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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 61| Part 4| April 2005| Pages m211-m214
doi:10.1107/S0108270105006323

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

CROSSMARK_Color_square_no_text.svg
M. Baby Mariyatra,a Krishnaswamy Panchanatheswaran,a John N. Lowb and Christopher Glidewellc*

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

(Received 25 February 2005; accepted 28 February 2005; online 25 March 2005)

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 space group 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′ = [{1\over 2}], where the complexes lie across inversion centres in space group 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)[link], Br for (II)[link] and I for (III)[link]], were first reported some years ago. For X = Cl (Bell et al., 1980[Bell, N. A., Goldstein, M., Jones, T. & Nowell, I. W. (1980). Inorg. Chim. Acta, 43, 87-93.]), 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[Bowmaker, G. A., Clase, H. J., Alcock, N. W., Kessler, J. M., Nelson, J. H. & Frye, J. S. (1993). Inorg. Chim. Acta, 210, 107-124.]), 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[Bell, N. A., March, L. A. & Nowell, I. W. (1989). Inorg. Chim. Acta, 156, 201-204.]) 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[Dix, J. & Jones, P. G. (1997). Private communication to the Cambridge Structural Database. Refcode JAHCOK01. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.]) deposited in the Cambridge Structural Database (CSD; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]; refcode JAHCOK01), based on a refinement using diffraction data collected at 173 K and giving R = 0.056. For each of (I)–(III)[link], 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.

[Scheme 1]

We have now taken the opportunity to redetermine the structures of (I)–(III)[link] using data collected at 120 K. For (I)[link] and (II)[link], 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)[link], we find a different phase from that reported previously. The previous reports (Bell et al., 1989[Bell, N. A., March, L. A. & Nowell, I. W. (1989). Inorg. Chim. Acta, 156, 201-204.]; Dix & Jones, 1997[Dix, J. & Jones, P. G. (1997). Private communication to the Cambridge Structural Database. Refcode JAHCOK01. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.]) describe a monoclinic structure having Z = 4 and Z′ = 1 at both 298 and 173 K, which is, in fact, isostructural with (II)[link].

We find here for (III)[link] a different monoclinic structure at 120 K, with Z = 2 and Z′ = [{1\over 2}], whose unit-cell dimensions are similar to those of (I)[link], but whose overall structure mimics the mirror image of (I)[link] (Figs. 1[link] and 2[link]). In this Z′ = [{1\over 2}] phase of (III)[link], 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)[link], where we have refined the structure without any of the constraints applied earlier (Bell et al., 1980[Bell, N. A., Goldstein, M., Jones, T. & Nowell, I. W. (1980). Inorg. Chim. Acta, 43, 87-93.]), and (III)[link], the precision is significantly better than reported previously. Thus, for example, for both (I)[link] and the Z′ = 1 polymorph of (III)[link], the previously reported s.u. values for the P—C bonds are 0.02–0.03 Å (Bell et al., 1980[Bell, N. A., Goldstein, M., Jones, T. & Nowell, I. W. (1980). Inorg. Chim. Acta, 43, 87-93.], 1989[Bell, N. A., March, L. A. & Nowell, I. W. (1989). Inorg. Chim. Acta, 156, 201-204.]), whereas from the present refinements of (I)[link] and the Z′ = [{1\over 2}] polymorph of (III)[link], these s.u. values are 0.003 and 0.004 Å, respectively (Tables 1[link] and 3[link]). In addition, the R values are very much lower for the present refinements of (I)[link] and (III)[link]. In each of (I)[link] and (III)[link], the long bridging Hg—X bonds (X = Cl and I) (Tables 1[link] and 3[link]) may be indicative of significant ionic character in these bonds.

As in the published report on the bromo complex (II)[link], 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)[link] (Fig. 1[link]), atoms C24 at (x, y, z) and (1 − x, 1 − y, 1 − z), which are both components of the complex centred at ([{1\over 2}], [{1\over 2}], [{1\over 2}]), act as hydrogen-bond donors (Table 2[link]) to the C31–C36 ar­yl rings at ([{1\over 2}] + x, [{1\over 2}] − y, −[{1\over 2}] + z) and ([{1\over 2}] − x, [{1\over 2}] + y, [3\over2] − 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\over 2}] + x, [{1\over 2}] − y, [{1\over 2}] + z) and ([3 \over 2] − x, [{1\over 2}] + y, [{1\over 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[link])

There is a single π–π stacking inter­action in the structure of (I)[link], 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[Bondi, A. (1964). J. Phys. Chem. 68, 441-451.]; Nyburg & Faerman, 1985[Nyburg, S. C. & Faerman, C. H. (1985). Acta Cryst. B41, 274-279.]; Navon et al., 1997[Navon, O., Bernstein, J. & Khodorkovsky, V. (1997). Angew. Chem. Int. Ed. Engl. 36, 601-603.]) and which can therefore be regarded as weak hydrogen bonds (Table 2[link]). 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[\overline1]) sheet.

Atoms C26 at (x, y, z) and (1 − x, 1 − y, 1 − z) act as donors to atoms Cl2 at (−[{1\over 2}] + x, [{1\over 2}] − y, −[{1\over 2}] + z) and ([3 \over 2] − x, [{1\over 2}] + y, [3\over2] − 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 ([{1\over 2}] + x, [{1\over 2}] − y, [{1\over 2}] + z) and ([{1\over 2}] − x, [{1\over 2}] + y, [{1\over 2}] − z), respectively, which are themselves components of the dimers centred at (1, 0, 1) and (0, 1, 0), so forming a (10[\overline1]) sheet (Fig. 4[link]). The combination of the (101) and (10[\overline1]) 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)[link] (Fig. 2[link]), the supramolecular aggregation involves C—H⋯π(arene) and C—H⋯I hydrogen bonds (Table 4[link]), augmented by a weak π–π stacking inter­action, just as in (I)[link], but the supramolecular structure is strictly two-dimensional, unlike that of (I)[link]. Atom C15 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to the C31–C36 ring at ([{1\over 2}] − x, −[{1\over 2}] + y, [{3\over 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[link]), similar to that formed in (I)[link]. 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)[link]. 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)[link]; the ring-centroid separation of 3.850 (3) Å is significantly larger than the corresponding distance in (I)[link], 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)[link].

In the Z′ = 1 polymorph of (III)[link] (CSD refcode JAHCOK01), reanalysis of the atom coordinates at 173 K (Dix & Jones, 1997[Dix, J. & Jones, P. G. (1997). Private communication to the Cambridge Structural Database. Refcode JAHCOK01. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.]) 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[link])

[Figure 1]
Figure 1
The dimeric mol­ecular unit in (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and atoms labelled with the suffix A are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 2]
Figure 2
The dimeric mol­ecular unit in (III)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and atoms labelled with the suffix A are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 3]
Figure 3
A stereoview of part of the crystal structure of (I)[link], showing the formation of a (101) sheet generated by a single C—H⋯π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I)[link], showing the formation of a (10[\overline 1]) sheet generated by a single C—H⋯Cl hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5]
Figure 5
A stereoview of part of the crystal structure of (III)[link], showing the formation of a (101) sheet generated by a single C—H⋯π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6]
Figure 6
A stereoview of part of the crystal structure of JAHCOK01 (Dix & Jones, 1997[Dix, J. & Jones, P. G. (1997). Private communication to the Cambridge Structural Database. Refcode JAHCOK01. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.]), showing the formation of a [001] chain generated by a single C—H⋯I hydrogen bond. The original atom coordinates have been employed; for clarity, H atoms not involved in the motif shown have been omitted.

Experimental

For the preparation of compounds (I)–(III)[link], 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]

Crystal data

  • [Hg2Cl4(C18H15P)2]

  • Mr = 1067.52

  • Monoclinic, P 21 /n

  • a = 12.1540 (2) Å

  • b = 11.2982 (3) Å

  • c = 13.2965 (3) Å

  • β = 93.3460 (16)°

  • V = 1822.74 (7) Å3

  • Z = 2

  • Dx = 1.945 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4163 reflections

  • θ = 3.4–27.5°

  • μ = 8.82 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.29 × 0.24 × 0.18 mm
Data collection

  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.095, Tmax = 0.206

  • 28 163 measured reflections

  • 4163 independent reflections

  • 3593 reflections with I > 2σ(I)

  • Rint = 0.042

  • θmax = 27.5°

  • h = −15 → 14

  • k = −14 → 14

  • l = −17 → 17
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.048

  • S = 1.07

  • 4163 reflections

  • 199 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0178P)2 + 1.6853P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.68 e Å−3

  • Δρmin = −1.02 e Å−3

Table 1
Selected interatomic distances (Å) for (I)[link]

Hg1—Cl1 2.4015 (8)
Hg1—Cl2 2.6101 (8)
Hg1—Cl2i 2.6506 (8)
Hg1—P1 2.3991 (8)
P1—C11 1.801 (3)
P1—C21 1.807 (3)
P1—C31 1.812 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

Cg3 is the centroid of ring C31–C36.
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+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+1, -y, -z+1; (iv) [x-{\script{1\over 2}}], [-y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (v) [x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Compound (III)[link]

Crystal data

  • [Hg2I4(C18H15P)2]

  • Mr = 1433.32

  • Monoclinic, P 21 /n

  • a = 11.4078 (2) Å

  • b = 12.4980 (4) Å

  • c = 13.9124 (4) Å

  • β = 96.3270 (17)°

  • V = 1971.47 (9) Å3

  • Z = 2

  • Dx = 2.415 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4516 reflections

  • θ = 3.6–27.5°

  • μ = 11.01 mm−1

  • T = 120 (2) K

  • Block, colourless

  • 0.35 × 0.26 × 0.24 mm
Data collection

  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.041, Tmax = 0.071

  • 24 795 measured reflections

  • 4516 independent reflections

  • 3935 reflections with I > 2σ(I)

  • Rint = 0.036

  • θmax = 27.5°

  • h = −14 → 14

  • k = −15 → 16

  • l = −18 → 18
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.025

  • wR(F2) = 0.055

  • S = 1.16

  • 4516 reflections

  • 199 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0203P)2 + 2.7697P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.002

  • Δρmax = 0.70 e Å−3

  • Δρmin = −1.31 e Å−3

Table 3
Selected interatomic distances (Å) for (III)[link]

Hg1—I1 2.6977 (3)
Hg1—I2 2.8422 (3)
Hg1—I2i 2.9863 (3)
Hg1—P1 2.4724 (10)
P1—C11 1.804 (4)
P1—C21 1.808 (4)
P1—C31 1.816 (4)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 4
Hydrogen-bond geometry (Å, °) for (III)[link]

Cg3 is the centroid of ring C31–C36.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C14—H14⋯I2iii 0.95 3.04 3.952 (4) 161
C15—H15⋯Cg3ii 0.95 2.89 3.770 (5) 154
Symmetry codes: (ii) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iii) -x+1, -y, -z+1.

For compounds (I)–(III)[link], the space groups P21/n, P21/c and P21/n, respectively, were uniquely assigned from the systematic absences. 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)[link], the refinement 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[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; structure solution: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); structure refinement: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information

Crystal structure: contains datablocks global, I, III. DOI: 10.1107/S0108270105006323/sk1821sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270105006323/sk1821Isup2.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270105006323/sk1821IIIsup3.hkl


Comment top

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)

Experimental top

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.

Refinement top

For compounds (I)–(III), the space groups P21/n, P21/c and P21/n, respectively, were uniquely assigned from the systematic absences. 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 refinement 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.

Computing details top

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The dimeric molecular unit in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and atoms labelled with the suffux A are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 2] Fig. 2. The dimeric molecular unit in (III) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level, and atoms labelled with the suffix A are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a (101) sheet generated by a single C—H···π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a (10–1) sheet generated by a single C—H···Cl hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 5] Fig. 5. A stereoview of part of the crystal structure of (III), showing the formation of a (101) sheet generated by a single C—H···π(arene) hydrogen bond. For clarity, H atoms not involved in the motif shown have been omitted.
[Figure 6] Fig. 6. A stereoview of part of the crystal structure of JAHCOK01 (Dix & Jones, 1997), showing the formation of a [001] chain generated by a single C—H···I hydrogen bond. The original atom coordinates have been employed; for clarity, H atoms not involved in the motif shown have been omitted.
(I) Di-µ-chloro-bis[chloro(triphenylphosphine)mercury(II)] top
Crystal data top
[Hg2Cl4(C18H15P)2]F(000) = 1008
Mr = 1067.52Dx = 1.945 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4163 reflections
a = 12.1540 (2) Åθ = 3.4–27.5°
b = 11.2982 (3) ŵ = 8.82 mm−1
c = 13.2965 (3) ÅT = 120 K
β = 93.3460 (16)°Block, colourless
V = 1822.74 (7) Å30.29 × 0.24 × 0.18 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		4163 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode3593 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.4°
ϕ and ω scansh = −15→14
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −14→14
Tmin = 0.095, Tmax = 0.206l = −17→17
28163 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048H-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 parametersΔρmax = 0.68 e Å−3
0 restraintsΔρmin = −1.02 e Å−3
Crystal data top
[Hg2Cl4(C18H15P)2]V = 1822.74 (7) Å3
Mr = 1067.52Z = 2
Monoclinic, P21/nMo Kα radiation
a = 12.1540 (2) ŵ = 8.82 mm−1
b = 11.2982 (3) ÅT = 120 K
c = 13.2965 (3) Å0.29 × 0.24 × 0.18 mm
β = 93.3460 (16)°
Data collection top
Nonius KappaCCD
diffractometer		4163 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		3593 reflections with I > 2σ(I)
Tmin = 0.095, Tmax = 0.206Rint = 0.042
28163 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.048H-atom parameters constrained
S = 1.07Δρmax = 0.68 e Å−3
4163 reflectionsΔρmin = −1.02 e Å−3
199 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg10.367411 (10)0.407649 (11)0.516114 (9)0.02284 (5)
Cl10.27867 (7)0.49128 (9)0.65634 (6)0.0346 (2)
Cl20.57435 (6)0.39891 (7)0.58025 (6)0.02321 (17)
P10.30893 (6)0.25929 (7)0.39545 (6)0.01729 (17)
C110.3327 (2)0.1129 (3)0.4456 (2)0.0192 (7)
C120.3016 (3)0.0887 (3)0.5432 (3)0.0266 (8)
C130.3128 (3)−0.0250 (4)0.5819 (3)0.0344 (9)
C140.3548 (3)−0.1146 (3)0.5240 (3)0.0317 (9)
C150.3878 (3)−0.0905 (3)0.4280 (3)0.0284 (8)
C160.3767 (3)0.0226 (3)0.3888 (2)0.0233 (7)
C210.3771 (2)0.2699 (3)0.2786 (2)0.0187 (7)
C220.4831 (3)0.3161 (3)0.2787 (3)0.0268 (8)
C230.5379 (3)0.3171 (4)0.1908 (3)0.0381 (10)
C240.4876 (3)0.2725 (4)0.1025 (3)0.0382 (10)
C250.3817 (3)0.2276 (4)0.1016 (3)0.0317 (8)
C260.3266 (3)0.2265 (3)0.1892 (2)0.0267 (8)
C310.1617 (2)0.2713 (3)0.3674 (2)0.0194 (7)
C320.0989 (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)
C360.1119 (3)0.3817 (3)0.3696 (3)0.0260 (8)
H120.27290.15010.58290.032*
H130.2916−0.04150.64810.041*
H140.3610−0.19270.55020.038*
H150.4181−0.15170.38910.034*
H160.39910.03880.32290.028*
H220.51760.34690.33910.032*
H230.61040.34840.19070.046*
H240.52600.27290.04230.046*
H250.34710.19770.04090.038*
H260.25370.19610.18880.032*
H320.13280.09570.33950.030*
H33−0.05670.11530.30080.039*
H34−0.14000.30080.30660.042*
H35−0.03480.46800.34940.042*
H360.15490.44990.38650.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.02689 (8)0.02351 (8)0.01807 (7)−0.00324 (5)0.00093 (5)−0.00585 (5)
Cl10.0239 (4)0.0573 (7)0.0231 (4)0.0073 (4)0.0055 (3)−0.0109 (4)
Cl20.0220 (4)0.0230 (4)0.0242 (4)0.0044 (3)−0.0027 (3)0.0073 (3)
P10.0162 (4)0.0206 (5)0.0152 (4)−0.0017 (3)0.0020 (3)−0.0021 (3)
C110.0178 (16)0.0196 (18)0.0200 (17)−0.0040 (13)−0.0005 (12)−0.0020 (13)
C120.0291 (18)0.029 (2)0.0228 (18)0.0014 (15)0.0079 (14)−0.0012 (15)
C130.038 (2)0.039 (2)0.027 (2)0.0017 (18)0.0101 (16)0.0094 (17)
C140.041 (2)0.022 (2)0.032 (2)0.0003 (16)−0.0012 (17)0.0069 (15)
C150.033 (2)0.0217 (19)0.030 (2)0.0044 (15)0.0019 (16)−0.0043 (15)
C160.0283 (18)0.0227 (19)0.0192 (17)0.0001 (14)0.0042 (13)−0.0041 (14)
C210.0199 (16)0.0213 (17)0.0151 (15)0.0009 (13)0.0031 (12)0.0012 (13)
C220.0230 (17)0.033 (2)0.0247 (18)−0.0066 (15)0.0046 (14)−0.0050 (15)
C230.0257 (19)0.059 (3)0.031 (2)−0.0150 (18)0.0135 (16)−0.0082 (19)
C240.037 (2)0.058 (3)0.0211 (19)−0.0006 (19)0.0163 (15)0.0001 (18)
C250.032 (2)0.046 (2)0.0170 (17)−0.0004 (17)0.0022 (14)−0.0021 (16)
C260.0234 (17)0.037 (2)0.0199 (17)−0.0022 (15)0.0016 (13)−0.0017 (15)
C310.0183 (15)0.0271 (18)0.0132 (15)−0.0003 (14)0.0035 (12)−0.0006 (13)
C320.0207 (17)0.035 (2)0.0200 (17)−0.0018 (14)0.0019 (13)−0.0096 (15)
C330.0234 (18)0.051 (3)0.0236 (19)−0.0089 (17)−0.0007 (14)−0.0124 (17)
C340.0194 (18)0.062 (3)0.0232 (19)0.0035 (18)0.0001 (14)0.0003 (18)
C350.031 (2)0.039 (2)0.034 (2)0.0128 (17)0.0029 (16)0.0099 (17)
C360.0214 (17)0.029 (2)0.0276 (19)0.0023 (14)0.0030 (14)0.0074 (15)
Geometric parameters (Å, º) top
Hg1—Cl12.4015 (8)C22—C231.379 (5)
Hg1—Cl22.6101 (8)C22—H220.95
Hg1—Cl2i2.6506 (8)C23—C241.386 (5)
Cl2—Hg1i2.6506 (8)C23—H230.95
Hg1—P12.3991 (8)C24—C251.383 (5)
P1—C111.801 (3)C24—H240.95
P1—C211.807 (3)C25—C261.378 (5)
P1—C311.812 (3)C25—H250.95
C11—C161.394 (4)C26—H260.95
C11—C121.399 (5)C31—C361.387 (5)
C12—C131.387 (5)C31—C321.394 (5)
C12—H120.95C32—C331.390 (5)
C13—C141.388 (5)C32—H320.95
C13—H130.95C33—C341.383 (6)
C14—C151.387 (5)C33—H330.95
C14—H140.95C34—C351.384 (5)
C15—C161.383 (5)C34—H340.95
C15—H150.95C35—C361.388 (5)
C16—H160.95C35—H350.95
C21—C221.389 (4)C36—H360.95
C21—C261.394 (4)
P1—Hg1—Cl1131.69 (3)C23—C22—C21119.8 (3)
P1—Hg1—Cl2115.74 (3)C23—C22—H22120.1
Cl1—Hg1—Cl2103.24 (3)C21—C22—H22120.1
P1—Hg1—Cl2i109.26 (3)C22—C23—C24120.2 (3)
Cl1—Hg1—Cl2i101.28 (3)C22—C23—H23119.9
Cl2—Hg1—Cl2i84.82 (2)C24—C23—H23119.9
Hg1—Cl2—Hg1i95.18 (2)C25—C24—C23120.3 (3)
C11—P1—C21107.91 (15)C25—C24—H24119.8
C11—P1—C31106.26 (15)C23—C24—H24119.8
C21—P1—C31108.36 (14)C26—C25—C24119.6 (3)
C11—P1—Hg1111.06 (10)C26—C25—H25120.2
C21—P1—Hg1113.32 (11)C24—C25—H25120.2
C31—P1—Hg1109.64 (11)C25—C26—C21120.4 (3)
C16—C11—C12119.5 (3)C25—C26—H26119.8
C16—C11—P1122.0 (2)C21—C26—H26119.8
C12—C11—P1118.5 (2)C36—C31—C32120.0 (3)
C13—C12—C11119.9 (3)C36—C31—P1119.3 (3)
C13—C12—H12120.0C32—C31—P1120.7 (3)
C11—C12—H12120.0C33—C32—C31119.6 (3)
C12—C13—C14120.0 (3)C33—C32—H32120.2
C12—C13—H13120.0C31—C32—H32120.2
C14—C13—H13120.0C34—C33—C32120.1 (3)
C15—C14—C13120.2 (3)C34—C33—H33119.9
C15—C14—H14119.9C32—C33—H33119.9
C13—C14—H14119.9C33—C34—C35120.3 (3)
C16—C15—C14120.0 (3)C33—C34—H34119.9
C16—C15—H15120.0C35—C34—H34119.9
C14—C15—H15120.0C34—C35—C36120.0 (3)
C15—C16—C11120.2 (3)C34—C35—H35120.0
C15—C16—H16119.9C36—C35—H35120.0
C11—C16—H16119.9C31—C36—C35120.0 (3)
C22—C21—C26119.7 (3)C31—C36—H36120.0
C22—C21—P1119.7 (2)C35—C36—H36120.0
C26—C21—P1120.5 (2)
P1—Hg1—Cl2—Hg1i108.90 (3)C31—P1—C21—C22150.9 (3)
Cl1—Hg1—Cl2—Hg1i−100.40 (3)Hg1—P1—C21—C2229.0 (3)
Cl2i—Hg1—Cl2—Hg1i0.0C11—P1—C21—C2682.3 (3)
Cl1—Hg1—P1—C11−82.11 (12)C31—P1—C21—C26−32.4 (3)
Cl2—Hg1—P1—C1158.25 (11)Hg1—P1—C21—C26−154.3 (3)
Cl2i—Hg1—P1—C11151.82 (11)C26—C21—C22—C23−1.0 (5)
Cl1—Hg1—P1—C21156.22 (11)P1—C21—C22—C23175.8 (3)
Cl2—Hg1—P1—C21−63.42 (11)C21—C22—C23—C240.2 (6)
Cl2i—Hg1—P1—C2130.16 (11)C22—C23—C24—C250.5 (7)
Cl1—Hg1—P1—C3135.02 (12)C23—C24—C25—C26−0.5 (6)
Cl2—Hg1—P1—C31175.38 (11)C24—C25—C26—C21−0.3 (6)
Cl2i—Hg1—P1—C31−91.05 (11)C22—C21—C26—C251.0 (5)
C21—P1—C11—C16−11.8 (3)P1—C21—C26—C25−175.7 (3)
C31—P1—C11—C16104.2 (3)C11—P1—C31—C36152.4 (3)
Hg1—P1—C11—C16−136.6 (2)C21—P1—C31—C36−91.9 (3)
C21—P1—C11—C12170.8 (3)Hg1—P1—C31—C3632.2 (3)
C31—P1—C11—C12−73.2 (3)C11—P1—C31—C32−29.1 (3)
Hg1—P1—C11—C1246.0 (3)C21—P1—C31—C3286.7 (3)
C16—C11—C12—C13−1.2 (5)Hg1—P1—C31—C32−149.2 (2)
P1—C11—C12—C13176.2 (3)C36—C31—C32—C33−0.4 (5)
C11—C12—C13—C140.1 (5)P1—C31—C32—C33−178.9 (3)
C12—C13—C14—C151.2 (6)C31—C32—C33—C34−0.2 (5)
C13—C14—C15—C16−1.4 (5)C32—C33—C34—C350.4 (5)
C14—C15—C16—C110.2 (5)C33—C34—C35—C360.0 (6)
C12—C11—C16—C151.1 (5)C32—C31—C36—C350.7 (5)
P1—C11—C16—C15−176.3 (3)P1—C31—C36—C35179.3 (3)
C11—P1—C21—C22−94.4 (3)C34—C35—C36—C31−0.6 (5)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···Cl1ii0.952.813.720 (4)161
C15—H15···Cl2iii0.952.833.520 (3)131
C26—H26···Cl2iv0.952.763.605 (4)148
C24—H24···Cg3v0.952.743.610 (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.
(III) Di-µ-chloro-bis[iodo(triphenylphosphine)mercury(II)] top
Crystal data top
[Hg2I4(C18H15P)2]F(000) = 1296
Mr = 1433.32Dx = 2.415 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4516 reflections
a = 11.4078 (2) Åθ = 3.6–27.5°
b = 12.4980 (4) ŵ = 11.01 mm−1
c = 13.9124 (4) ÅT = 120 K
β = 96.3270 (17)°Block, colourless
V = 1971.47 (9) Å30.35 × 0.26 × 0.24 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		4516 independent reflections
Radiation source: Bruker-Nonius FR91 rotating anode3935 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.6°
ϕ and ω scansh = −14→14
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −15→16
Tmin = 0.041, Tmax = 0.071l = −18→18
24795 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.055H-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 parametersΔρmax = 0.70 e Å−3
0 restraintsΔρmin = −1.31 e Å−3
Crystal data top
[Hg2I4(C18H15P)2]V = 1971.47 (9) Å3
Mr = 1433.32Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.4078 (2) ŵ = 11.01 mm−1
b = 12.4980 (4) ÅT = 120 K
c = 13.9124 (4) Å0.35 × 0.26 × 0.24 mm
β = 96.3270 (17)°
Data collection top
Nonius KappaCCD
diffractometer		4516 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		3935 reflections with I > 2σ(I)
Tmin = 0.041, Tmax = 0.071Rint = 0.036
24795 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.055H-atom parameters constrained
S = 1.16Δρmax = 0.70 e Å−3
4516 reflectionsΔρmin = −1.31 e Å−3
199 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg10.373922 (13)0.388225 (12)0.472916 (11)0.01758 (5)
I10.22510 (2)0.38993 (2)0.308186 (19)0.02360 (8)
I20.61659 (2)0.39136 (2)0.44371 (2)0.01903 (7)
P10.32330 (8)0.27969 (8)0.61108 (7)0.0124 (2)
C110.3545 (3)0.1403 (3)0.5918 (3)0.0144 (8)
C120.3218 (3)0.0984 (3)0.5002 (3)0.0195 (9)
C130.3375 (4)−0.0096 (3)0.4816 (3)0.0258 (10)
C140.3867 (4)−0.0752 (4)0.5551 (4)0.0293 (11)
C150.4209 (4)−0.0347 (4)0.6465 (3)0.0288 (10)
C160.4055 (4)0.0734 (3)0.6659 (3)0.0214 (9)
C210.3980 (3)0.3211 (3)0.7265 (3)0.0157 (8)
C220.5083 (4)0.3684 (3)0.7300 (3)0.0206 (9)
C230.5667 (4)0.4012 (4)0.8180 (3)0.0265 (10)
C240.5148 (4)0.3885 (3)0.9017 (3)0.0276 (10)
C250.4049 (4)0.3408 (5)0.8992 (3)0.0369 (12)
C260.3460 (4)0.3076 (4)0.8122 (3)0.0281 (11)
C310.1659 (3)0.2857 (3)0.6203 (3)0.0153 (8)
C320.1062 (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)
C360.1050 (4)0.3790 (3)0.5911 (3)0.0235 (9)
H120.28830.14400.44980.023*
H130.3146−0.03800.41900.031*
H140.3973−0.14910.54270.035*
H150.4550−0.08080.69630.035*
H160.42920.10150.72850.026*
H220.54400.37830.67220.025*
H230.64280.43260.82020.032*
H240.55430.41250.96150.033*
H250.36990.33090.95740.044*
H260.27030.27560.81050.034*
H320.14700.13670.67510.024*
H33−0.05250.15220.69360.032*
H34−0.15570.30730.64360.037*
H35−0.05670.45060.58130.039*
H360.14520.43690.56490.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.02282 (9)0.01667 (9)0.01345 (8)−0.00295 (6)0.00287 (6)0.00339 (6)
I10.02050 (14)0.03399 (17)0.01606 (14)0.00184 (11)0.00087 (11)−0.00018 (11)
I20.01982 (14)0.01288 (14)0.02532 (15)0.00109 (10)0.00667 (11)−0.00394 (10)
P10.0141 (5)0.0126 (5)0.0105 (5)−0.0009 (4)0.0014 (4)0.0016 (4)
C110.0147 (19)0.0121 (19)0.016 (2)−0.0018 (14)0.0022 (15)0.0036 (15)
C120.019 (2)0.020 (2)0.019 (2)0.0003 (16)−0.0003 (16)0.0006 (17)
C130.025 (2)0.023 (2)0.028 (2)−0.0060 (18)−0.0006 (18)−0.0076 (19)
C140.028 (2)0.009 (2)0.053 (3)−0.0004 (17)0.014 (2)0.000 (2)
C150.035 (3)0.020 (2)0.031 (3)0.0039 (19)0.003 (2)0.0097 (19)
C160.025 (2)0.022 (2)0.017 (2)0.0054 (17)−0.0006 (17)0.0045 (17)
C210.0189 (19)0.015 (2)0.0131 (19)0.0037 (15)−0.0004 (15)−0.0003 (15)
C220.023 (2)0.021 (2)0.017 (2)−0.0034 (16)0.0010 (17)0.0044 (16)
C230.023 (2)0.031 (3)0.023 (2)−0.0055 (18)−0.0091 (18)0.0044 (19)
C240.035 (3)0.026 (2)0.020 (2)0.0062 (19)−0.0053 (19)−0.0057 (19)
C250.031 (3)0.068 (4)0.012 (2)0.009 (2)0.0049 (18)−0.005 (2)
C260.017 (2)0.047 (3)0.020 (2)−0.0053 (19)0.0039 (17)−0.003 (2)
C310.0101 (18)0.022 (2)0.0133 (19)−0.0004 (15)−0.0006 (14)0.0014 (16)
C320.021 (2)0.021 (2)0.017 (2)−0.0003 (16)0.0029 (16)0.0010 (17)
C330.022 (2)0.032 (3)0.027 (2)−0.0080 (19)0.0032 (18)−0.002 (2)
C340.014 (2)0.054 (3)0.024 (2)0.005 (2)0.0040 (18)−0.002 (2)
C350.027 (2)0.046 (3)0.025 (3)0.016 (2)0.0068 (19)0.011 (2)
C360.023 (2)0.028 (2)0.021 (2)0.0075 (17)0.0048 (17)0.0078 (18)
Geometric parameters (Å, º) top
Hg1—I12.6977 (3)C22—C231.389 (6)
Hg1—I22.8422 (3)C22—H220.95
Hg1—I2i2.9863 (3)C23—C241.373 (7)
I2—Hg1i2.9863 (3)C23—H230.95
Hg1—P12.4724 (10)C24—C251.386 (7)
P1—C111.804 (4)C24—H240.95
P1—C211.808 (4)C25—C261.381 (6)
P1—C311.816 (4)C25—H250.95
C11—C121.391 (6)C26—H260.95
C11—C161.403 (5)C31—C321.386 (6)
C12—C131.389 (6)C31—C361.395 (5)
C12—H120.95C32—C331.380 (6)
C13—C141.381 (6)C32—H320.95
C13—H130.95C33—C341.385 (6)
C14—C151.385 (7)C33—H330.95
C14—H140.95C34—C351.384 (7)
C15—C161.393 (6)C34—H340.95
C15—H150.95C35—C361.394 (6)
C16—H160.95C35—H350.95
C21—C221.386 (6)C36—H360.95
C21—C261.399 (6)
P1—Hg1—I1119.06 (2)C21—C22—C23120.2 (4)
P1—Hg1—I2115.68 (2)C21—C22—H22119.9
I1—Hg1—I2114.213 (10)C23—C22—H22119.9
P1—Hg1—I2i101.87 (2)C24—C23—C22120.2 (4)
I1—Hg1—I2i108.372 (9)C24—C23—H23119.9
I2—Hg1—I2i92.787 (8)C22—C23—H23119.9
Hg1—I2—Hg1i87.213 (8)C23—C24—C25120.2 (4)
C11—P1—C21109.09 (18)C23—C24—H24119.9
C11—P1—C31105.29 (18)C25—C24—H24119.9
C21—P1—C31107.34 (18)C26—C25—C24120.2 (4)
C11—P1—Hg1110.32 (13)C26—C25—H25119.9
C21—P1—Hg1113.92 (13)C24—C25—H25119.9
C31—P1—Hg1110.48 (13)C25—C26—C21120.0 (4)
C12—C11—C16119.8 (4)C25—C26—H26120.0
C12—C11—P1117.6 (3)C21—C26—H26120.0
C16—C11—P1122.6 (3)C32—C31—C36119.7 (4)
C13—C12—C11120.6 (4)C32—C31—P1121.6 (3)
C13—C12—H12119.7C36—C31—P1118.6 (3)
C11—C12—H12119.7C33—C32—C31120.2 (4)
C14—C13—C12119.3 (4)C33—C32—H32119.9
C14—C13—H13120.3C31—C32—H32119.9
C12—C13—H13120.3C32—C33—C34120.3 (4)
C13—C14—C15120.9 (4)C32—C33—H33119.8
C13—C14—H14119.6C34—C33—H33119.8
C15—C14—H14119.6C35—C34—C33119.9 (4)
C14—C15—C16120.2 (4)C35—C34—H34120.1
C14—C15—H15119.9C33—C34—H34120.1
C16—C15—H15119.9C34—C35—C36120.1 (4)
C15—C16—C11119.2 (4)C34—C35—H35120.0
C15—C16—H16120.4C36—C35—H35120.0
C11—C16—H16120.4C35—C36—C31119.7 (4)
C22—C21—C26119.3 (4)C35—C36—H36120.2
C22—C21—P1119.4 (3)C31—C36—H36120.2
C26—C21—P1121.3 (3)
P1—Hg1—I2—Hg1i−104.59 (3)C31—P1—C21—C22−152.0 (3)
I1—Hg1—I2—Hg1i111.586 (10)Hg1—P1—C21—C22−29.4 (4)
I2i—Hg1—I2—Hg1i0.0C11—P1—C21—C26−86.4 (4)
I1—Hg1—P1—C1177.93 (13)C31—P1—C21—C2627.2 (4)
I2—Hg1—P1—C11−64.05 (13)Hg1—P1—C21—C26149.8 (3)
I2i—Hg1—P1—C11−163.04 (13)C26—C21—C22—C230.4 (6)
I1—Hg1—P1—C21−158.99 (13)P1—C21—C22—C23179.6 (3)
I2—Hg1—P1—C2159.03 (14)C21—C22—C23—C24−0.9 (6)
I2i—Hg1—P1—C21−39.96 (14)C22—C23—C24—C251.3 (7)
I1—Hg1—P1—C31−38.08 (15)C23—C24—C25—C26−1.2 (7)
I2—Hg1—P1—C31179.94 (14)C24—C25—C26—C210.7 (8)
I2i—Hg1—P1—C3180.95 (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—C1275.8 (3)C11—P1—C31—C3230.4 (4)
Hg1—P1—C11—C12−43.4 (3)C21—P1—C31—C32−85.7 (4)
C21—P1—C11—C1613.3 (4)Hg1—P1—C31—C32149.5 (3)
C31—P1—C11—C16−101.6 (3)C11—P1—C31—C36−150.6 (3)
Hg1—P1—C11—C16139.2 (3)C21—P1—C31—C3693.3 (3)
C16—C11—C12—C130.9 (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—C33177.3 (3)
C12—C13—C14—C15−0.2 (7)C31—C32—C33—C341.8 (6)
C13—C14—C15—C160.3 (7)C32—C33—C34—C35−1.2 (7)
C14—C15—C16—C110.3 (6)C33—C34—C35—C360.6 (7)
C12—C11—C16—C15−0.9 (6)C34—C35—C36—C31−0.6 (7)
P1—C11—C16—C15176.5 (3)C32—C31—C36—C351.2 (6)
C11—P1—C21—C2294.4 (3)P1—C31—C36—C35−177.9 (3)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···I2ii0.953.043.952 (4)161
C15—H15···Cg3iii0.952.893.770 (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]
Mr1067.521433.32
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/n
Temperature (K)120120
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)
Z22
Radiation typeMo KαMo Kα
µ (mm−1)8.8211.01
Crystal size (mm)0.29 × 0.24 × 0.180.35 × 0.26 × 0.24
Data collection
DiffractometerNonius KappaCCD
diffractometer		Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)		Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.095, 0.2060.041, 0.071
No. of measured, independent and
observed [I > 2σ(I)] reflections		28163, 4163, 3593 24795, 4516, 3935
Rint0.0420.036
(sin θ/λ)max (Å−1)0.6490.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.048, 1.07 0.025, 0.055, 1.16
No. of reflections41634516
No. of parameters199199
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.68, −1.020.70, −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).

Selected bond lengths (Å) for (I) top
Hg1—Cl12.4015 (8)P1—C111.801 (3)
Hg1—Cl22.6101 (8)P1—C211.807 (3)
Hg1—Cl2i2.6506 (8)P1—C311.812 (3)
Hg1—P12.3991 (8)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C13—H13···Cl1ii0.952.813.720 (4)161
C15—H15···Cl2iii0.952.833.520 (3)131
C26—H26···Cl2iv0.952.763.605 (4)148
C24—H24···Cg3v0.952.743.610 (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.
Selected bond lengths (Å) for (III) top
Hg1—I12.6977 (3)P1—C111.804 (4)
Hg1—I22.8422 (3)P1—C211.808 (4)
Hg1—I2i2.9863 (3)P1—C311.816 (4)
Hg1—P12.4724 (10)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
C14—H14···I2ii0.953.043.952 (4)161
C15—H15···Cg3iii0.952.893.770 (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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Journal logoSTRUCTURAL
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ISSN: 2053-2296
Volume 61| Part 4| April 2005| Pages m211-m214
doi:10.1107/S0108270105006323
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