Buy article online - an online subscription or single-article purchase is required to access this article.
N,N′-Dithiodiphthalimide, C
16H
8N
2O
4S
2, crystallizes from ethyl acetate with two independent molecules in the asymmetric unit, in which the N—S—S—N torsion angles are −83.59 (19) and 92.9 (2)°. The molecules are linked by C—H
O hydrogen bonds and aromatic π–π-stacking interactions into a three-dimensional framework. When crystallized from either dichloromethane or ethanol, solvates are formed in which the molecules of the title compound lie across twofold rotation axes in space group
C2/
c, with N—S—S—N torsion angles of 93.54 (7) and 96.14 (11)°. There are no hydrogen bonds in these solvates, but the molecules are linked by aromatic π–π-stacking interactions into chains, between which there are continuous channels. Disordered solvent molecules occupy these channels, which account for
ca 20% of the unit-cell volume.
Supporting information
CCDC references: 166990; 166991; 166992
A sample of compound (IV) was obtained from Aldrich. Crystals of forms (1), (2)
and (3) which suitable for single-crystal X-ray diffraction were obtained by
slow evaporation of solutions in ethyl acetate, dichloromethane and ethanol,
respectively.
The solvent-free form (1) of compound (IV) is monoclinic and the space group
P21/c was uniquely assigned from the systematic absences. For
the solvated forms (2) and (3), the systematic absences permitted Cc
and C2/c as possible space groups; C2/c was chosen
and confirmed by the successful structure solution and refinement. The
crystals of all three forms diffracted rather poorly. For form (1), two
complete data sets were collected at 150 (2) K, using two different crystals;
for both, only some 35% of the reflections were labelled `observed', and both
data sets gave rather high Rint values. The data set employed here is
marginally the better of the two. The crystal quality for form (1) is
uniformly indifferent, but no solvent system has yet been found which provides
better quality crystals of the solvent-free polymorph. Similarly for the
solvated forms (2) and (3), the diffraction was rather poor, with ca
49% labelled `observed' for the dichloromethane solvate at 295 (2) K and
ca 46% labelled `observed' for the ethanol solvate at 150 (2) K. It was
apparent from an early stage that (2) and (3) were both solvated, but the
disorder of the solvent molecules proved to be intractable in each case. With
the solvent omitted, PLATON (Spek, 2001) indicated void space of 368.2 Å3 per unit cell in (2) and 372.3 Å3 per unit cell in (3);
consequently, the SQUEEZE option in PLATON was employed, which
indicated that these voids accommodated electron density summing to 116 and
113 electrons per unit cell in (2) and (3), respectively. Final refinements
were made using the solvent-free reflection data. All H atoms were located
from difference maps and were treated as riding atoms with C—H distances in
the range 0.93–0.95 Å.
Data collection: KappaCCD Server Software (Nonius, 1997) for (1); SMART (Bruker, 1997) for (2), (3). Cell refinement: DENZO (Otwinowski & Minor, 1997) for (1); SAINT (Bruker, 1997) for (2), (3). Data reduction: DENZO for (1); SAINT for (2), (3). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
(1)
N,
N'-Dithiodiphthalimide
top
Crystal data top
C16H8N2O4S2 | F(000) = 1456 |
Mr = 356.38 | Dx = 1.540 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6037 (3) Å | Cell parameters from 6603 reflections |
b = 33.9046 (14) Å | θ = 2.9–27.4° |
c = 11.9404 (6) Å | µ = 0.37 mm−1 |
β = 93.058 (2)° | T = 150 K |
V = 3073.9 (2) Å3 | Needle, colourless |
Z = 8 | 0.15 × 0.09 × 0.08 mm |
Data collection top
KappaCCD diffractometer | 6603 independent reflections |
Radiation source: fine-focus sealed tube | 2314 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.176 |
ϕ scans, and ω scans with κ offsets | θmax = 27.4°, θmin = 2.9° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | h = −9→9 |
Tmin = 0.947, Tmax = 0.971 | k = −41→43 |
17261 measured reflections | l = −15→15 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0005P)2] where P = (Fo2 + 2Fc2)/3 |
6603 reflections | (Δ/σ)max = 0.001 |
433 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
Crystal data top
C16H8N2O4S2 | V = 3073.9 (2) Å3 |
Mr = 356.38 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6037 (3) Å | µ = 0.37 mm−1 |
b = 33.9046 (14) Å | T = 150 K |
c = 11.9404 (6) Å | 0.15 × 0.09 × 0.08 mm |
β = 93.058 (2)° | |
Data collection top
KappaCCD diffractometer | 6603 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 2314 reflections with I > 2σ(I) |
Tmin = 0.947, Tmax = 0.971 | Rint = 0.176 |
17261 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.37 e Å−3 |
6603 reflections | Δρmin = −0.48 e Å−3 |
433 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 | x | y | z | Uiso*/Ueq | |
S11 | −0.26801 (18) | 0.10476 (3) | 0.36742 (10) | 0.0397 (4) | |
N11 | −0.3266 (5) | 0.15252 (9) | 0.3769 (3) | 0.0315 (10) | |
O11 | −0.4394 (5) | 0.16311 (9) | 0.1953 (2) | 0.0463 (10) | |
C11 | −0.3928 (6) | 0.17565 (13) | 0.2861 (4) | 0.0343 (13) | |
O12 | −0.2213 (4) | 0.16348 (8) | 0.5610 (2) | 0.0412 (9) | |
C12 | −0.2780 (6) | 0.17629 (13) | 0.4726 (4) | 0.0322 (13) | |
C13 | −0.3153 (6) | 0.21735 (13) | 0.4361 (4) | 0.0295 (12) | |
C14 | −0.2831 (6) | 0.25195 (14) | 0.4945 (4) | 0.0366 (13) | |
H14 | −0.2335 | 0.2520 | 0.5692 | 0.044* | |
C15 | −0.3268 (6) | 0.28664 (14) | 0.4385 (4) | 0.0449 (15) | |
H15 | −0.3061 | 0.3111 | 0.4756 | 0.054* | |
C16 | −0.3995 (7) | 0.28659 (14) | 0.3305 (4) | 0.0454 (15) | |
H16 | −0.4285 | 0.3110 | 0.2949 | 0.054* | |
C17 | −0.4312 (6) | 0.25163 (14) | 0.2724 (4) | 0.0412 (14) | |
H17 | −0.4822 | 0.2515 | 0.1980 | 0.049* | |
C18 | −0.3858 (6) | 0.21714 (13) | 0.3271 (4) | 0.0286 (12) | |
S21 | −0.48138 (18) | 0.07314 (3) | 0.40542 (10) | 0.0432 (4) | |
N21 | −0.4728 (5) | 0.07114 (10) | 0.5464 (3) | 0.0321 (10) | |
O21 | −0.6047 (5) | 0.13174 (9) | 0.5776 (3) | 0.0498 (10) | |
C21 | −0.5386 (7) | 0.10175 (15) | 0.6143 (4) | 0.0389 (14) | |
O22 | −0.3289 (4) | 0.01118 (8) | 0.5783 (2) | 0.0387 (9) | |
C22 | −0.3994 (6) | 0.03997 (13) | 0.6142 (4) | 0.0331 (13) | |
C23 | −0.4282 (6) | 0.05189 (13) | 0.7308 (4) | 0.0294 (12) | |
C24 | −0.3840 (6) | 0.03171 (12) | 0.8285 (4) | 0.0358 (13) | |
H24 | −0.3283 | 0.0066 | 0.8279 | 0.043* | |
C25 | −0.4247 (6) | 0.04988 (14) | 0.9278 (4) | 0.0388 (14) | |
H25 | −0.3950 | 0.0370 | 0.9969 | 0.047* | |
C26 | −0.5074 (6) | 0.08621 (14) | 0.9295 (4) | 0.0412 (14) | |
H26 | −0.5350 | 0.0976 | 0.9991 | 0.049* | |
C27 | −0.5503 (6) | 0.10622 (13) | 0.8306 (4) | 0.0385 (14) | |
H27 | −0.6057 | 0.1313 | 0.8309 | 0.046* | |
C28 | −0.5095 (6) | 0.08822 (13) | 0.7315 (4) | 0.0317 (13) | |
S31 | 0.16960 (18) | 0.10948 (4) | 1.17982 (10) | 0.0426 (4) | |
N31 | 0.1563 (5) | 0.15862 (9) | 1.1644 (3) | 0.0322 (11) | |
O31 | 0.2624 (4) | 0.16513 (8) | 0.9862 (2) | 0.0445 (10) | |
C31 | 0.2096 (6) | 0.17991 (13) | 1.0691 (4) | 0.0360 (14) | |
O32 | 0.0326 (4) | 0.17349 (8) | 1.3335 (2) | 0.0434 (10) | |
C32 | 0.0899 (6) | 0.18402 (13) | 1.2462 (4) | 0.0331 (13) | |
C33 | 0.1090 (6) | 0.22442 (14) | 1.2005 (4) | 0.0313 (12) | |
C34 | 0.0649 (6) | 0.25976 (14) | 1.2479 (4) | 0.0402 (14) | |
H34 | 0.0129 | 0.2610 | 1.3184 | 0.048* | |
C35 | 0.1004 (7) | 0.29345 (14) | 1.1875 (4) | 0.0509 (15) | |
H35 | 0.0748 | 0.3186 | 1.2180 | 0.061* | |
C36 | 0.1729 (7) | 0.29128 (15) | 1.0827 (4) | 0.0520 (15) | |
H36 | 0.1938 | 0.3149 | 1.0426 | 0.062* | |
C37 | 0.2151 (6) | 0.25509 (14) | 1.0361 (4) | 0.0396 (14) | |
H37 | 0.2651 | 0.2534 | 0.9650 | 0.047* | |
C38 | 0.1813 (6) | 0.22192 (13) | 1.0972 (4) | 0.0308 (12) | |
S41 | −0.05242 (19) | 0.08796 (4) | 1.10208 (10) | 0.0480 (4) | |
N41 | 0.0036 (5) | 0.07794 (11) | 0.9706 (3) | 0.0346 (11) | |
O41 | 0.1626 (5) | 0.02058 (9) | 1.0088 (3) | 0.0478 (10) | |
C41 | 0.0948 (7) | 0.04332 (14) | 0.9422 (4) | 0.0361 (14) | |
O42 | −0.1123 (4) | 0.13295 (9) | 0.8769 (2) | 0.0456 (10) | |
C42 | −0.0414 (6) | 0.10112 (14) | 0.8742 (4) | 0.0332 (13) | |
C43 | 0.0145 (6) | 0.07772 (12) | 0.7784 (4) | 0.0270 (12) | |
C44 | −0.0003 (6) | 0.08596 (13) | 0.6651 (4) | 0.0366 (13) | |
H44 | −0.0525 | 0.1098 | 0.6380 | 0.044* | |
C45 | 0.0638 (7) | 0.05821 (16) | 0.5921 (4) | 0.0457 (15) | |
H45 | 0.0568 | 0.0631 | 0.5136 | 0.055* | |
C46 | 0.1381 (7) | 0.02335 (15) | 0.6335 (4) | 0.0458 (15) | |
H46 | 0.1780 | 0.0043 | 0.5823 | 0.055* | |
C47 | 0.1556 (6) | 0.01562 (13) | 0.7471 (4) | 0.0393 (14) | |
H47 | 0.2092 | −0.0080 | 0.7749 | 0.047* | |
C48 | 0.0923 (6) | 0.04351 (13) | 0.8185 (4) | 0.0307 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S11 | 0.0477 (10) | 0.0337 (8) | 0.0386 (8) | 0.0004 (7) | 0.0092 (7) | 0.0045 (6) |
N11 | 0.038 (3) | 0.024 (2) | 0.032 (2) | 0.002 (2) | 0.003 (2) | 0.0038 (19) |
O11 | 0.059 (3) | 0.047 (2) | 0.031 (2) | −0.0049 (19) | −0.006 (2) | 0.0017 (18) |
C11 | 0.030 (4) | 0.034 (4) | 0.039 (3) | 0.000 (3) | 0.000 (3) | 0.008 (3) |
O12 | 0.043 (3) | 0.050 (2) | 0.0299 (19) | −0.0011 (18) | −0.0066 (18) | 0.0095 (17) |
C12 | 0.029 (4) | 0.037 (3) | 0.031 (3) | −0.006 (3) | 0.003 (3) | −0.002 (3) |
C13 | 0.031 (3) | 0.025 (3) | 0.033 (3) | 0.001 (3) | 0.005 (3) | 0.008 (3) |
C14 | 0.037 (4) | 0.040 (3) | 0.034 (3) | −0.005 (3) | 0.004 (3) | −0.002 (3) |
C15 | 0.044 (4) | 0.036 (4) | 0.055 (4) | 0.003 (3) | 0.015 (3) | −0.004 (3) |
C16 | 0.047 (4) | 0.041 (4) | 0.048 (3) | 0.001 (3) | 0.006 (3) | 0.011 (3) |
C17 | 0.043 (4) | 0.048 (4) | 0.033 (3) | 0.003 (3) | 0.004 (3) | 0.007 (3) |
C18 | 0.023 (3) | 0.026 (3) | 0.037 (3) | 0.001 (2) | 0.004 (3) | 0.009 (3) |
S21 | 0.0521 (11) | 0.0359 (8) | 0.0409 (8) | −0.0120 (7) | −0.0031 (7) | 0.0063 (6) |
N21 | 0.037 (3) | 0.029 (2) | 0.031 (2) | 0.006 (2) | 0.006 (2) | 0.006 (2) |
O21 | 0.054 (3) | 0.034 (2) | 0.063 (2) | 0.010 (2) | 0.010 (2) | 0.0142 (19) |
C21 | 0.030 (4) | 0.033 (3) | 0.055 (4) | −0.007 (3) | 0.011 (3) | 0.012 (3) |
O22 | 0.044 (3) | 0.026 (2) | 0.047 (2) | 0.0026 (17) | 0.0057 (18) | −0.0007 (17) |
C22 | 0.032 (4) | 0.026 (3) | 0.042 (3) | −0.009 (3) | 0.003 (3) | 0.006 (3) |
C23 | 0.027 (3) | 0.031 (3) | 0.030 (3) | −0.002 (3) | 0.004 (2) | 0.000 (3) |
C24 | 0.039 (4) | 0.027 (3) | 0.042 (3) | −0.001 (3) | 0.006 (3) | 0.000 (3) |
C25 | 0.032 (4) | 0.045 (4) | 0.040 (3) | −0.005 (3) | 0.002 (3) | 0.006 (3) |
C26 | 0.040 (4) | 0.046 (4) | 0.039 (3) | −0.006 (3) | 0.014 (3) | −0.007 (3) |
C27 | 0.034 (4) | 0.029 (3) | 0.054 (3) | −0.004 (3) | 0.015 (3) | −0.001 (3) |
C28 | 0.030 (4) | 0.024 (3) | 0.043 (3) | −0.003 (3) | 0.015 (3) | 0.005 (3) |
S31 | 0.0546 (11) | 0.0337 (8) | 0.0390 (8) | −0.0031 (7) | −0.0029 (7) | 0.0004 (6) |
N31 | 0.046 (3) | 0.020 (2) | 0.031 (2) | −0.002 (2) | 0.008 (2) | −0.0002 (19) |
O31 | 0.054 (3) | 0.050 (2) | 0.0296 (19) | 0.0034 (19) | 0.0084 (18) | −0.0066 (17) |
C31 | 0.034 (4) | 0.043 (4) | 0.032 (3) | 0.002 (3) | 0.003 (3) | −0.003 (3) |
O32 | 0.044 (3) | 0.052 (2) | 0.035 (2) | −0.0077 (18) | 0.0115 (18) | −0.0011 (18) |
C32 | 0.022 (3) | 0.042 (4) | 0.035 (3) | −0.001 (3) | 0.003 (3) | −0.010 (3) |
C33 | 0.028 (3) | 0.028 (3) | 0.037 (3) | 0.002 (3) | −0.001 (2) | 0.002 (3) |
C34 | 0.042 (4) | 0.040 (3) | 0.039 (3) | 0.011 (3) | 0.001 (3) | −0.006 (3) |
C35 | 0.057 (4) | 0.037 (4) | 0.056 (4) | 0.006 (3) | −0.020 (3) | −0.013 (3) |
C36 | 0.054 (4) | 0.037 (4) | 0.062 (4) | −0.004 (3) | −0.020 (3) | 0.015 (3) |
C37 | 0.036 (4) | 0.040 (3) | 0.041 (3) | −0.010 (3) | −0.009 (3) | 0.004 (3) |
C38 | 0.030 (3) | 0.030 (3) | 0.032 (3) | −0.004 (3) | −0.004 (3) | −0.003 (3) |
S41 | 0.0566 (11) | 0.0515 (9) | 0.0368 (8) | −0.0178 (8) | 0.0100 (8) | −0.0044 (7) |
N41 | 0.041 (3) | 0.033 (3) | 0.030 (2) | −0.002 (2) | 0.005 (2) | 0.003 (2) |
O41 | 0.049 (3) | 0.044 (2) | 0.050 (2) | −0.0038 (19) | −0.006 (2) | 0.0183 (18) |
C41 | 0.039 (4) | 0.035 (4) | 0.035 (3) | −0.018 (3) | 0.004 (3) | −0.001 (3) |
O42 | 0.051 (3) | 0.030 (2) | 0.056 (2) | 0.0097 (19) | 0.007 (2) | −0.0014 (18) |
C42 | 0.027 (3) | 0.030 (3) | 0.043 (3) | −0.006 (3) | 0.005 (3) | −0.004 (3) |
C43 | 0.026 (3) | 0.025 (3) | 0.030 (3) | 0.003 (2) | 0.002 (2) | 0.003 (2) |
C44 | 0.029 (4) | 0.040 (3) | 0.040 (3) | −0.006 (3) | 0.000 (3) | 0.011 (3) |
C45 | 0.033 (4) | 0.071 (4) | 0.033 (3) | −0.005 (3) | 0.004 (3) | −0.001 (3) |
C46 | 0.032 (4) | 0.057 (4) | 0.049 (4) | −0.008 (3) | 0.007 (3) | −0.017 (3) |
C47 | 0.034 (4) | 0.030 (3) | 0.055 (4) | 0.000 (3) | 0.005 (3) | −0.001 (3) |
C48 | 0.025 (3) | 0.025 (3) | 0.042 (3) | −0.003 (3) | −0.001 (3) | −0.005 (3) |
Geometric parameters (Å, º) top
S11—S21 | 2.0164 (17) | C33—C34 | 1.374 (5) |
S11—N11 | 1.685 (3) | C33—C38 | 1.379 (5) |
N11—C11 | 1.410 (5) | C34—C35 | 1.385 (5) |
N11—C12 | 1.430 (5) | C35—C36 | 1.396 (5) |
O11—C11 | 1.200 (5) | C36—C37 | 1.392 (5) |
C11—C18 | 1.490 (5) | C37—C38 | 1.373 (5) |
O12—C12 | 1.200 (5) | S41—N41 | 1.683 (3) |
C12—C13 | 1.482 (5) | N41—C41 | 1.414 (5) |
C13—C14 | 1.380 (5) | N41—C42 | 1.421 (5) |
C13—C18 | 1.381 (6) | O41—C41 | 1.204 (5) |
C14—C15 | 1.384 (5) | C41—C48 | 1.476 (6) |
C15—C16 | 1.376 (6) | O42—C42 | 1.208 (5) |
C16—C17 | 1.388 (5) | C42—C43 | 1.473 (5) |
C17—C18 | 1.374 (5) | C43—C48 | 1.376 (5) |
S21—N21 | 1.683 (3) | C43—C44 | 1.380 (5) |
N21—C21 | 1.424 (5) | C44—C45 | 1.389 (5) |
N21—C22 | 1.427 (5) | C45—C46 | 1.390 (6) |
O21—C21 | 1.206 (5) | C46—C47 | 1.380 (5) |
C21—C28 | 1.479 (6) | C47—C48 | 1.377 (5) |
O22—C22 | 1.204 (5) | C14—H14 | 0.950 |
C22—C23 | 1.476 (5) | C15—H15 | 0.950 |
C23—C28 | 1.378 (5) | C16—H16 | 0.950 |
C23—C24 | 1.379 (5) | C17—H17 | 0.950 |
C24—C25 | 1.385 (5) | C24—H24 | 0.950 |
C25—C26 | 1.384 (5) | C25—H25 | 0.950 |
C26—C27 | 1.386 (6) | C26—H26 | 0.950 |
C27—C28 | 1.380 (5) | C27—H27 | 0.950 |
S31—S41 | 2.0190 (19) | C34—H34 | 0.950 |
S31—N31 | 1.679 (3) | C35—H35 | 0.950 |
N31—C32 | 1.415 (5) | C36—H36 | 0.950 |
N31—C31 | 1.424 (5) | C37—H37 | 0.950 |
O31—C31 | 1.198 (4) | C44—H44 | 0.950 |
C31—C38 | 1.482 (5) | C45—H45 | 0.950 |
O32—C32 | 1.206 (4) | C46—H46 | 0.950 |
C32—C33 | 1.484 (5) | C47—H47 | 0.950 |
| | | |
N11—S11—S21 | 106.08 (14) | C38—C37—C36 | 117.1 (4) |
C11—N11—C12 | 111.6 (4) | C37—C38—C33 | 121.3 (4) |
C11—N11—S11 | 124.6 (3) | C37—C38—C31 | 129.3 (4) |
C12—N11—S11 | 122.5 (3) | C33—C38—C31 | 109.3 (4) |
O11—C11—N11 | 125.1 (4) | N41—S41—S31 | 104.77 (14) |
O11—C11—C18 | 129.4 (5) | C41—N41—C42 | 111.4 (4) |
N11—C11—C18 | 105.5 (4) | C41—N41—S41 | 122.9 (3) |
O12—C12—N11 | 124.3 (4) | C42—N41—S41 | 125.6 (3) |
O12—C12—C13 | 130.8 (4) | O41—C41—N41 | 124.9 (4) |
N11—C12—C13 | 104.9 (4) | O41—C41—C48 | 130.2 (5) |
C14—C13—C18 | 122.0 (4) | N41—C41—C48 | 104.9 (4) |
C14—C13—C12 | 128.6 (5) | O42—C42—N41 | 124.1 (4) |
C18—C13—C12 | 109.4 (4) | O42—C42—C43 | 130.6 (5) |
C13—C14—C15 | 116.5 (5) | N41—C42—C43 | 105.3 (4) |
C16—C15—C14 | 121.7 (5) | C48—C43—C44 | 121.5 (4) |
C15—C16—C17 | 121.3 (5) | C48—C43—C42 | 108.7 (4) |
C18—C17—C16 | 117.2 (5) | C44—C43—C42 | 129.8 (5) |
C17—C18—C13 | 121.2 (4) | C43—C44—C45 | 117.7 (4) |
C17—C18—C11 | 130.1 (5) | C44—C45—C46 | 120.2 (4) |
C13—C18—C11 | 108.7 (4) | C47—C46—C45 | 121.8 (5) |
N21—S21—S11 | 104.95 (14) | C48—C47—C46 | 117.3 (5) |
C21—N21—C22 | 110.8 (4) | C43—C48—C47 | 121.4 (4) |
C21—N21—S21 | 123.0 (3) | C43—C48—C41 | 109.5 (4) |
C22—N21—S21 | 126.2 (3) | C47—C48—C41 | 129.1 (5) |
O21—C21—N21 | 124.1 (4) | C13—C14—H14 | 121.80 |
O21—C21—C28 | 130.1 (5) | C15—C14—H14 | 121.67 |
N21—C21—C28 | 105.9 (4) | C14—C15—H15 | 119.15 |
O22—C22—N21 | 124.5 (4) | C16—C15—H15 | 119.13 |
O22—C22—C23 | 130.5 (5) | C15—C16—H16 | 119.34 |
N21—C22—C23 | 105.0 (4) | C17—C16—H16 | 119.33 |
C28—C23—C24 | 121.8 (4) | C16—C17—H17 | 121.51 |
C28—C23—C22 | 109.9 (4) | C18—C17—H17 | 121.33 |
C24—C23—C22 | 128.3 (4) | C23—C24—H24 | 121.77 |
C23—C24—C25 | 116.6 (4) | C25—C24—H24 | 121.62 |
C26—C25—C24 | 122.1 (4) | C24—C25—H25 | 119.02 |
C25—C26—C27 | 120.7 (4) | C26—C25—H25 | 118.92 |
C28—C27—C26 | 117.4 (4) | C25—C26—H26 | 119.77 |
C23—C28—C27 | 121.5 (4) | C27—C26—H26 | 119.58 |
C23—C28—C21 | 108.4 (4) | C26—C27—H27 | 121.32 |
C27—C28—C21 | 130.1 (4) | C28—C27—H27 | 121.27 |
N31—S31—S41 | 105.31 (15) | C33—C34—H34 | 121.72 |
C32—N31—C31 | 111.7 (4) | C35—C34—H34 | 121.79 |
C32—N31—S31 | 123.4 (3) | C34—C35—H35 | 119.36 |
C31—N31—S31 | 124.9 (3) | C36—C35—H35 | 119.27 |
O31—C31—N31 | 124.8 (4) | C35—C36—H36 | 119.45 |
O31—C31—C38 | 130.4 (4) | C37—C36—H36 | 119.53 |
N31—C31—C38 | 104.8 (4) | C36—C37—H37 | 121.47 |
O32—C32—N31 | 125.1 (4) | C38—C37—H37 | 121.38 |
O32—C32—C33 | 129.7 (4) | C43—C44—H44 | 121.13 |
N31—C32—C33 | 105.2 (4) | C45—C44—H44 | 121.14 |
C34—C33—C38 | 122.6 (4) | C44—C45—H45 | 119.85 |
C34—C33—C32 | 128.5 (4) | C46—C45—H45 | 119.97 |
C38—C33—C32 | 108.9 (4) | C45—C46—H46 | 119.15 |
C33—C34—C35 | 116.5 (4) | C47—C46—H46 | 119.06 |
C34—C35—C36 | 121.3 (4) | C46—C47—H47 | 121.34 |
C37—C36—C35 | 121.0 (4) | C48—C47—H47 | 121.33 |
| | | |
N11—S11—S21—N21 | −83.59 (19) | N31—S31—S41—N41 | 92.9 (2) |
S21—S11—N11—C11 | −93.8 (4) | S41—S31—N31—C31 | −85.0 (4) |
S21—S11—N11—C12 | 100.5 (3) | S41—S31—N31—C32 | 95.1 (4) |
S11—S21—N21—C21 | 83.7 (4) | S31—S41—N41—C41 | 80.3 (4) |
S11—S21—N21—C22 | −95.5 (4) | S31—S41—N41—C42 | −103.5 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C44—H44···O12 | 0.95 | 2.38 | 3.325 (5) | 171 |
C46—H46···O22i | 0.95 | 2.35 | 3.204 (6) | 150 |
C36—H36···O21ii | 0.95 | 2.39 | 3.112 (6) | 132 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, −y+1/2, z+1/2. |
(2)
N,
N'-Dithiodiphthalimide
top
Crystal data top
C16H8N2O4S2 | F(000) = 728 |
Mr = 356.38 | Dx = 1.317 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.3782 (13) Å | Cell parameters from 2648 reflections |
b = 16.0723 (14) Å | θ = 1.9–30.2° |
c = 7.7910 (7) Å | µ = 0.32 mm−1 |
β = 93.256 (2)° | T = 295 K |
V = 1797.5 (3) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.10 × 0.04 mm |
Data collection top
Bruker SMART 1000 CCD diffractometer | 2648 independent reflections |
Radiation source: fine-focus sealed tube | 1286 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ–ω scans | θmax = 30.2°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −19→19 |
Tmin = 0.911, Tmax = 0.988 | k = −22→11 |
6105 measured reflections | l = −10→11 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0225P)2] where P = (Fo2 + 2Fc2)/3 |
2648 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C16H8N2O4S2 | V = 1797.5 (3) Å3 |
Mr = 356.38 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.3782 (13) Å | µ = 0.32 mm−1 |
b = 16.0723 (14) Å | T = 295 K |
c = 7.7910 (7) Å | 0.30 × 0.10 × 0.04 mm |
β = 93.256 (2)° | |
Data collection top
Bruker SMART 1000 CCD diffractometer | 2648 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1286 reflections with I > 2σ(I) |
Tmin = 0.911, Tmax = 0.988 | Rint = 0.030 |
6105 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.19 e Å−3 |
2648 reflections | Δρmin = −0.23 e Å−3 |
109 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.45435 (3) | 0.42888 (3) | 0.14589 (6) | 0.06466 (17) | |
N1 | 0.37143 (9) | 0.35978 (8) | 0.19143 (17) | 0.0537 (5) | |
C1 | 0.37358 (11) | 0.27380 (11) | 0.1519 (2) | 0.0525 (4) | |
O1 | 0.43600 (8) | 0.24002 (8) | 0.08386 (16) | 0.0717 (4) | |
C2 | 0.28892 (11) | 0.38182 (12) | 0.2758 (2) | 0.0553 (4) | |
O2 | 0.27258 (9) | 0.45025 (8) | 0.32559 (18) | 0.0780 (6) | |
C3 | 0.23594 (11) | 0.30352 (10) | 0.2826 (2) | 0.0516 (4) | |
C4 | 0.15030 (12) | 0.28889 (13) | 0.3514 (2) | 0.0627 (5) | |
C5 | 0.11807 (13) | 0.20822 (14) | 0.3465 (2) | 0.0710 (6) | |
C6 | 0.16830 (14) | 0.14466 (13) | 0.2782 (2) | 0.0721 (6) | |
C7 | 0.25377 (13) | 0.15926 (12) | 0.2087 (2) | 0.0636 (5) | |
C8 | 0.28575 (11) | 0.23962 (11) | 0.2134 (2) | 0.0511 (4) | |
H4 | 0.1163 | 0.3318 | 0.3982 | 0.075* | |
H5 | 0.0610 | 0.1963 | 0.3912 | 0.085* | |
H6 | 0.1446 | 0.0908 | 0.2783 | 0.087* | |
H7 | 0.2876 | 0.1166 | 0.1612 | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0526 (2) | 0.0503 (3) | 0.0935 (4) | −0.0007 (2) | 0.0253 (2) | 0.0166 (3) |
O2 | 0.0738 (9) | 0.0509 (8) | 0.1128 (11) | 0.0068 (7) | 0.0356 (8) | −0.0016 (8) |
O1 | 0.0664 (8) | 0.0643 (8) | 0.0876 (10) | 0.0079 (7) | 0.0325 (7) | −0.0048 (7) |
N1 | 0.0481 (8) | 0.0437 (8) | 0.0716 (9) | −0.0026 (6) | 0.0229 (7) | 0.0030 (7) |
C8 | 0.0511 (10) | 0.0501 (10) | 0.0530 (10) | −0.0022 (8) | 0.0106 (8) | 0.0025 (9) |
C7 | 0.0750 (12) | 0.0524 (11) | 0.0641 (12) | −0.0071 (10) | 0.0114 (10) | −0.0007 (10) |
C6 | 0.0778 (14) | 0.0670 (14) | 0.0721 (14) | −0.0266 (12) | 0.0094 (11) | 0.0063 (11) |
C5 | 0.0576 (12) | 0.0862 (16) | 0.0702 (13) | −0.0223 (11) | 0.0131 (10) | 0.0107 (12) |
C4 | 0.0520 (10) | 0.0729 (14) | 0.0648 (12) | −0.0019 (10) | 0.0182 (9) | 0.0068 (11) |
C3 | 0.0464 (9) | 0.0523 (10) | 0.0569 (11) | −0.0018 (8) | 0.0114 (8) | 0.0062 (9) |
C2 | 0.0499 (10) | 0.0494 (11) | 0.0680 (12) | 0.0043 (9) | 0.0162 (8) | 0.0084 (10) |
C1 | 0.0544 (10) | 0.0483 (10) | 0.0559 (11) | 0.0006 (8) | 0.0115 (8) | 0.0028 (9) |
Geometric parameters (Å, º) top
S1—S1i | 2.0281 (10) | C7—C6 | 1.391 (2) |
S1—N1 | 1.6819 (13) | C7—H7 | 0.9299 |
O2—C2 | 1.1940 (19) | C6—C5 | 1.375 (3) |
O1—C1 | 1.1981 (18) | C6—H6 | 0.9300 |
N1—C1 | 1.416 (2) | C5—C4 | 1.377 (2) |
N1—C2 | 1.433 (2) | C5—H5 | 0.9299 |
C8—C7 | 1.371 (2) | C4—C3 | 1.391 (2) |
C8—C3 | 1.379 (2) | C4—H4 | 0.9306 |
C8—C1 | 1.481 (2) | C3—C2 | 1.474 (2) |
| | | |
N1—S1—S1i | 105.41 (5) | C6—C5—H5 | 119.0 |
C1—N1—C2 | 111.70 (13) | C4—C5—H5 | 119.2 |
C1—N1—S1 | 125.02 (11) | C5—C4—C3 | 116.91 (18) |
C2—N1—S1 | 123.27 (12) | C5—C4—H4 | 121.7 |
C7—C8—C3 | 122.08 (16) | C3—C4—H4 | 121.4 |
C7—C8—C1 | 129.17 (16) | C8—C3—C4 | 121.04 (17) |
C3—C8—C1 | 108.75 (15) | C8—C3—C2 | 109.93 (14) |
C8—C7—C6 | 116.81 (19) | C4—C3—C2 | 128.99 (17) |
C8—C7—H7 | 121.6 | O2—C2—N1 | 124.06 (16) |
C6—C7—H7 | 121.6 | O2—C2—C3 | 131.55 (16) |
C5—C6—C7 | 121.36 (19) | N1—C2—C3 | 104.39 (15) |
C5—C6—H6 | 119.4 | O1—C1—N1 | 124.36 (15) |
C7—C6—H6 | 119.3 | O1—C1—C8 | 130.44 (16) |
C6—C5—C4 | 121.79 (18) | N1—C1—C8 | 105.19 (13) |
| | | |
N1—S1—S1i—N1i | 93.54 (7) | C2—N1—S1—S1i | 90.17 (12) |
C1—N1—S1—S1i | −90.03 (13) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
(3)
N,
N'-Dithiodiphthalimide
top
Crystal data top
C16H8N2O4S2 | F(000) = 728 |
Mr = 356.38 | Dx = 1.310 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.8129 (11) Å | Cell parameters from 3256 reflections |
b = 15.9280 (13) Å | θ = 1.9–32.5° |
c = 7.6616 (6) Å | µ = 0.32 mm−1 |
β = 91.671 (2)° | T = 150 K |
V = 1806.9 (2) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Data collection top
Bruker SMART 1000 CCD diffractometer | 3256 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1486 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ϕ–ω scans | θmax = 32.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −20→22 |
Tmin = 0.912, Tmax = 0.940 | k = −24→23 |
9221 measured reflections | l = −11→8 |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0935P)2] where P = (Fo2 + 2Fc2)/3 |
3256 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
Crystal data top
C16H8N2O4S2 | V = 1806.9 (2) Å3 |
Mr = 356.38 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.8129 (11) Å | µ = 0.32 mm−1 |
b = 15.9280 (13) Å | T = 150 K |
c = 7.6616 (6) Å | 0.30 × 0.20 × 0.20 mm |
β = 91.671 (2)° | |
Data collection top
Bruker SMART 1000 CCD diffractometer | 3256 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1486 reflections with I > 2σ(I) |
Tmin = 0.912, Tmax = 0.940 | Rint = 0.062 |
9221 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.184 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.50 e Å−3 |
3256 reflections | Δρmin = −0.41 e Å−3 |
109 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.45648 (4) | 0.42497 (4) | 0.14513 (9) | 0.0566 (2) | |
N1 | 0.37422 (13) | 0.35695 (12) | 0.1950 (3) | 0.0479 (5) | |
C1 | 0.37365 (17) | 0.27062 (15) | 0.1540 (3) | 0.0483 (6) | |
O1 | 0.43400 (14) | 0.23395 (12) | 0.0862 (3) | 0.0662 (5) | |
C2 | 0.29386 (15) | 0.38224 (15) | 0.2797 (3) | 0.0463 (5) | |
O2 | 0.27993 (14) | 0.45101 (11) | 0.3306 (3) | 0.0671 (6) | |
C3 | 0.23833 (16) | 0.30546 (15) | 0.2844 (3) | 0.0448 (5) | |
C4 | 0.15311 (17) | 0.29369 (18) | 0.3511 (3) | 0.0554 (6) | |
C5 | 0.1180 (2) | 0.2122 (2) | 0.3447 (4) | 0.0639 (8) | |
C6 | 0.1648 (2) | 0.14773 (19) | 0.2747 (4) | 0.0648 (8) | |
C7 | 0.2497 (2) | 0.15907 (16) | 0.2075 (3) | 0.0556 (6) | |
C8 | 0.28541 (16) | 0.23888 (15) | 0.2140 (3) | 0.0458 (5) | |
H4 | 0.1208 | 0.3380 | 0.3980 | 0.066* | |
H5 | 0.0613 | 0.2020 | 0.3894 | 0.077* | |
H6 | 0.1391 | 0.0945 | 0.2719 | 0.078* | |
H7 | 0.2813 | 0.1146 | 0.1599 | 0.067* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0433 (4) | 0.0480 (4) | 0.0792 (5) | −0.0023 (3) | 0.0139 (3) | 0.0166 (3) |
N1 | 0.0349 (10) | 0.0466 (11) | 0.0627 (13) | −0.0018 (8) | 0.0100 (9) | 0.0058 (9) |
C1 | 0.0482 (14) | 0.0489 (13) | 0.0477 (13) | 0.0041 (11) | 0.0035 (11) | 0.0016 (10) |
O1 | 0.0601 (12) | 0.0635 (12) | 0.0760 (13) | 0.0093 (10) | 0.0190 (10) | −0.0041 (9) |
C2 | 0.0402 (13) | 0.0464 (13) | 0.0525 (13) | 0.0031 (10) | 0.0054 (10) | 0.0075 (10) |
O2 | 0.0600 (12) | 0.0470 (10) | 0.0955 (15) | 0.0048 (9) | 0.0214 (10) | 0.0001 (10) |
C3 | 0.0404 (13) | 0.0474 (12) | 0.0466 (13) | −0.0036 (10) | 0.0012 (10) | 0.0066 (10) |
C4 | 0.0415 (14) | 0.0672 (16) | 0.0578 (16) | −0.0017 (12) | 0.0089 (11) | 0.0110 (12) |
C5 | 0.0479 (15) | 0.084 (2) | 0.0602 (16) | −0.0202 (14) | 0.0034 (12) | 0.0116 (14) |
C6 | 0.0696 (19) | 0.0663 (17) | 0.0581 (16) | −0.0236 (15) | −0.0080 (14) | 0.0125 (13) |
C7 | 0.0661 (17) | 0.0501 (14) | 0.0505 (14) | −0.0059 (13) | −0.0003 (12) | 0.0027 (11) |
C8 | 0.0444 (13) | 0.0497 (13) | 0.0432 (12) | −0.0029 (10) | −0.0009 (10) | 0.0060 (9) |
Geometric parameters (Å, º) top
S1—N1 | 1.683 (2) | C4—C5 | 1.398 (4) |
N1—C1 | 1.410 (3) | C5—C6 | 1.358 (4) |
N1—C2 | 1.430 (3) | C6—C7 | 1.384 (4) |
C1—O1 | 1.199 (3) | C7—C8 | 1.377 (3) |
C2—O2 | 1.183 (3) | C8—C3 | 1.387 (3) |
C1—C8 | 1.487 (3) | C4—H4 | 0.9300 |
C2—C3 | 1.475 (3) | C5—H5 | 0.9300 |
S1—S1i | 2.0307 (15) | C6—H6 | 0.9300 |
C3—C4 | 1.388 (3) | C7—H7 | 0.9300 |
| | | |
N1—S1—S1i | 105.52 (8) | C3—C4—C5 | 117.0 (3) |
C1—N1—C2 | 112.08 (19) | C3—C4—H4 | 121.5 |
C1—N1—S1 | 125.24 (16) | C5—C4—H4 | 121.5 |
C2—N1—S1 | 122.64 (16) | C6—C5—C4 | 121.5 (3) |
O1—C1—N1 | 124.9 (2) | C6—C5—H5 | 119.3 |
O1—C1—C8 | 129.9 (2) | C4—C5—H5 | 119.3 |
N1—C2—C3 | 104.46 (19) | C5—C6—C7 | 121.8 (3) |
N1—C1—C8 | 105.21 (19) | C5—C6—H6 | 119.1 |
C1—C8—C3 | 108.5 (2) | C7—C6—H6 | 119.1 |
C2—C3—C8 | 109.7 (2) | C8—C7—C6 | 117.3 (3) |
O2—C2—N1 | 124.5 (2) | C8—C7—H7 | 121.3 |
O2—C2—C3 | 131.1 (2) | C6—C7—H7 | 121.3 |
C8—C3—C4 | 120.8 (2) | C7—C8—C3 | 121.5 (2) |
C4—C3—C2 | 129.4 (2) | C7—C8—C1 | 130.0 (2) |
| | | |
C1—N1—S1—S1i | −91.6 (2) | N1—S1—S1i—N1i | 96.14 (11) |
C2—N1—S1—S1i | 91.0 (2) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
| (1) | (2) | (3) |
Crystal data |
Chemical formula | C16H8N2O4S2 | C16H8N2O4S2 | C16H8N2O4S2 |
Mr | 356.38 | 356.38 | 356.38 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 150 | 295 | 150 |
a, b, c (Å) | 7.6037 (3), 33.9046 (14), 11.9404 (6) | 14.3782 (13), 16.0723 (14), 7.7910 (7) | 14.8129 (11), 15.9280 (13), 7.6616 (6) |
β (°) | 93.058 (2) | 93.256 (2) | 91.671 (2) |
V (Å3) | 3073.9 (2) | 1797.5 (3) | 1806.9 (2) |
Z | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 0.32 | 0.32 |
Crystal size (mm) | 0.15 × 0.09 × 0.08 | 0.30 × 0.10 × 0.04 | 0.30 × 0.20 × 0.20 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | Bruker SMART 1000 CCD diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SADABS; Bruker, 1997) | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.947, 0.971 | 0.911, 0.988 | 0.912, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17261, 6603, 2314 | 6105, 2648, 1286 | 9221, 3256, 1486 |
Rint | 0.176 | 0.030 | 0.062 |
(sin θ/λ)max (Å−1) | 0.647 | 0.708 | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.115, 0.86 | 0.043, 0.079, 1.01 | 0.062, 0.184, 0.92 |
No. of reflections | 6603 | 2648 | 3256 |
No. of parameters | 433 | 109 | 109 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.48 | 0.19, −0.23 | 0.50, −0.41 |
Selected geometric parameters (Å, º) for (1) topS11—S21 | 2.0164 (17) | S31—S41 | 2.0190 (19) |
S11—N11 | 1.685 (3) | S31—N31 | 1.679 (3) |
N11—C11 | 1.410 (5) | N31—C32 | 1.415 (5) |
N11—C12 | 1.430 (5) | N31—C31 | 1.424 (5) |
S21—N21 | 1.683 (3) | S41—N41 | 1.683 (3) |
N21—C21 | 1.424 (5) | N41—C41 | 1.414 (5) |
N21—C22 | 1.427 (5) | N41—C42 | 1.421 (5) |
| | | |
N11—S11—S21 | 106.08 (14) | N31—S31—S41 | 105.31 (15) |
C11—N11—C12 | 111.6 (4) | C32—N31—C31 | 111.7 (4) |
C11—N11—S11 | 124.6 (3) | C32—N31—S31 | 123.4 (3) |
C12—N11—S11 | 122.5 (3) | C31—N31—S31 | 124.9 (3) |
N21—S21—S11 | 104.95 (14) | N41—S41—S31 | 104.77 (14) |
C21—N21—C22 | 110.8 (4) | C41—N41—C42 | 111.4 (4) |
C21—N21—S21 | 123.0 (3) | C41—N41—S41 | 122.9 (3) |
C22—N21—S21 | 126.2 (3) | C42—N41—S41 | 125.6 (3) |
| | | |
N11—S11—S21—N21 | −83.59 (19) | N31—S31—S41—N41 | 92.9 (2) |
S21—S11—N11—C11 | −93.8 (4) | S41—S31—N31—C31 | −85.0 (4) |
S11—S21—N21—C21 | 83.7 (4) | S31—S41—N41—C41 | 80.3 (4) |
Hydrogen-bond geometry (Å, º) for (1) top
D—H···A | D—H | H···A | D···A | D—H···A |
C44—H44···O12 | 0.95 | 2.38 | 3.325 (5) | 171 |
C46—H46···O22i | 0.95 | 2.35 | 3.204 (6) | 150 |
C36—H36···O21ii | 0.95 | 2.39 | 3.112 (6) | 132 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, −y+1/2, z+1/2. |
Selected geometric parameters (Å, º) for (2) topS1—S1i | 2.0281 (10) | N1—C1 | 1.416 (2) |
S1—N1 | 1.6819 (13) | N1—C2 | 1.433 (2) |
| | | |
N1—S1—S1i | 105.41 (5) | C1—N1—S1 | 125.02 (11) |
C1—N1—C2 | 111.70 (13) | C2—N1—S1 | 123.27 (12) |
| | | |
N1—S1—S1i—N1i | 93.54 (7) | C2—N1—S1—S1i | 90.17 (12) |
C1—N1—S1—S1i | −90.03 (13) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
In each of N-(2-nitrophenylthio)phthalimide, (I) (Iwasaki & Masuko, 1986), N-(2-nitrophenylthio)succinimide, (II) (Low et al., 2000), and N-(2-nitrophenylthio)saccharin, (III) (Glidewell et al., 2000a), the molecular conformations are dominated by the near orthogonality of the lone pairs at N and S. Similarly in diaryl disulfides, RSSR', the molecular conformations are dominated by the near orthogonality of the lone pairs on the two adjacent S atoms (Glidewell et al., 2000b). Developing these earlier studies, and combining the themes of lone-pair orthogonality in >N—S– and –S—S– pairs, we have now investigated the structure of N,N'-dithiobisphthalimide, (IV), where the central N—S—S—N fragment comprises four contiguous atoms bearing lone pairs with those on adjacent atoms expected to be pairwise orthogonal. Compound (IV) has been obtained both as an unsolvated form and as two different solvates, to which the term `pseudo-polymorph' (Kooijman et al., 2000) can be applied; in these solvated forms, there are channels containing disordered solvent molecules.
The title compound, (IV), crystallizes from ethyl acetate to yield a solvent-free polymorph (1), which is monoclinic, with Z' = 2 in P21/c. The dimensions of the two independent molecules (Fig. 1) are very similar (Table 1), and the molecular conformations are determined by the N—S—S—N and C—N—S—S torsion angles, which are all close to 90° (Table 1), indicating that N and S lone pairs are approximately orthogonal. The five-membered rings are planar, with internal bond angles which are all considerably less than the ideal value of 120° for each of the planar three-connected atoms within this ring. All other bond distances and angles are typical of their types.
The molecules in polymorph (1) are linked into a continuous three-dimensional framework by a combination of C—H···O hydrogen bonds and aromatic π–π-stacking interactions. Molecule A, containing S11 and S21 (Fig. 1), is a triple acceptor of C—H···O hydrogen bonds, while molecule B, containing S31 and S41, is a triple donor (Table 1); these hydrogen-bonding characteristics and the molecular conformations (Fig. 1) together preclude the possibility of any higher symmetry.
Utilizing the substructure approach (Gregson et al., 2000), the three-dimensional framework structure can readily be analysed in terms of a cyclic centrosymmetric tetramer containing two molecules of each type, and thence in terms of the connections between these tetramers. Within the selected asymmetric unit (Fig. 1), atom C44 in molecule B acts as hydrogen-bond donor to O12 in molecule A (Table 2); at the same time, C46 in molecule B at (x, y, z) acts as donor to O22 in molecule A at (-x, -y, 1 - z), while C46 at (-x, -y, 1 - z) acts as donor to O22 at (x, y, z). These two hydrogen bonds thus generate a tetramer, characterized by an R44(26) motif centred at (0, 0, 1/2) (Fig. 2); the second such tetramer in the unit cell is centred at (0, 1/2, 0).
The tetramers are linked into chains by means of aromatic π–π-stacking interactions. Ring C43–C48 in molecule B at (x, y, z) forms a stacking interaction with ring C23–C28 in molecule A at (1 + x, y, z); the angle between the ring planes is 0.3 (2)° and the minimum perpendicular distance between the planes is 3.375 (3) Å, with a centroid offset of ca 1.62 Å (Fig. 3). The symmetry-related ring C43–C48 within the tetramer centred at (0, 0, 1/2) is at (-x, -y, 1 - z) and this forms a stacking interaction with ring C23–C28 at (-1 - x, -y, 1 - z); hence, these stacking interactions link the tetramers into a continuous chain running parallel to [100] and lying along the line (x, 0, 1/2).
Finally, the [100] chains are all weakly linked together by a third C—H···O hydrogen bond: C36 in molecule B at (x, y, z) acts as hydrogen-bond donor to O21 in molecule A at (1 + x, 0.5 - y, 0.5 + z). The molecules at (1 + x, 0.5 - y, 0.5 + z) form part of the tetramer centred at (1, 1/2, 1) whose other components are at (1 - x, 0.5 + y, 1.5 - z), and this tetramer is a component of the [100] chain along (x, 1/2, 1). Atom C36 at (1 + x, 0.5 - y, 0.5 + z) acts as donor to O21 at (2 + x, y, 1 + z), a component of the chain along (x, 0, 1/2), while C36 at (1 - x, 0.5 + y, 1.5 - z) is donor to O21 at (-x, 1 - y, 1 - z), a component of the chain along (x, 1, 1/2). Propagation of this hydrogen bond by the space group serves to link all of the [100] chains. Thus, for example, the chain along (x, 1/2, 1) is thereby linked to the four chains along (x, 0, 1/2), (x, 0, 1.5), (x, 1, 1/2) and (x, 1, 1.5). It must be emphasized that although the C36—H36···O21ii hydrogen bond is probably fairly weak [symmetry code: (ii) 1 + x, 0.5 - y, 0.5 + z], as judged by the C—H···O angle, in all of the C—H···O hydrogen bonds observed here, the unnormalized H···O distances are below 2.40 Å and the C···O distances are below 3.40 Å, well within the currently accepted limits for such interactions (Desiraju, 1991).
By contrast, the title compound crystallizes from both dichloromethane and from ethanol as a solvate, in space group C2/c, where the molecules lie across twofold rotation axes (Fig. 4). The solvated crystals obtained from dichloromethane, form (2), provided a much better data set at ambient temperature than those obtained from ethanol, form (3), did even at 150 (2) K. It is clear, however, from the unit-cell dimensions and the refined atom coordinates that these forms have the same structure, and therefore only that of form (2) will be discussed in detail. Nonetheless, it may be noted that the unit-cell volume of form (2) at 295 (2) K is slightly less than that of form (3) at 150 (2) K. The molecular dimensions and molecular conformation are essentially the same as found in form (1); the important differences occur in the supramolecular structure.
There are no C—H···O hydrogen bonds between the molecules of (IV) in forms (2) and (3), despite the presence of four carbonyl groups per molecule. The molecules are, however, weakly linked by means of aromatic π–π-stacking interactions. The aromatic ring at (x, y, z) is a component of the molecule lying across the twofold rotation axis along (1/2, y, 1/4): this ring forms a π–π-stacking interaction, across the inversion centre at (1/4, 1/4, 1/2), with the aromatic ring at (0.5 - x, 0.5 - y, 1 - z) which is a component of the molecule lying across the rotation axis along (0, y, 3/4). The interplanar spacing is 3.409 (2) Å and the centroid offset is 1.476 (2) Å, and propagation of this interaction by the space group generates a chain of π–π-stacked molecules running parallel to the [101] direction (Fig. 5). This chain is generated by the glide plane at y = 0.25 and it lies in the domain 0.07 < y < 0.43: a second, similar chain lying in the domain 0.57 < y < 0.93 is generated by the glide plane at y = 0.75.
The molecules in these chains occupy only some 79.5% of the total volume of the unit cell in form (2) [and 79.4% of the slightly larger unit cell in form (3)]: the remaining space comprises two continuous channels per unit cell, running parallel to the [001] direction (Fig. 6). The average cross-sectional area of each channel is ca 23.6 Å3 in form (2) and 24.3 Å3 in form (3), corresponding to an average diameter of ca 5.5 Å in both forms. In these solvated forms, the dichloromethane molecules in form (2) and ethanol molecules in form (3) occupy the channels between the N,N'-dithiodphthalimide molecules within which they are intractably disordered and, indeed, possibly mobile.
The SQUEEZE option in PLATON (Spek, 2001) indicated that in form (2), the electron density within the channels summed to 116 electrons per unit cell; this is most simply interpreted as 2.76 molecules of CH2Cl2 per unit cell. Similarly, in form (3), with 113 electrons per unit cell in the channels, this is most simply interpreted as 4.35 molecules of ethanol per unit cell. Alternative assignments, such as four molecules of ethanol and 0.9 molecules of water per cell are also possible. However, a definitive distinction between these (and other, similar) formulations is not possible from analytical and spectroscopic evidence only. The crucial point, however, regardless of the precise assignment, is the very low density of the solvent molecules within the channels, which increases the likelihood of their being continuously mobile. The occurrence of the channel-forms (2) and (3) at both 295 (2) and 150 (2) K indicates that the choice of polymorph, solvated versus unsolvated, is determined largely by the crystallization solvent, rather than by temperature. The absence of any C—H···O hydrogen bonding between the molecules in forms (2) and (3) is most readily rationalized in terms of the π–π-stacking and the presence of the solvent molecules. Atom O1 is adjacent to a channel and may be utilized in C—H···O hydrogen-bond formation by dichloromethane and in O—H···O hydrogen-bond formation by the ethanol molecules, while the geometry of the π–π-stacking interactions effectively precludes formation of C—H···O hydrogen bonds to either acceptor.
The striking difference found here between the solvent-free form (1), and the open-channel solvates (2) and (3) is sufficient to provide a serious challenge for the attempted prediction from first principles of the crystal structures of comparatively simple molecular compounds (Lommerse et al., 2000).