# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2010

data_global
_journal_name_full               'Dalton Trans.'

_journal_coden_Cambridge         0222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Karl Wieghardt'
_publ_contact_author_email       WIEGHARDT@MPI-MUELHEIM.MPG.DE

_publ_section_title              
;
Electronic structure of the members
of the electron transfer series [NiL]z (z = 3+,2+,1+,0)
and [NiL(X)]n (X = Cl, CO, P(OCH3)3) species containing a tetradentate,
redox-noninnocent, Schiff base macrocyclic ligand L: An experimental
and density functional theoretical study.
;
loop_
_publ_author_name
'Karl Wieghardt'
'Meenakshi Ghosh'
'Thomas Weyhermuller'

# Attachment 'MGhosh3_Dalton.cif'

data_1
_database_code_depnum_ccdc_archive 'CCDC 743604'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '(C15 H20 N4 Ni), 0.5 (C4 H12 O)'
_chemical_formula_sum            'C17 H26 N4 Ni O0.50'
_chemical_formula_weight         353.13

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'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.5799(15)
_cell_length_b                   9.3919(16)
_cell_length_c                   10.7666(18)
_cell_angle_alpha                83.570(3)
_cell_angle_beta                 70.279(3)
_cell_angle_gamma                86.023(4)
_cell_volume                     811.1(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       'opaque parallelepiped'
_exptl_crystal_colour            'dark brown'
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             376
_exptl_absorpt_coefficient_mu    1.202
_exptl_absorpt_correction_type   Multi-Scan
_exptl_absorpt_correction_T_min  0.8892
_exptl_absorpt_correction_T_max  0.9535
_exptl_absorpt_process_details   'SADABS 2008/1, Bruker AXS (2008)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode, INCOATEC Multi-Layer Optics'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX II'
_diffrn_measurement_method       
'images at 0.5 deg. stepwise rotation in omega abd phi, 10 sec. frame'
_diffrn_detector_area_resol_mean 66.06
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            16523
_diffrn_reflns_av_R_equivalents  0.0893
_diffrn_reflns_av_sigmaI/netI    0.0785
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.39
_diffrn_reflns_theta_max         30.00
_reflns_number_total             4511
_reflns_number_gt                3555
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SAINT 6.34A'
_computing_cell_refinement       'Bruker SAINT 6.34A'
_computing_data_reduction        'Bruker SAINT 6.34A'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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^)+(0.1719P)^2^+4.3778P] 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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4511
_refine_ls_number_parameters     228
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.1227
_refine_ls_R_factor_gt           0.1034
_refine_ls_wR_factor_ref         0.2944
_refine_ls_wR_factor_gt          0.2731
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_restrained_S_all      1.097
_refine_ls_shift/su_max          0.000
_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
Ni1 Ni -0.23294(7) 0.02522(7) 0.07664(6) 0.0164(3) Uani 1 1 d . . .
N1 N -0.2628(5) -0.1543(5) 0.1654(4) 0.0201(9) Uani 1 1 d . . .
C2 C -0.3069(6) -0.1587(6) 0.3037(5) 0.0215(11) Uani 1 1 d . . .
C3 C -0.3754(7) -0.2812(6) 0.3828(5) 0.0224(11) Uani 1 1 d . . .
H3 H -0.3911 -0.2905 0.4750 0.027 Uiso 1 1 calc R . .
C4 C -0.4212(7) -0.3912(6) 0.3252(6) 0.0246(12) Uani 1 1 d . . .
H4 H -0.4597 -0.4786 0.3767 0.030 Uiso 1 1 calc R . .
C5 C -0.4102(6) -0.3722(6) 0.1926(6) 0.0241(12) Uani 1 1 d . . .
H5 H -0.4501 -0.4431 0.1557 0.029 Uiso 1 1 calc R . .
C6 C -0.3405(6) -0.2489(6) 0.1135(5) 0.0205(11) Uani 1 1 d . . .
C7 C -0.3386(6) -0.1993(6) -0.0144(5) 0.0211(11) Uani 1 1 d . . .
N8 N -0.2929(5) -0.0618(5) -0.0511(4) 0.0185(9) Uani 1 1 d . . .
C9 C -0.2856(7) 0.0006(6) -0.1835(5) 0.0219(11) Uani 1 1 d . . .
H9A H -0.3945 0.0461 -0.1796 0.026 Uiso 1 1 calc R . .
H9B H -0.2616 -0.0764 -0.2439 0.026 Uiso 1 1 calc R . .
C10 C -0.1530(7) 0.1114(7) -0.2378(5) 0.0257(12) Uani 1 1 d . . .
H10A H -0.1486 0.1475 -0.3289 0.031 Uiso 1 1 calc R . .
H10B H -0.0444 0.0638 -0.2437 0.031 Uiso 1 1 calc R . .
C11 C -0.1782(7) 0.2384(6) -0.1566(6) 0.0247(11) Uani 1 1 d . . .
H11A H -0.1097 0.3182 -0.2110 0.030 Uiso 1 1 calc R . .
H11B H -0.2958 0.2719 -0.1302 0.030 Uiso 1 1 calc R . .
N12 N -0.1306(5) 0.1974(5) -0.0347(4) 0.0200(9) Uani 1 1 d . . .
H12 H -0.0179 0.1738 -0.0666 0.024 Uiso 1 1 calc R . .
C13 C -0.1426(7) 0.3293(6) 0.0335(6) 0.0271(12) Uani 1 1 d . . .
H13A H -0.2581 0.3682 0.0591 0.032 Uiso 1 1 calc R . .
H13B H -0.0707 0.4025 -0.0289 0.032 Uiso 1 1 calc R . .
C14 C -0.0915(7) 0.3013(6) 0.1562(6) 0.0248(12) Uani 1 1 d . . .
H14A H 0.0142 0.2445 0.1340 0.030 Uiso 1 1 calc R . .
H14B H -0.0718 0.3941 0.1829 0.030 Uiso 1 1 calc R . .
C15 C -0.2191(8) 0.2221(6) 0.2724(6) 0.0279(13) Uani 1 1 d . . .
H15A H -0.1803 0.2120 0.3499 0.034 Uiso 1 1 calc R . .
H15B H -0.3243 0.2796 0.2960 0.034 Uiso 1 1 calc R . .
N16 N -0.2501(6) 0.0800(5) 0.2445(4) 0.0210(9) Uani 1 1 d . . .
C17 C -0.2797(6) -0.0270(6) 0.3437(5) 0.0202(10) Uani 1 1 d . . .
C18 C -0.2809(7) -0.0105(7) 0.4808(6) 0.0274(13) Uani 1 1 d . . .
H18A H -0.1681 0.0054 0.4783 0.041 Uiso 1 1 calc R . .
H18B H -0.3221 -0.0976 0.5386 0.041 Uiso 1 1 calc R . .
H18C H -0.3532 0.0717 0.5152 0.041 Uiso 1 1 calc R . .
C19 C -0.3844(7) -0.2901(7) -0.1031(6) 0.0285(13) Uani 1 1 d . . .
H19A H -0.4704 -0.2395 -0.1337 0.043 Uiso 1 1 calc R . .
H19B H -0.4261 -0.3814 -0.0536 0.043 Uiso 1 1 calc R . .
H19C H -0.2863 -0.3083 -0.1797 0.043 Uiso 1 1 calc R . .
O21 O -0.1890(10) -0.4464(9) 0.5994(8) 0.0283(19) Uani 0.50 1 d PD . .
C22 C -0.1514(17) -0.5621(17) 0.516(2) 0.030(4) Uani 0.50 1 d PD . .
H22A H -0.1852 -0.5356 0.4373 0.036 Uiso 0.50 1 calc PR . .
H22B H -0.2102 -0.6490 0.5656 0.036 Uiso 0.50 1 calc PR . .
C23 C 0.0343(14) -0.5890(16) 0.4760(16) 0.035(4) Uani 0.50 1 d PD . .
H23A H 0.0818 -0.6044 0.3809 0.042 Uiso 0.50 1 calc PR . .
H23B H 0.0619 -0.6740 0.5289 0.042 Uiso 0.50 1 calc PR . .
C24 C 0.0997(16) -0.4538(14) 0.504(2) 0.036(5) Uani 0.50 1 d PD . .
H24A H 0.1871 -0.4126 0.4242 0.043 Uiso 0.50 1 calc PR . .
H24B H 0.1452 -0.4738 0.5775 0.043 Uiso 0.50 1 calc PR . .
C25 C -0.0523(15) -0.3532(13) 0.5417(13) 0.025(3) Uani 0.50 1 d PD . .
H25A H -0.0459 -0.2887 0.6064 0.031 Uiso 0.50 1 calc PR . .
H25B H -0.0629 -0.2943 0.4626 0.031 Uiso 0.50 1 calc PR . .

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
Ni1 0.0163(3) 0.0193(4) 0.0131(4) -0.0094(3) -0.0007(2) -0.0051(2)
N1 0.0185(19) 0.026(2) 0.0144(19) -0.0111(17) 0.0008(15) -0.0077(16)
C2 0.017(2) 0.030(3) 0.017(2) -0.014(2) -0.0005(17) -0.0037(19)
C3 0.022(2) 0.025(3) 0.017(2) -0.006(2) -0.0012(18) -0.0032(19)
C4 0.024(2) 0.019(3) 0.028(3) -0.007(2) -0.001(2) -0.0043(19)
C5 0.020(2) 0.022(3) 0.028(3) -0.014(2) -0.0006(19) -0.0062(19)
C6 0.017(2) 0.022(2) 0.022(2) -0.014(2) -0.0009(18) -0.0031(18)
C7 0.016(2) 0.027(3) 0.019(2) -0.015(2) 0.0009(17) -0.0062(18)
N8 0.0197(19) 0.025(2) 0.0117(18) -0.0080(16) -0.0040(15) -0.0054(16)
C9 0.026(2) 0.028(3) 0.014(2) -0.009(2) -0.0055(18) -0.005(2)
C10 0.026(3) 0.032(3) 0.016(2) -0.007(2) -0.0004(19) -0.008(2)
C11 0.031(3) 0.024(3) 0.019(2) -0.005(2) -0.006(2) -0.007(2)
N12 0.0188(19) 0.021(2) 0.019(2) -0.0088(17) -0.0016(16) -0.0037(16)
C13 0.029(3) 0.021(3) 0.029(3) -0.012(2) -0.003(2) -0.008(2)
C14 0.026(2) 0.027(3) 0.021(2) -0.012(2) -0.003(2) -0.009(2)
C15 0.035(3) 0.023(3) 0.023(3) -0.015(2) -0.001(2) -0.010(2)
N16 0.022(2) 0.024(2) 0.017(2) -0.0121(17) -0.0031(16) -0.0038(17)
C17 0.019(2) 0.026(3) 0.015(2) -0.010(2) -0.0019(17) -0.0052(19)
C18 0.027(3) 0.034(3) 0.020(3) -0.016(2) -0.002(2) -0.005(2)
C19 0.025(2) 0.034(3) 0.027(3) -0.020(2) -0.003(2) -0.009(2)
O21 0.029(4) 0.032(5) 0.020(4) -0.010(3) 0.000(3) -0.006(3)
C22 0.033(9) 0.021(7) 0.034(9) -0.011(6) -0.006(8) -0.005(6)
C23 0.029(6) 0.044(9) 0.030(7) -0.023(7) -0.002(5) -0.002(6)
C24 0.033(9) 0.035(9) 0.034(9) -0.008(7) -0.001(8) -0.017(7)
C25 0.026(6) 0.027(7) 0.022(6) -0.005(5) -0.004(5) -0.005(5)

_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
Ni1 N1 1.832(5) . ?
Ni1 N16 1.890(4) . ?
Ni1 N8 1.900(4) . ?
Ni1 N12 1.969(5) . ?
N1 C2 1.403(7) . ?
N1 C6 1.411(6) . ?
C2 C3 1.390(8) . ?
C2 C17 1.413(7) . ?
C3 C4 1.404(7) . ?
C4 C5 1.390(9) . ?
C5 C6 1.398(8) . ?
C6 C7 1.398(8) . ?
C7 N8 1.353(7) . ?
C7 C19 1.508(7) . ?
N8 C9 1.462(7) . ?
C9 C10 1.516(8) . ?
C10 C11 1.518(8) . ?
C11 N12 1.505(8) . ?
N12 C13 1.489(7) . ?
C13 C14 1.518(9) . ?
C14 C15 1.516(8) . ?
C15 N16 1.461(7) . ?
N16 C17 1.351(8) . ?
C17 C18 1.498(8) . ?
O21 C22 1.435(13) . ?
O21 C25 1.435(12) . ?
C22 C23 1.515(15) . ?
C23 C24 1.521(15) . ?
C24 C25 1.522(15) . ?

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
N1 Ni1 N16 83.1(2) . . ?
N1 Ni1 N8 83.5(2) . . ?
N16 Ni1 N8 158.0(2) . . ?
N1 Ni1 N12 162.7(2) . . ?
N16 Ni1 N12 99.20(19) . . ?
N8 Ni1 N12 98.8(2) . . ?
C2 N1 C6 117.9(4) . . ?
C2 N1 Ni1 115.3(4) . . ?
C6 N1 Ni1 114.5(4) . . ?
C3 C2 N1 119.8(5) . . ?
C3 C2 C17 128.4(5) . . ?
N1 C2 C17 111.8(5) . . ?
C2 C3 C4 119.4(5) . . ?
C5 C4 C3 119.9(5) . . ?
C4 C5 C6 120.2(5) . . ?
C7 C6 C5 129.2(5) . . ?
C7 C6 N1 112.0(5) . . ?
C5 C6 N1 118.8(5) . . ?
N8 C7 C6 113.7(4) . . ?
N8 C7 C19 123.0(5) . . ?
C6 C7 C19 123.3(5) . . ?
C7 N8 C9 118.3(4) . . ?
C7 N8 Ni1 114.3(4) . . ?
C9 N8 Ni1 127.3(4) . . ?
N8 C9 C10 111.2(4) . . ?
C9 C10 C11 114.8(4) . . ?
N12 C11 C10 110.6(5) . . ?
C13 N12 C11 107.9(5) . . ?
C13 N12 Ni1 116.8(4) . . ?
C11 N12 Ni1 116.1(3) . . ?
N12 C13 C14 112.4(5) . . ?
C15 C14 C13 113.5(5) . . ?
N16 C15 C14 112.8(4) . . ?
C17 N16 C15 118.2(5) . . ?
C17 N16 Ni1 115.6(3) . . ?
C15 N16 Ni1 126.0(4) . . ?
N16 C17 C2 112.6(5) . . ?
N16 C17 C18 124.4(5) . . ?
C2 C17 C18 123.0(6) . . ?
C22 O21 C25 104.7(11) . . ?
O21 C22 C23 106.0(8) . . ?
C22 C23 C24 104.6(6) . . ?
C23 C24 C25 103.7(6) . . ?
O21 C25 C24 104.6(7) . . ?

_diffrn_measured_fraction_theta_max 0.956
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.971
_refine_diff_density_max         3.260
_refine_diff_density_min         -2.900
_refine_diff_density_rms         0.230