Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010903340X/fg3122sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010903340X/fg3122Isup2.hkl |
CCDC reference: 749737
To an acetone–water solution (1:1, 2.0 ml) of H2L (15.3 mg, 0.05 mmol) was added dropwise an ethanol–water solution (1:1, 3.0 ml) of bpp (30.8 mg, 0.1 mmol) with constant stirring. The mixture was further stirred for 1 h at room temperature and then filtered. The resulting yellow filtrate was allowed to evaporate at room temperature. Pale-yellow block-shaped crystals of (I) suitable for X-ray diffraction were obtained within one week in 62% yield. Elemental analysis calculated for C27H24N2O4S2: C 64.27, H 4.79, N 5.55%; found: C 64.27, H 4.55, N 5.63%.
H atoms were located in difference maps, but were subsequently placed in calculated positions and treated as riding, with C—H = 0.93 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C,O).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C14H10O4S2·C13H14N2 | F(000) = 1056 |
Mr = 504.60 | Dx = 1.306 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.9613 (13) Å | Cell parameters from 5139 reflections |
b = 9.3021 (5) Å | θ = 2.7–27.4° |
c = 13.3790 (8) Å | µ = 0.24 mm−1 |
β = 100.399 (1)° | T = 296 K |
V = 2565.8 (3) Å3 | Block, pale-yellow |
Z = 4 | 0.24 × 0.23 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 4508 independent reflections |
Radiation source: fine-focus sealed tube | 3399 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −24→24 |
Tmin = 0.944, Tmax = 0.967 | k = −11→6 |
12563 measured reflections | l = −15→15 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0608P)2 + 0.4257P] where P = (Fo2 + 2Fc2)/3 |
4508 reflections | (Δ/σ)max < 0.001 |
318 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C14H10O4S2·C13H14N2 | V = 2565.8 (3) Å3 |
Mr = 504.60 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.9613 (13) Å | µ = 0.24 mm−1 |
b = 9.3021 (5) Å | T = 296 K |
c = 13.3790 (8) Å | 0.24 × 0.23 × 0.14 mm |
β = 100.399 (1)° |
Bruker SMART CCD area-detector diffractometer | 4508 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 3399 reflections with I > 2σ(I) |
Tmin = 0.944, Tmax = 0.967 | Rint = 0.022 |
12563 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.23 e Å−3 |
4508 reflections | Δρmin = −0.21 e Å−3 |
318 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.79794 (3) | 0.50222 (6) | 0.43112 (4) | 0.05352 (18) | |
S2 | 0.69963 (3) | 0.52406 (7) | 0.41760 (5) | 0.05959 (19) | |
O1 | 0.97759 (7) | 0.25743 (17) | 0.48239 (12) | 0.0593 (4) | |
H1 | 1.0009 | 0.2826 | 0.4425 | 0.089* | |
O2 | 0.92221 (7) | 0.45284 (17) | 0.42348 (12) | 0.0597 (4) | |
O3 | 0.57347 (9) | 0.5632 (2) | 0.37477 (19) | 0.1046 (7) | |
O4 | 0.52542 (9) | 0.7740 (2) | 0.3773 (2) | 0.1032 (7) | |
H4' | 0.4955 | 0.7319 | 0.3411 | 0.155* | |
N1 | 0.04598 (8) | 0.32215 (19) | 0.34271 (12) | 0.0481 (4) | |
N2 | 0.42580 (10) | 0.6473 (3) | 0.26945 (19) | 0.0853 (7) | |
C1 | 0.12821 (10) | 0.4185 (2) | 0.07801 (15) | 0.0506 (5) | |
H1A | 0.0963 | 0.4699 | 0.0295 | 0.061* | |
H1B | 0.1380 | 0.3292 | 0.0465 | 0.061* | |
C2 | 0.19002 (10) | 0.5090 (2) | 0.10170 (15) | 0.0483 (5) | |
H2A | 0.2047 | 0.5316 | 0.0387 | 0.058* | |
H2B | 0.1804 | 0.5988 | 0.1327 | 0.058* | |
C3 | 0.24366 (10) | 0.4326 (2) | 0.17221 (16) | 0.0527 (5) | |
H3A | 0.2280 | 0.4102 | 0.2343 | 0.063* | |
H3B | 0.2517 | 0.3419 | 0.1409 | 0.063* | |
C4 | 0.03926 (10) | 0.4510 (2) | 0.29882 (16) | 0.0491 (5) | |
H4 | 0.0158 | 0.5208 | 0.3264 | 0.059* | |
C5 | 0.06527 (10) | 0.4862 (2) | 0.21468 (16) | 0.0485 (5) | |
H5 | 0.0598 | 0.5783 | 0.1875 | 0.058* | |
C6 | 0.09958 (9) | 0.3845 (2) | 0.17048 (14) | 0.0426 (5) | |
C7 | 0.10602 (10) | 0.2502 (2) | 0.21587 (16) | 0.0513 (5) | |
H7 | 0.1282 | 0.1776 | 0.1889 | 0.062* | |
C8 | 0.07943 (10) | 0.2245 (2) | 0.30104 (17) | 0.0548 (5) | |
H8 | 0.0852 | 0.1341 | 0.3310 | 0.066* | |
C9 | 0.41408 (13) | 0.5147 (3) | 0.2988 (3) | 0.0933 (10) | |
H9 | 0.4468 | 0.4670 | 0.3427 | 0.112* | |
C10 | 0.35668 (12) | 0.4449 (3) | 0.2680 (2) | 0.0745 (7) | |
H10 | 0.3508 | 0.3532 | 0.2925 | 0.089* | |
C11 | 0.30750 (10) | 0.5092 (2) | 0.20091 (16) | 0.0503 (5) | |
C12 | 0.32103 (11) | 0.6430 (3) | 0.16628 (19) | 0.0634 (6) | |
H12 | 0.2903 | 0.6898 | 0.1185 | 0.076* | |
C13 | 0.37976 (12) | 0.7081 (3) | 0.2018 (2) | 0.0790 (8) | |
H13 | 0.3874 | 0.7987 | 0.1771 | 0.095* | |
C14 | 0.88198 (9) | 0.3087 (2) | 0.54383 (14) | 0.0416 (4) | |
C15 | 0.82086 (9) | 0.3749 (2) | 0.53162 (14) | 0.0420 (4) | |
C16 | 0.77903 (11) | 0.3373 (2) | 0.59685 (16) | 0.0516 (5) | |
H16 | 0.7383 | 0.3801 | 0.5896 | 0.062* | |
C17 | 0.79756 (11) | 0.2367 (2) | 0.67258 (16) | 0.0558 (6) | |
H17 | 0.7690 | 0.2121 | 0.7155 | 0.067* | |
C18 | 0.85734 (11) | 0.1725 (2) | 0.68548 (16) | 0.0539 (5) | |
H18 | 0.8696 | 0.1059 | 0.7372 | 0.065* | |
C19 | 0.89902 (10) | 0.2081 (2) | 0.62092 (14) | 0.0471 (5) | |
H19 | 0.9394 | 0.1640 | 0.6290 | 0.057* | |
C20 | 0.92901 (9) | 0.3468 (2) | 0.47711 (14) | 0.0436 (5) | |
C21 | 0.62873 (10) | 0.7470 (2) | 0.47683 (18) | 0.0570 (6) | |
C22 | 0.68896 (10) | 0.6785 (2) | 0.49235 (16) | 0.0492 (5) | |
C23 | 0.73932 (10) | 0.7353 (2) | 0.56369 (16) | 0.0547 (6) | |
H23 | 0.7797 | 0.6908 | 0.5748 | 0.066* | |
C24 | 0.72980 (13) | 0.8566 (3) | 0.61777 (19) | 0.0680 (7) | |
H24 | 0.7637 | 0.8927 | 0.6656 | 0.082* | |
C25 | 0.67106 (14) | 0.9249 (3) | 0.6021 (2) | 0.0822 (8) | |
H25 | 0.6651 | 1.0074 | 0.6386 | 0.099* | |
C26 | 0.62084 (13) | 0.8701 (3) | 0.5317 (2) | 0.0772 (8) | |
H26 | 0.5809 | 0.9165 | 0.5208 | 0.093* | |
C27 | 0.57309 (11) | 0.6861 (3) | 0.4040 (2) | 0.0703 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0477 (3) | 0.0638 (4) | 0.0493 (3) | 0.0061 (2) | 0.0092 (2) | 0.0104 (3) |
S2 | 0.0445 (3) | 0.0669 (4) | 0.0624 (4) | 0.0006 (3) | −0.0039 (3) | −0.0068 (3) |
O1 | 0.0488 (9) | 0.0664 (10) | 0.0666 (10) | 0.0105 (7) | 0.0209 (7) | 0.0134 (8) |
O2 | 0.0561 (9) | 0.0667 (10) | 0.0605 (9) | 0.0086 (7) | 0.0220 (7) | 0.0180 (8) |
O3 | 0.0548 (11) | 0.0892 (15) | 0.151 (2) | 0.0041 (10) | −0.0310 (12) | −0.0230 (14) |
O4 | 0.0528 (11) | 0.0819 (14) | 0.158 (2) | 0.0061 (9) | −0.0258 (12) | 0.0129 (13) |
N1 | 0.0417 (9) | 0.0539 (11) | 0.0491 (10) | −0.0026 (8) | 0.0090 (7) | −0.0023 (8) |
N2 | 0.0461 (12) | 0.0859 (17) | 0.1156 (19) | −0.0028 (11) | −0.0076 (12) | 0.0264 (14) |
C1 | 0.0512 (12) | 0.0580 (13) | 0.0417 (11) | −0.0022 (10) | 0.0062 (9) | −0.0024 (10) |
C2 | 0.0448 (11) | 0.0578 (13) | 0.0428 (11) | 0.0000 (9) | 0.0091 (9) | 0.0038 (10) |
C3 | 0.0521 (13) | 0.0531 (13) | 0.0524 (12) | 0.0008 (10) | 0.0080 (10) | 0.0008 (10) |
C4 | 0.0436 (11) | 0.0511 (13) | 0.0534 (12) | −0.0025 (9) | 0.0104 (9) | −0.0127 (10) |
C5 | 0.0447 (11) | 0.0451 (12) | 0.0553 (12) | 0.0003 (9) | 0.0078 (10) | −0.0001 (10) |
C6 | 0.0353 (10) | 0.0499 (12) | 0.0405 (10) | −0.0048 (8) | 0.0011 (8) | −0.0052 (9) |
C7 | 0.0498 (12) | 0.0484 (13) | 0.0584 (13) | 0.0031 (9) | 0.0165 (10) | −0.0044 (10) |
C8 | 0.0529 (13) | 0.0488 (13) | 0.0646 (14) | 0.0019 (10) | 0.0156 (11) | 0.0074 (11) |
C9 | 0.0456 (15) | 0.105 (2) | 0.119 (3) | −0.0019 (14) | −0.0118 (15) | 0.0431 (19) |
C10 | 0.0514 (14) | 0.0774 (18) | 0.0902 (19) | −0.0014 (12) | 0.0004 (13) | 0.0281 (15) |
C11 | 0.0408 (11) | 0.0574 (13) | 0.0539 (12) | 0.0065 (9) | 0.0115 (9) | 0.0028 (10) |
C12 | 0.0430 (13) | 0.0647 (15) | 0.0783 (16) | 0.0011 (10) | −0.0006 (11) | 0.0150 (12) |
C13 | 0.0490 (14) | 0.0683 (17) | 0.114 (2) | −0.0002 (12) | 0.0007 (14) | 0.0251 (16) |
C14 | 0.0446 (11) | 0.0433 (11) | 0.0356 (10) | −0.0057 (9) | 0.0039 (8) | −0.0056 (9) |
C15 | 0.0456 (11) | 0.0424 (11) | 0.0371 (10) | −0.0049 (9) | 0.0051 (8) | −0.0038 (8) |
C16 | 0.0498 (12) | 0.0555 (13) | 0.0518 (12) | −0.0011 (10) | 0.0155 (10) | −0.0035 (10) |
C17 | 0.0673 (15) | 0.0551 (14) | 0.0498 (13) | −0.0112 (11) | 0.0234 (11) | −0.0017 (11) |
C18 | 0.0727 (16) | 0.0477 (12) | 0.0422 (11) | −0.0015 (11) | 0.0127 (10) | 0.0026 (10) |
C19 | 0.0523 (12) | 0.0471 (12) | 0.0403 (11) | 0.0016 (9) | 0.0036 (9) | −0.0018 (9) |
C20 | 0.0408 (11) | 0.0515 (13) | 0.0373 (10) | −0.0033 (9) | 0.0037 (8) | −0.0037 (9) |
C21 | 0.0432 (12) | 0.0558 (14) | 0.0701 (14) | −0.0009 (10) | 0.0048 (10) | 0.0088 (12) |
C22 | 0.0429 (11) | 0.0502 (12) | 0.0532 (12) | −0.0049 (9) | 0.0051 (9) | 0.0084 (10) |
C23 | 0.0449 (12) | 0.0628 (15) | 0.0544 (13) | −0.0038 (10) | 0.0037 (10) | 0.0023 (11) |
C24 | 0.0678 (16) | 0.0638 (16) | 0.0688 (16) | −0.0091 (13) | 0.0025 (13) | −0.0053 (13) |
C25 | 0.082 (2) | 0.0646 (17) | 0.096 (2) | 0.0035 (15) | 0.0065 (16) | −0.0124 (15) |
C26 | 0.0615 (16) | 0.0653 (17) | 0.103 (2) | 0.0126 (13) | 0.0105 (15) | 0.0037 (16) |
C27 | 0.0412 (13) | 0.0676 (17) | 0.0968 (19) | 0.0018 (12) | −0.0022 (12) | 0.0140 (15) |
S1—C15 | 1.791 (2) | C9—C10 | 1.364 (4) |
S1—S2 | 2.0459 (8) | C9—H9 | 0.9300 |
S2—C22 | 1.788 (2) | C10—C11 | 1.375 (3) |
O1—C20 | 1.307 (2) | C10—H10 | 0.9300 |
O1—H1 | 0.8200 | C11—C12 | 1.375 (3) |
O2—C20 | 1.213 (2) | C12—C13 | 1.377 (3) |
O3—C27 | 1.209 (3) | C12—H12 | 0.9300 |
O4—C27 | 1.290 (3) | C13—H13 | 0.9300 |
O4—H4' | 0.8200 | C14—C19 | 1.390 (3) |
N1—C8 | 1.330 (3) | C14—C15 | 1.404 (3) |
N1—C4 | 1.331 (3) | C14—C20 | 1.487 (3) |
N2—C13 | 1.325 (3) | C15—C16 | 1.389 (3) |
N2—C9 | 1.331 (3) | C16—C17 | 1.383 (3) |
C1—C6 | 1.503 (3) | C16—H16 | 0.9300 |
C1—C2 | 1.530 (3) | C17—C18 | 1.370 (3) |
C1—H1A | 0.9700 | C17—H17 | 0.9300 |
C1—H1B | 0.9700 | C18—C19 | 1.375 (3) |
C2—C3 | 1.509 (3) | C18—H18 | 0.9300 |
C2—H2A | 0.9700 | C19—H19 | 0.9300 |
C2—H2B | 0.9700 | C21—C26 | 1.386 (3) |
C3—C11 | 1.503 (3) | C21—C22 | 1.396 (3) |
C3—H3A | 0.9700 | C21—C27 | 1.490 (3) |
C3—H3B | 0.9700 | C22—C23 | 1.393 (3) |
C4—C5 | 1.376 (3) | C23—C24 | 1.374 (3) |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C5—C6 | 1.383 (3) | C24—C25 | 1.367 (4) |
C5—H5 | 0.9300 | C24—H24 | 0.9300 |
C6—C7 | 1.385 (3) | C25—C26 | 1.378 (4) |
C7—C8 | 1.377 (3) | C25—H25 | 0.9300 |
C7—H7 | 0.9300 | C26—H26 | 0.9300 |
C8—H8 | 0.9300 | ||
C15—S1—S2 | 105.16 (7) | C11—C12—C13 | 120.5 (2) |
C22—S2—S1 | 104.84 (7) | C11—C12—H12 | 119.7 |
C20—O1—H1 | 109.5 | C13—C12—H12 | 119.7 |
C27—O4—H4' | 109.5 | N2—C13—C12 | 122.9 (2) |
C8—N1—C4 | 116.86 (18) | N2—C13—H13 | 118.5 |
C13—N2—C9 | 116.5 (2) | C12—C13—H13 | 118.5 |
C6—C1—C2 | 113.23 (16) | C19—C14—C15 | 119.23 (18) |
C6—C1—H1A | 108.9 | C19—C14—C20 | 119.76 (18) |
C2—C1—H1A | 108.9 | C15—C14—C20 | 121.00 (17) |
C6—C1—H1B | 108.9 | C16—C15—C14 | 118.86 (18) |
C2—C1—H1B | 108.9 | C16—C15—S1 | 121.59 (16) |
H1A—C1—H1B | 107.7 | C14—C15—S1 | 119.54 (14) |
C3—C2—C1 | 112.21 (18) | C17—C16—C15 | 120.3 (2) |
C3—C2—H2A | 109.2 | C17—C16—H16 | 119.8 |
C1—C2—H2A | 109.2 | C15—C16—H16 | 119.8 |
C3—C2—H2B | 109.2 | C18—C17—C16 | 121.1 (2) |
C1—C2—H2B | 109.2 | C18—C17—H17 | 119.4 |
H2A—C2—H2B | 107.9 | C16—C17—H17 | 119.4 |
C11—C3—C2 | 117.71 (18) | C17—C18—C19 | 119.1 (2) |
C11—C3—H3A | 107.9 | C17—C18—H18 | 120.5 |
C2—C3—H3A | 107.9 | C19—C18—H18 | 120.5 |
C11—C3—H3B | 107.9 | C18—C19—C14 | 121.4 (2) |
C2—C3—H3B | 107.9 | C18—C19—H19 | 119.3 |
H3A—C3—H3B | 107.2 | C14—C19—H19 | 119.3 |
N1—C4—C5 | 123.31 (19) | O2—C20—O1 | 123.83 (18) |
N1—C4—H4 | 118.3 | O2—C20—C14 | 121.95 (18) |
C5—C4—H4 | 118.3 | O1—C20—C14 | 114.23 (18) |
C4—C5—C6 | 120.0 (2) | C26—C21—C22 | 119.3 (2) |
C4—C5—H5 | 120.0 | C26—C21—C27 | 120.4 (2) |
C6—C5—H5 | 120.0 | C22—C21—C27 | 120.3 (2) |
C5—C6—C7 | 116.49 (18) | C23—C22—C21 | 118.8 (2) |
C5—C6—C1 | 121.57 (19) | C23—C22—S2 | 122.15 (17) |
C7—C6—C1 | 121.94 (18) | C21—C22—S2 | 118.99 (17) |
C8—C7—C6 | 119.85 (19) | C24—C23—C22 | 120.5 (2) |
C8—C7—H7 | 120.1 | C24—C23—H23 | 119.7 |
C6—C7—H7 | 120.1 | C22—C23—H23 | 119.7 |
N1—C8—C7 | 123.4 (2) | C25—C24—C23 | 120.9 (2) |
N1—C8—H8 | 118.3 | C25—C24—H24 | 119.6 |
C7—C8—H8 | 118.3 | C23—C24—H24 | 119.6 |
N2—C9—C10 | 123.5 (2) | C24—C25—C26 | 119.3 (3) |
N2—C9—H9 | 118.3 | C24—C25—H25 | 120.4 |
C10—C9—H9 | 118.3 | C26—C25—H25 | 120.4 |
C9—C10—C11 | 120.5 (2) | C25—C26—C21 | 121.2 (2) |
C9—C10—H10 | 119.8 | C25—C26—H26 | 119.4 |
C11—C10—H10 | 119.8 | C21—C26—H26 | 119.4 |
C12—C11—C10 | 115.9 (2) | O3—C27—O4 | 124.0 (2) |
C12—C11—C3 | 124.81 (19) | O3—C27—C21 | 121.4 (2) |
C10—C11—C3 | 119.2 (2) | O4—C27—C21 | 114.6 (3) |
C15—S1—S2—C22 | 95.43 (10) | C14—C15—C16—C17 | 0.2 (3) |
C6—C1—C2—C3 | 62.0 (2) | S1—C15—C16—C17 | 178.77 (15) |
C1—C2—C3—C11 | 179.41 (18) | C15—C16—C17—C18 | 0.4 (3) |
C8—N1—C4—C5 | −0.4 (3) | C16—C17—C18—C19 | −0.8 (3) |
N1—C4—C5—C6 | 1.0 (3) | C17—C18—C19—C14 | 0.7 (3) |
C4—C5—C6—C7 | −0.5 (3) | C15—C14—C19—C18 | −0.2 (3) |
C4—C5—C6—C1 | 179.47 (18) | C20—C14—C19—C18 | 178.56 (18) |
C2—C1—C6—C5 | 76.3 (2) | C19—C14—C20—O2 | −164.63 (19) |
C2—C1—C6—C7 | −103.7 (2) | C15—C14—C20—O2 | 14.1 (3) |
C5—C6—C7—C8 | −0.6 (3) | C19—C14—C20—O1 | 14.9 (3) |
C1—C6—C7—C8 | 179.43 (19) | C15—C14—C20—O1 | −166.44 (18) |
C4—N1—C8—C7 | −0.8 (3) | C26—C21—C22—C23 | 0.7 (3) |
C6—C7—C8—N1 | 1.3 (3) | C27—C21—C22—C23 | −177.7 (2) |
C13—N2—C9—C10 | −4.4 (5) | C26—C21—C22—S2 | −177.50 (18) |
N2—C9—C10—C11 | 1.8 (5) | C27—C21—C22—S2 | 4.1 (3) |
C9—C10—C11—C12 | 1.8 (4) | S1—S2—C22—C23 | −16.22 (19) |
C9—C10—C11—C3 | −177.1 (3) | S1—S2—C22—C21 | 161.97 (16) |
C2—C3—C11—C12 | −1.2 (3) | C21—C22—C23—C24 | 0.0 (3) |
C2—C3—C11—C10 | 177.6 (2) | S2—C22—C23—C24 | 178.19 (17) |
C10—C11—C12—C13 | −2.8 (4) | C22—C23—C24—C25 | −0.7 (4) |
C3—C11—C12—C13 | 176.0 (2) | C23—C24—C25—C26 | 0.5 (4) |
C9—N2—C13—C12 | 3.3 (5) | C24—C25—C26—C21 | 0.2 (4) |
C11—C12—C13—N2 | 0.2 (4) | C22—C21—C26—C25 | −0.9 (4) |
C19—C14—C15—C16 | −0.3 (3) | C27—C21—C26—C25 | 177.6 (3) |
C20—C14—C15—C16 | −178.98 (18) | C26—C21—C27—O3 | −161.3 (3) |
C19—C14—C15—S1 | −178.90 (14) | C22—C21—C27—O3 | 17.1 (4) |
C20—C14—C15—S1 | 2.4 (2) | C26—C21—C27—O4 | 17.6 (4) |
S2—S1—C15—C16 | −14.37 (18) | C22—C21—C27—O4 | −164.0 (2) |
S2—S1—C15—C14 | 164.22 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 1.81 | 2.622 (2) | 172 |
O4—H4′···N2 | 0.82 | 1.78 | 2.597 (3) | 175 |
C18—H18···O2ii | 0.93 | 2.59 | 3.433 (3) | 150 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C14H10O4S2·C13H14N2 |
Mr | 504.60 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 20.9613 (13), 9.3021 (5), 13.3790 (8) |
β (°) | 100.399 (1) |
V (Å3) | 2565.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.24 × 0.23 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.944, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12563, 4508, 3399 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.117, 1.08 |
No. of reflections | 4508 |
No. of parameters | 318 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.21 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 1.81 | 2.622 (2) | 172 |
O4—H4'···N2 | 0.82 | 1.78 | 2.597 (3) | 175 |
C18—H18···O2ii | 0.93 | 2.59 | 3.433 (3) | 150 |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2. |
Recently, the design and preparation of cocrystals with desired structures has attracted considerable interest in supramolecular chemistry and crystal engineering fields, due to their potential application in materials science (Zaworotko, 2001; Beatty et al., 2002), molecular recognition (Ghosh et al., 2006) and pharmaceutical chemistry (Remenar et al., 2003). To date, the most extensively observed cocrystals are those prepared from carboxylic acid and pyridine-type molecules. In this regard, since it possesses multiple hydrogen-bonding sites, a relatively flexible conformation and a variable degree of deprotonation, 2,2'-dithiodibenzoic acid (H2L) is a promising candidate for binary or tertiary cocrystals. Several H2L-based cocrystals with 4,4-bipyridine-type bases (Bi et al., 2002; Hu et al., 2004; Broker & Tiekink, 2007), isonicotinohydrazide (Meng et al., 2008), isomeric n-pyridinealdazines (n = 2, 3, 4) (Broker et al., 2008), 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (Basiuk et al., 1999) or hexamethylenetetramine (Li et al., 2001), and/or common solvent molecules (Murugavel et al., 2001; Kang et al., 2002; Kresinski & Fackler, 1994; Cai et al., 2006), have been well documented, with the acid and base components forming chain-based polymer topologies via classical O—H···N hydrogen bonds.
To investigate further the influence of framework flexibility on the resulting topology of H2L-based cocrystals, 1,3-bis(4-pyridyl)propane (bpp) was selected to cocrystallize with H2L in a mixed solvent, to give the title 1:1 cocrystal, (I). In addition to offering two hydrogen-bonding acceptor sites, bpp can also exhibit anti–anti, anti–gauche and gauche–gauche conformations (Niu et al., 2006), resulting from free rotation about the C—C single bonds, which may potentially induce novel supramolecular aggregation patterns.
The asymmetric unit of (I) is shown in Fig. 1. When viewed along the central S—S bond, the H2L molecule adopts a characteristic L-shaped conformation [torsion angle C15—S1—S2—C22 = 95.43 (10)°]. A search of the Cambridge Structural Database (CSD, Version?; Allen, 2002) yielded a mean value over 40 hits for H2L type structures of ±86° for this C—S—S—C torsion angle. The carboxylic acid residues are almost coplanar with their respective benzene rings, and the carbonyl O atoms are adjacent to the S atoms, with S···O separations of 2.628 (2) and 2.665 (2) Å. In the neutral bpp molecule, the torsion angles C1—C2—C3—C11 [179.41 (18)°] and C6—C1—C2—C3 [62.0 (2)°] are consistent with an anti–gauche conformation.
In the crystal structure of (I), the neutral H2L and bpp molecules are linked alternately by O1—H1···N1 and O4—H4'···N2 hydrogen bonds (Table 1) which generate a twisted zigzag chain extending along the crystallographic a-axis direction. These chains are further linked into a two-dimensional layer parallel to the (010) plane by weak C—H···O interactions (Table 2 and Fig. 2). Weak C—H···π contacts involving C10—H10 of bpp and an adjacent C21–C26 ring of H2L are observed between the layers, leading to a three-dimensional network [H10···Cg1 = 2.75 Å, C10···Cg1 = 3.556 (3) Å and C10—H10···Cg1 = 145°, where Cg1 is the centroid of the C21–C26 ring at (1 - x, 1 - y, 1 - z)].
To explore the structural features of H2L in cocrystals, various kinds of multifunctional N-heterocycles have already been used as cocrystallization agents `B' with H2L (see Fig. 3). The stoichiometric ratios of the components in the known cocrystals are 1:2, 1:1, 2:1, 2:3 and 3:1 (see Fig. 3). What can be obtained depends in part on the molar ratio of the materials used, as well as on the steric congestion of the secondary cocrystal agents. Various 1:1 and 2:1 cocrystals can be isolated by controlling the molar ratio of the raw materials for the H2L and B components, but only a 2:3 H2L–2-pyridinealdazine (SODKIG; Broker et al., 2008) cocrystal can be reproducibly obtained despite the use of different molar ratios of the reactants. The O—Hacid···N synthon is always present in these systems. In addition, as a binary organic acid, H2L can potentially act as a neutral molecule or as a singly or a doubly deprotonated anion in cocrystals. Only eight examples are currently known (see Fig. 3) involving deprotonated HL- and/or L2- anions, and here the O—Hacid···N hydrogen-bond synthon is replaced by charge-assisted O—H···O- and N—H···N+ hydrogen bonds. The crystal structures all have a chain-based polymer topology, despite the variable binding stoichiometry. These hydrogen-bonded chains exhibit twisted-linear, zigzag and/or helical topologies. In addition, C—H···O and C—H···π contacts also contribute to the supramolecular aggregate patterns.
The H2L and B components can sometimes cocrystallize with solvent molecules such as H2O, CH2Cl2, dimethylformamide, tetrahydrofuran or EtOH, leading to ternary hydrogen-bonded compounds (see Fig. 3). Here, solvent interference in the cocrystallization process can significantly direct the crystallization towards a particular crystal structure. In the case of 2HL–trans-1,2-bis(4-pyridyl)ethane.2EtOH (SIQCEB; Broker & Tiekink, 2007), the solvent ethanol molecules are found in the rectangular columns formed by the HL- anions and bipyridinium dications. In contrast, the water molecules in H2L–hexamethylenetetramine.0.5H2O (MIPVAI; Li et al., 2001) act as a bridges in the formation of a ladder-like double-chain.
Thus, the degree of deprotonation, the available hydrogen-bonding sites and the flexible conformation of the components, together with any solvent molecule intervention, are all important factors in governing supramolecular structures.