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The title compound, C12H12N2O4S2, crystallizes in white and yellow polymeric forms as a result of inter­esting anti-anti and syn-anti conformational isomerism of the thio­carbon­yl and carbon­yl moieties relative to one another. This work is the first reported X-ray crystallographic structure determination of isomers of this class of bipodal ligand. The white form, anti-anti, (I), crystallizes with the benzene ring lying about a twofold rotation axis, resulting in both of the thio­carbon­yl and carbon­yl moieties being anti relative to each other. The yellow modification crystallizes as syn-anti, (II), with one thio­carbon­yl moiety syn and the other anti relative to the respective carbon­yl groups. The individual mol­ecules of both (I) and (II) are extensively linked through inter­molecular hydrogen bonds. Inter­molecular hydrogen bonding in (II) includes a network of bifurcated N-H...O and N-H...S hydrogen bonds, while mol­ecules of (I) include bifurcated C-H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105018494/rb1007sup1.cif
Contains datablocks general, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105018494/rb1007Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105018494/rb1007IIsup3.hkl
Contains datablock II

CCDC references: 278580; 278581

Comment top

Substituted acyl-thioureas with the general motif, RC(O)NHC(S)N(R')2 have been studied extensively as a result of their coordination chemistry, particularly to the softer transition metal ions (Hoyer et al., 1986; Köhler et al., 1986; König et al., 1983, 1986; Richter et al., 1989; Schröder et al., 2000). We have extensively studied these molecules and their bipodal analogues, (R')2NC(S)NHC(O)RC(O)NHC(S)N(R')2, as part of an investigation examining their potential uses in the platinum group metal industry (Bourne et al., 2005; Hallale et al., 2005; Koch, 2001; Koch et al., 1999).

Despite the several reported applications of these acyl-thiourea derivatives, there are few structural reports concerning the uncoordinated substituted thiourea derivatives (Bourne et al., 2005; Koch, 2001; Koch, Sacht & Bourne, 1995; Koch, Sacht, Grimmbacher & Bourne, 1995; Ramadas et al., 1993; Ugar et al., 2003). Recent work in our laboratory, however, has shown that these molecules show some interesting inter- and intramolecular hydrogen-bonding interactions in the solid state (Bourne et al., 2005). In this context, we have become interested in the synthesis and potential coordination chemistry of the structurally related O-alkyl-N-benzoylthiocarbamic acid esters, which, to our knowledge, have received very little attention in the literature.

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O-Alkylthiocarbamic acid esters have previously been reported as having potential as `collectors' in ore flotation (Azizyan & Ryaboi, 1989; Konev & Ryaboi, 1971), and have also been proposed as being the intermediates for the regio- and chemoselective de-oxygenation of primary and secondary aliphatic alcohols (Oba & Nishiyama, 1994). To date, the only crystal structures of uncoordinated molecules similar to the title compound that have been reported in the literature are that of O-isopropyl-N-(2-furoyl) thiocarbamate (Morales et al., 2000b), O-benzyl-N-(2-furoyl)thiocarbamate (Montiel-Ortega et al., 2004) and that of a recently reported bipodal thiocarbamic ester, O,O'-diethyl N,N'-(p-phenylene-dicarbonyl)bis(thiocarbamate) (Blewett et al., 2004).

We report here the molecular structures of a white, (I), and a yellow, (II), polymorph of O,O'-dimethyl N,N'-(m-phenylenedicarbonyl)bis(thiocarbamate), which differ only by the relative orientation of the thiocarbonyl moiety with respect to the aminocarbonyl groups. In (I), the orientations of both thiocarbamate acid O-ester groups are anti with respect to the aminocarbonyl moiety (Fig. 1), while in (II), one orientation is anti and the other is syn (Fig. 2).

The molecular structure of (I) is shown in Fig. 1, with selected bond lengths, angles and torsion angles listed in Table 1. Both the thiocarbonyl and carbonyl moieties within the asymmetric unit of (I) are anti relative to one another, with the complete molecule being generated by a twofold rotation axis passing through atoms C5 and C7 of the benzene ring.

The molecular structure of (II) is shown in Fig. 2, with selected bond lengths, bond angles and torsion angles listed in Table 3. The asymmetric unit of (II) consists of a complete molecule, and, in contrast to (I), does not contain internal symmetry. The relative orientations of the thiocarbonyl and carbonyl moieties, S1 and O2, are syn with respect to each other, while atoms O3 and S2 are anti relative to each other. The approximate anti orientation of the S and O atoms within the C(S)NHC(O) moieties of (I), and of atoms O3 and S2 in (II), is frequently observed in the closely related bipodal N',N',N''',N'''-tetraalkyl-N,N''-aroylbis(thioureas) reported previously (Koch et al., 2001, Ugar et al., 2003). This anti orientation of the S and O atoms is also frequently observed in the monopodal N-aroyl-N'-alkyl- and N-aroyl-N',N'-dialkyl thioureas (Koch, Sacht, Grimmbacher & Bourne, 1995; Morales et al., 1997, 2000a; Shanmuga Sundara Raj et al., 1999). The comparable uncommon syn orientation of the thiocarbonyl and carbonyl moieties (S1 and O2) observed in (II) was also observed in the structurally related O,O'-dimethyl N, N'-(p-phenylenedicarboyl)bis(thiocarbamate) (Blewett et al., 2004).

The anti–anti and syn–anti conformations of (I) and (II) have a significant effect on their molecular packing. The anti–anti conformation in (I) results in intermolecular N1—H1···O2 hydrogen bonds as well as bifurcated C5—H5···O2 hydrogen bonds between adjacent molecules causing molecules of (I) to pack in chains parallel to the c axis. Further distinctive intermolecular C6—H6···S1 hydrogen interactions cause these chains of molecules of (I) to expand as sheets parallel to (100) (Fig. 3 and Table 2).

In the yellow polymorph, (II), the syn--anti conformation results in these molecules packing with a network of bifurcated intermolecular N1—H1···O3, C5—H5···O3, N2—H2···O2 and N2—H2···S1 hydrogen bonds to adjacent molecules. As a result, each molecule of (II) interacts with two adjacent molecules via a series of hydrogen interactions, producing one-dimensional molecular chains parallel to [010] (Fig. 4 and Table 4). Crystallization and polymorphism are complex phenomena and an appreciation of polymorphism is fundamental to an understanding of the crystallization process itself (Desiraju, 1997). It has been suggested in the literature that our understanding of polymorphism is, however, still far from complete and the occurance of polymorphism cannot be safely predicted (Kirchner et al., 2004). In many cases in the literature, the pattern of hydrogen bonds formed within a molecule studied is said to constitute the basis for polymorphism within those molecules (Kirchner et al., 2004). It is possible that the hydrogen bonding observed in (I) and (II) contributes to the occurrence of the polymorphism observed. However, the overall packing of the molecules of (I) and (II) is undoubtedly dictated by a collection of subtleties, only some of which are the hydrogen-bond interactions reported.

The C2—N1 bond lengths in both (I) and (II), as well as C11—N2 in (II), are all shorter than that observed for the corresponding bonds within the bipodal 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) [1.4173 (16) Å; Ugar et al., 2003] and 3,3,3',3'-tetraethyl-1,1'-isophthaloylbis(thiourea) [1.428 (4) Å; Koch et al., 2001]. This fact indicates a greater degree of double-bond character in the C—N bonds in question in (I) and (II). Correspondingly, the C3—N1 bond length of (I), and C10—N2 of (II), are somewhat longer than the corresponding C—N bond lengths observed for 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) [1.3606 (17) Å; Ugar et al., 2003]. The C3—N1 bond in (II) is significantly longer than the comparable C—N bonds in both 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) [1.3606 (17) Å; Ugar et al., 2003] and 3,3,3',3'-tetraethyl-1,1'-isophthaloylbis(thiourea) at [1.381 (4) Å; Koch et al., 2001].

The conformation of the C(O)NHC(S)OCH3 branches of (I) are remarkably planar, with atom O1 deviating from the C4/C3/N1/C2/O1/C1 least-squares plane by only 0.070 (2) Å. Atoms O2 and S1 lie out of this plane by only −0.118 (3) and −0.291 (3) Å, respectively, in contrast to the situation observed for 3,3,3',3'-tetraethyl-1,1'-terephthaloylbis(thiourea) (Ugar et al., 2003) and 3,3,3',3'-tetraethyl-1,1'-isophthaloylbis(thiourea) (Koch et al., 2001). The anti coplanarity of S1 and O2 in (I) is further illustrated by the torsion angles listed in Table 1. In (I), the C4/C3/N1/C2/O1/C1 plane intersects the plane of the phenylene ring at 25.50 (9)°.

As was observed in (I), both C(O)NHC(S)OCH3 branches of (II) are also remarkably planar. For the syn branch of (II), atom C4A deviates from the C4/C3/N1/C2/O1/C1 least-squares plane by only 0.060 (2) Å, while atoms O2 and S1 deviate from this plane by −0.085 (7) Å and 0.185 (8) Å, respectively. The syn coplanarity of S1 and O2 in (II) is further illustrated by the torsion angles listed in Table 3. The C4/C3/N1/C2/O1/C1 plane intersects the plane of the phenylene ring at 16.5 (3)°. Similarly, atoms C10, O3 and S2 deviate from the least-squares plane defined through C9/C10/N2/C11/O4/C12 of the anti C(O)NHC(S)OCH3 branch of (II) by only 0.147 (3), 0.458 (5) and 0.230 (6) Å, respectively. The anti coplanarity of atoms S2 and O3 in (II) is further illustrated by the torsion angles listed in Table 3.

The asymmetry of the C5—C4—C3 and C6—C4—C3 bond angles (Table 1) in (I) may be the result of a repulsion in the N1—H1···H5—C5 system and an attraction in the C6—H6···O2 system. Similar observations pertain to (II), with an asymmetry in the C5—C4—C3 and C6—C4—C3 angles (Table 3) due to a possible repulsion in the N1—H1···H5–C5 system and an attraction between the C6—H6···O2 system. For the anti branch in (II), qualitatively similar interactions may be inferred from the asymmetry between C5—C9—C10 and C8—C9—C10 (Table 3), possibly as a result of repulsive interactions in the N2—H2···H8—C8 system and attractive interactions in the C5—H5···O3 system. Similar observations have been made for the O-isopropyl N-(2-furoyl)thiocarbamic ester (Morales et al., 2000b) and the bipodal O,O'-dimethyl N,N'-(p-phenylenedicarboyl)bis(thiocarbamate) (Blewett et al., 2004).

Experimental top

All syntheses were carried out under a dry argon atmosphere using standard Schlenk and vacuum-line techniques. Compounds (I) and (II) were synthesized using a modification of the procedure initially reported for the preparation of substituted thioureas (Douglas & Dains, 1934). The reagents isophthaloyl dichloride and KSCN were used as supplied without further purification. Acetone (calcium carbonate) and methanol (Mg, I2) were rendered anhydrous and distilled prior to use. Isophthaloyl dichloride (2.5 mmol) in acetone (25 ml) was added to KSCN (5 mmol) in acetone (25 ml) under an inert atmosphere. The mixture was heated under reflux for 1 h and then cooled to room temperature, after which ethanol (5 mmol) in acetone (25 ml) was added dropwise with stirring and the mixture was further warmed to 333 K for 2 h. Water (50 ml) was added, followed by extraction of the product into chloroform. Removal of the solvent in vacuo yielded the crude pale-yellow amorphous target product. The product was further purified by crystallization from a 1:1 mixture of chloroform and ethanol, yielding simultaneously both white and yellow crystals from the same sample batch suitable for single-crystal diffraction analysis [overall yield 81.3% (based on isophthaloyl dichloride used)]. 1H NMR (CDCl3): 10.30 (br, s, 2H), 8.62 (s, 1H, Ph), 8.13 (d, 1H, Ph), 8.11 (d, 1H, Ph), 7.56 (tr, 1H, Ph), 3.96 (s, 6H). 13C{1H} NMR (CDCl3): 190.6 (CS), 170.1 (CO), 134.1 (Ph), 134.0 (ipso-Ph), 130.4 (Ph), 127.3 (Ph), 68.4 (CH3). FT–IR (KBr disks) (I): 3265 (s), 1686 (s), 1529 (s), 1282 (s) cm−1; (II): 3299 (s), 1688 (s), 1520 (s), 1272 (s) cm−1.

Refinement top

All H atoms were placed in geometrically calculated positions, with C—H distance of 0.98 Å (for –CH3) and 0.95 Å (for phenyl), and were refined using a riding model with Uiso(H) values of 1.2Ueq(parent) (for phenyl and N-bound H atoms) or 1.5Ueq(parent) (for –CH3).

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. A twofold rotation axis passes through atoms C5 and C7 of the benzene ring. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x, y, 1/2 - z.]
[Figure 2] Fig. 2. The molecular structure (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 3] Fig. 3. A view of the structure of (I), showing the intermolecular C6—H6···S1i, C5—H5···O2ii, C5—H5···O2iii and N1—H1···O2ii hydrogen-bond interactions. All H atoms, apart from those participating in hydrogen bonding, have been omitted for clarity. [Symmetry codes: (i) x, 1 + y, z; (ii) x, 1 − y, z − 1/2; (iii) −x, 1 − y, 1 − z.]
[Figure 4] Fig. 4. A view of the structure of (II), showing the intermolecular N1—H1···O3i, N2—H2···S1ii, N2—H2···O2ii and C5—H5···O3i hydrogen-bond interactions. All H atoms, apart from those participating in hydrogen bonding, have been omitted for clarity. [Symmetry codes: (i) −x, −y, 2 − z; (ii) 1 − x, 1 − y, 2 - z.]
(I) O,O'-dimethyl N,N'-(m-phenylenedicarbonyl)dithiocarbamate top
Crystal data top
C12H12N2O4S2F(000) = 648
Mr = 312.36Dx = 1.512 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 19.336 (3) ÅCell parameters from 1347 reflections
b = 8.2864 (13) Åθ = 2.1–26.0°
c = 8.6590 (14) ŵ = 0.40 mm1
β = 98.435 (3)°T = 100 K
V = 1372.4 (4) Å3Needle, white
Z = 40.24 × 0.11 × 0.09 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
1347 independent reflections
Radiation source: fine-focus sealed tube1183 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 2322
Tmin = 0.948, Tmax = 0.964k = 910
3729 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0659P)2 + 1.4244P]
where P = (Fo2 + 2Fc2)/3
1507 reflections(Δ/σ)max < 0.001
93 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C12H12N2O4S2V = 1372.4 (4) Å3
Mr = 312.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 19.336 (3) ŵ = 0.40 mm1
b = 8.2864 (13) ÅT = 100 K
c = 8.6590 (14) Å0.24 × 0.11 × 0.09 mm
β = 98.435 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer
1347 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
1183 reflections with I > 2σ(I)
Tmin = 0.948, Tmax = 0.964Rint = 0.027
3729 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.06Δρmax = 0.50 e Å3
1507 reflectionsΔρmin = 0.25 e Å3
93 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.16236 (3)0.14181 (6)0.49592 (7)0.0277 (2)
O10.18079 (8)0.39041 (19)0.68924 (16)0.0236 (4)
O20.10169 (8)0.64974 (17)0.62533 (16)0.0214 (3)
N10.11436 (8)0.4391 (2)0.45795 (18)0.0175 (4)
H10.10450.41170.35900.021*
C10.22244 (12)0.2858 (3)0.8009 (2)0.0291 (5)
H110.19450.19200.82240.044*
H130.23710.34530.89800.044*
H120.26380.24940.75750.044*
C20.15354 (10)0.3276 (3)0.5541 (2)0.0188 (4)
C30.08886 (10)0.5868 (2)0.4969 (2)0.0167 (4)
C40.04207 (10)0.6689 (2)0.3672 (2)0.0161 (4)
C50.00000.5842 (3)0.25000.0149 (5)
H50.00000.46960.25000.018*
C60.04011 (11)0.8365 (3)0.3698 (2)0.0215 (5)
H60.06630.89370.45380.026*
C70.00000.9207 (4)0.25000.0250 (6)
H70.00001.03540.25000.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0297 (3)0.0215 (3)0.0292 (3)0.0018 (2)0.0040 (2)0.0010 (2)
O10.0239 (8)0.0336 (8)0.0114 (7)0.0067 (6)0.0038 (5)0.0015 (6)
O20.0258 (8)0.0258 (8)0.0110 (7)0.0039 (6)0.0022 (5)0.0007 (5)
N10.0183 (8)0.0246 (9)0.0084 (7)0.0014 (6)0.0018 (6)0.0014 (6)
C10.0277 (12)0.0420 (14)0.0159 (10)0.0105 (10)0.0027 (8)0.0076 (9)
C20.0139 (9)0.0265 (11)0.0159 (9)0.0022 (8)0.0017 (7)0.0032 (8)
C30.0138 (9)0.0244 (10)0.0116 (9)0.0054 (7)0.0007 (7)0.0024 (7)
C40.0152 (9)0.0236 (10)0.0098 (9)0.0005 (7)0.0021 (7)0.0015 (7)
C50.0143 (12)0.0205 (13)0.0101 (12)0.0000.0027 (9)0.000
C60.0229 (10)0.0248 (11)0.0161 (10)0.0051 (8)0.0002 (8)0.0033 (8)
C70.0318 (17)0.0179 (14)0.0243 (15)0.0000.0006 (12)0.000
Geometric parameters (Å, º) top
S1—C21.637 (2)C1—H120.9800
O1—C21.318 (2)C3—C41.498 (3)
O1—C11.451 (2)C4—C61.390 (3)
O2—C31.220 (2)C4—C51.393 (2)
N1—C31.380 (3)C5—H50.9500
N1—C21.391 (3)C6—C71.388 (3)
N1—H10.8800C6—H60.9500
C1—H110.9800C7—H70.9500
C1—H130.9800
C2—O1—C1117.78 (17)O2—C3—N1124.74 (17)
C3—N1—C2128.71 (16)O2—C3—C4120.59 (18)
C3—N1—H1115.6N1—C3—C4114.66 (16)
C2—N1—H1115.6C6—C4—C5120.03 (18)
O1—C1—H11109.5C6—C4—C3117.15 (17)
O1—C1—H13109.5C5—C4—C3122.78 (19)
H11—C1—H13109.5C4—C5—C4i119.6 (3)
O1—C1—H12109.5C4—C5—H5120.2
H11—C1—H12109.5C7—C6—C4120.24 (19)
H13—C1—H12109.5C7—C6—H6119.9
O1—C2—N1112.41 (18)C4—C6—H6119.9
O1—C2—S1126.76 (15)C6i—C7—H7120.2
N1—C2—S1120.84 (15)C6—C7—H7120.2
C1—O1—C2—N1179.47 (16)O2—C3—C4—C5149.28 (17)
C1—O1—C2—S10.9 (3)N1—C3—C4—C530.4 (2)
C3—N1—C2—O115.6 (3)C6—C4—C5—C4i2.22 (13)
C3—N1—C2—S1164.72 (16)C3—C4—C5—C4i179.9 (2)
C2—N1—C3—O25.8 (3)C5—C4—C6—C74.5 (3)
C2—N1—C3—C4173.86 (18)C3—C4—C6—C7177.50 (15)
O2—C3—C4—C628.7 (3)C4—C6—C7—C6i2.23 (13)
N1—C3—C4—C6151.65 (18)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···S1ii0.952.763.525 (2)138
C5—H5···O2iii0.952.583.068 (2)113
C5—H5···O2iv0.952.583.068 (2)113
N1—H1···O2iii0.882.082.948 (2)169
Symmetry codes: (ii) x, y+1, z; (iii) x, y+1, z1/2; (iv) x, y+1, z+1.
(II) N,N'-bis(methoxythiocarbonyl)isophthalamide top
Crystal data top
C12H12N2O4S2Z = 2
Mr = 312.36F(000) = 324
Triclinic, P1Dx = 1.547 Mg m3
a = 6.3603 (13) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.7016 (15) ÅCell parameters from 2617 reflections
c = 14.255 (3) Åθ = 2.7–26.0°
α = 92.496 (3)°µ = 0.41 mm1
β = 97.952 (3)°T = 100 K
γ = 103.496 (3)°Needle, yellow
V = 670.4 (2) Å30.24 × 0.11 × 0.09 mm
Data collection top
Bruker SMART APEX CCD
diffractometer
2617 independent reflections
Radiation source: fine-focus sealed tube2308 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 77
Tmin = 0.947, Tmax = 0.964k = 99
6812 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150H-atom parameters constrained
S = 1.26 w = 1/[σ2(Fo2) + (0.0573P)2 + 1.1105P]
where P = (Fo2 + 2Fc2)/3
2617 reflections(Δ/σ)max = 0.001
183 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.41 e Å3
Crystal data top
C12H12N2O4S2γ = 103.496 (3)°
Mr = 312.36V = 670.4 (2) Å3
Triclinic, P1Z = 2
a = 6.3603 (13) ÅMo Kα radiation
b = 7.7016 (15) ŵ = 0.41 mm1
c = 14.255 (3) ÅT = 100 K
α = 92.496 (3)°0.24 × 0.11 × 0.09 mm
β = 97.952 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2617 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
2308 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.964Rint = 0.034
6812 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0690 restraints
wR(F2) = 0.150H-atom parameters constrained
S = 1.26Δρmax = 0.53 e Å3
2617 reflectionsΔρmin = 0.41 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.

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.20470 (16)0.51190 (13)0.65805 (7)0.0229 (3)
S20.34344 (16)0.19024 (14)1.43417 (7)0.0230 (3)
O10.1107 (4)0.2702 (3)0.71338 (18)0.0177 (6)
O40.0028 (4)0.0837 (3)1.29744 (17)0.0144 (5)
O20.5568 (4)0.4532 (3)0.80550 (18)0.0170 (6)
O30.0924 (4)0.0006 (3)1.12460 (17)0.0150 (6)
N10.2017 (5)0.2994 (4)0.8056 (2)0.0138 (6)
H10.11920.21660.83430.017*
N20.3286 (5)0.1747 (4)1.2481 (2)0.0143 (6)
H20.45980.24751.26100.017*
C120.1316 (6)0.0412 (5)1.3716 (3)0.0202 (8)
H1230.09280.05801.40520.030*
H1210.28620.00631.34320.030*
H1220.10650.14651.41660.030*
C20.1001 (6)0.3614 (5)0.7269 (3)0.0148 (7)
C110.2166 (6)0.1450 (5)1.3246 (2)0.0135 (7)
C30.4235 (5)0.3552 (4)0.8447 (2)0.0122 (7)
C100.2656 (5)0.1075 (4)1.1551 (2)0.0116 (7)
C40.4891 (5)0.2899 (4)0.9389 (2)0.0120 (7)
C90.4272 (5)0.1783 (4)1.0908 (2)0.0108 (7)
C50.3464 (5)0.2137 (4)0.9996 (2)0.0107 (7)
H50.19300.18560.97880.013*
C60.7153 (5)0.3224 (4)0.9696 (3)0.0134 (7)
H60.81460.37230.92820.016*
C80.6523 (5)0.2112 (5)1.1199 (3)0.0131 (7)
H80.70780.18471.18160.016*
C70.7948 (6)0.2829 (5)1.0585 (3)0.0159 (8)
H70.94820.30481.07810.019*
C10.2541 (6)0.3119 (5)0.6343 (3)0.0221 (8)
H120.26040.43750.64300.033*
H110.40110.23420.63130.033*
H130.19790.29240.57510.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0194 (5)0.0230 (5)0.0193 (5)0.0080 (4)0.0014 (4)0.0104 (4)
S20.0173 (5)0.0337 (6)0.0113 (5)0.0073 (4)0.0020 (4)0.0021 (4)
O10.0106 (12)0.0194 (14)0.0207 (14)0.0006 (10)0.0007 (10)0.0055 (11)
O40.0077 (11)0.0197 (13)0.0139 (12)0.0025 (10)0.0046 (9)0.0036 (10)
O20.0106 (12)0.0192 (14)0.0196 (14)0.0023 (10)0.0060 (10)0.0057 (11)
O30.0089 (12)0.0168 (13)0.0143 (12)0.0069 (10)0.0018 (10)0.0023 (10)
N10.0116 (14)0.0128 (15)0.0139 (15)0.0045 (12)0.0032 (12)0.0055 (12)
N20.0062 (14)0.0174 (16)0.0154 (15)0.0057 (12)0.0031 (11)0.0007 (12)
C120.0154 (18)0.024 (2)0.021 (2)0.0017 (15)0.0122 (15)0.0052 (16)
C20.0133 (17)0.0125 (17)0.0160 (18)0.0023 (14)0.0030 (14)0.0011 (14)
C110.0149 (17)0.0113 (17)0.0137 (17)0.0001 (14)0.0045 (14)0.0041 (13)
C30.0126 (17)0.0092 (16)0.0138 (17)0.0017 (13)0.0063 (14)0.0004 (13)
C100.0076 (16)0.0108 (17)0.0157 (17)0.0001 (13)0.0019 (13)0.0030 (13)
C40.0099 (16)0.0078 (16)0.0162 (18)0.0028 (13)0.0042 (14)0.0028 (13)
C90.0090 (16)0.0067 (16)0.0159 (18)0.0013 (13)0.0048 (13)0.0014 (13)
C50.0072 (16)0.0072 (16)0.0149 (17)0.0040 (13)0.0030 (13)0.0037 (13)
C60.0096 (16)0.0121 (17)0.0180 (18)0.0023 (14)0.0086 (14)0.0001 (14)
C80.0101 (16)0.0129 (17)0.0149 (17)0.0008 (13)0.0003 (13)0.0029 (14)
C70.0083 (16)0.0149 (18)0.023 (2)0.0012 (14)0.0042 (14)0.0007 (15)
C10.0164 (19)0.025 (2)0.022 (2)0.0019 (16)0.0005 (16)0.0054 (16)
Geometric parameters (Å, º) top
S1—C21.634 (4)C12—H1220.9800
S2—C111.639 (4)C3—C41.495 (5)
O1—C21.343 (4)C10—C91.496 (4)
O1—C11.445 (4)C4—C51.388 (5)
O4—C111.327 (4)C4—C61.405 (5)
O4—C121.451 (4)C9—C51.393 (5)
O2—C31.212 (4)C9—C81.394 (5)
O3—C101.226 (4)C5—H50.9500
N1—C21.377 (5)C6—C71.373 (5)
N1—C31.401 (4)C6—H60.9500
N1—H10.8800C8—C71.385 (5)
N2—C101.372 (4)C8—H80.9500
N2—C111.381 (4)C7—H70.9500
N2—H20.8800C1—H120.9800
C12—H1230.9800C1—H110.9800
C12—H1210.9800C1—H130.9800
C2—O1—C1117.6 (3)N2—C10—C9114.3 (3)
C11—O4—C12117.2 (3)C5—C4—C6118.8 (3)
C2—N1—C3126.4 (3)C5—C4—C3125.4 (3)
C2—N1—H1116.8C6—C4—C3115.6 (3)
C3—N1—H1116.8C5—C9—C8119.9 (3)
C10—N2—C11129.5 (3)C5—C9—C10117.9 (3)
C10—N2—H2115.2C8—C9—C10122.2 (3)
C11—N2—H2115.2C4—C5—C9120.3 (3)
O4—C12—H123109.5C4—C5—H5119.8
O4—C12—H121109.5C9—C5—H5119.8
H123—C12—H121109.5C7—C6—C4120.8 (3)
O4—C12—H122109.5C7—C6—H6119.6
H123—C12—H122109.5C4—C6—H6119.6
H121—C12—H122109.5C7—C8—C9119.7 (3)
O1—C2—N1106.8 (3)C7—C8—H8120.1
O1—C2—S1124.1 (3)C9—C8—H8120.1
N1—C2—S1129.1 (3)C6—C7—C8120.3 (3)
O4—C11—N2112.1 (3)C6—C7—H7119.8
O4—C11—S2126.4 (3)C8—C7—H7119.8
N2—C11—S2121.4 (3)O1—C1—H12109.5
O2—C3—N1122.5 (3)O1—C1—H11109.5
O2—C3—C4121.0 (3)H12—C1—H11109.5
N1—C3—C4116.6 (3)O1—C1—H13109.5
O3—C10—N2124.6 (3)H12—C1—H13109.5
O3—C10—C9121.1 (3)H11—C1—H13109.5
C1—O1—C2—N1179.7 (3)N1—C3—C4—C6170.0 (3)
C1—O1—C2—S11.7 (5)O3—C10—C9—C538.1 (5)
C3—N1—C2—O1178.9 (3)N2—C10—C9—C5141.5 (3)
C3—N1—C2—S10.3 (6)O3—C10—C9—C8142.8 (3)
C12—O4—C11—N2177.8 (3)N2—C10—C9—C837.7 (5)
C12—O4—C11—S24.3 (5)C6—C4—C5—C93.0 (5)
C10—N2—C11—O419.8 (5)C3—C4—C5—C9171.9 (3)
C10—N2—C11—S2162.2 (3)C8—C9—C5—C43.1 (5)
C2—N1—C3—O28.4 (6)C10—C9—C5—C4176.0 (3)
C2—N1—C3—C4170.7 (3)C5—C4—C6—C71.2 (5)
C11—N2—C10—O32.7 (6)C3—C4—C6—C7174.2 (3)
C11—N2—C10—C9176.8 (3)C5—C9—C8—C71.4 (5)
O2—C3—C4—C5164.1 (3)C10—C9—C8—C7177.7 (3)
N1—C3—C4—C514.9 (5)C4—C6—C7—C80.5 (5)
O2—C3—C4—C611.0 (5)C9—C8—C7—C60.4 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.882.042.913 (4)169
N2—H2···S1ii0.882.573.421 (3)163
N2—H2···O2ii0.882.552.949 (4)108
C5—H5···O3i0.952.323.140 (4)145
Symmetry codes: (i) x, y, z+2; (ii) x+1, y+1, z+2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC12H12N2O4S2C12H12N2O4S2
Mr312.36312.36
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)100100
a, b, c (Å)19.336 (3), 8.2864 (13), 8.6590 (14)6.3603 (13), 7.7016 (15), 14.255 (3)
α, β, γ (°)90, 98.435 (3), 9092.496 (3), 97.952 (3), 103.496 (3)
V3)1372.4 (4)670.4 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.400.41
Crystal size (mm)0.24 × 0.11 × 0.090.24 × 0.11 × 0.09
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Bruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Multi-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.948, 0.9640.947, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
3729, 1347, 1183 6812, 2617, 2308
Rint0.0270.034
(sin θ/λ)max1)0.6170.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.119, 1.06 0.069, 0.150, 1.26
No. of reflections15072617
No. of parameters93183
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.250.53, 0.41

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), X-SEED.

Selected geometric parameters (Å, º) for (I) top
S1—C21.637 (2)N1—C31.380 (3)
O1—C21.318 (2)N1—C21.391 (3)
O2—C31.220 (2)
C6—C4—C3117.15 (17)C5—C4—C3122.78 (19)
C3—N1—C2—S1164.72 (16)C2—N1—C3—O25.8 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C6—H6···S1i0.952.763.525 (2)138
C5—H5···O2ii0.952.583.068 (2)113
C5—H5···O2iii0.952.583.068 (2)113
N1—H1···O2ii0.882.082.948 (2)169
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z1/2; (iii) x, y+1, z+1.
Selected geometric parameters (Å, º) for (II) top
S1—C21.634 (4)O3—C101.226 (4)
S2—C111.639 (4)N1—C21.377 (5)
O1—C21.343 (4)N1—C31.401 (4)
O4—C111.327 (4)N2—C101.372 (4)
O2—C31.212 (4)N2—C111.381 (4)
C5—C4—C3125.4 (3)C5—C9—C10117.9 (3)
C6—C4—C3115.6 (3)C8—C9—C10122.2 (3)
C3—N1—C2—S10.3 (6)C2—N1—C3—O28.4 (6)
C10—N2—C11—S2162.2 (3)C11—N2—C10—O32.7 (6)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O3i0.882.042.913 (4)169
N2—H2···S1ii0.882.573.421 (3)163
N2—H2···O2ii0.882.552.949 (4)108
C5—H5···O3i0.952.323.140 (4)145
Symmetry codes: (i) x, y, z+2; (ii) x+1, y+1, z+2.
 

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