In the title compound [Hg(NO3)(C12H16S3)-(C18H15P)][NO3].H2O.0.5C2H6O, the coordination sphere of the Hg2+ ion is a distorted trigonal bipyramid defined by the three S atoms of the trithiamacrocycle, the P atom of the triphenylphosphine group and an O atom of one nitrate group

Almajano Pablos, Mª Pilar

Casabó i Gispert, Jaume

Escriche Martínez, Lluís

Kivekäs, Raikko

Sillanpää, Reijo

Teixidor, Francesc

Diposit Digital de Documents de la UAB

JOHN C. BARNES, JENIFER MAIN AND JOHN D. PATON 1249 Table 2. Selected geometric parameters (.~, °) K(I)---O(I 5) 2.800 (3) C(23)---C(24) 1.399 K(I)---O(9) 2.839 (3) C(24)---C(25) K(I)---O(35) 2.852 (3) C(24)---N(34) K(I)---O(I 8) 2.873 (3) C(25)---C(26) K(I )------0(3) 2.878 (3) C(26)---N(37) K(1)---O(6) 2.887 (3) C(27)----C1(30) K( I )---O(12) 2.931 (4) C(27)---C1(29) K(1)----O(39') 3.038 (3) C(27)----C1(28) K(1)---O(36) 3.098 (3) N(31)---O(32) K(I)---N(34) 3.359 (3) N(31)---O(33) C(21)---C(26) ! .503 (4) N(34)----O(36) C(21 )----C(22) 1.504 (4) N(34)---O(35) C(21)----C(27) 1.553 (5) N(37)---O(38) C(22)---C(23) 1.35 i (4) N(37)---O(39) C(22)---N(31 ) 1.432 (4) O(15)---K(I)---O(35) 76.52 (10) O(18)--K(1)--O(36) O(9)----K(1)---O(35) 97.14 (10) O(3)---K(1)---O(36) O(35)--K(1)--O(18) 109.63 (9) O(6)---K(1)--O(36) O(35)---K(I)---O(3) 130.79 (9) O(12)---K(I )---O(36) O(I 5)---K(1)---O(6) 151.55 (9) C(26)---C(21)---C(22) O(35)--K(1)---O(6) 129.81 (9) C(26)---C(21 )---C(27) O(35)---K( 1 )----O(12) 84.29 (10) C(22)---C(21)---C(27) O(3)---K(1)---O(I 2) 144.33 (10) C(22)--C(23)---C(24) O(15)--K(1)---O(39 i) 94.74 (10) C(23)---C(24)---C(25) O(9)---K(1 )----0(39 i) 137.93 (9) C(26)---C(25)----C(24) O(35)---K(1)----O(39 i) 61.34 (9) C(25)---C(26)---C(21) O(18)---K(1)---O(39 i) 70.89 (8) C(21)---C(27)---C1(30) O(3)----K(I )----O(39 i ) 70.14(8) C(21)---C(27)---C1(29) O(6)---K( 1 )----0(39 i) 107.25 (8) C(21 )---C(27)---C1(28) O(12)---K(1)----O(39 i) 141.63 (10) O(32)---N(31)----O(33) O(15)--K(1)---O(36) 118.29 (10) O(36)---N(34)---O(35) O(9)---K(1)----O(36) 72.52 (9) O(38)----N(37)---O(39) O(35)--K(1)--O(36) 42.51 (8) Symmetry code: (i) 1 - x, 1 - y, 1 - z. 1.400 1.408 1.356 ! .433 ! .771 1.772 1.785 !.231 1.236 1.241 1.246 !.217 1.239 Enraf-Nonius (1989). CAD-4 Software. Version 5.0. Enraf-Nonius, (4) Delft, The Netherlands. (4) Meissenheimer, J. (1902). Ann. Chem. 322, 205-214. (4) Prout, C. K. & Kamenar, B. (1973). In Molecular Complexes, Vol. 1, (4) edited by R. Foster. London: Elek. (4) Sheldrick, G. M. (1976). SHELX76. Program for Crystal Structure (3) Determination. U iv. of Cambridge, England. (3) Sheldrick, G. M. (1990). Acta Cryst. A46, 467--473. (3) Sheldrick, G. M. (1994). J. Appl. Cryst. In preparation. (4) (4) Spek, A. L. (1992). PLUTON92. Molecular Graphics Program. Univ. (4) of Utrecht, The Netherlands. (4) Terrier, F. (1982). Chem. Rev. 82, 77-152. (4) (4) 138.03 (8) 111.44 (9) 87.32 (8) 99.20 (11 ) 107.8 (2) 112.1 (3) 110.9 (3) 119.9 (3) 119.6 (3) 119.9(3) 122.7 (3) 110.5 (2) 112.3 (2) 110.1 (2) 121.6 (3) 121.4(3) 122.8 (3) Data collection, cell refinement and data reduction: CAD-4 Software (Enraf-Nonius, 1989). The structure was solved us- ing the direct methods routine TREF in SHELXS86 (Sheldrick, 1990), which located the K ÷ ion, most of the 18-crown-6 molecule and part of the anion, and gave three unexpected strong peaks which were eventually interpreted as the C1 atoms of  the CC13 group. Routine least-squares refinement and differ- ence syntheses carried out using SHELX76 (Sheldrick, 1976), with SHELXL (Sheldrick, 1994) used for the last cycles, com- pleted the structure. Molecular graphics were prepared using PLUTON92 (Spek, 1992). We wish to thank Professor R. Foster and Dr J. A. Chudek (Dundee University) for suggesting the problem, providing a sample of (II) and valuable discussions of the results, and Drs C. K. Prout and D. J. Watkin, Oxford University, for the opportunity to use the diffractometer. Lists of structure factors, anisotropic displacement parameters, H-atom coordinates and complete geometry have been deposited with the IUCr (Reference: LI1100). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. References Barnes, J. C. & Collard, J. (1988). Acta Cryst. C44, 565-566. Acta Cryst. (1994). C50, 1249-1252 (N i t ra to -~cO)( t r ipheny lphosph ine-KP){3,6 ,9 -  t r i th iab icyc lo[9.4 .0]pent  adeca-  1 (11 ), 12,14-tr i -  ene-~S3'6 '9}mercury( I I )  N i t rate  Hydrate  Hemiethano l  So lvate  RAIKKO KIVEKAS* Department of Chemistry, P.O. Box 6, FIN-O0014 University of Helsinki, Finland RE[JO SILLANPAA Department of Chemistry, University of Turku, FIN-20500 Turku, Finland LLUIS ESCRICHE, MARiA-PILAR ALMAJANO, FRANCESC TEIXIDOR AND JAUME CASABO Departament de Quimica, Universitat Aut6noma de Barcelona nd Institut de Ci~ncia dels Mater&ls (CSIC), Campus de Bellaterra, 08193 Bellaterra, Barcelona, Spain (Received 17 August 1993; accepted 13 January 1994) Abstract In the title compound, [Hg(NO3) (C I2HI6S3)  - (CI8HIsP)][NO3].H20.O.5C2H60, the coordination sphere of the Hg 2+ ion is a distorted trigonal bipyra- mid defined by the three S atoms of the trithiamacro- cycle, the P atom of the triphenylphosphine group and an O atom of one nitrate group. Comment Among crown thioethers, 1,4,7-trithianonane (9S3) is unique in the unusual electronic and redox behaviour of its complexes (Blake & Scr6der, 1990). By exten- Barnes, J. C. & Golnazarians, W. (1987). Acta Cryst. C43, 549-552. Bunsel, E., Norris, A. R. & Russell, K. E. (1968). Q. Rev. 22, 123- sion, interest has been aroused in the coordinating 146. capabilities of related trithiamacrocycles, especially © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved Acta Crystallographica Section C ISSN 0108-2701 ©1994 1250 [Hg(NO3)(CI2H16S3)(CIsH15P)][NO3].H20.0.5C2H60 3,6,9-trithiabicyclo[9.4.0]pentadeca- I (11 ), 12,14-triene (oS3) (deGroot, Hannan& Loeb, 1991), which exhibits similar conformational trends as 9S3 (Lockhart, Mousley, Stuart Hill, Tomkinson, Teixidor, Almajano, Escriche, Casab6, Sillanp~i~i & Kivek~is, 1992). There is a potential use for these s s oS3 trithiamacrocycles a sensors for thiophilic metal ions. Experimental evidence has confirmed that these ligands are excellent sensors for silver(D-selective membrane lectrodes, ince they show little response towards Hg 2+ ions, which constitute the most severe interference in silver(I) detection (Casab6, Mestres, Escriche, Teixidor & Perez-Jimenez, 1991). Thus, we have aimed at synthesizing and structurally charac- terizing Hg" complexes of the oS3 ligand similar to those encountered in the membranes. Here we describe the structure of such a complex, (I). / "\ (I) The asymmetric unit of the stucture consists of the complex unit [Hg(oS3)(PPh3)(NO3)] ÷, one half of a nitrate ion at the twofold axis, one half of a dis- ordered nitrate ion occupying two positions in the vicinity of the twofold axis, one disordered crystal water molecule occuping two positions in the vicinity of the twofold axis and one half of a disordered ethanol molecule situated across a centre of inversion. Fig. 1 shows a perspective view of the [Hg(oS3)(PPh3)(NO3)I ÷ cation and the atomic numbering scheme adopted. The coordination sphere of the Hg 2÷ ion is defined by the three S atoms of the oS3 trithiamacrocycle, the P atom of the tri- phenylphosphine group and an O atom of the co- ordinated nitrate group. The bonds to Hg are non-equivalent, varying from 2.412 (3) to 2.877(12).~ [the greatest value representing the Hg--O(31) distance and indicating that the nitrate ion is only weakly coordinated to the metal]. The coordination sphere of Hg z+ may be described as a strongly distorted trigonal bipyramid, with the atoms 0(31) and S(3) occupying the elongated axial posi- tions and the atoms S(1), S(2) and P the equatorial positions. In addition, the Hg z+ ion deviates -0.196 (1) A from the plane defined by atoms S(1), S(2) and P, revealing a slight tendency towards square-pyramidal stereochemistry. It is interesting to note that bond angles defined by the Hg 2+ ion and the equatorial coordinating atoms are quite different. The S(1)--Hg--P bond angle is close to the ideal value for trigonal bipyramidal stereochemistry (120°), while angles S(2)--Hg--P and S(2)--Hg-- S(1) both differ significantly from this ideal value, evidently as a result of the steric interactions between the bulky triphenylphosphine group and the benzo moiety of oS3. C16 $2 03'd N3~ CIB C26' 027 ~ C29 30 ;23 05 cllL.f ~ c 1 2  ~ Fig. 1. View of the [Hg(oS3)(PPh3)(NO3)]" complex unit showing labelling of the non-H atoms. The S atoms of oS3 are in an overall endo-dentate conformation. This is in agreement with the known structural data for this ligand (deGroot & Loeb, 1990) and confirms its coordinating capability as a facial tridentate ligand. Experimental The ligand oS3 was synthesized by a previously reported procedure (deGroot, Hannan& Loeb, 1991). The Hg II complex was prepared by adding a solution of oS3 (0.05 g, 0.2 mmol) in ethanol/CH2C12 (10:1, 5 ml) to a solution of Hg(NO3)2.H20 (0.07 g, 0.2 mmol) and triphenylphosphine (0.05 g, 0.2 mmol) in ethanol (5 ml). The mixture was refluxed for 1 h and allowed to stand for 24 h at 268 K. The colourless prismatic R. KIVEK,AS et al. 1251 crystals that precipitated were filtered off and vacuum dried. Yield 23%. Crystals of the title compound were obtained directly from the synthesis. Crystal data [Hg(NO3)(CI2HI6S3)- Mo Ko~ radiation (CI8HIsP)][NO3].H20.- A = 0.71069 ,~ 0 .5C2H60 Cell parameters from 25 Mr = 884.4 ref lect ions Monoclinic 0 = 12.8-18.3 ° C2/c # = 4.52 mm-I  a = 30.198 (8) ,~ T = 296 K b = 15.642 (5) ,~, Plate c = 18.147 (5 )•  0.18 x 0.12 x 0.10 mm /3 = 122.60 (3) ° Colourless V = 7221 (4) ,~3 Z=8 Dx = 1.627 Mg m -3 Data collection Rigaku AFC-5S diffractome- ter w-20 scans Absorption correction: empirical Tmin = 0.81, Tmax = 1.00 12 563 measured reflections 6365 independent reflections 3587 observed reflections [F > 3o(F)]  Rint = 0.0631 0max = 25 ° h = -35  ~ 29 k = -18  ~ 18 l = 0 ---~ 21 3 standard reflections monitored every 150 reflections intensity variation: -36% (linear correction applied) Refinement Refinement on F R = 0.057 wR = 0.052 S = 1.80 3587 reflections 371 parameters H-atom parameters not refined w = 1/~r2(F) (A/or)max = 0.23 Aprnax = 1.3 e ,~-3 Apmin = -1 .1  e A -3 Extinction correction: none Atomic scattering factors from Xtal3.0 (Hall & Stewart, 1990) Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (~2)  Ueq = (I/3)Zi~jUija~a*. ai aj j • . x y z Ueq Hg 0.58058 (2) 0.32684 (3) 0.65893 (3) 0.0538 (3) S(1) 0.6060 (1) 0.3099 (2) 0.5390 (2) 0.061 (2) S(2) 0.4987 (1) 0.3962 (2) 0.5367 (2) 0.060 (2) S(3) 0.5130 (1) 0.1854 (2) 0.6053 (2) 0.072 (2) P 0.6475 (1) 0.2995 (2) 0.8101 (2) 0.046 (2) C(I) 0.6098 (6) 0.1360 (9) 0.5529 (8) 0.080 (9) C(2) 0.5879 (6) 0.0892 (8) 0.5902 (9) 0.08 (1) C(3) 0.6205 (7) 0.0312 (9) 0.657 (1) 0.12 (1) C(4) 0.6708 (8) 0.020 (1) 0.683 (1) 0.16 (1) C(5) 0.6892 (7) 0.062 (1) 0.644 (1) 0.13 (1) C(6) 0.6620 (6) 0.121 (1) 0.580 (1) 0.10 (1) C(7) 0.5815 (5) 0.2070 (8) 0.4865 (8) 0.074 (9) C(8) 0.5570 (5) 0.3848 (9) 0.4614 (8) 0.071 (8) C(9) 0.5030 (5) 0.3750 (9) 0.4427 (7) 0.066 (7) C(10) 0.4479 (5) 0.326 (1) 0.5251 (8) 0.082 (8) C(I 1) 0.4537 (5) 0.230 (1) 0.5132 (8) 0.091 (9) C(12) 0.5306 (7) 0.0965 (8) 0.557 (1) 0.10 (1) C(13) 0.6511 (4) 0.3744 (7) 0.8875 (7) 0.047 (7) C(14) 0.6396 (5) 0.4584 (8) 0.8640 (8) 0.073 (9) C(15) 0.6500 (6) 0.5191 (8) 0.9283 (9) 0.08 (1) C(16) 0.6719 (5) 0.4939 (8) 1.0146 (8) 0.070 (9) C(! 7) 0.6822 (5) 0.4097 (7) 1.0377 (8) 0.061 (81 C(18) 0.67 i 5 (5) 0.3502 (7) 0.9734 (7) 0.054 (7) C(19) 0.6387 (4) 0.1937 (7) 0.8410 (7) 0.047 (6) C(20) 0.591 ! (5) 0.1752 (7) 0.8294 (7) 0.056 (7) C(21) 0.5820 (5) 0.0929 (9) 0.8479 (8) 0.071 (9) C(22) 0.6210 (5) 0.0323 (8) 0.8799 (8) 0.076 (9) C(23) 0.6691 (5) 0.0520 (8) 0.8936 (9) 0.076 (9) C(24) 0.6774 (5) 0.1323 (8) 0.8738 (8) 0.061 (7) C(25) 0.7115 (4) 0.3003 (7) 0.8224 (7) 0.045 (6) C(26) 0.7534 (4) 0.3482 (7) 0.8865 (7) 0.050 (7) C(27) 0.8006 (4) 0.3469 (7) 0.8927 (8) 0.059 (7) C(28) 0.8066 (5) 0.2982 (8) 0.8368 (9) 0.069 (8) C(29) 0.7657 (5) 0.2491 (9) 0.7744 (9) 0.074 (9) C(30) 0.7180 (5) 0.2512 (8) 0.7655 (8) 0.063 (8) O(31) 0.6023 (4) 0.5016 (7) 0.6393 (7) 0.121 (4) 0(32) 0.6808 (5) 0.4759 (8) 0.7096 (8) 0.160 (5) 0(33) 0.6520 (5) 0.6005 (9) 0.7087 (9) 0.166 (5) N(34) 0.6484 (5) 0.5293 (8) 0.6908 (8) 0.111 (5) 0(35) 1/2 0.332 (1) 3/4 0.119 (5) 0(36) 0.5087 (4) 0.4510 (7) 0.7035 (7) 0.123 (4) N(37) 1/2 0.408 (1) 3/4 0.093 (6) O(38)t:1: 0.5546 (7) -0.156 (1) 0.673 (1) 0.067 (5) O(39)t~t 0.5000 (7) -0.061 (1) 0.661 (1) 0.128 (8) O(40)t:~ 0.5354 (8) -0.147 (1) 0.771 (1) 0.18 (1) N(41)~':~ 0.5300 (4) -0.1213 (7) 0.7017 (7) 0.067 (6) O(42W) t 0.5188 (7) 0.636 (1) 0.755 (1) 0.093 (7) O(43W) t 0.5962 (8) 0.697 (1) 0.774 (1) 0.112 (7) C(44)]'§ 0.789 (2) 0.321 (2) 0.592 (3) 0.15 (2) C(45)t 0.790 (2) 0.252 (4) 0.561 (3) 0.23 (2) C(46)t§ 0.747 (2) 0.209 (2) 0.476 (3) 0.15 (2) t Occupancy factor 0.5. :l: Disordered NO~- refined as a rigid group with N---O = 1.24 ,~. § O atom of ethanol solvate could not be distinguished. Table 2. Selected geometric parameters (~, o) Hg--S(1) 2.683 (5) P---C(19) 1.81 (1) Hg--S(2) 2.511 (3) P---C(25) 1.82 (1) Hg--S(3) 2.806 (4) C(1)---C(2) 1.38 (3) Hg--P 2.412 (3) C(1)--C(6) 1.39 (2) Hg--O(31) 2.877 (12) C(1)--C(7) 1.52 (2) S(1)--C(7) 1.81 (1) C(2)---C(3) 1.40 (2) S(1)---C(8) 1.82 (1) C(2)---C(12) 1.50 (3) S(2)---C(9) 1.81 (2) C(3)--C(4) 1.33 (3) S(2)--C(10) 1.80 (2) C(4)---C(5) 1.29 (3) S(3)--C(11) 1.81 (1) C(5)---C(6) 1.35 (2) S(3)----C(12) 1.87 (2) C(8)-.--C(9) 1.48 (2) P---C(13) 1.79 (1) C(10}--C(11) 1.54 (2) S(1)--Hg--S(2) 84.4 (1) C(2)--C(3)---C(4) 122 (2) S(I)---Hg--S(3) 96.6 (1) Hg--S(1)---C(8) 95.5 (6) S(1)--Hg--P 118.3 (1) C(7)---S(1)---C(8) 103.5 (5) S(I)--Hg---O(31) 79.0 (3) Hg--S(2)--C(9) 102.5 (4) S(2)---Hg---S(3) 81.3 (1) Hg--S(2)---C(10) 102.2 (4) S(2)----Hg--P 154.7 (1) C(9)---S(2)---C(10) 105.5 (7) S(2)---Hg---O(31) 70.2 (2) HgmS(3)---C(I 1) 101.0 (5) S(3)---Hg--P 105.2 (1) Hg--S(3)-.-C(12) 114.2 (6) S(3)---Hg--O(31) 151.4(2) C(I 1)--S(3)---C(12) 104.1 (7) P--Hg--O(3 i) 101.6 (2) Hg--P--C(I 3) 115.9 (3) Hg--S(I)--C(7) 107.4 (6) Hg--P---C(19) 109.9 (3) Hg--P--C(25) 108.8 (4) C(3)----C(4)----C(5) 119 (2) C(13)---P--C(19) 108.2 (6) C(4)---C(5)---C(6) 125 (2) C(I 3)---P--C(25) 106.7 (6) C(1)----C(6)---C(5) 118 (2) C(19)---P--C(25) 106.9 (6) S(I)---C(7)---C(1) 109.7 (8) C(2)--C(1)---C(6) 119 (1) S(1)---C(8)---C(9) 117 (1) C(2)----C(1)----C(7) 124 (1) S(2)---C(9)--.C(8) 113.2 (8) C(6)---.~(1)----C(7) 117 (2) S(2)-.--C(10)---C(11) 117 (1) C(1)---C(2)--C(3) 118 (2) S(3)---C(1 I)---C(10) 112.1 (8) C(1)-.-.C(2)--C(12) 121 (1) S(3)---C(12)---C(2) 115.3 (9) C(3)---C(2)--C(12) 121 (2) C(8)--S(1)---C(7)-----C(1) - 165 (1) C(2}---C(1)--C(7)--S(1) 104 (1) C(7)----S(1)---C(8)---C(9) 62 (1) C(6)----C(1)---C(7)---S(1) -72 (2) C(10)----S(2)--C(9)--C(8) - 147 (1) C(1)--C(2)---C(3)----C(4) - i (2) C(9)--S(2)---C(10)--C(11) 54 (1) C(12)--C(2)--C(3)--C(4) 176 (2) C(12)---S(3)---C(1 I)---C(10) -150 (1) C(1)----C(2)---C(12)---S(3) -86  (2) 1252 [Hg(NO3 )(Cj 2 H 16 S 3 )(C 18 H 15 P)] [NO3 ].Ha O.0.5C2 H60 C(II)--S(3)----C(12)---C(2) 138 (I) C(3)=-C(2)--C(12)---S(3) 98 (I) C(6)---C(I)---C(2)---C(3) 3 (2) C(2)--C(3)-=-C(4)--C(5) -2 (3) C(6)---C(I)--C(2)---C(12) -174(I) C(3)--C(4)---C(5)-=~(6) 4(3) C(7)---C(I)-=-C(2)---C(3) - 174 (I) C(4)--C(5)-42(6)---C(I) -2 (3) C(7)---C(I)--C(2)---C(12) 9 (2) S(I)--C(8)--C(9)--S(2) 65 (I) C(2)---C(I)--C(6)----C(5) - I  (2) S(2)---C(I0)--C(II)--S(3) 61 (I) C(7)----C( 1)---C(6)----C(5) 176 (I) Cell refinement, data collection and data reduction: Rigaku AFC-5S software. Program used to solve the structure: SHELXS86 (Sheldrick, 1985). Program used to refine the structure: XTAL3.0 (Hall & Stewart, 1990). Molecular graph- ics: PLUTO (Motherwell & Clegg, 1978). Programs used to prepare material for the publication: Xtal3.0 BONDLA and ATABLE. Lists of structure factors, anisotropic displacement parameters, H-atom coordinates, complete geometry and least-squares-planes data have been deposited with the IUCr (Reference: AB 1115). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH1 2HU, England. References Blake, A. J. & Scr6der, M. (1990). Adv. lnorg. Chem. 35, 1-79. Casab6, J., Mestres, L., Escriche, L., Teixidor, F. & Perez- Jimenez, C. (1991). J. Chem. Soc. Dalton Trans. pp. 1969-1971. deGroot, B., Hannan, G. S. & Loeb, S. J. (1991). Inorg. Chem. 30, 4645-4647. deGroot, B. & Loeb, S. J. (1990). Inorg. Chem. 29, 4084-4090. Hall, S. R. & Stewart, J. M. (1990). Editors. Xtal3.0 Reference Manual. Univs. of Western Australia, Australia, and Maryland, USA. Lockhart, J. C., Mousley, D., Stuart Hill, M. N., Tomkinson, N. P., Teixidor, F., Almajano, M. P., Escribe, L., Casab6, J., Sillanp~i/i, R. & Kivek~is, R. (1992). J. Chem. Soc. Dalton Trans. pp. 2889-2897. Motherwell, W. D. S. & Clegg, W. (1978). PLUTO. Program for Plotting Molecular and Crystal Structures. Univ. of Cambridge, England. Sheldrick, G. M. (1985). SHELXS86. Program for Crystal Struc- ture Determination. Univ. of G6ttingen, Germany. formed by the C(Pb) atoms of the three organic ligands. The axial positions are occupied by Br atoms [Pb(1)--Br(1) 2.985 (2), Pb(1)--Br(la) 2.885 (2)A], each Br atom bridging neighbouring molecules to form infinite Br(la)--Pb(1)--Br(1)-- Pb(lb) chains [Br(la)~Pb(1)--Br(1) 173.610(15), Pb(1)--Br(1)--Pb(lb) 122.73 (5)°], i.e. catena-poly- [(benzyldiphenyllead)-/z-bromo]. Comment The structures of three triorganolead halides are known to have been investigated by diffraction methods. In all cases, the Pb atom proved to be pentacoordinated: in Ph3PbX (X-C1,  Br) inter- molecular X--Pb coordination generates one- dimensional chains via unsymmetrical X- -Pb- -X  links (Preut & Huber, 1977), while in [PbI(C7H7)(C9HI2N)(C7H70)] (van der Kooi, den Brinker & de Kok, 1985), a compound with three different R groups attached to the Pb atom, penta- coordination is attained by intramolecular N--Pb coordination. Pentacoordination of Pb and for- mation of infinite chains by way of halogen bridging was also inferred from vibrational studies for tri- methyllead halides (Clark, Davies & Puddephatt, 1968) and for triphenyllead halides (Clark, Davies & Puddephatt, 1969). We report here the solid-state structure of a triorganolead compound, (I), with two types of R group on Pb. (I) Acta Cryst. (1994). C50, 1252-1254 Benzyl(bromo)diphenyllead UWE FAHRENKAMPF, MARKUS SCHURMANN AND FRIEDO HUBER Lehrstuhl ffir Anorganische Chemie II, Universita't Dortmund, D-44221 Dortmund, Germany (Received 12 August 1993; accepted 16 December 1993) Abstract The coordination polyhedron around Pb in the title compound, [PbBr(C6Hs)2(CTHT)], is a slightly dis- torted trigonal bipyramid, the trigonal plane being © 1994 International Union of Crystallography Printed in Great Britain - all rights reserved The coordination polyhedron around Pb can be described as a slightly distorted trigonal bipyramid, with C(1), C(21) and C(31) in the equatorial plane and two Br atoms in the axial positions. The struc- ture is similar to that of [PbBr(C6Hs)3] (Preut & Huber, 1977); however, some noteworthy differences exist. The distances Pb(1)--Br(1) and Pb(1)--Br(la) are more similar to each other in the title compound [2.985(2) and 2.885 (2)/1,, respectively], than in [PbBr(C6Hs)3] [2.852 (1) and 3.106 (1) A, respective- ly]. Hence, the difference between the Pb(1)--Br(1) and Pb(1)--Br(la) distances of 0.100/~ in the title compound is less marked than in [PbBr(C6Hs)3] (0.254/~), and this corresponds to a distinctly shorter distance of Pb from the plane defined by C(1), C(21) and C(31) in the title compound {0.052 (5) A, com- pared to 0.127 (10)A in [PbBr(C6H5)3] (Preut & Huber, 1977)}. In this respect, the distortion of the trigonal bipyramid is smaller than in [PbBr(C6Hs)3]; Acta Crystallographica Section C ISSN 0108-2701 ©1994 

(Nitrato-κO)(triphenylphosphine-κP){3,6,9-trithiabicyclo[9.4.0]pentadeca-1(11),12,14-triene-κ3S3,6,9}mercury(II) nitrate hydrate hemiethanol solvate

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