
C4A—O41A1.242 (3)C12X—H1E'0.9800
C4A—C5A1.445 (4)C12X—H1F'0.9800
C5A—C6A1.346 (4)O21X—C2X1.267 (6)
C5A—C51A1.477 (4)O21X—C2X'1.282 (9)
C51A—O51A1.213 (4)C3X—C2X1.529 (7)
C51A—O52A1.337 (4)C3X—N1X'1.538 (9)
O52A—H52A0.873 (18)C3X—H1XG0.9800
C6A—H6A0.9500C3X—H1XH0.9800
C11X—C2X'1.533 (10)C3X—H1XI0.9800
C11X—N1X1.536 (7)C3X—H1G'0.9800
C11X—H1XA0.9800C3X—H1H'0.9800
C11X—H1XB0.9800C3X—H1I'0.9800
C11X—H1XC0.9800N1X—C2X1.325 (8)
C11X—H1A'0.9800N1X'—C2X'1.350 (12)
C11X—H1B'0.9800
C6A—N1A—C2A122.1 (3)N1X—C12X—H1XE109.5
C6A—N1A—H1A121 (2)H1XD—C12X—H1XE109.5
C2A—N1A—H1A117 (2)N1X—C12X—H1XF109.5
O21A—C2A—N3A122.7 (3)H1XD—C12X—H1XF109.5
O21A—C2A—N1A122.3 (3)H1XE—C12X—H1XF109.5
N3A—C2A—N1A114.9 (2)N1X'—C12X—H1D'109.5
C2A—N3A—C4A126.4 (2)N1X'—C12X—H1E'109.5
C2A—N3A—H3A116 (2)H1D'—C12X—H1E'109.5
C4A—N3A—H3A118 (2)N1X'—C12X—H1F'109.5
O41A—C4A—N3A119.9 (3)H1D'—C12X—H1F'109.5
O41A—C4A—C5A124.6 (3)H1E'—C12X—H1F'109.5
N3A—C4A—C5A115.5 (3)C2X—C3X—H1XG109.5
C6A—C5A—C4A118.0 (3)C2X—C3X—H1XH109.5
C6A—C5A—C51A120.2 (3)H1XG—C3X—H1XH109.5
C4A—C5A—C51A121.8 (3)C2X—C3X—H1XI109.5
O51A—C51A—O52A120.2 (3)H1XG—C3X—H1XI109.5
O51A—C51A—C5A123.7 (3)H1XH—C3X—H1XI109.5
O52A—C51A—C5A116.1 (3)N1X'—C3X—H1G'109.5
C51A—O52A—H52A105 (2)N1X'—C3X—H1H'109.5
C5A—C6A—N1A123.0 (3)H1G'—C3X—H1H'109.5
C5A—C6A—H6A118.5N1X'—C3X—H1I'109.5
N1A—C6A—H6A118.5H1G'—C3X—H1I'109.5
N1X—C11X—H1XA109.5H1H'—C3X—H1I'109.5
N1X—C11X—H1XB109.5C2X—N1X—C12X122.5 (6)
H1XA—C11X—H1XB109.5C2X—N1X—C11X112.5 (5)
N1X—C11X—H1XC109.5C12X—N1X—C11X123.2 (4)
H1XA—C11X—H1XC109.5O21X—C2X—N1X120.7 (6)
H1XB—C11X—H1XC109.5O21X—C2X—C3X126.4 (5)
C2X'—C11X—H1A'109.5N1X—C2X—C3X112.8 (5)
C2X'—C11X—H1B'109.5C2X'—N1X'—C12X119.7 (8)
H1A'—C11X—H1B'109.5C2X'—N1X'—C3X112.0 (8)
C2X'—C11X—H1C'109.5C12X—N1X'—C3X128.1 (6)
H1A'—C11X—H1C'109.5O21X—C2X'—N1X'115.7 (9)
H1B'—C11X—H1C'109.5O21X—C2X'—C11X133.5 (7)
N1X—C12X—H1XD109.5N1X'—C2X'—C11X110.8 (8)
C6A—N1A—C2A—O21A179.6 (3)C4A—C5A—C51A—O52A2.1 (4)
C6A—N1A—C2A—N3A1.1 (4)C4A—C5A—C6A—N1A0.6 (4)
O21A—C2A—N3A—C4A177.9 (3)C51A—C5A—C6A—N1A177.6 (2)
N1A—C2A—N3A—C4A2.8 (4)C2A—N1A—C6A—C5A0.5 (4)
C2A—N3A—C4A—O41A177.0 (3)C12X—N1X—C2X—O21X173.7 (4)
C2A—N3A—C4A—C5A2.7 (4)C11X—N1X—C2X—O21X8.6 (6)
O41A—C4A—C5A—C6A178.8 (3)C12X—N1X—C2X—C3X11.1 (6)
N3A—C4A—C5A—C6A0.9 (4)C11X—N1X—C2X—C3X176.2 (3)
O41A—C4A—C5A—C51A0.6 (4)C12X—N1X'—C2X'—O21X176.3 (6)
N3A—C4A—C5A—C51A179.1 (2)C3X—N1X'—C2X'—O21X0.2 (9)
C6A—C5A—C51A—O51A2.7 (4)C12X—N1X'—C2X'—C11X2.1 (9)
C4A—C5A—C51A—O51A179.2 (3)C3X—N1X'—C2X'—C11X178.2 (5)
C6A—C5A—C51A—O52A176.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21X0.89 (2)1.79 (2)2.672 (3)170 (3)
O52A—H52A···O41A0.87 (2)1.77 (2)2.605 (3)158 (3)
N3A—H3A···O21Ai0.87 (2)1.98 (2)2.851 (3)172 (3)
Symmetry code: (i) x+1, y, z+1.
(V) 4-Oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid dimethylformamide monosolvate top
Crystal data top
C5H4N2O3S·C3H7NOF(000) = 512
Mr = 245.26Dx = 1.446 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.1742 (10) ÅCell parameters from 15516 reflections
b = 11.4616 (12) Åθ = 3.6–26.1°
c = 9.9715 (11) ŵ = 0.29 mm1
β = 104.318 (8)°T = 173 K
V = 1126.7 (2) Å3Block, colourless
Z = 40.40 × 0.30 × 0.30 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1796 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.045
ω scansθmax = 25.8°, θmin = 3.6°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 1112
Tmin = 0.499, Tmax = 1.000k = 1413
8433 measured reflectionsl = 1212
2163 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.049P)2 + 0.2199P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2163 reflectionsΔρmax = 0.27 e Å3
157 parametersΔρmin = 0.20 e Å3
Crystal data top
C5H4N2O3S·C3H7NOV = 1126.7 (2) Å3
Mr = 245.26Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.1742 (10) ŵ = 0.29 mm1
b = 11.4616 (12) ÅT = 173 K
c = 9.9715 (11) Å0.40 × 0.30 × 0.30 mm
β = 104.318 (8)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2163 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1796 reflections with I > 2σ(I)
Tmin = 0.499, Tmax = 1.000Rint = 0.045
8433 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0363 restraints
wR(F2) = 0.093H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.27 e Å3
2163 reflectionsΔρmin = 0.20 e Å3
157 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N1A0.12196 (16)0.62099 (12)0.62644 (16)0.0278 (3)
H1A0.103 (2)0.5523 (15)0.654 (2)0.033*
C2A0.21236 (18)0.62753 (15)0.54497 (18)0.0263 (4)
S21A0.27742 (5)0.50942 (4)0.49137 (5)0.03359 (16)
N3A0.24350 (16)0.73863 (12)0.51204 (15)0.0257 (3)
H3A0.3028 (19)0.7464 (17)0.461 (2)0.031*
C4A0.19450 (18)0.83982 (14)0.55586 (17)0.0251 (4)
O41A0.23399 (14)0.93613 (10)0.52405 (14)0.0328 (3)
C5A0.09886 (18)0.82528 (14)0.64013 (17)0.0252 (4)
C51A0.03890 (18)0.92657 (14)0.69386 (19)0.0271 (4)
O51A0.03996 (14)0.91647 (10)0.76718 (14)0.0336 (3)
O52A0.07515 (14)1.03106 (10)0.65730 (14)0.0316 (3)
H52A0.130 (2)1.0176 (19)0.612 (2)0.038*
C6A0.06725 (19)0.71524 (14)0.67164 (18)0.0262 (4)
H6A0.00470.70460.72720.031*
N1X0.55873 (16)0.68861 (13)0.22344 (16)0.0296 (3)
C11X0.6186 (3)0.8005 (2)0.2065 (3)0.0550 (7)
H1XA0.59090.82410.10910.083*0.55 (3)
H1XB0.71760.79440.23530.083*0.55 (3)
H1XC0.58770.85900.26370.083*0.55 (3)
H1XD0.68350.79110.14930.083*0.45 (3)
H1XE0.54710.85510.16130.083*0.45 (3)
H1XF0.66560.83130.29750.083*0.45 (3)
C12X0.6001 (2)0.58867 (17)0.1524 (2)0.0372 (5)
H2XA0.55420.51820.17320.056*
H2XB0.69860.57820.18420.056*
H2XC0.57540.60260.05240.056*
C2X0.46777 (19)0.67999 (15)0.29704 (18)0.0284 (4)
H2X0.43220.60470.30700.034*
O21X0.42527 (15)0.76303 (11)0.35421 (14)0.0370 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0346 (9)0.0204 (7)0.0335 (8)0.0003 (6)0.0180 (7)0.0020 (6)
C2A0.0293 (9)0.0243 (8)0.0264 (9)0.0008 (7)0.0089 (7)0.0002 (6)
S21A0.0438 (3)0.0244 (2)0.0384 (3)0.00722 (19)0.0212 (2)0.00143 (17)
N3A0.0290 (8)0.0240 (7)0.0290 (8)0.0007 (6)0.0163 (6)0.0011 (6)
C4A0.0261 (9)0.0240 (8)0.0264 (9)0.0013 (7)0.0089 (7)0.0014 (6)
O41A0.0378 (8)0.0233 (6)0.0433 (7)0.0016 (5)0.0217 (6)0.0041 (5)
C5A0.0263 (9)0.0242 (8)0.0274 (9)0.0011 (7)0.0109 (7)0.0003 (6)
C51A0.0268 (9)0.0230 (8)0.0328 (10)0.0024 (7)0.0096 (8)0.0013 (7)
O51A0.0348 (7)0.0278 (6)0.0446 (8)0.0017 (5)0.0220 (6)0.0047 (5)
O52A0.0388 (8)0.0208 (6)0.0400 (7)0.0012 (5)0.0187 (6)0.0003 (5)
C6A0.0280 (9)0.0255 (8)0.0287 (9)0.0019 (7)0.0137 (7)0.0002 (7)
N1X0.0313 (9)0.0272 (7)0.0348 (8)0.0001 (6)0.0166 (7)0.0001 (6)
C11X0.0659 (17)0.0409 (11)0.0741 (16)0.0173 (11)0.0474 (14)0.0096 (11)
C12X0.0443 (12)0.0358 (10)0.0360 (10)0.0070 (9)0.0181 (9)0.0025 (8)
C2X0.0291 (9)0.0281 (9)0.0294 (9)0.0006 (7)0.0099 (8)0.0017 (7)
O21X0.0416 (8)0.0349 (7)0.0423 (8)0.0016 (6)0.0250 (7)0.0018 (6)
Geometric parameters (Å, º) top
N1A—C6A1.343 (2)N1X—C2X1.319 (2)
N1A—C2A1.372 (2)N1X—C11X1.448 (3)
N1A—H1A0.872 (16)N1X—C12X1.462 (2)
C2A—N3A1.372 (2)C11X—H1XA0.9800
C2A—S21A1.6526 (17)C11X—H1XB0.9800
N3A—C4A1.376 (2)C11X—H1XC0.9800
N3A—H3A0.881 (16)C11X—H1XD0.9800
C4A—O41A1.242 (2)C11X—H1XE0.9800
C4A—C5A1.444 (2)C11X—H1XF0.9800
C5A—C6A1.358 (2)C12X—H2XA0.9800
C5A—C51A1.473 (2)C12X—H2XB0.9800
C51A—O51A1.217 (2)C12X—H2XC0.9800
C51A—O52A1.330 (2)C2X—O21X1.241 (2)
O52A—H52A0.819 (16)C2X—H2X0.9500
C6A—H6A0.9500
C6A—N1A—C2A123.30 (15)C2X—N1X—C12X122.44 (15)
C6A—N1A—H1A118.4 (14)C11X—N1X—C12X117.25 (15)
C2A—N1A—H1A118.2 (14)N1X—C11X—H1XA109.5
N1A—C2A—N3A114.90 (15)N1X—C11X—H1XB109.5
N1A—C2A—S21A121.85 (13)H1XA—C11X—H1XB109.5
N3A—C2A—S21A123.25 (13)N1X—C11X—H1XC109.5
C2A—N3A—C4A125.69 (15)H1XA—C11X—H1XC109.5
C2A—N3A—H3A117.6 (13)H1XB—C11X—H1XC109.5
C4A—N3A—H3A116.7 (13)N1X—C11X—H1XD109.5
O41A—C4A—N3A120.17 (16)N1X—C11X—H1XE109.5
O41A—C4A—C5A123.93 (15)H1XD—C11X—H1XE109.5
N3A—C4A—C5A115.90 (14)N1X—C11X—H1XF109.5
C6A—C5A—C4A118.31 (15)H1XD—C11X—H1XF109.5
C6A—C5A—C51A120.33 (15)H1XE—C11X—H1XF109.5
C4A—C5A—C51A121.34 (15)N1X—C12X—H2XA109.5
O51A—C51A—O52A121.25 (15)N1X—C12X—H2XB109.5
O51A—C51A—C5A122.51 (15)H2XA—C12X—H2XB109.5
O52A—C51A—C5A116.24 (15)N1X—C12X—H2XC109.5
C51A—O52A—H52A104.9 (16)H2XA—C12X—H2XC109.5
N1A—C6A—C5A121.88 (16)H2XB—C12X—H2XC109.5
N1A—C6A—H6A119.1O21X—C2X—N1X124.76 (17)
C5A—C6A—H6A119.1O21X—C2X—H2X117.6
C2X—N1X—C11X120.29 (16)N1X—C2X—H2X117.6
C6A—N1A—C2A—N3A0.1 (3)C6A—C5A—C51A—O51A0.1 (3)
C6A—N1A—C2A—S21A179.97 (14)C4A—C5A—C51A—O51A178.61 (17)
N1A—C2A—N3A—C4A1.4 (3)C6A—C5A—C51A—O52A179.74 (16)
S21A—C2A—N3A—C4A178.68 (14)C4A—C5A—C51A—O52A1.7 (2)
C2A—N3A—C4A—O41A177.08 (17)C2A—N1A—C6A—C5A0.5 (3)
C2A—N3A—C4A—C5A2.1 (3)C4A—C5A—C6A—N1A0.2 (3)
O41A—C4A—C5A—C6A177.76 (17)C51A—C5A—C6A—N1A178.78 (16)
N3A—C4A—C5A—C6A1.3 (2)C11X—N1X—C2X—O21X1.1 (3)
O41A—C4A—C5A—C51A0.8 (3)C12X—N1X—C2X—O21X176.82 (18)
N3A—C4A—C5A—C51A179.92 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O51Ai0.87 (2)1.92 (2)2.7846 (19)169 (2)
N3A—H3A···O21X0.88 (2)1.84 (2)2.723 (2)179 (2)
O52A—H52A···O41A0.82 (2)1.79 (2)2.5735 (18)159 (2)
C6A—H6A···O52Ai0.952.533.269 (2)135
Symmetry code: (i) x, y1/2, z+3/2.
(VI) 4-Oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid dimethyl sulfoxide monosolvate top
Crystal data top
C5H4N2O3S·C2H6OSZ = 2
Mr = 250.29F(000) = 260
Triclinic, P1Dx = 1.606 Mg m3
a = 7.0475 (9) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.9534 (12) ÅCell parameters from 5472 reflections
c = 9.2802 (13) Åθ = 3.5–26.1°
α = 115.79 (1)°µ = 0.51 mm1
β = 95.753 (11)°T = 173 K
γ = 95.791 (10)°Block, colourless
V = 517.72 (13) Å30.30 × 0.25 × 0.15 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1703 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.033
ω scansθmax = 25.8°, θmin = 3.5°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 88
Tmin = 0.746, Tmax = 1.000k = 1010
4538 measured reflectionsl = 1111
1976 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.070 w = 1/[σ2(Fo2) + (0.037P)2 + 0.1288P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1976 reflectionsΔρmax = 0.40 e Å3
147 parametersΔρmin = 0.23 e Å3
Crystal data top
C5H4N2O3S·C2H6OSγ = 95.791 (10)°
Mr = 250.29V = 517.72 (13) Å3
Triclinic, P1Z = 2
a = 7.0475 (9) ÅMo Kα radiation
b = 8.9534 (12) ŵ = 0.51 mm1
c = 9.2802 (13) ÅT = 173 K
α = 115.79 (1)°0.30 × 0.25 × 0.15 mm
β = 95.753 (11)°
Data collection top
Stoe IPDS II two-circle
diffractometer
1976 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1703 reflections with I > 2σ(I)
Tmin = 0.746, Tmax = 1.000Rint = 0.033
4538 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0273 restraints
wR(F2) = 0.070H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.40 e Å3
1976 reflectionsΔρmin = 0.23 e Å3
147 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.59088 (19)0.20626 (17)0.58016 (17)0.0190 (3)
H1A0.486 (2)0.190 (2)0.619 (2)0.023*
C2A0.7581 (2)0.16694 (19)0.63431 (19)0.0172 (3)
S21A0.76313 (6)0.08217 (5)0.76181 (5)0.02329 (13)
N3A0.91866 (18)0.20414 (17)0.57701 (17)0.0191 (3)
H3A1.028 (2)0.190 (2)0.622 (2)0.023*
C4A0.9224 (2)0.2689 (2)0.4674 (2)0.0195 (3)
O41A1.07581 (17)0.29605 (16)0.42167 (16)0.0276 (3)
C5A0.7396 (2)0.3040 (2)0.4134 (2)0.0198 (3)
C51A0.7227 (3)0.3754 (2)0.2961 (2)0.0252 (4)
O51A0.57451 (19)0.41422 (17)0.25516 (17)0.0325 (3)
O52A0.8826 (2)0.39130 (18)0.23516 (17)0.0325 (3)
H52A0.969 (3)0.360 (3)0.277 (3)0.039*
C6A0.5815 (2)0.27235 (19)0.47463 (19)0.0187 (3)
H6A0.46150.29750.44220.022*
S1X0.35729 (5)0.25809 (5)0.89806 (5)0.01963 (12)
O11X0.27606 (15)0.17703 (15)0.71689 (14)0.0231 (3)
C11X0.2801 (3)0.1028 (2)0.9612 (2)0.0292 (4)
H1XA0.14110.06310.92360.044*
H1XB0.30630.15201.07980.044*
H1XC0.35040.00800.91480.044*
C12X0.2052 (2)0.4063 (2)0.9970 (2)0.0242 (4)
H2XA0.21780.49640.96380.036*
H2XB0.24360.45421.11470.036*
H2XC0.07060.34990.96690.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0131 (6)0.0245 (7)0.0213 (7)0.0031 (5)0.0023 (5)0.0121 (6)
C2A0.0143 (7)0.0163 (7)0.0190 (8)0.0006 (6)0.0002 (6)0.0071 (6)
S21A0.0185 (2)0.0291 (2)0.0289 (2)0.00175 (16)0.00037 (17)0.0202 (2)
N3A0.0123 (6)0.0235 (7)0.0232 (7)0.0031 (5)0.0015 (5)0.0123 (6)
C4A0.0181 (8)0.0175 (8)0.0202 (8)0.0015 (6)0.0045 (6)0.0060 (7)
O41A0.0220 (6)0.0330 (7)0.0316 (7)0.0046 (5)0.0109 (5)0.0165 (6)
C5A0.0215 (8)0.0185 (8)0.0178 (8)0.0020 (6)0.0006 (6)0.0074 (7)
C51A0.0323 (9)0.0217 (8)0.0198 (9)0.0002 (7)0.0026 (7)0.0088 (7)
O51A0.0356 (7)0.0371 (7)0.0305 (7)0.0059 (6)0.0022 (6)0.0220 (6)
O52A0.0388 (8)0.0384 (8)0.0288 (7)0.0062 (6)0.0116 (6)0.0217 (6)
C6A0.0176 (7)0.0184 (7)0.0181 (8)0.0030 (6)0.0011 (6)0.0070 (7)
S1X0.01389 (19)0.0265 (2)0.0205 (2)0.00437 (15)0.00238 (15)0.01223 (17)
O11X0.0148 (5)0.0362 (7)0.0191 (6)0.0045 (5)0.0016 (5)0.0134 (5)
C11X0.0338 (9)0.0280 (9)0.0302 (10)0.0053 (8)0.0005 (8)0.0181 (8)
C12X0.0228 (8)0.0256 (8)0.0265 (9)0.0075 (7)0.0058 (7)0.0127 (7)
Geometric parameters (Å, º) top
N1A—C6A1.346 (2)C51A—O52A1.332 (2)
N1A—C2A1.372 (2)O52A—H52A0.825 (16)
N1A—H1A0.883 (15)C6A—H6A0.9500
C2A—N3A1.369 (2)S1X—O11X1.5306 (12)
C2A—S21A1.6600 (16)S1X—C12X1.7823 (17)
N3A—C4A1.374 (2)S1X—C11X1.7871 (18)
N3A—H3A0.886 (15)C11X—H1XA0.9800
C4A—O41A1.239 (2)C11X—H1XB0.9800
C4A—C5A1.449 (2)C11X—H1XC0.9800
C5A—C6A1.359 (2)C12X—H2XA0.9800
C5A—C51A1.485 (2)C12X—H2XB0.9800
C51A—O51A1.210 (2)C12X—H2XC0.9800
C6A—N1A—C2A123.20 (14)N1A—C6A—C5A121.57 (14)
C6A—N1A—H1A119.0 (13)N1A—C6A—H6A119.2
C2A—N1A—H1A117.8 (13)C5A—C6A—H6A119.2
N3A—C2A—N1A115.25 (14)O11X—S1X—C12X106.23 (8)
N3A—C2A—S21A122.94 (12)O11X—S1X—C11X104.29 (8)
N1A—C2A—S21A121.81 (12)C12X—S1X—C11X98.50 (9)
C2A—N3A—C4A125.63 (13)S1X—C11X—H1XA109.5
C2A—N3A—H3A114.8 (13)S1X—C11X—H1XB109.5
C4A—N3A—H3A119.4 (13)H1XA—C11X—H1XB109.5
O41A—C4A—N3A120.45 (14)S1X—C11X—H1XC109.5
O41A—C4A—C5A123.73 (15)H1XA—C11X—H1XC109.5
N3A—C4A—C5A115.81 (14)H1XB—C11X—H1XC109.5
C6A—C5A—C4A118.48 (15)S1X—C12X—H2XA109.5
C6A—C5A—C51A119.91 (14)S1X—C12X—H2XB109.5
C4A—C5A—C51A121.60 (15)H2XA—C12X—H2XB109.5
O51A—C51A—O52A121.60 (16)S1X—C12X—H2XC109.5
O51A—C51A—C5A123.16 (16)H2XA—C12X—H2XC109.5
O52A—C51A—C5A115.22 (15)H2XB—C12X—H2XC109.5
C51A—O52A—H52A108.5 (17)
C6A—N1A—C2A—N3A1.8 (2)N3A—C4A—C5A—C51A179.53 (15)
C6A—N1A—C2A—S21A178.80 (12)C6A—C5A—C51A—O51A3.0 (3)
N1A—C2A—N3A—C4A3.0 (2)C4A—C5A—C51A—O51A176.02 (17)
S21A—C2A—N3A—C4A177.66 (13)C6A—C5A—C51A—O52A175.72 (15)
C2A—N3A—C4A—O41A179.03 (15)C4A—C5A—C51A—O52A5.3 (2)
C2A—N3A—C4A—C5A1.8 (2)C2A—N1A—C6A—C5A0.4 (2)
O41A—C4A—C5A—C6A178.59 (16)C4A—C5A—C6A—N1A1.6 (2)
N3A—C4A—C5A—C6A0.5 (2)C51A—C5A—C6A—N1A179.42 (15)
O41A—C4A—C5A—C51A0.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O11X0.88 (2)1.83 (2)2.7087 (17)174 (2)
N3A—H3A···O11Xi0.89 (2)1.92 (2)2.7983 (18)175 (2)
O52A—H52A···O41A0.83 (2)1.80 (2)2.5738 (19)155 (2)
Symmetry code: (i) x+1, y, z.
(VII) 4-Oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid 1,4-dioxane sesquisolvate top
Crystal data top
C5H4N2O3S·1.5C4H8O2Z = 2
Mr = 304.32F(000) = 320
Triclinic, P1Dx = 1.459 Mg m3
a = 5.2819 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.3542 (12) ÅCell parameters from 6794 reflections
c = 13.0071 (15) Åθ = 3.7–26.1°
α = 89.377 (10)°µ = 0.26 mm1
β = 85.143 (10)°T = 173 K
γ = 77.70 (1)°Block, colourless
V = 692.51 (15) Å30.30 × 0.21 × 0.16 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
2272 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.045
ω scansθmax = 25.8°, θmin = 3.7°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 65
Tmin = 0.528, Tmax = 1.000k = 1212
5885 measured reflectionsl = 1515
2645 independent reflections
Refinement top
Refinement on F23 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.0652P)2 + 0.0475P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2645 reflectionsΔρmax = 0.30 e Å3
190 parametersΔρmin = 0.22 e Å3
Crystal data top
C5H4N2O3S·1.5C4H8O2γ = 77.70 (1)°
Mr = 304.32V = 692.51 (15) Å3
Triclinic, P1Z = 2
a = 5.2819 (7) ÅMo Kα radiation
b = 10.3542 (12) ŵ = 0.26 mm1
c = 13.0071 (15) ÅT = 173 K
α = 89.377 (10)°0.30 × 0.21 × 0.16 mm
β = 85.143 (10)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2645 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
2272 reflections with I > 2σ(I)
Tmin = 0.528, Tmax = 1.000Rint = 0.045
5885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0363 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.30 e Å3
2645 reflectionsΔρmin = 0.22 e Å3
190 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.5758 (3)0.33844 (13)0.12070 (9)0.0232 (3)
H1A0.597 (4)0.2659 (16)0.0860 (13)0.028*
C2A0.7455 (3)0.34583 (15)0.19351 (11)0.0227 (3)
S21A0.99858 (8)0.22538 (4)0.21249 (3)0.03074 (15)
N3A0.6876 (3)0.46087 (13)0.25010 (9)0.0241 (3)
H3A0.799 (4)0.4702 (19)0.2964 (13)0.029*
C4A0.4821 (3)0.56608 (15)0.23970 (11)0.0233 (3)
O41A0.4540 (2)0.66521 (11)0.29541 (8)0.0308 (3)
C5A0.3104 (3)0.54962 (15)0.16168 (11)0.0226 (3)
C51A0.0737 (3)0.65151 (15)0.14615 (12)0.0265 (3)
O51A0.0751 (2)0.64100 (12)0.08219 (9)0.0360 (3)
O52A0.0287 (2)0.75760 (12)0.20765 (9)0.0326 (3)
H52A0.150 (4)0.744 (2)0.2446 (15)0.039*
C6A0.3660 (3)0.43494 (15)0.10612 (11)0.0228 (3)
H6A0.25360.42240.05550.027*
O1X1.0271 (2)0.50814 (11)0.39123 (8)0.0307 (3)
C2X0.9442 (4)0.62568 (16)0.45447 (12)0.0322 (4)
H2X10.82500.69360.41730.039*
H2X21.09720.66180.46830.039*
C6X1.1922 (3)0.40586 (17)0.44515 (12)0.0316 (4)
H6X11.35300.43500.45890.038*
H6X21.24220.32530.40140.038*
O1Y0.3820 (3)0.89102 (14)0.48933 (12)0.0525 (4)
C2Y0.3206 (5)0.9769 (2)0.57690 (18)0.0567 (6)
H2Y10.27340.92660.63810.068*
H2Y20.16871.04810.56480.068*
C6Y0.4550 (5)0.9636 (2)0.40253 (17)0.0551 (6)
H6Y10.30571.03450.38680.066*
H6Y20.50320.90410.34170.066*
O1Z0.6295 (2)0.10460 (10)0.01198 (8)0.0282 (3)
C2Z0.7012 (3)0.01927 (15)0.06553 (13)0.0291 (3)
H2Z10.76680.00320.13230.035*
H2Z20.84230.07950.02380.035*
C6Z0.5295 (3)0.08283 (15)0.08431 (12)0.0272 (3)
H6Z10.66680.02490.12940.033*
H6Z20.47710.16820.11980.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0238 (7)0.0216 (6)0.0248 (6)0.0050 (5)0.0047 (5)0.0034 (5)
C2A0.0215 (7)0.0232 (7)0.0241 (7)0.0066 (6)0.0022 (6)0.0019 (5)
S21A0.0265 (2)0.0259 (2)0.0388 (2)0.00069 (16)0.00924 (17)0.00132 (16)
N3A0.0231 (7)0.0248 (7)0.0252 (6)0.0047 (5)0.0079 (5)0.0030 (5)
C4A0.0234 (8)0.0230 (7)0.0244 (7)0.0066 (6)0.0030 (6)0.0002 (6)
O41A0.0316 (6)0.0265 (6)0.0343 (6)0.0035 (5)0.0089 (5)0.0080 (5)
C5A0.0222 (8)0.0235 (7)0.0229 (7)0.0059 (6)0.0038 (6)0.0016 (5)
C51A0.0260 (8)0.0240 (8)0.0291 (7)0.0045 (6)0.0029 (6)0.0017 (6)
O51A0.0315 (7)0.0350 (7)0.0401 (6)0.0015 (5)0.0169 (5)0.0025 (5)
O52A0.0300 (7)0.0274 (6)0.0384 (6)0.0015 (5)0.0102 (5)0.0033 (5)
C6A0.0219 (8)0.0250 (7)0.0230 (7)0.0074 (6)0.0045 (6)0.0016 (5)
O1X0.0372 (7)0.0316 (6)0.0241 (5)0.0054 (5)0.0110 (5)0.0022 (4)
C2X0.0395 (10)0.0270 (8)0.0308 (8)0.0048 (7)0.0132 (7)0.0026 (6)
C6X0.0293 (9)0.0339 (9)0.0313 (8)0.0022 (7)0.0113 (7)0.0052 (6)
O1Y0.0603 (10)0.0385 (8)0.0635 (9)0.0206 (7)0.0080 (8)0.0012 (7)
C2Y0.0662 (15)0.0474 (12)0.0568 (12)0.0180 (11)0.0082 (11)0.0001 (10)
C6Y0.0744 (16)0.0448 (12)0.0495 (11)0.0152 (11)0.0172 (11)0.0015 (9)
O1Z0.0283 (6)0.0201 (5)0.0380 (6)0.0059 (4)0.0109 (5)0.0014 (4)
C2Z0.0287 (8)0.0220 (7)0.0377 (8)0.0041 (6)0.0123 (7)0.0004 (6)
C6Z0.0273 (8)0.0233 (8)0.0305 (7)0.0030 (6)0.0044 (6)0.0016 (6)
Geometric parameters (Å, º) top
N1A—C6A1.350 (2)C6X—C2Xi1.504 (3)
N1A—C2A1.3716 (19)C6X—H6X10.9900
N1A—H1A0.862 (15)C6X—H6X20.9900
C2A—N3A1.371 (2)O1Y—C6Y1.421 (3)
C2A—S21A1.6559 (15)O1Y—C2Y1.425 (3)
N3A—C4A1.379 (2)C2Y—C6Yii1.491 (4)
N3A—H3A0.898 (14)C2Y—H2Y10.9900
C4A—O41A1.2385 (19)C2Y—H2Y20.9900
C4A—C5A1.451 (2)C6Y—C2Yii1.491 (4)
C5A—C6A1.361 (2)C6Y—H6Y10.9900
C5A—C51A1.481 (2)C6Y—H6Y20.9900
C51A—O51A1.2131 (19)O1Z—C6Z1.4379 (18)
C51A—O52A1.334 (2)O1Z—C2Z1.4464 (18)
O52A—H52A0.821 (16)C2Z—C6Ziii1.505 (2)
C6A—H6A0.9500C2Z—H2Z10.9900
O1X—C6X1.4379 (19)C2Z—H2Z20.9900
O1X—C2X1.443 (2)C6Z—C2Ziii1.505 (2)
C2X—C6Xi1.504 (3)C6Z—H6Z10.9900
C2X—H2X10.9900C6Z—H6Z20.9900
C2X—H2X20.9900
C6A—N1A—C2A123.32 (13)C2Xi—C6X—H6X1109.5
C6A—N1A—H1A118.1 (13)O1X—C6X—H6X2109.5
C2A—N1A—H1A118.3 (13)C2Xi—C6X—H6X2109.5
N3A—C2A—N1A114.52 (13)H6X1—C6X—H6X2108.0
N3A—C2A—S21A122.58 (11)C6Y—O1Y—C2Y108.89 (16)
N1A—C2A—S21A122.90 (12)O1Y—C2Y—C6Yii111.2 (2)
C2A—N3A—C4A126.59 (13)O1Y—C2Y—H2Y1109.4
C2A—N3A—H3A116.6 (13)C6Yii—C2Y—H2Y1109.4
C4A—N3A—H3A116.8 (12)O1Y—C2Y—H2Y2109.4
O41A—C4A—N3A119.91 (13)C6Yii—C2Y—H2Y2109.4
O41A—C4A—C5A124.74 (14)H2Y1—C2Y—H2Y2108.0
N3A—C4A—C5A115.34 (13)O1Y—C6Y—C2Yii110.69 (18)
C6A—C5A—C4A118.19 (14)O1Y—C6Y—H6Y1109.5
C6A—C5A—C51A120.59 (13)C2Yii—C6Y—H6Y1109.5
C4A—C5A—C51A121.15 (13)O1Y—C6Y—H6Y2109.5
O51A—C51A—O52A120.62 (15)C2Yii—C6Y—H6Y2109.5
O51A—C51A—C5A123.09 (14)H6Y1—C6Y—H6Y2108.1
O52A—C51A—C5A116.30 (13)C6Z—O1Z—C2Z110.04 (11)
C51A—O52A—H52A104.6 (15)O1Z—C2Z—C6Ziii110.44 (13)
N1A—C6A—C5A122.02 (13)O1Z—C2Z—H2Z1109.6
N1A—C6A—H6A119.0C6Ziii—C2Z—H2Z1109.6
C5A—C6A—H6A119.0O1Z—C2Z—H2Z2109.6
C6X—O1X—C2X110.73 (11)C6Ziii—C2Z—H2Z2109.6
O1X—C2X—C6Xi110.26 (14)H2Z1—C2Z—H2Z2108.1
O1X—C2X—H2X1109.6O1Z—C6Z—C2Ziii110.14 (13)
C6Xi—C2X—H2X1109.6O1Z—C6Z—H6Z1109.6
O1X—C2X—H2X2109.6C2Ziii—C6Z—H6Z1109.6
C6Xi—C2X—H2X2109.6O1Z—C6Z—H6Z2109.6
H2X1—C2X—H2X2108.1C2Ziii—C6Z—H6Z2109.6
O1X—C6X—C2Xi110.90 (14)H6Z1—C6Z—H6Z2108.1
O1X—C6X—H6X1109.5
C6A—N1A—C2A—N3A0.9 (2)C6A—C5A—C51A—O52A176.76 (14)
C6A—N1A—C2A—S21A178.59 (11)C4A—C5A—C51A—O52A0.2 (2)
N1A—C2A—N3A—C4A0.6 (2)C2A—N1A—C6A—C5A1.7 (2)
S21A—C2A—N3A—C4A179.93 (12)C4A—C5A—C6A—N1A0.9 (2)
C2A—N3A—C4A—O41A179.16 (14)C51A—C5A—C6A—N1A177.92 (13)
C2A—N3A—C4A—C5A1.2 (2)C6X—O1X—C2X—C6Xi56.90 (19)
O41A—C4A—C5A—C6A179.95 (14)C2X—O1X—C6X—C2Xi57.26 (19)
N3A—C4A—C5A—C6A0.4 (2)C6Y—O1Y—C2Y—C6Yii57.8 (3)
O41A—C4A—C5A—C51A3.1 (2)C2Y—O1Y—C6Y—C2Yii57.5 (3)
N3A—C4A—C5A—C51A176.56 (13)C6Z—O1Z—C2Z—C6Ziii58.19 (18)
C6A—C5A—C51A—O51A2.7 (2)C2Z—O1Z—C6Z—C2Ziii58.01 (18)
C4A—C5A—C51A—O51A179.58 (15)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+2, z+1; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6A—H6A···O51Aiv0.952.263.1892 (18)166
N1A—H1A···O1Z0.86 (2)1.91 (2)2.7670 (17)178 (2)
N3A—H3A···O1X0.90 (1)1.89 (2)2.7889 (17)174 (2)
O52A—H52A···O41A0.82 (2)1.81 (2)2.5998 (16)160 (2)
Symmetry code: (iv) x, y+1, z.
(VIII) 4-Oxo-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylic acid top
Crystal data top
C5H4N2O3SF(000) = 704
Mr = 172.16Dx = 1.765 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 11.409 (3) ÅCell parameters from 5588 reflections
b = 15.552 (3) Åθ = 3.4–26.0°
c = 7.369 (2) ŵ = 0.45 mm1
β = 97.599 (19)°T = 173 K
V = 1296.0 (6) Å3Block, colourless
Z = 80.25 × 0.11 × 0.08 mm
Data collection top
Stoe IPDS II two-circle
diffractometer
1294 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray sourceRint = 0.149
ω scansθmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
h = 1114
Tmin = 0.149, Tmax = 1.000k = 1919
9985 measured reflectionsl = 98
2492 independent reflections
Refinement top
Refinement on F26 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.077H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164 w = 1/[σ2(Fo2) + (0.0547P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
2492 reflectionsΔρmax = 0.61 e Å3
217 parametersΔρmin = 0.32 e Å3
Crystal data top
C5H4N2O3SV = 1296.0 (6) Å3
Mr = 172.16Z = 8
Monoclinic, P21/cMo Kα radiation
a = 11.409 (3) ŵ = 0.45 mm1
b = 15.552 (3) ÅT = 173 K
c = 7.369 (2) Å0.25 × 0.11 × 0.08 mm
β = 97.599 (19)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2492 independent reflections
Absorption correction: multi-scan
(X-AREA; Stoe & Cie, 2001)
1294 reflections with I > 2σ(I)
Tmin = 0.149, Tmax = 1.000Rint = 0.149
9985 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0776 restraints
wR(F2) = 0.164H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.61 e Å3
2492 reflectionsΔρmin = 0.32 e Å3
217 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.4523 (5)0.8214 (3)0.1538 (7)0.0364 (14)
H1A0.519 (4)0.806 (4)0.219 (8)0.044*
C2A0.3863 (6)0.7515 (4)0.0896 (8)0.0342 (15)
S21A0.43438 (16)0.65141 (11)0.1289 (2)0.0379 (5)
N3A0.2805 (5)0.7715 (3)0.0096 (8)0.0376 (14)
H3A0.231 (5)0.731 (3)0.053 (9)0.045*
C4A0.2361 (6)0.8537 (4)0.0597 (9)0.0340 (15)
O41A0.1442 (4)0.8588 (3)0.1625 (7)0.0466 (13)
C5A0.3096 (6)0.9227 (4)0.0265 (8)0.0337 (16)
C51A0.2765 (7)1.0147 (4)0.0136 (8)0.0357 (16)
O51A0.3435 (5)1.0694 (3)0.0922 (7)0.0500 (14)
O52A0.1736 (4)1.0341 (3)0.0812 (6)0.0449 (13)
H52A0.155 (7)1.0864 (18)0.090 (10)0.054*
C6A0.4124 (6)0.9036 (4)0.1289 (8)0.0323 (16)
H6A0.45910.94910.18620.039*
N1B0.0603 (5)0.4502 (3)0.1906 (8)0.0376 (14)
H1B0.001 (4)0.460 (4)0.272 (7)0.045*
C2B0.1251 (6)0.5209 (4)0.1303 (8)0.0340 (16)
S21B0.08396 (16)0.62065 (10)0.1902 (2)0.0395 (5)
N3B0.2257 (5)0.5011 (3)0.0177 (7)0.0363 (14)
H3B0.266 (5)0.545 (3)0.029 (8)0.044*
C4B0.2689 (6)0.4203 (4)0.0411 (9)0.0337 (16)
O41B0.3576 (4)0.4154 (3)0.1522 (7)0.0463 (14)
C5B0.1964 (6)0.3496 (4)0.0393 (9)0.0348 (16)
C51B0.2222 (6)0.2579 (4)0.0058 (9)0.0403 (18)
O51B0.1522 (5)0.2029 (3)0.0751 (8)0.0566 (16)
O52B0.3212 (4)0.2395 (3)0.0942 (7)0.0436 (13)
H52B0.327 (7)0.1851 (14)0.097 (10)0.052*
C6B0.0945 (6)0.3694 (4)0.1497 (8)0.0395 (18)
H6B0.04530.32370.20000.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.031 (3)0.033 (3)0.041 (3)0.001 (2)0.012 (3)0.001 (2)
C2A0.037 (4)0.037 (4)0.030 (3)0.004 (3)0.009 (3)0.001 (3)
S21A0.0341 (10)0.0302 (9)0.0464 (10)0.0019 (7)0.0058 (8)0.0022 (7)
N3A0.039 (4)0.025 (3)0.045 (3)0.000 (2)0.008 (3)0.001 (2)
C4A0.029 (4)0.035 (4)0.037 (4)0.003 (3)0.000 (3)0.003 (3)
O41A0.034 (3)0.035 (3)0.064 (3)0.003 (2)0.021 (3)0.000 (2)
C5A0.041 (4)0.032 (4)0.029 (4)0.001 (3)0.005 (3)0.001 (3)
C51A0.041 (4)0.033 (4)0.033 (4)0.002 (3)0.002 (3)0.000 (3)
O51A0.052 (4)0.031 (3)0.061 (3)0.003 (2)0.013 (3)0.001 (2)
O52A0.039 (3)0.036 (3)0.055 (3)0.005 (2)0.010 (3)0.004 (2)
C6A0.035 (4)0.026 (3)0.034 (3)0.002 (3)0.002 (3)0.001 (2)
N1B0.032 (4)0.033 (3)0.043 (3)0.002 (3)0.010 (3)0.005 (2)
C2B0.035 (4)0.033 (4)0.034 (3)0.005 (3)0.005 (3)0.003 (3)
S21B0.0363 (10)0.0305 (9)0.0489 (10)0.0019 (7)0.0052 (8)0.0028 (7)
N3B0.035 (4)0.029 (3)0.042 (3)0.002 (3)0.007 (3)0.002 (2)
C4B0.034 (4)0.038 (4)0.030 (4)0.004 (3)0.009 (3)0.004 (3)
O41B0.038 (3)0.035 (3)0.060 (3)0.005 (2)0.017 (3)0.003 (2)
C5B0.035 (4)0.023 (3)0.043 (4)0.001 (3)0.007 (3)0.003 (3)
C51B0.028 (4)0.038 (4)0.052 (4)0.002 (3)0.008 (4)0.002 (3)
O51B0.049 (4)0.027 (3)0.085 (4)0.001 (2)0.024 (3)0.006 (2)
O52B0.038 (3)0.027 (3)0.060 (3)0.003 (2)0.015 (3)0.002 (2)
C6B0.040 (4)0.038 (4)0.038 (4)0.002 (3)0.004 (4)0.001 (3)
Geometric parameters (Å, º) top
N1A—C6A1.360 (8)N1B—C6B1.338 (8)
N1A—C2A1.371 (8)N1B—C2B1.367 (8)
N1A—H1A0.88 (2)N1B—H1B0.87 (2)
C2A—N3A1.362 (9)C2B—N3B1.359 (9)
C2A—S21A1.663 (6)C2B—S21B1.663 (7)
N3A—C4A1.407 (8)N3B—C4B1.397 (8)
N3A—H3A0.87 (2)N3B—H3B0.87 (2)
C4A—O41A1.212 (7)C4B—O41B1.217 (8)
C4A—C5A1.455 (9)C4B—C5B1.455 (9)
C5A—C6A1.342 (9)C5B—C6B1.363 (9)
C5A—C51A1.479 (9)C5B—C51B1.469 (9)
C51A—O51A1.236 (8)C51B—O51B1.234 (8)
C51A—O52A1.319 (8)C51B—O52B1.296 (8)
O52A—H52A0.84 (2)O52B—H52B0.85 (2)
C6A—H6A0.9500C6B—H6B0.9500
C6A—N1A—C2A122.7 (6)C6B—N1B—C2B123.6 (6)
C6A—N1A—H1A125 (4)C6B—N1B—H1B120 (5)
C2A—N1A—H1A112 (4)C2B—N1B—H1B115 (5)
N3A—C2A—N1A114.3 (5)N3B—C2B—N1B113.1 (5)
N3A—C2A—S21A123.8 (5)N3B—C2B—S21B124.1 (5)
N1A—C2A—S21A122.0 (5)N1B—C2B—S21B122.9 (5)
C2A—N3A—C4A127.7 (5)C2B—N3B—C4B129.0 (5)
C2A—N3A—H3A121 (5)C2B—N3B—H3B115 (5)
C4A—N3A—H3A111 (5)C4B—N3B—H3B116 (5)
O41A—C4A—N3A118.4 (6)O41B—C4B—N3B119.6 (6)
O41A—C4A—C5A128.7 (6)O41B—C4B—C5B127.1 (6)
N3A—C4A—C5A112.9 (5)N3B—C4B—C5B113.3 (6)
C6A—C5A—C4A119.5 (6)C6B—C5B—C4B117.8 (6)
C6A—C5A—C51A116.6 (6)C6B—C5B—C51B117.1 (5)
C4A—C5A—C51A123.9 (6)C4B—C5B—C51B125.0 (6)
O51A—C51A—O52A122.9 (6)O51B—C51B—O52B123.3 (6)
O51A—C51A—C5A119.9 (6)O51B—C51B—C5B119.9 (6)
O52A—C51A—C5A117.1 (6)O52B—C51B—C5B116.8 (6)
C51A—O52A—H52A117 (5)C51B—O52B—H52B107 (5)
C5A—C6A—N1A122.4 (6)N1B—C6B—C5B123.2 (6)
C5A—C6A—H6A118.8N1B—C6B—H6B118.4
N1A—C6A—H6A118.8C5B—C6B—H6B118.4
C6A—N1A—C2A—N3A3.5 (9)C6B—N1B—C2B—N3B2.7 (10)
C6A—N1A—C2A—S21A177.4 (6)C6B—N1B—C2B—S21B177.2 (6)
N1A—C2A—N3A—C4A3.6 (10)N1B—C2B—N3B—C4B0.1 (10)
S21A—C2A—N3A—C4A175.5 (5)S21B—C2B—N3B—C4B179.8 (6)
C2A—N3A—C4A—O41A173.5 (7)C2B—N3B—C4B—O41B175.3 (7)
C2A—N3A—C4A—C5A7.7 (10)C2B—N3B—C4B—C5B3.1 (10)
O41A—C4A—C5A—C6A176.3 (7)O41B—C4B—C5B—C6B174.4 (7)
N3A—C4A—C5A—C6A5.0 (9)N3B—C4B—C5B—C6B3.8 (9)
O41A—C4A—C5A—C51A5.7 (12)O41B—C4B—C5B—C51B3.4 (12)
N3A—C4A—C5A—C51A173.0 (7)N3B—C4B—C5B—C51B178.4 (6)
C6A—C5A—C51A—O51A1.3 (10)C6B—C5B—C51B—O51B0.8 (11)
C4A—C5A—C51A—O51A179.4 (7)C4B—C5B—C51B—O51B177.0 (7)
C6A—C5A—C51A—O52A177.6 (6)C6B—C5B—C51B—O52B177.7 (7)
C4A—C5A—C51A—O52A0.5 (10)C4B—C5B—C51B—O52B4.5 (10)
C4A—C5A—C6A—N1A1.0 (11)C2B—N1B—C6B—C5B1.8 (11)
C51A—C5A—C6A—N1A179.2 (6)C4B—C5B—C6B—N1B1.8 (11)
C2A—N1A—C6A—C5A5.8 (11)C51B—C5B—C6B—N1B179.7 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O52Bi0.88 (2)2.38 (3)3.239 (7)168 (6)
N1B—H1B···O52Aii0.87 (2)2.41 (3)3.235 (7)158 (6)
N3A—H3A···S21B0.87 (2)2.52 (2)3.393 (6)177 (6)
N3B—H3B···S21A0.87 (2)2.57 (3)3.409 (6)163 (6)
O52A—H52A···O51Biii0.84 (2)1.82 (3)2.639 (6)165 (8)
O52B—H52B···O51Aiv0.85 (2)1.81 (2)2.657 (6)177 (8)
N1A—H1A···O41Bi0.88 (2)2.32 (6)2.840 (7)118 (5)
C6A—H6A···O41Bi0.952.322.898 (8)118
N1B—H1B···O41Aii0.87 (2)2.27 (6)2.822 (7)121 (6)
C6B—H6B···O41Aii0.952.332.891 (8)117
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y1/2, z1/2; (iii) x, y+1, z; (iv) x, y1, z.
Crystallization of 5-(hydroxymethyl)uracil, (I), 5-carboxyuracil, (II)–(IV), and 5-carboxy-2-thiouracil, (V)–(VIII). All crystallization experiments were performed at room temperature. top
CrystalAmount (mg, mmol)Solvent
(I)2.4, 0.017H2O (200 µl)
(II)1.9, 0.012DMF (50 µl)
(III)2.7, 0.017DMSO (50 µl)
(IV)2.2, 0.014DMAC (25 µl)
(V)2.3, 0.013DMF (25 µl)
(VI)2.6, 0.015DMSO (25 µl)
(VII)2.3, 0.013Dioxane (300 µl)
(VIII)2.0, 0.012Methanol (500 µl)

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC5H6N2O3C5H4N2O4·C3H7NOC5H4N2O4·C2H6OSC5H4N2O4·C4H9NO
Mr142.12229.20234.23243.22
Crystal system, space groupTriclinic, P1Monoclinic, P21/cMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)173173173173
a, b, c (Å)4.874 (3), 7.663 (2), 8.325 (3)8.671 (3), 12.394 (2), 9.381 (2)6.9341 (9), 6.9015 (5), 20.919 (3)11.7707 (19), 6.1053 (10), 15.271 (3)
α, β, γ (°)66.97 (2), 88.09 (2), 87.07 (2)90, 90.17 (2), 9090, 96.604 (10), 9090, 90.858 (13), 90
V3)285.7 (2)1008.2 (4)994.5 (2)1097.3 (3)
Z2444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.140.130.330.12
Crystal size (mm)0.30 × 0.30 × 0.100.29 × 0.21 × 0.200.25 × 0.12 × 0.100.30 × 0.25 × 0.15
Data collection
DiffractometerStoe IPDS II two-circleStoe IPDS II two-circleStoe IPDS II two-circleStoe IPDS II two-circle
Absorption correctionMulti-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Tmin, Tmax0.221, 1.0000.415, 1.0000.565, 1.0000.317, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2369, 1091, 807 8325, 1955, 1180 7444, 1900, 1443 8148, 2119, 1328
Rint0.0460.1320.0740.065
(sin θ/λ)max1)0.6130.6200.6130.615
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.145, 1.05 0.064, 0.165, 1.00 0.046, 0.105, 1.06 0.060, 0.150, 0.99
No. of reflections1091195519002119
No. of parameters100156147185
No. of restraints333131
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.42, 0.300.22, 0.240.25, 0.440.17, 0.25


(V)(VI)(VII)(VIII)
Crystal data
Chemical formulaC5H4N2O3S·C3H7NOC5H4N2O3S·C2H6OSC5H4N2O3S·1.5C4H8O2C5H4N2O3S
Mr245.26250.29304.32172.16
Crystal system, space groupMonoclinic, P21/cTriclinic, P1Triclinic, P1Monoclinic, P21/c
Temperature (K)173173173173
a, b, c (Å)10.1742 (10), 11.4616 (12), 9.9715 (11)7.0475 (9), 8.9534 (12), 9.2802 (13)5.2819 (7), 10.3542 (12), 13.0071 (15)11.409 (3), 15.552 (3), 7.369 (2)
α, β, γ (°)90, 104.318 (8), 90115.79 (1), 95.753 (11), 95.791 (10)89.377 (10), 85.143 (10), 77.70 (1)90, 97.599 (19), 90
V3)1126.7 (2)517.72 (13)692.51 (15)1296.0 (6)
Z4228
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.290.510.260.45
Crystal size (mm)0.40 × 0.30 × 0.300.30 × 0.25 × 0.150.30 × 0.21 × 0.160.25 × 0.11 × 0.08
Data collection
DiffractometerStoe IPDS II two-circleStoe IPDS II two-circleStoe IPDS II two-circleStoe IPDS II two-circle
Absorption correctionMulti-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Multi-scan
(X-AREA; Stoe & Cie, 2001)
Tmin, Tmax0.499, 1.0000.746, 1.0000.528, 1.0000.149, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8433, 2163, 1796 4538, 1976, 1703 5885, 2645, 2272 9985, 2492, 1294
Rint0.0450.0330.0450.149
(sin θ/λ)max1)0.6130.6130.6130.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.093, 1.08 0.027, 0.070, 1.05 0.036, 0.100, 1.04 0.077, 0.164, 0.96
No. of reflections2163197626452492
No. of parameters157147190217
No. of restraints3336
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.200.40, 0.230.30, 0.220.61, 0.32

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008) and XP in SHELXTL-Plus (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21Ai0.872 (17)1.940 (18)2.804 (3)171 (3)
N3A—H3A···O41Aii0.899 (17)1.920 (18)2.817 (3)176 (3)
O51A—H51C···O21Aiii0.84 (4)1.97 (4)2.741 (3)151 (3)
Symmetry codes: (i) x+1, y+2, z; (ii) x, y+1, z+1; (iii) x+1, y1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21X0.902 (18)1.813 (19)2.712 (3)174 (3)
N3A—H3A···O51Ai0.882 (18)2.022 (19)2.902 (3)176 (4)
O52A—H52A···O41A0.859 (19)1.78 (2)2.590 (3)158 (4)
C6A—H6A···O41Aii0.952.193.061 (3)151.0
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O52A—H52A···O41A0.847 (18)1.76 (2)2.579 (3)162 (3)
N1A—H1A···O11X0.867 (17)1.881 (18)2.747 (3)176 (3)
N3A—H3A···O11Xi0.867 (17)1.852 (18)2.718 (3)177 (3)
C6A—H6A···O41Aii0.952.543.422 (3)154.2
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O21X0.888 (18)1.793 (19)2.672 (3)170 (3)
O52A—H52A···O41A0.873 (18)1.77 (2)2.605 (3)158 (3)
N3A—H3A···O21Ai0.873 (18)1.984 (19)2.851 (3)172 (3)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) for (V) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O51Ai0.872 (16)1.922 (16)2.7846 (19)169 (2)
N3A—H3A···O21X0.881 (16)1.842 (16)2.723 (2)179 (2)
O52A—H52A···O41A0.819 (16)1.791 (17)2.5735 (18)159 (2)
C6A—H6A···O52Ai0.952.533.269 (2)134.7
Symmetry code: (i) x, y1/2, z+3/2.
Hydrogen-bond geometry (Å, º) for (VI) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O11X0.883 (15)1.829 (15)2.7087 (17)174.1 (19)
N3A—H3A···O11Xi0.886 (15)1.915 (15)2.7983 (18)175.2 (19)
O52A—H52A···O41A0.825 (16)1.804 (18)2.5738 (19)155 (2)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (VII) top
D—H···AD—HH···AD···AD—H···A
C6A—H6A···O51Ai0.952.263.1892 (18)165.9
N1A—H1A···O1Z0.862 (15)1.905 (15)2.7670 (17)177.6 (19)
N3A—H3A···O1X0.898 (14)1.894 (15)2.7889 (17)174.3 (18)
O52A—H52A···O41A0.821 (16)1.814 (17)2.5998 (16)160 (2)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) for (VIII) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A···O52Bi0.88 (2)2.38 (3)3.239 (7)168 (6)
N1B—H1B···O52Aii0.87 (2)2.41 (3)3.235 (7)158 (6)
N3A—H3A···S21B0.87 (2)2.52 (2)3.393 (6)177 (6)
N3B—H3B···S21A0.87 (2)2.57 (3)3.409 (6)163 (6)
O52A—H52A···O51Biii0.84 (2)1.82 (3)2.639 (6)165 (8)
O52B—H52B···O51Aiv0.85 (2)1.81 (2)2.657 (6)177 (8)
N1A—H1A···O41Bi0.88 (2)2.32 (6)2.840 (7)118 (5)
C6A—H6A···O41Bi0.952.322.898 (8)118.2
N1B—H1B···O41Aii0.87 (2)2.27 (6)2.822 (7)121 (6)
C6B—H6B···O41Aii0.952.332.891 (8)117.4
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y1/2, z1/2; (iii) x, y+1, z; (iv) x, y1, z.
 

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