Source of material: source of material: see ref. 1.

Zeitschrift für Kristallographie New Crystal Structures 212, 2 4 5 - 2 4 6

© by R. Oldenbourg Verlag, München 1997

245

Crystal structure of tetracarbonyl^ ¹ -l,l-di-terí-butyl-3-(2,4,6-tri-terí- butylphenyl)-l,2-diphosphatriaz-2-ene)iron(0), C3oH47FeN04P2

M. Nieger, E. Niecke and M. Lysek

Universität Bonn, Institut für Anorganische Chemie, Gerhard-Domagk-Str. I, D-53121 Bonn, Germany Received September 2, 1996, CSD-No. 402616

Table 2. Final atomic coordinates and displacement parameters (in Â2)

«2 C63

Source of material: source of material: see ref. 1.

The diphosphatriazene is η'-coordinated by the lone pair of the trigonal planar configurated imino-phosphorus to a tetracarbonyl iron fragment. The bulky iminophosphane ligand adopts an equa- torial coordination site of the trigonal bipyramidal coordinated iron. The P-Fe bond (216.5(1) pm) is significant shorter than the P-Fe bond (221.5(1) pm) in a comparable diphosphene iron complex (see ref. 2). The P=N double bond (156.5(2) pm) is similar to that found in the uncomplexed compound (157.8(2) pm (see ref. 2)). The phosphino and the aryl ligand adopt a trans configuration relative to the P=N double bond (torsion angle C( 1 )-N( 1 )-P( 1 )-P(2) 179.0(2)°). For the chemistry of iminophos- phanes see ref. 3.

C30H47FeNO4P2, triclinic, PI (No. 2), a =10.720(1) Â,

b =11.371(1) Â, c =14380(1) Â, α =80.63(1)°, β =7631(1)°, γ=81.00(1)°, V=1667.6 Â3

, Ζ =2,

=0.045,

all data) =0.123.

Table 1. Parameters used for the X-ray data collection

Crystal: red block, size 0.40 χ 0.40 χ 0.55 mm Wavelength: Mo Ka radiation (0.71069 À)

μ: 5.80 cm"1

Diffractometer: Stoe-Siemens AED

Scan mode: profile fitting mode (see ref. 4)

Τ measurement" 293 Κ

28max: 50°

Ν (hkl)wúque' 5840

Criterion for /0: Io > 2 σ(/0)

Ν (pararnirtfinnT· 338

Programs: SHELXS-86, SHELXL-93

Atom Site Occ. X y ζ t/iso

H(3) 2i 0.3940(3) 0.6351(2) 0.1764(2) 0.054 H(5) 2i 0.2385(3) 0.4422(2) 0.4184(2) 0.062 H(22A) 2 i 0.7208(3) 0.6067(3) 0.2402(2) 0.087 H(22B) 2i 0.8193(3) 0.5881(3) 0.1426(2) 0.087 H(22C) 2 i 0.7814(3) 0.4768(3) 0.2184(2) 0.087 H(23A) 2 i 0.7034(3) 0.3843(3) 0.0915(2) 0.086 H(23B) ^{2 i} 0.7537(3) 0.4930(3) 0.0176(2) 0.086 H(23C) 2 i 0.6105(3) 0.4671(3) 0.0321(2) 0.086 H(24A) ²ⁱ 0.5757(3) 0.7283(3) 0.1399(2) 0.095 H(24B) 2i 0.5344(3) 0.6723(3) 0.0608(2) 0.095 H(24C) 21 0.6776(3) 0.6981(3) 0.0463(2) 0.095 C(42) ²ⁱ 0.820(3) 0.1738(5) 0.7543(4) 0.2915(4) 0.084(1) H(42A) 2i 0.820(3) 0.0918(5) 0.8013(4) 0.2888(4) 0.126 H(42B) 2i 0.820(3) 0.2380(5) 0.7817(4) 0.2367(4) 0.126 H(42C) ²ⁱ 0.820(3) 0.1983(5) 0.7630(4) 0.3498(4) 0.126 C(43) 2i 0.820(3) 0.0533(4) 0.5865(4) 0.3738(3) 0.078(1) H(43A) ^{2 i} 0.820(3) 0.0447(4) 0.5036(4) 0.3744(3) 0.117 H(43B) 2 i 0.820(3) -0.0261(4) 0.6352(4) 0.3661(3) 0.117 H(43C) 2 í 0.820(3) 0.0726(4) 0.5970(4) 0.4337(3) 0.117 C(44) 2 i 0.820(3) 0.1232(5) 0.6107(4) 0.1973(3) 0.083(1) H(44A) 2i 0.820(3) 0.1164(5) 0.5277(4) 0.1963(3) 0.125 H(44B) ^{2 i} 0.820(3) 0.1872(5) 0.6382(4) 0.1424(3) 0.125 H(44C) 2 i 0.820(3) 0.0411(5) 0.6576(4) 0.1950(3) 0.125 C(42') 2 i 0.180(3) 0.054(2) 0.553(2) 0.301(2) 0.084(1) H(42D) 2 i 0.180(3) -0.024(2) 0.606(2) 0.298(2) 0.126 H(42E) 2i 0.180(3) 0.043(2) 0.503(2) 0.363(2) 0.126 H(42F) 2i 0.180(3) 0.073(2) 0.503(2) 0.251(2) 0.126 C(43·) 2 i 0.180(3) 0.167(2) 0.723(1) 0.203(1) 0.078(1) H(43D) 2i 0.180(3) 0.239(2) 0.767(1) 0.198(1) 0.117 H(43E) 2i 0.180(3) 0.088(2) 0.776(1) 0.212(1) 0.117 H(43F) 2i 0.180(3) 0.178(2) 0.687(1) 0.146(1) 0.117 C(44') 2i 0.180(3) 0.129(2) 0.698(2) 0.379(1) 0.083(1) H(44D) 2/ 0.180(3) 0.197(2) 0.746(2) 0.375(1) 0.125 H(44E) 2i 0.180(3) 0.120(2) 0.643(2) 0.438(1) 0.125 H(44F) 2i 0.180(3) 0.049(2) 0.749(2) 0.378(1) 0.125 H(62A) 2i 0.2383(5) 0.3018(4) 0.5243(2) 0.155 H(62B) 2 i 0.3016(5) 0.3961(4) 0.5606(2) 0.155 H(62C) 2i 0.3214(5) 0.2600(4) 0.6027(2) 0.155 H(63A) 2 i 0.5398(4) 0.4008(3) 0.5131(2) 0.127 H(63B) ²ⁱ 0.6280(4) 0.2992(3) 0.4581(2) 0.127 H(63C) ^{2 i} 0.5508(4) 0.2680(3) 0.5642(2) 0.127 H(64A) 2 i 0.3736(4) 0.1519(3) 0.4258(3) 0.120 H(64B) ^{2 i} 0.4476(4) 0.1133(3) 0.5100(3) 0.120 H(64C) ²ⁱ 0.5248(4) 0.1445(3) 0.4038(3) 0.120 H(2'l) 2 i 1.0654(4) 0.3141(3) 0.1654(3) 0.119 H(2'2) ²ⁱ 0.9463(4) 0.3613(3) 0.1182(3) 0.119 H(2'3) ^{2 i} 1.0826(4) 0.3268(3) 0.0531(3) 0.119 H(3'l) ^li 0.9117(3) 0.0870(3) 0.0461(2) 0.104 H(3'2) 21 0.9881(3) 0.1874(3) -0.0205(2) 0.104 H(3'3) 21 0.8518(3) 0.2220(3) 0.0446(2) 0.104 H(4'l) 21 1.1027(3) 0.0119(4) 0.1155(3) 0.127 H(4'2) 2/ 1.1669(3) 0.0984(4) 0.1594(3) 0.127

246

Table 2. (Continued) Table 2. (Continued)

Atom Site Occ. χ Atom Site Occ. χ Uis

H(4'3) li 1.1760(3) H(2" 1 ) 21 0.9726(4) H(2"2) 21 0.9400(4) H(2"3) 2/ 0.8287(4) H(3"l) 2/ 0.8537(5)

0.1136(4) 0.0478(3) 0.127 0.3354(3) 0.3047(3) 0.122 0.3036(3) 0.4173(3) 0.122 0.3285(3) 0.3603(3) 0.122 0.0121(3) 0.4262(3) 0.132

H(3"2) 21 0.7553(5) H(3"3) 2/ 0.8667(5) H(4" 1 ) 2 i 1.0830(4) H(4"2) 2i 1.0929(4) H(4"3) 2/ 1.1300(4)

0.1293(3) 0.4354(3) 0.132 0.1044(3) 0.4924(3) 0.132 0.0239(4) 0.3415(3) 0.149 0.1169(4) 0.4081(3) 0.149 0.1484(4) 0.2955(3) 0.149

Table 3. Final atomic coordinates and displacement parameters (in À2)

Atom Site χ y ζ Ut ι Un t/33 Un U13 I/23 Fe(l) li 0.57717(4) 0.10335(3) 0.17566(3) 0.0465(2) 0.0438(2) 0.0576(3) -0.0073(2) -0.0133(2) -0.0109(2) P(l) 2i 0.68683(6) 0.20528(5) 0.23527(5) 0.0424(4) 0.0343(3) 0.0392(3) -0.0045(3) -0.0077(3) -0.0047(3) P(2) 2/ 0.88747(7) 0.11906(6) 0.24007(5) 0.0492(4) 0.0378(4) 0.0581(4) -0.0023(3) -0.0184<3) -0.0052(3) N(I) 21 0.6501(2) 0.3233(2) 0.2837(1) 0.055(1) 0.036(1) 0.037(1) -0.0041(9) -0.0076(9) -0.0032(8) C(l) 21 0.5315(3) 0.4010(2) 0.2919(2) 0.055(2) 0.034(1) 0.035(1) -0.004(1) -0.005(1) -0.007(1) C(2) li 0.5219(2) 0.5035(2) 0.2212(2) 0.048(1) 0.038(1) 0.037(1) -0.007(1) -0.004(1) -0.006(1) C(3) 2 Í 0.4015(3) 0.5705(2) 0.2244(2) 0.049(2) 0.038(1) 0.043(1) -0.003(1) -0.005(1) -0.003(1) C(4) li 0.2921(3) 0.5475(2) 0.2942(2) 0.049(2) 0.043(1) 0.044(1) -0.009(1) 0.000(1) -0.013(1) C(5) 2/ 0.3093(3) 0.4561(2) 0.3681(2) 0.059(2) 0.046(2) 0.042(2) -0.009(1) 0.008(1) -0.010(1) C(6) li 0.4254(3) 0.3837(2) 0.3718(2) 0.065(2) 0.038(1) 0.037(1) -0.007(1) 0.002(1) -0.005(1) C(21) 2/ 0.6380(3) 0.5464(2) 0.1436(2) 0.046(1) 0.039(1) 0.041(1) -0.004(1) -0.003(1) 0.002(1) C(22) 21 0.7505(3) 0.5553(3) 0.1906(2) 0.054(2) 0.056(2) 0.061(2) -0.014(1) -0.008(1) -0.002(1) C(23) 21 0.6804(3) 0.4651(3) 0.0637(2) 0.064(2) 0.059(2) 0.039(1) -0.004(1) 0.002(1) -0.003(1) C(24) 21 0.6031(3) 0.6732(3) 0.0929(2) 0.056(2) 0.052(2) 0.066(2) -0.005(1) 0.004(2) 0.014(1) C(41) li 0.1631(3) 0.6242(3) 0.2900(2) 0.047(2) 0.056(2) 0.056(2) -0.008(1) -0.001(1) -0.014(1) C(61) 2 i 0.4348(3) 0.2955(3) 0.4656(2) 0.090(2) 0.046(2) 0.038(2) -0.003(2) 0.007(2) 0.003(1) C(62) li 0.3125(5) 0.3152(4) 0.5459(2) 0.135(4) 0.084(3) 0.048(2) 0.020(2) 0.028(2) 0.012(2) C(63) 2 i 0.5489(4) 0.3179(3) 0.5038(2) 0.131(4) 0.070(2) 0.048(2) 0.003(2) -0.024(2) 0.000(2) C(64) li 0.4463(4) 0.1641(3) 0.4498(3) 0.110(3) 0.047(2) 0.064(2) -0.013(2) 0.011(2) 0.007(2) C(l') li 0.9950(3) 0.1797(3) 0.1225(2) 0.042(2) 0.056(2) 0.064(2) 0.001(1) -0.006(1) -0.011(1) C(2·) li 1.0251(4) 0.3071(3) 0.1140(3) 0.071(2) 0.064(2) 0.094(3) -0.019(2) 0.003(2) -0.005(2) C(3·) li 0.9306(3) 0.1679(3) 0.0405(2) 0.058(2) 0.088(2) 0.055(2) 0.004(2) -0.004(2) -0.015(2) C(4') li 1.1222(3) 0.0926(4) 0.1101(3) 0.053(2) 0.091(3) 0.101(3) 0.017(2) -0.011(2) -0.022(2) C(l") li 0.9321(3) 0.1619(3) 0.3478(2) 0.080(2) 0.062(2) 0.063(2) -0.005(2) -0.040(2) 0.000(2) C(2") li 0.9169(4) 0.2946(3) 0.3585(3) 0.117(3) 0.073(2) 0.074(2) -0.020(2) -0.053(2) -0.012(2) C(3") li 0.8437(5) 0.0958(3) 0.4335(3) 0.129(4) 0.076(2) 0.060(2) -0.008(2) -0.035(2) 0.007(2) C(4") li 1.0727(4) 0.1077(4) 0.3483(3) 0.096(3) 0.109(3) 0.106(3) 0.000(2) -0.066(3) 0.001(3) C ( l l ) li 0.6962(3) -0.0272(3) 0.1825(3) 0.069(2) 0.044(2) 0.086(2) -0.011(2) -0.026(2) -0.017(2) 0(11) li 0.7622(3) -0.1156(2) 0.1839(2) 0.098(2) 0.047(1) 0.163(3) 0.005(1) -0.053(2) -0.032(2) C(12) li 0.6006(3) 0.1029(3) 0.0479(3) 0.070(2) 0.066(2) 0.072(2) 0.012(2) -0.023(2) -0.022(2) 0(12) li 0.6192(3) 0.1014(3) -0.0333(2) 0.124(2) 0.129(3) 0.067(2) 0.043(2) -0.031(2) -0.036(2) C(13) li 0.4490(3) 0.2281(3) 0.1732(2) 0.052(2) 0.060(2) 0.065(2) -0.010(2) -0.017(1) -0.016(1) 0(13) li 0.3629(2) 0.2986(2) 0.1680(2) 0.063(1) 0.079(2) 0.104(2) 0.014(1) -0.034(1) -0.032(1) C(14) li 0.4586(4) 0.0104(3) 0.2474(3) 0.064(2) 0.064(2) 0.106(3) -0.020(2) -0.019(2) -0.004(2) 0(14) li 0.3854(3) -0.0481(3) 0.2922(3) 0.090(2) 0.103(2) 0.179(3) -0.053(2) -0.008(2) 0.022(2)

References

1. Lysek, M.: Aminodiphosphene und Iminophosphane mit sterisch an- spruchsvollen Stickstoffsubstituenten. Dissertation, Universität Bielefeld, Germany 1987.

2. Cowley, A. H.; Kilduff, J. E.; Lasch, J. G.; Norman, N. C ; Pakulski, M.;

Ando, F.; Wright, T. C.: Reactivity of Diphosphenes and Phosphaarsenes toward Metal Carbonyls. J. Am. Chem. Soc. 105 (1983) 7751-7752.

3. Niecke, E.; Gudat, D.: Iminophosphanes: Unconventional Compounds of Main Group Elements. Angew. Chem. Int. Ed. Engl. 30 (1991) 217-237.

4. Clegg, W.: Faster Data Collection Without Loss of Precession. An Exten- sion of the Leamt Profile Method. Acta Crystallogr. A37 (1981) 22-28.

4. Sheldrick, G. M.: SHELXS-86. Program for the solution of crystal struc- tures. University of Göttingen, Germany 1986.

5. Sheldrick, G. M.: SHELXL-93. Program for refining crystal structures.

University of Göttingen, Germany 1993.