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

Tutughamiarso, M.; Egert, E.

doi:10.1107/S0108270111037991

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 67| Part 11| November 2011| Pages o439-o445

doi:10.1107/S0108270111037991

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

Maya Tutughamiarso ^a and Ernst Egert ^a ^*

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

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

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

Comment

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

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

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

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

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

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

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

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

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

From the hydrogen-bond interactions in the three structures [(I)–(III)], it is not evident whether an N—H⋯O or an N—H⋯S hydrogen bond is stronger. A CSD search of six-membered ring compounds with hydrogen-bonding sites similar to 2-thiouracil yielded four different types of R₂²(8) patterns. 19 entries showed R₂²(8) motifs characterized by two N—H⋯O hydrogen bonds; the S atoms take part as acceptors only in five of them [refcodes LACJIJ (Tashkhodzhaev et al., 2002 ), XUHJIY (Pawlowski et al., 2009 ), XEXWAZ, XEXWED and XEXWIH (Balalaie et al., 2006 )], whereby chains stabilized by N—H⋯S hydrogen bonds are observed only in XUHJIY. Nine structures contain two different R₂²(8) patterns with either two N—H⋯O or two N—H⋯S hydrogen bonds [refcodes CASPUI (Hu et al., 2005 ), CUKBOA (Hori et al., 2009 ), GEMCAC (Read et al., 1988 ), PABPAL (Chierotti et al., 2010 ), RAPNAY (Long et al., 2005 ), TURCIL01 (Tiekink, 1989 ), TURCIL02 (Munshi & Guru Row, 2006 ), WIVJAM (Coxall et al., 2000 ) and ZEWDOU (Ferrari et al., 1995 )]. Furthermore, six entries showed R₂²(8) interactions consisting of two N—H⋯S hydrogen bonds [refcodes FALWOF (Orzeszko et al., 2004 ), JESWEK (Xue et al., 2006 ), MTURAC (Hawkinson, 1975 ), PABNIR (Chierotti et al., 2010), VOKBUT (Luo et al., 2008 ) and ZUWMUZ (Branch et al., 1996 )]. In three of these structures, the O atoms do not participate in hydrogen bonds. Finally, R₂²(8) motifs with one N—H⋯O and one N—H⋯S hydrogen bond are only observed in EAZTHY (Voutsas et al., 1978 ).

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

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

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

Figure 1
A perspective view of (I)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.

Figure 2
A packing diagram for (I)

. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) −x + 2, y − $[1 \over 2]$ , −z + $[1 \over 2]$ ; (ii) −x + 1, y − $[1 \over 2]$ , −z + $[3 \over 2]$ .]

Figure 3
Perspective views of (a) the first, (b) the second and (c) the third symmetry-independent complex molecules in the asymmetric unit of (II)

, showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.

Figure 4
A partial packing diagram for (II)

. Dashed lines indicate hydrogen bonds. The molecules are designated according to the atom-numbering scheme, with 6-propyl-2-thiouracil molecules marked with primes (see Fig. 3

Figure 5
A perspective view of (III)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.

Figure 6
A partial packing diagram for (III)

, showing chains of dimers running along the b axis. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) x, y − 1, z; (ii) x, y + 1, z.]

Figure 7
A packing diagram for (III)

, viewed down the b axis, showing the tubular arrangement of chains. Dashed lines indicate hydrogen bonds.

Experimental

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

Compound (I)

Crystal data

C₄H₅N₃·2C₇H₁₀N₂OS
M_r = 435.58
Monoclinic, P 2₁ /c
a = 7.6094 (5) Å
b = 12.9888 (6) Å
c = 20.8838 (14) Å
β = 99.179 (5)°
V = 2037.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.60 × 0.20 × 0.15 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009 ; Blessing, 1995 ) T_min = 0.844, T_max = 0.958
25516 measured reflections
3819 independent reflections
3163 reflections with I > 2σ(I)
R_int = 0.094

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.05
3819 reflections
289 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected torsion angles (°) for (I)

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

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

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

Compound (II)

Crystal data

C₉H₁₁N₃O₂·2C₇H₁₀N₂OS
M_r = 533.68
Orthorhombic, F d d 2
a = 37.9355 (12) Å
b = 76.880 (3) Å
c = 10.5666 (3) Å
V = 30817.3 (18) Å³
Z = 48
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 173 K
0.50 × 0.30 × 0.20 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) T_min = 0.885, T_max = 0.951
108254 measured reflections
14445 independent reflections
10225 reflections with I > 2σ(I)
R_int = 0.129

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.097
S = 0.91
14445 reflections
985 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 6784 Friedel pairs
Flack parameter: 0.12 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21A—H21A⋯O4′Dⁱ	0.88	2.03	2.904 (5)	169
N61A—H61A⋯O4′Eⁱⁱ	0.88	2.05	2.921 (5)	171
N21B—H21B⋯O4′A	0.88	2.04	2.906 (5)	170
N61B—H61B⋯O4′Fⁱⁱⁱ	0.88	2.03	2.893 (5)	169
N21C—H21C⋯O4′B	0.88	2.01	2.873 (5)	168
N61C—H61C⋯O4′C^iv	0.88	2.07	2.934 (5)	165
N1′A—H1′A⋯O24A	0.88	2.03	2.892 (4)	167
N3′A—H3′A⋯S2′D	0.88	2.42	3.279 (3)	166
N1′B—H1′B⋯O24B	0.88	2.00	2.859 (5)	165
N3′B—H3′B⋯S2′E	0.88	2.43	3.286 (4)	165
N1′C—H1′C⋯O24C	0.88	2.09	2.951 (4)	166
N3′C—H3′C⋯S2′F	0.88	2.45	3.313 (3)	166
N1′D—H1′D⋯O64A^v	0.88	2.00	2.870 (5)	168
N3′D—H3′D⋯S2′A	0.88	2.45	3.317 (3)	168
N1′E—H1′E⋯O64B^vi	0.88	2.06	2.919 (4)	166
N3′E—H3′E⋯S2′B	0.88	2.49	3.358 (3)	168
N1′F—H1′F⋯O64C^vii	0.88	2.08	2.944 (4)	166
N3′F—H3′F⋯S2′C	0.88	2.49	3.359 (3)	168
Symmetry codes: (i) -x, -y+1, z; (ii) $[-x+{\script{1\over 4}}, y-{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[-x+{\script{3\over 4}}, y-{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (iv) $[x-{\script{1\over 4}}, -y+{\script{5\over 4}}, z-{\script{1\over 4}}]$ ; (v) $[-x+{\script{1\over 4}}, y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (vi) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (vii) $[-x+{\script{5\over 4}}, y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Compound (III)

Crystal data

C₇H₁₀N₂OS
M_r = 170.23
Orthorhombic, P b c a
a = 10.4340 (6) Å
b = 11.1320 (6) Å
c = 28.7090 (17) Å
V = 3334.6 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 173 K
0.40 × 0.20 × 0.20 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) T_min = 0.879, T_max = 0.937
29872 measured reflections
3131 independent reflections
1990 reflections with I > 2σ(I)
R_int = 0.132

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.093
S = 0.91
3131 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 8
Selected torsion angles (°) for (III)

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

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

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

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

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

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

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

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

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

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

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

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

All H atoms were initially located by difference Fourier synthesis. Subsequently, H atoms bonded to C atoms were refined using a riding model, with methyl C—H = 0.98 Å, secondary C—H = 0.99 Å and aromatic C—H = 0.95 Å, and with U_iso(H) = 1.5U_eq(C) for methyl or 1.2U_eq(C) for secondary and aromatic H atoms. In (II) and (III), H atoms bonded to N atoms were refined using a riding model, with amide N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N), while in (I) they were refined isotropically. The methyl groups were allowed to rotate about their local threefold axes.

Owing to the systematic absences analysed by the program XPREP (Sheldrick, 2008 ), (II) was solved and refined in the noncentrosymmetric space group Fdd2. Structure validation with PLATON/ADDSYM (Le Page, 1987 , 1988 ; Spek, 2009) detected a pseudo-inversion centre at (0.126, 0.208, 0.466), which is not compatible with this space group. Since no correlation matrix elements larger than 0.5 are observed and the Flack (1983) parameter is consistent with a noncentrosymmetric structure, the space group was retained.

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

Supporting information

Crystal structure: contains datablocks I, II, III, global. DOI: 10.1107/S0108270111037991/sk3414sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270111037991/sk3414Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S0108270111037991/sk3414IIsup3.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270111037991/sk3414IIIsup4.hkl

Supporting information file. DOI: 10.1107/S0108270111037991/sk3414Isup5.cml

Supporting information file. DOI: 10.1107/S0108270111037991/sk3414IIsup6.cml

Supporting information file. DOI: 10.1107/S0108270111037991/sk3414IIIsup7.cml

Comment top

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

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

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

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

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

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

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

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

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

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

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

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

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

Related literature top

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

Experimental top

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

Computing details top

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

Figures top

	Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 2. A packing diagram for (I). Dashed lines indicate hydrogen bonds.
	Fig. 3. Perspective views of (a) the first, (b) the second and (c) the third symmetry-independent complex in the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 4. A partial packing diagram for (II). Dashed lines indicate hydrogen bonds. The molecules are designated according to the atom numbering.
	Fig. 5. A perspective view of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds.
	Fig. 6. A partial packing diagram for (III) showing chains of dimers running along the b axis. Dashed lines indicate hydrogen bonds.
	Fig. 7. A packing diagram for (III) showing the formation of tubes. Dashed lines indicate hydrogen bonds. [Please indicate the origin]

(I) 2-aminopyrimidine bis(6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one) top

Crystal data top

C₄H₅N₃·2C₇H₁₀N₂OS	F(000) = 920
M_r = 435.57	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.6094 (5) Å	Cell parameters from 18641 reflections
b = 12.9888 (6) Å	θ = 3.5–25.8°
c = 20.8838 (14) Å	µ = 0.29 mm⁻¹
β = 99.179 (5)°	T = 173 K
V = 2037.7 (2) Å³	Block, colourless
Z = 4	0.60 × 0.20 × 0.15 mm

Data collection top

Stoe IPDS II two-circle diffractometer	3819 independent reflections
Radiation source: fine-focus sealed tube	3163 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
ω scans	θ_max = 25.6°, θ_min = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −9→9
T_min = 0.844, T_max = 0.958	k = −15→14
25516 measured reflections	l = −25→25

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0617P)² + 0.2289P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3819 reflections	Δρ_max = 0.30 e Å⁻³
289 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (6)

Crystal data top

C₄H₅N₃·2C₇H₁₀N₂OS	V = 2037.7 (2) Å³
M_r = 435.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6094 (5) Å	µ = 0.29 mm⁻¹
b = 12.9888 (6) Å	T = 173 K
c = 20.8838 (14) Å	0.60 × 0.20 × 0.15 mm
β = 99.179 (5)°

Data collection top

Stoe IPDS II two-circle diffractometer	3819 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	3163 reflections with I > 2σ(I)
T_min = 0.844, T_max = 0.958	R_int = 0.094
25516 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.30 e Å⁻³
3819 reflections	Δρ_min = −0.29 e Å⁻³
289 parameters

Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.70342 (19)	0.49488 (12)	0.54717 (7)	0.0197 (3)
C2	0.7299 (2)	0.44500 (14)	0.49259 (8)	0.0188 (4)
N3	0.7939 (2)	0.48800 (12)	0.44186 (7)	0.0207 (3)
C4	0.8376 (3)	0.58776 (14)	0.44800 (9)	0.0238 (4)
H4	0.8828	0.6205	0.4134	0.029*
C5	0.8201 (3)	0.64541 (14)	0.50220 (9)	0.0249 (4)
H5	0.8550	0.7156	0.5061	0.030*
C6	0.7484 (2)	0.59469 (14)	0.55068 (9)	0.0216 (4)
H6	0.7305	0.6326	0.5880	0.026*
N21	0.6877 (2)	0.34417 (13)	0.48783 (9)	0.0280 (4)
H211	0.664 (3)	0.3122 (19)	0.5234 (11)	0.038 (6)*
H212	0.721 (3)	0.3089 (19)	0.4568 (12)	0.036 (6)*
N1A	0.9954 (2)	0.29340 (12)	0.25432 (7)	0.0181 (3)
H1A	1.009 (3)	0.2326 (18)	0.2442 (11)	0.029 (6)*
C2A	0.9322 (2)	0.31518 (13)	0.31017 (8)	0.0179 (4)
N3A	0.9080 (2)	0.41733 (11)	0.32194 (7)	0.0184 (3)
H3A	0.873 (3)	0.4340 (17)	0.3584 (11)	0.028 (6)*
C4A	0.9442 (2)	0.49830 (13)	0.28190 (8)	0.0187 (4)
C5A	1.0058 (2)	0.46774 (14)	0.22268 (9)	0.0215 (4)
H5A	1.0278	0.5185	0.1922	0.026*
C6A	1.0321 (2)	0.36715 (14)	0.21066 (8)	0.0195 (4)
S2A	0.88847 (6)	0.22183 (4)	0.36131 (2)	0.02233 (15)
O4A	0.92311 (18)	0.58839 (9)	0.29822 (6)	0.0246 (3)
C7A	1.1080 (3)	0.32542 (15)	0.15363 (10)	0.0293 (5)
H7A1	1.0447	0.2607	0.1395	0.035*
H7A2	1.2344	0.3076	0.1685	0.035*
C8A	1.0986 (3)	0.39622 (15)	0.09466 (9)	0.0256 (4)
H8A1	1.1863	0.3728	0.0675	0.031*
H8A2	1.1314	0.4670	0.1096	0.031*
C9A	0.9153 (3)	0.3977 (2)	0.05403 (12)	0.0458 (6)
H9A1	0.8825	0.3278	0.0389	0.069*
H9A2	0.9160	0.4431	0.0166	0.069*
H9A3	0.8286	0.4232	0.0803	0.069*
N1B	0.4997 (2)	0.31722 (12)	0.74197 (7)	0.0176 (3)
H1B	0.485 (3)	0.2579 (18)	0.7530 (11)	0.029 (6)*
C2B	0.5533 (2)	0.33663 (13)	0.68388 (8)	0.0182 (4)
N3B	0.57733 (19)	0.43775 (11)	0.67011 (7)	0.0184 (3)
H3B	0.611 (3)	0.4512 (17)	0.6328 (11)	0.028 (6)*
C4B	0.5526 (2)	0.52082 (13)	0.71078 (9)	0.0195 (4)
C5B	0.4991 (2)	0.49254 (14)	0.77175 (9)	0.0211 (4)
H5B	0.4822	0.5446	0.8021	0.025*
C6B	0.4729 (2)	0.39260 (13)	0.78597 (8)	0.0183 (4)
S2B	0.58686 (7)	0.24071 (4)	0.63318 (2)	0.02457 (15)
O4B	0.57692 (18)	0.61003 (10)	0.69342 (6)	0.0265 (3)
C7B	0.4101 (3)	0.35478 (14)	0.84640 (9)	0.0212 (4)
H7B1	0.4551	0.2839	0.8555	0.025*
H7B2	0.2784	0.3515	0.8383	0.025*
C8B	0.4680 (3)	0.42045 (16)	0.90602 (9)	0.0304 (5)
H8B1	0.4281	0.4923	0.8969	0.036*
H8B2	0.5995	0.4205	0.9165	0.036*
C9B	0.3900 (3)	0.37976 (16)	0.96403 (9)	0.0349 (5)
H9B1	0.2597	0.3825	0.9544	0.052*
H9B2	0.4318	0.4223	1.0022	0.052*
H9B3	0.4283	0.3084	0.9728	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0235 (8)	0.0186 (8)	0.0184 (7)	0.0016 (6)	0.0079 (6)	0.0003 (6)
C2	0.0204 (9)	0.0180 (9)	0.0186 (9)	0.0015 (7)	0.0051 (7)	0.0016 (7)
N3	0.0280 (8)	0.0180 (8)	0.0181 (8)	0.0016 (6)	0.0095 (6)	0.0010 (6)
C4	0.0314 (10)	0.0196 (10)	0.0231 (9)	0.0012 (8)	0.0131 (8)	0.0035 (7)
C5	0.0324 (10)	0.0153 (9)	0.0293 (10)	−0.0009 (8)	0.0118 (8)	−0.0008 (7)
C6	0.0253 (9)	0.0200 (9)	0.0207 (9)	0.0023 (7)	0.0075 (7)	−0.0026 (7)
N21	0.0447 (10)	0.0177 (8)	0.0260 (9)	−0.0049 (7)	0.0194 (8)	−0.0022 (7)
N1A	0.0262 (8)	0.0116 (8)	0.0178 (8)	0.0017 (6)	0.0072 (6)	−0.0010 (6)
C2A	0.0206 (8)	0.0159 (9)	0.0176 (8)	−0.0019 (7)	0.0045 (7)	−0.0018 (7)
N3A	0.0275 (8)	0.0141 (8)	0.0156 (7)	0.0013 (6)	0.0093 (6)	−0.0016 (6)
C4A	0.0228 (9)	0.0161 (9)	0.0180 (9)	0.0004 (7)	0.0051 (7)	0.0006 (7)
C5A	0.0289 (9)	0.0161 (9)	0.0215 (9)	0.0017 (7)	0.0098 (7)	0.0033 (7)
C6A	0.0233 (9)	0.0178 (9)	0.0185 (9)	0.0013 (7)	0.0069 (7)	0.0009 (7)
S2A	0.0343 (3)	0.0145 (3)	0.0206 (3)	−0.00223 (17)	0.01194 (19)	0.00127 (16)
O4A	0.0404 (8)	0.0132 (6)	0.0227 (7)	0.0006 (5)	0.0125 (6)	−0.0023 (5)
C7A	0.0451 (12)	0.0204 (10)	0.0268 (10)	0.0089 (9)	0.0192 (9)	0.0031 (8)
C8A	0.0359 (11)	0.0211 (10)	0.0237 (10)	−0.0023 (8)	0.0171 (8)	−0.0004 (8)
C9A	0.0465 (14)	0.0547 (16)	0.0368 (13)	−0.0054 (11)	0.0086 (10)	0.0132 (11)
N1B	0.0265 (8)	0.0125 (8)	0.0151 (7)	−0.0004 (6)	0.0069 (6)	0.0001 (6)
C2B	0.0204 (8)	0.0164 (9)	0.0182 (9)	0.0012 (7)	0.0045 (7)	0.0008 (7)
N3B	0.0276 (8)	0.0153 (8)	0.0139 (8)	−0.0003 (6)	0.0080 (6)	0.0008 (6)
C4B	0.0230 (9)	0.0155 (9)	0.0201 (9)	−0.0015 (7)	0.0043 (7)	−0.0004 (7)
C5B	0.0308 (10)	0.0146 (9)	0.0193 (9)	−0.0010 (7)	0.0085 (7)	−0.0025 (7)
C6B	0.0215 (9)	0.0160 (9)	0.0177 (9)	−0.0006 (7)	0.0041 (7)	−0.0010 (7)
S2B	0.0412 (3)	0.0152 (3)	0.0209 (3)	0.00032 (19)	0.0160 (2)	−0.00253 (17)
O4B	0.0431 (8)	0.0145 (7)	0.0239 (7)	−0.0021 (6)	0.0119 (6)	0.0023 (5)
C7B	0.0308 (10)	0.0162 (9)	0.0186 (9)	−0.0035 (7)	0.0101 (7)	−0.0013 (7)
C8B	0.0490 (12)	0.0244 (11)	0.0214 (10)	−0.0128 (9)	0.0163 (9)	−0.0048 (8)
C9B	0.0616 (14)	0.0259 (11)	0.0217 (10)	−0.0126 (10)	0.0202 (10)	−0.0052 (8)

Geometric parameters (Å, º) top

N1—C6	1.340 (2)	C8A—C9A	1.513 (3)
N1—C2	1.354 (2)	C8A—H8A1	0.9900
C2—N21	1.348 (2)	C8A—H8A2	0.9900
C2—N3	1.355 (2)	C9A—H9A1	0.9800
N3—C4	1.339 (2)	C9A—H9A2	0.9800
C4—C5	1.381 (3)	C9A—H9A3	0.9800
C4—H4	0.9500	N1B—C2B	1.364 (2)
C5—C6	1.390 (3)	N1B—C6B	1.380 (2)
C5—H5	0.9500	N1B—H1B	0.82 (2)
C6—H6	0.9500	C2B—N3B	1.363 (2)
N21—H211	0.89 (2)	C2B—S2B	1.6807 (17)
N21—H212	0.87 (2)	N3B—C4B	1.404 (2)
N1A—C2A	1.361 (2)	N3B—H3B	0.88 (2)
N1A—C6A	1.381 (2)	C4B—O4B	1.237 (2)
N1A—H1A	0.83 (2)	C4B—C5B	1.445 (2)
C2A—N3A	1.367 (2)	C5B—C6B	1.353 (2)
C2A—S2A	1.6836 (18)	C5B—H5B	0.9500
N3A—C4A	1.398 (2)	C6B—C7B	1.502 (2)
N3A—H3A	0.87 (2)	C7B—C8B	1.516 (3)
C4A—O4A	1.236 (2)	C7B—H7B1	0.9900
C4A—C5A	1.446 (2)	C7B—H7B2	0.9900
C5A—C6A	1.351 (2)	C8B—C9B	1.526 (2)
C5A—H5A	0.9500	C8B—H8B1	0.9900
C6A—C7A	1.505 (2)	C8B—H8B2	0.9900
C7A—C8A	1.529 (3)	C9B—H9B1	0.9800
C7A—H7A1	0.9900	C9B—H9B2	0.9800
C7A—H7A2	0.9900	C9B—H9B3	0.9800

C6—N1—C2	115.98 (15)	C9A—C8A—H8A2	109.1
N21—C2—N1	117.45 (15)	H8A1—C8A—H8A2	107.9
N21—C2—N3	117.00 (16)	C8A—C9A—H9A1	109.5
N1—C2—N3	125.54 (17)	C8A—C9A—H9A2	109.5
C4—N3—C2	116.03 (15)	H9A1—C9A—H9A2	109.5
N3—C4—C5	123.26 (17)	C8A—C9A—H9A3	109.5
N3—C4—H4	118.4	H9A1—C9A—H9A3	109.5
C5—C4—H4	118.4	H9A2—C9A—H9A3	109.5
C4—C5—C6	116.12 (17)	C2B—N1B—C6B	123.92 (15)
C4—C5—H5	121.9	C2B—N1B—H1B	120.0 (16)
C6—C5—H5	121.9	C6B—N1B—H1B	116.0 (16)
N1—C6—C5	123.03 (17)	N1B—C2B—N3B	115.80 (15)
N1—C6—H6	118.5	N1B—C2B—S2B	121.36 (13)
C5—C6—H6	118.5	N3B—C2B—S2B	122.85 (13)
C2—N21—H211	117.9 (15)	C2B—N3B—C4B	125.26 (15)
C2—N21—H212	118.3 (16)	C2B—N3B—H3B	116.6 (15)
H211—N21—H212	120 (2)	C4B—N3B—H3B	118.2 (15)
C2A—N1A—C6A	123.91 (15)	O4B—C4B—N3B	120.12 (16)
C2A—N1A—H1A	119.5 (15)	O4B—C4B—C5B	124.95 (16)
C6A—N1A—H1A	116.5 (15)	N3B—C4B—C5B	114.93 (15)
N3A—C2A—N1A	115.60 (15)	C6B—C5B—C4B	120.62 (16)
N3A—C2A—S2A	122.62 (13)	C6B—C5B—H5B	119.7
N1A—C2A—S2A	121.78 (13)	C4B—C5B—H5B	119.7
C2A—N3A—C4A	125.28 (15)	C5B—C6B—N1B	119.46 (16)
C2A—N3A—H3A	117.8 (15)	C5B—C6B—C7B	125.16 (16)
C4A—N3A—H3A	116.9 (15)	N1B—C6B—C7B	115.35 (15)
O4A—C4A—N3A	120.03 (15)	C6B—C7B—C8B	114.62 (15)
O4A—C4A—C5A	124.72 (16)	C6B—C7B—H7B1	108.6
N3A—C4A—C5A	115.25 (15)	C8B—C7B—H7B1	108.6
C6A—C5A—C4A	120.14 (16)	C6B—C7B—H7B2	108.6
C6A—C5A—H5A	119.9	C8B—C7B—H7B2	108.6
C4A—C5A—H5A	119.9	H7B1—C7B—H7B2	107.6
C5A—C6A—N1A	119.76 (16)	C7B—C8B—C9B	111.01 (16)
C5A—C6A—C7A	125.60 (17)	C7B—C8B—H8B1	109.4
N1A—C6A—C7A	114.58 (15)	C9B—C8B—H8B1	109.4
C6A—C7A—C8A	116.50 (16)	C7B—C8B—H8B2	109.4
C6A—C7A—H7A1	108.2	C9B—C8B—H8B2	109.4
C8A—C7A—H7A1	108.2	H8B1—C8B—H8B2	108.0
C6A—C7A—H7A2	108.2	C8B—C9B—H9B1	109.5
C8A—C7A—H7A2	108.2	C8B—C9B—H9B2	109.5
H7A1—C7A—H7A2	107.3	H9B1—C9B—H9B2	109.5
C7A—C8A—C9A	112.32 (17)	C8B—C9B—H9B3	109.5
C7A—C8A—H8A1	109.1	H9B1—C9B—H9B3	109.5
C9A—C8A—H8A1	109.1	H9B2—C9B—H9B3	109.5
C7A—C8A—H8A2	109.1

C6—N1—C2—N21	179.34 (16)	C2A—N1A—C6A—C7A	177.62 (17)
C6—N1—C2—N3	−1.3 (3)	C5A—C6A—C7A—C8A	−20.7 (3)
N21—C2—N3—C4	−179.01 (17)	N1A—C6A—C7A—C8A	162.10 (17)
N1—C2—N3—C4	1.6 (3)	C6A—C7A—C8A—C9A	−78.4 (2)
C2—N3—C4—C5	0.1 (3)	C6B—N1B—C2B—N3B	−1.1 (3)
N3—C4—C5—C6	−1.8 (3)	C6B—N1B—C2B—S2B	178.90 (13)
C2—N1—C6—C5	−0.7 (3)	N1B—C2B—N3B—C4B	0.5 (3)
C4—C5—C6—N1	2.2 (3)	S2B—C2B—N3B—C4B	−179.49 (14)
C6A—N1A—C2A—N3A	−0.9 (3)	C2B—N3B—C4B—O4B	−179.51 (17)
C6A—N1A—C2A—S2A	179.54 (13)	C2B—N3B—C4B—C5B	0.6 (2)
N1A—C2A—N3A—C4A	−0.5 (3)	O4B—C4B—C5B—C6B	178.89 (18)
S2A—C2A—N3A—C4A	179.04 (14)	N3B—C4B—C5B—C6B	−1.2 (3)
C2A—N3A—C4A—O4A	−177.58 (16)	C4B—C5B—C6B—N1B	0.7 (3)
C2A—N3A—C4A—C5A	2.3 (3)	C4B—C5B—C6B—C7B	−177.31 (16)
O4A—C4A—C5A—C6A	177.03 (18)	C2B—N1B—C6B—C5B	0.5 (3)
N3A—C4A—C5A—C6A	−2.9 (3)	C2B—N1B—C6B—C7B	178.74 (16)
C4A—C5A—C6A—N1A	1.7 (3)	C5B—C6B—C7B—C8B	−31.6 (3)
C4A—C5A—C6A—C7A	−175.31 (17)	N1B—C6B—C7B—C8B	150.28 (17)
C2A—N1A—C6A—C5A	0.3 (3)	C6B—C7B—C8B—C9B	176.90 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H211···S2B	0.89 (2)	2.63 (2)	3.5145 (17)	173 (2)
N21—H212···S2A	0.87 (2)	2.77 (2)	3.6234 (18)	168 (2)
N1A—H1A···O4Aⁱ	0.83 (2)	2.17 (2)	2.983 (2)	167 (2)
N3A—H3A···N3	0.87 (2)	2.06 (2)	2.926 (2)	174 (2)
N1B—H1B···O4Bⁱⁱ	0.82 (2)	2.31 (2)	3.107 (2)	166 (2)
N3B—H3B···N1	0.88 (2)	2.10 (2)	2.975 (2)	175 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y−1/2, −z+3/2.

(II) N-(6-acetamidopyridin-2-yl)acetamide bis(6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one) top

Crystal data top

C₉H₁₁N₃O₂·2C₇H₁₀N₂OS	D_x = 1.380 Mg m⁻³
M_r = 533.67	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 37383 reflections
a = 37.9355 (12) Å	θ = 3.3–25.9°
b = 76.880 (3) Å	µ = 0.25 mm⁻¹
c = 10.5666 (3) Å	T = 173 K
V = 30817.3 (18) Å³	Block, colourless
Z = 48	0.50 × 0.30 × 0.20 mm
F(000) = 13536

Data collection top

Stoe IPDS II two-circle diffractometer	14445 independent reflections
Radiation source: fine-focus sealed tube	10225 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.129
ω scans	θ_max = 25.7°, θ_min = 3.3°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −45→46
T_min = 0.885, T_max = 0.951	k = −93→93
108254 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0392P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max = 0.002
14445 reflections	Δρ_max = 0.22 e Å⁻³
985 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 6784 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (7)

Crystal data top

C₉H₁₁N₃O₂·2C₇H₁₀N₂OS	V = 30817.3 (18) Å³
M_r = 533.67	Z = 48
Orthorhombic, Fdd2	Mo Kα radiation
a = 37.9355 (12) Å	µ = 0.25 mm⁻¹
b = 76.880 (3) Å	T = 173 K
c = 10.5666 (3) Å	0.50 × 0.30 × 0.20 mm

Data collection top

Stoe IPDS II two-circle diffractometer	14445 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	10225 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.951	R_int = 0.129
108254 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.097	Δρ_max = 0.22 e Å⁻³
S = 0.91	Δρ_min = −0.25 e Å⁻³
14445 reflections	Absolute structure: Flack (1983), 6784 Friedel pairs
985 parameters	Absolute structure parameter: 0.12 (7)
1 restraint

Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1A	0.04637 (8)	0.41911 (4)	0.3404 (3)	0.0205 (7)
C2A	0.06441 (11)	0.43341 (5)	0.3765 (3)	0.0210 (9)
C3A	0.10109 (12)	0.43423 (6)	0.3785 (4)	0.0293 (10)
H3A	0.1131	0.4445	0.4048	0.035*
C4A	0.11922 (11)	0.41971 (6)	0.3409 (5)	0.0323 (10)
H4A	0.1443	0.4200	0.3402	0.039*
C5A	0.10196 (12)	0.40476 (5)	0.3041 (4)	0.0270 (10)
H5A	0.1145	0.3947	0.2785	0.032*
C6A	0.06491 (12)	0.40519 (5)	0.3064 (3)	0.0223 (9)
N21A	0.04261 (10)	0.44734 (4)	0.4136 (3)	0.0240 (7)
H21A	0.0202	0.4448	0.4258	0.029*
C22A	0.05194 (11)	0.46425 (5)	0.4327 (3)	0.0235 (9)
C23A	0.02307 (12)	0.47639 (6)	0.4719 (4)	0.0354 (10)
H23A	0.0327	0.4853	0.5284	0.053*
H23B	0.0047	0.4698	0.5163	0.053*
H23C	0.0130	0.4819	0.3967	0.053*
O24A	0.08282 (8)	0.46960 (4)	0.4170 (3)	0.0334 (7)
N61A	0.04430 (10)	0.39090 (4)	0.2680 (3)	0.0222 (7)
H61A	0.0219	0.3931	0.2526	0.027*
C62A	0.05486 (12)	0.37402 (5)	0.2519 (4)	0.0249 (9)
C63A	0.02653 (12)	0.36131 (5)	0.2129 (4)	0.0315 (10)
H63A	0.0321	0.3566	0.1290	0.047*
H63B	0.0037	0.3673	0.2100	0.047*
H63C	0.0254	0.3518	0.2744	0.047*
O64A	0.08540 (9)	0.36925 (4)	0.2725 (3)	0.0359 (7)
N1B	0.29331 (10)	0.50438 (4)	0.6043 (3)	0.0198 (7)
C2B	0.31130 (11)	0.51879 (5)	0.5776 (3)	0.0210 (9)
C3B	0.34789 (12)	0.51984 (6)	0.5756 (4)	0.0275 (10)
H3B	0.3597	0.5304	0.5560	0.033*
C4B	0.36629 (13)	0.50483 (6)	0.6033 (5)	0.0348 (11)
H4B	0.3913	0.5050	0.6021	0.042*
C5B	0.34889 (12)	0.48959 (6)	0.6326 (4)	0.0279 (10)
H5B	0.3615	0.4793	0.6532	0.033*
C6B	0.31265 (12)	0.48984 (5)	0.6310 (3)	0.0227 (9)
N21B	0.28956 (10)	0.53334 (4)	0.5495 (3)	0.0225 (8)
H21B	0.2671	0.5312	0.5367	0.027*
C22B	0.29998 (12)	0.55044 (5)	0.5400 (3)	0.0235 (9)
C23B	0.27049 (13)	0.56306 (6)	0.5079 (4)	0.0341 (10)
H23D	0.2664	0.5709	0.5798	0.051*
H23E	0.2489	0.5565	0.4897	0.051*
H23F	0.2771	0.5699	0.4335	0.051*
O24B	0.33021 (8)	0.55548 (4)	0.5558 (3)	0.0324 (7)
N61B	0.29157 (9)	0.47512 (4)	0.6587 (3)	0.0234 (8)
H61B	0.2691	0.4771	0.6735	0.028*
C62B	0.30265 (11)	0.45815 (5)	0.6649 (3)	0.0230 (9)
C63B	0.27454 (12)	0.44515 (5)	0.6982 (4)	0.0326 (10)
H63D	0.2638	0.4406	0.6205	0.049*
H63E	0.2564	0.4508	0.7498	0.049*
H63F	0.2851	0.4355	0.7461	0.049*
O64B	0.33312 (8)	0.45376 (4)	0.6441 (3)	0.0326 (7)
N1C	0.53966 (7)	0.58569 (5)	0.3414 (3)	0.0215 (6)
C2C	0.55780 (12)	0.60074 (5)	0.3528 (3)	0.0217 (9)
C3C	0.59398 (14)	0.60159 (6)	0.3500 (5)	0.0368 (11)
H3C	0.6060	0.6123	0.3596	0.044*
C4C	0.61234 (11)	0.58609 (7)	0.3324 (6)	0.0448 (12)
H4C	0.6373	0.5863	0.3275	0.054*
C5C	0.59504 (12)	0.57067 (6)	0.3221 (4)	0.0336 (11)
H5C	0.6076	0.5600	0.3126	0.040*
C6C	0.55822 (11)	0.57096 (5)	0.3261 (3)	0.0201 (8)
N21C	0.53634 (10)	0.61562 (4)	0.3698 (3)	0.0233 (8)
H21C	0.5138	0.6137	0.3846	0.028*
C22C	0.54652 (12)	0.63266 (5)	0.3660 (4)	0.0245 (9)
C23C	0.51835 (13)	0.64592 (6)	0.3921 (4)	0.0350 (11)
H23G	0.5203	0.6499	0.4799	0.052*
H23H	0.4951	0.6407	0.3789	0.052*
H23I	0.5213	0.6558	0.3347	0.052*
O24C	0.57706 (8)	0.63735 (4)	0.3401 (3)	0.0290 (7)
N61C	0.53781 (10)	0.55587 (4)	0.3123 (3)	0.0247 (8)
H61C	0.5152	0.5575	0.2982	0.030*
C62C	0.54898 (11)	0.53895 (5)	0.3182 (3)	0.0237 (9)
C63C	0.52117 (12)	0.52517 (5)	0.2950 (4)	0.0331 (10)
H63G	0.5308	0.5161	0.2395	0.050*
H63H	0.5006	0.5305	0.2546	0.050*
H63I	0.5142	0.5200	0.3758	0.050*
O64C	0.57937 (8)	0.53474 (3)	0.3428 (2)	0.0302 (7)
N1'A	0.13439 (9)	0.49684 (4)	0.4535 (3)	0.0209 (7)
H1'A	0.1164	0.4897	0.4486	0.025*
C2'A	0.12755 (11)	0.51404 (5)	0.4722 (3)	0.0211 (8)
N3'A	0.15686 (9)	0.52431 (4)	0.4775 (3)	0.0218 (7)
H3'A	0.1533	0.5356	0.4856	0.026*
C4'A	0.19187 (11)	0.51875 (5)	0.4714 (3)	0.0230 (9)
C5'A	0.19626 (11)	0.50059 (5)	0.4509 (3)	0.0234 (9)
H5'A	0.2193	0.4958	0.4436	0.028*
C6'A	0.16765 (11)	0.48996 (5)	0.4418 (3)	0.0209 (8)
S2'A	0.08665 (3)	0.521886 (13)	0.48871 (10)	0.0289 (2)
O4'A	0.21543 (8)	0.52978 (4)	0.4852 (3)	0.0303 (7)
C7'A	0.16891 (11)	0.47065 (5)	0.4192 (3)	0.0223 (8)
H7'1	0.1550	0.4680	0.3422	0.027*
H7'2	0.1573	0.4647	0.4912	0.027*
C8'A	0.20564 (11)	0.46300 (5)	0.4032 (4)	0.0298 (9)
H8'1	0.2195	0.4650	0.4812	0.036*
H8'2	0.2178	0.4689	0.3323	0.036*
C9'A	0.20376 (12)	0.44355 (6)	0.3768 (4)	0.0363 (11)
H9'1	0.1940	0.4376	0.4508	0.054*
H9'2	0.2275	0.4391	0.3594	0.054*
H9'3	0.1886	0.4415	0.3033	0.054*
N1'B	0.38184 (10)	0.58121 (4)	0.4941 (3)	0.0213 (7)
H1'B	0.3637	0.5742	0.5018	0.026*
C2'B	0.37563 (12)	0.59809 (5)	0.4675 (3)	0.0203 (9)
N3'B	0.40486 (10)	0.60829 (4)	0.4569 (3)	0.0238 (8)
H3'B	0.4014	0.6195	0.4435	0.029*
C4'B	0.43985 (12)	0.60269 (5)	0.4653 (4)	0.0214 (9)
C5'B	0.44406 (12)	0.58472 (5)	0.4949 (4)	0.0243 (9)
H5'B	0.4671	0.5800	0.5039	0.029*
C6'B	0.41576 (12)	0.57434 (5)	0.5102 (3)	0.0209 (9)
S2'B	0.33509 (3)	0.606102 (13)	0.44351 (9)	0.0257 (2)
O4'B	0.46371 (8)	0.61343 (4)	0.4453 (3)	0.0311 (7)
C7'B	0.41645 (12)	0.55538 (5)	0.5413 (4)	0.0242 (9)
H7'3	0.4051	0.5489	0.4713	0.029*
H7'4	0.4022	0.5534	0.6184	0.029*
C8'B	0.45326 (12)	0.54784 (5)	0.5632 (4)	0.0263 (9)
H8'3	0.4650	0.5543	0.6327	0.032*
H8'4	0.4676	0.5493	0.4857	0.032*
C9'B	0.45136 (13)	0.52837 (6)	0.5973 (4)	0.0337 (10)
H9'4	0.4359	0.5268	0.6707	0.050*
H9'5	0.4750	0.5241	0.6176	0.050*
H9'6	0.4419	0.5218	0.5252	0.050*
N1'C	0.63084 (9)	0.66318 (4)	0.4136 (3)	0.0203 (7)
H1'C	0.6123	0.6565	0.4005	0.024*
C2'C	0.62536 (11)	0.68026 (5)	0.4414 (3)	0.0194 (8)
N3'C	0.65513 (9)	0.68986 (4)	0.4591 (3)	0.0209 (7)
H3'C	0.6523	0.7011	0.4730	0.025*
C4'C	0.68971 (11)	0.68358 (5)	0.4571 (3)	0.0227 (9)
C5'C	0.69303 (12)	0.66564 (5)	0.4251 (3)	0.0226 (9)
H5'C	0.7158	0.6606	0.4178	0.027*
C6'C	0.66410 (11)	0.65572 (5)	0.4051 (3)	0.0190 (8)
S2'C	0.58490 (3)	0.688842 (13)	0.45544 (9)	0.0266 (2)
O4'C	0.71390 (8)	0.69381 (4)	0.4805 (3)	0.0280 (7)
C7'C	0.66410 (12)	0.63658 (5)	0.3752 (4)	0.0230 (9)
H7'5	0.6505	0.6347	0.2964	0.028*
H7'6	0.6517	0.6303	0.4441	0.028*
C8'C	0.70052 (12)	0.62859 (5)	0.3587 (4)	0.0289 (10)
H8'5	0.7128	0.6343	0.2872	0.035*
H8'6	0.7146	0.6306	0.4362	0.035*
C9'C	0.69790 (14)	0.60927 (6)	0.3334 (5)	0.0406 (12)
H9'7	0.6879	0.6034	0.4076	0.061*
H9'8	0.7214	0.6046	0.3161	0.061*
H9'9	0.6826	0.6073	0.2600	0.061*
N1'D	0.11197 (9)	0.59257 (4)	0.5034 (3)	0.0234 (7)
H1'D	0.1303	0.5996	0.5052	0.028*
C2'D	0.11786 (10)	0.57519 (5)	0.4990 (3)	0.0204 (8)
N3'D	0.08833 (9)	0.56501 (4)	0.4948 (3)	0.0235 (7)
H3'D	0.0915	0.5537	0.4925	0.028*
C4'D	0.05337 (11)	0.57097 (5)	0.4937 (4)	0.0252 (9)
C5'D	0.04972 (11)	0.58954 (5)	0.5003 (4)	0.0250 (9)
H5'D	0.0269	0.5946	0.5013	0.030*
C6'D	0.07851 (10)	0.59991 (5)	0.5053 (3)	0.0187 (8)
S2'D	0.15874 (3)	0.566847 (13)	0.49901 (11)	0.0322 (2)
O4'D	0.02949 (8)	0.56006 (4)	0.4886 (3)	0.0310 (7)
C7'D	0.07832 (11)	0.61952 (5)	0.5136 (4)	0.0242 (9)
H7'7	0.0900	0.6229	0.5936	0.029*
H7'8	0.0928	0.6241	0.4433	0.029*
C8'D	0.04280 (12)	0.62824 (5)	0.5086 (4)	0.0314 (10)
H8'7	0.0277	0.6237	0.5776	0.038*
H8'8	0.0312	0.6255	0.4270	0.038*
C9'D	0.04670 (12)	0.64801 (5)	0.5227 (4)	0.0351 (10)
H9'X	0.0559	0.6507	0.6071	0.053*
H9'Y	0.0236	0.6536	0.5116	0.053*
H9'Z	0.0631	0.6524	0.4583	0.053*
N1'E	0.36296 (9)	0.67688 (4)	0.4185 (3)	0.0205 (7)
H1'E	0.3817	0.6836	0.4153	0.025*
C2'E	0.36797 (12)	0.65940 (5)	0.4210 (4)	0.0237 (9)
N3'E	0.33807 (10)	0.64972 (4)	0.4297 (3)	0.0238 (8)
H3'E	0.3408	0.6384	0.4336	0.029*
C4'E	0.30356 (11)	0.65599 (5)	0.4332 (4)	0.0216 (9)
C5'E	0.30064 (11)	0.67473 (5)	0.4282 (4)	0.0233 (9)
H5'E	0.2780	0.6800	0.4302	0.028*
C6'E	0.32987 (12)	0.68475 (5)	0.4208 (3)	0.0220 (9)
S2'E	0.40831 (3)	0.650629 (14)	0.41640 (11)	0.0315 (3)
O4'E	0.27904 (8)	0.64556 (4)	0.4411 (3)	0.0315 (7)
C7'E	0.33083 (11)	0.70422 (5)	0.4139 (3)	0.0228 (8)
H7'9	0.3425	0.7077	0.3339	0.027*
H7'X	0.3455	0.7086	0.4845	0.027*
C8'E	0.29459 (11)	0.71310 (5)	0.4200 (4)	0.0303 (10)
H8'9	0.2831	0.7104	0.5020	0.036*
H8'X	0.2793	0.7086	0.3513	0.036*
C9'E	0.29917 (13)	0.73295 (6)	0.4060 (5)	0.0417 (12)
H9'A	0.3147	0.7373	0.4730	0.063*
H9'B	0.2761	0.7386	0.4127	0.063*
H9'C	0.3096	0.7356	0.3232	0.063*
N1'F	0.61587 (9)	0.75861 (4)	0.5395 (3)	0.0213 (7)
H1'F	0.6347	0.7651	0.5501	0.026*
C2'F	0.62052 (11)	0.74121 (5)	0.5208 (3)	0.0208 (9)
N3'F	0.59025 (9)	0.73191 (4)	0.5054 (3)	0.0211 (7)
H3'F	0.5926	0.7206	0.4940	0.025*
C4'F	0.55616 (11)	0.73843 (5)	0.5060 (4)	0.0236 (9)
C5'F	0.55347 (11)	0.75687 (5)	0.5256 (3)	0.0224 (9)
H5'F	0.5310	0.7623	0.5266	0.027*
C6'F	0.58300 (11)	0.76663 (5)	0.5426 (3)	0.0200 (8)
S2'F	0.66055 (3)	0.732086 (13)	0.51839 (10)	0.0279 (2)
O4'F	0.53115 (8)	0.72836 (3)	0.4878 (3)	0.0298 (7)
C7'F	0.58398 (12)	0.78580 (5)	0.5630 (4)	0.0259 (9)
H7'Y	0.5975	0.7911	0.4928	0.031*
H7'Z	0.5971	0.7881	0.6422	0.031*
C8'F	0.54838 (12)	0.79484 (5)	0.5712 (4)	0.0323 (10)
H8'Y	0.5346	0.7898	0.6417	0.039*
H8'Z	0.5351	0.7928	0.4918	0.039*
C9'F	0.55272 (13)	0.81434 (5)	0.5925 (5)	0.0425 (12)
H9'D	0.5655	0.8163	0.6717	0.064*
H9'E	0.5294	0.8198	0.5976	0.064*
H9'F	0.5660	0.8194	0.5220	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0183 (15)	0.0184 (18)	0.0248 (14)	−0.0009 (14)	−0.0025 (15)	−0.0015 (12)
C2A	0.022 (2)	0.018 (2)	0.0230 (18)	−0.0036 (16)	0.0004 (15)	−0.0020 (14)
C3A	0.020 (2)	0.025 (2)	0.043 (2)	−0.0026 (18)	−0.0082 (17)	−0.0020 (17)
C4A	0.018 (2)	0.024 (3)	0.054 (2)	0.0000 (18)	−0.005 (2)	−0.008 (2)
C5A	0.018 (2)	0.018 (2)	0.045 (2)	0.0021 (17)	−0.0018 (17)	−0.0069 (17)
C6A	0.023 (2)	0.020 (2)	0.0244 (18)	−0.0025 (17)	−0.0037 (16)	−0.0007 (15)
N21A	0.0175 (18)	0.0208 (18)	0.0337 (17)	−0.0009 (14)	0.0039 (13)	−0.0044 (13)
C22A	0.026 (2)	0.020 (2)	0.0243 (18)	−0.0038 (17)	−0.0007 (16)	−0.0013 (15)
C23A	0.030 (2)	0.026 (2)	0.051 (3)	−0.0003 (19)	0.002 (2)	−0.0077 (18)
O24A	0.0224 (16)	0.0236 (16)	0.0543 (17)	−0.0057 (12)	0.0059 (13)	−0.0070 (13)
N61A	0.0171 (19)	0.0167 (18)	0.0327 (16)	0.0020 (13)	−0.0038 (13)	−0.0037 (13)
C62A	0.022 (2)	0.022 (2)	0.0309 (19)	−0.0036 (17)	0.0022 (17)	−0.0025 (16)
C63A	0.025 (2)	0.021 (2)	0.048 (2)	−0.0004 (18)	−0.0025 (19)	−0.0044 (18)
O64A	0.0222 (18)	0.0185 (16)	0.0669 (19)	0.0058 (13)	−0.0019 (14)	−0.0039 (13)
N1B	0.0157 (18)	0.0188 (17)	0.0251 (15)	−0.0008 (14)	0.0017 (13)	0.0031 (12)
C2B	0.018 (2)	0.022 (2)	0.0230 (18)	0.0014 (17)	−0.0033 (16)	−0.0035 (15)
C3B	0.018 (2)	0.016 (2)	0.049 (2)	−0.0023 (16)	0.0010 (18)	0.0007 (17)
C4B	0.013 (2)	0.030 (3)	0.062 (3)	−0.0021 (19)	−0.002 (2)	0.001 (2)
C5B	0.020 (2)	0.021 (2)	0.042 (2)	0.0032 (18)	0.0031 (17)	0.0024 (17)
C6B	0.021 (2)	0.017 (2)	0.0294 (19)	−0.0018 (17)	0.0008 (16)	−0.0008 (15)
N21B	0.0174 (19)	0.0163 (18)	0.0336 (17)	−0.0015 (14)	−0.0045 (13)	0.0038 (13)
C22B	0.025 (2)	0.019 (2)	0.0261 (19)	−0.0021 (17)	−0.0020 (15)	0.0018 (15)
C23B	0.030 (3)	0.022 (2)	0.050 (2)	0.0023 (18)	−0.014 (2)	0.0028 (19)
O24B	0.0217 (17)	0.0247 (16)	0.0508 (17)	−0.0074 (12)	−0.0031 (13)	0.0021 (12)
N61B	0.0113 (17)	0.0197 (18)	0.0391 (18)	0.0025 (13)	0.0070 (14)	0.0040 (14)
C62B	0.022 (2)	0.018 (2)	0.0284 (19)	0.0052 (16)	0.0011 (16)	0.0034 (15)
C63B	0.025 (2)	0.018 (2)	0.056 (3)	0.0046 (17)	0.0106 (19)	0.0047 (19)
O64B	0.0192 (16)	0.0247 (16)	0.0540 (17)	0.0052 (13)	0.0066 (13)	0.0051 (13)
N1C	0.0192 (15)	0.0178 (18)	0.0275 (13)	0.0017 (15)	0.0019 (15)	0.0006 (12)
C2C	0.020 (2)	0.024 (2)	0.0213 (18)	0.0025 (18)	−0.0016 (15)	0.0001 (15)
C3C	0.028 (3)	0.021 (2)	0.062 (3)	−0.0048 (19)	−0.002 (2)	−0.005 (2)
C4C	0.0122 (19)	0.040 (3)	0.083 (3)	0.001 (2)	−0.001 (3)	0.004 (2)
C5C	0.014 (2)	0.024 (2)	0.062 (3)	0.0028 (18)	0.0038 (19)	−0.001 (2)
C6C	0.013 (2)	0.024 (2)	0.0227 (17)	0.0013 (16)	−0.0028 (15)	0.0011 (15)
N21C	0.0125 (18)	0.0211 (19)	0.0362 (18)	0.0026 (14)	0.0034 (13)	−0.0025 (13)
C22C	0.020 (2)	0.025 (2)	0.0286 (19)	−0.0032 (17)	0.0003 (16)	−0.0026 (16)
C23C	0.031 (3)	0.026 (2)	0.048 (2)	−0.0017 (19)	0.011 (2)	−0.0053 (18)
O24C	0.0230 (17)	0.0215 (15)	0.0427 (15)	−0.0057 (12)	0.0043 (12)	−0.0034 (12)
N61C	0.0155 (18)	0.0228 (19)	0.0358 (17)	0.0023 (14)	−0.0045 (14)	−0.0010 (13)
C62C	0.020 (2)	0.023 (2)	0.0273 (19)	0.0007 (16)	−0.0016 (16)	−0.0022 (16)
C63C	0.029 (2)	0.023 (2)	0.048 (2)	−0.0019 (18)	−0.0073 (19)	−0.0069 (18)
O64C	0.0236 (16)	0.0236 (15)	0.0433 (15)	0.0071 (12)	−0.0057 (12)	−0.0057 (12)
N1'A	0.0151 (17)	0.0177 (18)	0.0298 (16)	−0.0030 (13)	−0.0024 (13)	0.0009 (12)
C2'A	0.019 (2)	0.017 (2)	0.0266 (18)	−0.0063 (16)	−0.0002 (15)	0.0033 (14)
N3'A	0.0170 (18)	0.0156 (17)	0.0329 (16)	−0.0017 (13)	−0.0044 (14)	0.0004 (12)
C4'A	0.017 (2)	0.023 (2)	0.029 (2)	−0.0025 (17)	0.0005 (15)	0.0063 (16)
C5'A	0.017 (2)	0.025 (2)	0.0290 (19)	0.0013 (17)	−0.0011 (15)	0.0018 (16)
C6'A	0.022 (2)	0.017 (2)	0.0233 (17)	0.0016 (16)	−0.0024 (15)	0.0022 (14)
S2'A	0.0172 (5)	0.0218 (5)	0.0478 (6)	−0.0001 (4)	−0.0004 (5)	0.0026 (4)
O4'A	0.0162 (16)	0.0244 (16)	0.0502 (17)	−0.0042 (12)	−0.0025 (13)	−0.0006 (13)
C7'A	0.020 (2)	0.017 (2)	0.0296 (18)	−0.0018 (16)	−0.0017 (15)	−0.0022 (15)
C8'A	0.025 (2)	0.026 (2)	0.039 (2)	0.0018 (18)	−0.0005 (17)	−0.0046 (17)
C9'A	0.025 (2)	0.025 (2)	0.058 (3)	0.0035 (19)	0.009 (2)	−0.0163 (19)
N1'B	0.0165 (19)	0.0191 (18)	0.0285 (16)	−0.0020 (14)	0.0004 (13)	0.0017 (13)
C2'B	0.024 (2)	0.015 (2)	0.0214 (18)	−0.0001 (17)	−0.0010 (15)	−0.0020 (14)
N3'B	0.021 (2)	0.0169 (18)	0.0333 (17)	0.0007 (14)	0.0004 (15)	0.0000 (14)
C4'B	0.018 (2)	0.015 (2)	0.031 (2)	−0.0017 (16)	0.0049 (16)	−0.0048 (15)
C5'B	0.021 (3)	0.020 (2)	0.033 (2)	0.0005 (17)	0.0000 (17)	0.0015 (16)
C6'B	0.021 (2)	0.023 (2)	0.0189 (16)	0.0057 (17)	−0.0041 (15)	−0.0004 (14)
S2'B	0.0173 (5)	0.0177 (5)	0.0421 (5)	0.0003 (4)	−0.0012 (4)	−0.0005 (4)
O4'B	0.0211 (18)	0.0221 (16)	0.0503 (17)	−0.0074 (13)	0.0069 (14)	−0.0003 (13)
C7'B	0.022 (2)	0.019 (2)	0.032 (2)	−0.0029 (17)	−0.0033 (16)	0.0012 (15)
C8'B	0.025 (2)	0.018 (2)	0.035 (2)	−0.0009 (17)	−0.0016 (17)	0.0031 (16)
C9'B	0.028 (3)	0.022 (2)	0.051 (3)	−0.0058 (19)	−0.007 (2)	0.0037 (19)
N1'C	0.0147 (18)	0.0183 (17)	0.0278 (16)	−0.0026 (13)	−0.0004 (12)	−0.0028 (13)
C2'C	0.015 (2)	0.019 (2)	0.0235 (17)	−0.0052 (15)	0.0012 (15)	0.0044 (14)
N3'C	0.0175 (18)	0.0132 (17)	0.0320 (16)	0.0003 (13)	−0.0008 (13)	−0.0042 (12)
C4'C	0.019 (2)	0.022 (2)	0.0273 (18)	−0.0016 (17)	−0.0029 (16)	0.0038 (15)
C5'C	0.015 (2)	0.020 (2)	0.033 (2)	0.0032 (16)	0.0021 (16)	0.0015 (16)
C6'C	0.018 (2)	0.015 (2)	0.0241 (17)	−0.0018 (16)	−0.0014 (15)	0.0029 (14)
S2'C	0.0166 (5)	0.0210 (5)	0.0422 (5)	0.0012 (4)	0.0001 (4)	−0.0007 (4)
O4'C	0.0198 (16)	0.0219 (15)	0.0424 (16)	−0.0028 (12)	−0.0044 (12)	−0.0007 (12)
C7'C	0.022 (2)	0.019 (2)	0.0285 (18)	0.0012 (17)	0.0011 (16)	−0.0024 (15)
C8'C	0.020 (2)	0.024 (2)	0.042 (2)	−0.0006 (18)	0.0020 (17)	−0.0034 (18)
C9'C	0.029 (3)	0.029 (3)	0.063 (3)	0.007 (2)	0.005 (2)	−0.006 (2)
N1'D	0.0189 (19)	0.0174 (18)	0.0340 (16)	−0.0031 (14)	−0.0001 (14)	0.0001 (13)
C2'D	0.014 (2)	0.020 (2)	0.0278 (18)	−0.0008 (16)	−0.0022 (15)	−0.0002 (16)
N3'D	0.0194 (19)	0.0150 (17)	0.0360 (16)	−0.0002 (14)	−0.0017 (15)	0.0008 (13)
C4'D	0.019 (2)	0.028 (2)	0.0283 (19)	−0.0009 (18)	0.0015 (17)	0.0045 (17)
C5'D	0.018 (2)	0.025 (2)	0.0321 (19)	0.0008 (17)	−0.0010 (16)	0.0027 (17)
C6'D	0.017 (2)	0.018 (2)	0.0206 (16)	0.0019 (16)	0.0006 (15)	0.0010 (14)
S2'D	0.0173 (5)	0.0199 (6)	0.0594 (6)	0.0001 (4)	−0.0012 (5)	0.0007 (5)
O4'D	0.0209 (17)	0.0254 (16)	0.0468 (15)	−0.0086 (13)	−0.0031 (13)	0.0048 (12)
C7'D	0.023 (2)	0.018 (2)	0.0318 (19)	−0.0028 (16)	0.0006 (16)	−0.0012 (15)
C8'D	0.028 (2)	0.020 (2)	0.047 (2)	0.0019 (18)	0.0035 (19)	0.0022 (19)
C9'D	0.029 (3)	0.020 (2)	0.057 (3)	−0.0010 (18)	0.006 (2)	−0.0036 (19)
N1'E	0.0163 (19)	0.0132 (17)	0.0321 (16)	−0.0007 (13)	0.0019 (13)	0.0011 (13)
C2'E	0.026 (3)	0.017 (2)	0.0285 (19)	−0.0011 (18)	0.0030 (17)	−0.0012 (16)
N3'E	0.018 (2)	0.0149 (18)	0.0388 (17)	−0.0025 (14)	0.0026 (15)	−0.0009 (14)
C4'E	0.017 (2)	0.019 (2)	0.0283 (19)	−0.0022 (17)	0.0050 (17)	−0.0022 (16)
C5'E	0.012 (2)	0.021 (2)	0.037 (2)	−0.0004 (16)	−0.0021 (16)	−0.0008 (17)
C6'E	0.021 (2)	0.021 (2)	0.0238 (18)	0.0035 (17)	0.0022 (16)	0.0031 (15)
S2'E	0.0175 (6)	0.0191 (6)	0.0581 (7)	0.0012 (4)	0.0041 (5)	0.0013 (5)
O4'E	0.0189 (18)	0.0213 (16)	0.0543 (18)	−0.0036 (13)	0.0064 (14)	−0.0058 (13)
C7'E	0.017 (2)	0.018 (2)	0.034 (2)	−0.0005 (16)	−0.0011 (16)	−0.0025 (16)
C8'E	0.020 (2)	0.019 (2)	0.052 (3)	0.0023 (17)	0.0013 (18)	0.0052 (18)
C9'E	0.027 (3)	0.025 (2)	0.073 (3)	0.0040 (19)	−0.005 (2)	0.004 (2)
N1'F	0.0164 (18)	0.0151 (17)	0.0324 (16)	−0.0065 (13)	−0.0001 (13)	−0.0023 (12)
C2'F	0.017 (2)	0.019 (2)	0.0258 (18)	−0.0025 (16)	0.0024 (15)	0.0003 (15)
N3'F	0.0192 (19)	0.0116 (16)	0.0324 (16)	0.0016 (13)	0.0000 (14)	−0.0034 (13)
C4'F	0.022 (2)	0.024 (2)	0.0250 (18)	0.0008 (18)	0.0010 (16)	0.0021 (16)
C5'F	0.015 (2)	0.021 (2)	0.031 (2)	0.0016 (16)	−0.0012 (15)	0.0013 (15)
C6'F	0.017 (2)	0.019 (2)	0.0235 (17)	0.0006 (16)	0.0008 (14)	−0.0009 (14)
S2'F	0.0174 (5)	0.0200 (5)	0.0463 (6)	0.0009 (4)	−0.0013 (4)	−0.0008 (4)
O4'F	0.0193 (17)	0.0195 (15)	0.0505 (17)	−0.0068 (12)	−0.0074 (13)	0.0011 (12)
C7'F	0.022 (2)	0.019 (2)	0.036 (2)	−0.0023 (16)	0.0029 (17)	−0.0017 (15)
C8'F	0.022 (2)	0.023 (2)	0.052 (3)	0.0013 (17)	−0.0007 (18)	−0.0023 (19)
C9'F	0.032 (3)	0.020 (2)	0.076 (3)	−0.0010 (19)	0.011 (2)	−0.007 (2)

Geometric parameters (Å, º) top

N1A—C6A	1.330 (5)	N3'B—C4'B	1.398 (6)
N1A—C2A	1.350 (5)	N3'B—H3'B	0.8800
C2A—C3A	1.393 (6)	C4'B—O4'B	1.243 (5)
C2A—N21A	1.409 (5)	C4'B—C5'B	1.425 (6)
C3A—C4A	1.369 (6)	C5'B—C6'B	1.348 (6)
C3A—H3A	0.9500	C5'B—H5'B	0.9500
C4A—C5A	1.379 (6)	C6'B—C7'B	1.494 (5)
C4A—H4A	0.9500	C7'B—C8'B	1.530 (6)
C5A—C6A	1.406 (6)	C7'B—H7'3	0.9900
C5A—H5A	0.9500	C7'B—H7'4	0.9900
C6A—N61A	1.408 (5)	C8'B—C9'B	1.541 (6)
N21A—C22A	1.363 (5)	C8'B—H8'3	0.9900
N21A—H21A	0.8800	C8'B—H8'4	0.9900
C22A—O24A	1.253 (5)	C9'B—H9'4	0.9800
C22A—C23A	1.497 (6)	C9'B—H9'5	0.9800
C23A—H23A	0.9800	C9'B—H9'6	0.9800
C23A—H23B	0.9800	N1'C—C2'C	1.362 (5)
C23A—H23C	0.9800	N1'C—C6'C	1.389 (5)
N61A—C62A	1.369 (5)	N1'C—H1'C	0.8800
N61A—H61A	0.8800	C2'C—N3'C	1.362 (5)
C62A—O64A	1.235 (5)	C2'C—S2'C	1.677 (4)
C62A—C63A	1.510 (6)	N3'C—C4'C	1.398 (5)
C63A—H63A	0.9800	N3'C—H3'C	0.8800
C63A—H63B	0.9800	C4'C—O4'C	1.233 (5)
C63A—H63C	0.9800	C4'C—C5'C	1.426 (5)
N1B—C2B	1.331 (5)	C5'C—C6'C	1.353 (6)
N1B—C6B	1.366 (5)	C5'C—H5'C	0.9500
C2B—C3B	1.390 (6)	C6'C—C7'C	1.505 (5)
C2B—N21B	1.421 (5)	C7'C—C8'C	1.522 (6)
C3B—C4B	1.380 (7)	C7'C—H7'5	0.9900
C3B—H3B	0.9500	C7'C—H7'6	0.9900
C4B—C5B	1.380 (6)	C8'C—C9'C	1.512 (6)
C4B—H4B	0.9500	C8'C—H8'5	0.9900
C5B—C6B	1.375 (6)	C8'C—H8'6	0.9900
C5B—H5B	0.9500	C9'C—H9'7	0.9800
C6B—N61B	1.416 (5)	C9'C—H9'8	0.9800
N21B—C22B	1.376 (5)	C9'C—H9'9	0.9800
N21B—H21B	0.8800	N1'D—C2'D	1.355 (5)
C22B—O24B	1.222 (5)	N1'D—C6'D	1.390 (5)
C22B—C23B	1.519 (6)	N1'D—H1'D	0.8800
C23B—H23D	0.9800	C2'D—N3'D	1.367 (5)
C23B—H23E	0.9800	C2'D—S2'D	1.678 (4)
C23B—H23F	0.9800	N3'D—C4'D	1.403 (5)
N61B—C62B	1.372 (5)	N3'D—H3'D	0.8800
N61B—H61B	0.8800	C4'D—O4'D	1.236 (5)
C62B—O64B	1.224 (5)	C4'D—C5'D	1.435 (6)
C62B—C63B	1.503 (6)	C5'D—C6'D	1.353 (6)
C63B—H63D	0.9800	C5'D—H5'D	0.9500
C63B—H63E	0.9800	C6'D—C7'D	1.510 (5)
C63B—H63F	0.9800	C7'D—C8'D	1.506 (6)
N1C—C6C	1.343 (5)	C7'D—H7'7	0.9900
N1C—C2C	1.351 (5)	C7'D—H7'8	0.9900
C2C—C3C	1.374 (7)	C8'D—C9'D	1.534 (6)
C2C—N21C	1.416 (5)	C8'D—H8'7	0.9900
C3C—C4C	1.393 (7)	C8'D—H8'8	0.9900
C3C—H3C	0.9500	C9'D—H9'X	0.9800
C4C—C5C	1.360 (7)	C9'D—H9'Y	0.9800
C4C—H4C	0.9500	C9'D—H9'Z	0.9800
C5C—C6C	1.398 (6)	N1'E—C2'E	1.357 (5)
C5C—H5C	0.9500	N1'E—C6'E	1.394 (5)
C6C—N61C	1.402 (5)	N1'E—H1'E	0.8800
N21C—C22C	1.366 (5)	C2'E—N3'E	1.360 (6)
N21C—H21C	0.8800	C2'E—S2'E	1.673 (5)
C22C—O24C	1.244 (5)	N3'E—C4'E	1.396 (6)
C22C—C23C	1.503 (6)	N3'E—H3'E	0.8800
C23C—H23G	0.9800	C4'E—O4'E	1.231 (5)
C23C—H23H	0.9800	C4'E—C5'E	1.447 (6)
C23C—H23I	0.9800	C5'E—C6'E	1.352 (6)
N61C—C62C	1.370 (5)	C5'E—H5'E	0.9500
N61C—H61C	0.8800	C6'E—C7'E	1.499 (5)
C62C—O64C	1.225 (5)	C7'E—C8'E	1.536 (6)
C62C—C63C	1.515 (6)	C7'E—H7'9	0.9900
C63C—H63G	0.9800	C7'E—H7'X	0.9900
C63C—H63H	0.9800	C8'E—C9'E	1.543 (6)
C63C—H63I	0.9800	C8'E—H8'9	0.9900
N1'A—C2'A	1.362 (5)	C8'E—H8'X	0.9900
N1'A—C6'A	1.374 (5)	C9'E—H9'A	0.9800
N1'A—H1'A	0.8800	C9'E—H9'B	0.9800
C2'A—N3'A	1.365 (5)	C9'E—H9'C	0.9800
C2'A—S2'A	1.674 (4)	N1'F—C2'F	1.364 (5)
N3'A—C4'A	1.397 (5)	N1'F—C6'F	1.392 (5)
N3'A—H3'A	0.8800	N1'F—H1'F	0.8800
C4'A—O4'A	1.240 (5)	C2'F—N3'F	1.362 (5)
C4'A—C5'A	1.423 (6)	C2'F—S2'F	1.673 (4)
C5'A—C6'A	1.362 (6)	N3'F—C4'F	1.387 (5)
C5'A—H5'A	0.9500	N3'F—H3'F	0.8800
C6'A—C7'A	1.505 (5)	C4'F—O4'F	1.239 (5)
C7'A—C8'A	1.522 (6)	C4'F—C5'F	1.436 (5)
C7'A—H7'1	0.9900	C5'F—C6'F	1.360 (6)
C7'A—H7'2	0.9900	C5'F—H5'F	0.9500
C8'A—C9'A	1.523 (6)	C6'F—C7'F	1.490 (5)
C8'A—H8'1	0.9900	C7'F—C8'F	1.521 (6)
C8'A—H8'2	0.9900	C7'F—H7'Y	0.9900
C9'A—H9'1	0.9800	C7'F—H7'Z	0.9900
C9'A—H9'2	0.9800	C8'F—C9'F	1.525 (6)
C9'A—H9'3	0.9800	C8'F—H8'Y	0.9900
N1'B—C2'B	1.348 (5)	C8'F—H8'Z	0.9900
N1'B—C6'B	1.402 (5)	C9'F—H9'D	0.9800
N1'B—H1'B	0.8800	C9'F—H9'E	0.9800
C2'B—N3'B	1.363 (5)	C9'F—H9'F	0.9800
C2'B—S2'B	1.676 (4)

C6A—N1A—C2A	117.6 (3)	C6'B—C5'B—C4'B	120.8 (4)
N1A—C2A—C3A	123.2 (4)	C6'B—C5'B—H5'B	119.6
N1A—C2A—N21A	113.6 (4)	C4'B—C5'B—H5'B	119.6
C3A—C2A—N21A	123.2 (4)	C5'B—C6'B—N1'B	119.5 (4)
C4A—C3A—C2A	117.4 (4)	C5'B—C6'B—C7'B	126.2 (4)
C4A—C3A—H3A	121.3	N1'B—C6'B—C7'B	114.2 (4)
C2A—C3A—H3A	121.3	C6'B—C7'B—C8'B	114.8 (4)
C3A—C4A—C5A	121.5 (4)	C6'B—C7'B—H7'3	108.6
C3A—C4A—H4A	119.2	C8'B—C7'B—H7'3	108.6
C5A—C4A—H4A	119.2	C6'B—C7'B—H7'4	108.6
C4A—C5A—C6A	116.8 (4)	C8'B—C7'B—H7'4	108.6
C4A—C5A—H5A	121.6	H7'3—C7'B—H7'4	107.6
C6A—C5A—H5A	121.6	C7'B—C8'B—C9'B	111.1 (4)
N1A—C6A—C5A	123.5 (4)	C7'B—C8'B—H8'3	109.4
N1A—C6A—N61A	114.3 (4)	C9'B—C8'B—H8'3	109.4
C5A—C6A—N61A	122.1 (4)	C7'B—C8'B—H8'4	109.4
C22A—N21A—C2A	127.9 (4)	C9'B—C8'B—H8'4	109.4
C22A—N21A—H21A	116.1	H8'3—C8'B—H8'4	108.0
C2A—N21A—H21A	116.1	C8'B—C9'B—H9'4	109.5
O24A—C22A—N21A	122.4 (4)	C8'B—C9'B—H9'5	109.5
O24A—C22A—C23A	121.1 (4)	H9'4—C9'B—H9'5	109.5
N21A—C22A—C23A	116.5 (4)	C8'B—C9'B—H9'6	109.5
C22A—C23A—H23A	109.5	H9'4—C9'B—H9'6	109.5
C22A—C23A—H23B	109.5	H9'5—C9'B—H9'6	109.5
H23A—C23A—H23B	109.5	C2'C—N1'C—C6'C	123.4 (3)
C22A—C23A—H23C	109.5	C2'C—N1'C—H1'C	118.3
H23A—C23A—H23C	109.5	C6'C—N1'C—H1'C	118.3
H23B—C23A—H23C	109.5	N1'C—C2'C—N3'C	115.2 (4)
C62A—N61A—C6A	127.8 (4)	N1'C—C2'C—S2'C	122.6 (3)
C62A—N61A—H61A	116.1	N3'C—C2'C—S2'C	122.3 (3)
C6A—N61A—H61A	116.1	C2'C—N3'C—C4'C	126.1 (3)
O64A—C62A—N61A	122.3 (4)	C2'C—N3'C—H3'C	116.9
O64A—C62A—C63A	121.6 (4)	C4'C—N3'C—H3'C	116.9
N61A—C62A—C63A	116.1 (4)	O4'C—C4'C—N3'C	118.4 (4)
C62A—C63A—H63A	109.5	O4'C—C4'C—C5'C	126.8 (4)
C62A—C63A—H63B	109.5	N3'C—C4'C—C5'C	114.9 (4)
H63A—C63A—H63B	109.5	C6'C—C5'C—C4'C	120.7 (4)
C62A—C63A—H63C	109.5	C6'C—C5'C—H5'C	119.6
H63A—C63A—H63C	109.5	C4'C—C5'C—H5'C	119.6
H63B—C63A—H63C	109.5	C5'C—C6'C—N1'C	119.6 (3)
C2B—N1B—C6B	116.7 (4)	C5'C—C6'C—C7'C	125.8 (4)
N1B—C2B—C3B	124.2 (4)	N1'C—C6'C—C7'C	114.7 (4)
N1B—C2B—N21B	113.7 (4)	C6'C—C7'C—C8'C	114.7 (4)
C3B—C2B—N21B	122.1 (4)	C6'C—C7'C—H7'5	108.6
C4B—C3B—C2B	117.0 (4)	C8'C—C7'C—H7'5	108.6
C4B—C3B—H3B	121.5	C6'C—C7'C—H7'6	108.6
C2B—C3B—H3B	121.5	C8'C—C7'C—H7'6	108.6
C5B—C4B—C3B	121.0 (5)	H7'5—C7'C—H7'6	107.6
C5B—C4B—H4B	119.5	C9'C—C8'C—C7'C	110.9 (4)
C3B—C4B—H4B	119.5	C9'C—C8'C—H8'5	109.5
C6B—C5B—C4B	117.6 (4)	C7'C—C8'C—H8'5	109.5
C6B—C5B—H5B	121.2	C9'C—C8'C—H8'6	109.5
C4B—C5B—H5B	121.2	C7'C—C8'C—H8'6	109.5
N1B—C6B—C5B	123.4 (4)	H8'5—C8'C—H8'6	108.0
N1B—C6B—N61B	113.2 (4)	C8'C—C9'C—H9'7	109.5
C5B—C6B—N61B	123.4 (4)	C8'C—C9'C—H9'8	109.5
C22B—N21B—C2B	126.9 (4)	H9'7—C9'C—H9'8	109.5
C22B—N21B—H21B	116.6	C8'C—C9'C—H9'9	109.5
C2B—N21B—H21B	116.6	H9'7—C9'C—H9'9	109.5
O24B—C22B—N21B	124.2 (4)	H9'8—C9'C—H9'9	109.5
O24B—C22B—C23B	121.3 (4)	C2'D—N1'D—C6'D	123.5 (3)
N21B—C22B—C23B	114.5 (4)	C2'D—N1'D—H1'D	118.3
C22B—C23B—H23D	109.5	C6'D—N1'D—H1'D	118.3
C22B—C23B—H23E	109.5	N1'D—C2'D—N3'D	115.5 (3)
H23D—C23B—H23E	109.5	N1'D—C2'D—S2'D	122.0 (3)
C22B—C23B—H23F	109.5	N3'D—C2'D—S2'D	122.6 (3)
H23D—C23B—H23F	109.5	C2'D—N3'D—C4'D	126.0 (3)
H23E—C23B—H23F	109.5	C2'D—N3'D—H3'D	117.0
C62B—N61B—C6B	126.6 (4)	C4'D—N3'D—H3'D	117.0
C62B—N61B—H61B	116.7	O4'D—C4'D—N3'D	118.1 (4)
C6B—N61B—H61B	116.7	O4'D—C4'D—C5'D	127.3 (4)
O64B—C62B—N61B	122.9 (4)	N3'D—C4'D—C5'D	114.6 (4)
O64B—C62B—C63B	121.9 (4)	C6'D—C5'D—C4'D	120.7 (4)
N61B—C62B—C63B	115.2 (4)	C6'D—C5'D—H5'D	119.7
C62B—C63B—H63D	109.5	C4'D—C5'D—H5'D	119.7
C62B—C63B—H63E	109.5	C5'D—C6'D—N1'D	119.8 (4)
H63D—C63B—H63E	109.5	C5'D—C6'D—C7'D	125.9 (4)
C62B—C63B—H63F	109.5	N1'D—C6'D—C7'D	114.3 (3)
H63D—C63B—H63F	109.5	C8'D—C7'D—C6'D	116.5 (4)
H63E—C63B—H63F	109.5	C8'D—C7'D—H7'7	108.2
C6C—N1C—C2C	117.8 (3)	C6'D—C7'D—H7'7	108.2
N1C—C2C—C3C	123.2 (4)	C8'D—C7'D—H7'8	108.2
N1C—C2C—N21C	114.2 (4)	C6'D—C7'D—H7'8	108.2
C3C—C2C—N21C	122.6 (4)	H7'7—C7'D—H7'8	107.3
C2C—C3C—C4C	117.5 (4)	C7'D—C8'D—C9'D	110.6 (4)
C2C—C3C—H3C	121.3	C7'D—C8'D—H8'7	109.5
C4C—C3C—H3C	121.3	C9'D—C8'D—H8'7	109.5
C5C—C4C—C3C	121.0 (4)	C7'D—C8'D—H8'8	109.5
C5C—C4C—H4C	119.5	C9'D—C8'D—H8'8	109.5
C3C—C4C—H4C	119.5	H8'7—C8'D—H8'8	108.1
C4C—C5C—C6C	117.8 (4)	C8'D—C9'D—H9'X	109.5
C4C—C5C—H5C	121.1	C8'D—C9'D—H9'Y	109.5
C6C—C5C—H5C	121.1	H9'X—C9'D—H9'Y	109.5
N1C—C6C—C5C	122.7 (4)	C8'D—C9'D—H9'Z	109.5
N1C—C6C—N61C	114.9 (4)	H9'X—C9'D—H9'Z	109.5
C5C—C6C—N61C	122.4 (4)	H9'Y—C9'D—H9'Z	109.5
C22C—N21C—C2C	127.5 (4)	C2'E—N1'E—C6'E	123.7 (4)
C22C—N21C—H21C	116.3	C2'E—N1'E—H1'E	118.1
C2C—N21C—H21C	116.3	C6'E—N1'E—H1'E	118.1
O24C—C22C—N21C	123.2 (4)	N1'E—C2'E—N3'E	115.2 (4)
O24C—C22C—C23C	120.4 (4)	N1'E—C2'E—S2'E	121.8 (3)
N21C—C22C—C23C	116.4 (4)	N3'E—C2'E—S2'E	123.0 (3)
C22C—C23C—H23G	109.5	C2'E—N3'E—C4'E	126.5 (3)
C22C—C23C—H23H	109.5	C2'E—N3'E—H3'E	116.7
H23G—C23C—H23H	109.5	C4'E—N3'E—H3'E	116.7
C22C—C23C—H23I	109.5	O4'E—C4'E—N3'E	119.1 (4)
H23G—C23C—H23I	109.5	O4'E—C4'E—C5'E	126.4 (4)
H23H—C23C—H23I	109.5	N3'E—C4'E—C5'E	114.5 (4)
C62C—N61C—C6C	127.6 (4)	C6'E—C5'E—C4'E	120.4 (4)
C62C—N61C—H61C	116.2	C6'E—C5'E—H5'E	119.8
C6C—N61C—H61C	116.2	C4'E—C5'E—H5'E	119.8
O64C—C62C—N61C	123.5 (4)	C5'E—C6'E—N1'E	119.5 (4)
O64C—C62C—C63C	120.3 (4)	C5'E—C6'E—C7'E	126.3 (4)
N61C—C62C—C63C	116.2 (4)	N1'E—C6'E—C7'E	114.2 (4)
C62C—C63C—H63G	109.5	C6'E—C7'E—C8'E	114.8 (4)
C62C—C63C—H63H	109.5	C6'E—C7'E—H7'9	108.6
H63G—C63C—H63H	109.5	C8'E—C7'E—H7'9	108.6
C62C—C63C—H63I	109.5	C6'E—C7'E—H7'X	108.6
H63G—C63C—H63I	109.5	C8'E—C7'E—H7'X	108.6
H63H—C63C—H63I	109.5	H7'9—C7'E—H7'X	107.5
C2'A—N1'A—C6'A	124.2 (3)	C7'E—C8'E—C9'E	109.6 (4)
C2'A—N1'A—H1'A	117.9	C7'E—C8'E—H8'9	109.8
C6'A—N1'A—H1'A	117.9	C9'E—C8'E—H8'9	109.8
N1'A—C2'A—N3'A	114.3 (4)	C7'E—C8'E—H8'X	109.8
N1'A—C2'A—S2'A	122.8 (3)	C9'E—C8'E—H8'X	109.8
N3'A—C2'A—S2'A	122.9 (3)	H8'9—C8'E—H8'X	108.2
C2'A—N3'A—C4'A	126.6 (3)	C8'E—C9'E—H9'A	109.5
C2'A—N3'A—H3'A	116.7	C8'E—C9'E—H9'B	109.5
C4'A—N3'A—H3'A	116.7	H9'A—C9'E—H9'B	109.5
O4'A—C4'A—N3'A	118.1 (4)	C8'E—C9'E—H9'C	109.5
O4'A—C4'A—C5'A	127.2 (4)	H9'A—C9'E—H9'C	109.5
N3'A—C4'A—C5'A	114.8 (4)	H9'B—C9'E—H9'C	109.5
C6'A—C5'A—C4'A	120.4 (4)	C2'F—N1'F—C6'F	123.6 (3)
C6'A—C5'A—H5'A	119.8	C2'F—N1'F—H1'F	118.2
C4'A—C5'A—H5'A	119.8	C6'F—N1'F—H1'F	118.2
C5'A—C6'A—N1'A	119.6 (4)	N3'F—C2'F—N1'F	115.0 (4)
C5'A—C6'A—C7'A	125.3 (4)	N3'F—C2'F—S2'F	122.9 (3)
N1'A—C6'A—C7'A	115.1 (3)	N1'F—C2'F—S2'F	122.1 (3)
C6'A—C7'A—C8'A	115.4 (3)	C2'F—N3'F—C4'F	126.6 (3)
C6'A—C7'A—H7'1	108.4	C2'F—N3'F—H3'F	116.7
C8'A—C7'A—H7'1	108.4	C4'F—N3'F—H3'F	116.7
C6'A—C7'A—H7'2	108.4	O4'F—C4'F—N3'F	119.2 (4)
C8'A—C7'A—H7'2	108.4	O4'F—C4'F—C5'F	125.8 (4)
H7'1—C7'A—H7'2	107.5	N3'F—C4'F—C5'F	115.0 (4)
C7'A—C8'A—C9'A	110.9 (3)	C6'F—C5'F—C4'F	120.3 (4)
C7'A—C8'A—H8'1	109.5	C6'F—C5'F—H5'F	119.8
C9'A—C8'A—H8'1	109.5	C4'F—C5'F—H5'F	119.8
C7'A—C8'A—H8'2	109.5	C5'F—C6'F—N1'F	119.4 (4)
C9'A—C8'A—H8'2	109.5	C5'F—C6'F—C7'F	125.8 (4)
H8'1—C8'A—H8'2	108.0	N1'F—C6'F—C7'F	114.8 (4)
C8'A—C9'A—H9'1	109.5	C6'F—C7'F—C8'F	116.0 (4)
C8'A—C9'A—H9'2	109.5	C6'F—C7'F—H7'Y	108.3
H9'1—C9'A—H9'2	109.5	C8'F—C7'F—H7'Y	108.3
C8'A—C9'A—H9'3	109.5	C6'F—C7'F—H7'Z	108.3
H9'1—C9'A—H9'3	109.5	C8'F—C7'F—H7'Z	108.3
H9'2—C9'A—H9'3	109.5	H7'Y—C7'F—H7'Z	107.4
C2'B—N1'B—C6'B	123.3 (4)	C7'F—C8'F—C9'F	111.2 (4)
C2'B—N1'B—H1'B	118.4	C7'F—C8'F—H8'Y	109.4
C6'B—N1'B—H1'B	118.4	C9'F—C8'F—H8'Y	109.4
N1'B—C2'B—N3'B	115.4 (4)	C7'F—C8'F—H8'Z	109.4
N1'B—C2'B—S2'B	123.1 (3)	C9'F—C8'F—H8'Z	109.4
N3'B—C2'B—S2'B	121.5 (3)	H8'Y—C8'F—H8'Z	108.0
C2'B—N3'B—C4'B	126.2 (3)	C8'F—C9'F—H9'D	109.5
C2'B—N3'B—H3'B	116.9	C8'F—C9'F—H9'E	109.5
C4'B—N3'B—H3'B	116.9	H9'D—C9'F—H9'E	109.5
O4'B—C4'B—N3'B	118.4 (4)	C8'F—C9'F—H9'F	109.5
O4'B—C4'B—C5'B	126.8 (4)	H9'D—C9'F—H9'F	109.5
N3'B—C4'B—C5'B	114.7 (4)	H9'E—C9'F—H9'F	109.5

C6A—N1A—C2A—C3A	0.7 (6)	S2'B—C2'B—N3'B—C4'B	−174.8 (3)
C6A—N1A—C2A—N21A	−178.6 (3)	C2'B—N3'B—C4'B—O4'B	175.3 (3)
N1A—C2A—C3A—C4A	0.3 (6)	C2'B—N3'B—C4'B—C5'B	−3.7 (5)
N21A—C2A—C3A—C4A	179.5 (4)	O4'B—C4'B—C5'B—C6'B	−177.7 (4)
C2A—C3A—C4A—C5A	−0.8 (7)	N3'B—C4'B—C5'B—C6'B	1.3 (5)
C3A—C4A—C5A—C6A	0.3 (7)	C4'B—C5'B—C6'B—N1'B	1.4 (6)
C2A—N1A—C6A—C5A	−1.2 (6)	C4'B—C5'B—C6'B—C7'B	−180.0 (3)
C2A—N1A—C6A—N61A	−179.0 (3)	C2'B—N1'B—C6'B—C5'B	−2.2 (5)
C4A—C5A—C6A—N1A	0.8 (6)	C2'B—N1'B—C6'B—C7'B	179.1 (3)
C4A—C5A—C6A—N61A	178.4 (4)	C5'B—C6'B—C7'B—C8'B	3.1 (6)
N1A—C2A—N21A—C22A	−167.1 (4)	N1'B—C6'B—C7'B—C8'B	−178.2 (3)
C3A—C2A—N21A—C22A	13.7 (6)	C6'B—C7'B—C8'B—C9'B	178.8 (3)
C2A—N21A—C22A—O24A	0.9 (6)	C6'C—N1'C—C2'C—N3'C	0.8 (5)
C2A—N21A—C22A—C23A	179.9 (3)	C6'C—N1'C—C2'C—S2'C	−178.2 (3)
N1A—C6A—N61A—C62A	−166.1 (4)	N1'C—C2'C—N3'C—C4'C	−3.3 (5)
C5A—C6A—N61A—C62A	16.1 (6)	S2'C—C2'C—N3'C—C4'C	175.7 (3)
C6A—N61A—C62A—O64A	1.2 (6)	C2'C—N3'C—C4'C—O4'C	−176.8 (3)
C6A—N61A—C62A—C63A	178.5 (4)	C2'C—N3'C—C4'C—C5'C	4.4 (5)
C6B—N1B—C2B—C3B	−0.2 (6)	O4'C—C4'C—C5'C—C6'C	178.1 (4)
C6B—N1B—C2B—N21B	179.3 (3)	N3'C—C4'C—C5'C—C6'C	−3.1 (5)
N1B—C2B—C3B—C4B	0.1 (6)	C4'C—C5'C—C6'C—N1'C	1.1 (5)
N21B—C2B—C3B—C4B	−179.4 (4)	C4'C—C5'C—C6'C—C7'C	−177.8 (3)
C2B—C3B—C4B—C5B	−0.6 (7)	C2'C—N1'C—C6'C—C5'C	0.1 (5)
C3B—C4B—C5B—C6B	1.2 (7)	C2'C—N1'C—C6'C—C7'C	179.2 (3)
C2B—N1B—C6B—C5B	0.8 (6)	C5'C—C6'C—C7'C—C8'C	−4.2 (5)
C2B—N1B—C6B—N61B	179.8 (3)	N1'C—C6'C—C7'C—C8'C	176.9 (3)
C4B—C5B—C6B—N1B	−1.3 (6)	C6'C—C7'C—C8'C—C9'C	178.1 (3)
C4B—C5B—C6B—N61B	179.8 (4)	C6'D—N1'D—C2'D—N3'D	0.8 (5)
N1B—C2B—N21B—C22B	167.9 (3)	C6'D—N1'D—C2'D—S2'D	−179.1 (3)
C3B—C2B—N21B—C22B	−12.6 (6)	N1'D—C2'D—N3'D—C4'D	0.5 (5)
C2B—N21B—C22B—O24B	−0.5 (6)	S2'D—C2'D—N3'D—C4'D	−179.6 (3)
C2B—N21B—C22B—C23B	179.7 (3)	C2'D—N3'D—C4'D—O4'D	179.4 (4)
N1B—C6B—N61B—C62B	166.5 (3)	C2'D—N3'D—C4'D—C5'D	−1.3 (5)
C5B—C6B—N61B—C62B	−14.5 (6)	O4'D—C4'D—C5'D—C6'D	−179.9 (4)
C6B—N61B—C62B—O64B	−1.3 (6)	N3'D—C4'D—C5'D—C6'D	0.9 (5)
C6B—N61B—C62B—C63B	179.1 (4)	C4'D—C5'D—C6'D—N1'D	0.3 (5)
C6C—N1C—C2C—C3C	−0.2 (6)	C4'D—C5'D—C6'D—C7'D	−179.5 (3)
C6C—N1C—C2C—N21C	−179.4 (3)	C2'D—N1'D—C6'D—C5'D	−1.2 (5)
N1C—C2C—C3C—C4C	1.0 (7)	C2'D—N1'D—C6'D—C7'D	178.6 (3)
N21C—C2C—C3C—C4C	−179.9 (4)	C5'D—C6'D—C7'D—C8'D	−3.5 (6)
C2C—C3C—C4C—C5C	−1.8 (8)	N1'D—C6'D—C7'D—C8'D	176.7 (3)
C3C—C4C—C5C—C6C	1.8 (8)	C6'D—C7'D—C8'D—C9'D	178.0 (3)
C2C—N1C—C6C—C5C	0.2 (6)	C6'E—N1'E—C2'E—N3'E	−1.9 (5)
C2C—N1C—C6C—N61C	−178.8 (3)	C6'E—N1'E—C2'E—S2'E	179.3 (3)
C4C—C5C—C6C—N1C	−1.0 (7)	N1'E—C2'E—N3'E—C4'E	1.6 (6)
C4C—C5C—C6C—N61C	177.9 (4)	S2'E—C2'E—N3'E—C4'E	−179.5 (3)
N1C—C2C—N21C—C22C	−169.8 (4)	C2'E—N3'E—C4'E—O4'E	179.9 (4)
C3C—C2C—N21C—C22C	11.0 (6)	C2'E—N3'E—C4'E—C5'E	−0.8 (6)
C2C—N21C—C22C—O24C	3.6 (6)	O4'E—C4'E—C5'E—C6'E	179.3 (4)
C2C—N21C—C22C—C23C	−177.8 (4)	N3'E—C4'E—C5'E—C6'E	0.1 (6)
N1C—C6C—N61C—C62C	−167.2 (3)	C4'E—C5'E—C6'E—N1'E	−0.3 (6)
C5C—C6C—N61C—C62C	13.8 (6)	C4'E—C5'E—C6'E—C7'E	179.4 (3)
C6C—N61C—C62C—O64C	3.3 (6)	C2'E—N1'E—C6'E—C5'E	1.3 (5)
C6C—N61C—C62C—C63C	−177.9 (3)	C2'E—N1'E—C6'E—C7'E	−178.5 (3)
C6'A—N1'A—C2'A—N3'A	0.6 (5)	C5'E—C6'E—C7'E—C8'E	1.9 (6)
C6'A—N1'A—C2'A—S2'A	−178.8 (3)	N1'E—C6'E—C7'E—C8'E	−178.4 (3)
N1'A—C2'A—N3'A—C4'A	−3.0 (5)	C6'E—C7'E—C8'E—C9'E	−177.4 (3)
S2'A—C2'A—N3'A—C4'A	176.4 (3)	C6'F—N1'F—C2'F—N3'F	−0.2 (5)
C2'A—N3'A—C4'A—O4'A	−175.8 (3)	C6'F—N1'F—C2'F—S2'F	−179.7 (3)
C2'A—N3'A—C4'A—C5'A	3.5 (5)	N1'F—C2'F—N3'F—C4'F	0.6 (5)
O4'A—C4'A—C5'A—C6'A	177.7 (4)	S2'F—C2'F—N3'F—C4'F	−179.9 (3)
N3'A—C4'A—C5'A—C6'A	−1.5 (5)	C2'F—N3'F—C4'F—O4'F	178.3 (4)
C4'A—C5'A—C6'A—N1'A	−0.5 (5)	C2'F—N3'F—C4'F—C5'F	−0.4 (5)
C4'A—C5'A—C6'A—C7'A	179.4 (3)	O4'F—C4'F—C5'F—C6'F	−179.0 (4)
C2'A—N1'A—C6'A—C5'A	1.1 (5)	N3'F—C4'F—C5'F—C6'F	−0.3 (5)
C2'A—N1'A—C6'A—C7'A	−178.9 (3)	C4'F—C5'F—C6'F—N1'F	0.7 (5)
C5'A—C6'A—C7'A—C8'A	−1.3 (5)	C4'F—C5'F—C6'F—C7'F	179.6 (3)
N1'A—C6'A—C7'A—C8'A	178.7 (3)	C2'F—N1'F—C6'F—C5'F	−0.4 (5)
C6'A—C7'A—C8'A—C9'A	−178.2 (3)	C2'F—N1'F—C6'F—C7'F	−179.4 (3)
C6'B—N1'B—C2'B—N3'B	0.0 (5)	C5'F—C6'F—C7'F—C8'F	3.0 (5)
C6'B—N1'B—C2'B—S2'B	177.9 (3)	N1'F—C6'F—C7'F—C8'F	−178.0 (3)
N1'B—C2'B—N3'B—C4'B	3.1 (5)	C6'F—C7'F—C8'F—C9'F	179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N21A—H21A···O4′Dⁱ	0.88	2.03	2.904 (5)	169
N61A—H61A···O4′Eⁱⁱ	0.88	2.05	2.921 (5)	171
N21B—H21B···O4′A	0.88	2.04	2.906 (5)	170
N61B—H61B···O4′Fⁱⁱⁱ	0.88	2.03	2.893 (5)	169
N21C—H21C···O4′B	0.88	2.01	2.873 (5)	168
N61C—H61C···O4′C^iv	0.88	2.07	2.934 (5)	165
N1′A—H1′A···O24A	0.88	2.03	2.892 (4)	167
N3′A—H3′A···S2′D	0.88	2.42	3.279 (3)	166
N1′B—H1′B···O24B	0.88	2.00	2.859 (5)	165
N3′B—H3′B···S2′E	0.88	2.43	3.286 (4)	165
N1′C—H1′C···O24C	0.88	2.09	2.951 (4)	166
N3′C—H3′C···S2′F	0.88	2.45	3.313 (3)	166
N1′D—H1′D···O64A^v	0.88	2.00	2.870 (5)	168
N3′D—H3′D···S2′A	0.88	2.45	3.317 (3)	168
N1′E—H1′E···O64B^vi	0.88	2.06	2.919 (4)	166
N3′E—H3′E···S2′B	0.88	2.49	3.358 (3)	168
N1′F—H1′F···O64C^vii	0.88	2.08	2.944 (4)	166
N3′F—H3′F···S2′C	0.88	2.49	3.359 (3)	168

Symmetry codes: (i) −x, −y+1, z; (ii) −x+1/4, y−1/4, z−1/4; (iii) −x+3/4, y−1/4, z+1/4; (iv) x−1/4, −y+5/4, z−1/4; (v) −x+1/4, y+1/4, z+1/4; (vi) −x+3/4, y+1/4, z−1/4; (vii) −x+5/4, y+1/4, z+1/4.

(III) 6-propyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one top

Crystal data top

C₇H₁₀N₂OS	D_x = 1.356 Mg m⁻³
M_r = 170.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9432 reflections
a = 10.4340 (6) Å	θ = 3.4–25.9°
b = 11.1320 (6) Å	µ = 0.33 mm⁻¹
c = 28.7090 (17) Å	T = 173 K
V = 3334.6 (3) Å³	Block, colourless
Z = 16	0.40 × 0.20 × 0.20 mm
F(000) = 1440

Data collection top

Stoe IPDS II two-circle diffractometer	3131 independent reflections
Radiation source: fine-focus sealed tube	1990 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.132
ω scans	θ_max = 25.6°, θ_min = 3.4°
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	h = −12→12
T_min = 0.879, T_max = 0.937	k = −13→13
29872 measured reflections	l = −31→34

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0362P)²] where P = (F_o² + 2F_c²)/3
3131 reflections	(Δ/σ)_max = 0.001
201 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₇H₁₀N₂OS	V = 3334.6 (3) Å³
M_r = 170.23	Z = 16
Orthorhombic, Pbca	Mo Kα radiation
a = 10.4340 (6) Å	µ = 0.33 mm⁻¹
b = 11.1320 (6) Å	T = 173 K
c = 28.7090 (17) Å	0.40 × 0.20 × 0.20 mm

Data collection top

Stoe IPDS II two-circle diffractometer	3131 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995)	1990 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.937	R_int = 0.132
29872 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 0.91	Δρ_max = 0.19 e Å⁻³
3131 reflections	Δρ_min = −0.25 e Å⁻³
201 parameters

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1A	0.8859 (2)	0.2776 (2)	0.57732 (8)	0.0214 (5)
H1A	0.8838	0.1990	0.5806	0.026*
C2A	0.9065 (3)	0.3450 (2)	0.61574 (9)	0.0181 (6)
S2A	0.92485 (8)	0.28630 (6)	0.66912 (2)	0.02394 (17)
N3A	0.9118 (2)	0.46603 (19)	0.60853 (8)	0.0206 (5)
H3A	0.9252	0.5120	0.6330	0.025*
C4A	0.8978 (3)	0.5223 (2)	0.56577 (10)	0.0212 (6)
O4A	0.9048 (2)	0.63362 (16)	0.56353 (7)	0.0288 (5)
C5A	0.8741 (3)	0.4450 (2)	0.52715 (11)	0.0230 (6)
H5A	0.8625	0.4781	0.4969	0.028*
C6A	0.8680 (3)	0.3243 (2)	0.53336 (10)	0.0196 (6)
C7A	0.8417 (3)	0.2344 (3)	0.49555 (11)	0.0242 (7)
H7A1	0.7952	0.1654	0.5093	0.029*
H7A2	0.9246	0.2040	0.4836	0.029*
C8A	0.7643 (3)	0.2822 (3)	0.45478 (13)	0.0349 (8)
H8A1	0.6842	0.3189	0.4667	0.042*
H8A2	0.8140	0.3458	0.4389	0.042*
C9A	0.7306 (3)	0.1846 (3)	0.41987 (13)	0.0337 (8)
H9A1	0.8095	0.1474	0.4082	0.050*
H9A2	0.6833	0.2201	0.3938	0.050*
H9A3	0.6774	0.1236	0.4350	0.050*
N1B	0.8939 (2)	0.98578 (19)	0.67050 (8)	0.0215 (5)
H1B	0.8903	1.0644	0.6675	0.026*
C2B	0.9147 (3)	0.9196 (2)	0.63148 (10)	0.0209 (6)
S2B	0.93405 (8)	0.98091 (6)	0.57878 (3)	0.02508 (19)
N3B	0.9176 (2)	0.79850 (19)	0.63823 (8)	0.0205 (5)
H3B	0.9312	0.7531	0.6136	0.025*
C4B	0.9008 (3)	0.7404 (2)	0.68095 (11)	0.0239 (7)
O4B	0.9026 (2)	0.62950 (17)	0.68242 (7)	0.0300 (5)
C5B	0.8849 (3)	0.8183 (3)	0.72011 (10)	0.0244 (6)
H5B	0.8791	0.7849	0.7505	0.029*
C6B	0.8780 (3)	0.9383 (3)	0.71454 (10)	0.0221 (6)
C7B	0.8538 (3)	1.0276 (3)	0.75279 (12)	0.0303 (7)
H7B1	0.8129	1.0996	0.7391	0.036*
H7B2	0.9374	1.0529	0.7659	0.036*
C8B	0.7705 (4)	0.9829 (3)	0.79208 (15)	0.0402 (9)
H8B1	0.8120	0.9123	0.8067	0.048*
H8B2	0.6871	0.9565	0.7793	0.048*
C9B	0.7475 (3)	1.0777 (3)	0.82892 (14)	0.0383 (8)
H9B1	0.8299	1.1075	0.8405	0.057*
H9B2	0.6987	1.0427	0.8547	0.057*
H9B3	0.6989	1.1444	0.8154	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0306 (13)	0.0130 (10)	0.0205 (13)	−0.0002 (9)	−0.0014 (10)	−0.0006 (11)
C2A	0.0181 (14)	0.0156 (13)	0.0205 (14)	0.0002 (11)	0.0011 (11)	−0.0007 (11)
S2A	0.0348 (4)	0.0190 (3)	0.0180 (3)	−0.0003 (3)	−0.0025 (3)	0.0004 (3)
N3A	0.0266 (13)	0.0146 (11)	0.0207 (13)	−0.0019 (10)	−0.0020 (11)	−0.0022 (9)
C4A	0.0268 (16)	0.0147 (13)	0.0220 (15)	0.0010 (11)	0.0030 (12)	−0.0021 (12)
O4A	0.0481 (13)	0.0141 (9)	0.0241 (10)	−0.0006 (9)	0.0010 (10)	−0.0008 (8)
C5A	0.0312 (16)	0.0192 (14)	0.0186 (15)	−0.0014 (12)	0.0009 (12)	0.0013 (12)
C6A	0.0211 (14)	0.0179 (13)	0.0196 (15)	0.0007 (11)	0.0012 (11)	0.0024 (12)
C7A	0.0349 (17)	0.0168 (15)	0.0210 (16)	−0.0018 (12)	−0.0001 (12)	−0.0028 (12)
C8A	0.046 (2)	0.0318 (17)	0.027 (2)	0.0062 (16)	−0.0132 (14)	−0.0023 (16)
C9A	0.0393 (18)	0.0331 (17)	0.029 (2)	−0.0054 (14)	−0.0051 (14)	0.0012 (15)
N1B	0.0322 (14)	0.0135 (11)	0.0189 (13)	0.0006 (9)	−0.0005 (10)	−0.0008 (10)
C2B	0.0204 (14)	0.0195 (13)	0.0227 (15)	0.0000 (12)	−0.0027 (12)	−0.0031 (11)
S2B	0.0378 (4)	0.0177 (3)	0.0197 (4)	0.0041 (3)	0.0017 (3)	0.0002 (3)
N3B	0.0289 (13)	0.0130 (11)	0.0196 (12)	0.0017 (10)	0.0007 (11)	−0.0027 (9)
C4B	0.0224 (16)	0.0222 (15)	0.0270 (17)	0.0005 (11)	−0.0027 (13)	0.0007 (11)
O4B	0.0490 (14)	0.0135 (10)	0.0275 (11)	0.0024 (9)	0.0004 (10)	0.0021 (8)
C5B	0.0343 (17)	0.0211 (14)	0.0178 (15)	−0.0033 (12)	−0.0037 (12)	0.0010 (12)
C6B	0.0249 (15)	0.0219 (15)	0.0195 (16)	−0.0028 (12)	−0.0043 (12)	−0.0035 (12)
C7B	0.050 (2)	0.0196 (14)	0.0209 (16)	0.0004 (13)	−0.0001 (14)	−0.0072 (14)
C8B	0.047 (2)	0.0318 (18)	0.041 (2)	−0.0016 (16)	0.0135 (17)	−0.0075 (17)
C9B	0.049 (2)	0.0366 (17)	0.030 (2)	0.0089 (15)	0.0075 (15)	−0.0035 (17)

Geometric parameters (Å, º) top

N1A—C2A	1.351 (4)	N1B—C2B	1.358 (4)
N1A—C6A	1.378 (4)	N1B—C6B	1.380 (4)
N1A—H1A	0.8800	N1B—H1B	0.8800
C2A—N3A	1.364 (3)	C2B—N3B	1.363 (3)
C2A—S2A	1.677 (3)	C2B—S2B	1.672 (3)
N3A—C4A	1.386 (4)	N3B—C4B	1.397 (4)
N3A—H3A	0.8800	N3B—H3B	0.8800
C4A—O4A	1.243 (3)	C4B—O4B	1.236 (3)
C4A—C5A	1.425 (4)	C4B—C5B	1.429 (4)
C5A—C6A	1.357 (4)	C5B—C6B	1.348 (4)
C5A—H5A	0.9500	C5B—H5B	0.9500
C6A—C7A	1.502 (4)	C6B—C7B	1.503 (4)
C7A—C8A	1.519 (5)	C7B—C8B	1.508 (5)
C7A—H7A1	0.9900	C7B—H7B1	0.9900
C7A—H7A2	0.9900	C7B—H7B2	0.9900
C8A—C9A	1.519 (5)	C8B—C9B	1.514 (5)
C8A—H8A1	0.9900	C8B—H8B1	0.9900
C8A—H8A2	0.9900	C8B—H8B2	0.9900
C9A—H9A1	0.9800	C9B—H9B1	0.9800
C9A—H9A2	0.9800	C9B—H9B2	0.9800
C9A—H9A3	0.9800	C9B—H9B3	0.9800

C2A—N1A—C6A	124.0 (2)	C2B—N1B—C6B	124.6 (2)
C2A—N1A—H1A	118.0	C2B—N1B—H1B	117.7
C6A—N1A—H1A	118.0	C6B—N1B—H1B	117.7
N1A—C2A—N3A	115.5 (2)	N1B—C2B—N3B	115.0 (3)
N1A—C2A—S2A	123.2 (2)	N1B—C2B—S2B	123.0 (2)
N3A—C2A—S2A	121.3 (2)	N3B—C2B—S2B	122.0 (2)
C2A—N3A—C4A	125.2 (2)	C2B—N3B—C4B	125.4 (2)
C2A—N3A—H3A	117.4	C2B—N3B—H3B	117.3
C4A—N3A—H3A	117.4	C4B—N3B—H3B	117.3
O4A—C4A—N3A	119.4 (3)	O4B—C4B—N3B	119.4 (3)
O4A—C4A—C5A	124.9 (3)	O4B—C4B—C5B	125.5 (3)
N3A—C4A—C5A	115.7 (2)	N3B—C4B—C5B	115.1 (2)
C6A—C5A—C4A	120.3 (3)	C6B—C5B—C4B	120.9 (3)
C6A—C5A—H5A	119.9	C6B—C5B—H5B	119.5
C4A—C5A—H5A	119.9	C4B—C5B—H5B	119.5
C5A—C6A—N1A	119.2 (3)	C5B—C6B—N1B	118.8 (3)
C5A—C6A—C7A	125.0 (3)	C5B—C6B—C7B	125.3 (3)
N1A—C6A—C7A	115.8 (2)	N1B—C6B—C7B	115.9 (2)
C6A—C7A—C8A	114.9 (2)	C6B—C7B—C8B	115.2 (3)
C6A—C7A—H7A1	108.6	C6B—C7B—H7B1	108.5
C8A—C7A—H7A1	108.6	C8B—C7B—H7B1	108.5
C6A—C7A—H7A2	108.6	C6B—C7B—H7B2	108.5
C8A—C7A—H7A2	108.6	C8B—C7B—H7B2	108.5
H7A1—C7A—H7A2	107.5	H7B1—C7B—H7B2	107.5
C9A—C8A—C7A	112.4 (3)	C7B—C8B—C9B	112.6 (3)
C9A—C8A—H8A1	109.1	C7B—C8B—H8B1	109.1
C7A—C8A—H8A1	109.1	C9B—C8B—H8B1	109.1
C9A—C8A—H8A2	109.1	C7B—C8B—H8B2	109.1
C7A—C8A—H8A2	109.1	C9B—C8B—H8B2	109.1
H8A1—C8A—H8A2	107.9	H8B1—C8B—H8B2	107.8
C8A—C9A—H9A1	109.5	C8B—C9B—H9B1	109.5
C8A—C9A—H9A2	109.5	C8B—C9B—H9B2	109.5
H9A1—C9A—H9A2	109.5	H9B1—C9B—H9B2	109.5
C8A—C9A—H9A3	109.5	C8B—C9B—H9B3	109.5
H9A1—C9A—H9A3	109.5	H9B1—C9B—H9B3	109.5
H9A2—C9A—H9A3	109.5	H9B2—C9B—H9B3	109.5

C6A—N1A—C2A—N3A	−1.5 (4)	C6B—N1B—C2B—N3B	0.8 (4)
C6A—N1A—C2A—S2A	178.6 (2)	C6B—N1B—C2B—S2B	−179.7 (2)
N1A—C2A—N3A—C4A	0.1 (4)	N1B—C2B—N3B—C4B	0.2 (4)
S2A—C2A—N3A—C4A	179.9 (2)	S2B—C2B—N3B—C4B	−179.2 (2)
C2A—N3A—C4A—O4A	−179.9 (3)	C2B—N3B—C4B—O4B	178.3 (3)
C2A—N3A—C4A—C5A	1.0 (4)	C2B—N3B—C4B—C5B	−2.7 (4)
O4A—C4A—C5A—C6A	−179.8 (3)	O4B—C4B—C5B—C6B	−176.7 (3)
N3A—C4A—C5A—C6A	−0.8 (4)	N3B—C4B—C5B—C6B	4.4 (4)
C4A—C5A—C6A—N1A	−0.5 (4)	C4B—C5B—C6B—N1B	−3.6 (4)
C4A—C5A—C6A—C7A	179.0 (3)	C4B—C5B—C6B—C7B	176.3 (3)
C2A—N1A—C6A—C5A	1.7 (4)	C2B—N1B—C6B—C5B	0.9 (4)
C2A—N1A—C6A—C7A	−177.8 (3)	C2B—N1B—C6B—C7B	−179.0 (3)
C5A—C6A—C7A—C8A	−26.6 (4)	C5B—C6B—C7B—C8B	−31.3 (5)
N1A—C6A—C7A—C8A	152.9 (3)	N1B—C6B—C7B—C8B	148.6 (3)
C6A—C7A—C8A—C9A	−174.9 (3)	C6B—C7B—C8B—C9B	−178.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S2Bⁱ	0.88	2.48	3.341 (2)	165
N3A—H3A···O4B	0.88	1.94	2.797 (3)	163
N1B—H1B···S2Aⁱⁱ	0.88	2.50	3.361 (2)	167
N3B—H3B···O4A	0.88	1.98	2.826 (3)	161

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

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₄H₅N₃·2C₇H₁₀N₂OS	C₉H₁₁N₃O₂·2C₇H₁₀N₂OS	C₇H₁₀N₂OS
M_r	435.57	533.67	170.23
Crystal system, space group	Monoclinic, P2₁/c	Orthorhombic, Fdd2	Orthorhombic, Pbca
Temperature (K)	173	173	173
a, b, c (Å)	7.6094 (5), 12.9888 (6), 20.8838 (14)	37.9355 (12), 76.880 (3), 10.5666 (3)	10.4340 (6), 11.1320 (6), 28.7090 (17)
α, β, γ (°)	90, 99.179 (5), 90	90, 90, 90	90, 90, 90
V (Å³)	2037.7 (2)	30817.3 (18)	3334.6 (3)
Z	4	48	16
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.29	0.25	0.33
Crystal size (mm)	0.60 × 0.20 × 0.15	0.50 × 0.30 × 0.20	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Stoe IPDS II two-circle diffractometer	Stoe IPDS II two-circle diffractometer	Stoe IPDS II two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)	Multi-scan (MULABS; Spek, 2009; Blessing, 1995)
T_min, T_max	0.844, 0.958	0.885, 0.951	0.879, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	25516, 3819, 3163	108254, 14445, 10225	29872, 3131, 1990
R_int	0.094	0.129	0.132
(sin θ/λ)_max (Å⁻¹)	0.609	0.609	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.105, 1.05	0.047, 0.097, 0.91	0.046, 0.093, 0.91
No. of reflections	3819	14445	3131
No. of parameters	289	985	201
No. of restraints	0	1	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29	0.22, −0.25	0.19, −0.25
Absolute structure	?	Flack (1983), 6784 Friedel pairs	?
Absolute structure parameter	?	0.12 (7)	?

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

Selected torsion angles (º) for (I) top

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

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
N21—H211···S2B	0.89 (2)	2.63 (2)	3.5145 (17)	173 (2)
N21—H212···S2A	0.87 (2)	2.77 (2)	3.6234 (18)	168 (2)
N1A—H1A···O4Aⁱ	0.83 (2)	2.17 (2)	2.983 (2)	167 (2)
N3A—H3A···N3	0.87 (2)	2.06 (2)	2.926 (2)	174 (2)
N1B—H1B···O4Bⁱⁱ	0.82 (2)	2.31 (2)	3.107 (2)	166 (2)
N3B—H3B···N1	0.88 (2)	2.10 (2)	2.975 (2)	175 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
N21A—H21A···O4'Dⁱ	0.88	2.03	2.904 (5)	169
N61A—H61A···O4'Eⁱⁱ	0.88	2.05	2.921 (5)	171
N21B—H21B···O4'A	0.88	2.04	2.906 (5)	170
N61B—H61B···O4'Fⁱⁱⁱ	0.88	2.03	2.893 (5)	169
N21C—H21C···O4'B	0.88	2.01	2.873 (5)	168
N61C—H61C···O4'C^iv	0.88	2.07	2.934 (5)	165
N1'A—H1'A···O24A	0.88	2.03	2.892 (4)	167
N3'A—H3'A···S2'D	0.88	2.42	3.279 (3)	166
N1'B—H1'B···O24B	0.88	2.00	2.859 (5)	165
N3'B—H3'B···S2'E	0.88	2.43	3.286 (4)	165
N1'C—H1'C···O24C	0.88	2.09	2.951 (4)	166
N3'C—H3'C···S2'F	0.88	2.45	3.313 (3)	166
N1'D—H1'D···O64A^v	0.88	2.00	2.870 (5)	168
N3'D—H3'D···S2'A	0.88	2.45	3.317 (3)	168
N1'E—H1'E···O64B^vi	0.88	2.06	2.919 (4)	166
N3'E—H3'E···S2'B	0.88	2.49	3.358 (3)	168
N1'F—H1'F···O64C^vii	0.88	2.08	2.944 (4)	166
N3'F—H3'F···S2'C	0.88	2.49	3.359 (3)	168

Selected torsion angles (º) for (III) top

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

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S2Bⁱ	0.88	2.48	3.341 (2)	164.6
N3A—H3A···O4B	0.88	1.94	2.797 (3)	162.6
N1B—H1B···S2Aⁱⁱ	0.88	2.50	3.361 (2)	167.3
N3B—H3B···O4A	0.88	1.98	2.826 (3)	161.3

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

R.m.s. deviations (Å) for all non-H atoms and selected geometric parameters (°) of 6-propyl-2-thiouracil for (II). top

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

Selected geometric parameters (°) of N-(6-acetamidopyridin-2-yl)acetamide for (II). top

Molecule	N1—C2—N21—C22	C2—N21—C22—C23	N1—C6—N61—C62	C6—N61—C62—C63
A	-167.1 (4)	179.9 (3)	-166.1 (4)	178.5 (4)
B	167.9 (3)	179.7 (3)	166.5 (3)	179.1 (4)
C	-169.8 (4)	-177.8 (4)	-167.2 (3)	-177.9 (3)

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

Molecule	α	β
A	13.4 (1)	15.4 (1)
B	12.6 (1)	14.6 (1)
C	12.6 (1)	15.6 (1)

Dihedral angles (°) within the three symmetry-independent complexes for (II). γ designates the angle between two 6-propyl-2-thiouracil molecules and δ designates the angle between the pyridine ring and the central 6-propyl-2-thiouracil molecule. top

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

Acknowledgements

The authors thank Dr Michael Bolte for helpful discussions.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Antoniadis, C. D., Blake, A. J., Hadjikakou, S. K., Hadjiliadis, N., Hubberstey, P., Schröder, M. & Wilson, C. (2006). Acta Cryst. B62, 580–591. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Antoniadis, C. D., Corban, G. J., Hadjikakou, S. K., Hadjiliadis, N., Kubicki, M., Warner, S. & Butler, I. S. (2003). Eur. J. Inorg. Chem. pp. 1635–1640. CSD CrossRef Google Scholar
Bahn, R. S., Burch, H. S., Cooper, D. S., Garber, J. R., Greenlee, C. M., Klein, I. L., Laurberg, P., McDougall, I. R., Rivkees, S. A., Ross, D., Sosa, J. A. & Stan, M. N. (2009). Thyroid, 19, 673–674. CrossRef PubMed CAS Google Scholar
Balalaie, S., Bararjanian, M. & Rominger, F. (2006). J. Heterocycl. Chem. 43, 821–826. CrossRef CAS Google Scholar
Basilio Janke, E. M., Dunger, A., Limbach, H.-H. & Weisz, K. (2001). Magn. Reson. Chem. 39, 177–182. CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Biswal, H. S. & Wategaonkar, S. (2009). J. Phys. Chem. A, 113, 12763–12773. Web of Science CrossRef PubMed CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Branch, C. L., Eggleston, D. S., Haltiwanger, R. C., Kaura, A. C. & Tyler, J. W. (1996). Synth. Commun. 26, 2075–2084. CrossRef CAS Web of Science Google Scholar
Chierotti, M. R., Ferrero, L., Garino, N., Gobetto, R., Pellegrino, L., Braga, D., Grepioni, F. & Maini, L. (2010). Chem. Eur. J. 16, 4347–4358. Web of Science CSD CrossRef CAS PubMed Google Scholar
Cooper, D. S. (2005). N. Engl. J. Med. 352, 905–917. Web of Science CrossRef PubMed CAS Google Scholar
Coxall, R. A., Harris, S. G., Henderson, D. K., Parsons, S., Tasker, P. A. & Winpenny, R. E. P. (2000). J. Chem. Soc. Dalton Trans. pp. 2349–2356. Web of Science CSD CrossRef Google Scholar
Domagała, M., Grabowski, S. J., Urbaniak, K. & Mlostón, G. (2003). J. Phys. Chem. A, 107, 2730–2736. Google Scholar
Favre, A., Saintomé, C., Fourrey, J.-L., Clivio, P. & Laugâa, P. (1998). J. Photochem. Photobiol. B, 42, 109–124. CrossRef CAS PubMed Google Scholar
Ferrari, M. B., Fava, G. G., Pelosi, G., Rodriguez-Argüelles, M. C. & Tarasconi, P. (1995). J. Chem. Soc. Dalton Trans. pp. 3035–3040. CSD CrossRef Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hawkinson, S. W. (1975). Acta Cryst. B31, 2153–2156. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Hori, A., Ishida, Y., Kikuchi, T., Miyamoto, K. & Sakaguchi, H. (2009). Acta Cryst. C65, o593–o597. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hu, S.-L., Yin, G.-D. & Wu, A.-X. (2005). Acta Cryst. E61, o2408–o2409. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lautié, A. & Novak, A. (1980). Chem. Phys. Lett. 71, 290–293. Google Scholar
Le Page, Y. (1987). J. Appl. Cryst. 20, 264–269. CrossRef CAS Web of Science IUCr Journals Google Scholar
Le Page, Y. (1988). J. Appl. Cryst. 21, 983–984. CrossRef Web of Science IUCr Journals Google Scholar
Long, T., Zhou, H.-B. & Wu, A.-X. (2005). Acta Cryst. E61, o2169–o2171. Web of Science CSD CrossRef IUCr Journals Google Scholar
Luo, W., Yu, Q.-S., Tweedie, D., Deschamps, J., Parrish, D., Holloway, H. W., Li, Y., Brossi, A. & Greig, N. H. (2008). Synthesis, 21, 3415–3422. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Munshi, P. & Guru Row, T. N. (2006). Acta Cryst. B62, 612–626. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Okabe, N., Fujiwara, T., Yamagata, Y. & Tomita, K. (1983). Bull. Chem. Soc. Jpn, 56, 1543–1544. CrossRef CAS Web of Science Google Scholar
Orzeszko, B., Kazimierczuk, Z., Maurin, J. K., Laudy, A. E., Starościak, B. J., Vilpo, J., Vilpo, L., Balzarini, J. & Orzeszko, A. (2004). Il Farmaco, 59, 929–937. CrossRef PubMed CAS Google Scholar
Pawlowski, M., Lendzion, A., Szawkalo, J., Leniewski, A., Maurin, J. K. & Czarnocki, Z. (2009). Phosphorus Sulfur Silicon Relat. Elem. 184, 1307–1313. CAS Google Scholar
Read, G., Randal, R., Hursthouse, M. B. & Short, R. (1988). J. Chem. Soc. Perkin Trans. 2, pp. 1103–1105. CSD CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Šponer, J., Leszczynski, J. & Hobza, P. (1997). J. Phys. Chem. A, 101, 9489–9495. Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
Tashkhodzhaev, B., Turgunov, K. K., Usmanova, B., Averkiev, B. B., Antipin, M. Yu. & Shakhidoyatov, Kh. M. (2002). Zh. Strukt. Khim. 43, 944–948. Google Scholar
Testa, S. M., Disney, M. D., Turner, D. H. & Kierzek, R. (1999). Biochemistry, 38, 16655–16662. Web of Science CrossRef PubMed CAS Google Scholar
Tiekink, E. R. T. (1989). Z. Kristallogr. 187, 79–84. CrossRef CAS Web of Science Google Scholar
Voutsas, G. P., Venetopoulos, C. C., Kálmán, A., Párkányi, L., Hornyák, G. & Lempert, K. (1978). Tetrahedron Lett. 19, 4431–4434. CSD CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xue, S.-J., Wang, Q.-D. & Li, J.-Z. (2006). Acta Cryst. C62, o666–o668. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2053-2296

Volume 67| Part 11| November 2011| Pages o439-o445

doi:10.1107/S0108270111037991