# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2005


data_global

_journal_coden_Cambridge         182

loop_
_publ_author_name
'Howard Alper'
'Jai Jun Kim.'

_publ_contact_author_name        'Dr Howard Alper'
_publ_contact_author_address     
;
Centre for Catalysis Research and Innovation, Department of Chemistry
University of Ottawa
10 Marie Curie
Ottawa
Ontario
K1N6N5
CANADA
;

_publ_contact_author_email       ?

_publ_requested_journal          'Chemical Communications'

_publ_section_title              
;
Ionic diamine rhodium (I) complexes highly active
catalysts for the hydroformylation of olefins
;

data_complex_2
_database_code_depnum_ccdc_archive 'CCDC 264125'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C11 H20 Cl N Rh'
_chemical_formula_weight         304.64

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Rh Rh -1.1178 0.9187 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2/n

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y, -z+1/2'
'-x, -y, -z'
'x-1/2, -y, z-1/2'

_cell_length_a                   10.9386(18)
_cell_length_b                   9.6760(16)
_cell_length_c                   11.3108(19)
_cell_angle_alpha                90.00
_cell_angle_beta                 99.428(3)
_cell_angle_gamma                90.00
_cell_volume                     1181.0(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    205(2)
_cell_measurement_reflns_used    723
_cell_measurement_theta_min      2.79
_cell_measurement_theta_max      25.43

_exptl_crystal_description       block
_exptl_crystal_colour            light
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.713
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             620
_exptl_absorpt_coefficient_mu    1.635
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  .77
_exptl_absorpt_correction_T_max  1.
_exptl_absorpt_process_details   'SADABS, Bruker (2000)'

_exptl_special_details           
;
Data collection is performed with three batch runs at phi = 0.00 deg
(606 frames), at phi = 90.00 deg (435 frames), and at phi = 180 deg
(230 frames) A fourth batch run is collected at phi = 0.00 deg (50 frames)
to monitor crystal and diffractometer stability. Frame width = 0.30 deg in
omega. Data is merged, corrected for decay (if any), and treated with
multi-scan absorption corrections (if required). All symmetry-equivalent
reflections are merged for centrosymmetric data. Friedel pairs are not merged
for noncentrosymmetric data.
;

_diffrn_ambient_temperature      205(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            7324
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_av_sigmaI/netI    0.0635
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         2.10
_diffrn_reflns_theta_max         28.27
_reflns_number_total             2804
_reflns_number_gt                2145
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0290P)^2^+1.0940P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2804
_refine_ls_number_parameters     130
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0488
_refine_ls_wR_factor_ref         0.0849
_refine_ls_wR_factor_gt          0.0798
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_restrained_S_all      1.097
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Rh1 Rh 0.2500 0.54885(5) 0.7500 0.02028(14) Uani 1 2 d S . .
Rh2 Rh -0.2500 0.74083(5) 0.7500 0.02049(14) Uani 1 2 d S . .
Cl3 Cl -0.25189(10) 0.56631(12) 0.60137(10) 0.0290(3) Uani 1 1 d . . .
C4 C -0.1685(4) 0.8814(5) 0.8793(4) 0.0275(10) Uani 1 1 d . . .
H4A H -0.1298 0.8376 0.9554 0.033 Uiso 1 1 calc R . .
C5 C -0.0840(4) 0.9832(5) 0.8289(4) 0.0305(11) Uani 1 1 d . . .
H5A H -0.0003 0.9442 0.8375 0.037 Uiso 1 1 calc R . .
H5B H -0.0792 1.0690 0.8756 0.037 Uiso 1 1 calc R . .
C6 C -0.1300(4) 1.0168(5) 0.6958(4) 0.0303(11) Uani 1 1 d . . .
H6A H -0.1833 1.0987 0.6898 0.036 Uiso 1 1 calc R . .
H6B H -0.0589 1.0376 0.6562 0.036 Uiso 1 1 calc R . .
C7 C -0.2026(4) 0.8947(5) 0.6326(4) 0.0273(10) Uani 1 1 d . . .
H7A H -0.1674 0.8577 0.5638 0.033 Uiso 1 1 calc R . .
C8 C 0.1449(4) 0.8235(5) 0.6420(4) 0.0315(11) Uani 1 1 d . . .
H8A H 0.1648 0.9055 0.6924 0.038 Uiso 1 1 calc R . .
H8B H 0.0739 0.8461 0.5804 0.038 Uiso 1 1 calc R . .
C9 C 0.1097(4) 0.7056(5) 0.7189(4) 0.0255(10) Uani 1 1 d . . .
H9A H 0.0250 0.6693 0.6927 0.031 Uiso 1 1 calc R . .
C10 C 0.1527(4) 0.6914(5) 0.8415(4) 0.0264(10) Uani 1 1 d . . .
H10A H 0.0920 0.6474 0.8857 0.032 Uiso 1 1 calc R . .
C11 C 0.2433(4) 0.7870(5) 0.9187(4) 0.0313(11) Uani 1 1 d . . .
H11A H 0.2727 0.7421 0.9958 0.038 Uiso 1 1 calc R . .
H11B H 0.2003 0.8722 0.9346 0.038 Uiso 1 1 calc R . .
N12 N 0.1175(3) 0.3802(4) 0.7480(3) 0.0211(8) Uani 1 1 d . . .
C13 C 0.1939(4) 0.2542(4) 0.7811(4) 0.0279(10) Uani 1 1 d . . .
H13A H 0.1440 0.1715 0.7580 0.033 Uiso 1 1 calc R . .
H13B H 0.2208 0.2518 0.8681 0.033 Uiso 1 1 calc R . .
C14 C 0.0210(4) 0.3883(5) 0.8260(4) 0.0292(11) Uani 1 1 d . . .
H14A H 0.0604 0.3978 0.9089 0.044 Uiso 1 1 calc R . .
H14B H -0.0285 0.3046 0.8170 0.044 Uiso 1 1 calc R . .
H14C H -0.0318 0.4676 0.8032 0.044 Uiso 1 1 calc R . .
C15 C 0.0524(4) 0.3681(5) 0.6220(4) 0.0295(11) Uani 1 1 d . . .
H15A H 0.1126 0.3715 0.5679 0.044 Uiso 1 1 calc R . .
H15B H -0.0057 0.4439 0.6042 0.044 Uiso 1 1 calc R . .
H15C H 0.0080 0.2811 0.6118 0.044 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Rh1 0.0181(2) 0.0187(3) 0.0241(3) 0.000 0.00373(19) 0.000
Rh2 0.0207(3) 0.0224(3) 0.0185(3) 0.000 0.00344(18) 0.000
Cl3 0.0337(6) 0.0289(6) 0.0255(6) -0.0043(5) 0.0078(5) -0.0006(5)
C4 0.032(2) 0.030(3) 0.019(2) -0.004(2) -0.0007(19) -0.004(2)
C5 0.026(2) 0.030(3) 0.034(3) -0.002(2) 0.001(2) -0.002(2)
C6 0.028(2) 0.030(3) 0.034(3) 0.006(2) 0.008(2) -0.003(2)
C7 0.034(3) 0.030(3) 0.020(2) 0.001(2) 0.008(2) -0.002(2)
C8 0.031(3) 0.028(3) 0.032(3) 0.000(2) -0.002(2) 0.003(2)
C9 0.018(2) 0.025(2) 0.033(3) -0.003(2) 0.0032(18) 0.0053(18)
C10 0.020(2) 0.026(2) 0.034(3) -0.003(2) 0.0068(19) 0.0062(19)
C11 0.038(3) 0.024(3) 0.031(3) -0.007(2) 0.000(2) 0.004(2)
N12 0.0192(17) 0.023(2) 0.0210(19) 0.0019(16) 0.0039(14) -0.0008(15)
C13 0.027(2) 0.022(2) 0.035(3) 0.004(2) 0.005(2) -0.0019(19)
C14 0.028(2) 0.029(3) 0.031(3) -0.003(2) 0.008(2) -0.005(2)
C15 0.029(2) 0.034(3) 0.024(2) -0.002(2) 0.0001(19) -0.004(2)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Rh1 C10 2.114(4) . ?
Rh1 C10 2.114(4) 2_556 ?
Rh1 C9 2.145(4) 2_556 ?
Rh1 C9 2.145(4) . ?
Rh1 N12 2.180(3) . ?
Rh1 N12 2.180(3) 2_556 ?
Rh2 C4 2.087(4) . ?
Rh2 C4 2.087(4) 2_456 ?
Rh2 C7 2.115(4) 2_456 ?
Rh2 C7 2.115(4) . ?
Rh2 Cl3 2.3805(12) . ?
Rh2 Cl3 2.3805(12) 2_456 ?
C4 C7 1.401(6) 2_456 ?
C4 C5 1.524(6) . ?
C5 C6 1.542(6) . ?
C6 C7 1.534(6) . ?
C7 C4 1.401(6) 2_456 ?
C8 C9 1.522(6) . ?
C8 C11 1.539(6) 2_556 ?
C9 C10 1.396(6) . ?
C10 C11 1.522(6) . ?
C11 C8 1.539(6) 2_556 ?
N12 C14 1.484(5) . ?
N12 C15 1.490(5) . ?
N12 C13 1.491(5) . ?
C13 C13 1.511(9) 2_556 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C10 Rh1 C10 98.5(3) . 2_556 ?
C10 Rh1 C9 82.09(17) . 2_556 ?
C10 Rh1 C9 38.27(16) 2_556 2_556 ?
C10 Rh1 C9 38.27(16) . . ?
C10 Rh1 C9 82.09(17) 2_556 . ?
C9 Rh1 C9 90.0(2) 2_556 . ?
C10 Rh1 N12 96.08(15) . . ?
C10 Rh1 N12 150.54(15) 2_556 . ?
C9 Rh1 N12 170.86(15) 2_556 . ?
C9 Rh1 N12 94.06(15) . . ?
C10 Rh1 N12 150.54(15) . 2_556 ?
C10 Rh1 N12 96.08(15) 2_556 2_556 ?
C9 Rh1 N12 94.06(15) 2_556 2_556 ?
C9 Rh1 N12 170.86(15) . 2_556 ?
N12 Rh1 N12 83.11(18) . 2_556 ?
C4 Rh2 C4 98.7(3) . 2_456 ?
C4 Rh2 C7 38.95(17) . 2_456 ?
C4 Rh2 C7 81.97(17) 2_456 2_456 ?
C4 Rh2 C7 81.97(17) . . ?
C4 Rh2 C7 38.95(17) 2_456 . ?
C7 Rh2 C7 90.5(2) 2_456 . ?
C4 Rh2 Cl3 155.55(13) . . ?
C4 Rh2 Cl3 90.82(13) 2_456 . ?
C7 Rh2 Cl3 165.44(13) 2_456 . ?
C7 Rh2 Cl3 91.76(13) . . ?
C4 Rh2 Cl3 90.82(13) . 2_456 ?
C4 Rh2 Cl3 155.55(13) 2_456 2_456 ?
C7 Rh2 Cl3 91.76(13) 2_456 2_456 ?
C7 Rh2 Cl3 165.44(13) . 2_456 ?
Cl3 Rh2 Cl3 89.63(6) . 2_456 ?
C7 C4 C5 124.6(4) 2_456 . ?
C7 C4 Rh2 71.6(3) 2_456 . ?
C5 C4 Rh2 112.1(3) . . ?
C4 C5 C6 112.3(4) . . ?
C7 C6 C5 110.7(4) . . ?
C4 C7 C6 123.5(4) 2_456 . ?
C4 C7 Rh2 69.5(2) 2_456 . ?
C6 C7 Rh2 114.3(3) . . ?
C9 C8 C11 112.2(4) . 2_556 ?
C10 C9 C8 124.4(4) . . ?
C10 C9 Rh1 69.7(2) . . ?
C8 C9 Rh1 112.5(3) . . ?
C9 C10 C11 126.3(4) . . ?
C9 C10 Rh1 72.1(2) . . ?
C11 C10 Rh1 110.2(3) . . ?
C10 C11 C8 111.9(4) . 2_556 ?
C14 N12 C15 107.4(3) . . ?
C14 N12 C13 108.5(3) . . ?
C15 N12 C13 109.6(3) . . ?
C14 N12 Rh1 119.4(3) . . ?
C15 N12 Rh1 106.3(3) . . ?
C13 N12 Rh1 105.3(2) . . ?
N12 C13 C13 110.4(3) . 2_556 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C4 Rh2 C4 C7 65.6(2) 2_456 . . 2_456 ?
C7 Rh2 C4 C7 100.9(3) . . . 2_456 ?
Cl3 Rh2 C4 C7 177.3(2) . . . 2_456 ?
Cl3 Rh2 C4 C7 -91.8(3) 2_456 . . 2_456 ?
C4 Rh2 C4 C5 -55.1(3) 2_456 . . . ?
C7 Rh2 C4 C5 -120.7(4) 2_456 . . . ?
C7 Rh2 C4 C5 -19.8(3) . . . . ?
Cl3 Rh2 C4 C5 56.6(5) . . . . ?
Cl3 Rh2 C4 C5 147.5(3) 2_456 . . . ?
C7 C4 C5 C6 -49.8(6) 2_456 . . . ?
Rh2 C4 C5 C6 32.5(5) . . . . ?
C4 C5 C6 C7 -28.8(5) . . . . ?
C5 C6 C7 C4 93.1(5) . . . 2_456 ?
C5 C6 C7 Rh2 12.4(5) . . . . ?
C4 Rh2 C7 C4 -114.6(3) . . . 2_456 ?
C7 Rh2 C7 C4 -76.5(3) 2_456 . . 2_456 ?
Cl3 Rh2 C7 C4 89.1(3) . . . 2_456 ?
Cl3 Rh2 C7 C4 -175.6(4) 2_456 . . 2_456 ?
C4 Rh2 C7 C6 3.9(3) . . . . ?
C4 Rh2 C7 C6 118.5(4) 2_456 . . . ?
C7 Rh2 C7 C6 42.0(3) 2_456 . . . ?
Cl3 Rh2 C7 C6 -152.4(3) . . . . ?
Cl3 Rh2 C7 C6 -57.1(7) 2_456 . . . ?
C11 C8 C9 C10 93.4(5) 2_556 . . . ?
C11 C8 C9 Rh1 13.3(5) 2_556 . . . ?
C10 Rh1 C9 C10 -114.7(3) 2_556 . . . ?
C9 Rh1 C9 C10 -77.1(3) 2_556 . . . ?
N12 Rh1 C9 C10 94.7(3) . . . . ?
N12 Rh1 C9 C10 166.2(9) 2_556 . . . ?
C10 Rh1 C9 C8 119.9(4) . . . . ?
C10 Rh1 C9 C8 5.2(3) 2_556 . . . ?
C9 Rh1 C9 C8 42.8(3) 2_556 . . . ?
N12 Rh1 C9 C8 -145.4(3) . . . . ?
N12 Rh1 C9 C8 -73.8(10) 2_556 . . . ?
C8 C9 C10 C11 -1.7(7) . . . . ?
Rh1 C9 C10 C11 102.2(4) . . . . ?
C8 C9 C10 Rh1 -103.9(4) . . . . ?
C10 Rh1 C10 C9 65.5(2) 2_556 . . . ?
C9 Rh1 C10 C9 100.2(3) 2_556 . . . ?
N12 Rh1 C10 C9 -88.8(3) . . . . ?
N12 Rh1 C10 C9 -175.6(3) 2_556 . . . ?
C10 Rh1 C10 C11 -57.5(3) 2_556 . . . ?
C9 Rh1 C10 C11 -22.8(3) 2_556 . . . ?
C9 Rh1 C10 C11 -123.0(5) . . . . ?
N12 Rh1 C10 C11 148.2(3) . . . . ?
N12 Rh1 C10 C11 61.5(5) 2_556 . . . ?
C9 C10 C11 C8 -45.5(6) . . . 2_556 ?
Rh1 C10 C11 C8 36.7(5) . . . 2_556 ?
C10 Rh1 N12 C14 -13.8(3) . . . . ?
C10 Rh1 N12 C14 -133.2(4) 2_556 . . . ?
C9 Rh1 N12 C14 64.2(10) 2_556 . . . ?
C9 Rh1 N12 C14 -52.2(3) . . . . ?
N12 Rh1 N12 C14 136.6(3) 2_556 . . . ?
C10 Rh1 N12 C15 107.7(3) . . . . ?
C10 Rh1 N12 C15 -11.8(5) 2_556 . . . ?
C9 Rh1 N12 C15 -174.3(9) 2_556 . . . ?
C9 Rh1 N12 C15 69.3(3) . . . . ?
N12 Rh1 N12 C15 -101.9(3) 2_556 . . . ?
C10 Rh1 N12 C13 -136.0(3) . . . . ?
C10 Rh1 N12 C13 104.6(4) 2_556 . . . ?
C9 Rh1 N12 C13 -58.0(10) 2_556 . . . ?
C9 Rh1 N12 C13 -174.3(3) . . . . ?
N12 Rh1 N12 C13 14.4(2) 2_556 . . . ?
C14 N12 C13 C13 -170.5(4) . . . 2_556 ?
C15 N12 C13 C13 72.5(5) . . . 2_556 ?
Rh1 N12 C13 C13 -41.6(5) . . . 2_556 ?

_diffrn_measured_fraction_theta_max 0.957
_diffrn_reflns_theta_full        28.27
_diffrn_measured_fraction_theta_full 0.957
_refine_diff_density_max         0.805
_refine_diff_density_min         -1.610
_refine_diff_density_rms         0.131