1

Supporting Information for

Carbene-based Lewis Pairs for Hydrogen Activation

Jason W. Runyon,A,C Oliver Steinhof,A H. V. Rasika Dias,B§ Joseph C. Calabrese,B William J. Marshall,B Anthony J. Arduengo, III,A,C

A Deptartment of Chemistry, The University of Alabama, 3068 Shelby Hall,Tuscaloosa, Alabama 35487-0336, USA.B Central Research and Development Department, E. I. du Pont deNemours & Company, Experimental Station, Wilmington, Delaware 19880-0328.C Corresponding authors. Email: jwrunyon@crimson.ua.edu, aj@ajarduengo.net

Table of Contents:

1. Crystallographic Data Parameters …............................................. 2

2. ORTEP Plots and Select Measurements …............................................. 3

3. Atomic Coordinates …............................................. 7

§ Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019-0065, USA.

dem051Typewritten Text10.1071/CH11246_ACCSIRO 2011Australian Journal of Chemistry 2011, 64(8), 1165-1172

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Table 1. Crystallographic Data and Data Collection Parameters for 9, 11, and 20.

Parameter 9 11 20

empirical formula C5H13B1N2 C23H34N2 C16H20N2O5Fe1

formula weight (g/mol) 111.98 338.54 376.19

crystal system monoclinic monoclinic orthorhombic

space group P21/c P21/n P212121

a (Å) 8.6906(15) 16.858(3) 9.129(4)

b (Å) 15.716(3) 6.566(1) 13.547(6)

c (Å) 11.367(2) 17.671(3) 14.320(6)

β (°) 93.177(4) 107.06(1)

V (Å3) 1550.2(5) 1869.9 1771.0(14)

Z 8 4 4

Dx (g/cm3) 0.960 1.202 1.411

absorption coeff. (mm-1) 0.06 0.65 0.88

Temperature (oC) -100. -68. -100.

crystal color, form colorless, plates colorless, trapezoidal yellow, irregular

crystal size (mm) 0.320x0.300x0.040 0.36x0.12x0.52 0.500x0.480x0.480

h, k, l 7, 20, 15 21, 8, 22 12, 17, 19

Max diff./pk. hole (e/Å3) 1.91, -1.63 0.293, -0.342 0.257, -0.178

refltns collected 3657 (l ≥ 4.0σ(I)) 1763 (l ≥ 2.0σ(I)) 4588 (l ≥ 4.0σ(I))

wR2 0.0587 0.0841 0.0601

GOF on F2 1.00 0.991 1.02

data/parameter 16.78 6.78 20.76

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ORTEP Plot of 9.

The asymmetric unit contains two carbene molecules and two BH4 counterions with thermal ellipsoids

drawn to the 50% probability level. One of the BH4 groups is disordered and the occupancies and

thermal parameters for the hydrogens were allowed to refine.

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ORTEP Plot of 11.

The asymmetric unit contains eight molecules with thermal ellipsoids drawn to the 50% probability

level. As expected, the nitrogens are significantly pyramidal, forcing the imidazoline ring to be non-

planar (C2 is 0.29Å out of the N, N3, C4, C5 plane). The average C-N ring distance is 1.492Å, ~0.12Å.

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ORTEP Plot of 20.

The asymmetric unit contains one molecule with thermal ellipsoids drawn to the 50% probability level.

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Table 1. Atomic coordinates ( x 10^4) and equivalent isotropicdisplacement parameters (A^2 x 10^3) for 9. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Atom X Y Z U(eq)N11 8727(2) 1002(1) 4192(2) 45(1)C21 9392(2) 1612(2) 3595(2) 50(1)N31 10054(2) 1268(1) 2693(2) 50(1)C41 9823(2) 403(1) 2728(2) 48(1)C51 8999(2) 238(1) 3659(2) 45(1)C61 10965(3) 1734(2) 1859(2) 85(1)C71 7871(3) 1126(2) 5256(2) 74(1)N111 4312(2) -1074(1) 7987(2) 52(1)C121 3671(3) -539(1) 8715(2) 49(1)N131 3917(2) 245(1) 8346(2) 49(1)C141 4719(3) 208(2) 7360(2) 63(1)C151 4979(3) -609(2) 7137(2) 62(1)C161 3354(4) 1028(2) 8883(3) 84(1)C171 4299(3) -2007(2) 8083(3) 97(1)B11 7043(3) -1649(2) 4897(2) 48(1)B22 1751(4) -1262(2) 11119(3) 53(1)

Table 2. Bond lengths [A] and angles [deg] for 9. _____________________________________________________________

Atom AngleN11-C21 1.326(3)N11-C51 1.371(2)N11-C71 1.467(3)C21-N31 1.319(3)N31-C41 1.375(3)N31-C61 1.464(3)C41-C51 1.336(3)

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111-C121 1.324(3)N111-C151 1.367(3)N111-C171 1.471(3)C121-N131 1.323(3)N131-C141 1.353(3)N131-C161 1.470(3)C141-C151 1.330(3)C21-N11-C51 108.42(19)C21-N11-C71 125.5(2)C51-N11-C71 126.04(19)N31-C21-N11 108.8(2)C21-N31-C41 108.19(19)C21-N31-C61 124.9(2)C41-N31-C61 126.7(2)C51-C41-N31 107.47(19)C41-C51-N11 107.07(18)121-N111-C151 108.2(2)C121-N111-C171 125.6(2)C151-N111-C171 126.2(2)N131-C121-N111 108.2(2)C121-N131-C141 108.83(19)C121-N131-C161 125.8(2)C141-N131-C161 125.3(2)C151-C141-N131 107.5(2)C141-C151-N111 107.3(2)

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Table 3. Anisotropic displacement parameters (A^2 x 10^3) for 9. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ].

Atom U11 U22 U33 U23 U13 U12N11 42(1) 46(1) 47(1) 1(1) 3(1) 5(1)C21 47(1) 41(1) 60(2) 2(1) -8(1) -1(1)N31 44(1) 54(1) 50(1) 8(1) -1(1) -10(1)C41 46(1) 49(1) 49(1) -6(1) 1(1) 1(1)C51 43(1) 37(1) 54(1) 3(1) -1(1) 0(1)C61 69(2) 108(2) 77(2) 36(2) 3(1) -28(2)C71 73(2) 90(2) 59(2) -1(1) 19(1) 24(1)N111 54(1) 44(1) 58(1) -2(1) -8(1) 7(1)C121 51(1) 53(1) 43(1) 4(1) 1(1) 6(1)N131 51(1) 44(1) 53(1) -6(1) 0(1) 0(1)C141 64(2) 62(2) 64(2) 4(1) 15(1) -12(1)C151 54(2) 79(2) 55(2) -11(1) 12(1) 4(1)C161 99(2) 61(2) 90(2) -26(2) -13(2) 20(2)C171 108(2) 42(2) 136(3) -1(2) -30(2) 17(1)B11 54(2) 39(1) 52(2) -2(1) 7(1) -1(1)B22 74(2) 40(2) 46(2) -2(1) 11(2) -3(1)

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Table 4. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 9.

Atom X Y Z U(eq)H4A1 0.10 -3 2189 58H5A1 8665 -306 3906 54H6A1 10830 2347 1973 127H6B1 10618 1580 1052 127H6C1 12056 1587 1995 127

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H7A1 8578 1321 5902 110H7B1 7399 586 5475 110H7C1 7064 1553 5101 110H14A1 5037 679 6910 76H15A1 5528 -828 6504 75H16A1 2798 884 9583 126H16B1 2659 1327 8314 126H16C1 4230 1397 9111 126H17A1 3474 -2183 8585 145H17B1 5293 -2203 8431 145H17C1 4120 -2257 7297 145H21 9370(20) 2197(16) 3820(20) 66(7)H121 3090(30) -684(15) 9400(20) 73(8)H1A1 7480(20) -1051(14) 5405(19) 63(6)H1B1 7570(30) -1687(16) 3980(20) 92(8)H1C1 7410(30) -2230(20) 5350(30) 122(11)H1D1 5750(40) -1651(18) 4850(30) 123(11)H2A2 2060(90) -1760(40) 10410(60) 110(30)H2B2 2100(70) -560(30) 11040(40) 90(30)H2C2 930(60) -1460(20) 11890(40) 90(20)H2D2 2220(100) -1500(40) 12100(70) 160(50)H2E2 2910(110) -1680(50) 10990(70) 90(40)H2F2 3000(200) -880(80) 11360(100) 180(80)H2G2 420(90) -1340(40) 11000(70) 30(40)H2H2 980(120) -710(70) 10490(80) 110(60)H2I2 1220(90) -1380(50) 10250(70) 40(40)

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Table 5. Torsion angles [deg] for 9. ________________________________________________________________

Dihedral AngleC51-N11-C21-N31 1.0(2)C71-N11-C21-N31 179.99(19)N11-C21-N31-C41 -1.0(2)N11-C21-N31-C61 -177.03(19)C21-N31-C41-C51 0.6(2)C61-N31-C41-C51 176.6(2)N31-C41-C51-N11 0.0(2)C21-N11-C51-C41 -0.6(2)C71-N11-C51-C41 -179.57(19)C151-N111-C121-N131 0.0(2)C171-N111-C121-N131 -179.9(2)N111-C121-N131-C141 0.5(2)N111-C121-N131-C161 177.9(2)C121-N131-C141-C151 -0.8(3)C161-N131-C141-C151 -178.3(2)N131-C141-C151-N111 0.8(3)C121-N111-C151-C141 -0.5(3)C171-N111-C151-C141 179.4(2)

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Table 6. Fractional Coordinates for 11.

Atom X Y ZN(1) 0.29293(17) 0.36060(50) 0.58579(16)N(3) 0.19980(17) 0.32990(50) 0.66122(16)C(2) 0.20750(20) 0.41580(60) 0.58580(20)C(4) 0.26490(20) 0.18740(60) 0.68550(20)C(5) 0.31700(20) 0.20320(60) 0.64280(20)C(101) 0.30510(20) 0.32550(60) 0.50698(19)

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C(102) 0.27680(20) 0.51650(60) 0.45650(20)C(103) 0.29130(20) 0.49170(70) 0.37530(20)C(104) 0.24290(30) 0.30610(70) 0.33360(20)C(105) 0.27270(30) 0.11640(70) 0.38330(20)C(106) 0.36500(30) 0.08470(70) 0.39460(30)C(107) 0.41280(30) 0.26900(70) 0.43650(20)C(108) 0.39790(20) 0.29390(70) 0.51780(20)C(109) 0.25680(20) 0.14010(60) 0.46350(20)C(110) 0.38370(30) 0.46010(70) 0.38640(30)C(201) 0.11510(20) 0.26630(60) 0.66180(20)C(202) 0.05650(20) 0.44660(60) 0.63200(20)C(203) -0.03090(20) 0.39430(60) 0.63510(20)C(204) -0.06280(20) 0.20650(60) 0.58430(20)C(205) -0.00520(20) 0.02550(60) 0.61560(20)C(206) -0.00180(20) -0.01840(60) 0.70140(20)C(207) 0.03030(20) 0.17060(60) 0.75250(20)C(208) 0.11770(20) 0.22030(60) 0.74815(19)C(209) 0.08300(20) 0.07820(60) 0.61190(20)C(210) -0.02820(20) 0.34880(60) 0.72090(20)

Table 7. Thermal parameters for 11. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

Atom U11 or Uiso U22 U33 U32 U12 U13 U(eq)N1 0.02370(99) 0.03120(99) 0.02380(99) 0.00440(99) 0.01090(99) 0.00570(99) 0.02539(97)N3 0.02400(99) 0.02840(99) 0.02190(99) 0.00250(99) 0.00920(99) 0.00330(99) 0.02424(97)C2 0.02800(99) 0.03400(99) 0.02900(99) 0.00160(99) 0.01550(99) 0.00550(99) 0.02881(99)C4 0.02490(99) 0.03700(99) 0.02770(99) 0.00900(99) 0.00690(99) 0.00110(99) 0.03004(99)C5 0.02800(99) 0.03800(99) 0.02800(99) 0.01130(99) 0.01140(99) 0.00610(99) 0.03065(99)C101 0.02100(99) 0.02300(99) 0.02320(99) 0.00040(99) 0.01030(99) -0.00020(99) 0.02158(99)C102 0.02900(99) 0.02900(99) 0.03000(99) 0.00250(99) 0.01570(99) 0.00080(99) 0.02783(99)C103 0.04400(99) 0.03200(99) 0.03300(99) 0.00600(99) 0.02180(99) 0.00400(99) 0.03409(99)C104 0.05500(99) 0.06300(99) 0.02500(99) -0.00500(99) 0.01700(99) 0.00400(99) 0.04654(99)C105 0.05700(99) 0.04000(99) 0.04200(99) -0.01400(99) 0.02500(99) -0.01300(99) 0.04409(99)

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C106 0.07600(99) 0.04000(99) 0.05500(99) -0.00200(99) 0.04400(99) 0.01100(99) 0.05170(99)C107 0.03900(99) 0.04600(99) 0.04200(99) 0.00400(99) 0.03000(99) 0.00900(99) 0.03846(99)C108 0.02600(99) 0.03500(99) 0.04000(99) 0.00500(99) 0.01440(99) 0.00500(99) 0.03266(99)C109 0.04200(99) 0.02700(99) 0.04000(99) -0.00600(99) 0.02370(99) -0.00700(99) 0.03384(99)C110 0.05000(99) 0.04600(99) 0.04500(99) 0.00500(99) 0.03500(99) -0.00100(99) 0.04249(99)C201 0.02240(99) 0.02300(99) 0.02200(99) -0.00270(99) 0.00950(99) -0.00190(99) 0.02183(99)C202 0.03100(99) 0.02100(99) 0.02800(99) 0.00100(99) 0.01580(99) 0.00120(99) 0.02514(99)C203 0.02700(99) 0.02500(99) 0.04100(99) 0.00120(99) 0.01340(99) 0.00400(99) 0.03027(99)C204 0.02300(99) 0.03700(99) 0.04000(99) -0.00300(99) 0.00670(99) -0.00300(99) 0.03388(99)C205 0.03100(99) 0.02100(99) 0.03300(99) -0.00620(99) 0.00430(99) -0.00440(99) 0.02942(99)C206 0.03100(99) 0.02400(99) 0.04300(99) 0.00400(99) 0.01350(99) -0.00060(99) 0.03210(99)C207 0.03600(99) 0.03200(99) 0.02700(99) -0.00420(99) 0.01890(99) -0.00820(99) 0.02960(99)C208 0.02920(99) 0.02500(99) 0.01860(99) -0.00600(99) 0.00680(99) -0.00700(99) 0.02431(99)C209 0.03400(99) 0.02700(99) 0.02170(99) -0.00130(99) 0.00910(99) 0.00680(99) 0.02737(99)C210 0.02900(99) 0.03300(99) 0.04600(99) -0.00300(99) 0.02070(99) -0.00320(99) 0.03392(99)H2 0.02500(99)H2' 0.05600(99)H4 0.02100(99)H5 0.05400(99)H102 0.03600(99)H103 0.04600(99)H104 0.04500(99)H105 0.05400(99)H106 0.04000(99)H107 0.06400(99)H108 0.03300(99)H109 0.04000(99)H110 0.02900(99)H202 0.05500(99)H203 0.04300(99)H204 0.04000(99)H205 0.01800(99)H206 0.04200(99)H207 0.02400(99)H208 0.03000(99)H209 0.01800(99)H210 0.01800(99)H302 0.03500(99)

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H304 0.05800(99)H306 0.06700(99)H308 0.02600(99)H309 0.04100(99)H310 0.06700(99)H402 0.02100(99)H404 0.04800(99)H406 0.04200(99)H408 0.01100(99)H409 0.01600(99)H410 0.02600(99)

Table 8. Bond lengths [A] for 11.

Atoms Length Atoms Length Atoms Length Atoms Length

N(1)-C(2) 1.4851(47) N(1)-C(5) 1.4170(48) N(1)-C(101) 1.4840(43) N(3)-C(2) 1.4875(45)

N(3)-C(4) 1.4098(48) N(3)-C(201) 1.4906(47) C(4)-C(5) 1.3192(49) C(101)-C(102) 1.5318(53)

C(101)-C(108) 1.5335(50) C(101)-C(109) 1.5389(53) C(102)-C(103) 1.5333(48) C(103)-C(104) 1.5301(61)

C(103)-C(110) 1.5260(64) C(104)-C(105) 1.5219(61) C(105)-C(106) 1.5238(74) C(105)-C(109) 1.5256(51)

C(106)-C(107) 1.5205(66) C(107)-C(108) 1.5380(51) C(107)-C(110) 1.5310(64) C(201)-C(202) 1.5328(53)

C(201)-C(208) 1.5435(47) C(201)-C(209) 1.5218(53) C(202)-C(203) 1.5294(50) C(203)-C(204) 1.5272(53)

C(203)-C(210) 1.5328(48) C(204)-C(205) 1.5317(53) C(205)-C(206) 1.5278(48) C(205)-C(209) 1.5466(50)

C(206)-C(207) 1.5367(53) C(207)-C(208) 1.5329(50) C(207)-C(210) 1.5265(53)

Table 9: Bond angles [deg.] for 11.

Atoms AngleC5-N1-C101 117.7(3)C5-N1-C2 104.7(3)C101-N1-C2 116.0(3)C4-N3-C2 105.1(3)C4-N3-C201 118.3(3)C2-N3-C201 116.6(3)N1-C2-N3 104.3(3)C5-C4-N3 111.3(3)C4-C5-N1 111.4(3)N1-C101-C102 108.3(3)

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N1-C101-C108 108.7(3)C102-C101-C108 108.4(3)N1-C101-C109 113.1(3)C102-C101-C109 109.2(3)C108-C101-C109 109.0(3)C101-C102-C103 110.5(3)C110-C103-C104 109.5(4)C110-C103-C102 109.3(3)C104-C103-C102 109.0(3)C105-C104-C103 109.5(3)C104-C105-C109 109.6(4)C104-C105-C106 109.8(4)C109-C105-C106 110.1(4)C107-C106-C105 109.3(4)C106-C107-C110 109.7(4)C106-C107-C108 109.3(3)C110-C107-C108 109.9(3)C101-C108-C107 109.8(3)C105-C109-C101 109.4(3)C103-C110-C107 109.2(3)N3-C201-C209 113.7(3)N3-C201-C202 107.7(3)C209-C201-C202 110.1(3)N3-C201-C208 108.2(3)C209-C201-C208 108.4(3)C202-C201-C208 108.6(3)C203-C202-C201 110.2(3)C204-C203-C202 109.7(3)C204-C203-C210 109.1(3)C202-C203-C210 109.2(3)C203-C204-C205 109.8(3)C206-C205-C204 109.8(3)C206-C205-C209 109.2(3)C204-C205-C209 109.0(3)C205-C206-C207 109.6(3)C210-C207-C208 110.2(3)C210-C207-C206 109.0(3)C208-C207-C206 108.7(3)

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C207-C208-C201 110.0(3)C201-C209-C205 109.9(3)C207-C210-C203 109.9(3)

Table 10. Torsion angles for 11.

Dihedral AngleC5-N1-C2-N3 17.5(4)C101-N1-C2-N3 149.0(3)C4-N3-C2-N1 -17.1(4)C201-N3-C2-N1 -150.2(3)C2-N3-C4-C5 10.7(4)C201-N3-C4-C5 142.8(3)N3-C4-C5-N1 0.8(5)C101-N1-C5-C4 -142.4(3)C2-N1-C5-C4 -11.9(4)C5-N1-C101-C102 -178.7(3)C2-N1-C101-C102 56.3(4)C5-N1-C101-C108 -61.1(4)C2-N1-C101-C108 173.8(3)C5-N1-C101-C109 60.2(4)C2-N1-C101-C109 -64.9(4)N1-C101-C102-C103 177.7(3)C108-C101-C102-C103 60.0(4)C109-C101-C102-C103 -58.7(4)C101-C102-C103-C110 -60.6(4)C101-C102-C103-C104 59.1(4)C110-C103-C104-C105 59.7(4)C102-C103-C104-C105 -59.9(4)C103-C104-C105-C109 61.3(4)C103-C104-C105-C106 -59.7(4)C104-C105-C106-C107 60.1(5)C109-C105-C106-C107 -60.6(5)

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C105-C106-C107-C110 -60.3(4)C105-C106-C107-C108 60.2(5)N1-C101-C108-C107 -176.9(3)C102-C101-C108-C107 -59.3(4)C109-C101-C108-C107 59.4(4)C106-C107-C108-C101 -60.2(5)C110-C107-C108-C101 60.1(5)C104-C105-C109-C101 -60.8(5)C106-C105-C109-C101 60.0(5)N1-C101-C109-C105 179.8(3)C102-C101-C109-C105 59.1(4)C108-C101-C109-C105 -59.1(4)C104-C103-C110-C107 -59.8(4)C102-C103-C110-C107 59.6(5)C106-C107-C110-C103 60.4(4)C108-C107-C110-C103 -59.8(5)C4-N3-C201-C209 -56.9(4)C2-N3-C201-C209 69.9(4)C4-N3-C201-C202 -179.3(3)C2-N3-C201-C202 -52.5(4)C4-N3-C201-C208 63.6(4)C2-N3-C201-C208 -169.6(3)N3-C201-C202-C203 -177.2(3)C209-C201-C202-C203 58.2(4)C208-C201-C202-C203 -60.3(4)C201-C202-C203-C204 -58.7(4)C201-C202-C203-C210 60.8(4)C202-C203-C204-C205 60.0(4)C210-C203-C204-C205 -59.5(4)C203-C204-C205-C206 59.5(4)C203-C204-C205-C209 -60.1(4)C204-C205-C206-C207 -59.4(4)C209-C205-C206-C207 60.2(4)

17

C205-C206-C207-C210 59.7(4)C205-C206-C207-C208 -60.4(4)C210-C207-C208-C201 -58.7(4)C206-C207-C208-C201 60.7(4)N3-C201-C208-C207 175.5(3)C209-C201-C208-C207 -60.7(4)C202-C201-C208-C207 58.9(4)N3-C201-C209-C205 -179.5(3)C202-C201-C209-C205 -58.5(4)C208-C201-C209-C205 60.1(4)C206-C205-C209-C201 -60.5(4)C204-C205-C209-C201 59.5(4)C208-C207-C210-C203 58.8(4)C206-C207-C210-C203 -60.5(4)C204-C203-C210-C207 60.5(4)C202-C203-C210-C207 -59.4(4)

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Table 11. Atomic coordinates (*10^4) and equivalent isotropic displacement parameters (A^2 x 10^3) for 20. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. Atom X Y Z UeqO(1) 2266(1) 37(1) 7031(1) 28(1)N(1) 1516(1) -80(1) 4939(1) 19(1)C(2) 1290(1) 445(1) 4159(1) 20(1)N(3) 604(1) 1284(1) 4366(1) 20(1)C(4) 352(1) 1289(1) 5323(1) 23(1)C(5) 926(1) 449(1) 5689(1) 20(1)C(6) 2180(2) -1102(1) 4953(1) 24(1)C(7) 2113(2) -1528(1) 3962(1) 34(1)C(8) 3770(2) -1026(1) 5278(1) 31(1)C(9) 1256(2) -1747(1) 5597(1) 34(1)

18

C(10) 154(1) 2090(1) 3703(1) 24(1)C(11) 516(2) 1770(1) 2711(1) 48(1)C(12) 1009(2) 3017(1) 3958(1) 46(1)C(13) -1484(2) 2260(1) 3814(1) 45(1)C(14) 1027(1) 209(1) 6733(1) 21(1)O(15) 505(1) -1111(1) 8815(1) 40(1)C(15) -8(2) -566(1) 8292(1) 28(1)C(16) -2401(2) 505(1) 8194(1) 37(1)O(16) -3418(1) 664(1) 8644(1) 63(1)O(17) 132(2) 2359(1) 7581(1) 47(1)C(17) -264(2) 1558(1) 7549(1) 29(1)O(18) -2544(2) -537(1) 5947(1) 57(1)C(18) -1859(2) -206(1) 6535(1) 34(1)

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Table 12. Bond lengths [A] and angles [deg] for 20. _____________________________________________________________

Atoms LengthFe(1)-C(17) 1.7751(16)Fe(1)-C(15) 1.7945(15)Fe(1)-C(16) 1.7977(16)Fe(1)-C(18) 1.8090(16)Fe(1)-C(14) 1.9926(14)O(1)-C(14) 1.2304(16)N(1)-C(2) 1.3400(16)N(1)-C(5) 1.3988(15)N(1)-C(6) 1.5121(16)C(2)-N(3) 1.3317(17)N(3)-C(4) 1.3887(16)N(3)-C(10) 1.5039(16)C(4)-C(5) 1.3584(18)C(5)-C(14) 1.5330(16)C(6)-C(9) 1.5248(19)

19

C(6)-C(8) 1.528(2)C(6)-C(7) 1.5329(18)C(10)-C(13) 1.522(2)C(10)-C(11) 1.522(2)C(10)-C(12) 1.523(2)O(15)-C(15) 1.1510(17)C(16)-O(16) 1.1500(18)O(17)-C(17) 1.1450(17)O(18)-C(18) 1.1406(19)

Table 13. Bond angles [deg] for 20.

Atoms AngleC(17)-Fe(1)-C(15) 119.02(7)C(17)-Fe(1)-C(16) 92.80(7)C(15)-Fe(1)-C(16) 93.94(7)C(17)-Fe(1)-C(18) 123.21(7)C(15)-Fe(1)-C(18) 116.87(7)C(16)-Fe(1)-C(18) 92.78(7)C(17)-Fe(1)-C(14) 81.64(6)C(15)-Fe(1)-C(14) 88.29(6)C(16)-Fe(1)-C(14) 174.41(6)C(18)-Fe(1)-C(14) 90.78(6)C(2)-N(1)-C(5) 108.06(10)C(2)-N(1)-C(6) 123.91(10)C(5)-N(1)-C(6) 127.83(9)N(3)-C(2)-N(1) 109.81(10)C(2)-N(3)-C(4) 107.58(10)C(2)-N(3)-C(10) 127.39(10)C(4)-N(3)-C(10) 125.03(11)C(5)-C(4)-N(3) 108.26(11)C(4)-C(5)-N(1) 106.28(10)

20

C(4)-C(5)-C(14) 125.32(10)N(1)-C(5)-C(14) 128.12(10)N(1)-C(6)-C(9) 108.10(11)N(1)-C(6)-C(8) 108.84(10)C(9)-C(6)-C(8) 112.27(12)N(1)-C(6)-C(7) 108.47(10)C(9)-C(6)-C(7) 108.83(12)C(8)-C(6)-C(7) 110.23(11)N(3)-C(10)-C(13) 108.18(11)N(3)-C(10)-C(11) 108.88(11)C(13)-C(10)-C(11) 110.72(14)N(3)-C(10)-C(12) 107.91(11)C(13)-C(10)-C(12) 110.72(14)C(11)-C(10)-C(12) 110.35(13)O(1)-C(14)-C(5) 115.69(10)O(1)-C(14)-Fe(1) 126.34(9)C(5)-C(14)-Fe(1) 117.80(9)O(15)-C(15)-Fe(1) 179.11(13)O(16)-C(16)-Fe(1) 178.06(16)O(17)-C(17)-Fe(1) 177.56(13)O(18)-C(18)-Fe(1) 178.49(15)

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Table 14. Anisotropic displacement parameters (A^2 x 10^3) for 20. The anisotropic displacement factor exponent takes the form: -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]

Atom U11 U22 U33 U23 U13 U12Fe(1) 23(1) 25(1) 19(1) 1(1) 4(1) 1(1)O(1) 26(1) 38(1) 21(1) 0(1) -1(1) 8(1)N(1) 20(1) 20(1) 17(1) 0(1) 0(1) 1(1)

21

C(2) 20(1) 24(1) 17(1) 0(1) 1(1) 1(1)N(3) 21(1) 23(1) 17(1) 3(1) 1(1) 3(1)C(4) 23(1) 27(1) 17(1) 0(1) 2(1) 5(1)C(5) 20(1) 22(1) 16(1) 0(1) 2(1) 1(1)C(6) 32(1) 18(1) 21(1) -1(1) 2(1) 4(1)C(7) 50(1) 27(1) 25(1) -6(1) 0(1) 8(1)C(8) 30(1) 35(1) 29(1) 2(1) 0(1) 11(1)C(9) 50(1) 21(1) 32(1) 1(1) 10(1) -3(1)C(10) 26(1) 27(1) 20(1) 6(1) 0(1) 6(1)C(11) 71(1) 50(1) 22(1) 8(1) 2(1) 28(1)C(12) 58(1) 36(1) 44(1) 15(1) -5(1) -8(1)C(13) 29(1) 53(1) 52(1) 19(1) 0(1) 13(1)C(14) 27(1) 20(1) 16(1) 0(1) 1(1) 2(1)O(15) 49(1) 36(1) 33(1) 10(1) -8(1) -4(1)C(15) 32(1) 28(1) 24(1) 0(1) 3(1) -5(1)C(16) 32(1) 44(1) 34(1) 2(1) 9(1) -1(1)O(16) 41(1) 82(1) 66(1) -6(1) 28(1) 1(1)O(17) 71(1) 24(1) 46(1) -3(1) 13(1) 3(1)C(17) 36(1) 27(1) 24(1) 0(1) 7(1) 7(1)O(18) 44(1) 79(1) 47(1) -13(1) -10(1) -14(1)C(18) 27(1) 42(1) 32(1) -1(1) 2(1) -1(1)

___________________________________________________________________ Table 15. Hydrogen coordinates ( x 10^4) and isotropic displacement parameters (A^2 x 10^3) for 20. Atom X Y Z U(eq)H(4A) -127 1783 5655 27H(7A) 2697 -1129 3551 51H(7B) 1116 -1530 3749 51H(7C) 2484 -2191 3965 51H(8A) 4309 -614 4855 47H(8B) 4200 -1672 5292 47

22

H(8C) 3799 -744 5893 47H(9A) 1286 -1484 6219 52H(9B) 1639 -2407 5598 52H(9C) 262 -1755 5379 52H(11A) -29 1185 2559 71H(11B) 1546 1634 2663 71H(11C) 260 2288 2284 71H(12A) 784 3204 4589 69H(12B) 741 3543 3543 69H(12C) 2040 2889 3904 69H(13A) -2003 1670 3645 67H(13B) -1786 2791 3415 67H(13C) -1697 2424 4452 67H(2) 1531(16) 266(11) 3588(11) 25(4)

Table 16. Torsion angles [deg] for 20. ________________________________________________________________ Dihedral AngleC(5)-N(1)-C(2)-N(3) 0.66(14)C(6)-N(1)-C(2)-N(3) 175.87(10)N(1)-C(2)-N(3)-C(4) -1.21(14)N(1)-C(2)-N(3)-C(10) 179.36(11)C(2)-N(3)-C(4)-C(5) 1.31(14)C(10)-N(3)-C(4)-C(5) -179.24(11)N(3)-C(4)-C(5)-N(1) -0.89(14)N(3)-C(4)-C(5)-C(14) 173.42(11)C(2)-N(1)-C(5)-C(4) 0.17(14)C(6)-N(1)-C(5)-C(4) -174.79(11)C(2)-N(1)-C(5)-C(14) -173.94(12)C(6)-N(1)-C(5)-C(14) 11.10(19)C(2)-N(1)-C(6)-C(9) -134.20(12)

23

C(5)-N(1)-C(6)-C(9) 40.02(16)C(2)-N(1)-C(6)-C(8) 103.60(13)C(5)-N(1)-C(6)-C(8) -82.18(14)C(2)-N(1)-C(6)-C(7) -16.35(16)C(5)-N(1)-C(6)-C(7) 157.88(12)C(2)-N(3)-C(10)-C(13) 124.27(14)C(4)-N(3)-C(10)-C(13) -55.07(17)C(2)-N(3)-C(10)-C(11) 3.89(18)C(4)-N(3)-C(10)-C(11) -175.45(13)C(2)-N(3)-C(10)-C(12) -115.90(15)C(4)-N(3)-C(10)-C(12) 64.77(16)C(4)-C(5)-C(14)-O(1) -122.62(14)N(1)-C(5)-C(14)-O(1) 50.44(18)C(4)-C(5)-C(14)-Fe(1) 52.98(16)N(1)-C(5)-C(14)-Fe(1) -133.96(11)C(17)-Fe(1)-C(14)-O(1) 89.83(13)C(15)-Fe(1)-C(14)-O(1) -29.84(12)C(16)-Fe(1)-C(14)-O(1) 83.8(6)C(18)-Fe(1)-C(14)-O(1) -146.70(13)C(17)-Fe(1)-C(14)-C(5) -85.25(10)C(15)-Fe(1)-C(14)-C(5) 155.08(10)C(16)-Fe(1)-C(14)-C(5) -91.3(6)C(18)-Fe(1)-C(14)-C(5) 38.22(10)C(17)-Fe(1)-C(15)-O(15) 19(9)C(16)-Fe(1)-C(15)-O(15) -77(9)C(18)-Fe(1)-C(15)-O(15) -172(100)C(14)-Fe(1)-C(15)-O(15) 98(9)C(17)-Fe(1)-C(16)-O(16) 8(4)C(15)-Fe(1)-C(16)-O(16) 127(4)C(18)-Fe(1)-C(16)-O(16) -115(4)C(14)-Fe(1)-C(16)-O(16) 14(5)C(15)-Fe(1)-C(17)-O(17) 61(3)C(16)-Fe(1)-C(17)-O(17) 157(3)

24

C(18)-Fe(1)-C(17)-O(17) -108(3)C(14)-Fe(1)-C(17)-O(17) -22(3)C(17)-Fe(1)-C(18)-O(18) -140(6)C(15)-Fe(1)-C(18)-O(18) 51(6)C(16)-Fe(1)-C(18)-O(18) -44(6)C(14)-Fe(1)-C(18)-O(18) 140(6)