Cocrystallization of imidazole or 4-methylimidazole with 2,2′-dithiodibenzoic acid from methanol solution yields the title 2:1 and 1:1 organic salts, 2C
3H
5N
2+·C
14H
10O
4S
22−, (I), and C
4H
7N
2+·C
14H
10O
4S
2−, (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
CCDC references: 749716; 749717
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.
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).
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).
(I) bis(imidazolium) 2,2'-dithiodibenzoate
top
Crystal data top
2C3H5N2+·C14H8O4S22− | F(000) = 920 |
Mr = 442.50 | Dx = 1.472 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2506 reflections |
a = 17.0142 (13) Å | θ = 2.4–25.4° |
b = 5.9064 (4) Å | µ = 0.30 mm−1 |
c = 19.9254 (15) Å | T = 297 K |
β = 94.228 (1)° | Plate, colourless |
V = 1996.9 (3) Å3 | 0.30 × 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 tube | 1721 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
0.3° wide ω exposures scans | θmax = 27.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −22→22 |
Tmin = 0.905, Tmax = 0.988 | k = −7→7 |
10805 measured reflections | l = −25→25 |
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) = 0.129 | H-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 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
2C3H5N2+·C14H8O4S22− | V = 1996.9 (3) Å3 |
Mr = 442.50 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 17.0142 (13) Å | µ = 0.30 mm−1 |
b = 5.9064 (4) Å | T = 297 K |
c = 19.9254 (15) Å | 0.30 × 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 = 0.988 | Rint = 0.038 |
10805 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.38 e Å−3 |
2283 reflections | Δρmin = −0.26 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.48149 (3) | 0.04094 (10) | 0.69993 (3) | 0.0397 (2) | |
O1 | 0.30395 (8) | 0.0444 (3) | 0.53687 (7) | 0.0412 (4) | |
O2 | 0.43265 (8) | 0.0302 (3) | 0.56336 (7) | 0.0417 (4) | |
C1 | 0.35552 (11) | 0.2582 (3) | 0.63087 (9) | 0.0325 (5) | |
C2 | 0.40456 (11) | 0.2497 (3) | 0.69097 (10) | 0.0338 (5) | |
C3 | 0.39232 (14) | 0.4048 (4) | 0.74170 (10) | 0.0457 (6) | |
H3 | 0.4237 | 0.3988 | 0.7819 | 0.055* | |
C4 | 0.33418 (15) | 0.5676 (4) | 0.73326 (12) | 0.0542 (7) | |
H4 | 0.3266 | 0.6693 | 0.7678 | 0.065* | |
C5 | 0.28745 (15) | 0.5803 (4) | 0.67411 (13) | 0.0527 (6) | |
H5 | 0.2490 | 0.6920 | 0.6681 | 0.063* | |
C6 | 0.29824 (13) | 0.4252 (4) | 0.62376 (11) | 0.0412 (5) | |
H6 | 0.2662 | 0.4330 | 0.5840 | 0.049* | |
C7 | 0.36484 (11) | 0.0979 (3) | 0.57310 (9) | 0.0308 (4) | |
N1 | 0.15372 (10) | 0.0371 (3) | 0.56232 (9) | 0.0392 (4) | |
H1 | 0.2020 | 0.0694 | 0.5562 | 0.047* | |
C2' | 0.11896 (12) | −0.1578 (4) | 0.54832 (10) | 0.0386 (5) | |
H2' | 0.1423 | −0.2833 | 0.5298 | 0.046* | |
N3 | 0.04561 (10) | −0.1459 (3) | 0.56494 (8) | 0.0395 (4) | |
H3' | 0.0114 | −0.2531 | 0.5609 | 0.047* | |
C4' | 0.03301 (13) | 0.0661 (4) | 0.58975 (11) | 0.0412 (5) | |
H4' | −0.0138 | 0.1207 | 0.6048 | 0.049* | |
C5' | 0.10054 (13) | 0.1795 (4) | 0.58818 (11) | 0.0423 (5) | |
H5' | 0.1097 | 0.3280 | 0.6021 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0390 (3) | 0.0432 (4) | 0.0352 (3) | 0.0051 (2) | −0.0082 (2) | −0.0061 (2) |
O1 | 0.0290 (7) | 0.0547 (10) | 0.0386 (8) | −0.0038 (7) | −0.0048 (6) | −0.0140 (7) |
O2 | 0.0274 (8) | 0.0514 (10) | 0.0459 (9) | −0.0008 (6) | 0.0004 (6) | −0.0161 (7) |
C1 | 0.0276 (10) | 0.0403 (12) | 0.0294 (9) | −0.0039 (8) | 0.0008 (7) | −0.0036 (8) |
C2 | 0.0323 (10) | 0.0370 (11) | 0.0314 (9) | −0.0011 (8) | −0.0012 (8) | −0.0007 (8) |
C3 | 0.0528 (13) | 0.0523 (15) | 0.0307 (10) | 0.0050 (11) | −0.0070 (9) | −0.0075 (10) |
C4 | 0.0646 (16) | 0.0530 (16) | 0.0444 (13) | 0.0156 (12) | −0.0001 (11) | −0.0180 (11) |
C5 | 0.0527 (14) | 0.0497 (15) | 0.0544 (14) | 0.0170 (12) | −0.0053 (11) | −0.0090 (12) |
C6 | 0.0380 (12) | 0.0481 (14) | 0.0362 (11) | 0.0040 (10) | −0.0061 (9) | −0.0054 (9) |
C7 | 0.0302 (10) | 0.0341 (11) | 0.0282 (9) | −0.0039 (8) | 0.0013 (7) | −0.0015 (8) |
N1 | 0.0326 (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) |
N3 | 0.0319 (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—C2 | 1.798 (2) | C5—H5 | 0.9300 |
S1—S1i | 2.0476 (10) | C6—H6 | 0.9300 |
O1—C7 | 1.259 (2) | N1—C2' | 1.315 (3) |
O2—C7 | 1.250 (2) | N1—C5' | 1.364 (3) |
C1—C6 | 1.387 (3) | N1—H1 | 0.8600 |
C1—C2 | 1.409 (3) | C2'—N3 | 1.316 (3) |
C1—C7 | 1.508 (3) | C2'—H2' | 0.9300 |
C2—C3 | 1.391 (3) | N3—C4' | 1.369 (3) |
C3—C4 | 1.381 (3) | N3—H3' | 0.8600 |
C3—H3 | 0.9300 | C4'—C5' | 1.332 (3) |
C4—C5 | 1.374 (3) | C4'—H4' | 0.9300 |
C4—H4 | 0.9300 | C5'—H5' | 0.9300 |
C5—C6 | 1.381 (3) | | |
| | | |
C2—S1—S1i | 105.44 (7) | O2—C7—O1 | 124.11 (18) |
C6—C1—C2 | 118.69 (18) | O2—C7—C1 | 118.02 (16) |
C6—C1—C7 | 118.77 (17) | O1—C7—C1 | 117.85 (17) |
C2—C1—C7 | 122.51 (18) | C2'—N1—C5' | 108.63 (18) |
C3—C2—C1 | 118.88 (19) | C2'—N1—H1 | 125.7 |
C3—C2—S1 | 121.77 (16) | C5'—N1—H1 | 125.7 |
C1—C2—S1 | 119.34 (15) | N1—C2'—N3 | 108.64 (19) |
C4—C3—C2 | 121.0 (2) | N1—C2'—H2' | 125.7 |
C4—C3—H3 | 119.5 | N3—C2'—H2' | 125.7 |
C2—C3—H3 | 119.5 | C2'—N3—C4' | 108.45 (19) |
C5—C4—C3 | 120.4 (2) | C2'—N3—H3' | 125.8 |
C5—C4—H4 | 119.8 | C4'—N3—H3' | 125.8 |
C3—C4—H4 | 119.8 | C5'—C4'—N3 | 107.03 (18) |
C4—C5—C6 | 119.2 (2) | C5'—C4'—H4' | 126.5 |
C4—C5—H5 | 120.4 | N3—C4'—H4' | 126.5 |
C6—C5—H5 | 120.4 | C4'—C5'—N1 | 107.2 (2) |
C5—C6—C1 | 121.8 (2) | C4'—C5'—H5' | 126.4 |
C5—C6—H6 | 119.1 | N1—C5'—H5' | 126.4 |
C1—C6—H6 | 119.1 | | |
| | | |
C6—C1—C2—C3 | 1.8 (3) | C2—C1—C6—C5 | −0.9 (3) |
C7—C1—C2—C3 | 179.61 (19) | C7—C1—C6—C5 | −178.8 (2) |
C6—C1—C2—S1 | −177.77 (15) | C6—C1—C7—O2 | 145.2 (2) |
C7—C1—C2—S1 | 0.0 (3) | C2—C1—C7—O2 | −32.6 (3) |
S1i—S1—C2—C3 | 13.6 (2) | C6—C1—C7—O1 | −33.3 (3) |
S1i—S1—C2—C1 | −166.81 (15) | C2—C1—C7—O1 | 148.9 (2) |
C1—C2—C3—C4 | −1.2 (3) | C5'—N1—C2'—N3 | −0.6 (2) |
S1—C2—C3—C4 | 178.38 (19) | N1—C2'—N3—C4' | 0.7 (2) |
C2—C3—C4—C5 | −0.4 (4) | C2'—N3—C4'—C5' | −0.6 (2) |
C3—C4—C5—C6 | 1.4 (4) | N3—C4'—C5'—N1 | 0.2 (2) |
C4—C5—C6—C1 | −0.7 (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···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.81 | 2.643 (2) | 162 |
N3—H3′···O2ii | 0.86 | 1.86 | 2.710 (2) | 172 |
C2′—H2′···O1iii | 0.93 | 2.27 | 3.185 (3) | 167 |
Symmetry codes: (ii) x−1/2, y−1/2, z; (iii) −x+1/2, −y−1/2, −z+1. |
(II) 4-methylimidazolium 2-[(2-carboxyphenyl)disulfanyl]benzoate
top
Crystal data top
C4H7N2+·C14H9O4S2− | Z = 2 |
Mr = 388.45 | F(000) = 404 |
Triclinic, P1 | Dx = 1.461 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2486 (5) Å | Cell parameters from 4099 reflections |
b = 10.1528 (6) Å | θ = 2.4–27.1° |
c = 11.3724 (7) Å | µ = 0.33 mm−1 |
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 tube | 2884 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
0.3° wide ω exposures scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −10→10 |
Tmin = 0.927, Tmax = 0.968 | k = −12→12 |
9067 measured reflections | l = −14→13 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-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 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C4H7N2+·C14H9O4S2− | γ = 81.285 (1)° |
Mr = 388.45 | V = 882.81 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.2486 (5) Å | Mo Kα radiation |
b = 10.1528 (6) Å | µ = 0.33 mm−1 |
c = 11.3724 (7) Å | T = 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 = 0.968 | Rint = 0.021 |
9067 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.34 e Å−3 |
3427 reflections | Δρmin = −0.24 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
S1 | 0.40313 (8) | 0.49732 (6) | 0.70899 (6) | 0.0541 (2) | |
S2 | 0.49337 (8) | 0.29164 (6) | 0.73126 (6) | 0.0546 (2) | |
O1 | 0.0402 (2) | 0.87131 (17) | 0.66759 (18) | 0.0576 (5) | |
O2 | 0.2896 (2) | 0.76894 (17) | 0.63337 (17) | 0.0574 (5) | |
O3 | 0.8771 (2) | −0.0548 (2) | 0.8536 (2) | 0.0743 (6) | |
H3' | 0.9161 | −0.0833 | 0.7951 | 0.112* | |
O4 | 0.6796 (2) | 0.0501 (2) | 0.72731 (19) | 0.0661 (5) | |
C1 | 0.0871 (3) | 0.6228 (2) | 0.7525 (2) | 0.0427 (5) | |
C2 | 0.1921 (3) | 0.4962 (2) | 0.7750 (2) | 0.0454 (5) | |
C3 | 0.1321 (3) | 0.3711 (3) | 0.8489 (3) | 0.0567 (6) | |
H3A | 0.2021 | 0.2873 | 0.8652 | 0.068* | |
C4 | −0.0307 (3) | 0.3694 (3) | 0.8985 (3) | 0.0637 (7) | |
H4 | −0.0688 | 0.2849 | 0.9489 | 0.076* | |
C5 | −0.1360 (3) | 0.4915 (3) | 0.8738 (3) | 0.0634 (7) | |
H5 | −0.2461 | 0.4902 | 0.9054 | 0.076* | |
C6 | −0.0767 (3) | 0.6160 (3) | 0.8016 (3) | 0.0541 (6) | |
H6 | −0.1485 | 0.6987 | 0.7851 | 0.065* | |
C7 | 0.1444 (3) | 0.7638 (2) | 0.6788 (2) | 0.0441 (5) | |
C21 | 0.6739 (3) | 0.1013 (2) | 0.9165 (2) | 0.0455 (5) | |
C22 | 0.5612 (3) | 0.2231 (2) | 0.8853 (2) | 0.0441 (5) | |
C23 | 0.5036 (3) | 0.2881 (3) | 0.9757 (2) | 0.0559 (6) | |
H23 | 0.4296 | 0.3694 | 0.9560 | 0.067* | |
C24 | 0.5563 (4) | 0.2320 (3) | 1.0946 (3) | 0.0631 (7) | |
H24 | 0.5166 | 0.2757 | 1.1544 | 0.076* | |
C25 | 0.6663 (4) | 0.1126 (3) | 1.1256 (3) | 0.0623 (7) | |
H25 | 0.7003 | 0.0752 | 1.2061 | 0.075* | |
C26 | 0.7256 (3) | 0.0491 (3) | 1.0373 (3) | 0.0570 (6) | |
H26 | 0.8019 | −0.0305 | 1.0580 | 0.068* | |
C27 | 0.7414 (3) | 0.0309 (2) | 0.8226 (2) | 0.0503 (6) | |
N1 | 0.6211 (3) | 0.7748 (2) | 0.5533 (2) | 0.0611 (6) | |
H1 | 0.5259 | 0.7570 | 0.5924 | 0.073* | |
C2' | 0.6829 (4) | 0.8952 (3) | 0.5230 (3) | 0.0628 (7) | |
H2' | 0.6317 | 0.9747 | 0.5419 | 0.075* | |
N3 | 0.8284 (3) | 0.8848 (2) | 0.4619 (2) | 0.0566 (5) | |
H3 | 0.8906 | 0.9514 | 0.4309 | 0.068* | |
C4' | 0.8661 (3) | 0.7503 (3) | 0.4550 (2) | 0.0543 (6) | |
C41 | 1.0260 (4) | 0.7038 (4) | 0.3964 (3) | 0.0820 (9) | |
H41A | 1.0287 | 0.6071 | 0.4018 | 0.123* | |
H41B | 1.1137 | 0.7133 | 0.4394 | 0.123* | |
H41C | 1.0394 | 0.7609 | 0.3099 | 0.123* | |
C5' | 0.7343 (3) | 0.6828 (3) | 0.5120 (3) | 0.0575 (6) | |
H5' | 0.7221 | 0.5900 | 0.5216 | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0462 (4) | 0.0369 (3) | 0.0689 (4) | 0.0037 (2) | 0.0053 (3) | −0.0112 (3) |
S2 | 0.0596 (4) | 0.0433 (3) | 0.0574 (4) | 0.0121 (3) | −0.0081 (3) | −0.0183 (3) |
O1 | 0.0471 (10) | 0.0378 (9) | 0.0784 (12) | 0.0073 (7) | −0.0034 (8) | −0.0126 (8) |
O2 | 0.0472 (10) | 0.0420 (9) | 0.0732 (11) | −0.0003 (7) | 0.0110 (8) | −0.0144 (8) |
O3 | 0.0648 (12) | 0.0660 (12) | 0.0866 (14) | 0.0285 (10) | −0.0144 (10) | −0.0299 (11) |
O4 | 0.0696 (12) | 0.0586 (11) | 0.0732 (13) | 0.0134 (9) | −0.0109 (10) | −0.0326 (10) |
C1 | 0.0419 (12) | 0.0390 (11) | 0.0480 (12) | −0.0022 (9) | −0.0051 (9) | −0.0159 (9) |
C2 | 0.0434 (12) | 0.0400 (12) | 0.0523 (13) | −0.0021 (9) | −0.0037 (10) | −0.0157 (10) |
C3 | 0.0542 (15) | 0.0396 (12) | 0.0714 (16) | −0.0036 (11) | −0.0053 (12) | −0.0127 (11) |
C4 | 0.0629 (17) | 0.0521 (15) | 0.0731 (17) | −0.0201 (13) | 0.0035 (13) | −0.0140 (13) |
C5 | 0.0459 (14) | 0.0630 (17) | 0.0828 (19) | −0.0134 (12) | 0.0071 (13) | −0.0276 (14) |
C6 | 0.0418 (13) | 0.0487 (13) | 0.0723 (16) | −0.0002 (10) | −0.0016 (11) | −0.0237 (12) |
C7 | 0.0437 (12) | 0.0393 (11) | 0.0482 (12) | 0.0012 (9) | −0.0048 (10) | −0.0150 (9) |
C21 | 0.0389 (12) | 0.0362 (11) | 0.0587 (14) | −0.0059 (9) | −0.0023 (10) | −0.0120 (10) |
C22 | 0.0373 (11) | 0.0381 (11) | 0.0556 (13) | −0.0044 (9) | 0.0002 (9) | −0.0154 (10) |
C23 | 0.0520 (14) | 0.0527 (14) | 0.0654 (16) | 0.0007 (11) | −0.0030 (12) | −0.0258 (12) |
C24 | 0.0642 (17) | 0.0687 (17) | 0.0623 (16) | −0.0085 (14) | 0.0012 (13) | −0.0310 (14) |
C25 | 0.0645 (17) | 0.0646 (17) | 0.0565 (15) | −0.0131 (14) | −0.0096 (12) | −0.0138 (13) |
C26 | 0.0544 (15) | 0.0405 (12) | 0.0692 (16) | −0.0064 (11) | −0.0103 (12) | −0.0066 (11) |
C27 | 0.0471 (13) | 0.0347 (11) | 0.0646 (16) | −0.0006 (10) | −0.0013 (11) | −0.0135 (10) |
N1 | 0.0496 (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) |
N3 | 0.0517 (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) |
C41 | 0.0672 (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—C2 | 1.798 (2) | C22—C23 | 1.395 (3) |
S1—S2 | 2.0504 (8) | C23—C24 | 1.381 (4) |
S2—C22 | 1.789 (2) | C23—H23 | 0.9300 |
O1—C7 | 1.264 (3) | C24—C25 | 1.373 (4) |
O2—C7 | 1.239 (3) | C24—H24 | 0.9300 |
O3—C27 | 1.319 (3) | C25—C26 | 1.367 (4) |
O3—H3' | 0.8200 | C25—H25 | 0.9300 |
O4—C27 | 1.205 (3) | C26—H26 | 0.9300 |
C1—C6 | 1.392 (3) | N1—C2' | 1.315 (4) |
C1—C2 | 1.404 (3) | N1—C5' | 1.370 (3) |
C1—C7 | 1.504 (3) | N1—H1 | 0.8600 |
C2—C3 | 1.387 (3) | C2'—N3 | 1.310 (4) |
C3—C4 | 1.384 (4) | C2'—H2' | 0.9300 |
C3—H3A | 0.9300 | N3—C4' | 1.380 (3) |
C4—C5 | 1.370 (4) | N3—H3 | 0.8600 |
C4—H4 | 0.9300 | C4'—C5' | 1.344 (4) |
C5—C6 | 1.375 (4) | C4'—C41 | 1.480 (4) |
C5—H5 | 0.9300 | C41—H41A | 0.9600 |
C6—H6 | 0.9300 | C41—H41B | 0.9600 |
C21—C26 | 1.397 (4) | C41—H41C | 0.9600 |
C21—C22 | 1.402 (3) | C5'—H5' | 0.9300 |
C21—C27 | 1.480 (3) | | |
| | | |
C2—S1—S2 | 106.45 (8) | C25—C24—C23 | 120.9 (3) |
C22—S2—S1 | 105.29 (8) | C25—C24—H24 | 119.5 |
C27—O3—H3' | 109.5 | C23—C24—H24 | 119.5 |
C6—C1—C2 | 117.9 (2) | C26—C25—C24 | 119.5 (3) |
C6—C1—C7 | 119.2 (2) | C26—C25—H25 | 120.3 |
C2—C1—C7 | 122.9 (2) | C24—C25—H25 | 120.3 |
C3—C2—C1 | 119.5 (2) | C25—C26—C21 | 121.4 (2) |
C3—C2—S1 | 120.52 (18) | C25—C26—H26 | 119.3 |
C1—C2—S1 | 119.96 (17) | C21—C26—H26 | 119.3 |
C4—C3—C2 | 120.7 (2) | O4—C27—O3 | 123.3 (2) |
C4—C3—H3A | 119.6 | O4—C27—C21 | 123.6 (2) |
C2—C3—H3A | 119.6 | O3—C27—C21 | 113.1 (2) |
C5—C4—C3 | 120.4 (2) | C2'—N1—C5' | 108.3 (2) |
C5—C4—H4 | 119.8 | C2'—N1—H1 | 125.8 |
C3—C4—H4 | 119.8 | C5'—N1—H1 | 125.8 |
C4—C5—C6 | 119.1 (2) | N3—C2'—N1 | 108.9 (2) |
C4—C5—H5 | 120.5 | N3—C2'—H2' | 125.6 |
C6—C5—H5 | 120.5 | N1—C2'—H2' | 125.6 |
C5—C6—C1 | 122.4 (2) | C2'—N3—C4' | 109.3 (2) |
C5—C6—H6 | 118.8 | C2'—N3—H3 | 125.4 |
C1—C6—H6 | 118.8 | C4'—N3—H3 | 125.4 |
O2—C7—O1 | 123.6 (2) | C5'—C4'—N3 | 105.7 (2) |
O2—C7—C1 | 119.0 (2) | C5'—C4'—C41 | 132.1 (3) |
O1—C7—C1 | 117.5 (2) | N3—C4'—C41 | 122.2 (2) |
C26—C21—C22 | 118.9 (2) | C4'—C41—H41A | 109.5 |
C26—C21—C27 | 120.1 (2) | C4'—C41—H41B | 109.5 |
C22—C21—C27 | 120.9 (2) | H41A—C41—H41B | 109.5 |
C23—C22—C21 | 119.1 (2) | C4'—C41—H41C | 109.5 |
C23—C22—S2 | 121.29 (18) | H41A—C41—H41C | 109.5 |
C21—C22—S2 | 119.60 (18) | H41B—C41—H41C | 109.5 |
C24—C23—C22 | 120.1 (2) | C4'—C5'—N1 | 107.8 (2) |
C24—C23—H23 | 119.9 | C4'—C5'—H5' | 126.1 |
C22—C23—H23 | 119.9 | N1—C5'—H5' | 126.1 |
| | | |
C2—S1—S2—C22 | −85.58 (11) | C27—C21—C22—S2 | 1.8 (3) |
C6—C1—C2—C3 | −2.7 (3) | S1—S2—C22—C23 | 20.0 (2) |
C7—C1—C2—C3 | 176.9 (2) | S1—S2—C22—C21 | −160.28 (16) |
C6—C1—C2—S1 | 177.66 (18) | C21—C22—C23—C24 | −0.6 (3) |
C7—C1—C2—S1 | −2.8 (3) | S2—C22—C23—C24 | 179.15 (19) |
S2—S1—C2—C3 | 12.9 (2) | C22—C23—C24—C25 | 0.4 (4) |
S2—S1—C2—C1 | −167.48 (16) | C23—C24—C25—C26 | 0.5 (4) |
C1—C2—C3—C4 | 1.2 (4) | C24—C25—C26—C21 | −1.4 (4) |
S1—C2—C3—C4 | −179.1 (2) | C22—C21—C26—C25 | 1.2 (4) |
C2—C3—C4—C5 | 1.0 (4) | C27—C21—C26—C25 | 179.5 (2) |
C3—C4—C5—C6 | −1.6 (4) | C26—C21—C27—O4 | 163.7 (2) |
C4—C5—C6—C1 | 0.0 (4) | C22—C21—C27—O4 | −18.1 (3) |
C2—C1—C6—C5 | 2.1 (4) | C26—C21—C27—O3 | −16.5 (3) |
C7—C1—C6—C5 | −177.5 (2) | C22—C21—C27—O3 | 161.6 (2) |
C6—C1—C7—O2 | −178.7 (2) | C5'—N1—C2'—N3 | 1.4 (3) |
C2—C1—C7—O2 | 1.7 (3) | N1—C2'—N3—C4' | −1.9 (3) |
C6—C1—C7—O1 | 1.7 (3) | C2'—N3—C4'—C5' | 1.6 (3) |
C2—C1—C7—O1 | −177.9 (2) | C2'—N3—C4'—C41 | −177.2 (3) |
C26—C21—C22—C23 | −0.3 (3) | N3—C4'—C5'—N1 | −0.7 (3) |
C27—C21—C22—C23 | −178.5 (2) | C41—C4'—C5'—N1 | 177.9 (3) |
C26—C21—C22—S2 | −179.97 (17) | C2'—N1—C5'—C4' | −0.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.94 | 2.764 (3) | 161 |
N1—H1···S1 | 0.86 | 2.80 | 3.408 (2) | 129 |
N3—H3···O1i | 0.86 | 1.90 | 2.720 (3) | 159 |
O3—H3′···O1ii | 0.82 | 1.81 | 2.613 (3) | 168 |
C2′—H2′···O4iii | 0.93 | 2.57 | 3.209 (3) | 127 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y−1, z; (iii) x, y+1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | 2C3H5N2+·C14H8O4S22− | C4H7N2+·C14H9O4S2− |
Mr | 442.50 | 388.45 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 297 | 300 |
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), 90 | 70.359 (1), 82.112 (2), 81.285 (1) |
V (Å3) | 1996.9 (3) | 882.81 (9) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.30 | 0.33 |
Crystal size (mm) | 0.30 × 0.30 × 0.04 | 0.20 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.905, 0.988 | 0.927, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10805, 2283, 1721 | 9067, 3427, 2884 |
Rint | 0.038 | 0.021 |
(sin θ/λ)max (Å−1) | 0.650 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.129, 1.06 | 0.041, 0.136, 1.13 |
No. of reflections | 2283 | 3427 |
No. of parameters | 136 | 236 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.26 | 0.34, −0.24 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 1.81 | 2.643 (2) | 162 |
N3—H3'···O2i | 0.86 | 1.86 | 2.710 (2) | 172 |
C2'—H2'···O1ii | 0.93 | 2.27 | 3.185 (3) | 167 |
Symmetry codes: (i) x−1/2, y−1/2, z; (ii) −x+1/2, −y−1/2, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 1.94 | 2.764 (3) | 161 |
N1—H1···S1 | 0.86 | 2.80 | 3.408 (2) | 129 |
N3—H3···O1i | 0.86 | 1.90 | 2.720 (3) | 159 |
O3—H3'···O1ii | 0.82 | 1.81 | 2.613 (3) | 168 |
C2'—H2'···O4iii | 0.93 | 2.57 | 3.209 (3) | 127 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x+1, y−1, z; (iii) x, y+1, z. |
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 π–π 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 π–π 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)].