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Cocrystallization of imidazole or 4-methyl­imidazole with 2,2′-dithio­dibenzoic acid from methanol solution yields the title 2:1 and 1:1 organic salts, 2C3H5N2+·C14H10O4S22−, (I), and C4H7N2+·C14H10O4S2, (II), respectively. Compound (I) crystallizes in the monoclinic C2/c space group with the mid-point of the S—S bond lying on a twofold axis. The component ions in (I) are linked by inter­molecular N—H...O hydrogen bonds to form a two-dimensional network, which is further linked by C—H...O hydrogen bonds into a three-dimensional network. In contrast, by means of N—H...O, N—H...S and O—H...O hydrogen bonds, the component ions in (II) are linked into a tape and adjacent tapes are further linked by π–π, C—H...O and C—H...π inter­actions, resulting in a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109030686/fg3123sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030686/fg3123Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109030686/fg3123IIsup3.hkl
Contains datablock II

CCDC references: 749716; 749717

Comment top

2,2'-Dithiodibenzoic acid (H2DTBB), possessing two carboxylic groups, has often been employed in coordination complexes (Wang et al., 2007, 2008; Murugavel et al., 2001). However, due to its poor solubility in water, molecular adducts based on H2DTBB have been reported for only a few cases up to now (Meng et al., 2008; Li et al., 2001; Cai et al., 2006; Kang et al., 2002; Hu et al., 2004). In order to investigate the crystal engineering involving two hydrogen-bonded R-COOH groups and an N-containing heterocycle in the solid state, we used H2DTBB and imidazole (Im) or 4-methylimidazole (4-MeIm) as potential cocrystallization agents in our experiments. We report here the crystal structures of the title compounds, (I) and (II).

In (I), half of a 2,2'-dithiodibenzoate dianion (DTBB2-) and one imidazolium (Im+) cation comprise the asymmetric unit, linked by an N1—H1···O1 hydrogen bond (see Fig. 1 and Table 1). The two halves of the DTBB2- ion are related by a twofold axis lying across the midpoint of the S—S bond. Both the dihedral angle between the two phenyl rings [76.80 (11)°] and the bridging S—S bond length [2.0476 (10) Å] are comparable with those observed in some analogous compounds [Cambridge Structural Database (CSD, Version?; Allen 2002) refcodes MIPVAI (Li et al., 2001), MUFNIK (Bi et al., 2002), WUBHOQ (Kang et al., 2002), XEBDEO (Cai et al., 2006) and XEXFOV (Basiuk et al., 1999)]. The deprotonation of the H2DTBB molecule and protonation of the imidazole moiety were very clearly shown in difference map plots and the relevant dimensions are fully in accord with this: C7—O1 = 1.259 (2) and C7—O2 = 1.250 (2) Å, and C2'—N1 = 1.315 (3) and C2'—N3 = 1.316 (3) Å. Compound (I) can be regarded as a binary 1:2 organic salt, according to Aakeröy & Salmon (2005).

The asymmetric unit of (II) (Fig. 2) has a 4-methylimidazolium (4-MeIm+) ion and a hydrogen 2,2'-dithiodibenzoate anion (HDTBB-), both lying in general positions, forming a 1:1 salt. As with (I), the H atoms involved in the hydrogen bonding were unequivocally located from difference map plots and the resulting ion dimensions are fully in accord with these H-atom locations: at the deprotonated carboxyl group C7—O1 = 1.264 (3) and C7—O2 = 1.239 (3) Å. For the other carboxylic group, the main bond lengths are C27—O3(H) = 1.320 (3) and C27—O4 = 1.205 (3) Å, again in accord with the location of the carboxyl H atom at O3. In the 4-MeIm+ cation, the C2'—N1 and C2'—N3 bond lengths of 1.311 (4) and 1.314 (4) Å, respectively, are almost the same as those found in (I), consistent with the delocalization of the imidazole ring.

In the crystal packing of (I), the DTBB2- anion and the Im+ cation are linked into a two-dimensional network by the N1—H1···O1 and N3—H3···O2i hydrogen bonds (see Table 2 and Fig. 3; symmetry code as in Table 2) running parallel to the (001) plane in the domain 0.530 < z < 0.970. These adjacent networks are linked by a C2'—H2'···O1ii hydrogen bond, resulting in a three-dimensional network (Fig. 3). PLATON (Spek, 2009) calculations show that there are no significant C—H···π or ππ interactions in the packing of (I).

In the structure of (II), the HDTBB- anion and 4-MeIm+ cation are linked by means of N—H···O, N—H···S and O—H···O hydrogen bonds to generate a tape extending in the [110] direction, as shown in Fig. 4 with details in Table 2. The N3—H3···O1i (symmetry code as in Table 2) and N1—H1..O2 hydrogen bonds serve to generate a centrosymmetric R44(16) ring (Bernstein et al., 1995). These R44(16) rings are linked by an O3—H3···O1ii (symmetry code as in Table 2) hydrogen bond to form the tape shown in Fig. 4. These tapes are further linked to form a three-dimensional network (Fig. 5) by a combination of ππ interactions [Cg1···Cg1(-x, 1 - y, 2 - z); centroid-to-centroid distance = 3.9798 (17) Å and interplanar spacing = 3.6820 (12) Å, where Cg1 is the centroid of the C1–C6 phenyl ring], a C2'—H2'···O4iii interaction (Table 2; symmetry code as in Table 2)) and a C4—H4···Cg2 interaction [H4···Cg2 = 2.94 Å and C4—H4···Cg2 = 136°, where Cg2 is the centroid of the C21–C26 phenyl ring at (x - 1, y, z)].

Experimental top

2,2'-Dithiodibenzoic acid (0.2 mmol, 0.0612 g) and imidazole (0.2 mmol, 0.0136 g) were dissolved in 95% methanol (10 ml). The resulting clear solution was kept in air for 3 d. Colourless plate crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown by slow evaporation of the solution (yield 17.7 mg, 40%, based on 1:2 cocrystallization). Similarly, colourless block crystals of compound (II) were obtained by mixing equivalent molar amounts of 2,2'-dithiodibenzoic acid (0.2 mmol, 0.0612 g) and 4-methylimidazole (0.2 mmol, 0.0164 g) in 95% methanol (10 ml) (yield 43.5 mg, 56%, based on 1:1 cocrystallization).

According to the ΔpKa rule (Meng et al., 2009; Childs et al., 2007), a 1:1 type of organic salt for the combination of H2DTBB and Im, and a 1:2 organic salt (acid to base) for H2DTBB and 4-MeIm, should both exist theoretically [for (I), ΔpKa1 = 11.1 and ΔpKa2 = 10.4; for (II), ΔpKa1 = 11.5 and ΔpKa2 = 10.8]. However, when H2DTBB and Im were mixed and stirred in methanol solution in a molar ratio of 1:1, only some of the H2DTBB was dissolved, showing that the preparation of the target compound was hampered by the poor solubility of H2DTBB in methanol. For the second combination, although H2DTBB and 4-MeIm can be easily dissolved in methanol in a molar ratio of 1:2, the result is an oil-like compound when the humidity level in the air exceeds 20%. Further research on this will be carried out for the 1:1 and 1:2 organic salts of (I) and (II), respectively.

Refinement top

For both compounds, all H atoms were clearly visible in difference maps and were subsequently allowed for as riding atoms in the refinements, with C—H = 0.93 Å for both aromatic and methyl H atoms and Uiso(H) = 1.2Ueq(aromatic C) or 1.5Ueq(methyl C), and with N—H = 0.86 Å and O—H = 0.82 Å, with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O).

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure 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. Hydrogen bonds are shown as dashed lines. [Symmetry code: (i) 1 - x, y, 3/2 - z.]
[Figure 2] Fig. 2. The molecular structure 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. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the three-dimensional network formed only by N—H···O and C—H···O hydrogen bonds. Hydrogen bonds are shown as short dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted. The area outlined by a continuous dashed line shows the (001) layer in the domain 0.530 < z < 0.970.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of the one-dimensional tape running parallel to the [110] direction. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted. See Table 2 for symmetry codes.
[Figure 5] Fig. 5. Part of the crystal structure of (II), showing the formation of the three-dimensional network. Hydrogen bonds are shown as short dashed lines. For the sake of clarity, H atoms not involved in the motif have been omitted. The are outlined by a continuous dashed line shows part of the [110] tape.
(I) bis(imidazolium) 2,2'-dithiodibenzoate top
Crystal data top
2C3H5N2+·C14H8O4S22F(000) = 920
Mr = 442.50Dx = 1.472 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2506 reflections
a = 17.0142 (13) Åθ = 2.4–25.4°
b = 5.9064 (4) ŵ = 0.30 mm1
c = 19.9254 (15) ÅT = 297 K
β = 94.228 (1)°Plate, colourless
V = 1996.9 (3) Å30.30 × 0.30 × 0.04 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2283 independent reflections
Radiation source: fine-focus sealed Siemens Mo tube1721 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
0.3° wide ω exposures scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 2222
Tmin = 0.905, Tmax = 0.988k = 77
10805 measured reflectionsl = 2525
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0702P)2 + 0.7582P]
where P = (Fo2 + 2Fc2)/3
2283 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
2C3H5N2+·C14H8O4S22V = 1996.9 (3) Å3
Mr = 442.50Z = 4
Monoclinic, C2/cMo Kα radiation
a = 17.0142 (13) ŵ = 0.30 mm1
b = 5.9064 (4) ÅT = 297 K
c = 19.9254 (15) Å0.30 × 0.30 × 0.04 mm
β = 94.228 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2283 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
1721 reflections with I > 2σ(I)
Tmin = 0.905, Tmax = 0.988Rint = 0.038
10805 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.129H-atom parameters constrained
S = 1.06Δρmax = 0.38 e Å3
2283 reflectionsΔρmin = 0.26 e Å3
136 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.48149 (3)0.04094 (10)0.69993 (3)0.0397 (2)
O10.30395 (8)0.0444 (3)0.53687 (7)0.0412 (4)
O20.43265 (8)0.0302 (3)0.56336 (7)0.0417 (4)
C10.35552 (11)0.2582 (3)0.63087 (9)0.0325 (5)
C20.40456 (11)0.2497 (3)0.69097 (10)0.0338 (5)
C30.39232 (14)0.4048 (4)0.74170 (10)0.0457 (6)
H30.42370.39880.78190.055*
C40.33418 (15)0.5676 (4)0.73326 (12)0.0542 (7)
H40.32660.66930.76780.065*
C50.28745 (15)0.5803 (4)0.67411 (13)0.0527 (6)
H50.24900.69200.66810.063*
C60.29824 (13)0.4252 (4)0.62376 (11)0.0412 (5)
H60.26620.43300.58400.049*
C70.36484 (11)0.0979 (3)0.57310 (9)0.0308 (4)
N10.15372 (10)0.0371 (3)0.56232 (9)0.0392 (4)
H10.20200.06940.55620.047*
C2'0.11896 (12)0.1578 (4)0.54832 (10)0.0386 (5)
H2'0.14230.28330.52980.046*
N30.04561 (10)0.1459 (3)0.56494 (8)0.0395 (4)
H3'0.01140.25310.56090.047*
C4'0.03301 (13)0.0661 (4)0.58975 (11)0.0412 (5)
H4'0.01380.12070.60480.049*
C5'0.10054 (13)0.1795 (4)0.58818 (11)0.0423 (5)
H5'0.10970.32800.60210.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0390 (3)0.0432 (4)0.0352 (3)0.0051 (2)0.0082 (2)0.0061 (2)
O10.0290 (7)0.0547 (10)0.0386 (8)0.0038 (7)0.0048 (6)0.0140 (7)
O20.0274 (8)0.0514 (10)0.0459 (9)0.0008 (6)0.0004 (6)0.0161 (7)
C10.0276 (10)0.0403 (12)0.0294 (9)0.0039 (8)0.0008 (7)0.0036 (8)
C20.0323 (10)0.0370 (11)0.0314 (9)0.0011 (8)0.0012 (8)0.0007 (8)
C30.0528 (13)0.0523 (15)0.0307 (10)0.0050 (11)0.0070 (9)0.0075 (10)
C40.0646 (16)0.0530 (16)0.0444 (13)0.0156 (12)0.0001 (11)0.0180 (11)
C50.0527 (14)0.0497 (15)0.0544 (14)0.0170 (12)0.0053 (11)0.0090 (12)
C60.0380 (12)0.0481 (14)0.0362 (11)0.0040 (10)0.0061 (9)0.0054 (9)
C70.0302 (10)0.0341 (11)0.0282 (9)0.0039 (8)0.0013 (7)0.0015 (8)
N10.0326 (9)0.0449 (11)0.0403 (10)0.0046 (8)0.0039 (7)0.0016 (8)
C2'0.0367 (11)0.0415 (13)0.0371 (10)0.0007 (10)0.0013 (8)0.0065 (9)
N30.0319 (9)0.0445 (11)0.0412 (9)0.0062 (8)0.0035 (7)0.0001 (8)
C4'0.0373 (12)0.0451 (13)0.0415 (11)0.0076 (10)0.0064 (9)0.0027 (10)
C5'0.0488 (13)0.0355 (12)0.0432 (12)0.0011 (10)0.0066 (10)0.0028 (9)
Geometric parameters (Å, º) top
S1—C21.798 (2)C5—H50.9300
S1—S1i2.0476 (10)C6—H60.9300
O1—C71.259 (2)N1—C2'1.315 (3)
O2—C71.250 (2)N1—C5'1.364 (3)
C1—C61.387 (3)N1—H10.8600
C1—C21.409 (3)C2'—N31.316 (3)
C1—C71.508 (3)C2'—H2'0.9300
C2—C31.391 (3)N3—C4'1.369 (3)
C3—C41.381 (3)N3—H3'0.8600
C3—H30.9300C4'—C5'1.332 (3)
C4—C51.374 (3)C4'—H4'0.9300
C4—H40.9300C5'—H5'0.9300
C5—C61.381 (3)
C2—S1—S1i105.44 (7)O2—C7—O1124.11 (18)
C6—C1—C2118.69 (18)O2—C7—C1118.02 (16)
C6—C1—C7118.77 (17)O1—C7—C1117.85 (17)
C2—C1—C7122.51 (18)C2'—N1—C5'108.63 (18)
C3—C2—C1118.88 (19)C2'—N1—H1125.7
C3—C2—S1121.77 (16)C5'—N1—H1125.7
C1—C2—S1119.34 (15)N1—C2'—N3108.64 (19)
C4—C3—C2121.0 (2)N1—C2'—H2'125.7
C4—C3—H3119.5N3—C2'—H2'125.7
C2—C3—H3119.5C2'—N3—C4'108.45 (19)
C5—C4—C3120.4 (2)C2'—N3—H3'125.8
C5—C4—H4119.8C4'—N3—H3'125.8
C3—C4—H4119.8C5'—C4'—N3107.03 (18)
C4—C5—C6119.2 (2)C5'—C4'—H4'126.5
C4—C5—H5120.4N3—C4'—H4'126.5
C6—C5—H5120.4C4'—C5'—N1107.2 (2)
C5—C6—C1121.8 (2)C4'—C5'—H5'126.4
C5—C6—H6119.1N1—C5'—H5'126.4
C1—C6—H6119.1
C6—C1—C2—C31.8 (3)C2—C1—C6—C50.9 (3)
C7—C1—C2—C3179.61 (19)C7—C1—C6—C5178.8 (2)
C6—C1—C2—S1177.77 (15)C6—C1—C7—O2145.2 (2)
C7—C1—C2—S10.0 (3)C2—C1—C7—O232.6 (3)
S1i—S1—C2—C313.6 (2)C6—C1—C7—O133.3 (3)
S1i—S1—C2—C1166.81 (15)C2—C1—C7—O1148.9 (2)
C1—C2—C3—C41.2 (3)C5'—N1—C2'—N30.6 (2)
S1—C2—C3—C4178.38 (19)N1—C2'—N3—C4'0.7 (2)
C2—C3—C4—C50.4 (4)C2'—N3—C4'—C5'0.6 (2)
C3—C4—C5—C61.4 (4)N3—C4'—C5'—N10.2 (2)
C4—C5—C6—C10.7 (4)C2'—N1—C5'—C4'0.3 (2)
Symmetry code: (i) x+1, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.812.643 (2)162
N3—H3···O2ii0.861.862.710 (2)172
C2—H2···O1iii0.932.273.185 (3)167
Symmetry codes: (ii) x1/2, y1/2, z; (iii) x+1/2, y1/2, z+1.
(II) 4-methylimidazolium 2-[(2-carboxyphenyl)disulfanyl]benzoate top
Crystal data top
C4H7N2+·C14H9O4S2Z = 2
Mr = 388.45F(000) = 404
Triclinic, P1Dx = 1.461 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2486 (5) ÅCell parameters from 4099 reflections
b = 10.1528 (6) Åθ = 2.4–27.1°
c = 11.3724 (7) ŵ = 0.33 mm1
α = 70.359 (1)°T = 300 K
β = 82.112 (2)°Block, colourless
γ = 81.285 (1)°0.20 × 0.20 × 0.10 mm
V = 882.81 (9) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3427 independent reflections
Radiation source: fine focus sealed Siemens Mo tube2884 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
0.3° wide ω exposures scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
h = 1010
Tmin = 0.927, Tmax = 0.968k = 1212
9067 measured reflectionsl = 1413
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0695P)2 + 0.3053P]
where P = (Fo2 + 2Fc2)/3
3427 reflections(Δ/σ)max < 0.001
236 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H7N2+·C14H9O4S2γ = 81.285 (1)°
Mr = 388.45V = 882.81 (9) Å3
Triclinic, P1Z = 2
a = 8.2486 (5) ÅMo Kα radiation
b = 10.1528 (6) ŵ = 0.33 mm1
c = 11.3724 (7) ÅT = 300 K
α = 70.359 (1)°0.20 × 0.20 × 0.10 mm
β = 82.112 (2)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3427 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)
2884 reflections with I > 2σ(I)
Tmin = 0.927, Tmax = 0.968Rint = 0.021
9067 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.13Δρmax = 0.34 e Å3
3427 reflectionsΔρmin = 0.24 e Å3
236 parameters
Special details top

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

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.40313 (8)0.49732 (6)0.70899 (6)0.0541 (2)
S20.49337 (8)0.29164 (6)0.73126 (6)0.0546 (2)
O10.0402 (2)0.87131 (17)0.66759 (18)0.0576 (5)
O20.2896 (2)0.76894 (17)0.63337 (17)0.0574 (5)
O30.8771 (2)0.0548 (2)0.8536 (2)0.0743 (6)
H3'0.91610.08330.79510.112*
O40.6796 (2)0.0501 (2)0.72731 (19)0.0661 (5)
C10.0871 (3)0.6228 (2)0.7525 (2)0.0427 (5)
C20.1921 (3)0.4962 (2)0.7750 (2)0.0454 (5)
C30.1321 (3)0.3711 (3)0.8489 (3)0.0567 (6)
H3A0.20210.28730.86520.068*
C40.0307 (3)0.3694 (3)0.8985 (3)0.0637 (7)
H40.06880.28490.94890.076*
C50.1360 (3)0.4915 (3)0.8738 (3)0.0634 (7)
H50.24610.49020.90540.076*
C60.0767 (3)0.6160 (3)0.8016 (3)0.0541 (6)
H60.14850.69870.78510.065*
C70.1444 (3)0.7638 (2)0.6788 (2)0.0441 (5)
C210.6739 (3)0.1013 (2)0.9165 (2)0.0455 (5)
C220.5612 (3)0.2231 (2)0.8853 (2)0.0441 (5)
C230.5036 (3)0.2881 (3)0.9757 (2)0.0559 (6)
H230.42960.36940.95600.067*
C240.5563 (4)0.2320 (3)1.0946 (3)0.0631 (7)
H240.51660.27571.15440.076*
C250.6663 (4)0.1126 (3)1.1256 (3)0.0623 (7)
H250.70030.07521.20610.075*
C260.7256 (3)0.0491 (3)1.0373 (3)0.0570 (6)
H260.80190.03051.05800.068*
C270.7414 (3)0.0309 (2)0.8226 (2)0.0503 (6)
N10.6211 (3)0.7748 (2)0.5533 (2)0.0611 (6)
H10.52590.75700.59240.073*
C2'0.6829 (4)0.8952 (3)0.5230 (3)0.0628 (7)
H2'0.63170.97470.54190.075*
N30.8284 (3)0.8848 (2)0.4619 (2)0.0566 (5)
H30.89060.95140.43090.068*
C4'0.8661 (3)0.7503 (3)0.4550 (2)0.0543 (6)
C411.0260 (4)0.7038 (4)0.3964 (3)0.0820 (9)
H41A1.02870.60710.40180.123*
H41B1.11370.71330.43940.123*
H41C1.03940.76090.30990.123*
C5'0.7343 (3)0.6828 (3)0.5120 (3)0.0575 (6)
H5'0.72210.59000.52160.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0462 (4)0.0369 (3)0.0689 (4)0.0037 (2)0.0053 (3)0.0112 (3)
S20.0596 (4)0.0433 (3)0.0574 (4)0.0121 (3)0.0081 (3)0.0183 (3)
O10.0471 (10)0.0378 (9)0.0784 (12)0.0073 (7)0.0034 (8)0.0126 (8)
O20.0472 (10)0.0420 (9)0.0732 (11)0.0003 (7)0.0110 (8)0.0144 (8)
O30.0648 (12)0.0660 (12)0.0866 (14)0.0285 (10)0.0144 (10)0.0299 (11)
O40.0696 (12)0.0586 (11)0.0732 (13)0.0134 (9)0.0109 (10)0.0326 (10)
C10.0419 (12)0.0390 (11)0.0480 (12)0.0022 (9)0.0051 (9)0.0159 (9)
C20.0434 (12)0.0400 (12)0.0523 (13)0.0021 (9)0.0037 (10)0.0157 (10)
C30.0542 (15)0.0396 (12)0.0714 (16)0.0036 (11)0.0053 (12)0.0127 (11)
C40.0629 (17)0.0521 (15)0.0731 (17)0.0201 (13)0.0035 (13)0.0140 (13)
C50.0459 (14)0.0630 (17)0.0828 (19)0.0134 (12)0.0071 (13)0.0276 (14)
C60.0418 (13)0.0487 (13)0.0723 (16)0.0002 (10)0.0016 (11)0.0237 (12)
C70.0437 (12)0.0393 (11)0.0482 (12)0.0012 (9)0.0048 (10)0.0150 (9)
C210.0389 (12)0.0362 (11)0.0587 (14)0.0059 (9)0.0023 (10)0.0120 (10)
C220.0373 (11)0.0381 (11)0.0556 (13)0.0044 (9)0.0002 (9)0.0154 (10)
C230.0520 (14)0.0527 (14)0.0654 (16)0.0007 (11)0.0030 (12)0.0258 (12)
C240.0642 (17)0.0687 (17)0.0623 (16)0.0085 (14)0.0012 (13)0.0310 (14)
C250.0645 (17)0.0646 (17)0.0565 (15)0.0131 (14)0.0096 (12)0.0138 (13)
C260.0544 (15)0.0405 (12)0.0692 (16)0.0064 (11)0.0103 (12)0.0066 (11)
C270.0471 (13)0.0347 (11)0.0646 (16)0.0006 (10)0.0013 (11)0.0135 (10)
N10.0496 (12)0.0575 (13)0.0670 (14)0.0021 (10)0.0012 (10)0.0125 (11)
C2'0.0603 (17)0.0507 (15)0.0735 (18)0.0056 (12)0.0089 (14)0.0190 (13)
N30.0517 (12)0.0476 (12)0.0661 (13)0.0050 (9)0.0071 (10)0.0123 (10)
C4'0.0529 (14)0.0497 (14)0.0574 (14)0.0040 (11)0.0046 (11)0.0146 (11)
C410.0672 (19)0.084 (2)0.097 (2)0.0083 (17)0.0136 (17)0.0414 (19)
C5'0.0533 (15)0.0489 (13)0.0667 (16)0.0044 (11)0.0006 (12)0.0169 (12)
Geometric parameters (Å, º) top
S1—C21.798 (2)C22—C231.395 (3)
S1—S22.0504 (8)C23—C241.381 (4)
S2—C221.789 (2)C23—H230.9300
O1—C71.264 (3)C24—C251.373 (4)
O2—C71.239 (3)C24—H240.9300
O3—C271.319 (3)C25—C261.367 (4)
O3—H3'0.8200C25—H250.9300
O4—C271.205 (3)C26—H260.9300
C1—C61.392 (3)N1—C2'1.315 (4)
C1—C21.404 (3)N1—C5'1.370 (3)
C1—C71.504 (3)N1—H10.8600
C2—C31.387 (3)C2'—N31.310 (4)
C3—C41.384 (4)C2'—H2'0.9300
C3—H3A0.9300N3—C4'1.380 (3)
C4—C51.370 (4)N3—H30.8600
C4—H40.9300C4'—C5'1.344 (4)
C5—C61.375 (4)C4'—C411.480 (4)
C5—H50.9300C41—H41A0.9600
C6—H60.9300C41—H41B0.9600
C21—C261.397 (4)C41—H41C0.9600
C21—C221.402 (3)C5'—H5'0.9300
C21—C271.480 (3)
C2—S1—S2106.45 (8)C25—C24—C23120.9 (3)
C22—S2—S1105.29 (8)C25—C24—H24119.5
C27—O3—H3'109.5C23—C24—H24119.5
C6—C1—C2117.9 (2)C26—C25—C24119.5 (3)
C6—C1—C7119.2 (2)C26—C25—H25120.3
C2—C1—C7122.9 (2)C24—C25—H25120.3
C3—C2—C1119.5 (2)C25—C26—C21121.4 (2)
C3—C2—S1120.52 (18)C25—C26—H26119.3
C1—C2—S1119.96 (17)C21—C26—H26119.3
C4—C3—C2120.7 (2)O4—C27—O3123.3 (2)
C4—C3—H3A119.6O4—C27—C21123.6 (2)
C2—C3—H3A119.6O3—C27—C21113.1 (2)
C5—C4—C3120.4 (2)C2'—N1—C5'108.3 (2)
C5—C4—H4119.8C2'—N1—H1125.8
C3—C4—H4119.8C5'—N1—H1125.8
C4—C5—C6119.1 (2)N3—C2'—N1108.9 (2)
C4—C5—H5120.5N3—C2'—H2'125.6
C6—C5—H5120.5N1—C2'—H2'125.6
C5—C6—C1122.4 (2)C2'—N3—C4'109.3 (2)
C5—C6—H6118.8C2'—N3—H3125.4
C1—C6—H6118.8C4'—N3—H3125.4
O2—C7—O1123.6 (2)C5'—C4'—N3105.7 (2)
O2—C7—C1119.0 (2)C5'—C4'—C41132.1 (3)
O1—C7—C1117.5 (2)N3—C4'—C41122.2 (2)
C26—C21—C22118.9 (2)C4'—C41—H41A109.5
C26—C21—C27120.1 (2)C4'—C41—H41B109.5
C22—C21—C27120.9 (2)H41A—C41—H41B109.5
C23—C22—C21119.1 (2)C4'—C41—H41C109.5
C23—C22—S2121.29 (18)H41A—C41—H41C109.5
C21—C22—S2119.60 (18)H41B—C41—H41C109.5
C24—C23—C22120.1 (2)C4'—C5'—N1107.8 (2)
C24—C23—H23119.9C4'—C5'—H5'126.1
C22—C23—H23119.9N1—C5'—H5'126.1
C2—S1—S2—C2285.58 (11)C27—C21—C22—S21.8 (3)
C6—C1—C2—C32.7 (3)S1—S2—C22—C2320.0 (2)
C7—C1—C2—C3176.9 (2)S1—S2—C22—C21160.28 (16)
C6—C1—C2—S1177.66 (18)C21—C22—C23—C240.6 (3)
C7—C1—C2—S12.8 (3)S2—C22—C23—C24179.15 (19)
S2—S1—C2—C312.9 (2)C22—C23—C24—C250.4 (4)
S2—S1—C2—C1167.48 (16)C23—C24—C25—C260.5 (4)
C1—C2—C3—C41.2 (4)C24—C25—C26—C211.4 (4)
S1—C2—C3—C4179.1 (2)C22—C21—C26—C251.2 (4)
C2—C3—C4—C51.0 (4)C27—C21—C26—C25179.5 (2)
C3—C4—C5—C61.6 (4)C26—C21—C27—O4163.7 (2)
C4—C5—C6—C10.0 (4)C22—C21—C27—O418.1 (3)
C2—C1—C6—C52.1 (4)C26—C21—C27—O316.5 (3)
C7—C1—C6—C5177.5 (2)C22—C21—C27—O3161.6 (2)
C6—C1—C7—O2178.7 (2)C5'—N1—C2'—N31.4 (3)
C2—C1—C7—O21.7 (3)N1—C2'—N3—C4'1.9 (3)
C6—C1—C7—O11.7 (3)C2'—N3—C4'—C5'1.6 (3)
C2—C1—C7—O1177.9 (2)C2'—N3—C4'—C41177.2 (3)
C26—C21—C22—C230.3 (3)N3—C4'—C5'—N10.7 (3)
C27—C21—C22—C23178.5 (2)C41—C4'—C5'—N1177.9 (3)
C26—C21—C22—S2179.97 (17)C2'—N1—C5'—C4'0.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.861.942.764 (3)161
N1—H1···S10.862.803.408 (2)129
N3—H3···O1i0.861.902.720 (3)159
O3—H3···O1ii0.821.812.613 (3)168
C2—H2···O4iii0.932.573.209 (3)127
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y1, z; (iii) x, y+1, z.

Experimental details

(I)(II)
Crystal data
Chemical formula2C3H5N2+·C14H8O4S22C4H7N2+·C14H9O4S2
Mr442.50388.45
Crystal system, space groupMonoclinic, C2/cTriclinic, P1
Temperature (K)297300
a, b, c (Å)17.0142 (13), 5.9064 (4), 19.9254 (15)8.2486 (5), 10.1528 (6), 11.3724 (7)
α, β, γ (°)90, 94.228 (1), 9070.359 (1), 82.112 (2), 81.285 (1)
V3)1996.9 (3)882.81 (9)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.300.33
Crystal size (mm)0.30 × 0.30 × 0.040.20 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1997)
Multi-scan
(SADABS; Sheldrick, 1997)
Tmin, Tmax0.905, 0.9880.927, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
10805, 2283, 1721 9067, 3427, 2884
Rint0.0380.021
(sin θ/λ)max1)0.6500.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.129, 1.06 0.041, 0.136, 1.13
No. of reflections22833427
No. of parameters136236
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.260.34, 0.24

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.812.643 (2)162
N3—H3'···O2i0.861.862.710 (2)172
C2'—H2'···O1ii0.932.273.185 (3)167
Symmetry codes: (i) x1/2, y1/2, z; (ii) x+1/2, y1/2, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.861.942.764 (3)161
N1—H1···S10.862.803.408 (2)129
N3—H3···O1i0.861.902.720 (3)159
O3—H3'···O1ii0.821.812.613 (3)168
C2'—H2'···O4iii0.932.573.209 (3)127
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+1, y1, z; (iii) x, y+1, z.
 

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