Direct observation of key intermediates by negative-ion electrospray ionization mass spectrometry in palladium-catalyzed cross-coupling

Transcription

1 Direct observation of key intermediates by negative-ion electrospray ionization mass spectrometry in palladium-catalyzed cross-coupling Krista L. Vikse, a Matthew A. Henderson, a Allen G. Oliver b and J. Scott McIndoe a * a Department of Chemistry, University of Victoria, P.O. Box 3065 Victoria, BC V8W3V6, Canada. Fax: +1 (250) ; Tel: +1 (250) ; mcindoe@uvic.ca. b Department of Chemistry and Biochemistry, University of Notre Dame, 251 Nieuwland Science Hall, Notre Dame, IN , USA. Figure SI1. Negative-ion ESI-MS/MS of [Pd(1)(Ph)(I)(HNC 5 H 10 )(HC 2 Ph)]. Analogous data was obtained for the complex with morpholine in place of piperidine.

2 Figure SI2. Summary of all negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(Ar)(C 2 Ph)], showing the precursor ion and the four product ions, at a collision voltage of 15 V. This plot uses peak height instead of the integral. The leftmost bar in each set is the most electron-releasing substituent (NH 2 ), the rightmost is the most electron-withdrawing (NO 2 ), and the remainder are plotted in order of their Hammett σ p parameter. Figure SI3. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 COMe)(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V.

3 Figure SI4. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 OMe)(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V. Figure SI5. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 Me)(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V.

4 Figure SI6. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 F)(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V. Figure SI7. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 NH 2 )(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V.

5 Figure SI8. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 CF 3 )(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V. Figure SI9. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 CN)(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V.

6 Figure SI10. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 5 )(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V. Figure SI11. Negative-ion ESI-MS/MS of [Pd(1)(PPh 3 )(C 6 H 4 NO 2 )(C 2 Ph)], showing reductive elimination to [Pd(1)(PPh 3 )], at a collision voltage of 15 V.

7 X-ray Structure Report for [Ph 3 NPh 3 ] + [PPh 2 (m-c 6 H 4 SO 3 )] = [PPN][1] Crystal data for C 54 H 44 NO 3 P 3 S; M r = ; triclinic; space group P-1; a = (12) Å; b = (17) Å; c = (17) Å; α = (10) ; β = (10) ; γ = (10) ; V = (4) Å 3 ; Z = 2; T = 150(2) K; λ(mo-kα) = Å; μ(mo-kα) = mm -1 ; d calc = 1.324g.cm -3 ; reflections collected; unique (R int = ); giving R 1 = , wr 2 = for 9273 data with [I>2σ(I)] and R 1 = , wr 2 = for all data. Residual electron density (e.å -3 ) max/min: 0.502/ An arbitrary sphere of data were collected on a colourless block-like crystal, having approximate dimensions of mm, on a Bruker APEX-II diffractometer using a combination of ω- and φ-scans of 0.3. Data were corrected for absorption and polarization effects and analyzed for space group determination. The structure was solved by direct methods and expanded routinely. The model was refined by full-matrix least-squares analysis of F 2 against all reflections. All non-hydrogen atoms were refined with anisotropic thermal displacement parameters. Unless otherwise noted, hydrogen atoms were included in calculated positions. Thermal parameters for the hydrogens were tied to the isotropic thermal parameter of the atom to which they are bonded ( 1.2 for all H). Figure SI12. Labeled ORTEP plot of [Ph 3 NPh 3 ] + [PPh 2 (m-c 6 H 4 SO 3 )] = [PPN][1].

8 Table 1. Crystal data and structure refinement for jsm009. Identification code jsm009 Empirical formula C 54 H 44 NO 3 P 3 S Formula weight Temperature 150(2) K Wavelength Å Crystal system triclinic Space group P-1 Unit cell dimensions a = (12) Å α = (10) b = (17) Å β = (10) c = (17) Å γ = (10) Volume (4) Å 3 Z 2 Density (calculated) g.cm -3 Absorption coefficient (μ) mm -1 F(000) 920 Crystal size mm 3 θ range for data collection 2.24 to Index ranges -13 h 13, -19 k 20, -20 l 19 Reflections collected Independent reflections [R int = ] Completeness to θ = % Absorption correction empirical Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 559 Goodness-of-fit on F Final R indices [I>2σ(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3

9 Table 2. Atomic coordinates and equivalent isotropic displacement parameters (Å 2 ) for jsm009. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) S(1) (4) (2) (2) 0.021(1) P(1) (4) (3) (3) 0.022(1) P(2) (3) (2) (2) 0.016(1) P(3) (3) (2) (2) 0.016(1) O(1) (11) (7) (8) 0.027(1) O(2) (12) (9) (8) 0.034(1) O(3) (12) (8) (9) 0.034(1) N(1) (11) (8) (8) 0.020(1) C(11) (14) (10) (10) 0.021(1) C(12) (14) (10) (9) 0.020(1) C(13) (14) (10) (9) 0.020(1) C(14) (15) (10) (11) 0.025(1) C(15) (16) (11) (12) 0.030(1) C(16) (15) (11) (11) 0.027(1) C(21) (15) (10) (10) 0.023(1) C(22) (15) (10) (11) 0.026(1) C(23) (17) (11) (12) 0.032(1) C(24) (19) (12) (13) 0.037(1) C(25) (2) (13) (12) 0.039(1) C(26) (18) (12) (11) 0.033(1) C(31) (14) (10) (10) 0.023(1) C(32) (17) (11) (11) 0.030(1) C(33) (2) (12) (12) 0.037(1) C(34) (19) (13) (12) 0.037(1) C(35) (18) (12) (12) 0.033(1) C(36) (16) (10) (11) 0.028(1) C(41) (13) (9) (9) 0.019(1) C(42) (15) (11) (10) 0.025(1) C(43) (16) (12) (11) 0.031(1) C(44) (17) (12) (11) 0.032(1) C(45) (17) (11) (11) 0.029(1) C(46) (15) (10) (10) 0.024(1) C(51) (13) (10) (9) 0.020(1) C(52) (14) (10) (10) 0.022(1) C(53) (15) (11) (10) 0.027(1) C(54) (17) (13) (11) 0.033(1) C(55) (18) (13) (12) 0.036(1) C(56) (16) (11) (11) 0.028(1) C(61) (14) (9) (10) 0.020(1) C(62) (15) (11) (11) 0.028(1) C(63) (17) (11) (13) 0.036(1)

10 C(64) (19) (11) (12) 0.035(1) C(65) (19) (11) (12) 0.036(1) C(66) (17) (10) (11) 0.029(1) C(71) (13) (10) (9) 0.019(1) C(72) (15) (10) (10) 0.025(1) C(73) (18) (12) (11) 0.034(1) C(74) (18) (13) (11) 0.035(1) C(75) (18) (13) (12) 0.034(1) C(76) (16) (11) (10) 0.027(1) C(81) (13) (9) (9) 0.018(1) C(82) (14) (10) (10) 0.021(1) C(83) (15) (11) (11) 0.025(1) C(84) (15) (11) (10) 0.027(1) C(85) (16) (11) (10) 0.026(1) C(86) (14) (10) (10) 0.022(1) C(91) (13) (9) (10) 0.019(1) C(92) (14) (10) (10) 0.022(1) C(93) (15) (10) (11) 0.025(1) C(94) (16) (10) (11) 0.028(1) C(95) (16) (10) (11) 0.028(1) C(96) (15) (10) (10) 0.024(1) H(12A) H(14A) H(15A) H(16A) H(22A) H(23A) H(24A) H(25A) H(26A) H(32A) H(33A) H(34A) H(35A) H(36A) H(42A) H(43A) H(44A) H(45A) H(46A) H(52A) H(53A) H(54A) H(55A) H(56A) H(62A)

11 H(63A) H(64A) H(65A) H(66A) H(72A) H(73A) H(74A) H(75A) H(76A) H(82A) H(83A) H(84A) H(85A) H(86A) H(92A) H(93A) H(94A) H(95A) H(96A)

12 Table 3. Anisotropic displacement parameters (Å 2 ) for jsm009. The anisotropic displacement factor exponent takes the form: -2π 2 [h 2 a* 2 U hka*b*U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 S(1) (2) (2) (2) (1) (1) (1) P(1) (2) (2) (2) (1) (1) (1) P(2) (2) (2) (2) (1) (1) (1) P(3) (2) (2) (2) (1) (1) (1) O(1) (5) (5) (6) (4) (4) (4) O(2) (6) (7) (6) (5) (5) (5) O(3) (6) (5) (7) (5) (5) (5) N(1) (5) (5) (6) (4) (4) (4) C(11) (7) (7) (7) (5) (5) (5) C(12) (6) (7) (7) (5) (5) (5) C(13) (7) (7) (6) (5) (5) (5) C(14) (7) (7) (8) (6) (6) (6) C(15) (7) (8) (9) (7) (6) (6) C(16) (7) (7) (9) (6) (6) (6) C(21) (7) (6) (7) (5) (6) (5) C(22) (8) (7) (8) (6) (6) (6) C(23) (8) (8) (10) (7) (7) (6) C(24) (10) (8) (10) (7) (8) (7) C(25) (11) (9) (8) (7) (7) (8) C(26) (9) (9) (8) (7) (6) (7) C(31) (7) (7) (7) (6) (6) (5) C(32) (9) (7) (8) (6) (7) (6) C(33) (11) (9) (8) (7) (7) (8) C(34) (11) (9) (9) (7) (7) (8) C(35) (9) (8) (9) (7) (7) (7) C(36) (8) (7) (8) (6) (6) (6) C(41) (6) (6) (7) (5) (5) (5) C(42) (7) (8) (7) (6) (5) (6) C(43) (8) (9) (8) (7) (6) (7) C(44) (8) (8) (8) (7) (6) (7) C(45) (8) (8) (7) (6) (6) (7) C(46) (7) (7) (7) (6) (5) (6) C(51) (6) (7) (7) (5) (5) (5) C(52) (7) (7) (7) (5) (5) (5) C(53) (7) (8) (7) (6) (6) (6) C(54) (8) (10) (7) (7) (6) (7) C(55) (10) (10) (9) (7) (7) (8) C(56) (8) (8) (8) (6) (6) (6) C(61) (7) (6) (7) (5) (5) (5) C(62) (7) (7) (9) (6) (6) (6)

13 C(63) (8) (7) (11) (7) (7) (6) C(64) (10) (7) (10) (6) (8) (7) C(65) (10) (8) (9) (7) (7) (7) C(66) (8) (7) (8) (6) (6) (6) C(71) (6) (7) (6) (5) (5) (5) C(72) (8) (7) (7) (6) (6) (6) C(73) (10) (8) (8) (6) (7) (7) C(74) (10) (10) (8) (7) (7) (8) C(75) (9) (9) (8) (7) (7) (7) C(76) (8) (7) (7) (6) (6) (6) C(81) (6) (6) (6) (5) (5) (5) C(82) (7) (6) (7) (5) (5) (5) C(83) (7) (7) (8) (6) (5) (5) C(84) (7) (8) (8) (6) (6) (6) C(85) (8) (7) (7) (6) (6) (6) C(86) (7) (7) (7) (5) (5) (5) C(91) (6) (6) (7) (5) (5) (5) C(92) (7) (6) (7) (5) (5) (5) C(93) (7) (7) (8) (6) (6) (6) C(94) (8) (7) (9) (6) (6) (6) C(95) (8) (7) (8) (6) (6) (6) C(96) (7) (7) (7) (6) (5) (5)

14 Table 4. Bond lengths [Å] for jsm009. atom-atom distance atom-atom distance S(1)-O(2) (12) S(1)-O(3) (12) S(1)-O(1) (11) S(1)-C(13) (14) P(1)-C(11) (15) P(1)-C(31) (16) P(1)-C(21) (15) P(2)-N(1) (12) P(2)-C(61) (14) P(2)-C(41) (14) P(2)-C(51) (14) P(3)-N(1) (12) P(3)-C(81) (14) P(3)-C(71) (14) P(3)-C(91) (14) C(11)-C(16) 1.393(2) C(11)-C(12) (19) C(12)-C(13) (19) C(13)-C(14) 1.389(2) C(14)-C(15) 1.387(2) C(15)-C(16) 1.387(2) C(21)-C(26) 1.395(2) C(21)-C(22) 1.395(2) C(22)-C(23) 1.389(2) C(23)-C(24) 1.381(3) C(24)-C(25) 1.378(3) C(25)-C(26) 1.392(2) C(31)-C(32) 1.395(2) C(31)-C(36) 1.400(2) C(32)-C(33) 1.387(2) C(33)-C(34) 1.380(2) C(34)-C(35) 1.391(3) C(35)-C(36) 1.382(2) C(41)-C(42) 1.391(2) C(41)-C(46) 1.401(2) C(42)-C(43) 1.395(2) C(43)-C(44) 1.381(2) C(44)-C(45) 1.389(2) C(45)-C(46) 1.381(2) C(51)-C(56) 1.394(2) C(51)-C(52) 1.400(2) C(52)-C(53) 1.384(2) C(53)-C(54) 1.384(2) C(54)-C(55) 1.380(3) C(55)-C(56) 1.392(2) C(61)-C(62) 1.392(2) C(61)-C(66) 1.393(2) C(62)-C(63) 1.391(2) C(63)-C(64) 1.379(3) C(64)-C(65) 1.384(3) C(65)-C(66) 1.386(2) C(71)-C(76) 1.391(2) C(71)-C(72) 1.391(2) C(72)-C(73) 1.388(2) C(73)-C(74) 1.382(2) C(74)-C(75) 1.381(2) C(75)-C(76) 1.393(2) C(81)-C(86) (19) C(81)-C(82) (19) C(82)-C(83) 1.391(2) C(83)-C(84) 1.387(2) C(84)-C(85) 1.384(2) C(85)-C(86) 1.390(2) C(91)-C(96) 1.397(2) C(91)-C(92) (19) C(92)-C(93) 1.390(2) C(93)-C(94) 1.391(2) C(94)-C(95) 1.388(2) C(95)-C(96) 1.390(2) C(12)-H(12A) C(14)-H(14A) C(15)-H(15A) C(16)-H(16A) C(22)-H(22A) C(23)-H(23A) C(24)-H(24A) C(25)-H(25A) C(26)-H(26A) C(32)-H(32A) C(33)-H(33A) C(34)-H(34A) C(35)-H(35A) C(36)-H(36A) C(42)-H(42A)

15 C(43)-H(43A) C(44)-H(44A) C(45)-H(45A) C(46)-H(46A) C(52)-H(52A) C(53)-H(53A) C(54)-H(54A) C(55)-H(55A) C(56)-H(56A) C(62)-H(62A) C(63)-H(63A) C(64)-H(64A) C(65)-H(65A) C(66)-H(66A) C(72)-H(72A) C(73)-H(73A) C(74)-H(74A) C(75)-H(75A) C(76)-H(76A) C(82)-H(82A) C(83)-H(83A) C(84)-H(84A) C(85)-H(85A) C(86)-H(86A) C(92)-H(92A) C(93)-H(93A) C(94)-H(94A) C(95)-H(95A) C(96)-H(96A) Symmetry transformations used to generate equivalent atoms:

16 Table 5. Bond angles [ ] for jsm009. atom-atom-atom angle atom-atom-atom angle O(2)-S(1)-O(3) (8) O(2)-S(1)-O(1) (7) O(3)-S(1)-O(1) (7) O(2)-S(1)-C(13) (6) O(3)-S(1)-C(13) (7) O(1)-S(1)-C(13) (6) C(11)-P(1)-C(31) (7) C(11)-P(1)-C(21) (7) C(31)-P(1)-C(21) (7) N(1)-P(2)-C(61) (6) N(1)-P(2)-C(41) (6) C(61)-P(2)-C(41) (6) N(1)-P(2)-C(51) (6) C(61)-P(2)-C(51) (7) C(41)-P(2)-C(51) (6) N(1)-P(3)-C(81) (6) N(1)-P(3)-C(71) (6) C(81)-P(3)-C(71) (6) N(1)-P(3)-C(91) (6) C(81)-P(3)-C(91) (6) C(71)-P(3)-C(91) (6) P(3)-N(1)-P(2) (8) C(16)-C(11)-C(12) (13) C(16)-C(11)-P(1) (11) C(12)-C(11)-P(1) (11) C(13)-C(12)-C(11) (13) C(14)-C(13)-C(12) (13) C(14)-C(13)-S(1) (11) C(12)-C(13)-S(1) (11) C(15)-C(14)-C(13) (14) C(14)-C(15)-C(16) (14) C(15)-C(16)-C(11) (14) C(26)-C(21)-C(22) (14) C(26)-C(21)-P(1) (12) C(22)-C(21)-P(1) (12) C(23)-C(22)-C(21) (15) C(24)-C(23)-C(22) (16) C(25)-C(24)-C(23) (15) C(24)-C(25)-C(26) (16) C(25)-C(26)-C(21) (16) C(32)-C(31)-C(36) (14) C(32)-C(31)-P(1) (11) C(36)-C(31)-P(1) (12) C(33)-C(32)-C(31) (15) C(34)-C(33)-C(32) (16) C(33)-C(34)-C(35) (16) C(36)-C(35)-C(34) (15) C(35)-C(36)-C(31) (15) C(42)-C(41)-C(46) (13) C(42)-C(41)-P(2) (11) C(46)-C(41)-P(2) (11) C(41)-C(42)-C(43) (14) C(44)-C(43)-C(42) (14) C(43)-C(44)-C(45) (15) C(46)-C(45)-C(44) (14) C(45)-C(46)-C(41) (14) C(56)-C(51)-C(52) (13) C(56)-C(51)-P(2) (11) C(52)-C(51)-P(2) (11) C(53)-C(52)-C(51) (14) C(52)-C(53)-C(54) (15) C(55)-C(54)-C(53) (15) C(54)-C(55)-C(56) (15) C(55)-C(56)-C(51) (15) C(62)-C(61)-C(66) (13) C(62)-C(61)-P(2) (11) C(66)-C(61)-P(2) (11) C(63)-C(62)-C(61) (15) C(64)-C(63)-C(62) (16) C(63)-C(64)-C(65) (15) C(64)-C(65)-C(66) (16) C(65)-C(66)-C(61) (15) C(76)-C(71)-C(72) (13) C(76)-C(71)-P(3) (11) C(72)-C(71)-P(3) (11) C(73)-C(72)-C(71) (14) C(74)-C(73)-C(72) (15) C(75)-C(74)-C(73) (15) C(74)-C(75)-C(76) (15) C(71)-C(76)-C(75) (14) C(86)-C(81)-C(82) (13) C(86)-C(81)-P(3) (11) C(82)-C(81)-P(3) (11) C(83)-C(82)-C(81) (13)

17 C(84)-C(83)-C(82) (14) C(85)-C(84)-C(83) (14) C(84)-C(85)-C(86) (14) C(85)-C(86)-C(81) (14) C(96)-C(91)-C(92) (13) C(96)-C(91)-P(3) (11) C(92)-C(91)-P(3) (10) C(93)-C(92)-C(91) (14) C(92)-C(93)-C(94) (14) C(95)-C(94)-C(93) (14) C(94)-C(95)-C(96) (14) C(95)-C(96)-C(91) (14) C(13)-C(12)-H(12A) C(11)-C(12)-H(12A) C(15)-C(14)-H(14A) C(13)-C(14)-H(14A) C(14)-C(15)-H(15A) C(16)-C(15)-H(15A) C(15)-C(16)-H(16A) C(11)-C(16)-H(16A) C(23)-C(22)-H(22A) C(21)-C(22)-H(22A) C(24)-C(23)-H(23A) C(22)-C(23)-H(23A) C(25)-C(24)-H(24A) C(23)-C(24)-H(24A) C(24)-C(25)-H(25A) C(26)-C(25)-H(25A) C(25)-C(26)-H(26A) C(21)-C(26)-H(26A) C(33)-C(32)-H(32A) C(31)-C(32)-H(32A) C(34)-C(33)-H(33A) C(32)-C(33)-H(33A) C(33)-C(34)-H(34A) C(35)-C(34)-H(34A) C(36)-C(35)-H(35A) C(34)-C(35)-H(35A) C(35)-C(36)-H(36A) C(31)-C(36)-H(36A) C(41)-C(42)-H(42A) C(43)-C(42)-H(42A) C(44)-C(43)-H(43A) C(42)-C(43)-H(43A) C(43)-C(44)-H(44A) C(45)-C(44)-H(44A) C(46)-C(45)-H(45A) C(44)-C(45)-H(45A) C(45)-C(46)-H(46A) C(41)-C(46)-H(46A) C(53)-C(52)-H(52A) C(51)-C(52)-H(52A) C(52)-C(53)-H(53A) C(54)-C(53)-H(53A) C(55)-C(54)-H(54A) C(53)-C(54)-H(54A) C(54)-C(55)-H(55A) C(56)-C(55)-H(55A) C(55)-C(56)-H(56A) C(51)-C(56)-H(56A) C(63)-C(62)-H(62A) C(61)-C(62)-H(62A) C(64)-C(63)-H(63A) C(62)-C(63)-H(63A) C(63)-C(64)-H(64A) C(65)-C(64)-H(64A) C(64)-C(65)-H(65A) C(66)-C(65)-H(65A) C(65)-C(66)-H(66A) C(61)-C(66)-H(66A) C(73)-C(72)-H(72A) C(71)-C(72)-H(72A) C(74)-C(73)-H(73A) C(72)-C(73)-H(73A) C(75)-C(74)-H(74A) C(73)-C(74)-H(74A) C(74)-C(75)-H(75A) C(76)-C(75)-H(75A) C(71)-C(76)-H(76A) C(75)-C(76)-H(76A) C(83)-C(82)-H(82A) C(81)-C(82)-H(82A) C(84)-C(83)-H(83A) C(82)-C(83)-H(83A) C(85)-C(84)-H(84A) C(83)-C(84)-H(84A) C(84)-C(85)-H(85A) C(86)-C(85)-H(85A) C(85)-C(86)-H(86A) C(81)-C(86)-H(86A) C(93)-C(92)-H(92A) C(91)-C(92)-H(92A) 120.1

18 C(92)-C(93)-H(93A) C(94)-C(93)-H(93A) C(95)-C(94)-H(94A) C(93)-C(94)-H(94A) C(94)-C(95)-H(95A) C(96)-C(95)-H(95A) C(95)-C(96)-H(96A) C(91)-C(96)-H(96A) Symmetry transformations used to generate equivalent atoms:

19 Table 6. Torsion angles [ ] for jsm009. atom-atom-atom-atom angle atom-atom-atom-atom angle C(81)-P(3)-N(1)-P(2) (12) C(71)-P(3)-N(1)-P(2) (13) C(91)-P(3)-N(1)-P(2) 11.54(15) C(61)-P(2)-N(1)-P(3) (12) C(41)-P(2)-N(1)-P(3) 51.39(14) C(51)-P(2)-N(1)-P(3) (14) C(31)-P(1)-C(11)-C(16) (14) C(21)-P(1)-C(11)-C(16) 32.70(14) C(31)-P(1)-C(11)-C(12) (12) C(21)-P(1)-C(11)-C(12) (11) C(16)-C(11)-C(12)-C(13) -0.2(2) P(1)-C(11)-C(12)-C(13) (10) C(11)-C(12)-C(13)-C(14) 0.4(2) C(11)-C(12)-C(13)-S(1) (11) O(2)-S(1)-C(13)-C(14) (13) O(3)-S(1)-C(13)-C(14) 35.36(13) O(1)-S(1)-C(13)-C(14) (12) O(2)-S(1)-C(13)-C(12) 93.15(12) O(3)-S(1)-C(13)-C(12) (12) O(1)-S(1)-C(13)-C(12) (13) C(12)-C(13)-C(14)-C(15) -0.2(2) S(1)-C(13)-C(14)-C(15) (12) C(13)-C(14)-C(15)-C(16) -0.3(2) C(14)-C(15)-C(16)-C(11) 0.6(2) C(12)-C(11)-C(16)-C(15) -0.4(2) P(1)-C(11)-C(16)-C(15) (12) C(11)-P(1)-C(21)-C(26) (13) C(31)-P(1)-C(21)-C(26) (12) C(11)-P(1)-C(21)-C(22) (14) C(31)-P(1)-C(21)-C(22) 25.49(14) C(26)-C(21)-C(22)-C(23) -1.0(2) P(1)-C(21)-C(22)-C(23) (12) C(21)-C(22)-C(23)-C(24) 1.3(2) C(22)-C(23)-C(24)-C(25) -0.8(3) C(23)-C(24)-C(25)-C(26) 0.1(3) C(24)-C(25)-C(26)-C(21) 0.2(3) C(22)-C(21)-C(26)-C(25) 0.3(2) P(1)-C(21)-C(26)-C(25) (14) C(11)-P(1)-C(31)-C(32) -9.68(14) C(21)-P(1)-C(31)-C(32) (13) C(11)-P(1)-C(31)-C(36) (11) C(21)-P(1)-C(31)-C(36) 68.11(12) C(36)-C(31)-C(32)-C(33) -0.1(2) P(1)-C(31)-C(32)-C(33) (13) C(31)-C(32)-C(33)-C(34) -0.6(3) C(32)-C(33)-C(34)-C(35) 0.5(3) C(33)-C(34)-C(35)-C(36) 0.3(3) C(34)-C(35)-C(36)-C(31) -1.0(2) C(32)-C(31)-C(36)-C(35) 0.9(2) P(1)-C(31)-C(36)-C(35) (12) N(1)-P(2)-C(41)-C(42) (12) C(61)-P(2)-C(41)-C(42) (12) C(51)-P(2)-C(41)-C(42) -0.37(14) N(1)-P(2)-C(41)-C(46) 47.32(13) C(61)-P(2)-C(41)-C(46) (12) C(51)-P(2)-C(41)-C(46) (11) C(46)-C(41)-C(42)-C(43) -1.9(2) P(2)-C(41)-C(42)-C(43) (12) C(41)-C(42)-C(43)-C(44) 1.1(2) C(42)-C(43)-C(44)-C(45) 0.4(3) C(43)-C(44)-C(45)-C(46) -1.1(3) C(44)-C(45)-C(46)-C(41) 0.3(2) C(42)-C(41)-C(46)-C(45) 1.2(2) P(2)-C(41)-C(46)-C(45) (12) N(1)-P(2)-C(51)-C(56) (13) C(61)-P(2)-C(51)-C(56) 6.81(14) C(41)-P(2)-C(51)-C(56) (12) N(1)-P(2)-C(51)-C(52) 64.66(13) C(61)-P(2)-C(51)-C(52) (11) C(41)-P(2)-C(51)-C(52) (12) C(56)-C(51)-C(52)-C(53) 1.0(2) P(2)-C(51)-C(52)-C(53) (11) C(51)-C(52)-C(53)-C(54) -0.6(2) C(52)-C(53)-C(54)-C(55) -0.1(2) C(53)-C(54)-C(55)-C(56) 0.2(3) C(54)-C(55)-C(56)-C(51) 0.2(3) C(52)-C(51)-C(56)-C(55) -0.8(2) P(2)-C(51)-C(56)-C(55) (12) N(1)-P(2)-C(61)-C(62) (12) C(41)-P(2)-C(61)-C(62) (14) C(51)-P(2)-C(61)-C(62) 86.26(13) N(1)-P(2)-C(61)-C(66) 33.57(14) C(41)-P(2)-C(61)-C(66) (12) C(51)-P(2)-C(61)-C(66) (13)

20 C(66)-C(61)-C(62)-C(63) 0.9(2) P(2)-C(61)-C(62)-C(63) (12) C(61)-C(62)-C(63)-C(64) 1.4(3) C(62)-C(63)-C(64)-C(65) -2.3(3) C(63)-C(64)-C(65)-C(66) 0.8(3) C(64)-C(65)-C(66)-C(61) 1.5(3) C(62)-C(61)-C(66)-C(65) -2.4(2) P(2)-C(61)-C(66)-C(65) (13) N(1)-P(3)-C(71)-C(76) (12) C(81)-P(3)-C(71)-C(76) (13) C(91)-P(3)-C(71)-C(76) 40.11(14) N(1)-P(3)-C(71)-C(72) (13) C(81)-P(3)-C(71)-C(72) (12) C(91)-P(3)-C(71)-C(72) (11) C(76)-C(71)-C(72)-C(73) 0.1(2) P(3)-C(71)-C(72)-C(73) (13) C(71)-C(72)-C(73)-C(74) 1.3(3) C(72)-C(73)-C(74)-C(75) -1.4(3) C(73)-C(74)-C(75)-C(76) 0.1(3) C(72)-C(71)-C(76)-C(75) -1.4(2) P(3)-C(71)-C(76)-C(75) (12) C(74)-C(75)-C(76)-C(71) 1.3(3) N(1)-P(3)-C(81)-C(86) (13) C(71)-P(3)-C(81)-C(86) (11) C(91)-P(3)-C(81)-C(86) (12) N(1)-P(3)-C(81)-C(82) (11) C(71)-P(3)-C(81)-C(82) 44.20(13) C(91)-P(3)-C(81)-C(82) (12) C(86)-C(81)-C(82)-C(83) -0.2(2) P(3)-C(81)-C(82)-C(83) (11) C(81)-C(82)-C(83)-C(84) -0.6(2) C(82)-C(83)-C(84)-C(85) 0.9(2) C(83)-C(84)-C(85)-C(86) -0.5(2) C(84)-C(85)-C(86)-C(81) -0.3(2) C(82)-C(81)-C(86)-C(85) 0.6(2) P(3)-C(81)-C(86)-C(85) (11) N(1)-P(3)-C(91)-C(96) (12) C(81)-P(3)-C(91)-C(96) (13) C(71)-P(3)-C(91)-C(96) (12) N(1)-P(3)-C(91)-C(92) (13) C(81)-P(3)-C(91)-C(92) (11) C(71)-P(3)-C(91)-C(92) 56.50(13) C(96)-C(91)-C(92)-C(93) -3.2(2) P(3)-C(91)-C(92)-C(93) (11) C(91)-C(92)-C(93)-C(94) 1.9(2) C(92)-C(93)-C(94)-C(95) 0.9(2) C(93)-C(94)-C(95)-C(96) -2.4(2) C(94)-C(95)-C(96)-C(91) 1.1(2) C(92)-C(91)-C(96)-C(95) 1.7(2) P(3)-C(91)-C(96)-C(95) (12) Symmetry transformations used to generate equivalent atoms: