Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108001972/sk3194sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108001972/sk3194Isup2.hkl |
CCDC reference: 682790
Compound (I) was synthesized according to a method described by Nusbaumer (2004). To cobalt(II) chloride hexahydrate (236 mg) in water (10 ml) was added 1,10-phenanthroline hydrate (596 mg) in methanol (2 ml), and the mixture was stirred at room temperature for 30 min. Bromine (0.1 ml) in water (8 ml) was added dropwise, whereupon a red–brown powder precipitated. The temperature was elevated to 318–323 K to complete the oxidation. Immediately after the oxidation step, the counter-ions were exchanged by adding silver trifluoromethanesulfonate (0.567 mg) in methanol (2.5 ml). The Ag halide precipitate was filtered off, leaving an orange solution. Evaporation under reduced pressure led to large orange crystals.
All atoms except those of the disordered trifluoromethanesulfonate anion were refined anisotropically. The final model describes the disorder by considering three different orientations of the disordered trifluoromethanesulfonate group (refered to as A, B and C). Restraints were used in order to equalize the C—S bond lengths (of A, B and C) and the C—F, S—O and C···O distances (separately for A and B). Occupancies were constrained to add up to unity and were fixed after convergence to 35% (A), 30% (B) and 35% (C). All H-atom parameters were refined, giving C—H distances in the range 0.88 (3)–0.96 (2).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Co(C12H8N2)3](CF3O3S)3·2H2O | Z = 2 |
Mr = 1082.78 | F(000) = 1096 |
Triclinic, P1 | Dx = 1.738 Mg m−3 |
a = 12.4096 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.0039 (4) Å | Cell parameters from 9027 reflections |
c = 13.4669 (4) Å | θ = 2.7–33.3° |
α = 92.764 (1)° | µ = 0.68 mm−1 |
β = 107.367 (1)° | T = 140 K |
γ = 91.878 (1)° | Triangular, orange |
V = 2069.2 (1) Å3 | 0.28 × 0.20 × 0.15 mm |
Bruker SMART 6000 diffractometer | 14813 independent reflections |
Radiation source: fine-focus sealed tube | 13149 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 33.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −18→19 |
Tmin = 0.77, Tmax = 0.90 | k = −19→20 |
36176 measured reflections | l = −20→19 |
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)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.107 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0536P)2 + 1.3093P] where P = (Fo2 + 2Fc2)/3 |
14813 reflections | (Δ/σ)max = 0.005 |
758 parameters | Δρmax = 0.75 e Å−3 |
21 restraints | Δρmin = −0.63 e Å−3 |
[Co(C12H8N2)3](CF3O3S)3·2H2O | γ = 91.878 (1)° |
Mr = 1082.78 | V = 2069.2 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.4096 (4) Å | Mo Kα radiation |
b = 13.0039 (4) Å | µ = 0.68 mm−1 |
c = 13.4669 (4) Å | T = 140 K |
α = 92.764 (1)° | 0.28 × 0.20 × 0.15 mm |
β = 107.367 (1)° |
Bruker SMART 6000 diffractometer | 14813 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 13149 reflections with I > 2σ(I) |
Tmin = 0.77, Tmax = 0.90 | Rint = 0.018 |
36176 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 21 restraints |
wR(F2) = 0.107 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.75 e Å−3 |
14813 reflections | Δρmin = −0.63 e Å−3 |
758 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 | Occ. (<1) | |
Co1 | 0.207589 (14) | 0.295187 (13) | 0.740936 (13) | 0.01400 (4) | |
N1 | 0.31395 (9) | 0.37027 (9) | 0.68838 (8) | 0.01688 (19) | |
N2 | 0.32690 (9) | 0.30877 (8) | 0.87328 (8) | 0.01570 (18) | |
N3 | 0.14688 (9) | 0.42076 (9) | 0.77994 (8) | 0.01643 (19) | |
N4 | 0.10192 (9) | 0.22723 (9) | 0.80048 (9) | 0.01689 (19) | |
N5 | 0.09296 (9) | 0.27995 (9) | 0.60603 (9) | 0.01682 (19) | |
N6 | 0.26006 (10) | 0.16664 (9) | 0.69638 (9) | 0.01743 (19) | |
C1 | 0.30038 (12) | 0.40487 (12) | 0.59405 (11) | 0.0220 (3) | |
H1 | 0.2296 (17) | 0.3872 (15) | 0.5424 (15) | 0.019 (4)* | |
C2 | 0.38513 (13) | 0.46582 (13) | 0.57235 (11) | 0.0243 (3) | |
H2 | 0.369 (2) | 0.4898 (18) | 0.5062 (19) | 0.035 (6)* | |
C3 | 0.48628 (12) | 0.48898 (12) | 0.64793 (11) | 0.0220 (2) | |
H3 | 0.5391 (19) | 0.5294 (17) | 0.6352 (17) | 0.029 (5)* | |
C4 | 0.50387 (11) | 0.45031 (10) | 0.74743 (10) | 0.0178 (2) | |
C5 | 0.60628 (11) | 0.46729 (11) | 0.83209 (11) | 0.0214 (2) | |
H4 | 0.6644 (17) | 0.5031 (16) | 0.8199 (16) | 0.022 (5)* | |
C6 | 0.61457 (11) | 0.43116 (11) | 0.92720 (11) | 0.0213 (2) | |
H5 | 0.6822 (18) | 0.4399 (17) | 0.9826 (17) | 0.027 (5)* | |
C7 | 0.52134 (11) | 0.37717 (10) | 0.94690 (10) | 0.0172 (2) | |
C8 | 0.52011 (12) | 0.34374 (11) | 1.04458 (10) | 0.0206 (2) | |
H6 | 0.5852 (18) | 0.3568 (17) | 1.1035 (17) | 0.028 (5)* | |
C9 | 0.42333 (13) | 0.29686 (11) | 1.05445 (10) | 0.0214 (2) | |
H7 | 0.4153 (19) | 0.2785 (18) | 1.1186 (18) | 0.032 (6)* | |
C10 | 0.32720 (12) | 0.28012 (10) | 0.96740 (10) | 0.0184 (2) | |
H8 | 0.2593 (18) | 0.2480 (16) | 0.9715 (16) | 0.024 (5)* | |
C11 | 0.42174 (10) | 0.35813 (9) | 0.86389 (9) | 0.0152 (2) | |
C12 | 0.41418 (10) | 0.39303 (10) | 0.76381 (10) | 0.0159 (2) | |
C13 | 0.17646 (12) | 0.51882 (11) | 0.77135 (10) | 0.0200 (2) | |
H9 | 0.2331 (17) | 0.5319 (16) | 0.7421 (16) | 0.022 (5)* | |
C14 | 0.12186 (14) | 0.60044 (11) | 0.80428 (11) | 0.0244 (3) | |
H10 | 0.1480 (19) | 0.6664 (18) | 0.7985 (17) | 0.032 (6)* | |
C15 | 0.03454 (13) | 0.58101 (12) | 0.84499 (11) | 0.0245 (3) | |
H11 | 0.002 (2) | 0.6337 (18) | 0.8688 (18) | 0.034 (6)* | |
C16 | 0.00054 (12) | 0.47831 (11) | 0.85325 (10) | 0.0209 (2) | |
C17 | −0.08995 (12) | 0.44700 (13) | 0.89268 (11) | 0.0256 (3) | |
H12 | −0.1340 (19) | 0.4972 (18) | 0.9100 (17) | 0.031 (5)* | |
C18 | −0.11397 (12) | 0.34641 (14) | 0.90308 (12) | 0.0261 (3) | |
H13 | −0.172 (2) | 0.3242 (19) | 0.9257 (19) | 0.037 (6)* | |
C19 | −0.04890 (12) | 0.26681 (12) | 0.87481 (11) | 0.0219 (2) | |
C20 | −0.06533 (13) | 0.16089 (13) | 0.88639 (13) | 0.0274 (3) | |
H14 | −0.120 (2) | 0.1386 (18) | 0.9163 (18) | 0.036 (6)* | |
C21 | 0.00211 (14) | 0.09213 (12) | 0.85603 (13) | 0.0267 (3) | |
H15 | −0.008 (2) | 0.024 (2) | 0.8617 (19) | 0.038 (6)* | |
C22 | 0.08535 (12) | 0.12739 (11) | 0.81250 (11) | 0.0214 (2) | |
H16 | 0.1319 (17) | 0.0816 (16) | 0.7931 (15) | 0.022 (5)* | |
C23 | 0.03639 (11) | 0.29570 (10) | 0.83203 (10) | 0.0173 (2) | |
C24 | 0.06117 (11) | 0.40097 (10) | 0.82130 (10) | 0.0172 (2) | |
C25 | 0.00934 (11) | 0.34118 (11) | 0.56340 (11) | 0.0200 (2) | |
H17 | 0.0018 (17) | 0.3992 (16) | 0.5983 (16) | 0.022 (5)* | |
C26 | −0.06853 (12) | 0.31526 (12) | 0.46494 (11) | 0.0237 (3) | |
H18 | −0.124 (2) | 0.3606 (18) | 0.4380 (18) | 0.034 (6)* | |
C27 | −0.05974 (13) | 0.22616 (12) | 0.40981 (11) | 0.0240 (3) | |
H19 | −0.1092 (18) | 0.2089 (17) | 0.3453 (17) | 0.027 (5)* | |
C28 | 0.02872 (12) | 0.16109 (11) | 0.45286 (10) | 0.0207 (2) | |
C29 | 0.04867 (14) | 0.06720 (12) | 0.40237 (11) | 0.0260 (3) | |
H20 | 0.0034 (19) | 0.0510 (17) | 0.3372 (18) | 0.029 (5)* | |
C30 | 0.13543 (15) | 0.00812 (12) | 0.44850 (12) | 0.0267 (3) | |
H21 | 0.151 (2) | −0.049 (2) | 0.415 (2) | 0.043 (7)* | |
C31 | 0.21172 (13) | 0.03825 (11) | 0.55007 (11) | 0.0218 (2) | |
C32 | 0.30569 (14) | −0.01707 (12) | 0.60305 (12) | 0.0257 (3) | |
H22 | 0.323 (2) | −0.075 (2) | 0.5756 (19) | 0.039 (6)* | |
C33 | 0.37377 (13) | 0.02118 (12) | 0.69901 (12) | 0.0247 (3) | |
H23 | 0.434 (2) | −0.0125 (18) | 0.7371 (18) | 0.035 (6)* | |
C34 | 0.34901 (12) | 0.11353 (11) | 0.74413 (11) | 0.0207 (2) | |
H24 | 0.3917 (17) | 0.1396 (16) | 0.8055 (16) | 0.021 (5)* | |
C35 | 0.19334 (11) | 0.12998 (10) | 0.60041 (10) | 0.0178 (2) | |
C36 | 0.10198 (11) | 0.19125 (10) | 0.55168 (10) | 0.0176 (2) | |
S1A | 0.21955 (18) | 0.26890 (17) | 0.2397 (2) | 0.0134 (3)* | 0.35 |
C37A | 0.2948 (7) | 0.1503 (6) | 0.2860 (7) | 0.0182 (17)* | 0.35 |
O1A | 0.3168 (5) | 0.3439 (4) | 0.2765 (5) | 0.0350 (10)* | 0.35 |
O2A | 0.1792 (4) | 0.2542 (5) | 0.1306 (4) | 0.0235 (8)* | 0.35 |
O3A | 0.1315 (6) | 0.2725 (5) | 0.2910 (6) | 0.0190 (11)* | 0.35 |
F1A | 0.2296 (5) | 0.0659 (3) | 0.2550 (5) | 0.0227 (7)* | 0.35 |
F2A | 0.3846 (4) | 0.1409 (4) | 0.2516 (4) | 0.0247 (8)* | 0.35 |
F3A | 0.3482 (5) | 0.1556 (6) | 0.3862 (5) | 0.0432 (13)* | 0.35 |
S1B | 0.2083 (2) | 0.2529 (2) | 0.2269 (2) | 0.0383 (8)* | 0.30 |
C37B | 0.3105 (7) | 0.1652 (6) | 0.3013 (6) | 0.040 (2)* | 0.30 |
O1B | 0.2855 (6) | 0.3524 (5) | 0.2575 (5) | 0.0461 (15)* | 0.30 |
O2B | 0.1732 (6) | 0.2289 (6) | 0.1227 (5) | 0.049 (2)* | 0.30 |
O3B | 0.1218 (6) | 0.2562 (5) | 0.2789 (6) | 0.0321 (19)* | 0.30 |
F1B | 0.2549 (6) | 0.0711 (6) | 0.2755 (6) | 0.062 (3)* | 0.30 |
F2B | 0.4008 (5) | 0.1655 (5) | 0.2698 (4) | 0.0465 (15)* | 0.30 |
F3B | 0.3302 (6) | 0.1698 (5) | 0.4004 (4) | 0.0407 (12)* | 0.30 |
S1C | 0.23023 (15) | 0.27610 (14) | 0.25737 (14) | 0.0266 (6)* | 0.35 |
C37C | 0.2874 (9) | 0.1488 (8) | 0.2745 (8) | 0.037 (3)* | 0.35 |
O1C | 0.3103 (5) | 0.3553 (4) | 0.3056 (4) | 0.0423 (12)* | 0.35 |
O2C | 0.2002 (5) | 0.2802 (5) | 0.1448 (5) | 0.0494 (17)* | 0.35 |
O3C | 0.1485 (4) | 0.2738 (5) | 0.3105 (4) | 0.0308 (15)* | 0.35 |
F1C | 0.2079 (4) | 0.0725 (4) | 0.2369 (4) | 0.0451 (17)* | 0.35 |
F2C | 0.3699 (4) | 0.1339 (3) | 0.2285 (3) | 0.0328 (11)* | 0.35 |
F3C | 0.3235 (4) | 0.1380 (3) | 0.3814 (3) | 0.0314 (8)* | 0.35 |
C38 | 0.38610 (17) | 0.79792 (13) | 0.34817 (14) | 0.0322 (3) | |
C39 | 0.32757 (14) | 0.97148 (12) | 1.00627 (12) | 0.0275 (3) | |
S2 | 0.28934 (3) | 0.72498 (3) | 0.40090 (3) | 0.02283 (7) | |
S3 | 0.27390 (3) | 0.86882 (3) | 0.90444 (3) | 0.02393 (7) | |
F4 | 0.49070 (10) | 0.76594 (10) | 0.38110 (11) | 0.0452 (3) | |
F5 | 0.39003 (13) | 0.89755 (9) | 0.37673 (12) | 0.0507 (3) | |
F6 | 0.35369 (14) | 0.78822 (12) | 0.24434 (10) | 0.0554 (4) | |
F7 | 0.41173 (12) | 0.94161 (11) | 1.08339 (10) | 0.0540 (4) | |
F8 | 0.24641 (12) | 1.00139 (11) | 1.04551 (11) | 0.0528 (4) | |
F9 | 0.36432 (13) | 1.05392 (9) | 0.96969 (10) | 0.0458 (3) | |
O4 | 0.34057 (13) | 0.74230 (11) | 0.51177 (9) | 0.0361 (3) | |
O5 | 0.18310 (11) | 0.77275 (11) | 0.35997 (11) | 0.0360 (3) | |
O6 | 0.29251 (11) | 0.62038 (9) | 0.36088 (10) | 0.0315 (2) | |
O7 | 0.17961 (13) | 0.91199 (12) | 0.83166 (12) | 0.0454 (4) | |
O8 | 0.36892 (12) | 0.85314 (10) | 0.86495 (11) | 0.0366 (3) | |
O9 | 0.24785 (14) | 0.78508 (10) | 0.96084 (12) | 0.0410 (3) | |
O10 | 0.12487 (11) | 0.47292 (11) | 0.39099 (10) | 0.0302 (2) | |
H25 | 0.125 (2) | 0.421 (2) | 0.363 (2) | 0.039 (7)* | |
H26 | 0.168 (2) | 0.508 (2) | 0.376 (2) | 0.045 (7)* | |
O11 | 0.33191 (12) | 0.68523 (11) | 0.71035 (10) | 0.0320 (3) | |
H27 | 0.337 (2) | 0.698 (2) | 0.656 (2) | 0.046 (7)* | |
H28 | 0.346 (2) | 0.738 (2) | 0.743 (2) | 0.040 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01305 (8) | 0.01605 (8) | 0.01317 (8) | 0.00044 (5) | 0.00425 (6) | 0.00176 (5) |
N1 | 0.0147 (4) | 0.0215 (5) | 0.0151 (4) | 0.0008 (4) | 0.0049 (4) | 0.0040 (4) |
N2 | 0.0159 (4) | 0.0167 (5) | 0.0148 (4) | 0.0009 (4) | 0.0048 (4) | 0.0022 (3) |
N3 | 0.0159 (4) | 0.0172 (5) | 0.0153 (4) | 0.0006 (4) | 0.0033 (4) | 0.0013 (4) |
N4 | 0.0158 (4) | 0.0186 (5) | 0.0165 (5) | −0.0006 (4) | 0.0053 (4) | 0.0010 (4) |
N5 | 0.0152 (4) | 0.0193 (5) | 0.0158 (4) | 0.0003 (4) | 0.0045 (4) | 0.0017 (4) |
N6 | 0.0179 (5) | 0.0190 (5) | 0.0166 (5) | 0.0022 (4) | 0.0066 (4) | 0.0025 (4) |
C1 | 0.0195 (6) | 0.0310 (7) | 0.0164 (5) | 0.0022 (5) | 0.0059 (5) | 0.0074 (5) |
C2 | 0.0235 (6) | 0.0324 (7) | 0.0205 (6) | 0.0027 (5) | 0.0104 (5) | 0.0099 (5) |
C3 | 0.0208 (6) | 0.0251 (6) | 0.0243 (6) | 0.0016 (5) | 0.0125 (5) | 0.0067 (5) |
C4 | 0.0157 (5) | 0.0193 (5) | 0.0202 (5) | 0.0016 (4) | 0.0079 (4) | 0.0024 (4) |
C5 | 0.0153 (5) | 0.0240 (6) | 0.0256 (6) | −0.0010 (4) | 0.0074 (5) | 0.0019 (5) |
C6 | 0.0149 (5) | 0.0242 (6) | 0.0231 (6) | 0.0004 (4) | 0.0032 (5) | −0.0002 (5) |
C7 | 0.0163 (5) | 0.0173 (5) | 0.0169 (5) | 0.0030 (4) | 0.0033 (4) | 0.0011 (4) |
C8 | 0.0217 (6) | 0.0214 (6) | 0.0162 (5) | 0.0035 (5) | 0.0014 (4) | 0.0019 (4) |
C9 | 0.0260 (6) | 0.0230 (6) | 0.0145 (5) | 0.0023 (5) | 0.0043 (5) | 0.0038 (4) |
C10 | 0.0205 (6) | 0.0192 (6) | 0.0164 (5) | 0.0006 (4) | 0.0067 (4) | 0.0036 (4) |
C11 | 0.0154 (5) | 0.0153 (5) | 0.0152 (5) | 0.0019 (4) | 0.0048 (4) | 0.0018 (4) |
C12 | 0.0148 (5) | 0.0183 (5) | 0.0154 (5) | 0.0020 (4) | 0.0054 (4) | 0.0028 (4) |
C13 | 0.0214 (6) | 0.0183 (6) | 0.0182 (5) | −0.0012 (4) | 0.0027 (5) | 0.0017 (4) |
C14 | 0.0303 (7) | 0.0179 (6) | 0.0205 (6) | 0.0021 (5) | 0.0010 (5) | 0.0000 (5) |
C15 | 0.0292 (7) | 0.0224 (6) | 0.0189 (6) | 0.0090 (5) | 0.0021 (5) | −0.0011 (5) |
C16 | 0.0193 (6) | 0.0262 (6) | 0.0153 (5) | 0.0064 (5) | 0.0021 (4) | −0.0006 (4) |
C17 | 0.0200 (6) | 0.0363 (8) | 0.0206 (6) | 0.0083 (5) | 0.0062 (5) | −0.0023 (5) |
C18 | 0.0182 (6) | 0.0401 (8) | 0.0219 (6) | 0.0021 (5) | 0.0091 (5) | −0.0003 (6) |
C19 | 0.0173 (5) | 0.0304 (7) | 0.0188 (6) | −0.0012 (5) | 0.0070 (4) | 0.0012 (5) |
C20 | 0.0242 (7) | 0.0329 (8) | 0.0283 (7) | −0.0058 (6) | 0.0132 (6) | 0.0043 (6) |
C21 | 0.0283 (7) | 0.0236 (7) | 0.0302 (7) | −0.0061 (5) | 0.0120 (6) | 0.0047 (5) |
C22 | 0.0226 (6) | 0.0185 (6) | 0.0235 (6) | −0.0022 (5) | 0.0079 (5) | 0.0019 (5) |
C23 | 0.0150 (5) | 0.0213 (6) | 0.0156 (5) | 0.0000 (4) | 0.0048 (4) | 0.0006 (4) |
C24 | 0.0156 (5) | 0.0208 (6) | 0.0142 (5) | 0.0014 (4) | 0.0029 (4) | 0.0003 (4) |
C25 | 0.0174 (5) | 0.0229 (6) | 0.0192 (6) | 0.0024 (4) | 0.0044 (4) | 0.0028 (5) |
C26 | 0.0180 (6) | 0.0310 (7) | 0.0198 (6) | 0.0012 (5) | 0.0017 (5) | 0.0052 (5) |
C27 | 0.0215 (6) | 0.0310 (7) | 0.0165 (6) | −0.0036 (5) | 0.0015 (5) | 0.0029 (5) |
C28 | 0.0212 (6) | 0.0248 (6) | 0.0150 (5) | −0.0046 (5) | 0.0047 (4) | −0.0003 (4) |
C29 | 0.0320 (7) | 0.0277 (7) | 0.0173 (6) | −0.0055 (6) | 0.0074 (5) | −0.0040 (5) |
C30 | 0.0361 (8) | 0.0234 (7) | 0.0223 (6) | −0.0030 (6) | 0.0126 (6) | −0.0049 (5) |
C31 | 0.0277 (6) | 0.0202 (6) | 0.0203 (6) | 0.0007 (5) | 0.0119 (5) | 0.0002 (5) |
C32 | 0.0329 (7) | 0.0215 (6) | 0.0274 (7) | 0.0065 (5) | 0.0155 (6) | 0.0020 (5) |
C33 | 0.0273 (7) | 0.0228 (6) | 0.0272 (7) | 0.0085 (5) | 0.0118 (5) | 0.0054 (5) |
C34 | 0.0207 (6) | 0.0226 (6) | 0.0197 (6) | 0.0047 (5) | 0.0067 (5) | 0.0041 (5) |
C35 | 0.0191 (5) | 0.0187 (5) | 0.0169 (5) | −0.0002 (4) | 0.0077 (4) | 0.0010 (4) |
C36 | 0.0183 (5) | 0.0194 (5) | 0.0154 (5) | −0.0014 (4) | 0.0058 (4) | 0.0008 (4) |
C38 | 0.0434 (9) | 0.0256 (7) | 0.0339 (8) | 0.0007 (6) | 0.0209 (7) | 0.0033 (6) |
C39 | 0.0317 (7) | 0.0246 (7) | 0.0253 (7) | −0.0065 (6) | 0.0085 (6) | −0.0003 (5) |
S2 | 0.02964 (17) | 0.02101 (15) | 0.02015 (15) | 0.00264 (12) | 0.01068 (13) | 0.00227 (11) |
S3 | 0.02834 (17) | 0.01895 (15) | 0.02268 (16) | 0.00063 (12) | 0.00528 (13) | −0.00077 (12) |
F4 | 0.0371 (6) | 0.0398 (6) | 0.0657 (8) | −0.0010 (5) | 0.0271 (6) | −0.0012 (6) |
F5 | 0.0671 (9) | 0.0214 (5) | 0.0751 (9) | −0.0024 (5) | 0.0393 (8) | 0.0031 (5) |
F6 | 0.0775 (10) | 0.0646 (9) | 0.0323 (6) | −0.0073 (7) | 0.0290 (6) | 0.0111 (6) |
F7 | 0.0560 (8) | 0.0533 (8) | 0.0341 (6) | −0.0055 (6) | −0.0138 (5) | 0.0027 (5) |
F8 | 0.0586 (8) | 0.0501 (7) | 0.0577 (8) | −0.0124 (6) | 0.0358 (7) | −0.0251 (6) |
F9 | 0.0696 (9) | 0.0237 (5) | 0.0467 (7) | −0.0157 (5) | 0.0239 (6) | −0.0008 (4) |
O4 | 0.0485 (8) | 0.0411 (7) | 0.0193 (5) | −0.0002 (6) | 0.0113 (5) | 0.0016 (5) |
O5 | 0.0332 (6) | 0.0370 (7) | 0.0392 (7) | 0.0106 (5) | 0.0116 (5) | 0.0058 (5) |
O6 | 0.0401 (6) | 0.0205 (5) | 0.0366 (6) | 0.0000 (4) | 0.0161 (5) | −0.0013 (4) |
O7 | 0.0393 (7) | 0.0430 (8) | 0.0394 (7) | 0.0120 (6) | −0.0099 (6) | −0.0074 (6) |
O8 | 0.0460 (7) | 0.0317 (6) | 0.0386 (7) | 0.0084 (5) | 0.0220 (6) | 0.0023 (5) |
O9 | 0.0574 (9) | 0.0266 (6) | 0.0420 (7) | −0.0145 (6) | 0.0217 (7) | −0.0006 (5) |
O10 | 0.0294 (6) | 0.0333 (6) | 0.0262 (5) | 0.0035 (5) | 0.0057 (5) | 0.0022 (5) |
O11 | 0.0404 (7) | 0.0340 (6) | 0.0220 (5) | −0.0047 (5) | 0.0103 (5) | 0.0034 (5) |
Co1—N1 | 1.9330 (11) | C25—H17 | 0.89 (2) |
Co1—N3 | 1.9349 (11) | C26—C27 | 1.371 (2) |
Co1—N4 | 1.9399 (11) | C26—H18 | 0.93 (2) |
Co1—N5 | 1.9410 (11) | C27—C28 | 1.409 (2) |
Co1—N2 | 1.9435 (11) | C27—H19 | 0.91 (2) |
Co1—N6 | 1.9458 (11) | C28—C36 | 1.3984 (18) |
N1—C1 | 1.3330 (16) | C28—C29 | 1.433 (2) |
N1—C12 | 1.3635 (16) | C29—C30 | 1.355 (2) |
N2—C10 | 1.3373 (16) | C29—H20 | 0.90 (2) |
N2—C11 | 1.3639 (16) | C30—C31 | 1.439 (2) |
N3—C13 | 1.3353 (17) | C30—H21 | 0.91 (3) |
N3—C24 | 1.3629 (17) | C31—C35 | 1.4023 (19) |
N4—C22 | 1.3330 (18) | C31—C32 | 1.412 (2) |
N4—C23 | 1.3608 (17) | C32—C33 | 1.375 (2) |
N5—C25 | 1.3353 (17) | C32—H22 | 0.88 (3) |
N5—C36 | 1.3618 (17) | C33—C34 | 1.404 (2) |
N6—C34 | 1.3334 (17) | C33—H23 | 0.91 (2) |
N6—C35 | 1.3635 (17) | C34—H24 | 0.88 (2) |
C1—C2 | 1.404 (2) | C35—C36 | 1.4200 (19) |
C1—H1 | 0.96 (2) | S1A—O2A | 1.404 (5) |
C2—C3 | 1.373 (2) | S1A—O3A | 1.458 (5) |
C2—H2 | 0.92 (2) | S1A—O1A | 1.474 (6) |
C3—C4 | 1.4120 (19) | S1A—C37A | 1.866 (7) |
C3—H3 | 0.89 (2) | C37A—F3A | 1.312 (10) |
C4—C12 | 1.3965 (18) | C37A—F1A | 1.315 (9) |
C4—C5 | 1.4339 (19) | C37A—F2A | 1.335 (8) |
C5—C6 | 1.362 (2) | S1B—O2B | 1.356 (7) |
C5—H4 | 0.91 (2) | S1B—O3B | 1.447 (6) |
C6—C7 | 1.4318 (19) | S1B—O1B | 1.546 (6) |
C6—H5 | 0.94 (2) | S1B—C37B | 1.834 (8) |
C7—C11 | 1.4025 (17) | C37B—F3B | 1.281 (9) |
C7—C8 | 1.4094 (19) | C37B—F2B | 1.310 (8) |
C8—C9 | 1.374 (2) | C37B—F1B | 1.362 (9) |
C8—H6 | 0.95 (2) | S1C—O1C | 1.398 (6) |
C9—C10 | 1.4029 (19) | S1C—O3C | 1.405 (5) |
C9—H7 | 0.94 (2) | S1C—O2C | 1.453 (6) |
C10—H8 | 0.95 (2) | S1C—C37C | 1.820 (9) |
C11—C12 | 1.4204 (17) | C37C—F1C | 1.342 (11) |
C13—C14 | 1.401 (2) | C37C—F2C | 1.360 (11) |
C13—H9 | 0.92 (2) | C37C—F3C | 1.390 (11) |
C14—C15 | 1.374 (2) | C38—F4 | 1.328 (2) |
C14—H10 | 0.92 (2) | C38—F5 | 1.329 (2) |
C15—C16 | 1.407 (2) | C38—F6 | 1.333 (2) |
C15—H11 | 0.90 (2) | C38—S2 | 1.8290 (18) |
C16—C24 | 1.4013 (18) | C39—F7 | 1.318 (2) |
C16—C17 | 1.434 (2) | C39—F9 | 1.3240 (19) |
C17—C18 | 1.355 (2) | C39—F8 | 1.330 (2) |
C17—H12 | 0.93 (2) | C39—S3 | 1.8239 (16) |
C18—C19 | 1.438 (2) | S2—O4 | 1.4408 (13) |
C18—H13 | 0.91 (2) | S2—O5 | 1.4424 (13) |
C19—C23 | 1.3972 (18) | S2—O6 | 1.4449 (12) |
C19—C20 | 1.409 (2) | S3—O7 | 1.4341 (14) |
C20—C21 | 1.373 (2) | S3—O9 | 1.4389 (14) |
C20—H14 | 0.93 (2) | S3—O8 | 1.4473 (14) |
C21—C22 | 1.406 (2) | O10—H25 | 0.75 (3) |
C21—H15 | 0.90 (3) | O10—H26 | 0.77 (3) |
C22—H16 | 0.92 (2) | O11—H27 | 0.77 (3) |
C23—C24 | 1.4169 (19) | O11—H28 | 0.78 (3) |
C25—C26 | 1.4058 (19) | ||
N1—Co1—N3 | 92.35 (5) | N3—C24—C16 | 123.35 (13) |
N1—Co1—N4 | 176.25 (5) | N3—C24—C23 | 115.95 (12) |
N3—Co1—N4 | 84.50 (5) | C16—C24—C23 | 120.70 (12) |
N1—Co1—N5 | 93.62 (5) | N5—C25—C26 | 121.27 (13) |
N3—Co1—N5 | 92.63 (5) | N5—C25—H17 | 119.6 (13) |
N4—Co1—N5 | 88.58 (5) | C26—C25—H17 | 119.1 (13) |
N1—Co1—N2 | 84.76 (5) | C27—C26—C25 | 120.47 (14) |
N3—Co1—N2 | 89.11 (5) | C27—C26—H18 | 121.3 (15) |
N4—Co1—N2 | 93.13 (5) | C25—C26—H18 | 118.2 (15) |
N5—Co1—N2 | 177.67 (5) | C26—C27—C28 | 119.15 (13) |
N1—Co1—N6 | 89.26 (5) | C26—C27—H19 | 121.3 (14) |
N3—Co1—N6 | 176.72 (5) | C28—C27—H19 | 119.5 (14) |
N4—Co1—N6 | 93.98 (5) | C36—C28—C27 | 117.13 (13) |
N5—Co1—N6 | 84.42 (5) | C36—C28—C29 | 118.23 (13) |
N2—Co1—N6 | 93.88 (5) | C27—C28—C29 | 124.64 (13) |
C1—N1—C12 | 118.41 (12) | C30—C29—C28 | 121.52 (14) |
C1—N1—Co1 | 129.59 (10) | C30—C29—H20 | 121.3 (14) |
C12—N1—Co1 | 111.92 (8) | C28—C29—H20 | 117.1 (14) |
C10—N2—C11 | 118.40 (11) | C29—C30—C31 | 120.91 (14) |
C10—N2—Co1 | 130.15 (9) | C29—C30—H21 | 121.6 (16) |
C11—N2—Co1 | 111.43 (8) | C31—C30—H21 | 117.4 (16) |
C13—N3—C24 | 118.52 (12) | C35—C31—C32 | 116.91 (13) |
C13—N3—Co1 | 129.69 (10) | C35—C31—C30 | 118.23 (13) |
C24—N3—Co1 | 111.79 (9) | C32—C31—C30 | 124.86 (14) |
C22—N4—C23 | 118.42 (12) | C33—C32—C31 | 119.24 (13) |
C22—N4—Co1 | 129.79 (10) | C33—C32—H22 | 118.8 (16) |
C23—N4—Co1 | 111.79 (9) | C31—C32—H22 | 121.9 (16) |
C25—N5—C36 | 118.51 (12) | C32—C33—C34 | 120.19 (14) |
C25—N5—Co1 | 129.52 (10) | C32—C33—H23 | 122.6 (15) |
C36—N5—Co1 | 111.94 (9) | C34—C33—H23 | 117.2 (15) |
C34—N6—C35 | 118.26 (12) | N6—C34—C33 | 121.80 (13) |
C34—N6—Co1 | 129.98 (10) | N6—C34—H24 | 116.5 (13) |
C35—N6—Co1 | 111.75 (9) | C33—C34—H24 | 121.7 (13) |
N1—C1—C2 | 121.53 (13) | N6—C35—C31 | 123.59 (13) |
N1—C1—H1 | 116.7 (12) | N6—C35—C36 | 115.90 (12) |
C2—C1—H1 | 121.8 (12) | C31—C35—C36 | 120.51 (12) |
C3—C2—C1 | 120.35 (13) | N5—C36—C28 | 123.45 (13) |
C3—C2—H2 | 122.2 (15) | N5—C36—C35 | 115.93 (11) |
C1—C2—H2 | 117.4 (15) | C28—C36—C35 | 120.60 (12) |
C2—C3—C4 | 119.05 (13) | O2A—S1A—O3A | 114.5 (4) |
C2—C3—H3 | 120.6 (14) | O2A—S1A—O1A | 113.3 (4) |
C4—C3—H3 | 120.4 (14) | O3A—S1A—O1A | 118.3 (4) |
C12—C4—C3 | 117.11 (12) | O2A—S1A—C37A | 105.7 (4) |
C12—C4—C5 | 118.48 (12) | O3A—S1A—C37A | 104.0 (3) |
C3—C4—C5 | 124.41 (13) | O1A—S1A—C37A | 98.2 (4) |
C6—C5—C4 | 120.72 (13) | F3A—C37A—F1A | 112.7 (7) |
C6—C5—H4 | 121.7 (13) | F3A—C37A—F2A | 98.0 (7) |
C4—C5—H4 | 117.6 (13) | F1A—C37A—F2A | 107.9 (6) |
C5—C6—C7 | 121.50 (12) | F3A—C37A—S1A | 113.7 (6) |
C5—C6—H5 | 121.4 (13) | F1A—C37A—S1A | 112.5 (6) |
C7—C6—H5 | 117.1 (13) | F2A—C37A—S1A | 111.0 (5) |
C11—C7—C8 | 116.74 (12) | O2B—S1B—O3B | 116.8 (5) |
C11—C7—C6 | 118.12 (12) | O2B—S1B—O1B | 113.1 (4) |
C8—C7—C6 | 125.11 (12) | O3B—S1B—O1B | 109.7 (4) |
C9—C8—C7 | 119.54 (12) | O2B—S1B—C37B | 113.9 (4) |
C9—C8—H6 | 120.8 (13) | O3B—S1B—C37B | 104.3 (4) |
C7—C8—H6 | 119.6 (13) | O1B—S1B—C37B | 97.0 (4) |
C8—C9—C10 | 120.26 (12) | F3B—C37B—F2B | 115.0 (7) |
C8—C9—H7 | 123.3 (14) | F3B—C37B—F1B | 100.3 (7) |
C10—C9—H7 | 116.3 (14) | F2B—C37B—F1B | 109.1 (7) |
N2—C10—C9 | 121.45 (12) | F3B—C37B—S1B | 117.3 (6) |
N2—C10—H8 | 116.2 (13) | F2B—C37B—S1B | 110.3 (6) |
C9—C10—H8 | 122.4 (13) | F1B—C37B—S1B | 103.3 (6) |
N2—C11—C7 | 123.56 (11) | O1C—S1C—O3C | 107.5 (4) |
N2—C11—C12 | 116.03 (11) | O1C—S1C—O2C | 109.9 (4) |
C7—C11—C12 | 120.39 (12) | O3C—S1C—O2C | 122.3 (3) |
N1—C12—C4 | 123.49 (12) | O1C—S1C—C37C | 112.8 (4) |
N1—C12—C11 | 115.81 (11) | O3C—S1C—C37C | 103.2 (4) |
C4—C12—C11 | 120.66 (12) | O2C—S1C—C37C | 100.9 (4) |
N3—C13—C14 | 121.42 (14) | F1C—C37C—F2C | 107.2 (7) |
N3—C13—H9 | 118.3 (13) | F1C—C37C—F3C | 104.4 (8) |
C14—C13—H9 | 120.3 (13) | F2C—C37C—F3C | 113.3 (8) |
C15—C14—C13 | 120.35 (14) | F1C—C37C—S1C | 112.7 (7) |
C15—C14—H10 | 122.4 (14) | F2C—C37C—S1C | 113.3 (7) |
C13—C14—H10 | 117.2 (14) | F3C—C37C—S1C | 105.8 (6) |
C14—C15—C16 | 119.30 (13) | F4—C38—F5 | 107.65 (16) |
C14—C15—H11 | 119.8 (15) | F4—C38—F6 | 107.08 (15) |
C16—C15—H11 | 120.8 (15) | F5—C38—F6 | 108.00 (15) |
C24—C16—C15 | 117.01 (13) | F4—C38—S2 | 111.93 (12) |
C24—C16—C17 | 117.80 (14) | F5—C38—S2 | 110.75 (12) |
C15—C16—C17 | 125.18 (13) | F6—C38—S2 | 111.24 (14) |
C18—C17—C16 | 121.66 (14) | F7—C39—F9 | 107.79 (15) |
C18—C17—H12 | 119.6 (14) | F7—C39—F8 | 108.03 (15) |
C16—C17—H12 | 118.8 (14) | F9—C39—F8 | 106.88 (15) |
C17—C18—C19 | 120.87 (14) | F7—C39—S3 | 111.69 (12) |
C17—C18—H13 | 123.5 (15) | F9—C39—S3 | 111.57 (11) |
C19—C18—H13 | 115.6 (16) | F8—C39—S3 | 110.67 (12) |
C23—C19—C20 | 117.15 (13) | O4—S2—O5 | 114.78 (8) |
C23—C19—C18 | 118.16 (14) | O4—S2—O6 | 114.69 (8) |
C20—C19—C18 | 124.69 (13) | O5—S2—O6 | 115.13 (8) |
C21—C20—C19 | 119.25 (13) | O4—S2—C38 | 102.55 (9) |
C21—C20—H14 | 120.9 (15) | O5—S2—C38 | 103.63 (8) |
C19—C20—H14 | 119.8 (15) | O6—S2—C38 | 103.75 (8) |
C20—C21—C22 | 120.10 (14) | O7—S3—O9 | 116.31 (10) |
C20—C21—H15 | 120.5 (16) | O7—S3—O8 | 113.83 (10) |
C22—C21—H15 | 119.3 (16) | O9—S3—O8 | 114.47 (9) |
N4—C22—C21 | 121.59 (14) | O7—S3—C39 | 104.06 (8) |
N4—C22—H16 | 117.9 (13) | O9—S3—C39 | 102.88 (8) |
C21—C22—H16 | 120.5 (13) | O8—S3—C39 | 102.97 (8) |
N4—C23—C19 | 123.49 (13) | H25—O10—H26 | 106 (3) |
N4—C23—C24 | 115.79 (11) | H27—O11—H28 | 104 (3) |
C19—C23—C24 | 120.70 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H26···O6 | 0.77 (3) | 2.15 (3) | 2.913 (2) | 170 (3) |
O10—H25···O3A | 0.75 (3) | 2.14 (3) | 2.891 (7) | 177 (3) |
O10—H25···O3B | 0.75 (3) | 2.38 (3) | 3.126 (7) | 178 (3) |
O10—H25···O3C | 0.75 (3) | 2.08 (3) | 2.817 (6) | 170 (3) |
O11—H27···O4 | 0.77 (3) | 2.07 (3) | 2.841 (2) | 175 (3) |
O11—H28···O8 | 0.78 (3) | 2.12 (3) | 2.870 (2) | 162 (3) |
Experimental details
Crystal data | |
Chemical formula | [Co(C12H8N2)3](CF3O3S)3·2H2O |
Mr | 1082.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 140 |
a, b, c (Å) | 12.4096 (4), 13.0039 (4), 13.4669 (4) |
α, β, γ (°) | 92.764 (1), 107.367 (1), 91.878 (1) |
V (Å3) | 2069.2 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.28 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART 6000 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.77, 0.90 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36176, 14813, 13149 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.777 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.107, 1.05 |
No. of reflections | 14813 |
No. of parameters | 758 |
No. of restraints | 21 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.75, −0.63 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H26···O6 | 0.77 (3) | 2.15 (3) | 2.913 (2) | 170 (3) |
O10—H25···O3A | 0.75 (3) | 2.14 (3) | 2.891 (7) | 177 (3) |
O10—H25···O3B | 0.75 (3) | 2.38 (3) | 3.126 (7) | 178 (3) |
O10—H25···O3C | 0.75 (3) | 2.08 (3) | 2.817 (6) | 170 (3) |
O11—H27···O4 | 0.77 (3) | 2.07 (3) | 2.841 (2) | 175 (3) |
O11—H28···O8 | 0.78 (3) | 2.12 (3) | 2.870 (2) | 162 (3) |
Motif | Co···Co | Interplanar distancei | C···Cii |
(a) | 9.1 | 3.1 | 6.4 (C36···C25iii) |
(b) | 9.7 | 3.4 | 4.0 (C11···C6iv) |
(c) | 10.0 | 3.5 | 3.9 (C36···C30v) |
(d) | 11.1 | 3.0 | 4.2 (C24···C17vi) |
Notes: (i) the distance between the two ligand planes in the OFF motif; (ii) the shortest distance between a C atom equivalent to C11 (assuming D3 symmetry) and any C atom of the second phenanthroline ligand of the OFF motif. Symmetry codes: (iii) -x, -y+1, -z+1; (iv) -x+1, -y+1, -z+2; (v) -x, -y, -z+1; (vi) -x, -y+1, -z+2. |
Motif | Total | vdW | Coulombic | Primary motif | Totalpheni | vdWpheni | Coulombicpheni |
(a) | 12.4 | -8.6 | 21.0 | OFF | -0.2 | -1.3 | 1.1 |
(b) | 3.0 | -16.5 | 19.5 | OFF | -6.5 | -9.4 | 2.9 |
EF | -0.3 | -2.8 | 2.5 | ||||
(c) | 5.0 | -14.2 | 19.2 | OFF | -6.8 | -9.5 | 2.7 |
(d) | 8.9 | -6.9 | 15.8 | OFF | -0.9 | -4.7 | 3.8 |
Notes: (i) the calculated energy considering only the two phenanthroline ligands that characterize a primary motif. Note that the EF motif exists twice per cation pair. |
The tris(1,10-phenanthroline)cobalt(III) complex was first synthesized by Pfeiffer & Werdelmann (1950). It has been used in conjunction with the tris(1,10-phenanthroline)cobalt(II) complex as a redox couple in dye-sensitized solar cells (Nusbaumer, 2004), serving as an alternative to the prolific I-/I3- couple (Grätzel, 2005). Co complexes with various ligands have been used with trifluoromethanesulfonate counter-ions (Wen et al., 2000; Nusbaumer, 2004), where [Co(C12H8N2)3](CF3SO3)3·2H2O, compound (I), is an example of such a complex.
Compound (I) crystallizes into a racemic triclinic structure with two water molecules per complex cation. Powder X-ray diffraction confirms that the synthesis of (I) yields a stoichiometric compound with only one crystal structure.
The asymmetric unit contains one [Co(phen)3]3+ cation, three trifluoromethanesulfonate anions and two water molecules. The three trifluoromethanesulfonate ions interact with the two water molecules to form a chain, bridged by hydrogen bonds (Fig. 1 and Table 1). The complex cations are not isolated by the anions and water molecules, but rather they interact with one another in motifs that have been described in the literature (Russell et al., 2001). The structure contains four different pairs of cations with a significant van der Waals interaction between ligands (Figs. 2a–2d).
In general, two types of motifs are distinguished, depending on whether the planes of the interacting ligands are parallel (face-to-face) or perpendicular (edge-to-face) to one another. Offset face-to-face (OFF) interactions are clearly present in the motifs shown in Figs. 2(b) and 2(c), and even an edge-to-face (EF) interaction can be recognized in Fig. 2(b). However, the motifs presented in Figs. 2(a) and 2(d) have limited OFF or EF characteristics. This is supported by additional geometric parameters given in Table 2. It should be noted that Russell et al. limited their characterization of OFF ligand interactions to those complex pairs that fulfilled certain geometric criteria. In our context, where all motifs are centrosymmetric, these translate to a plane-to-plane distance in the range 3.2–3.6 Å and a shortest C···C distance between a C atom equivalent to C11 (assuming D3 symmetry for the complex cation) and any C atom of the second phenanthroline ligand not exceeding 4.0 Å (Russell et al., 2001). As motifs (a) and (d) do not comply with these requirements, they will be considered to be weak interactions compared with (b) and (c).
Further characterization of these motifs was carried out by calculating the energy contributions arising from van der Waals and Coulombic interactions, considering either a complete pair of complex cations or only a pair of ligands forming an OFF or EF motif. This was achieved using the methodology of Russell et al. (2001). The atomic charge distribution of a complex cation was approximated on the basis of the charge distribution of an [Fe(phen)3]2+ cation (Russell et al., 2001), multiplying each partial charge by 1.5 to achieve the correct total charge. Although this procedure does not take into account details such as electronegativity in distributing the additional charge, other approaches (such as adding an equal fractional charge to each atom) only result in minor quantitative deviations. The obtained values for the interactions (Table 3) show that only OFF interaction motifs (b) and (c) contribute significantly to a favorable attractive energy. The total intermolecular energy is positive in all cases, however, owing to the high total charge of the complex cations.
It is interesting to note that motif (a), in which the distance between the two Co atoms is shortest, has the least favorable interaction energy. The close proximity of the cations leads to a strong Coulombic repulsion and only a weak van der Waals attraction between ligands, since their close approach causes them to avoid one another.
The packing of the complex cations can be described as infinite chains along [111] that are formed through the strong interaction motifs (b) and (c), as shown in Fig. 2(e). These chains are interconnected in two directions by the weaker interaction motifs (a) and (d), and form a three-dimensional network similar to a distorted diamond structure. The voids and channels of this network are then filled with the short chains of anions and water molecules. The two ordered trifluoromethanesulfonate anions are located in channels (rings), whereas the disordered trifluoromethanesulfonate group points into a void (cage). This might provide enough freedom to allow a rocking motion of the anion, resulting in the observed disorder. Such anionic and solvent disorder is a common phenomenon found in crystals containing [M(phen)3]n+ complex cations (Anderson, 1973; Baker et al., 1975; Boys et al., 1984; Deacon et al., 1979; Freire et al., 1998; Goodwin et al., 1984; Koh et al., 1994; Luck et al., 2000).