Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105043088/ga1111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105043088/ga1111Isup2.hkl |
CCDC reference: 299620
Diiodo(1,10-phenanthroline)copper(II), Cu(phen)I2, and diiodo(1,10-phenanthroline)mercury(II), Hg(phen)I2, were prepared by the literature methods (Li et al., 2000). Black precipitates were produced from the reaction of Cu(phen)I2 (1.00 mmol) with Hg(phen)I2 (1.10 mmol) in acetonitrile. This solid was dissolved in a DMSO–water mixture and allowed to crystallize slowly. Two differently colored types of crystals were formed; most of the crsytals were black, but a small number of pale-green crystals of (I) were collected for X-ray study. Analysis calculated for C38H32CuHg2I6N6O2S: C 24.50, H 1.73, N 4.51%; found C 25.53, H 1.44, N 4.59%
One water H atom on OW2 was located in a difference Fourier map and refined with Uiso(H) values of 1.5Ueq(O); the other water H atom was not located. All other H atoms were refined using a riding model, with idealized geometry (C—H = 0.93–0.96 Å) and with Uiso(H) values of 1.2Ueq(C) or 1.5Ueq(C). The reflection (032) was omitted from the final cycles as an outlier reflection.
Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. ORTEP-3 (Farrugia, 1997) diagram of (I), showing the atom-numbering scheme and 30% probability ellipsoids. |
[Cu(C12H8N2)3][Hg2I6]·C2H6OS·H2O | F(000) = 3364 |
Mr = 1862.88 | Dx = 2.589 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4449 reflections |
a = 12.6628 (10) Å | θ = 2.3–22.3° |
b = 18.8367 (15) Å | µ = 10.81 mm−1 |
c = 20.1380 (16) Å | T = 295 K |
β = 95.789 (1)° | Block, pale-green |
V = 4778.9 (7) Å3 | 0.25 × 0.17 × 0.10 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 9373 independent reflections |
Radiation source: fine-focus sealed tube | 5667 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −15→15 |
Tmin = 0.123, Tmax = 0.339 | k = −20→23 |
29955 measured reflections | l = −24→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0346P)2 + 0.3539P] where P = (Fo2 + 2Fc2)/3 |
9373 reflections | (Δ/σ)max = 0.001 |
503 parameters | Δρmax = 0.97 e Å−3 |
1 restraint | Δρmin = −0.80 e Å−3 |
[Cu(C12H8N2)3][Hg2I6]·C2H6OS·H2O | V = 4778.9 (7) Å3 |
Mr = 1862.88 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.6628 (10) Å | µ = 10.81 mm−1 |
b = 18.8367 (15) Å | T = 295 K |
c = 20.1380 (16) Å | 0.25 × 0.17 × 0.10 mm |
β = 95.789 (1)° |
Bruker SMART CCD area-detector diffractometer | 9373 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 5667 reflections with I > 2σ(I) |
Tmin = 0.123, Tmax = 0.339 | Rint = 0.046 |
29955 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.97 e Å−3 |
9373 reflections | Δρmin = −0.80 e Å−3 |
503 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 | ||
Hg1 | 0.53965 (3) | 0.19334 (2) | 0.32123 (2) | 0.07655 (14) | |
Hg2 | 0.78518 (3) | 0.32874 (2) | 0.34363 (2) | 0.07752 (14) | |
I1 | 0.55199 (4) | 0.08333 (3) | 0.23408 (3) | 0.06933 (19) | |
I2 | 0.36353 (5) | 0.20453 (4) | 0.38488 (3) | 0.0784 (2) | |
I3 | 0.75655 (4) | 0.42870 (3) | 0.43599 (3) | 0.06960 (19) | |
I4 | 0.96517 (5) | 0.31916 (4) | 0.28361 (3) | 0.0737 (2) | |
I5 | 0.58883 (5) | 0.32360 (3) | 0.25383 (3) | 0.07090 (19) | |
I6 | 0.73985 (5) | 0.19213 (3) | 0.40651 (3) | 0.0711 (2) | |
Cu | 0.15622 (6) | 0.29850 (5) | 0.58155 (4) | 0.0389 (2) | |
N1 | 0.1440 (5) | 0.3743 (3) | 0.5033 (3) | 0.0460 (16) | |
C2 | 0.0571 (6) | 0.4054 (4) | 0.4771 (4) | 0.057 (2) | |
H2 | −0.0064 | 0.3949 | 0.4945 | 0.068* | |
C3 | 0.0554 (7) | 0.4531 (5) | 0.4246 (5) | 0.067 (3) | |
H3 | −0.0082 | 0.4727 | 0.4060 | 0.080* | |
C4 | 0.1492 (8) | 0.4706 (5) | 0.4010 (4) | 0.068 (3) | |
H4 | 0.1500 | 0.5032 | 0.3663 | 0.081* | |
C5 | 0.2438 (7) | 0.4399 (5) | 0.4285 (4) | 0.056 (2) | |
C6 | 0.3452 (8) | 0.4548 (5) | 0.4081 (4) | 0.072 (3) | |
H6 | 0.3507 | 0.4861 | 0.3729 | 0.087* | |
C7 | 0.4340 (7) | 0.4249 (6) | 0.4382 (5) | 0.083 (3) | |
H7 | 0.4993 | 0.4372 | 0.4241 | 0.100* | |
C8 | 0.4309 (6) | 0.3755 (5) | 0.4903 (5) | 0.062 (2) | |
C9 | 0.5206 (7) | 0.3423 (6) | 0.5237 (6) | 0.082 (3) | |
H9 | 0.5879 | 0.3526 | 0.5116 | 0.098* | |
C10 | 0.5091 (7) | 0.2949 (6) | 0.5738 (5) | 0.080 (3) | |
H10 | 0.5678 | 0.2716 | 0.5951 | 0.096* | |
C11 | 0.4087 (6) | 0.2823 (5) | 0.5923 (4) | 0.061 (2) | |
H11 | 0.4019 | 0.2515 | 0.6278 | 0.073* | |
N12 | 0.3214 (5) | 0.3117 (3) | 0.5623 (3) | 0.0476 (16) | |
C13 | 0.3319 (6) | 0.3581 (4) | 0.5128 (4) | 0.0439 (19) | |
C14 | 0.2377 (5) | 0.3908 (4) | 0.4809 (4) | 0.0406 (18) | |
N15 | 0.1630 (5) | 0.3753 (3) | 0.6562 (3) | 0.0441 (16) | |
C16 | 0.2451 (7) | 0.4128 (5) | 0.6784 (5) | 0.065 (2) | |
H16 | 0.3080 | 0.4059 | 0.6592 | 0.078* | |
C17 | 0.2441 (7) | 0.4630 (5) | 0.7297 (5) | 0.068 (3) | |
H17 | 0.3046 | 0.4890 | 0.7442 | 0.081* | |
C18 | 0.1518 (7) | 0.4722 (5) | 0.7575 (4) | 0.063 (2) | |
H18 | 0.1488 | 0.5048 | 0.7920 | 0.075* | |
C19 | 0.0624 (6) | 0.4340 (4) | 0.7351 (4) | 0.047 (2) | |
C20 | −0.0380 (7) | 0.4388 (5) | 0.7629 (4) | 0.060 (2) | |
H20 | −0.0440 | 0.4700 | 0.7981 | 0.072* | |
C21 | −0.1224 (6) | 0.4004 (5) | 0.7401 (4) | 0.061 (2) | |
H21 | −0.1857 | 0.4054 | 0.7594 | 0.073* | |
C22 | −0.1166 (6) | 0.3513 (4) | 0.6859 (4) | 0.050 (2) | |
C23 | −0.2007 (6) | 0.3089 (5) | 0.6582 (5) | 0.067 (3) | |
H23 | −0.2658 | 0.3105 | 0.6758 | 0.080* | |
C24 | −0.1876 (7) | 0.2659 (5) | 0.6064 (5) | 0.071 (3) | |
H24 | −0.2434 | 0.2377 | 0.5879 | 0.085* | |
C25 | −0.0907 (7) | 0.2640 (4) | 0.5809 (4) | 0.061 (2) | |
H25 | −0.0830 | 0.2347 | 0.5445 | 0.073* | |
N26 | −0.0084 (5) | 0.3016 (3) | 0.6058 (3) | 0.0483 (16) | |
C27 | −0.0208 (6) | 0.3460 (4) | 0.6576 (4) | 0.048 (2) | |
C28 | 0.0714 (5) | 0.3857 (4) | 0.6834 (4) | 0.0419 (18) | |
N29 | 0.1277 (5) | 0.2120 (3) | 0.5166 (3) | 0.0494 (16) | |
C30 | 0.0904 (6) | 0.2128 (5) | 0.4529 (4) | 0.060 (2) | |
H30 | 0.0767 | 0.2563 | 0.4319 | 0.072* | |
C31 | 0.0707 (7) | 0.1506 (6) | 0.4162 (4) | 0.072 (3) | |
H31 | 0.0407 | 0.1527 | 0.3722 | 0.086* | |
C32 | 0.0954 (7) | 0.0881 (5) | 0.4449 (5) | 0.072 (3) | |
H32 | 0.0836 | 0.0466 | 0.4202 | 0.086* | |
C33 | 0.1385 (6) | 0.0839 (4) | 0.5114 (4) | 0.053 (2) | |
C34 | 0.1698 (7) | 0.0200 (5) | 0.5461 (5) | 0.071 (3) | |
H34 | 0.1634 | −0.0229 | 0.5232 | 0.085* | |
C35 | 0.2084 (7) | 0.0201 (5) | 0.6110 (5) | 0.068 (3) | |
H35 | 0.2278 | −0.0226 | 0.6321 | 0.082* | |
C36 | 0.2197 (6) | 0.0848 (5) | 0.6474 (4) | 0.055 (2) | |
C37 | 0.2587 (7) | 0.0885 (5) | 0.7136 (5) | 0.070 (3) | |
H37 | 0.2819 | 0.0475 | 0.7362 | 0.084* | |
C38 | 0.2634 (7) | 0.1515 (5) | 0.7459 (4) | 0.067 (3) | |
H38 | 0.2885 | 0.1533 | 0.7909 | 0.081* | |
C39 | 0.2309 (6) | 0.2144 (5) | 0.7122 (4) | 0.056 (2) | |
H39 | 0.2336 | 0.2574 | 0.7350 | 0.067* | |
N40 | 0.1962 (4) | 0.2124 (3) | 0.6477 (3) | 0.0465 (16) | |
C41 | 0.1902 (5) | 0.1492 (4) | 0.6155 (4) | 0.0447 (19) | |
C42 | 0.1513 (5) | 0.1485 (4) | 0.5462 (4) | 0.0454 (19) | |
S | 0.6139 (3) | 0.4490 (2) | 0.05364 (17) | 0.1205 (12) | |
C43 | 0.5597 (8) | 0.4968 (6) | 0.1164 (6) | 0.116 (4) | |
H43A | 0.6021 | 0.5382 | 0.1274 | 0.174* | |
H43B | 0.5586 | 0.4675 | 0.1553 | 0.174* | |
H43C | 0.4886 | 0.5110 | 0.1010 | 0.174* | |
C44 | 0.5211 (9) | 0.3839 (7) | 0.0498 (7) | 0.148 (5) | |
H44A | 0.5354 | 0.3501 | 0.0163 | 0.222* | |
H44B | 0.4521 | 0.4043 | 0.0388 | 0.222* | |
H44C | 0.5233 | 0.3606 | 0.0923 | 0.222* | |
O1 | 0.7139 (9) | 0.4193 (6) | 0.0868 (6) | 0.198 (5) | |
O2W | 0.9239 (7) | 0.4118 (5) | 0.1136 (5) | 0.131 (3) | |
H2W | 0.857 (5) | 0.398 (9) | 0.116 (9) | 0.197* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0749 (2) | 0.0728 (3) | 0.0854 (3) | −0.0067 (2) | 0.0252 (2) | −0.0172 (2) |
Hg2 | 0.0711 (2) | 0.0786 (3) | 0.0847 (3) | −0.0098 (2) | 0.0169 (2) | −0.0245 (2) |
I1 | 0.0584 (3) | 0.0716 (5) | 0.0789 (4) | 0.0013 (3) | 0.0119 (3) | −0.0201 (3) |
I2 | 0.0774 (4) | 0.0849 (5) | 0.0769 (5) | 0.0132 (4) | 0.0270 (3) | 0.0044 (4) |
I3 | 0.0614 (3) | 0.0689 (4) | 0.0809 (5) | −0.0098 (3) | 0.0188 (3) | −0.0215 (3) |
I4 | 0.0659 (4) | 0.0858 (5) | 0.0707 (4) | −0.0017 (3) | 0.0132 (3) | −0.0136 (3) |
I5 | 0.0746 (4) | 0.0654 (4) | 0.0684 (4) | −0.0077 (3) | −0.0135 (3) | 0.0154 (3) |
I6 | 0.0824 (4) | 0.0581 (4) | 0.0689 (4) | −0.0023 (3) | −0.0123 (3) | 0.0090 (3) |
Cu | 0.0401 (5) | 0.0380 (6) | 0.0388 (5) | 0.0016 (4) | 0.0057 (4) | 0.0007 (4) |
N1 | 0.048 (4) | 0.043 (4) | 0.048 (4) | 0.004 (3) | 0.006 (3) | −0.006 (3) |
C2 | 0.058 (5) | 0.056 (6) | 0.056 (6) | −0.003 (4) | 0.008 (4) | −0.007 (5) |
C3 | 0.069 (6) | 0.069 (7) | 0.060 (6) | 0.005 (5) | −0.002 (5) | −0.004 (5) |
C4 | 0.097 (7) | 0.046 (6) | 0.057 (6) | 0.010 (5) | −0.003 (5) | 0.009 (4) |
C5 | 0.076 (6) | 0.053 (6) | 0.041 (5) | −0.007 (5) | 0.013 (4) | 0.000 (4) |
C6 | 0.091 (7) | 0.074 (7) | 0.057 (6) | −0.015 (6) | 0.033 (5) | 0.013 (5) |
C7 | 0.061 (6) | 0.109 (9) | 0.086 (8) | −0.024 (6) | 0.037 (5) | 0.019 (7) |
C8 | 0.053 (5) | 0.068 (7) | 0.068 (6) | −0.019 (5) | 0.017 (5) | 0.002 (5) |
C9 | 0.043 (5) | 0.098 (9) | 0.106 (9) | −0.013 (5) | 0.012 (5) | 0.005 (7) |
C10 | 0.045 (5) | 0.102 (9) | 0.091 (8) | −0.005 (5) | 0.001 (5) | 0.010 (7) |
C11 | 0.058 (5) | 0.065 (6) | 0.058 (6) | 0.005 (5) | −0.001 (4) | 0.002 (4) |
N12 | 0.050 (4) | 0.048 (4) | 0.045 (4) | −0.005 (3) | 0.007 (3) | −0.003 (3) |
C13 | 0.060 (5) | 0.037 (5) | 0.036 (5) | −0.010 (4) | 0.010 (4) | −0.006 (4) |
C14 | 0.044 (4) | 0.038 (5) | 0.042 (5) | −0.007 (4) | 0.018 (3) | −0.007 (4) |
N15 | 0.041 (3) | 0.046 (4) | 0.046 (4) | 0.001 (3) | 0.006 (3) | 0.006 (3) |
C16 | 0.060 (5) | 0.071 (7) | 0.067 (6) | 0.011 (5) | 0.020 (5) | 0.008 (5) |
C17 | 0.057 (5) | 0.079 (7) | 0.067 (7) | −0.004 (5) | 0.006 (5) | −0.005 (5) |
C18 | 0.071 (6) | 0.055 (6) | 0.061 (6) | 0.016 (5) | −0.001 (5) | −0.014 (4) |
C19 | 0.053 (5) | 0.047 (5) | 0.041 (5) | 0.012 (4) | 0.002 (4) | 0.000 (4) |
C20 | 0.073 (6) | 0.066 (6) | 0.042 (5) | 0.022 (5) | 0.016 (4) | 0.003 (4) |
C21 | 0.048 (5) | 0.078 (7) | 0.060 (6) | 0.013 (5) | 0.020 (4) | 0.007 (5) |
C22 | 0.050 (5) | 0.057 (6) | 0.045 (5) | 0.012 (4) | 0.012 (4) | 0.008 (4) |
C23 | 0.041 (4) | 0.080 (7) | 0.081 (7) | 0.005 (5) | 0.016 (5) | 0.001 (6) |
C24 | 0.069 (6) | 0.067 (7) | 0.076 (7) | −0.008 (5) | 0.004 (5) | −0.013 (5) |
C25 | 0.064 (6) | 0.051 (6) | 0.067 (6) | 0.006 (5) | 0.009 (5) | −0.010 (5) |
N26 | 0.059 (4) | 0.039 (4) | 0.046 (4) | 0.003 (3) | 0.004 (3) | −0.001 (3) |
C27 | 0.050 (5) | 0.048 (5) | 0.044 (5) | 0.004 (4) | 0.003 (4) | 0.010 (4) |
C28 | 0.045 (4) | 0.039 (5) | 0.042 (5) | 0.011 (4) | 0.007 (4) | 0.009 (4) |
N29 | 0.052 (4) | 0.045 (4) | 0.053 (4) | 0.001 (3) | 0.013 (3) | 0.003 (3) |
C30 | 0.061 (5) | 0.064 (6) | 0.054 (6) | 0.002 (5) | 0.002 (4) | 0.002 (5) |
C31 | 0.088 (7) | 0.079 (8) | 0.045 (6) | −0.006 (6) | −0.004 (5) | −0.015 (5) |
C32 | 0.086 (7) | 0.070 (7) | 0.061 (7) | 0.011 (6) | 0.015 (5) | −0.017 (5) |
C33 | 0.061 (5) | 0.046 (6) | 0.055 (6) | 0.002 (4) | 0.018 (4) | −0.003 (4) |
C34 | 0.103 (7) | 0.038 (6) | 0.075 (7) | 0.001 (5) | 0.023 (6) | 0.000 (5) |
C35 | 0.092 (7) | 0.039 (6) | 0.079 (7) | 0.012 (5) | 0.032 (6) | 0.006 (5) |
C36 | 0.061 (5) | 0.050 (6) | 0.054 (6) | 0.009 (4) | 0.010 (4) | 0.006 (4) |
C37 | 0.072 (6) | 0.061 (7) | 0.078 (7) | 0.011 (5) | 0.005 (5) | 0.013 (5) |
C38 | 0.077 (6) | 0.074 (7) | 0.050 (6) | 0.010 (5) | 0.003 (4) | 0.007 (5) |
C39 | 0.058 (5) | 0.059 (6) | 0.051 (6) | 0.002 (4) | 0.007 (4) | −0.007 (4) |
N40 | 0.046 (4) | 0.041 (4) | 0.053 (4) | 0.000 (3) | 0.011 (3) | −0.001 (3) |
C41 | 0.043 (4) | 0.042 (5) | 0.051 (5) | −0.004 (4) | 0.012 (4) | 0.001 (4) |
C42 | 0.047 (4) | 0.039 (5) | 0.052 (5) | 0.008 (4) | 0.018 (4) | −0.002 (4) |
S | 0.117 (2) | 0.155 (3) | 0.091 (2) | 0.030 (3) | 0.0185 (19) | 0.040 (2) |
C43 | 0.101 | 0.068 | 0.174 (12) | 0.003 (6) | −0.008 (8) | −0.014 (8) |
C44 | 0.105 | 0.121 | 0.215 (15) | −0.040 (8) | −0.005 (10) | 0.007 (11) |
O1 | 0.176 (9) | 0.138 | 0.278 (15) | 0.062 (7) | 0.016 (9) | 0.078 (8) |
O2W | 0.160 (8) | 0.090 (6) | 0.150 (8) | −0.003 (6) | 0.046 (7) | 0.002 (5) |
Cu—N1 | 2.120 (6) | C20—C21 | 1.335 (11) |
Cu—N12 | 2.179 (6) | C20—H20 | 0.9300 |
Cu—N15 | 2.082 (6) | C21—C22 | 1.438 (11) |
Cu—N26 | 2.189 (6) | C21—H21 | 0.9300 |
Cu—N29 | 2.098 (6) | C22—C27 | 1.395 (10) |
Cu—N40 | 2.128 (6) | C22—C23 | 1.401 (11) |
Hg1—I1 | 2.7301 (7) | C23—C24 | 1.345 (12) |
Hg1—I2 | 2.6903 (8) | C23—H23 | 0.9300 |
Hg1—I5 | 2.9020 (8) | C24—C25 | 1.377 (11) |
Hg1—I6 | 2.9151 (7) | C24—H24 | 0.9300 |
Hg2—I3 | 2.6967 (7) | C25—N26 | 1.317 (9) |
Hg2—I4 | 2.6914 (8) | C25—H25 | 0.9300 |
Hg2—I5 | 2.9248 (7) | N26—C27 | 1.358 (9) |
Hg2—I6 | 2.9499 (8) | C27—C28 | 1.439 (10) |
N1—C2 | 1.309 (9) | N29—C30 | 1.320 (9) |
N1—C14 | 1.347 (8) | N29—C42 | 1.357 (9) |
C2—C3 | 1.386 (12) | C30—C31 | 1.394 (12) |
C2—H2 | 0.9300 | C30—H30 | 0.9300 |
C3—C4 | 1.364 (12) | C31—C32 | 1.335 (12) |
C3—H3 | 0.9300 | C31—H31 | 0.9300 |
C4—C5 | 1.393 (11) | C32—C33 | 1.396 (11) |
C4—H4 | 0.9300 | C32—H32 | 0.9300 |
C5—C14 | 1.413 (10) | C33—C42 | 1.406 (10) |
C5—C6 | 1.416 (11) | C33—C34 | 1.426 (11) |
C6—C7 | 1.346 (12) | C34—C35 | 1.350 (12) |
C6—H6 | 0.9300 | C34—H34 | 0.9300 |
C7—C8 | 1.406 (12) | C35—C36 | 1.422 (11) |
C7—H7 | 0.9300 | C35—H35 | 0.9300 |
C8—C9 | 1.407 (11) | C36—C37 | 1.375 (11) |
C8—C13 | 1.415 (10) | C36—C41 | 1.406 (10) |
C9—C10 | 1.366 (13) | C37—C38 | 1.352 (12) |
C9—H9 | 0.9300 | C37—H37 | 0.9300 |
C10—C11 | 1.382 (11) | C38—C39 | 1.406 (11) |
C10—H10 | 0.9300 | C38—H38 | 0.9300 |
C11—N12 | 1.326 (9) | C39—N40 | 1.329 (9) |
C11—H11 | 0.9300 | C39—H39 | 0.9300 |
N12—C13 | 1.343 (9) | N40—C41 | 1.353 (9) |
C13—C14 | 1.435 (10) | C41—C42 | 1.432 (10) |
N15—C16 | 1.297 (10) | S—O1 | 1.480 (10) |
N15—C28 | 1.346 (9) | S—C44 | 1.694 (11) |
C16—C17 | 1.401 (12) | S—C43 | 1.748 (12) |
C16—H16 | 0.9300 | C43—H43A | 0.9600 |
C17—C18 | 1.358 (11) | C43—H43B | 0.9600 |
C17—H17 | 0.9300 | C43—H43C | 0.9600 |
C18—C19 | 1.379 (10) | C44—H44A | 0.9600 |
C18—H18 | 0.9300 | C44—H44B | 0.9600 |
C19—C28 | 1.396 (10) | C44—H44C | 0.9600 |
C19—C20 | 1.442 (11) | O2W—H2W | 0.89 (8) |
N1—Cu—N12 | 77.9 (2) | C28—C19—C20 | 118.2 (7) |
N1—Cu—N15 | 93.6 (2) | C21—C20—C19 | 122.6 (8) |
N1—Cu—N26 | 98.5 (2) | C21—C20—H20 | 118.7 |
N1—Cu—N29 | 93.7 (2) | C19—C20—H20 | 118.7 |
N1—Cu—N40 | 166.8 (2) | C20—C21—C22 | 120.6 (8) |
N12—Cu—N15 | 94.5 (2) | C20—C21—H21 | 119.7 |
N12—Cu—N26 | 171.5 (2) | C22—C21—H21 | 119.7 |
N12—Cu—N29 | 94.9 (2) | C27—C22—C23 | 117.0 (8) |
N12—Cu—N40 | 91.5 (2) | C27—C22—C21 | 118.0 (7) |
N15—Cu—N26 | 78.0 (2) | C23—C22—C21 | 125.0 (8) |
N15—Cu—N29 | 169.1 (2) | C24—C23—C22 | 120.3 (8) |
N15—Cu—N40 | 95.1 (2) | C24—C23—H23 | 119.9 |
N26—Cu—N29 | 93.0 (2) | C22—C23—H23 | 119.9 |
N26—Cu—N40 | 93.0 (2) | C23—C24—C25 | 119.2 (8) |
N29—Cu—N40 | 79.2 (2) | C23—C24—H24 | 120.4 |
I1—Hg1—I2 | 118.02 (2) | C25—C24—H24 | 120.4 |
I1—Hg1—I5 | 108.19 (2) | N26—C25—C24 | 123.1 (8) |
I1—Hg1—I6 | 105.66 (2) | N26—C25—H25 | 118.5 |
I2—Hg1—I5 | 112.57 (2) | C24—C25—H25 | 118.5 |
I2—Hg1—I6 | 115.68 (3) | C25—N26—C27 | 118.3 (7) |
I5—Hg1—I6 | 93.86 (2) | C25—N26—Cu | 129.5 (6) |
I3—Hg2—I4 | 122.37 (2) | C27—N26—Cu | 112.0 (5) |
I3—Hg2—I5 | 106.53 (2) | N26—C27—C22 | 122.0 (7) |
I3—Hg2—I6 | 105.52 (3) | N26—C27—C28 | 116.4 (7) |
I4—Hg2—I5 | 115.20 (2) | C22—C27—C28 | 121.5 (8) |
I4—Hg2—I6 | 110.15 (2) | N15—C28—C19 | 122.5 (7) |
I5—Hg2—I6 | 92.661 (19) | N15—C28—C27 | 118.6 (7) |
Hg1—I5—Hg2 | 87.016 (19) | C19—C28—C27 | 118.9 (7) |
Hg1—I6—Hg2 | 86.309 (19) | C30—N29—C42 | 118.6 (7) |
C2—N1—C14 | 119.7 (7) | C30—N29—Cu | 128.2 (6) |
C2—N1—Cu | 126.5 (6) | C42—N29—Cu | 113.2 (5) |
C14—N1—Cu | 113.8 (5) | N29—C30—C31 | 122.2 (8) |
N1—C2—C3 | 123.0 (8) | N29—C30—H30 | 118.9 |
N1—C2—H2 | 118.5 | C31—C30—H30 | 118.9 |
C3—C2—H2 | 118.5 | C32—C31—C30 | 119.3 (9) |
C4—C3—C2 | 118.5 (8) | C32—C31—H31 | 120.3 |
C4—C3—H3 | 120.8 | C30—C31—H31 | 120.3 |
C2—C3—H3 | 120.8 | C31—C32—C33 | 121.1 (9) |
C3—C4—C5 | 120.3 (8) | C31—C32—H32 | 119.4 |
C3—C4—H4 | 119.9 | C33—C32—H32 | 119.4 |
C5—C4—H4 | 119.9 | C32—C33—C42 | 116.3 (8) |
C4—C5—C14 | 117.4 (8) | C32—C33—C34 | 125.4 (9) |
C4—C5—C6 | 124.9 (9) | C42—C33—C34 | 118.2 (8) |
C14—C5—C6 | 117.7 (8) | C35—C34—C33 | 122.0 (8) |
C7—C6—C5 | 121.9 (8) | C35—C34—H34 | 119.0 |
C7—C6—H6 | 119.0 | C33—C34—H34 | 119.0 |
C5—C6—H6 | 119.0 | C34—C35—C36 | 120.5 (8) |
C6—C7—C8 | 121.9 (8) | C34—C35—H35 | 119.7 |
C6—C7—H7 | 119.1 | C36—C35—H35 | 119.7 |
C8—C7—H7 | 119.1 | C37—C36—C41 | 116.8 (8) |
C7—C8—C9 | 124.7 (8) | C37—C36—C35 | 123.5 (8) |
C7—C8—C13 | 119.0 (8) | C41—C36—C35 | 119.7 (8) |
C9—C8—C13 | 116.3 (8) | C38—C37—C36 | 120.4 (9) |
C10—C9—C8 | 120.1 (8) | C38—C37—H37 | 119.8 |
C10—C9—H9 | 119.9 | C36—C37—H37 | 119.8 |
C8—C9—H9 | 119.9 | C37—C38—C39 | 120.6 (8) |
C9—C10—C11 | 118.8 (8) | C37—C38—H38 | 119.7 |
C9—C10—H10 | 120.6 | C39—C38—H38 | 119.7 |
C11—C10—H10 | 120.6 | N40—C39—C38 | 120.1 (8) |
N12—C11—C10 | 123.6 (9) | N40—C39—H39 | 120.0 |
N12—C11—H11 | 118.2 | C38—C39—H39 | 120.0 |
C10—C11—H11 | 118.2 | C39—N40—C41 | 119.3 (7) |
C11—N12—C13 | 118.0 (7) | C39—N40—Cu | 128.6 (6) |
C11—N12—Cu | 130.0 (6) | C41—N40—Cu | 111.9 (5) |
C13—N12—Cu | 112.0 (5) | N40—C41—C36 | 122.7 (7) |
N12—C13—C8 | 123.1 (7) | N40—C41—C42 | 118.2 (7) |
N12—C13—C14 | 118.1 (7) | C36—C41—C42 | 119.1 (7) |
C8—C13—C14 | 118.8 (7) | N29—C42—C33 | 122.3 (7) |
N1—C14—C5 | 121.1 (7) | N29—C42—C41 | 117.3 (7) |
N1—C14—C13 | 118.2 (7) | C33—C42—C41 | 120.4 (7) |
C5—C14—C13 | 120.7 (7) | O1—S—C44 | 107.7 (7) |
C16—N15—C28 | 118.3 (7) | O1—S—C43 | 104.4 (7) |
C16—N15—Cu | 126.9 (6) | C44—S—C43 | 94.8 (6) |
C28—N15—Cu | 114.8 (5) | S—C43—H43A | 109.5 |
N15—C16—C17 | 123.7 (8) | S—C43—H43B | 109.5 |
N15—C16—H16 | 118.1 | H43A—C43—H43B | 109.5 |
C17—C16—H16 | 118.1 | S—C43—H43C | 109.5 |
C18—C17—C16 | 117.5 (8) | H43A—C43—H43C | 109.5 |
C18—C17—H17 | 121.2 | H43B—C43—H43C | 109.5 |
C16—C17—H17 | 121.2 | S—C44—H44A | 109.5 |
C17—C18—C19 | 120.8 (8) | S—C44—H44B | 109.5 |
C17—C18—H18 | 119.6 | H44A—C44—H44B | 109.5 |
C19—C18—H18 | 119.6 | S—C44—H44C | 109.5 |
C18—C19—C28 | 117.2 (7) | H44A—C44—H44C | 109.5 |
C18—C19—C20 | 124.5 (8) | H44B—C44—H44C | 109.5 |
I2—Hg1—I5—Hg2 | 116.86 (2) | C22—C23—C24—C25 | 0.1 (14) |
I1—Hg1—I5—Hg2 | −110.91 (2) | C23—C24—C25—N26 | 1.2 (14) |
I6—Hg1—I5—Hg2 | −3.03 (2) | C24—C25—N26—C27 | −2.1 (12) |
I4—Hg2—I5—Hg1 | 116.76 (3) | C24—C25—N26—Cu | 172.3 (6) |
I3—Hg2—I5—Hg1 | −104.05 (3) | N15—Cu—N26—C25 | −178.7 (7) |
I6—Hg2—I5—Hg1 | 2.99 (2) | N29—Cu—N26—C25 | −4.9 (7) |
I2—Hg1—I6—Hg2 | −114.34 (3) | N1—Cu—N26—C25 | 89.4 (7) |
I1—Hg1—I6—Hg2 | 113.12 (2) | N40—Cu—N26—C25 | −84.2 (7) |
I5—Hg1—I6—Hg2 | 3.01 (2) | N15—Cu—N26—C27 | −4.1 (5) |
I4—Hg2—I6—Hg1 | −121.08 (2) | N29—Cu—N26—C27 | 169.8 (5) |
I3—Hg2—I6—Hg1 | 104.99 (2) | N1—Cu—N26—C27 | −95.9 (5) |
I5—Hg2—I6—Hg1 | −2.98 (2) | N40—Cu—N26—C27 | 90.5 (5) |
N15—Cu—N1—C2 | −84.0 (6) | C25—N26—C27—C22 | 1.7 (11) |
N29—Cu—N1—C2 | 88.0 (6) | Cu—N26—C27—C22 | −173.7 (6) |
N40—Cu—N1—C2 | 145.1 (9) | C25—N26—C27—C28 | 179.6 (6) |
N12—Cu—N1—C2 | −177.8 (7) | Cu—N26—C27—C28 | 4.2 (8) |
N26—Cu—N1—C2 | −5.6 (7) | C23—C22—C27—N26 | −0.5 (11) |
N15—Cu—N1—C14 | 95.2 (5) | C21—C22—C27—N26 | −179.3 (7) |
N29—Cu—N1—C14 | −92.8 (5) | C23—C22—C27—C28 | −178.3 (7) |
N40—Cu—N1—C14 | −35.7 (13) | C21—C22—C27—C28 | 2.9 (11) |
N12—Cu—N1—C14 | 1.4 (5) | C16—N15—C28—C19 | −1.4 (11) |
N26—Cu—N1—C14 | 173.6 (5) | Cu—N15—C28—C19 | 178.4 (5) |
C14—N1—C2—C3 | 2.7 (12) | C16—N15—C28—C27 | 178.1 (7) |
Cu—N1—C2—C3 | −178.1 (6) | Cu—N15—C28—C27 | −2.1 (8) |
N1—C2—C3—C4 | −2.7 (13) | C18—C19—C28—N15 | 0.9 (11) |
C2—C3—C4—C5 | 1.2 (13) | C20—C19—C28—N15 | −177.2 (7) |
C3—C4—C5—C14 | 0.0 (12) | C18—C19—C28—C27 | −178.5 (7) |
C3—C4—C5—C6 | −179.5 (9) | C20—C19—C28—C27 | 3.4 (11) |
C4—C5—C6—C7 | 177.9 (9) | N26—C27—C28—N15 | −1.6 (10) |
C14—C5—C6—C7 | −1.6 (14) | C22—C27—C28—N15 | 176.3 (7) |
C5—C6—C7—C8 | 2.0 (16) | N26—C27—C28—C19 | 177.9 (7) |
C6—C7—C8—C9 | 179.9 (10) | C22—C27—C28—C19 | −4.2 (11) |
C6—C7—C8—C13 | −1.6 (16) | N15—Cu—N29—C30 | 118.1 (12) |
C7—C8—C9—C10 | −180.0 (11) | N1—Cu—N29—C30 | −14.0 (7) |
C13—C8—C9—C10 | 1.5 (14) | N40—Cu—N29—C30 | 177.2 (7) |
C8—C9—C10—C11 | −2.2 (16) | N12—Cu—N29—C30 | −92.2 (7) |
C9—C10—C11—N12 | 2.7 (16) | N26—Cu—N29—C30 | 84.7 (7) |
C10—C11—N12—C13 | −2.4 (12) | N15—Cu—N29—C42 | −61.4 (14) |
C10—C11—N12—Cu | 178.8 (7) | N1—Cu—N29—C42 | 166.5 (5) |
N15—Cu—N12—C11 | 85.4 (7) | N40—Cu—N29—C42 | −2.3 (5) |
N29—Cu—N12—C11 | −89.1 (7) | N12—Cu—N29—C42 | 88.3 (5) |
N1—Cu—N12—C11 | 178.2 (7) | N26—Cu—N29—C42 | −94.8 (5) |
N40—Cu—N12—C11 | −9.8 (7) | C42—N29—C30—C31 | 2.5 (12) |
N15—Cu—N12—C13 | −93.4 (5) | Cu—N29—C30—C31 | −177.0 (6) |
N29—Cu—N12—C13 | 92.1 (5) | N29—C30—C31—C32 | −3.6 (14) |
N1—Cu—N12—C13 | −0.6 (5) | C30—C31—C32—C33 | 1.2 (15) |
N40—Cu—N12—C13 | 171.4 (5) | C31—C32—C33—C42 | 1.8 (13) |
C11—N12—C13—C8 | 1.7 (11) | C31—C32—C33—C34 | −178.4 (9) |
Cu—N12—C13—C8 | −179.3 (6) | C32—C33—C34—C35 | −178.2 (9) |
C11—N12—C13—C14 | −179.1 (7) | C42—C33—C34—C35 | 1.6 (13) |
Cu—N12—C13—C14 | −0.2 (8) | C33—C34—C35—C36 | −0.3 (14) |
C7—C8—C13—N12 | −179.9 (8) | C34—C35—C36—C37 | −179.9 (9) |
C9—C8—C13—N12 | −1.3 (12) | C34—C35—C36—C41 | 0.2 (13) |
C7—C8—C13—C14 | 1.0 (12) | C41—C36—C37—C38 | 2.6 (13) |
C9—C8—C13—C14 | 179.6 (8) | C35—C36—C37—C38 | −177.4 (9) |
C2—N1—C14—C5 | −1.4 (11) | C36—C37—C38—C39 | −1.4 (14) |
Cu—N1—C14—C5 | 179.4 (6) | C37—C38—C39—N40 | −0.8 (13) |
C2—N1—C14—C13 | 177.3 (7) | C38—C39—N40—C41 | 1.6 (11) |
Cu—N1—C14—C13 | −2.0 (8) | C38—C39—N40—Cu | −173.5 (6) |
C4—C5—C14—N1 | 0.0 (11) | N15—Cu—N40—C39 | −10.1 (7) |
C6—C5—C14—N1 | 179.6 (7) | N29—Cu—N40—C39 | 179.3 (7) |
C4—C5—C14—C13 | −178.6 (7) | N1—Cu—N40—C39 | 120.7 (11) |
C6—C5—C14—C13 | 0.9 (11) | N12—Cu—N40—C39 | 84.5 (7) |
N12—C13—C14—N1 | 1.5 (10) | N26—Cu—N40—C39 | −88.3 (7) |
C8—C13—C14—N1 | −179.3 (7) | N15—Cu—N40—C41 | 174.4 (5) |
N12—C13—C14—C5 | −179.9 (7) | N29—Cu—N40—C41 | 3.8 (5) |
C8—C13—C14—C5 | −0.7 (11) | N1—Cu—N40—C41 | −54.7 (12) |
N29—Cu—N15—C16 | 148.8 (11) | N12—Cu—N40—C41 | −90.9 (5) |
N1—Cu—N15—C16 | −79.0 (7) | N26—Cu—N40—C41 | 96.3 (5) |
N40—Cu—N15—C16 | 91.0 (7) | C39—N40—C41—C36 | −0.4 (11) |
N12—Cu—N15—C16 | −0.9 (7) | Cu—N40—C41—C36 | 175.6 (6) |
N26—Cu—N15—C16 | −176.9 (7) | C39—N40—C41—C42 | 179.2 (7) |
N29—Cu—N15—C28 | −31.0 (15) | Cu—N40—C41—C42 | −4.8 (8) |
N1—Cu—N15—C28 | 101.2 (5) | C37—C36—C41—N40 | −1.8 (12) |
N40—Cu—N15—C28 | −88.8 (5) | C35—C36—C41—N40 | 178.2 (7) |
N12—Cu—N15—C28 | 179.4 (5) | C37—C36—C41—C42 | 178.7 (7) |
N26—Cu—N15—C28 | 3.3 (5) | C35—C36—C41—C42 | −1.4 (11) |
C28—N15—C16—C17 | 0.8 (12) | C30—N29—C42—C33 | 0.8 (11) |
Cu—N15—C16—C17 | −179.0 (6) | Cu—N29—C42—C33 | −179.6 (6) |
N15—C16—C17—C18 | 0.3 (14) | C30—N29—C42—C41 | −179.1 (7) |
C16—C17—C18—C19 | −0.7 (13) | Cu—N29—C42—C41 | 0.5 (8) |
C17—C18—C19—C28 | 0.2 (12) | C32—C33—C42—N29 | −2.9 (12) |
C17—C18—C19—C20 | 178.1 (8) | C34—C33—C42—N29 | 177.3 (7) |
C18—C19—C20—C21 | −179.5 (8) | C32—C33—C42—C41 | 177.0 (7) |
C28—C19—C20—C21 | −1.5 (12) | C34—C33—C42—C41 | −2.8 (11) |
C19—C20—C21—C22 | 0.3 (13) | N40—C41—C42—N29 | 3.1 (10) |
C20—C21—C22—C27 | −1.0 (12) | C36—C41—C42—N29 | −177.3 (7) |
C20—C21—C22—C23 | −179.6 (8) | N40—C41—C42—C33 | −176.9 (7) |
C27—C22—C23—C24 | −0.4 (13) | C36—C41—C42—C33 | 2.7 (11) |
C21—C22—C23—C24 | 178.3 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2W···O1 | 0.89 (8) | 1.89 (10) | 2.664 (14) | 144 (15) |
C4—H4···Cgi | 0.93 | 2.74 | 3.619 (10) | 160 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H8N2)3][Hg2I6]·C2H6OS·H2O |
Mr | 1862.88 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 12.6628 (10), 18.8367 (15), 20.1380 (16) |
β (°) | 95.789 (1) |
V (Å3) | 4778.9 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.81 |
Crystal size (mm) | 0.25 × 0.17 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.123, 0.339 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29955, 9373, 5667 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.094, 1.00 |
No. of reflections | 9373 |
No. of parameters | 503 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.97, −0.80 |
Computer programs: SMART (Bruker, 2002), SMART, SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Cu—N1 | 2.120 (6) | Hg1—I2 | 2.6903 (8) |
Cu—N12 | 2.179 (6) | Hg1—I5 | 2.9020 (8) |
Cu—N15 | 2.082 (6) | Hg1—I6 | 2.9151 (7) |
Cu—N26 | 2.189 (6) | Hg2—I3 | 2.6967 (7) |
Cu—N29 | 2.098 (6) | Hg2—I4 | 2.6914 (8) |
Cu—N40 | 2.128 (6) | Hg2—I5 | 2.9248 (7) |
Hg1—I1 | 2.7301 (7) | Hg2—I6 | 2.9499 (8) |
N1—Cu—N12 | 77.9 (2) | I1—Hg1—I2 | 118.02 (2) |
N1—Cu—N40 | 166.8 (2) | I5—Hg1—I6 | 93.86 (2) |
N12—Cu—N26 | 171.5 (2) | I3—Hg2—I4 | 122.37 (2) |
N15—Cu—N26 | 78.0 (2) | I5—Hg2—I6 | 92.661 (19) |
N15—Cu—N29 | 169.1 (2) | Hg1—I5—Hg2 | 87.016 (19) |
N29—Cu—N40 | 79.2 (2) | Hg1—I6—Hg2 | 86.309 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2W···O1 | 0.89 (8) | 1.89 (10) | 2.664 (14) | 144 (15) |
C4—H4···Cgi | 0.93 | 2.74 | 3.619 (10) | 160 |
Symmetry code: (i) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Examples of monomeric tris-chelated complexes of copper(II) involving neutral N,N'-donors are limited and uncommon because of pronounced Jahn–Teller distortions (Anderson, 1972, 1973; Bertini et al., 1979; Cullen & Lingafelter et al., 1970; Folgado et al., 1990; Majumdar et al., 1998). The generalized synthetic device for this type of compound was developed by Goswani and co-workers (Choudhury et al., 1992; Choudhury, Deb & Goswami, 1994; Choudhury, Deb, Kharmawaphlang & Goswami, 1994; Deb et al., 1991; Kakoti et al., 1992; Kharmawaphlang et al., 1995), following the silver(I)-assisted metal exchange strategy. In the present work, we examined the exchange reaction between Cu(phen)I2 and Hg(phen)I2 (phen is 1,10-phenanthroline), with the hope of preparing tris chelates of CuII. Since HgII is a much softer Lewis acid than CuII, it was expected that the HgII center in Hg(phen)I2 would accept softer iodide ions from Cu(phen)I2, and provide a harder phen molecule, a typical N,N'-donor ligand, to the CuII center (Pearson, 1963).
A black solid was produced from the reaction of Cu(phen)I2 with Hg(phen)I2. When this solid was recrystallized, two differently colored crystals were formed in a dimethyl sulfoxide (DMSO)–water mixture; most of the sample crystallized as black crystallites, later identified by the elemental analysis as the bis-complex Cu(phen)2HgI4. The crystal structure of the minor product, pale-green crystals, (I), is presented here.
Selected bond distances and bond angles for (I) are summarized in Table 1. The crystal structure of (I) consists of discrete [Cu(phen)3]2+ cations and [Hg2I6]2− anions in a 1:1 ratio (Fig. 1). The CuII center in the [Cu(phen)3]2+ cation is six-coordinated with six N atoms of three phen ligands to form a distorted octahedral CuIIN6 chromophore. The [Cu(phen)3]2+ ion exhibits a static Jahn–Teller effect, with two long Cu—N bonds of similar distances at the axial site (Cu—N12 and Cu—N26). However, the remaining four shorter Cu—N bond distances on the equatorial plane are not equivalent, with a range of 2.082 (6)–2.128 (6) Å. In this respect, the distortion in the cation of (I) differs from those observed previously for other tris-chelated CuII complexes involving N,N'-donors, such as [Cu(byp)3](ClO4)2 (byp is 2,2'-bipyridine; Majumdar et al., 1998), [Cu(en)3](ClO4)2 (en is ethylenediamine; Bertini et al., 1979; Cullen & Lingafelter et al., 1970) and [Cu(phen)3](ClO4)2 (Anderson, 1973). The three larger N—Cu—N bond angles, where the two N atoms are in trans positions, differ by 8.5–13.2° from the ideal value of 180° for a perfect octahedron. The three dihedral angles between the N—Cu—N planes of the coordinated phen ligands are 85.2 (2), 86.9 (2) and 87.2 (2)°, respectively.
The bridging Hg—I bond distances in (I) range from 2.9020 (8) to 2.9499 (8) Å, and those in the terminal positions range from 2.6903 (8) to 2.7301 (7) Å. These values are well within the reported bond distances (2.864–3.005 Å for bridging iodide and 2.574–2.756 Å for terminal iodide) in [Hg2I6]2− anions (Bell et al., 2002; Fabry & Maximov, 1991; Pickardt & Wischlinski, 1999).
Packing stability of the structure of (I) is provided by hydrogen-bonding interactions between the DMSO molecule and the water molecule, and by C4—H4···Cgi [where Cgi is the centroid of ring C19–C22/C27/C28] interactions (see Table 2). There is also a probable hydrogen bond between the H atom (not located) of water O2W and the mercurate iodide atom I4 [O2W···I4 = 3.830 (10) Å]. The intermolecular distance between the two parallel aromatic rings of the coordinated phen ligands in the packing structure is longer than 4.11 Å, indicating an absence of significant π–π interactions between them.