Buy article online - an online subscription or single-article purchase is required to access this article.
The rigid organic linkers
N-(4-bromophenylsulfonyl)dithiocarbimate(2−) and
N-(4-iodophenylsulfonyl)dithiocarbimate(2−) crystallize with two potassium cations and two water molecules in their asymmetric units, forming the title coordination polymers, [K
2(C
7H
4BrNO
2S
3)(H
2O)
2]
n and [K
2(C
7H
4INO
2S
3)(H
2O)
2]
n. The anions and the water molecules link the potassium cations into broad two-dimensional networks, which are further linked by K
halide interactions.
Supporting information
CCDC references: 914639; 914640
The title compounds were obtained as described previously (Franca et al.
2006). Yellowish single crystals of both (I) and (II) were obtained by
recrystallization from solution in ethanol:water (1:1 v/v)
mixtures.
C-bound H atoms were located in their geometric positions, with C—H = 0.93 Å, and with the Uiso(H) = 1.2Ueq(C). Water H atoms were
located from Δρ maps and their positions were refined, with Uiso(H)
= 1.5Ueq(O).
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(I) Poly[di-µ-aqua-[µ
6-
N-(4-
bromophenylsulfonyl)dithiocarbimato]dipotassium]
top
Crystal data top
[K2(C7H4BrNO2S3)(H2O)2] | F(000) = 840 |
Mr = 424.43 | Dx = 1.975 Mg m−3 Dm = 1.97 Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 856 reflections |
a = 6.1869 (12) Å | θ = 2.9–27.0° |
b = 7.2241 (14) Å | µ = 3.90 mm−1 |
c = 31.941 (6) Å | T = 295 K |
β = 90.42 (3)° | Parallelepiped, yellow |
V = 1427.6 (5) Å3 | 0.28 × 0.14 × 0.11 mm |
Z = 4 | |
Data collection top
Kuma KM-4 diffractometer with CCD detector | 3365 independent reflections |
Radiation source: fine-focus sealed tube | 1881 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
ω scans | θmax = 28.6°, θmin = 2.9° |
Absorption correction: numerical CrysAlis RED ( Oxford Diffraction, 2007) | h = −7→8 |
Tmin = 0.411, Tmax = 0.675 | k = −8→9 |
16622 measured reflections | l = −37→43 |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0419P)2] where P = (Fo2 + 2Fc2)/3 |
3365 reflections | (Δ/σ)max = 0.001 |
175 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
Crystal data top
[K2(C7H4BrNO2S3)(H2O)2] | V = 1427.6 (5) Å3 |
Mr = 424.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.1869 (12) Å | µ = 3.90 mm−1 |
b = 7.2241 (14) Å | T = 295 K |
c = 31.941 (6) Å | 0.28 × 0.14 × 0.11 mm |
β = 90.42 (3)° | |
Data collection top
Kuma KM-4 diffractometer with CCD detector | 3365 independent reflections |
Absorption correction: numerical CrysAlis RED ( Oxford Diffraction, 2007) | 1881 reflections with I > 2σ(I) |
Tmin = 0.411, Tmax = 0.675 | Rint = 0.080 |
16622 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.110 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.63 e Å−3 |
3365 reflections | Δρmin = −0.47 e Å−3 |
175 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
K1 | 0.7308 (2) | 0.35351 (18) | 0.02764 (4) | 0.0384 (3) | |
K2 | 0.66877 (19) | 0.76993 (17) | 0.10735 (4) | 0.0360 (3) | |
Br1 | 1.50252 (10) | 0.35087 (9) | 0.290276 (18) | 0.0431 (2) | |
C1 | 1.0822 (8) | 0.2672 (7) | 0.17087 (16) | 0.0261 (13) | |
C2 | 1.2908 (9) | 0.3379 (8) | 0.16832 (17) | 0.0365 (14) | |
H2 | 1.3491 | 0.3672 | 0.1424 | 0.044* | |
C3 | 1.4087 (9) | 0.3640 (7) | 0.20370 (17) | 0.0343 (14) | |
H3 | 1.5461 | 0.4158 | 0.2021 | 0.041* | |
C4 | 1.3265 (10) | 0.3142 (8) | 0.24232 (16) | 0.0332 (14) | |
C5 | 1.1236 (9) | 0.2450 (8) | 0.24508 (16) | 0.0365 (15) | |
H5 | 1.0674 | 0.2154 | 0.2712 | 0.044* | |
C6 | 1.0004 (9) | 0.2182 (8) | 0.20973 (17) | 0.0349 (14) | |
H6 | 0.8627 | 0.1675 | 0.2117 | 0.042* | |
S3 | 0.9207 (2) | 0.2479 (2) | 0.12510 (4) | 0.0282 (3) | |
O1 | 0.7504 (6) | 0.1171 (5) | 0.13255 (11) | 0.0360 (10) | |
O2 | 0.8446 (6) | 0.4325 (5) | 0.11534 (11) | 0.0383 (10) | |
N1 | 1.0774 (7) | 0.1956 (6) | 0.08663 (12) | 0.0272 (11) | |
C7 | 1.1834 (7) | 0.0316 (7) | 0.08480 (15) | 0.0234 (12) | |
S1 | 1.1699 (2) | −0.1426 (2) | 0.12082 (4) | 0.0309 (3) | |
S2 | 1.3424 (2) | 0.0047 (2) | 0.04102 (4) | 0.0343 (4) | |
O3 | 0.3396 (7) | 0.5089 (6) | 0.05540 (13) | 0.0401 (11) | |
H31 | 0.259 (10) | 0.413 (9) | 0.0585 (19) | 0.060* | |
H32 | 0.304 (11) | 0.584 (9) | 0.071 (2) | 0.060* | |
O4 | 0.8796 (7) | 0.7196 (7) | 0.02613 (14) | 0.0456 (12) | |
H41 | 0.980 (11) | 0.755 (10) | 0.037 (2) | 0.068* | |
H42 | 0.827 (11) | 0.806 (9) | 0.0092 (19) | 0.068* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
K1 | 0.0469 (8) | 0.0371 (8) | 0.0311 (7) | 0.0072 (7) | 0.0003 (6) | −0.0004 (6) |
K2 | 0.0273 (6) | 0.0322 (8) | 0.0485 (8) | 0.0058 (6) | −0.0011 (6) | −0.0056 (6) |
Br1 | 0.0514 (4) | 0.0450 (4) | 0.0326 (3) | −0.0025 (3) | −0.0086 (3) | −0.0051 (3) |
C1 | 0.036 (3) | 0.022 (3) | 0.020 (3) | 0.006 (3) | 0.000 (2) | −0.006 (2) |
C2 | 0.039 (4) | 0.038 (4) | 0.033 (3) | −0.003 (3) | 0.002 (3) | 0.002 (3) |
C3 | 0.032 (3) | 0.028 (4) | 0.043 (4) | −0.002 (3) | 0.001 (3) | 0.001 (3) |
C4 | 0.047 (4) | 0.028 (4) | 0.025 (3) | 0.010 (3) | −0.013 (3) | −0.004 (2) |
C5 | 0.044 (4) | 0.048 (4) | 0.017 (3) | −0.005 (3) | 0.013 (3) | −0.002 (3) |
C6 | 0.031 (3) | 0.044 (4) | 0.030 (3) | −0.003 (3) | 0.005 (3) | 0.003 (3) |
S3 | 0.0319 (8) | 0.0245 (8) | 0.0281 (7) | 0.0042 (7) | −0.0006 (6) | −0.0018 (7) |
O1 | 0.028 (2) | 0.029 (2) | 0.050 (2) | −0.0007 (18) | 0.0018 (18) | −0.0108 (19) |
O2 | 0.047 (2) | 0.025 (2) | 0.042 (2) | 0.016 (2) | −0.0082 (19) | 0.0024 (18) |
N1 | 0.038 (3) | 0.028 (3) | 0.015 (2) | 0.007 (2) | 0.000 (2) | −0.0012 (19) |
C7 | 0.017 (3) | 0.025 (3) | 0.028 (3) | −0.002 (2) | −0.004 (2) | −0.004 (2) |
S1 | 0.0293 (7) | 0.0286 (8) | 0.0350 (8) | 0.0042 (7) | 0.0024 (6) | 0.0076 (7) |
S2 | 0.0408 (9) | 0.0319 (9) | 0.0303 (8) | 0.0055 (7) | 0.0091 (7) | −0.0013 (7) |
O3 | 0.049 (3) | 0.034 (3) | 0.038 (3) | 0.002 (2) | 0.007 (2) | −0.002 (2) |
O4 | 0.046 (3) | 0.050 (3) | 0.040 (3) | 0.000 (2) | −0.010 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
K1—O4 | 2.801 (5) | C2—H2 | 0.9300 |
K1—O3 | 2.817 (4) | C3—C4 | 1.385 (7) |
K1—O3i | 2.863 (4) | C3—H3 | 0.9300 |
K1—O2 | 2.939 (4) | C4—C5 | 1.355 (7) |
K1—O4ii | 3.016 (5) | C5—C6 | 1.372 (7) |
K1—N1 | 3.065 (4) | C5—H5 | 0.9300 |
K1—S2iii | 3.420 (2) | C6—H6 | 0.9300 |
K2—O1iv | 2.681 (4) | S3—O1 | 1.436 (4) |
K2—O2 | 2.681 (4) | S3—O2 | 1.447 (4) |
K2—O4 | 2.935 (5) | S3—N1 | 1.616 (4) |
K2—S1v | 3.1827 (19) | N1—C7 | 1.355 (6) |
K2—S1iv | 3.1902 (19) | C7—S1 | 1.708 (5) |
K2—O3 | 3.226 (4) | C7—S2 | 1.727 (5) |
K2—S2v | 3.373 (2) | O3—H31 | 0.86 (6) |
C1—C6 | 1.390 (7) | O3—H32 | 0.76 (6) |
C1—C2 | 1.391 (7) | O4—H41 | 0.75 (6) |
C1—S3 | 1.771 (5) | O4—H42 | 0.89 (7) |
C2—C3 | 1.354 (7) | | |
| | | |
K2···Br1vi | 3.4941 (16) | | |
| | | |
O4—K1—O3 | 84.98 (14) | S1iv—K2—K1iv | 79.72 (4) |
O4—K1—O3i | 72.79 (13) | O3—K2—K1iv | 106.54 (9) |
O3—K1—O3i | 91.62 (12) | S2v—K2—K1iv | 45.23 (3) |
O4—K1—O2 | 75.92 (12) | Br1vi—K2—K1iv | 111.39 (3) |
O3—K1—O2 | 79.81 (12) | K1—K2—K1iv | 107.97 (4) |
O3i—K1—O2 | 148.15 (13) | O1iv—K2—K1i | 120.87 (9) |
O4—K1—O4ii | 83.76 (15) | O2—K2—K1i | 96.71 (9) |
O3—K1—O4ii | 160.21 (13) | O4—K2—K1i | 55.92 (9) |
O3i—K1—O4ii | 69.51 (13) | S1v—K2—K1i | 71.36 (4) |
O2—K1—O4ii | 112.94 (12) | S1iv—K2—K1i | 128.40 (5) |
O4—K1—N1 | 97.66 (13) | O3—K2—K1i | 31.97 (8) |
O3—K1—N1 | 123.63 (12) | S2v—K2—K1i | 42.54 (3) |
O3i—K1—N1 | 143.11 (12) | Br1vi—K2—K1i | 132.91 (4) |
O2—K1—N1 | 47.51 (10) | K1—K2—K1i | 50.52 (3) |
O4ii—K1—N1 | 74.12 (12) | K1iv—K2—K1i | 75.48 (3) |
O4—K1—S3 | 96.66 (10) | O1iv—K2—H32 | 135.0 (13) |
O3—K1—S3 | 95.34 (10) | O2—K2—H32 | 86.0 (13) |
O3i—K1—S3 | 166.83 (10) | O4—K2—H32 | 86.3 (13) |
O2—K1—S3 | 25.01 (7) | S1v—K2—H32 | 52.3 (13) |
O4ii—K1—S3 | 102.08 (10) | S1iv—K2—H32 | 155.3 (12) |
N1—K1—S3 | 28.29 (8) | O3—K2—H32 | 12.7 (12) |
O4—K1—S2iii | 138.19 (11) | S2v—K2—H32 | 61.0 (13) |
O3—K1—S2iii | 113.17 (10) | Br1vi—K2—H32 | 102.5 (13) |
O3i—K1—S2iii | 69.51 (10) | K1—K2—H32 | 57.4 (12) |
O2—K1—S2iii | 141.96 (9) | K1iv—K2—H32 | 104.7 (13) |
O4ii—K1—S2iii | 66.73 (9) | K1i—K2—H32 | 35.7 (13) |
N1—K1—S2iii | 101.61 (9) | O1iv—K2—H41 | 98.0 (13) |
S3—K1—S2iii | 117.36 (5) | O2—K2—H41 | 76.9 (14) |
O4—K1—S2vii | 154.87 (11) | O4—K2—H41 | 14.6 (12) |
O3—K1—S2vii | 69.96 (10) | S1v—K2—H41 | 138.1 (13) |
O3i—K1—S2vii | 105.22 (10) | S1iv—K2—H41 | 58.3 (13) |
O2—K1—S2vii | 100.53 (9) | O3—K2—H41 | 90.0 (13) |
O4ii—K1—S2vii | 119.62 (10) | S2v—K2—H41 | 86.1 (13) |
N1—K1—S2vii | 97.73 (9) | Br1vi—K2—H41 | 156.4 (13) |
S3—K1—S2vii | 87.69 (5) | K1—K2—H41 | 54.5 (13) |
S2iii—K1—S2vii | 56.45 (5) | K1iv—K2—H41 | 65.7 (13) |
O4—K1—K1i | 73.97 (10) | K1i—K2—H41 | 70.3 (13) |
O3—K1—K1i | 46.28 (9) | H32—K2—H41 | 100.7 (17) |
O3i—K1—K1i | 45.34 (9) | C4—Br1—K2viii | 123.89 (19) |
O2—K1—K1i | 119.23 (9) | C6—C1—C2 | 119.4 (5) |
O4ii—K1—K1i | 114.61 (10) | C6—C1—S3 | 120.7 (4) |
N1—K1—K1i | 166.49 (9) | C2—C1—S3 | 119.9 (4) |
S3—K1—K1i | 140.38 (6) | C3—C2—C1 | 119.8 (5) |
S2iii—K1—K1i | 91.54 (5) | C3—C2—H2 | 120.1 |
S2vii—K1—K1i | 86.90 (5) | C1—C2—H2 | 120.1 |
O4—K1—K2 | 47.74 (10) | C2—C3—C4 | 120.5 (5) |
O3—K1—K2 | 53.67 (10) | C2—C3—H3 | 119.7 |
O3i—K1—K2 | 108.49 (9) | C4—C3—H3 | 119.7 |
O2—K1—K2 | 42.59 (7) | C5—C4—C3 | 120.0 (5) |
O4ii—K1—K2 | 125.48 (10) | C5—C4—Br1 | 121.8 (4) |
N1—K1—K2 | 87.60 (8) | C3—C4—Br1 | 118.1 (4) |
S3—K1—K2 | 67.49 (4) | C4—C5—C6 | 120.5 (5) |
S2iii—K1—K2 | 166.84 (5) | C4—C5—H5 | 119.7 |
S2vii—K1—K2 | 113.41 (5) | C6—C5—H5 | 119.7 |
K1i—K1—K2 | 78.92 (5) | C5—C6—C1 | 119.7 (5) |
O4—K1—K1ii | 43.78 (10) | C5—C6—H6 | 120.2 |
O3—K1—K1ii | 126.75 (11) | C1—C6—H6 | 120.2 |
O3i—K1—K1ii | 64.22 (10) | O1—S3—O2 | 113.8 (2) |
O2—K1—K1ii | 96.55 (9) | O1—S3—N1 | 114.7 (2) |
O4ii—K1—K1ii | 39.98 (9) | O2—S3—N1 | 104.3 (2) |
N1—K1—K1ii | 84.01 (9) | O1—S3—C1 | 109.0 (2) |
S3—K1—K1ii | 102.75 (5) | O2—S3—C1 | 106.6 (2) |
S2iii—K1—K1ii | 101.94 (5) | N1—S3—C1 | 107.9 (2) |
S2vii—K1—K1ii | 158.30 (6) | O1—S3—K1 | 92.88 (16) |
K1i—K1—K1ii | 96.39 (5) | O2—S3—K1 | 59.15 (15) |
K2—K1—K1ii | 88.24 (5) | N1—S3—K1 | 64.04 (15) |
O1iv—K2—O2 | 138.30 (12) | C1—S3—K1 | 157.81 (19) |
O1iv—K2—O4 | 107.29 (12) | S3—O1—K2ix | 134.6 (2) |
O2—K2—O4 | 77.81 (13) | S3—O2—K2 | 171.7 (2) |
O1iv—K2—S1v | 87.40 (8) | S3—O2—K1 | 95.84 (18) |
O2—K2—S1v | 124.11 (10) | K2—O2—K1 | 89.51 (11) |
O4—K2—S1v | 125.58 (10) | C7—N1—S3 | 122.0 (3) |
O1iv—K2—S1iv | 66.01 (8) | C7—N1—K1 | 129.4 (3) |
O2—K2—S1iv | 76.94 (9) | S3—N1—K1 | 87.67 (17) |
O4—K2—S1iv | 72.89 (9) | N1—C7—S1 | 126.1 (4) |
S1v—K2—S1iv | 152.25 (7) | N1—C7—S2 | 114.3 (4) |
O1iv—K2—O3 | 144.89 (12) | S1—C7—S2 | 119.6 (3) |
O2—K2—O3 | 76.81 (12) | C7—S1—K2x | 90.18 (17) |
O4—K2—O3 | 75.88 (11) | C7—S1—K2ix | 96.15 (17) |
S1v—K2—O3 | 64.93 (8) | K2x—S1—K2ix | 152.25 (7) |
S1iv—K2—O3 | 142.60 (9) | C7—S2—K2x | 83.68 (17) |
O1iv—K2—S2v | 80.14 (9) | C7—S2—K1iii | 122.06 (18) |
O2—K2—S2v | 139.25 (9) | K2x—S2—K1iii | 95.63 (5) |
O4—K2—S2v | 77.00 (10) | C7—S2—K1xi | 114.37 (18) |
S1v—K2—S2v | 53.74 (4) | K2x—S2—K1xi | 91.74 (5) |
S1iv—K2—S2v | 124.18 (5) | K1iii—S2—K1xi | 123.55 (5) |
O3—K2—S2v | 66.30 (9) | K1—O3—K1i | 88.38 (12) |
O1iv—K2—Br1vi | 67.68 (8) | K1—O3—K2 | 81.61 (12) |
O2—K2—Br1vi | 100.88 (9) | K1i—O3—K2 | 111.39 (14) |
O4—K2—Br1vi | 171.04 (9) | K1—O3—H31 | 102 (4) |
S1v—K2—Br1vi | 62.56 (4) | K1i—O3—H31 | 108 (4) |
S1iv—K2—Br1vi | 98.15 (5) | K2—O3—H31 | 141 (4) |
O3—K2—Br1vi | 112.61 (8) | K1—O3—H32 | 137 (5) |
S2v—K2—Br1vi | 108.62 (4) | K1i—O3—H32 | 108 (5) |
O1iv—K2—K1 | 152.18 (9) | K2—O3—H32 | 56 (5) |
O2—K2—K1 | 47.90 (8) | H31—O3—H32 | 109 (7) |
O4—K2—K1 | 44.93 (10) | K1—O4—K2 | 87.33 (14) |
S1v—K2—K1 | 109.64 (5) | K1—O4—K1ii | 96.24 (15) |
S1iv—K2—K1 | 97.96 (5) | K2—O4—K1ii | 152.52 (17) |
O3—K2—K1 | 44.71 (8) | K1—O4—H41 | 125 (6) |
S2v—K2—K1 | 92.21 (4) | K2—O4—H41 | 85 (6) |
Br1vi—K2—K1 | 139.47 (4) | K1ii—O4—H41 | 70 (5) |
O1iv—K2—K1iv | 48.80 (8) | K1—O4—H42 | 124 (4) |
O2—K2—K1iv | 142.36 (9) | K2—O4—H42 | 107 (4) |
O4—K2—K1iv | 67.27 (10) | K1ii—O4—H42 | 94 (4) |
S1v—K2—K1iv | 88.82 (4) | H41—O4—H42 | 110 (7) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z; (iii) −x+2, −y, −z; (iv) x, y+1, z; (v) x−1, y+1, z; (vi) −x+2, y+1/2, −z+1/2; (vii) x−1, y, z; (viii) −x+2, y−1/2, −z+1/2; (ix) x, y−1, z; (x) x+1, y−1, z; (xi) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···N1vii | 0.86 (6) | 2.13 (6) | 2.962 (6) | 162 (6) |
O3—H32···S1v | 0.76 (6) | 2.68 (6) | 3.440 (4) | 177 (7) |
O4—H41···S2iv | 0.75 (6) | 2.88 (7) | 3.556 (5) | 150 (7) |
O4—H42···S2ii | 0.89 (7) | 2.35 (7) | 3.227 (5) | 171 (6) |
Symmetry codes: (ii) −x+2, −y+1, −z; (iv) x, y+1, z; (v) x−1, y+1, z; (vii) x−1, y, z. |
(II) Poly[di-µ-aqua-[µ
4-
N-(4-
iodophenylsulfonyl)dithiocarbimato]dipotassium]
top
Crystal data top
[K2(C7H4INO2S3)(H2O)2] | F(000) = 912 |
Mr = 471.42 | Dx = 2.089 Mg m−3 Dm = 2.08 Mg m−3 Dm measured by flotation |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 687 reflections |
a = 16.155 (3) Å | θ = 3.0–27.5° |
b = 6.3794 (13) Å | µ = 3.11 mm−1 |
c = 14.549 (3) Å | T = 295 K |
β = 91.86 (3)° | Parallelepiped, yellow |
V = 1498.7 (5) Å3 | 0.28 × 0.14 × 0.11 mm |
Z = 4 | |
Data collection top
Kuma KM-4 diffractometer with CCD detector | 3712 independent reflections |
Radiation source: fine-focus sealed tube | 2653 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 29.0°, θmin = 3.0° |
Absorption correction: numerical CrysAlis RED ( Oxford Diffraction, 2007) | h = −21→21 |
Tmin = 0.479, Tmax = 0.728 | k = −8→5 |
18295 measured reflections | l = −18→19 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.024P)2] where P = (Fo2 + 2Fc2)/3 |
3712 reflections | (Δ/σ)max = 0.002 |
175 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.87 e Å−3 |
Crystal data top
[K2(C7H4INO2S3)(H2O)2] | V = 1498.7 (5) Å3 |
Mr = 471.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.155 (3) Å | µ = 3.11 mm−1 |
b = 6.3794 (13) Å | T = 295 K |
c = 14.549 (3) Å | 0.28 × 0.14 × 0.11 mm |
β = 91.86 (3)° | |
Data collection top
Kuma KM-4 diffractometer with CCD detector | 3712 independent reflections |
Absorption correction: numerical CrysAlis RED ( Oxford Diffraction, 2007) | 2653 reflections with I > 2σ(I) |
Tmin = 0.479, Tmax = 0.728 | Rint = 0.044 |
18295 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.89 e Å−3 |
3712 reflections | Δρmin = −0.87 e Å−3 |
175 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
K1 | 0.94257 (4) | 0.32931 (12) | 0.17673 (5) | 0.0474 (2) | |
K2 | 0.78812 (4) | 0.15291 (10) | 0.39108 (4) | 0.03357 (16) | |
I1 | 0.425239 (12) | 1.02845 (3) | 0.628119 (16) | 0.04446 (8) | |
C1 | 0.66742 (16) | 0.5846 (4) | 0.62402 (18) | 0.0257 (6) | |
C2 | 0.67515 (17) | 0.7878 (4) | 0.6565 (2) | 0.0325 (7) | |
H2 | 0.7268 | 0.8404 | 0.6747 | 0.039* | |
C3 | 0.60516 (18) | 0.9117 (5) | 0.6615 (2) | 0.0349 (7) | |
H3 | 0.6095 | 1.0487 | 0.6830 | 0.042* | |
C4 | 0.52888 (17) | 0.8309 (4) | 0.63450 (19) | 0.0295 (7) | |
C5 | 0.52129 (18) | 0.6254 (5) | 0.6059 (2) | 0.0362 (7) | |
H5 | 0.4693 | 0.5701 | 0.5910 | 0.043* | |
C6 | 0.59095 (18) | 0.5027 (4) | 0.5996 (2) | 0.0336 (7) | |
H6 | 0.5864 | 0.3651 | 0.5790 | 0.040* | |
S3 | 0.75653 (4) | 0.42488 (11) | 0.61685 (5) | 0.02754 (17) | |
O1 | 0.73725 (13) | 0.2514 (3) | 0.55665 (13) | 0.0367 (5) | |
O2 | 0.78083 (12) | 0.3627 (3) | 0.70952 (13) | 0.0386 (5) | |
N1 | 0.83201 (13) | 0.5704 (3) | 0.58595 (15) | 0.0273 (5) | |
C7 | 0.83282 (16) | 0.6712 (4) | 0.50487 (18) | 0.0250 (6) | |
S1 | 0.75896 (5) | 0.65259 (11) | 0.41794 (5) | 0.02992 (17) | |
S2 | 0.91817 (5) | 0.83120 (12) | 0.49106 (5) | 0.03318 (18) | |
O3 | 0.90292 (15) | 0.7276 (5) | 0.24635 (17) | 0.0523 (7) | |
H31 | 0.885 (2) | 0.801 (6) | 0.204 (3) | 0.079* | |
H32 | 0.869 (2) | 0.726 (6) | 0.284 (3) | 0.079* | |
O4 | 0.94218 (16) | 0.3527 (4) | 0.36815 (17) | 0.0522 (7) | |
H41 | 0.934 (3) | 0.463 (6) | 0.386 (3) | 0.078* | |
H42 | 0.978 (2) | 0.303 (6) | 0.399 (3) | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
K1 | 0.0380 (4) | 0.0672 (5) | 0.0371 (4) | −0.0022 (4) | 0.0033 (3) | −0.0012 (4) |
K2 | 0.0437 (4) | 0.0319 (4) | 0.0254 (3) | 0.0013 (3) | 0.0048 (3) | −0.0016 (3) |
I1 | 0.03126 (12) | 0.04811 (15) | 0.05430 (15) | 0.00669 (10) | 0.00566 (9) | −0.00461 (11) |
C1 | 0.0279 (15) | 0.0306 (16) | 0.0191 (14) | 0.0003 (13) | 0.0058 (12) | −0.0010 (12) |
C2 | 0.0248 (15) | 0.0350 (17) | 0.0378 (18) | −0.0050 (13) | 0.0018 (13) | −0.0022 (14) |
C3 | 0.0355 (17) | 0.0278 (16) | 0.0417 (19) | −0.0020 (14) | 0.0042 (14) | −0.0046 (14) |
C4 | 0.0267 (15) | 0.0349 (18) | 0.0273 (16) | 0.0033 (13) | 0.0046 (12) | 0.0037 (13) |
C5 | 0.0274 (16) | 0.0420 (19) | 0.0391 (18) | −0.0065 (14) | −0.0019 (14) | −0.0008 (16) |
C6 | 0.0380 (17) | 0.0293 (17) | 0.0333 (17) | −0.0042 (14) | 0.0003 (13) | −0.0079 (14) |
S3 | 0.0326 (4) | 0.0303 (4) | 0.0201 (4) | 0.0028 (3) | 0.0062 (3) | 0.0043 (3) |
O1 | 0.0505 (13) | 0.0282 (11) | 0.0322 (12) | −0.0013 (10) | 0.0133 (10) | −0.0023 (9) |
O2 | 0.0444 (13) | 0.0470 (13) | 0.0248 (11) | 0.0082 (10) | 0.0064 (9) | 0.0116 (10) |
N1 | 0.0254 (12) | 0.0344 (14) | 0.0221 (12) | 0.0006 (11) | 0.0024 (10) | 0.0033 (11) |
C7 | 0.0262 (14) | 0.0251 (15) | 0.0239 (14) | 0.0047 (12) | 0.0060 (12) | −0.0024 (12) |
S1 | 0.0350 (4) | 0.0284 (4) | 0.0260 (4) | −0.0014 (3) | −0.0042 (3) | 0.0024 (3) |
S2 | 0.0278 (4) | 0.0398 (5) | 0.0321 (4) | −0.0051 (3) | 0.0029 (3) | 0.0048 (4) |
O3 | 0.0431 (15) | 0.0783 (19) | 0.0359 (15) | 0.0120 (14) | 0.0058 (11) | 0.0125 (13) |
O4 | 0.0495 (15) | 0.0640 (19) | 0.0431 (15) | 0.0210 (14) | −0.0011 (12) | 0.0044 (13) |
Geometric parameters (Å, º) top
K1—O4 | 2.789 (3) | C2—H2 | 0.9300 |
K1—O3 | 2.817 (3) | C3—C4 | 1.381 (4) |
K1—O3i | 2.779 (3) | C3—H3 | 0.9300 |
K1—O2ii | 2.939 (2) | C4—C5 | 1.379 (4) |
K1—N1ii | 3.359 (2) | C5—C6 | 1.377 (4) |
K1—S2i | 3.3734 (12) | C5—H5 | 0.9300 |
K1—S2iii | 3.4749 (12) | C6—H6 | 0.9300 |
K2—O2ii | 2.642 (2) | S3—O1 | 1.439 (2) |
K2—O1 | 2.646 (2) | S3—O2 | 1.4474 (19) |
K2—O4 | 2.826 (3) | S3—N1 | 1.608 (2) |
K2—S1 | 3.248 (2) | N1—C7 | 1.344 (3) |
K2—S1iv | 3.252 (2) | C7—S1 | 1.714 (3) |
K2—S2iv | 3.248 (2) | C7—S2 | 1.732 (3) |
I1—C4 | 2.095 (3) | O3—H31 | 0.82 (4) |
C1—C6 | 1.377 (4) | O3—H32 | 0.79 (4) |
C1—C2 | 1.384 (4) | O4—H41 | 0.76 (4) |
C1—S3 | 1.770 (3) | O4—H42 | 0.79 (4) |
C2—C3 | 1.384 (4) | | |
| | | |
K2···I1v | 3.6380 (10) | | |
| | | |
O3i—K1—O4 | 68.99 (8) | O2—S3—C1 | 107.43 (12) |
O3i—K1—O3 | 106.11 (8) | N1—S3—C1 | 108.05 (12) |
O4—K1—O3 | 65.47 (7) | O1—S3—K1vi | 87.84 (9) |
O3i—K1—O2ii | 128.98 (7) | O2—S3—K1vi | 55.70 (8) |
O4—K1—O2ii | 80.17 (7) | N1—S3—K1vi | 71.59 (8) |
O3—K1—O2ii | 95.96 (7) | C1—S3—K1vi | 161.04 (9) |
O3i—K1—N1ii | 116.13 (7) | O2—S3—K2 | 130.25 (9) |
O4—K1—N1ii | 114.50 (7) | N1—S3—K2 | 84.06 (9) |
O3—K1—N1ii | 134.58 (7) | C1—S3—K2 | 116.77 (9) |
O2ii—K1—N1ii | 44.21 (5) | K1vi—S3—K2 | 82.18 (3) |
O2ii—K2—O1 | 156.06 (7) | S3—O1—K2 | 132.01 (11) |
O2ii—K2—O4 | 84.82 (7) | S3—O2—K2vi | 160.64 (12) |
O1—K2—O4 | 107.53 (7) | S3—O2—K1vi | 100.30 (10) |
O2ii—K2—I1v | 84.26 (5) | K2vi—O2—K1vi | 97.80 (7) |
O1—K2—I1v | 79.86 (5) | C7—N1—S3 | 123.41 (19) |
O4—K2—I1v | 166.01 (5) | C7—N1—K1vi | 133.49 (17) |
S2iv—K2—I1v | 115.53 (3) | S3—N1—K1vi | 81.39 (9) |
S1—K2—I1v | 100.40 (2) | N1—C7—S1 | 126.0 (2) |
S1iv—K2—I1v | 63.672 (18) | N1—C7—S2 | 114.5 (2) |
C4—I1—K2v | 124.46 (8) | S1—C7—S2 | 119.52 (16) |
C6—C1—C2 | 120.9 (3) | C7—S1—K2 | 93.25 (9) |
C6—C1—S3 | 119.4 (2) | C7—S1—K2vii | 85.44 (9) |
C2—C1—S3 | 119.7 (2) | K2—S1—K2vii | 157.94 (3) |
C3—C2—C1 | 119.2 (3) | C7—S2—K2vii | 85.32 (9) |
C3—C2—H2 | 120.4 | C7—S2—K1viii | 129.35 (9) |
C1—C2—H2 | 120.4 | K2vii—S2—K1viii | 96.61 (3) |
C4—C3—C2 | 119.6 (3) | C7—S2—K1ix | 110.34 (9) |
C4—C3—H3 | 120.2 | K2vii—S2—K1ix | 90.56 (3) |
C2—C3—H3 | 120.2 | K1viii—S2—K1ix | 120.22 (3) |
C5—C4—C3 | 120.7 (3) | K1viii—O3—K1 | 98.26 (8) |
C5—C4—I1 | 119.7 (2) | K1viii—O3—H31 | 117 (3) |
C3—C4—I1 | 119.5 (2) | K1—O3—H31 | 109 (3) |
C6—C5—C4 | 119.7 (3) | K1viii—O3—H32 | 112 (3) |
C6—C5—H5 | 120.1 | K1—O3—H32 | 114 (3) |
C4—C5—H5 | 120.1 | H31—O3—H32 | 108 (4) |
C5—C6—C1 | 119.7 (3) | K1—O4—K2 | 97.15 (9) |
C5—C6—H6 | 120.2 | K1—O4—H41 | 114 (4) |
C1—C6—H6 | 120.2 | K2—O4—H41 | 102 (3) |
O1—S3—O2 | 113.76 (12) | K1—O4—H42 | 121 (3) |
O1—S3—N1 | 115.13 (12) | K2—O4—H42 | 113 (3) |
O2—S3—N1 | 103.50 (12) | H41—O4—H42 | 108 (4) |
O1—S3—C1 | 108.55 (13) | | |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, y−1, z; (v) −x+1, −y+1, −z+1; (vi) x, −y+1/2, z+1/2; (vii) x, y+1, z; (viii) −x+2, y+1/2, −z+1/2; (ix) x, −y+3/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···N1iii | 0.82 (4) | 2.06 (4) | 2.871 (3) | 168 (4) |
O3—H32···S1 | 0.79 (4) | 2.72 (4) | 3.500 (3) | 170 (4) |
O4—H41···S2 | 0.76 (4) | 2.82 (4) | 3.565 (3) | 167 (4) |
O4—H42···S2x | 0.79 (4) | 2.43 (4) | 3.219 (3) | 173 (4) |
Symmetry codes: (iii) x, −y+3/2, z−1/2; (x) −x+2, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [K2(C7H4BrNO2S3)(H2O)2] | [K2(C7H4INO2S3)(H2O)2] |
Mr | 424.43 | 471.42 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 6.1869 (12), 7.2241 (14), 31.941 (6) | 16.155 (3), 6.3794 (13), 14.549 (3) |
β (°) | 90.42 (3) | 91.86 (3) |
V (Å3) | 1427.6 (5) | 1498.7 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 3.90 | 3.11 |
Crystal size (mm) | 0.28 × 0.14 × 0.11 | 0.28 × 0.14 × 0.11 |
|
Data collection |
Diffractometer | Kuma KM-4 diffractometer with CCD detector | Kuma KM-4 diffractometer with CCD detector |
Absorption correction | Numerical CrysAlis RED ( Oxford Diffraction, 2007) | Numerical CrysAlis RED ( Oxford Diffraction, 2007) |
Tmin, Tmax | 0.411, 0.675 | 0.479, 0.728 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16622, 3365, 1881 | 18295, 3712, 2653 |
Rint | 0.080 | 0.044 |
(sin θ/λ)max (Å−1) | 0.674 | 0.683 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.110, 1.00 | 0.032, 0.059, 1.01 |
No. of reflections | 3365 | 3712 |
No. of parameters | 175 | 175 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.63, −0.47 | 0.89, −0.87 |
Selected interatomic distances (Å) for (I) topK1—O4 | 2.801 (5) | K2—O1iv | 2.681 (4) |
K1—O3 | 2.817 (4) | K2—O2 | 2.681 (4) |
K1—O3i | 2.863 (4) | K2—O4 | 2.935 (5) |
K1—O2 | 2.939 (4) | K2—S1v | 3.1827 (19) |
K1—O4ii | 3.016 (5) | K2—S1iv | 3.1902 (19) |
K1—N1 | 3.065 (4) | K2—O3 | 3.226 (4) |
K1—S2iii | 3.420 (2) | K2—S2v | 3.373 (2) |
| | | |
K2···Br1vi | 3.4941 (16) | | |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z; (iii) −x+2, −y, −z; (iv) x, y+1, z; (v) x−1, y+1, z; (vi) −x+2, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···N1vii | 0.86 (6) | 2.13 (6) | 2.962 (6) | 162 (6) |
O3—H32···S1v | 0.76 (6) | 2.68 (6) | 3.440 (4) | 177 (7) |
O4—H41···S2iv | 0.75 (6) | 2.88 (7) | 3.556 (5) | 150 (7) |
O4—H42···S2ii | 0.89 (7) | 2.35 (7) | 3.227 (5) | 171 (6) |
Symmetry codes: (ii) −x+2, −y+1, −z; (iv) x, y+1, z; (v) x−1, y+1, z; (vii) x−1, y, z. |
Selected interatomic distances (Å) for (II) topK1—O4 | 2.789 (3) | K2—O2ii | 2.642 (2) |
K1—O3 | 2.817 (3) | K2—O1 | 2.646 (2) |
K1—O3i | 2.779 (3) | K2—O4 | 2.826 (3) |
K1—O2ii | 2.939 (2) | K2—S1 | 3.248 (2) |
K1—N1ii | 3.359 (2) | K2—S1iv | 3.252 (2) |
K1—S2i | 3.3734 (12) | K2—S2iv | 3.248 (2) |
K1—S2iii | 3.4749 (12) | | |
| | | |
K2···I1v | 3.6380 (10) | | |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) x, y−1, z; (v) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H31···N1iii | 0.82 (4) | 2.06 (4) | 2.871 (3) | 168 (4) |
O3—H32···S1 | 0.79 (4) | 2.72 (4) | 3.500 (3) | 170 (4) |
O4—H41···S2 | 0.76 (4) | 2.82 (4) | 3.565 (3) | 167 (4) |
O4—H42···S2vi | 0.79 (4) | 2.43 (4) | 3.219 (3) | 173 (4) |
Symmetry codes: (iii) x, −y+3/2, z−1/2; (vi) −x+2, −y+1, −z+1. |
Comparison of C—S distances (Å) in related structures topStructure | Cation | C—S |
(I) | K | 1.708 (5), 1.727 (5) |
(II) | K | 1.714 (3), 1.732 (3) |
(III)a | Zn | 1.738 (3), 1.739 (3) |
(IV)b | Ni | 1.734 (3), 1.738 (3) |
(V)c | Ni | 1.725 (3), 1.764 (3) |
(VI)d | Ni | 1.735 (3), 1.737 (3) |
References: (a) Alves et al. (2009); (b) Franca et al.
(2006);
(c) Oliveira et al. (2002); (d) Oliveira et al.
(2011). |
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.
The chemistry of dithiocarbamates (R2NCS2)2- and their metal complexes has attracted considerable attention for a long time, due to their applications as very active accelerators of vulcanization and as antiozonants in the rubber industry (Nakagawa et al., 1992). Many metal dithiocarbamate complexes have shown biological activity and are used as fungicides (Leroux, 1996; Coucouvanis, 1969). The use of dithiocarbamates with polar solvents is effective in removing both renal and hepatic deposits of platinum from rats without decreasing the antitumour efficacy of cisplatin (Shimada et al., 1993). However, the chemistry of dithiocarbimate anions, especially those from sulfonylamides, (RSO2N═CS2)2-, and their metal complexes, is less known. Metal–dithiocarbimate complexes, similar to the metal–dithiocarbamate complexes, exhibit antifungal and vulcanization activities (Perpétuo et al., 2003; Oliveira et al., 2007; Mariano et al., 2007; Alves et al. 2009; Amim et al., 2011). A literature survey showed that the majority of the 40 metal–dithiocarbimate structures reported to date were studied during the last decade (CSD, Version 5.33, Date of release?; Allen, 2002). The majority of the known metal–dithiocarbimate structures contain transition metal ions [Ni2+ (26 structures), Zn2+ (three), Cu2+ (two), Pt2+ (two) and Pd2+ (two)] and only a few structures contain metal ions of the main groups (Hummel & Korn, 1989; Amim et al., 2008).
N-(4-Bromophenylsulfonyl)dithiocarbimate (hereinafter L1) and N-(4-iodophenylsulfonyl)dithiocarbimate (hereinafter L2) potassium salts are well soluble in water, so they have been used as substrates for the syntheses of complexes with transition metal ions like Ni2+ or Zn2+ (Alves et al. 2009; Franca et al., 2006; Oliveira et al., 2002, 2003, 2011). However, to date, the X-ray crystal structures of potassium salts of the L12- and L22- ligands are unknown. The IR spectroscopic investigation of these potassium dithiocarbimates indicated that these compounds are hydrated (Franca et al., 2006). Therefore, we decided to obtain good quality single crystals of these salts for structural studies. In this work, we descibe the crystal structures of [K2(L1)(H2O)2]n, (I), and [K2(L2)(H2O)2]n, (II).
The asymmetric units of (I) and (II) contain one L12- or L22- anion, two potassium cations (K1 and K2) and two water molecules (O3 and O4) (Figs. 1a and 1b). Although the compounds possess almost identical compositions, their structures exhibit differences. In (I), the environment of K1 consists of one (N,O) pair from an L12- dithiocarbimate ligand, one S atom from another symmetry-related L12- ligand and four water O atoms. K2, instead, is linked to three different L12- ligands, one through (O) and two chelating through (S,O) and (S,S) pairs, plus two water molecules. In (II), the coordination environments of the potassium ions are slightly different. Both K1 and K2 are linked to three different L22- ligands, but in different manners. The coordination of K1 is made up of two S atoms of different L22- ligands, one (O,N)-chelating L22- ligand and three water molecules. The second potassium cation, K2, is coordinated through one (O), one (O,S) and one (S,S) groups, with one water molecule completing the polyhedron.
Inspection of these potassium coordination environments shows the presence of two different substructures, each involving only one type of K cation.
While the two K2 substructures are rather similar, the K1 substructures are not. In (I), the K1 substructure consists of a chain running along the a axis, with inversion-related K1 cations bridged by water molecules (O3 and O4) to form a [K2(H2O)4]n one-dimensional polymer or K1 chain. Each K1 cation in this polymer interacts with one L12- anionic ligand, which acts as an O,N-donor, forming the final K1 substructure (Fig. 2a). Within the K1 chain, the bridging of atom O3 is stronger than that of O4 (Table 1). The equivalent K1 substructure in (II) consists instead of a chain running along the b axis (Fig. 2b) and, in contrast with that of (I), K1 cations within the chain are related by a screw axis and bridged by atom O3, while the remaining water molecule (O4) interacts only with one K1 within the K1 chain and one K2 from the K2 chain (Table 3), thus linking both substructures. Water molecules O3 bridge K1 cations to form a wave-like [K(H2O)]n polymer (Fig. 2b). Each cation within the chain interacts with one L22- ligand, which acts as an O,N-donor, forming the final K1 substructure.
As stated above, the two K2 substructures are similar. That in (I) is a two-dimensional array parallel to (001) (Fig. 3a), while that in (II) is a two-dimensional array parallel to (100) (Fig. 3b). In these substructures, L12- and L22- act as O,O-donor ligands to bridge the K2 cations into chains, along [010] in (I) and [001] in (II). Additionally, the ligands interconnect these chains via the bridging S1 atoms, forming planar K2 substructures.
The planar K2 substructures bind to the K1 substructures on opposite sides in a `sandwich-like' fashion, forming broad layers parallel to (001) in (I) and to (100) in (II) (Fig. 4). Within these layers, some weak O—H···N and O—H···S interactions are present (Tables 2 and 4). The layers are interconnected via K···Br contacts in (I) and K···I contacts in (II) (Tables 1 and 3) into a three-dimensional network.
In conclusion, in (I) water molecules O3 and O4 bridge symmetry-related K1 cations, whereas in (II) these cations are bridged by O3 water molecules only. Additionally, in both compounds the anionic ligands bind through O in a stronger fashion than through S. This is in contrast with what was found in the known structures of N—R-sulfonyldithiocarbimate complexes with transition metal ions, in which the N—R-sulfonyldithiocarbimate(2-) anions act as S,S-donor chelating ligands, and it agrees with the soft–hard acid–base theory (Pearson, 1963), according to which the hard acid K+ prefers to interact with O, a harder base than S in the N—R-sulfonyldithiocarbimate(2-) anions. This implies that the C—S bonds in (I) should not be perturbed by interaction with a metal cation as is the case for transition metal complexes, and in fact they are either similar to or slightly shorter than those in the N-4-bromo- and N-4-iodophenylsulfonyldithiocarbimate nickel or zinc complexes, as shown in Table 5.