l -1,10-Bis(diphenylphosphino)ferrocene-j 2P :P 0-bis{[(Z )-O -isopropyl N -(4-nitro-phenyl)thiocarbamato-j S ]gold(I)}chloroform disolvate
Soo Yei Ho a and Edward R.T.Tiekink b *
a
Department of Chemistry,National University of Singapore,Singapore 117543,and b Department of Chemistry,University of Malaya,50603Kuala Lumpur,Malaysia Correspondence e-mail:************************
Received 22October 2009;accepted 23October 2009
Key indicators:single-crystal X-ray study;T =223K;mean (C–C)=0.011A
˚;R factor =0.045;wR factor =0.104;data-to-parameter ratio =20.0.
The dinuclear title molecule,[Au 2Fe(C 10H 11N 2O 3S)2-(C 17H 14P)2]Á2CHCl 3,has crystallographic twofold symmetry with the Fe atom (bonded to two 5-cyclopentadienyl rings)situated on the rotation axis.The Au atom exists within a linear geometry defined by an S ,P -donor t with a deviation from linearity [S—Au—P =176.86(6) ]due to the clo approach of the thiocarbamate O atom [Au ÁÁÁO =
3.108(5)A
˚].The molecule has a U-shaped geometry which facilitates the formation of an intramolecular Au ÁÁÁAu
interaction [3.0231(5)A
˚].In the crystal,the prence of C—H ÁÁÁO nitro contacts leads to the formation of layers with substantial voids;the are occupied by the solvent molecules of crystallization,which are held in place by C—H ÁÁÁS contacts.
Related literature
行动的力量For structural systematics and luminescence properties of
phosphinegold(I)carbonimidothioates,e:Ho et al.(2006);Ho &Tiekink (2007);Kuan et al.(2008).For the synthesis,e:Hall et al.
(1993).
Experimental
Crystal data
[Au 2Fe(C 10H 11N 2O 3S)2-(C 17H 14P)2]Á2CHCl 3M r =1665.56Monoclinic,C 2=c
a =25.9661(13)A ˚
b =11.5544(6)A ˚
c =23.3615(13)A
˚ =117.293(1)
V =6228.7(6)A
˚3Z =4
Mo K radiation =5.36mm À1T =223K
0.36Â0.07Â0.04mm
Data collection
Bruker SMART CCD diffractometer
Absorption correction:multi-scan (SADABS ;Bruker,2000)T min =0.572,T max =1
21839measured reflections 7148independent reflections 4988reflections with I >2 (I )R int =0.056树叶画金鱼
Refinement
R [F 2>2 (F 2)]=0.045wR (F 2)=0.104S =0.97
7148reflections
357parameters
H-atom parameters constrained
Á max =2.08e A ˚À3Á min =À0.74e A
˚À3Table 1
Selected geometric parameters (A
˚, ).Au—S1
2.3127(16)
Au—P1
2.2594(15)
Table 2
Hydrogen-bond geometry (A
˚, ).D —H ÁÁÁA D —H H ÁÁÁA D ÁÁÁA D —H ÁÁÁA C21—H21ÁÁÁO2i
0.94 2.54 3.403(9)154C25—H25ÁÁÁO3ii 0.94 2.46 3.254(12)142C28—H28ÁÁÁS1iii
0.99
2.61
3.527(8)
154
Symmetry codes:(i)Àx ;y þ1;Àz þ12;(ii)x ;Ày ;z À12;(iii)x ;Ày ;z þ1
2.
Data collection:SMART (Bruker,2000);cell refinement:SAINT (Bruker,2000);data reduction:SAINT ;program(s)ud to solve structure:PATTY in DIRDIF92(Beurskens et al.,1992);program(s)ud to refine structure:SHELXL97(Sheldrick,2008);molecular graphics:DIAMOND (Brandenburg,2006);software ud to prepare material for publication:SHELXL97.
The National University of Singapore (grant No.R-143–000–213–112)is thanked for support.
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference:HB5168).
References
Beurskens,P .T.,Admiraal,G.,Beurskens,G.,Bosman,W.P .,Garcia-Granda,S.,Gould,R.O.,Smits,J.M.M.&Smykalla,C.(1992).The DIRDIF Program System .Technical Report.Crystallography Laboratory,University of Nijmegen,The Netherlands.
Brandenburg,K.(2006).DIAMOND .Crystal Impact GbR,Bonn,Germany.Bruker (2000).SMART ,SAINT and SADABS .Bruker AXS Inc.,Madison,Wisconsin,USA.
市场失灵
Hall,V .J.,Siasios,G.&Tiekink,E.R.T.(1993).Aust.J.Chem.46,561–570.Ho,S.Y.,Cheng,E.C.-C.,Tiekink,E.R.T.&Yam,V .W.-W.(2006).al-organic compounds
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
Ho,S.Y.&Tiekink,E.R.T.(2007).CrystEngComm,9,368–378.
Kuan, F.S.,Ho,S.Y.,Tadbuppa,P.P.&Tiekink, E.R.T.(2008). CrystEngComm,10,548–564.Sheldrick,G.M.(2008).Acta Cryst.A64,112–122.
metal-organic compounds
supplementary materials
supplementary materials Acta Cryst. (2009). E65, m1466-m1467 [ doi:10.1107/S1600536809043864 ]
-1,1'-Bis(diphenylphosphino)ferrocene-2P:P'-bis{[(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-S]gold(I)} chloroform disolvate
S. Y. Ho and E. R. T. Tiekink
Comment
The dinuclear title compound, dppf{Au[SC(O-i Pr)NC6H4NO2-p]}2, was investigated as a part of systematic studies of phosphinegold(I) thiocarbamides (Ho et al. 2006; Ho & Tiekink, 2007; Kuan et al., 2008). Crystals were isolated as the di-chloroform solvate, (I), and are isomorphous with the methoxy analogue (Ho et al., 2006). The dinuclear molecule has crystallographic twofold symmetry with the Fe atom lying on the axis; the asymmetric unit compris half a dinuclear molecule and one chloroform molecule. The gold atom exists in the expected linear geometry defined by a SP donor
t, Table 1, and the deviation from linearity is ascribed to the clo approach of the O1 atom, Au···O = 3.108 (5) Å. The anion, with a Z configuration about the C1═N1 bond, shows the expected characteristics. Overall, the molecule has a U-shaped configuration which allows for the formation of an aurophilic interaction, Au···Au i = 3.0231 (5) Å; (i): -x, y, 1/2 - z.
In the crystal structure of (I), supramolecular layers are formed in the bc plane that are mediated by C—H···O interactions, Table 2 and Fig. 2. The resulting framework has solvent accessible voids and the are occupied by the chloroform molecules which are connected via C—H···S contacts, Table 2. Layer thus formed stack along the a direction.
Experimental
夜宿山寺The unsolvated compound was prepared following the standard literature procedure from the reaction of dppf(AuCl)2 and i-PrOC(═S)N(H)C6H4NO2-4 in the prence of ba (Hall et al., 1993); m. pt. 409–410 K. Analysis for C54H50Au2FeN4O6P2S2: found (calculated): C: 45.64 (45.45); H: 3.49 (3.53). IR (cm-1): ν(C—S) 1100 s, 899m; ν(C—N) 1585 s; ν(C—O) 1153 s. 31P{1H} NMR: δ 32.0 Orange crystals of the di-chloroform solvate (I) were obtained from the layering of ethanol on a chloroform solution of the characterized product.
Refinement
The H atoms were geometrically placed (C—H = 0.94–0.99 Å) and refined as riding with U iso(H) = 1.2–1.5U eq(C). The maximum and minimum residual electron density peaks of 2.08 and 0.74 e Å-3, respectively, were located 0.83 Å and 0.74Å from the Au atom.
supplementary materials
Figures
Fig. 1. Molecular structure of the dinuclear complex in (I) showing displacement ellipsoids at
the 35% probability level. The molecule has twofold symmetry and unlabelled atoms are gen-
erated by the symmetry operation -x, y, 1/2 - z.
Fig. 2. Supramolecular layer formation in (I) mediated by C—H···O contacts (blue dashed
lines). The chloroform molecules are connected via C—H···S contacts (orange dashed lines).
Colour code: Au, orange; Cl, cyan; S, yellow; P, pink; O, red; N, blue; C, grey; and H, green.
µ-1,1'-Bis(diphenylphosphino)ferrocene-κ2P:P'- bis{[(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-
κS]gold(I)} chloroform disolvate
Crystal data
[Au2Fe(C10H11N2O3S)2(C17H14P)2]·2CHCl3F000 = 3248
M r = 1665.56D x = 1.776 Mg m−3
Monoclinic, C2/c Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc Cell parameters from 3297 reflections
a = 25.9661 (13) Åθ = 4.4–23.2º养生秘诀
b = 11.5544 (6) ŵ = 5.36 mm−1
c = 23.3615 (13) ÅT = 223 K
β = 117.293 (1)ºNeedle, orange
思前想后的意思V = 6228.7 (6) Å30.36 × 0.07 × 0.04 mm
Z = 4
Data collection
Bruker SMART CCD
diffractometer7148 independent reflections
Radiation source: fine-focus aled tube4988 reflections with I > 2σ(I)
wood文档
Monochromator: graphite R int = 0.056
T = 223 Kθmax = 27.5º
ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)h = −31→33口红唇膏
T min = 0.572, T max = 1k = −15→15
21839 measured reflections l = −30→16
