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The structures of two conformationally similar 1,4-di­hydro­pyrimidines with a novel carbamoyl substitution, viz. 6-methyl-5-(N-methyl­carbamoyl)-4-phenyl-1,2,3,4-tetrahydro­py­rimidine-2-thione monohydrate, C13H15N3OS·H2O, (I), and 4-(4-chloro­phenyl)-6-methyl-5-(N-methyl­carbamoyl)-1,2,3,4-tetra­hydro­pyrimidine-2-thione monohydrate, C13H14ClN3OS·H2O, (II), exhibit the structural features of 1,4-di­hydro­pyridine calcium channel blockers. In both structures, the pyrimidine ring adopts a flattened boat conformation and the carbamoyl side chain is in an extended conformation with an anticlinal orientation. The phenyl ring occupies a pseudo-axial position with respect to the pyrimidine ring in these structures. Both compounds crystallize with one mol­ecule of water, which participates in a two-dimensional hydrogen-bonding network. The mol­ecules are linked into dimers by N-H...S hydrogen bonds in both structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028926/sk1782sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028926/sk1782Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028926/sk1782IIsup3.hkl
Contains datablock II

CCDC references: 263060; 263061

Comment top

Pyrimidines, being critical components of naturally occurring nucleic acid, are an integral part of medically important compounds including antiviral, antitumour and cardiovascular agents (Atwal et al., 1989). Owing to their biological importance, these compounds have been the focus of synthetic activity during the past few years (Weis & van der Plas, 1986). The structural relation and potential mimicking of the clinically important dihydropyridine (DHP) calcium channel blockers led us to studies of substituted 1,4-dihydropyrimidines (DHPMs). Furthermore, being inherently asymmetric, dihydropyrimidines provide an opportunity to study the effect of chirality on biological activity. To gain insight into the conformational aspect of various substitutions at the phenyl ring as well as to obtain the possible relationship between structure and activity, an X-ray study of a series of phenyl substituted 1,4-dihydropyrimidines – having a novel carbamoyl group at C3 and a thione group at C6 of the dihydropyrimidine ring – has been undertaken. We report here the crystal and molecular structures of 1,4-dihydro-6-methyl-5-N-methyl carbamoyl-4-phenyl-2(3H)- pyrimidinethione, (I), and 1,4-dihydro-6-methyl-5-N– methyl carbamoyl-4-(4'-chlorophenyl-2(3H)-pyrimidinethione), (II).

In all essential details, the geometry of the molecules (Figs. 1 and 2) in terms of interatomic distances and angles are in good agreement with those in similar structures (Kojic-Prodic et al., 1976; Sulmon et al., 1989; Chandra Mohan et al., 2003). The two compounds are isomorphous, both crystallizing as a monohydrate in the centrosymmetrical space group P1. An r.m.s overlay (pyrimidine plane; r.m.s deviation 0.019 Å) of the two compounds shows significant similarities (Fig. 3), differing only at the periphery of the phenyl ring. The DPHM in both the structures exist more or less in a flattened boat-like conformation [DS(C4)=0.041 (1) for (I) and DS(C4)= 0.048 (1) for (II) (Nardelli, 1983)] with atom N1 and C4 defining the stern and bow positions. Atoms N1 and C4 lie 0.113 (1) and 0.204 (1) Å in (I), and 0.137 (2) and 0.255 (2) Å in (II), respectively, from the least-squares plane defined by the remaining four atoms (C2, C3, N5 and C6) of the DPHM ring. A similar type of conformation was observed in another DPHM (Atwal et al., 1990; Kappe et al., 1997). In both the structures, the torsion angles about the C4-atom ring bonds are greater than those for the N1-atom bonds, indicating that the puckering is more influenced at atom C4. The DPHM ring exists in the thione form; the C6—S1 distance [1.698 (1) in (I) and 1.693 (2) Å in (II)] essentially has double-bond character (Trinajstic, 1968). In addition, this C—S distance in both the structures is longer than 1.61 Å, the distance expected for a C=S double bond (Pauling, 1960). A similar lengthening has been reported and discussed as due to the substantial hydrogen bonding involving the S atom (Tiekink, 1989). It can been seen in both the structures that the S atom participates in a network of hydrogen bonds.

The carbamoyl side chain in both the structures is in a fully extended conformation with C3—C31—N33—-C34 torsion angles of 179.5 (1) [for (I)] and −179.9 (2)° [for (II)]. The spatial arrangement of the carbonyl group at atom C3 adopts an anticlinal (ac) orientation about the C3—C31 bond in both structures [C2—C3—C31—O32 = −132.1 (2)° in (I) and −134.9 (2)° in (II)]. This orientation may probably be attributed to intermolecular N—H···O hydrogen bonding involving the above-mentioned carbonyl oxygen O32 atom.

The phenyl ring in both structures is significantly planar within experimental limits. It is oriented perpendicular to the DHPM ring system [C3—C4—C7—C8 = 91.6 (2)° in (I) and 99.5 (2)° in (II)]. Furthermore, the phenyl ring is positioned pseudoaxially [107.2 (1) in (I) and 103.2 (2)° in (II), as defined by the average magnitude of the C2—C3—C4—C7 and C6—N5—C4—C7 torsion angles], with respect to the C4 position of the DPHM ring.

Triggle et al. (1989), on the basis of three-dimensional structural characteristics important for calcium channel antagonist activity in DPH, proposed that a flattened boat conformation of DHP with the phenyl ring in a pseudoaxial position and a near perpendicular orientation of the phenyl ring with respect to the DHP ring corresponds to high activity. Viewing the DHPM structures of (I) and (II), a striking similarity in conformational features is observed, suggesting that these compounds may be potential mimics of prototypical DHP calcium channel blockers. Owing to a lack of pharmacological data, such a conclusion is speculation? at this stage.

A packing diagram of (I) only is shown in Fig. 4, since the compounds are isostructural. The molecules exist as dimers utilizing N—H···S hydrogen bonds (Tables 2 and 4) between centrosymmetrically related molecules described by an R22(8) ring motif. The most striking feature in the crystal packing is the hydrogen-bonding network formed by the water molecule, which is present in both the structures. The water molecule links the dimers into infinite chains along the a axis via OW—H···S and N—H···OW hydrogen bonds, thereby acting as a donor and an acceptor. Furthermore, the water molecule interlinks the dimer chain along the b axis via OW—H···S hydrogen bonds. Interestingly, the water molecule also forms a dimer with its centrosymmetric counterpart via an OW—H···OW hydrogen bond running parallel to the a axis. The carbamoyl side chains are self-linked with the N—H···O hydrogen bond. In addition, a possible bifurcated hydrogen bond is observed in (I), between the water mlecule and the S atom, while in (II) the distance between the S atom and the water molecule is 3.818 (3) Å. The hydrogen-bond networks thus formed facilitate alternate hydrophobic and hydrophilic environments in the crystal packing. Possible weak C—H···O and C—H···N interactions are also seen in both structures.

Experimental top

Compounds (I) and (II) were prepared by known synthetic methods (Sadanandam et al., 1992) and recrystallized from a methanol/ water (90:10) solution.

Refinement top

After location of the H atoms in difference density maps, all C and N-bound H atoms were positioned using SHELXL97 HFIX instructions (Sheldrick, 1997) and treated as riding atoms, with C—H distances in the range 0.93–0.98 Å and an N—H distance of 0.86 Å, and with Uiso(H) values of 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Water H atoms (H1W and H2W) for (I) were refined with an O—H distance restraint (please specify) (Table 2). In (II), only one H atom of the water molecule was located. Since (I) and (II) are isomorphous, the positions of the water H atoms in (I)? were utilized in (II). However, attempts to refine the coordinates of these H atoms were unsuccessful, and hence the positional and displacement parameters of water H atoms in (II) were constrained (specify constraints). Examination of both the structures with PLATON (Spek, 2003) showed that there were no solvent-accessible voids in the crystal lattice.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001). Data reduction: SAINT for (I); SAINT (Bruker, 2001) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. An r.m.s overlay of (I) and (II), showing the similarities in conformation.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of the three-dimensional framework from the two component (001) and (110) chains built by water molecules. For clarity, the substituents at the DPHM ring have been omitted.
(I) 6-methyl-5-(N-methylcarbamoyl)-4-phenyl-1,2,3,4-dihydropyrimidine-2-thione monohydrate top
Crystal data top
C13H15N3OS·H2OZ = 2
Mr = 279.36F(000) = 296
Triclinic, P1Dx = 1.32 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.0116 (3) ÅCell parameters from 5613 reflections
b = 8.9507 (6) Åθ = 2.3–28.0°
c = 16.0882 (11) ŵ = 0.23 mm1
α = 86.095 (1)°T = 273 K
β = 84.841 (1)°Needle, colorless
γ = 78.241 (1)°0.20 × 0.15 × 0.10 mm
V = 702.75 (8) Å3
Data collection top
CCD Area Detector
diffractometer
2971 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Graphite monochromatorθmax = 28.0°, θmin = 2.3°
ω scanh = 66
8102 measured reflectionsk = 1111
3227 independent reflectionsl = 2120
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0601P)2 + 0.1834P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.115(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.24 e Å3
3227 reflectionsΔρmin = 0.24 e Å3
182 parameters
Crystal data top
C13H15N3OS·H2Oγ = 78.241 (1)°
Mr = 279.36V = 702.75 (8) Å3
Triclinic, P1Z = 2
a = 5.0116 (3) ÅMo Kα radiation
b = 8.9507 (6) ŵ = 0.23 mm1
c = 16.0882 (11) ÅT = 273 K
α = 86.095 (1)°0.20 × 0.15 × 0.10 mm
β = 84.841 (1)°
Data collection top
CCD Area Detector
diffractometer
2971 reflections with I > 2σ(I)
8102 measured reflectionsRint = 0.017
3227 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.24 e Å3
3227 reflectionsΔρmin = 0.24 e Å3
182 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.27882 (9)0.80405 (4)0.51855 (2)0.04755 (14)
N10.3380 (2)0.98831 (14)0.38552 (7)0.0397 (3)
H1N0.45081.02090.41360.048*
C20.2771 (3)1.06121 (15)0.30772 (8)0.0354 (3)
C30.1503 (3)0.99441 (15)0.25557 (8)0.0342 (3)
C40.0663 (3)0.84337 (16)0.28020 (8)0.0361 (3)
H40.12500.85330.26820.043*
N50.0839 (3)0.80925 (14)0.37017 (7)0.0414 (3)
H5N0.00780.74430.39360.050*
C60.2295 (3)0.87017 (16)0.41850 (8)0.0370 (3)
C70.2370 (3)0.71526 (16)0.22954 (9)0.0392 (3)
C80.4744 (3)0.62708 (19)0.25705 (12)0.0524 (4)
H80.53270.64460.30810.063*
C90.6271 (4)0.5121 (2)0.20875 (15)0.0679 (5)
H90.78710.45300.22770.081*
C100.5432 (5)0.4854 (2)0.13347 (14)0.0724 (6)
H100.64540.40800.10150.087*
C110.3093 (5)0.5728 (2)0.10550 (12)0.0720 (6)
H110.25340.55520.05410.086*
C120.1546 (4)0.6872 (2)0.15304 (10)0.0554 (4)
H120.00530.74570.13360.067*
C210.3578 (4)1.21356 (18)0.29560 (10)0.0470 (3)
H21A0.29131.26390.24470.070*
H21B0.55341.19980.29240.070*
H21C0.28051.27480.34190.070*
C310.0790 (3)1.05908 (15)0.17068 (8)0.0353 (3)
O320.1512 (2)1.06625 (14)0.14737 (7)0.0526 (3)
N330.2787 (2)1.10168 (15)0.12043 (7)0.0415 (3)
H33N0.43811.09120.13850.050*
C340.2366 (3)1.1651 (2)0.03617 (9)0.0524 (4)
H34A0.10361.25890.03820.079*
H34B0.17241.09370.00500.079*
H34C0.40621.18480.00960.079*
O1W0.8083 (3)0.56801 (18)0.43422 (11)0.0712 (4)
H1W0.672 (6)0.611 (4)0.469 (2)0.161 (16)*
H2W0.844 (7)0.476 (2)0.452 (2)0.131 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0653 (3)0.0488 (2)0.0318 (2)0.01859 (18)0.00912 (16)0.00317 (14)
N10.0474 (6)0.0451 (6)0.0313 (5)0.0186 (5)0.0093 (5)0.0003 (5)
C20.0362 (6)0.0383 (6)0.0323 (6)0.0095 (5)0.0031 (5)0.0002 (5)
C210.0622 (9)0.0428 (8)0.0407 (7)0.0203 (7)0.0089 (6)0.0002 (6)
C30.0311 (6)0.0389 (6)0.0331 (6)0.0081 (5)0.0035 (5)0.0003 (5)
C310.0308 (6)0.0391 (7)0.0360 (6)0.0055 (5)0.0069 (5)0.0021 (5)
O320.0320 (5)0.0764 (8)0.0505 (6)0.0124 (5)0.0131 (4)0.0060 (5)
N330.0342 (6)0.0582 (7)0.0335 (6)0.0126 (5)0.0084 (4)0.0055 (5)
C340.0570 (9)0.0655 (10)0.0350 (7)0.0143 (8)0.0078 (6)0.0078 (7)
C40.0353 (6)0.0443 (7)0.0320 (6)0.0146 (5)0.0051 (5)0.0007 (5)
N50.0490 (7)0.0484 (7)0.0318 (6)0.0231 (5)0.0021 (5)0.0010 (5)
C60.0396 (7)0.0402 (7)0.0315 (6)0.0088 (5)0.0021 (5)0.0027 (5)
C70.0448 (7)0.0394 (7)0.0367 (7)0.0173 (6)0.0010 (5)0.0003 (5)
C80.0492 (8)0.0493 (9)0.0601 (10)0.0120 (7)0.0075 (7)0.0030 (7)
C90.0564 (10)0.0506 (10)0.0914 (15)0.0049 (8)0.0065 (10)0.0007 (9)
C100.0948 (15)0.0521 (10)0.0652 (12)0.0142 (10)0.0271 (11)0.0117 (9)
C110.1112 (17)0.0625 (11)0.0417 (9)0.0176 (11)0.0057 (10)0.0116 (8)
C120.0748 (11)0.0556 (9)0.0368 (8)0.0129 (8)0.0079 (7)0.0041 (7)
O1W0.0640 (8)0.0603 (8)0.0913 (11)0.0215 (7)0.0097 (8)0.0136 (8)
Geometric parameters (Å, º) top
S1—C61.6982 (14)C4—N51.4657 (16)
N1—C61.3422 (18)C4—C71.5209 (19)
N1—C21.4008 (16)C4—H40.9800
N1—H1N0.8600N5—C61.3252 (18)
C2—C31.3358 (18)N5—H5N0.8600
C2—C211.4952 (19)C7—C81.378 (2)
C21—H21A0.9600C7—C121.387 (2)
C21—H21B0.9600C8—C91.389 (3)
C21—H21C0.9600C8—H80.9300
C3—C311.4912 (17)C9—C101.368 (3)
C3—C41.5137 (18)C9—H90.9300
C31—O321.2326 (16)C10—C111.364 (3)
C31—N331.3299 (18)C10—H100.9300
N33—C341.4499 (18)C11—C121.383 (3)
N33—H33N0.8600C11—H110.9300
C34—H34A0.9600C12—H120.9300
C34—H34B0.9600O1W—H1W0.886 (18)
C34—H34C0.9600O1W—H2W0.844 (18)
C6—N1—C2123.37 (11)C3—C4—C7111.27 (11)
C6—N1—H1N118.3N5—C4—H4108.0
C2—N1—H1N118.3C3—C4—H4108.0
C3—C2—N1119.28 (12)C7—C4—H4108.0
C3—C2—C21127.80 (13)C6—N5—C4125.46 (11)
N1—C2—C21112.87 (11)C6—N5—H5N117.3
C2—C21—H21A109.5C4—N5—H5N117.3
C2—C21—H21B109.5N5—C6—N1117.38 (12)
H21A—C21—H21B109.5N5—C6—S1122.21 (11)
C2—C21—H21C109.5N1—C6—S1120.41 (10)
H21A—C21—H21C109.5C8—C7—C12118.84 (15)
H21B—C21—H21C109.5C8—C7—C4121.74 (13)
C2—C3—C31124.31 (12)C12—C7—C4119.41 (14)
C2—C3—C4120.96 (12)C7—C8—C9120.24 (18)
C31—C3—C4114.73 (11)C7—C8—H8119.9
O32—C31—N33121.91 (13)C9—C8—H8119.9
O32—C31—C3121.25 (12)C10—C9—C8120.34 (19)
N33—C31—C3116.77 (11)C10—C9—H9119.8
C31—N33—C34122.21 (12)C8—C9—H9119.8
C31—N33—H33N118.9C11—C10—C9119.83 (18)
C34—N33—H33N118.9C11—C10—H10120.1
N33—C34—H34A109.5C9—C10—H10120.1
N33—C34—H34B109.5C10—C11—C12120.50 (19)
H34A—C34—H34B109.5C10—C11—H11119.8
N33—C34—H34C109.5C12—C11—H11119.8
H34A—C34—H34C109.5C11—C12—C7120.25 (18)
H34B—C34—H34C109.5C11—C12—H12119.9
N5—C4—C3109.98 (10)C7—C12—H12119.9
N5—C4—C7111.55 (11)H1W—O1W—H2W104 (3)
C6—N1—C2—C313.9 (2)C7—C4—N5—C6103.84 (16)
C6—N1—C2—C21163.75 (14)C4—N5—C6—N110.2 (2)
N1—C2—C3—C31178.88 (12)C4—N5—C6—S1170.10 (11)
C21—C2—C3—C313.9 (2)C2—N1—C6—N58.3 (2)
N1—C2—C3—C41.41 (19)C2—N1—C6—S1171.46 (10)
C21—C2—C3—C4175.86 (14)N5—C4—C7—C831.61 (18)
C2—C3—C31—O32132.12 (15)C3—C4—C7—C891.62 (16)
C4—C3—C31—O3247.60 (18)N5—C4—C7—C12149.30 (13)
C2—C3—C31—N3350.90 (19)C3—C4—C7—C1287.48 (16)
C4—C3—C31—N33129.37 (13)C12—C7—C8—C90.2 (2)
O32—C31—N33—C342.6 (2)C4—C7—C8—C9179.25 (14)
C3—C31—N33—C34179.52 (13)C7—C8—C9—C100.0 (3)
C2—C3—C4—N513.51 (18)C8—C9—C10—C110.4 (3)
C31—C3—C4—N5166.23 (11)C9—C10—C11—C120.6 (3)
C2—C3—C4—C7110.62 (14)C10—C11—C12—C70.5 (3)
C31—C3—C4—C769.64 (14)C8—C7—C12—C110.1 (3)
C3—C4—N5—C620.12 (19)C4—C7—C12—C11179.03 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···S10.88 (3)2.45 (3)3.2868 (18)157 (3)
O1W—H2W···O1Wi0.84 (2)2.60 (3)3.014 (3)112 (3)
O1W—H2W···S1ii0.84 (2)2.70 (2)3.4708 (15)153 (3)
N1—H1N···S1iii0.862.623.4499 (12)164
N5—H5N···O1Wiv0.862.032.8791 (19)171
N33—H33N···O32v0.862.042.8788 (15)164
C8—H8···O1W0.932.533.391 (2)153
C21—H21A···N330.962.563.138 (2)119
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1, z+1; (iii) x+1, y+2, z+1; (iv) x1, y, z; (v) x+1, y, z.
(II) 4-(4-chlorophenyl)-6-methyl-5-(N-methylcarbamoyl)-1,2,3,4-dihydropyrimidine- 2-thione monohydrate top
Crystal data top
C13H14ClN3OS·H2OZ = 2
Mr = 313.8F(000) = 328
Triclinic, P1Dx = 1.408 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.8853 (3) ÅCell parameters from 4058 reflections
b = 9.7093 (7) Åθ = 2.3–29.4°
c = 16.0343 (11) ŵ = 0.40 mm1
α = 79.506 (1)°T = 273 K
β = 84.792 (1)°Plate, colorless
γ = 82.834 (1)°0.18 × 0.15 × 0.08 mm
V = 740.18 (9) Å3
Data collection top
CCD Area Detector
diffractometer
2988 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 28.0°, θmin = 2.2°
ω scanh = 66
8550 measured reflectionsk = 1212
3391 independent reflectionsl = 2120
Refinement top
Refinement on F22 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.055 w = 1/[σ2(Fo2) + (0.0789P)2 + 0.438P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.150(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.68 e Å3
3391 reflectionsΔρmin = 0.46 e Å3
183 parameters
Crystal data top
C13H14ClN3OS·H2Oγ = 82.834 (1)°
Mr = 313.8V = 740.18 (9) Å3
Triclinic, P1Z = 2
a = 4.8853 (3) ÅMo Kα radiation
b = 9.7093 (7) ŵ = 0.40 mm1
c = 16.0343 (11) ÅT = 273 K
α = 79.506 (1)°0.18 × 0.15 × 0.08 mm
β = 84.792 (1)°
Data collection top
CCD Area Detector
diffractometer
2988 reflections with I > 2σ(I)
8550 measured reflectionsRint = 0.023
3391 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0552 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.09Δρmax = 0.68 e Å3
3391 reflectionsΔρmin = 0.46 e Å3
183 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.75794 (19)0.41129 (8)0.11627 (6)0.0814 (3)
S10.25270 (16)0.81350 (8)0.53336 (4)0.0596 (2)
N10.3387 (4)0.9822 (2)0.38652 (11)0.0434 (4)
H10.46231.01260.41120.052*
C20.2788 (4)1.0501 (2)0.30423 (12)0.0366 (4)
C30.1422 (4)0.9851 (2)0.25714 (12)0.0341 (4)
C40.0499 (4)0.8417 (2)0.29214 (12)0.0381 (4)
H40.14180.84350.27820.046*
N50.0548 (4)0.8141 (2)0.38475 (11)0.0436 (4)
H50.05280.75570.41300.052*
C60.2132 (4)0.8724 (2)0.42864 (13)0.0416 (5)
C70.2244 (4)0.7272 (2)0.25137 (13)0.0381 (4)
C80.4407 (5)0.6419 (2)0.29067 (15)0.0469 (5)
H80.47640.65050.34540.056*
C90.6045 (6)0.5440 (3)0.25009 (18)0.0561 (6)
H90.74930.48700.27710.067*
C100.5499 (6)0.5322 (2)0.16902 (16)0.0530 (6)
C110.3337 (6)0.6135 (3)0.12904 (15)0.0552 (6)
H110.29720.60340.07470.066*
C120.1715 (5)0.7100 (3)0.17028 (14)0.0494 (5)
H120.02380.76480.14350.059*
C210.3697 (5)1.1941 (2)0.28217 (14)0.0482 (5)
H21A0.29821.24100.22930.072*
H21B0.56811.18700.27680.072*
H21C0.30141.24710.32620.072*
C310.0694 (4)1.0440 (2)0.16846 (12)0.0347 (4)
O320.1642 (3)1.03907 (19)0.14632 (10)0.0500 (4)
N330.2700 (3)1.0941 (2)0.11453 (10)0.0406 (4)
H330.43161.09050.13260.049*
C340.2285 (5)1.1544 (3)0.02662 (14)0.0537 (6)
H34A0.08751.11010.00700.081*
H34B0.39821.13950.00740.081*
H34C0.17241.25370.02190.081*
O1W0.7517 (6)0.5760 (3)0.4771 (2)0.1086 (9)
H1W0.62690.63720.49360.080*
H2W0.82310.55600.52540.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0999 (6)0.0593 (4)0.0844 (6)0.0026 (4)0.0235 (4)0.0298 (4)
S10.0812 (5)0.0698 (4)0.0302 (3)0.0246 (3)0.0066 (3)0.0026 (3)
N10.0492 (10)0.0541 (11)0.0311 (8)0.0182 (8)0.0069 (7)0.0082 (7)
C20.0361 (10)0.0436 (11)0.0312 (9)0.0061 (8)0.0010 (7)0.0084 (8)
C210.0615 (14)0.0475 (12)0.0396 (11)0.0174 (11)0.0039 (10)0.0106 (9)
C30.0287 (9)0.0421 (10)0.0327 (9)0.0047 (7)0.0013 (7)0.0089 (8)
C310.0288 (9)0.0406 (10)0.0358 (10)0.0007 (7)0.0062 (7)0.0106 (8)
O320.0291 (7)0.0704 (11)0.0519 (9)0.0047 (7)0.0112 (6)0.0104 (8)
N330.0304 (8)0.0590 (11)0.0318 (8)0.0046 (7)0.0066 (6)0.0048 (7)
C340.0542 (14)0.0693 (16)0.0349 (11)0.0045 (12)0.0057 (10)0.0022 (10)
C40.0351 (10)0.0494 (12)0.0327 (10)0.0128 (8)0.0032 (7)0.0084 (8)
N50.0491 (10)0.0528 (11)0.0320 (9)0.0206 (8)0.0034 (7)0.0082 (7)
C60.0447 (11)0.0488 (12)0.0322 (10)0.0072 (9)0.0000 (8)0.0090 (8)
C70.0436 (11)0.0378 (10)0.0348 (10)0.0140 (8)0.0014 (8)0.0057 (8)
C80.0530 (13)0.0487 (12)0.0417 (11)0.0096 (10)0.0086 (9)0.0098 (9)
C90.0604 (15)0.0463 (13)0.0613 (15)0.0025 (11)0.0077 (12)0.0091 (11)
C100.0678 (15)0.0386 (11)0.0539 (14)0.0149 (11)0.0129 (12)0.0136 (10)
C110.0780 (17)0.0532 (14)0.0380 (11)0.0148 (12)0.0003 (11)0.0143 (10)
C120.0606 (14)0.0516 (13)0.0380 (11)0.0058 (11)0.0101 (10)0.0100 (9)
O1W0.0989 (19)0.0979 (19)0.120 (2)0.0142 (15)0.0207 (17)0.0125 (17)
Geometric parameters (Å, º) top
Cl1—C101.742 (2)C34—H34C0.9600
S1—C61.693 (2)C4—N51.462 (2)
N1—C61.340 (3)C4—C71.522 (3)
N1—C21.402 (3)C4—H40.9800
N1—H10.8600N5—C61.329 (3)
C2—C31.336 (3)N5—H50.8600
C2—C211.491 (3)C7—C81.383 (3)
C21—H21A0.9600C7—C121.392 (3)
C21—H21B0.9600C8—C91.381 (3)
C21—H21C0.9600C8—H80.9300
C3—C311.490 (3)C9—C101.378 (4)
C3—C41.510 (3)C9—H90.9300
C31—O321.235 (2)C10—C111.371 (4)
C31—N331.325 (3)C11—C121.375 (3)
N33—C341.447 (3)C11—H110.9300
N33—H330.8600C12—H120.9300
C34—H34A0.9600O1W—H1W0.86
C34—H34B0.9600O1W—H2W0.86
C6—N1—C2123.36 (18)C3—C4—C7111.22 (16)
C6—N1—H1118.3N5—C4—H4107.9
C2—N1—H1118.3C3—C4—H4107.9
C3—C2—N1118.88 (19)C7—C4—H4107.9
C3—C2—C21127.93 (19)C6—N5—C4124.90 (18)
N1—C2—C21113.13 (17)C6—N5—H5117.5
C2—C21—H21A109.5C4—N5—H5117.5
C2—C21—H21B109.5N5—C6—N1116.97 (18)
H21A—C21—H21B109.5N5—C6—S1122.10 (17)
C2—C21—H21C109.5N1—C6—S1120.92 (16)
H21A—C21—H21C109.5C8—C7—C12118.3 (2)
H21B—C21—H21C109.5C8—C7—C4122.56 (18)
C2—C3—C31124.41 (18)C12—C7—C4119.13 (19)
C2—C3—C4120.74 (18)C9—C8—C7121.1 (2)
C31—C3—C4114.85 (16)C9—C8—H8119.4
O32—C31—N33122.35 (19)C7—C8—H8119.4
O32—C31—C3120.64 (18)C10—C9—C8119.0 (2)
N33—C31—C3116.91 (16)C10—C9—H9120.5
C31—N33—C34122.80 (17)C8—C9—H9120.5
C31—N33—H33118.6C11—C10—C9121.2 (2)
C34—N33—H33118.6C11—C10—Cl1119.2 (2)
N33—C34—H34A109.5C9—C10—Cl1119.6 (2)
N33—C34—H34B109.5C10—C11—C12119.2 (2)
H34A—C34—H34B109.5C10—C11—H11120.4
N33—C34—H34C109.5C12—C11—H11120.4
H34A—C34—H34C109.5C11—C12—C7121.2 (2)
H34B—C34—H34C109.5C11—C12—H12119.4
N5—C4—C3109.68 (16)C7—C12—H12119.4
N5—C4—C7112.14 (17)H1W—O1W—H2W93.4
C6—N1—C2—C316.4 (3)C4—N5—C6—N112.6 (3)
C6—N1—C2—C21160.8 (2)C4—N5—C6—S1168.37 (17)
N1—C2—C3—C31178.96 (18)C2—N1—C6—N59.9 (3)
C21—C2—C3—C314.2 (3)C2—N1—C6—S1169.13 (16)
N1—C2—C3—C40.8 (3)N5—C4—C7—C823.7 (3)
C21—C2—C3—C4176.0 (2)C3—C4—C7—C899.5 (2)
C2—C3—C31—O32134.9 (2)N5—C4—C7—C12158.35 (19)
C4—C3—C31—O3245.3 (3)C3—C4—C7—C1278.4 (2)
C2—C3—C31—N3348.6 (3)C12—C7—C8—C91.4 (3)
C4—C3—C31—N33131.18 (19)C4—C7—C8—C9176.5 (2)
O32—C31—N33—C343.6 (3)C7—C8—C9—C100.1 (4)
C3—C31—N33—C34179.9 (2)C8—C9—C10—C111.4 (4)
C2—C3—C4—N517.3 (3)C8—C9—C10—Cl1178.97 (19)
C31—C3—C4—N5162.85 (16)C9—C10—C11—C121.1 (4)
C2—C3—C4—C7107.3 (2)Cl1—C10—C11—C12179.26 (19)
C31—C3—C4—C772.5 (2)C10—C11—C12—C70.5 (4)
C3—C4—N5—C625.1 (3)C8—C7—C12—C111.7 (4)
C7—C4—N5—C699.0 (2)C4—C7—C12—C11176.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···S10.862.473.321 (3)177
O1W—H2W···O1Wi0.862.302.764 (4)114
N1—H1···S1ii0.862.633.457 (2)161
N5—H5···O1Wiii0.862.142.990 (4)167
N33—H33···O32iv0.862.002.824 (2)161
C8—H8···O1W0.932.553.397 (4)151
C21—H21A···N(33)0.962.553.116 (3)118
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+2, z+1; (iii) x1, y, z; (iv) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H15N3OS·H2OC13H14ClN3OS·H2O
Mr279.36313.8
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)273273
a, b, c (Å)5.0116 (3), 8.9507 (6), 16.0882 (11)4.8853 (3), 9.7093 (7), 16.0343 (11)
α, β, γ (°)86.095 (1), 84.841 (1), 78.241 (1)79.506 (1), 84.792 (1), 82.834 (1)
V3)702.75 (8)740.18 (9)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.230.40
Crystal size (mm)0.20 × 0.15 × 0.100.18 × 0.15 × 0.08
Data collection
DiffractometerCCD Area Detector
diffractometer
CCD Area Detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8102, 3227, 2971 8550, 3391, 2988
Rint0.0170.023
(sin θ/λ)max1)0.6610.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.05 0.055, 0.150, 1.09
No. of reflections32273391
No. of parameters182183
No. of restraints22
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.240.68, 0.46

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 and PARST (Nardelli, 1995).

Selected geometric parameters (Å, º) for (I) top
N1—C61.3422 (18)C31—O321.2326 (16)
N1—C21.4008 (16)C31—N331.3299 (18)
C2—C31.3358 (18)C4—N51.4657 (16)
C3—C41.5137 (18)N5—C61.3252 (18)
C6—N1—C2—C313.9 (2)C3—C4—N5—C620.12 (19)
C2—C3—C4—N513.51 (18)C2—N1—C6—N58.3 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···S10.88 (3)2.45 (3)3.2868 (18)157 (3)
O1W—H2W···O1Wi0.84 (2)2.60 (3)3.014 (3)112 (3)
O1W—H2W···S1ii0.84 (2)2.70 (2)3.4708 (15)153 (3)
N1—H1N···S1iii0.862.623.4499 (12)164
N5—H5N···O1Wiv0.862.032.8791 (19)171
N33—H33N···O32v0.862.042.8788 (15)164
C8—H8···O1W0.932.533.391 (2)153
C21—H21A···N330.962.563.138 (2)119
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+1, z+1; (iii) x+1, y+2, z+1; (iv) x1, y, z; (v) x+1, y, z.
Selected geometric parameters (Å, º) for (II) top
Cl1—C101.742 (2)C3—C41.510 (3)
N1—C61.340 (3)C31—O321.235 (2)
N1—C21.402 (3)C31—N331.325 (3)
C2—C31.336 (3)C4—N51.462 (2)
C6—N1—C2—C316.4 (3)C3—C4—N5—C625.1 (3)
C2—C3—C4—N517.3 (3)C2—N1—C6—N59.9 (3)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···S10.862.473.321 (3)177
O1W—H2W···O1Wi0.862.302.764 (4)114
N1—H1···S1ii0.862.633.457 (2)161
N5—H5···O1Wiii0.862.142.990 (4)167
N33—H33···O32iv0.862.002.824 (2)161
C8—H8···O1W0.932.553.397 (4)151
C21—H21A···N(33)0.962.553.116 (3)118
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+1, y+2, z+1; (iii) x1, y, z; (iv) x+1, y, z.
 

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