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metal-organic compounds
Di-μ-halogeno-bis[halogeno(triphenylphosphine)mercury(II)], [Ph3PHgX(μ-X)2XHgPPh3], reinvestigated at 120 K for X = Cl and Br, and a second polymorph for X = I, also at 120 K
aDepartment of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu 620 024, India, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk
Di-μ-chloro-bis[chloro(triphenylphosphine)mercury(II)], [Hg2Cl4(C18H15P)2], (I), and di-μ-bromo-bis[bromo(triphenylphosphine)mercury(II)], [Hg2Br4(C18H15P)2], (II), have been reinvestigated at 120 K. The molecules of (I) lie across inversion centres in P21/n, and in both (I) and (II) the complexes are linked into three-dimensional frameworks by a combination of C—H⋯X (X = Cl and Br) and C—H⋯π(arene) hydrogen bonds. At 120 K, di-μ-iodo-bis[iodo(triphenylphosphine)mercury(II)], [Hg2I4(C18H15P)2], (III), crystallizes as a new polymorphic form having Z′ = , where the complexes lie across inversion centres in P21/n; the complexes are linked into sheets by a combination of C—H⋯I and C—H⋯π(arene) hydrogen bonds. In the Z′ = 1 polymorph of this compound, a single C—H⋯I hydrogen bond generates simple chains.
Comment
The structures of the title compounds, Ph3PHgX(μ2-X)2XHgPPh3] [X = Cl for (I), Br for (II)
and I for (III)
], were first reported some years ago. For X = Cl (Bell et al., 1980
), the structure was refined to R = 0.083 using diffraction data collected at ambient temperature. Only Hg, Cl and P atoms were refined anisotropically, and the phenyl rings were all constrained to be rigid hexagons; no H atoms were included in the A very similar was used for X = Br (Bowmaker et al., 1993
), although in this case H atoms were included in calculated positions, giving a final R value of 0.070. The use of ambient-temperature diffraction data for X = I (Bell et al., 1989
) allowed anisotropic of most of the C atoms, although several remained isotropic, possibly indicating some difficulties with the which terminated at R = 0.094. There is an otherwise unpublished set of coordinates for this same compound (Dix & Jones, 1997
) deposited in the Cambridge Structural Database (CSD; Allen, 2002
; refcode JAHCOK01), based on a using diffraction data collected at 173 K and giving R = 0.056. For each of (I)–(III)
, the gross structure of the complex is similar, containing halogen-bridged dimers which are crystallographically centrosymmetric for X = Cl and approximately centrosymmetric for X = Br or I; however, none of the published reports identified any supramolecular aggregation beyond the formation of the halogen-bridged dimers.
We have now taken the opportunity to redetermine the structures of (I)–(III) using data collected at 120 K. For (I)
and (II)
, we find the same phases at 120 K as those previously reported at ambient temperature. It is clear that in both structures there are significant C—H⋯π(arene) and C—H⋯X (X = Cl and Br) hydrogen bonds, which together link the dimeric complexes into continuous three-dimensional framework structures. On the other hand, for (III)
, we find a different phase from that reported previously. The previous reports (Bell et al., 1989
; Dix & Jones, 1997
) describe a monoclinic structure having Z = 4 and Z′ = 1 at both 298 and 173 K, which is, in fact, isostructural with (II)
.
We find here for (III) a different monoclinic structure at 120 K, with Z = 2 and Z′ =
, whose unit-cell dimensions are similar to those of (I)
, but whose overall structure mimics the mirror image of (I)
(Figs. 1
and 2
). In this Z′ =
phase of (III)
, the centrosymmetric dimers are linked into sheets by a combination of C—H⋯π(arene) and C—H⋯I hydrogen bonds and an aromatic π–π stacking interaction.
For both (I), where we have refined the structure without any of the constraints applied earlier (Bell et al., 1980
), and (III)
, the precision is significantly better than reported previously. Thus, for example, for both (I)
and the Z′ = 1 polymorph of (III)
, the previously reported s.u. values for the P—C bonds are 0.02–0.03 Å (Bell et al., 1980
, 1989
), whereas from the present refinements of (I)
and the Z′ =
polymorph of (III)
, these s.u. values are 0.003 and 0.004 Å, respectively (Tables 1
and 3
). In addition, the R values are very much lower for the present refinements of (I)
and (III)
. In each of (I)
and (III)
, the long bridging Hg—X bonds (X = Cl and I) (Tables 1
and 3
) may be indicative of significant ionic character in these bonds.
As in the published report on the bromo complex (II), some difficulty was experienced even using data collected at 120 K, and attempts to refine the C atoms anisotropically consistently led to unacceptable displacement ellipsoids, although refinements with these atoms assigned isotropic displacement parameters appeared to be satisfactory. Accordingly, we do not discuss this structure in detail, beyond confirming that the same phase occurs at 120 K as at ambient temperature and noting that the dimeric complexes are linked into a three-dimensional framework by hydrogen bonds.
In compound (I) (Fig. 1
), atoms C24 at (x, y, z) and (1 − x, 1 − y, 1 − z), which are both components of the complex centred at (
,
,
), act as hydrogen-bond donors (Table 2
) to the C31–C36 aryl rings at (
+ x,
− y, −
+ z) and (
− x,
+ y,
− z), respectively, which themselves are components of the complexes centred at (1, 0, 0) and (0, 1, 1), respectively. Similarly, the C31–C36 aryl rings at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C24 at (−
+ x,
− y,
+ z) and (
− x,
+ y,
− z), which lie in the complexes centred at (0, 0, 1) and (1, 1, 0), respectively. By this means, the dimeric complexes are linked by a single C—H⋯π(arene) hydrogen bond into sheets lying parallel to (101) (Fig. 3
)
There is a single π–π stacking interaction in the structure of (I), which serves to reinforce the (101) sheet. The C11–C16 rings in the molecules at (x, y, z) and (1 − x, −y, 1 − z), which lie in the same sheet, are parallel, with an interplanar spacing of 3.539 (2) Å; the ring-centroid separation is 3.782 (2) Å, corresponding to a near-ideal centroid offset of 1.334 (2) Å. In addition, there are a number of fairly short C—H⋯Cl interactions whose H⋯Cl distances are well within the van der Waals sum (Bondi, 1964
; Nyburg & Faerman, 1985
; Navon et al., 1997
) and which can therefore be regarded as weak hydrogen bonds (Table 2
). Two of the three C—H⋯Cl hydrogen bonds lie within a single (101) sheet, thus providing further reinforcement of the sheet, while the third such bond serves to generate a (10
) sheet.
Atoms C26 at (x, y, z) and (1 − x, 1 − y, 1 − z) act as donors to atoms Cl2 at (− + x,
− y, −
+ z) and (
− x,
+ y,
− z), respectively, which form parts of the dimeric complexes centred at (0, 0, 0) and (1, 1, 1). In like manner, atoms Cl2 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C26 at (
+ x,
− y,
+ z) and (
− x,
+ y,
− z), respectively, which are themselves components of the dimers centred at (1, 0, 1) and (0, 1, 0), so forming a (10
) sheet (Fig. 4
). The combination of the (101) and (10
) sheets, each generated by a single hydrogen bond, is sufficient to link all of the dimers into a single three-dimensional framework structure.
In compound (III) (Fig. 2
), the supramolecular aggregation involves C—H⋯π(arene) and C—H⋯I hydrogen bonds (Table 4
), augmented by a weak π–π stacking interaction, just as in (I)
, but the supramolecular structure is strictly two-dimensional, unlike that of (I)
. Atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C31–C36 ring at (
− x, −
+ y,
− z), which lies in the dimer centred at (0, 0, 1); propagation by the of this interaction then generates a (101) sheet (Fig. 5
), similar to that formed in (I)
. The single C—H⋯I hydrogen bond lies within this sheet, although its participants do not mimic those of either of the intrasheet C—H⋯Cl hydrogen bonds in (I)
. The C11–C16 rings in the molecules at (x, y, z) and (1 − x, −y, 1 − z), which lie in the same sheet, are parallel, with an interplanar spacing of 3.368 (3) Å, much smaller than the corresponding spacing in (I)
; the ring-centroid separation of 3.850 (3) Å is significantly larger than the corresponding distance in (I)
, and the ring-centroid offset is 1.865 (3) Å, indicating only a weak interaction. There are thus no direction-specific interactions between adjacent (101) sheets in (III)
.
In the Z′ = 1 polymorph of (III) (CSD refcode JAHCOK01), reanalysis of the atom coordinates at 173 K (Dix & Jones, 1997
) shows that C—H⋯π(arene) and aromatic π–π stacking interactions are both absent, and that the dimers are linked by a single C—H⋯I hydrogen bond into chains running parallel to the [001] direction and generated by the c-glide planes (Fig. 6
)
![]() | Figure 1 The dimeric molecular unit in (I) ![]() |
![]() | Figure 2 The dimeric molecular unit in (III) ![]() |
![]() | Figure 3 A stereoview of part of the crystal structure of (I) ![]() |
![]() | Figure 4 A stereoview of part of the crystal structure of (I) ![]() ![]() |
![]() | Figure 5 A stereoview of part of the crystal structure of (III) ![]() |
![]() | Figure 6 A stereoview of part of the crystal structure of JAHCOK01 (Dix & Jones, 1997 ![]() |
Experimental
For the preparation of compounds (I)–(III), an excess of triphenylphosphonium fluorenylide in CHCl3 solution was added dropwise at 273 K to a solution of the appropriate mercury(II) halide, also in chloroform, with a molar ratio of ylide to mercury in the range 1 to 2, and this mixture was then stirred at 303 K for 3 h. The solvent was removed and the solid residue was dissolved in dry tetrahydrofuran; after several days at 273 K, crystals suitable for single-crystal X-ray diffraction were obtained.
Compound (I)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
|
Refinement
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Compound (III)![[link]](../../../../../../logos/arrows/c_arr.gif)
Crystal data
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Refinement
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For compounds (I)–(III), the space groups P21/n, P21/c and P21/n, respectively, were uniquely assigned from the All H atoms were located in difference maps and then treated as riding, with C—H distances of 0.95 Å and Uiso(H) values of 1.2Ueq(C). For (II)
, the proceeded in an apparently satisfactory manner, with individual isotropic displacement parameters for the C atoms, to R = 0.051 and wR2 = 0.110 for 217 parameters and 6070 and 8349 data, respectively, but attempts to refine the C atoms anisotropically led to unacceptable displacement ellipsoids.
For compounds (I) and (III), data collection: COLLECT (Hooft, 1999); cell DENZO (Otwinowski & Minor, 1997
) and COLLECT; data reduction: DENZO and COLLECT; structure solution: OSCAIL (McArdle, 2003
) and SHELXS97 (Sheldrick, 1997
); structure OSCAIL and SHELXL97 (Sheldrick, 1997
); molecular graphics: PLATON (Spek, 2003
); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999
).
Supporting information
10.1107/S0108270105006323/sk1821sup1.cif
contains datablocks global, I, III. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270105006323/sk1821Isup2.hkl
Structure factors: contains datablock III. DOI: 10.1107/S0108270105006323/sk1821IIIsup3.hkl
For the preparation of compounds (I)–(III), an excess of triphenylphosphoniumfluorenylide in CHCl3 solution was added dropwise at 273 K to a solution of the appropriate mercury(II) halide, also in chloroform, with a molar ratio of ylide to mercury in the range 1 to 2, and this mixture was then stirred at 303 K for 3 h. The solvent was removed and the solid residue was dissolved in dry tetrahydrofuran; after several days at 273 K, crystals suitable for single-crystal X-ray diffraction were obtained.
For compounds (I)–(III), the space groups P21/n, P21/c and P21/n, respectively, were uniquely assigned from the
All H atoms were located from difference maps and then treated as riding, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C). For (II), the proceeded in an apparently satisfactory manner with individual isotropic displacement parameters for the C atoms to R = 0.051 and wR2 = 0.110 for 217 parameters and 6070 and 8349 data, respectively, but attempts to refine the C atoms anisotropically led to unacceptable displacement ellipsoids.For both compounds, data collection: COLLECT (Hooft, 1999); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).[Hg2Cl4(C18H15P)2] | F(000) = 1008 |
Mr = 1067.52 | Dx = 1.945 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4163 reflections |
a = 12.1540 (2) Å | θ = 3.4–27.5° |
b = 11.2982 (3) Å | µ = 8.82 mm−1 |
c = 13.2965 (3) Å | T = 120 K |
β = 93.3460 (16)° | Block, colourless |
V = 1822.74 (7) Å3 | 0.29 × 0.24 × 0.18 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 4163 independent reflections |
Radiation source: Bruker-Nonius FR91 rotating anode | 3593 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
ϕ and ω scans | h = −15→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.095, Tmax = 0.206 | l = −17→17 |
28163 measured reflections |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.048 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0178P)2 + 1.6853P] where P = (Fo2 + 2Fc2)/3 |
4163 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
[Hg2Cl4(C18H15P)2] | V = 1822.74 (7) Å3 |
Mr = 1067.52 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.1540 (2) Å | µ = 8.82 mm−1 |
b = 11.2982 (3) Å | T = 120 K |
c = 13.2965 (3) Å | 0.29 × 0.24 × 0.18 mm |
β = 93.3460 (16)° |
Nonius KappaCCD diffractometer | 4163 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3593 reflections with I > 2σ(I) |
Tmin = 0.095, Tmax = 0.206 | Rint = 0.042 |
28163 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.048 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.68 e Å−3 |
4163 reflections | Δρmin = −1.02 e Å−3 |
199 parameters |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.367411 (10) | 0.407649 (11) | 0.516114 (9) | 0.02284 (5) | |
Cl1 | 0.27867 (7) | 0.49128 (9) | 0.65634 (6) | 0.0346 (2) | |
Cl2 | 0.57435 (6) | 0.39891 (7) | 0.58025 (6) | 0.02321 (17) | |
P1 | 0.30893 (6) | 0.25929 (7) | 0.39545 (6) | 0.01729 (17) | |
C11 | 0.3327 (2) | 0.1129 (3) | 0.4456 (2) | 0.0192 (7) | |
C12 | 0.3016 (3) | 0.0887 (3) | 0.5432 (3) | 0.0266 (8) | |
C13 | 0.3128 (3) | −0.0250 (4) | 0.5819 (3) | 0.0344 (9) | |
C14 | 0.3548 (3) | −0.1146 (3) | 0.5240 (3) | 0.0317 (9) | |
C15 | 0.3878 (3) | −0.0905 (3) | 0.4280 (3) | 0.0284 (8) | |
C16 | 0.3767 (3) | 0.0226 (3) | 0.3888 (2) | 0.0233 (7) | |
C21 | 0.3771 (2) | 0.2699 (3) | 0.2786 (2) | 0.0187 (7) | |
C22 | 0.4831 (3) | 0.3161 (3) | 0.2787 (3) | 0.0268 (8) | |
C23 | 0.5379 (3) | 0.3171 (4) | 0.1908 (3) | 0.0381 (10) | |
C24 | 0.4876 (3) | 0.2725 (4) | 0.1025 (3) | 0.0382 (10) | |
C25 | 0.3817 (3) | 0.2276 (4) | 0.1016 (3) | 0.0317 (8) | |
C26 | 0.3266 (3) | 0.2265 (3) | 0.1892 (2) | 0.0267 (8) | |
C31 | 0.1617 (2) | 0.2713 (3) | 0.3674 (2) | 0.0194 (7) | |
C32 | 0.0989 (3) | 0.1714 (3) | 0.3415 (2) | 0.0250 (8) | |
C33 | −0.0136 (3) | 0.1831 (4) | 0.3187 (3) | 0.0327 (9) | |
C34 | −0.0630 (3) | 0.2932 (4) | 0.3219 (3) | 0.0349 (9) | |
C35 | −0.0006 (3) | 0.3925 (4) | 0.3473 (3) | 0.0348 (9) | |
C36 | 0.1119 (3) | 0.3817 (3) | 0.3696 (3) | 0.0260 (8) | |
H12 | 0.2729 | 0.1501 | 0.5829 | 0.032* | |
H13 | 0.2916 | −0.0415 | 0.6481 | 0.041* | |
H14 | 0.3610 | −0.1927 | 0.5502 | 0.038* | |
H15 | 0.4181 | −0.1517 | 0.3891 | 0.034* | |
H16 | 0.3991 | 0.0388 | 0.3229 | 0.028* | |
H22 | 0.5176 | 0.3469 | 0.3391 | 0.032* | |
H23 | 0.6104 | 0.3484 | 0.1907 | 0.046* | |
H24 | 0.5260 | 0.2729 | 0.0423 | 0.046* | |
H25 | 0.3471 | 0.1977 | 0.0409 | 0.038* | |
H26 | 0.2537 | 0.1961 | 0.1888 | 0.032* | |
H32 | 0.1328 | 0.0957 | 0.3395 | 0.030* | |
H33 | −0.0567 | 0.1153 | 0.3008 | 0.039* | |
H34 | −0.1400 | 0.3008 | 0.3066 | 0.042* | |
H35 | −0.0348 | 0.4680 | 0.3494 | 0.042* | |
H36 | 0.1549 | 0.4499 | 0.3865 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.02689 (8) | 0.02351 (8) | 0.01807 (7) | −0.00324 (5) | 0.00093 (5) | −0.00585 (5) |
Cl1 | 0.0239 (4) | 0.0573 (7) | 0.0231 (4) | 0.0073 (4) | 0.0055 (3) | −0.0109 (4) |
Cl2 | 0.0220 (4) | 0.0230 (4) | 0.0242 (4) | 0.0044 (3) | −0.0027 (3) | 0.0073 (3) |
P1 | 0.0162 (4) | 0.0206 (5) | 0.0152 (4) | −0.0017 (3) | 0.0020 (3) | −0.0021 (3) |
C11 | 0.0178 (16) | 0.0196 (18) | 0.0200 (17) | −0.0040 (13) | −0.0005 (12) | −0.0020 (13) |
C12 | 0.0291 (18) | 0.029 (2) | 0.0228 (18) | 0.0014 (15) | 0.0079 (14) | −0.0012 (15) |
C13 | 0.038 (2) | 0.039 (2) | 0.027 (2) | 0.0017 (18) | 0.0101 (16) | 0.0094 (17) |
C14 | 0.041 (2) | 0.022 (2) | 0.032 (2) | 0.0003 (16) | −0.0012 (17) | 0.0069 (15) |
C15 | 0.033 (2) | 0.0217 (19) | 0.030 (2) | 0.0044 (15) | 0.0019 (16) | −0.0043 (15) |
C16 | 0.0283 (18) | 0.0227 (19) | 0.0192 (17) | 0.0001 (14) | 0.0042 (13) | −0.0041 (14) |
C21 | 0.0199 (16) | 0.0213 (17) | 0.0151 (15) | 0.0009 (13) | 0.0031 (12) | 0.0012 (13) |
C22 | 0.0230 (17) | 0.033 (2) | 0.0247 (18) | −0.0066 (15) | 0.0046 (14) | −0.0050 (15) |
C23 | 0.0257 (19) | 0.059 (3) | 0.031 (2) | −0.0150 (18) | 0.0135 (16) | −0.0082 (19) |
C24 | 0.037 (2) | 0.058 (3) | 0.0211 (19) | −0.0006 (19) | 0.0163 (15) | 0.0001 (18) |
C25 | 0.032 (2) | 0.046 (2) | 0.0170 (17) | −0.0004 (17) | 0.0022 (14) | −0.0021 (16) |
C26 | 0.0234 (17) | 0.037 (2) | 0.0199 (17) | −0.0022 (15) | 0.0016 (13) | −0.0017 (15) |
C31 | 0.0183 (15) | 0.0271 (18) | 0.0132 (15) | −0.0003 (14) | 0.0035 (12) | −0.0006 (13) |
C32 | 0.0207 (17) | 0.035 (2) | 0.0200 (17) | −0.0018 (14) | 0.0019 (13) | −0.0096 (15) |
C33 | 0.0234 (18) | 0.051 (3) | 0.0236 (19) | −0.0089 (17) | −0.0007 (14) | −0.0124 (17) |
C34 | 0.0194 (18) | 0.062 (3) | 0.0232 (19) | 0.0035 (18) | 0.0001 (14) | 0.0003 (18) |
C35 | 0.031 (2) | 0.039 (2) | 0.034 (2) | 0.0128 (17) | 0.0029 (16) | 0.0099 (17) |
C36 | 0.0214 (17) | 0.029 (2) | 0.0276 (19) | 0.0023 (14) | 0.0030 (14) | 0.0074 (15) |
Hg1—Cl1 | 2.4015 (8) | C22—C23 | 1.379 (5) |
Hg1—Cl2 | 2.6101 (8) | C22—H22 | 0.95 |
Hg1—Cl2i | 2.6506 (8) | C23—C24 | 1.386 (5) |
Cl2—Hg1i | 2.6506 (8) | C23—H23 | 0.95 |
Hg1—P1 | 2.3991 (8) | C24—C25 | 1.383 (5) |
P1—C11 | 1.801 (3) | C24—H24 | 0.95 |
P1—C21 | 1.807 (3) | C25—C26 | 1.378 (5) |
P1—C31 | 1.812 (3) | C25—H25 | 0.95 |
C11—C16 | 1.394 (4) | C26—H26 | 0.95 |
C11—C12 | 1.399 (5) | C31—C36 | 1.387 (5) |
C12—C13 | 1.387 (5) | C31—C32 | 1.394 (5) |
C12—H12 | 0.95 | C32—C33 | 1.390 (5) |
C13—C14 | 1.388 (5) | C32—H32 | 0.95 |
C13—H13 | 0.95 | C33—C34 | 1.383 (6) |
C14—C15 | 1.387 (5) | C33—H33 | 0.95 |
C14—H14 | 0.95 | C34—C35 | 1.384 (5) |
C15—C16 | 1.383 (5) | C34—H34 | 0.95 |
C15—H15 | 0.95 | C35—C36 | 1.388 (5) |
C16—H16 | 0.95 | C35—H35 | 0.95 |
C21—C22 | 1.389 (4) | C36—H36 | 0.95 |
C21—C26 | 1.394 (4) | ||
P1—Hg1—Cl1 | 131.69 (3) | C23—C22—C21 | 119.8 (3) |
P1—Hg1—Cl2 | 115.74 (3) | C23—C22—H22 | 120.1 |
Cl1—Hg1—Cl2 | 103.24 (3) | C21—C22—H22 | 120.1 |
P1—Hg1—Cl2i | 109.26 (3) | C22—C23—C24 | 120.2 (3) |
Cl1—Hg1—Cl2i | 101.28 (3) | C22—C23—H23 | 119.9 |
Cl2—Hg1—Cl2i | 84.82 (2) | C24—C23—H23 | 119.9 |
Hg1—Cl2—Hg1i | 95.18 (2) | C25—C24—C23 | 120.3 (3) |
C11—P1—C21 | 107.91 (15) | C25—C24—H24 | 119.8 |
C11—P1—C31 | 106.26 (15) | C23—C24—H24 | 119.8 |
C21—P1—C31 | 108.36 (14) | C26—C25—C24 | 119.6 (3) |
C11—P1—Hg1 | 111.06 (10) | C26—C25—H25 | 120.2 |
C21—P1—Hg1 | 113.32 (11) | C24—C25—H25 | 120.2 |
C31—P1—Hg1 | 109.64 (11) | C25—C26—C21 | 120.4 (3) |
C16—C11—C12 | 119.5 (3) | C25—C26—H26 | 119.8 |
C16—C11—P1 | 122.0 (2) | C21—C26—H26 | 119.8 |
C12—C11—P1 | 118.5 (2) | C36—C31—C32 | 120.0 (3) |
C13—C12—C11 | 119.9 (3) | C36—C31—P1 | 119.3 (3) |
C13—C12—H12 | 120.0 | C32—C31—P1 | 120.7 (3) |
C11—C12—H12 | 120.0 | C33—C32—C31 | 119.6 (3) |
C12—C13—C14 | 120.0 (3) | C33—C32—H32 | 120.2 |
C12—C13—H13 | 120.0 | C31—C32—H32 | 120.2 |
C14—C13—H13 | 120.0 | C34—C33—C32 | 120.1 (3) |
C15—C14—C13 | 120.2 (3) | C34—C33—H33 | 119.9 |
C15—C14—H14 | 119.9 | C32—C33—H33 | 119.9 |
C13—C14—H14 | 119.9 | C33—C34—C35 | 120.3 (3) |
C16—C15—C14 | 120.0 (3) | C33—C34—H34 | 119.9 |
C16—C15—H15 | 120.0 | C35—C34—H34 | 119.9 |
C14—C15—H15 | 120.0 | C34—C35—C36 | 120.0 (3) |
C15—C16—C11 | 120.2 (3) | C34—C35—H35 | 120.0 |
C15—C16—H16 | 119.9 | C36—C35—H35 | 120.0 |
C11—C16—H16 | 119.9 | C31—C36—C35 | 120.0 (3) |
C22—C21—C26 | 119.7 (3) | C31—C36—H36 | 120.0 |
C22—C21—P1 | 119.7 (2) | C35—C36—H36 | 120.0 |
C26—C21—P1 | 120.5 (2) | ||
P1—Hg1—Cl2—Hg1i | 108.90 (3) | C31—P1—C21—C22 | 150.9 (3) |
Cl1—Hg1—Cl2—Hg1i | −100.40 (3) | Hg1—P1—C21—C22 | 29.0 (3) |
Cl2i—Hg1—Cl2—Hg1i | 0.0 | C11—P1—C21—C26 | 82.3 (3) |
Cl1—Hg1—P1—C11 | −82.11 (12) | C31—P1—C21—C26 | −32.4 (3) |
Cl2—Hg1—P1—C11 | 58.25 (11) | Hg1—P1—C21—C26 | −154.3 (3) |
Cl2i—Hg1—P1—C11 | 151.82 (11) | C26—C21—C22—C23 | −1.0 (5) |
Cl1—Hg1—P1—C21 | 156.22 (11) | P1—C21—C22—C23 | 175.8 (3) |
Cl2—Hg1—P1—C21 | −63.42 (11) | C21—C22—C23—C24 | 0.2 (6) |
Cl2i—Hg1—P1—C21 | 30.16 (11) | C22—C23—C24—C25 | 0.5 (7) |
Cl1—Hg1—P1—C31 | 35.02 (12) | C23—C24—C25—C26 | −0.5 (6) |
Cl2—Hg1—P1—C31 | 175.38 (11) | C24—C25—C26—C21 | −0.3 (6) |
Cl2i—Hg1—P1—C31 | −91.05 (11) | C22—C21—C26—C25 | 1.0 (5) |
C21—P1—C11—C16 | −11.8 (3) | P1—C21—C26—C25 | −175.7 (3) |
C31—P1—C11—C16 | 104.2 (3) | C11—P1—C31—C36 | 152.4 (3) |
Hg1—P1—C11—C16 | −136.6 (2) | C21—P1—C31—C36 | −91.9 (3) |
C21—P1—C11—C12 | 170.8 (3) | Hg1—P1—C31—C36 | 32.2 (3) |
C31—P1—C11—C12 | −73.2 (3) | C11—P1—C31—C32 | −29.1 (3) |
Hg1—P1—C11—C12 | 46.0 (3) | C21—P1—C31—C32 | 86.7 (3) |
C16—C11—C12—C13 | −1.2 (5) | Hg1—P1—C31—C32 | −149.2 (2) |
P1—C11—C12—C13 | 176.2 (3) | C36—C31—C32—C33 | −0.4 (5) |
C11—C12—C13—C14 | 0.1 (5) | P1—C31—C32—C33 | −178.9 (3) |
C12—C13—C14—C15 | 1.2 (6) | C31—C32—C33—C34 | −0.2 (5) |
C13—C14—C15—C16 | −1.4 (5) | C32—C33—C34—C35 | 0.4 (5) |
C14—C15—C16—C11 | 0.2 (5) | C33—C34—C35—C36 | 0.0 (6) |
C12—C11—C16—C15 | 1.1 (5) | C32—C31—C36—C35 | 0.7 (5) |
P1—C11—C16—C15 | −176.3 (3) | P1—C31—C36—C35 | 179.3 (3) |
C11—P1—C21—C22 | −94.4 (3) | C34—C35—C36—C31 | −0.6 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···Cl1ii | 0.95 | 2.81 | 3.720 (4) | 161 |
C15—H15···Cl2iii | 0.95 | 2.83 | 3.520 (3) | 131 |
C26—H26···Cl2iv | 0.95 | 2.76 | 3.605 (4) | 148 |
C24—H24···Cg3v | 0.95 | 2.74 | 3.610 (4) | 153 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2; (v) x+1/2, −y+1/2, z−1/2. |
[Hg2I4(C18H15P)2] | F(000) = 1296 |
Mr = 1433.32 | Dx = 2.415 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4516 reflections |
a = 11.4078 (2) Å | θ = 3.6–27.5° |
b = 12.4980 (4) Å | µ = 11.01 mm−1 |
c = 13.9124 (4) Å | T = 120 K |
β = 96.3270 (17)° | Block, colourless |
V = 1971.47 (9) Å3 | 0.35 × 0.26 × 0.24 mm |
Z = 2 |
Nonius KappaCCD diffractometer | 4516 independent reflections |
Radiation source: Bruker-Nonius FR91 rotating anode | 3935 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→16 |
Tmin = 0.041, Tmax = 0.071 | l = −18→18 |
24795 measured reflections |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0203P)2 + 2.7697P] where P = (Fo2 + 2Fc2)/3 |
4516 reflections | (Δ/σ)max = 0.002 |
199 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −1.31 e Å−3 |
[Hg2I4(C18H15P)2] | V = 1971.47 (9) Å3 |
Mr = 1433.32 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4078 (2) Å | µ = 11.01 mm−1 |
b = 12.4980 (4) Å | T = 120 K |
c = 13.9124 (4) Å | 0.35 × 0.26 × 0.24 mm |
β = 96.3270 (17)° |
Nonius KappaCCD diffractometer | 4516 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3935 reflections with I > 2σ(I) |
Tmin = 0.041, Tmax = 0.071 | Rint = 0.036 |
24795 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.70 e Å−3 |
4516 reflections | Δρmin = −1.31 e Å−3 |
199 parameters |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.373922 (13) | 0.388225 (12) | 0.472916 (11) | 0.01758 (5) | |
I1 | 0.22510 (2) | 0.38993 (2) | 0.308186 (19) | 0.02360 (8) | |
I2 | 0.61659 (2) | 0.39136 (2) | 0.44371 (2) | 0.01903 (7) | |
P1 | 0.32330 (8) | 0.27969 (8) | 0.61108 (7) | 0.0124 (2) | |
C11 | 0.3545 (3) | 0.1403 (3) | 0.5918 (3) | 0.0144 (8) | |
C12 | 0.3218 (3) | 0.0984 (3) | 0.5002 (3) | 0.0195 (9) | |
C13 | 0.3375 (4) | −0.0096 (3) | 0.4816 (3) | 0.0258 (10) | |
C14 | 0.3867 (4) | −0.0752 (4) | 0.5551 (4) | 0.0293 (11) | |
C15 | 0.4209 (4) | −0.0347 (4) | 0.6465 (3) | 0.0288 (10) | |
C16 | 0.4055 (4) | 0.0734 (3) | 0.6659 (3) | 0.0214 (9) | |
C21 | 0.3980 (3) | 0.3211 (3) | 0.7265 (3) | 0.0157 (8) | |
C22 | 0.5083 (4) | 0.3684 (3) | 0.7300 (3) | 0.0206 (9) | |
C23 | 0.5667 (4) | 0.4012 (4) | 0.8180 (3) | 0.0265 (10) | |
C24 | 0.5148 (4) | 0.3885 (3) | 0.9017 (3) | 0.0276 (10) | |
C25 | 0.4049 (4) | 0.3408 (5) | 0.8992 (3) | 0.0369 (12) | |
C26 | 0.3460 (4) | 0.3076 (4) | 0.8122 (3) | 0.0281 (11) | |
C31 | 0.1659 (3) | 0.2857 (3) | 0.6203 (3) | 0.0153 (8) | |
C32 | 0.1062 (3) | 0.2011 (3) | 0.6569 (3) | 0.0200 (9) | |
C33 | −0.0125 (4) | 0.2098 (4) | 0.6668 (3) | 0.0270 (10) | |
C34 | −0.0737 (4) | 0.3022 (4) | 0.6379 (3) | 0.0305 (11) | |
C35 | −0.0151 (4) | 0.3869 (4) | 0.6005 (3) | 0.0322 (11) | |
C36 | 0.1050 (4) | 0.3790 (3) | 0.5911 (3) | 0.0235 (9) | |
H12 | 0.2883 | 0.1440 | 0.4498 | 0.023* | |
H13 | 0.3146 | −0.0380 | 0.4190 | 0.031* | |
H14 | 0.3973 | −0.1491 | 0.5427 | 0.035* | |
H15 | 0.4550 | −0.0808 | 0.6963 | 0.035* | |
H16 | 0.4292 | 0.1015 | 0.7285 | 0.026* | |
H22 | 0.5440 | 0.3783 | 0.6722 | 0.025* | |
H23 | 0.6428 | 0.4326 | 0.8202 | 0.032* | |
H24 | 0.5543 | 0.4125 | 0.9615 | 0.033* | |
H25 | 0.3699 | 0.3309 | 0.9574 | 0.044* | |
H26 | 0.2703 | 0.2756 | 0.8105 | 0.034* | |
H32 | 0.1470 | 0.1367 | 0.6751 | 0.024* | |
H33 | −0.0525 | 0.1522 | 0.6936 | 0.032* | |
H34 | −0.1557 | 0.3073 | 0.6436 | 0.037* | |
H35 | −0.0567 | 0.4506 | 0.5813 | 0.039* | |
H36 | 0.1452 | 0.4369 | 0.5649 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.02282 (9) | 0.01667 (9) | 0.01345 (8) | −0.00295 (6) | 0.00287 (6) | 0.00339 (6) |
I1 | 0.02050 (14) | 0.03399 (17) | 0.01606 (14) | 0.00184 (11) | 0.00087 (11) | −0.00018 (11) |
I2 | 0.01982 (14) | 0.01288 (14) | 0.02532 (15) | 0.00109 (10) | 0.00667 (11) | −0.00394 (10) |
P1 | 0.0141 (5) | 0.0126 (5) | 0.0105 (5) | −0.0009 (4) | 0.0014 (4) | 0.0016 (4) |
C11 | 0.0147 (19) | 0.0121 (19) | 0.016 (2) | −0.0018 (14) | 0.0022 (15) | 0.0036 (15) |
C12 | 0.019 (2) | 0.020 (2) | 0.019 (2) | 0.0003 (16) | −0.0003 (16) | 0.0006 (17) |
C13 | 0.025 (2) | 0.023 (2) | 0.028 (2) | −0.0060 (18) | −0.0006 (18) | −0.0076 (19) |
C14 | 0.028 (2) | 0.009 (2) | 0.053 (3) | −0.0004 (17) | 0.014 (2) | 0.000 (2) |
C15 | 0.035 (3) | 0.020 (2) | 0.031 (3) | 0.0039 (19) | 0.003 (2) | 0.0097 (19) |
C16 | 0.025 (2) | 0.022 (2) | 0.017 (2) | 0.0054 (17) | −0.0006 (17) | 0.0045 (17) |
C21 | 0.0189 (19) | 0.015 (2) | 0.0131 (19) | 0.0037 (15) | −0.0004 (15) | −0.0003 (15) |
C22 | 0.023 (2) | 0.021 (2) | 0.017 (2) | −0.0034 (16) | 0.0010 (17) | 0.0044 (16) |
C23 | 0.023 (2) | 0.031 (3) | 0.023 (2) | −0.0055 (18) | −0.0091 (18) | 0.0044 (19) |
C24 | 0.035 (3) | 0.026 (2) | 0.020 (2) | 0.0062 (19) | −0.0053 (19) | −0.0057 (19) |
C25 | 0.031 (3) | 0.068 (4) | 0.012 (2) | 0.009 (2) | 0.0049 (18) | −0.005 (2) |
C26 | 0.017 (2) | 0.047 (3) | 0.020 (2) | −0.0053 (19) | 0.0039 (17) | −0.003 (2) |
C31 | 0.0101 (18) | 0.022 (2) | 0.0133 (19) | −0.0004 (15) | −0.0006 (14) | 0.0014 (16) |
C32 | 0.021 (2) | 0.021 (2) | 0.017 (2) | −0.0003 (16) | 0.0029 (16) | 0.0010 (17) |
C33 | 0.022 (2) | 0.032 (3) | 0.027 (2) | −0.0080 (19) | 0.0032 (18) | −0.002 (2) |
C34 | 0.014 (2) | 0.054 (3) | 0.024 (2) | 0.005 (2) | 0.0040 (18) | −0.002 (2) |
C35 | 0.027 (2) | 0.046 (3) | 0.025 (3) | 0.016 (2) | 0.0068 (19) | 0.011 (2) |
C36 | 0.023 (2) | 0.028 (2) | 0.021 (2) | 0.0075 (17) | 0.0048 (17) | 0.0078 (18) |
Hg1—I1 | 2.6977 (3) | C22—C23 | 1.389 (6) |
Hg1—I2 | 2.8422 (3) | C22—H22 | 0.95 |
Hg1—I2i | 2.9863 (3) | C23—C24 | 1.373 (7) |
I2—Hg1i | 2.9863 (3) | C23—H23 | 0.95 |
Hg1—P1 | 2.4724 (10) | C24—C25 | 1.386 (7) |
P1—C11 | 1.804 (4) | C24—H24 | 0.95 |
P1—C21 | 1.808 (4) | C25—C26 | 1.381 (6) |
P1—C31 | 1.816 (4) | C25—H25 | 0.95 |
C11—C12 | 1.391 (6) | C26—H26 | 0.95 |
C11—C16 | 1.403 (5) | C31—C32 | 1.386 (6) |
C12—C13 | 1.389 (6) | C31—C36 | 1.395 (5) |
C12—H12 | 0.95 | C32—C33 | 1.380 (6) |
C13—C14 | 1.381 (6) | C32—H32 | 0.95 |
C13—H13 | 0.95 | C33—C34 | 1.385 (6) |
C14—C15 | 1.385 (7) | C33—H33 | 0.95 |
C14—H14 | 0.95 | C34—C35 | 1.384 (7) |
C15—C16 | 1.393 (6) | C34—H34 | 0.95 |
C15—H15 | 0.95 | C35—C36 | 1.394 (6) |
C16—H16 | 0.95 | C35—H35 | 0.95 |
C21—C22 | 1.386 (6) | C36—H36 | 0.95 |
C21—C26 | 1.399 (6) | ||
P1—Hg1—I1 | 119.06 (2) | C21—C22—C23 | 120.2 (4) |
P1—Hg1—I2 | 115.68 (2) | C21—C22—H22 | 119.9 |
I1—Hg1—I2 | 114.213 (10) | C23—C22—H22 | 119.9 |
P1—Hg1—I2i | 101.87 (2) | C24—C23—C22 | 120.2 (4) |
I1—Hg1—I2i | 108.372 (9) | C24—C23—H23 | 119.9 |
I2—Hg1—I2i | 92.787 (8) | C22—C23—H23 | 119.9 |
Hg1—I2—Hg1i | 87.213 (8) | C23—C24—C25 | 120.2 (4) |
C11—P1—C21 | 109.09 (18) | C23—C24—H24 | 119.9 |
C11—P1—C31 | 105.29 (18) | C25—C24—H24 | 119.9 |
C21—P1—C31 | 107.34 (18) | C26—C25—C24 | 120.2 (4) |
C11—P1—Hg1 | 110.32 (13) | C26—C25—H25 | 119.9 |
C21—P1—Hg1 | 113.92 (13) | C24—C25—H25 | 119.9 |
C31—P1—Hg1 | 110.48 (13) | C25—C26—C21 | 120.0 (4) |
C12—C11—C16 | 119.8 (4) | C25—C26—H26 | 120.0 |
C12—C11—P1 | 117.6 (3) | C21—C26—H26 | 120.0 |
C16—C11—P1 | 122.6 (3) | C32—C31—C36 | 119.7 (4) |
C13—C12—C11 | 120.6 (4) | C32—C31—P1 | 121.6 (3) |
C13—C12—H12 | 119.7 | C36—C31—P1 | 118.6 (3) |
C11—C12—H12 | 119.7 | C33—C32—C31 | 120.2 (4) |
C14—C13—C12 | 119.3 (4) | C33—C32—H32 | 119.9 |
C14—C13—H13 | 120.3 | C31—C32—H32 | 119.9 |
C12—C13—H13 | 120.3 | C32—C33—C34 | 120.3 (4) |
C13—C14—C15 | 120.9 (4) | C32—C33—H33 | 119.8 |
C13—C14—H14 | 119.6 | C34—C33—H33 | 119.8 |
C15—C14—H14 | 119.6 | C35—C34—C33 | 119.9 (4) |
C14—C15—C16 | 120.2 (4) | C35—C34—H34 | 120.1 |
C14—C15—H15 | 119.9 | C33—C34—H34 | 120.1 |
C16—C15—H15 | 119.9 | C34—C35—C36 | 120.1 (4) |
C15—C16—C11 | 119.2 (4) | C34—C35—H35 | 120.0 |
C15—C16—H16 | 120.4 | C36—C35—H35 | 120.0 |
C11—C16—H16 | 120.4 | C35—C36—C31 | 119.7 (4) |
C22—C21—C26 | 119.3 (4) | C35—C36—H36 | 120.2 |
C22—C21—P1 | 119.4 (3) | C31—C36—H36 | 120.2 |
C26—C21—P1 | 121.3 (3) | ||
P1—Hg1—I2—Hg1i | −104.59 (3) | C31—P1—C21—C22 | −152.0 (3) |
I1—Hg1—I2—Hg1i | 111.586 (10) | Hg1—P1—C21—C22 | −29.4 (4) |
I2i—Hg1—I2—Hg1i | 0.0 | C11—P1—C21—C26 | −86.4 (4) |
I1—Hg1—P1—C11 | 77.93 (13) | C31—P1—C21—C26 | 27.2 (4) |
I2—Hg1—P1—C11 | −64.05 (13) | Hg1—P1—C21—C26 | 149.8 (3) |
I2i—Hg1—P1—C11 | −163.04 (13) | C26—C21—C22—C23 | 0.4 (6) |
I1—Hg1—P1—C21 | −158.99 (13) | P1—C21—C22—C23 | 179.6 (3) |
I2—Hg1—P1—C21 | 59.03 (14) | C21—C22—C23—C24 | −0.9 (6) |
I2i—Hg1—P1—C21 | −39.96 (14) | C22—C23—C24—C25 | 1.3 (7) |
I1—Hg1—P1—C31 | −38.08 (15) | C23—C24—C25—C26 | −1.2 (7) |
I2—Hg1—P1—C31 | 179.94 (14) | C24—C25—C26—C21 | 0.7 (8) |
I2i—Hg1—P1—C31 | 80.95 (14) | C22—C21—C26—C25 | −0.3 (7) |
C21—P1—C11—C12 | −169.2 (3) | P1—C21—C26—C25 | −179.5 (4) |
C31—P1—C11—C12 | 75.8 (3) | C11—P1—C31—C32 | 30.4 (4) |
Hg1—P1—C11—C12 | −43.4 (3) | C21—P1—C31—C32 | −85.7 (4) |
C21—P1—C11—C16 | 13.3 (4) | Hg1—P1—C31—C32 | 149.5 (3) |
C31—P1—C11—C16 | −101.6 (3) | C11—P1—C31—C36 | −150.6 (3) |
Hg1—P1—C11—C16 | 139.2 (3) | C21—P1—C31—C36 | 93.3 (3) |
C16—C11—C12—C13 | 0.9 (6) | Hg1—P1—C31—C36 | −31.5 (4) |
P1—C11—C12—C13 | −176.6 (3) | C36—C31—C32—C33 | −1.8 (6) |
C11—C12—C13—C14 | −0.4 (6) | P1—C31—C32—C33 | 177.3 (3) |
C12—C13—C14—C15 | −0.2 (7) | C31—C32—C33—C34 | 1.8 (6) |
C13—C14—C15—C16 | 0.3 (7) | C32—C33—C34—C35 | −1.2 (7) |
C14—C15—C16—C11 | 0.3 (6) | C33—C34—C35—C36 | 0.6 (7) |
C12—C11—C16—C15 | −0.9 (6) | C34—C35—C36—C31 | −0.6 (7) |
P1—C11—C16—C15 | 176.5 (3) | C32—C31—C36—C35 | 1.2 (6) |
C11—P1—C21—C22 | 94.4 (3) | P1—C31—C36—C35 | −177.9 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···I2ii | 0.95 | 3.04 | 3.952 (4) | 161 |
C15—H15···Cg3iii | 0.95 | 2.89 | 3.770 (5) | 154 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+1/2, y−1/2, −z+3/2. |
Experimental details
(I) | (III) | |
Crystal data | ||
Chemical formula | [Hg2Cl4(C18H15P)2] | [Hg2I4(C18H15P)2] |
Mr | 1067.52 | 1433.32 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 12.1540 (2), 11.2982 (3), 13.2965 (3) | 11.4078 (2), 12.4980 (4), 13.9124 (4) |
β (°) | 93.3460 (16) | 96.3270 (17) |
V (Å3) | 1822.74 (7) | 1971.47 (9) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 8.82 | 11.01 |
Crystal size (mm) | 0.29 × 0.24 × 0.18 | 0.35 × 0.26 × 0.24 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.095, 0.206 | 0.041, 0.071 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28163, 4163, 3593 | 24795, 4516, 3935 |
Rint | 0.042 | 0.036 |
(sin θ/λ)max (Å−1) | 0.649 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.048, 1.07 | 0.025, 0.055, 1.16 |
No. of reflections | 4163 | 4516 |
No. of parameters | 199 | 199 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −1.02 | 0.70, −1.31 |
Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
Hg1—Cl1 | 2.4015 (8) | P1—C11 | 1.801 (3) |
Hg1—Cl2 | 2.6101 (8) | P1—C21 | 1.807 (3) |
Hg1—Cl2i | 2.6506 (8) | P1—C31 | 1.812 (3) |
Hg1—P1 | 2.3991 (8) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···Cl1ii | 0.95 | 2.81 | 3.720 (4) | 161 |
C15—H15···Cl2iii | 0.95 | 2.83 | 3.520 (3) | 131 |
C26—H26···Cl2iv | 0.95 | 2.76 | 3.605 (4) | 148 |
C24—H24···Cg3v | 0.95 | 2.74 | 3.610 (4) | 153 |
Symmetry codes: (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+1, −y, −z+1; (iv) x−1/2, −y+1/2, z−1/2; (v) x+1/2, −y+1/2, z−1/2. |
Hg1—I1 | 2.6977 (3) | P1—C11 | 1.804 (4) |
Hg1—I2 | 2.8422 (3) | P1—C21 | 1.808 (4) |
Hg1—I2i | 2.9863 (3) | P1—C31 | 1.816 (4) |
Hg1—P1 | 2.4724 (10) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···I2ii | 0.95 | 3.04 | 3.952 (4) | 161 |
C15—H15···Cg3iii | 0.95 | 2.89 | 3.770 (5) | 154 |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) −x+1/2, y−1/2, −z+3/2. |
Acknowledgements
X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants which have provided computing facilities for this work.
References
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The structures of the title compounds, Ph3PHgX(µ2-X)2XHgPPh3] [X = Cl for (I), Br for (II) and I for (III)], were first reported some years ago. For X = Cl (Bell et al., 1980), the structure was refined to R = 0.083 using diffraction data collected at ambient temperature; only Hg, Cl and P atoms were refined anisotropically and the phenyl rings were all constrained to be rigid hexagons; no H atoms were included in the refinement. A very similar refinement was used for X = Br (Bowmaker et al., 1993), although in this case H atoms were included in calculated positions, giving a final R of 0.070. The use of ambient-temperature diffraction data for X = I (Bell et al., 1989) allowed anisotropic refinement of most of the C atoms, although several remained isotropic, possibly indicating some difficulties with the refinement, which terminated at R = 0.094. There is an otherwise unpublished set of coordinates for this same compound (Dix & Jones, 1997) deposited in the Cambridge Structural Database (CSD; Allen, 2002; refcode JAHCOK01), based on a refinement using diffraction data collected at 173 K and giving R = 0.056. For each of (I)–(III), the gross structure of the complex is similar, containing halogen-bridged dimers which are crystallographically centrosymmetric for X = Cl and approximately centrosymmetric for X = Br or I; however, none of the published reports identified any supramolecular aggregation beyond the formation of the halogen-bridged dimers.
We have now taken the opportunity to redetermine the structures of (I)–(III) using data collected at 120 K. For (I) and (II), we find the same phases at 120 K as those previously reported at ambient temperature. It is clear that in both structures there are significant C—H···π(arene) and C—H···X (X = Cl and Br) hydrogen bonds, which together link the dimeric complexes into continuous three-dimensional framework structures. On the other hand, for (III), we find a different phase from that previously reported. The previous reports (Bell et al., 1989; Dix & Jones, 1997) describe a monoclinic structure having Z = 4 and Z' = 1 at both 298 and 173 K, which is, in fact, isostructural with (II).
We find here for (III) a different monoclinic structure at 120 K, with Z = 2 and Z' = 1/2, whose unit-cell dimensions are somewhat similar to those of (I), but whose overall structure mimics the mirror image of (I) (Figs. 1 and 2). In this Z' = 1/2 phase of (III), the centrosymmetric dimers are linked into sheets by a combination of C—H···π(arene) and C—H···I hydrogen bonds and an aromatic π–π stacking interaction.
For both (I), where we have refined the structure without any of the constraints applied earlier (Bell et al., 1980), and (III), the precision is significantly better than reported previously. Thus, for example, for both (I) and the Z' = 1 polymorph of (III), the reported s.u. values for the P—C bonds are 0.02–0.03 Å (Bell et al., 1980, 1989), whereas from the present refinements of (I) and the Z' = 1/2 polymorph of (III), these s.u.values are 0.003 and 0.004 Å, respectively (Tables 1 and 3). In addition, the R values are very much lower from the present refinements for (I) and (III). In each of (I) and (III), the long bridging Hg—X bonds (X = Cl and I) (Tables 1 and 3) may be indicative of significant ionic character in these bonds.
As in the published report on the bromo complex (II), some difficulty was experienced even using data collected at 120 K, and attempts to refine the C atoms anisotropically consistently led to unacceptable displacement ellipsoids, although refinements with these atoms assigned isotropic displacement parameters appeared to be satisfactory. Accordingly, we do not discuss this structure in detail, beyond confirming that the same phase occurs at 120 K as at ambient temperature, and noting that the dimeric complexes are linked into a three-dimensional framework by hydrogen bonds.
In compound (I) (Fig. 1), atoms C24 at (x, y, z) and (1 − x, 1 − y, 1 − z), which are both components of the complex centred at (1/2, 1/2, 1/2), acts as hydrogen-bond donors (Table 2) to the C31–C36 aryl rings at (1/2 + x, 1/2 − y, −1/2 + z) and (1/2 − x, 1/2 + y, 1.5 − z), respectively, which themselves are components of the complexes centred at (1, 0, 0) and (0, 1, 1), respectively. Similarly, the C31–C36 aryl rings at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C24 at (−1/2 + x, 1/2 − y, 1/2 + z) and (1.5 − x, 1/2 + y, 1/2 − z), which lie in the complexes centred at (0, 0, 1) and (1, 1, 0), respectively. By this means, the dimeric complexes are linked by a single C—H···π(arene) hydrogen bond into sheets lying parallel to (101) (Fig. 3)
There is a single π–π stacking interaction in the structure of (I), which serves to reinforce the (101) sheet. The C11–C16 rings in the molecules at (x, y, z) and (1 − x, −y, 1 − z), which lie in the same sheet, are parallel, with an interplanar spacing of 3.539 (2) Å; the ring-centroid separation is 3.782 (2) Å, corresponding to a near-ideal centroid offset of 1.334 (2) Å. In addition, there are a number of fairly short C—H···Cl interactions whose H···Cl distances are well within the van der Waals sum (Bondi, 1964; Nyburg & Faerman, 1985; Navon et al., 1997), which can therefore be regarded as weak hydrogen bonds (Table 2). Two of the three C—H···Cl hydrogen bonds lie within a single (101) sheet, thus providing further reinforcement of the sheet, while the third such bond serves to generate a (10–1) sheet.
Atoms C26 at (x, y, z) and (1 − x, 1 − y, 1 − z) act as donors to atoms Cl2 at (−1/2 + x, 1/2 − y, −1/2 + z) and (1.5 − x, 1/2 + y, 1.5 − z), respectively, which form parts of the dimeric complex centred at (0, 0, 0) and (1, 1, 1). In like manner, atoms Cl2 at (x, y, z) and (1 − x, 1 − y, 1 − z) accept hydrogen bonds from atoms C26 at (1/2 + x, 1/2 − y, 1/2 + z) and (1/2 − x, 1/2 + y, 1/2 − z), respectively, which are themselves components of the dimers centred at (1, 0, 1) and (0, 1, 0), so forming a (10–1) sheet (Fig. 4). The combination of the (101) and (10–1) sheets, each generated by a single hydrogen bond, is sufficient to link all of the dimers into a single three-dimensional framework structure.
In compound (III) (Fig. 2), the supramolecular aggregation involves C—H···π(arene) and C—H···I hydrogen bonds (Table 4), augmented by a rather weak π–π stacking interaction, just as in compound (I), but the supramolecular structure is strictly two-dimensional, unlike that of (I). Atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the C31–C36 ring at (1/2 − x, −1/2 + y, 3/2 − z), which lies in the dimer centred at (0, 0, 1); propagation by the space group of this interaction then generates a (101) sheet (Fig. 5), similar to that formed in (I). The single C—H···I hydrogen bond lies within this sheet, although its participants do not mimic those of either of the intrasheet C—H···Cl hydrogen bonds in (I). The C11–C16 rings in the molecules at (x, y, z) and (1 − x, −y, 1 − z), which lie in the same sheet, are parallel, with an interplanar spacing of 3.368 (3) Å, much smaller than the corresponding spacing in (I); the ring-centroid separation of 3.850 (3) Å is significantly larger than the corresponding distance in (I), and the ring-centroid offset is 1.865 (3) Å, indicating only a weak interaction. There are thus no direction-specific interactions between adjacent (101) sheets in (III).
In the Z' = 1 polymorph of (III) (CSD refcode JAHCOK01), reanalysis of the atom coordinates at 173 K (Dix & Jones, 1997) shows that C—H···π(arene) and aromatic π–π stacking interactions are both absent, and that the dimers are linked by a single C—H···I hydrogen bond into chains running parallel to the [001] direction and generated by the c-glide planes (Fig. 6)