# Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2000
# CCDC Number: 186/1770
 
data_ms404 
 
_audit_creation_method            SHELXL-97 
_chemical_name_systematic 
; 
 (5,10,15,20-Tetra(n-butyl)-2,3,7,8,12,13,17,18-
 octaethylporphyrinato)nickel(II) 
; 
_chemical_name_common             Ni(II)TnBuOEP 
_chemical_formula_moiety          'C52 H76 N4 Ni' 
_chemical_formula_sum 
 'C52 H76 N4 Ni' 
_chemical_formula_weight          815.88 
 
loop_ 
 _atom_type_symbol 
 _atom_type_description 
 _atom_type_scat_dispersion_real 
 _atom_type_scat_dispersion_imag 
 _atom_type_scat_source 
 'C'  'C'   0.0181   0.0091 
 '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'   0.0311   0.0180 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 'Ni'  'Ni'  -3.0029   0.5091 
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 
 
_symmetry_cell_setting            monoclinic 
_symmetry_space_group_name_H-M    C2/c 
 
loop_ 
 _symmetry_equiv_pos_as_xyz 
 'x, y, z' 
 '-x, y, -z+1/2' 
 'x+1/2, y+1/2, z' 
 '-x+1/2, y+1/2, -z+1/2' 
 '-x, -y, -z' 
 'x, -y, z-1/2' 
 '-x+1/2, -y+1/2, -z' 
 'x+1/2, -y+1/2, z-1/2' 
 
_cell_length_a                    26.581(11) 
_cell_length_b                    7.566(2) 
_cell_length_c                    25.967(12) 
_cell_angle_alpha                 90.00 
_cell_angle_beta                  119.62(3) 
_cell_angle_gamma                 90.00 
_cell_volume                      4540(3) 
_cell_formula_units_Z             4 
_cell_measurement_temperature     126(2) 
_cell_measurement_reflns_used     32 
_cell_measurement_theta_min       24 
_cell_measurement_theta_max       33 
 
_exptl_crystal_description        block
_exptl_crystal_colour             green 
_exptl_crystal_size_max           0.60 
_exptl_crystal_size_mid           0.60 
_exptl_crystal_size_min           0.60 
_exptl_crystal_density_meas       n/d 
_exptl_crystal_density_diffrn     1.194 
_exptl_crystal_density_method     'not measured' 
_exptl_crystal_F_000              1776 
_exptl_absorpt_coefficient_mu     0.897 
_exptl_absorpt_correction_type    'empirical, XABS2' 
_exptl_absorpt_correction_T_min   0.6153 
_exptl_absorpt_correction_T_max   0.6153 
 
_exptl_special_details 
; 
 ? 
; 
 
_diffrn_ambient_temperature       126(2) 
_diffrn_radiation_wavelength      1.54178 
_diffrn_radiation_type            CuK\a 
_diffrn_radiation_source          'fine-focus sealed tube' 
_diffrn_radiation_monochromator   graphite 
_diffrn_measurement_device_type   'Syntex P21' 
_diffrn_measurement_method        '2theta-theta' 
_diffrn_detector_area_resol_mean  n/a 
_diffrn_standards_number          2
_diffrn_standards_interval_count  198 
_diffrn_standards_interval_time   ? 
_diffrn_standards_decay_%         stable 
_diffrn_reflns_number             3431 
_diffrn_reflns_av_R_equivalents   0.1080 
_diffrn_reflns_av_sigmaI/netI     0.0283 
_diffrn_reflns_limit_h_min        -28 
_diffrn_reflns_limit_h_max        24 
_diffrn_reflns_limit_k_min        0 
_diffrn_reflns_limit_k_max        8 
_diffrn_reflns_limit_l_min        0 
_diffrn_reflns_limit_l_max        28 
_diffrn_reflns_theta_min          3.83 
_diffrn_reflns_theta_max          57.08 
_reflns_number_total              3058 
_reflns_number_gt                 2780 
_reflns_threshold_expression      >2sigma(I) 
 
_computing_data_collection        'Siemens, P3' 
_computing_cell_refinement        'Siemens, P3' 
_computing_data_reduction         'XDISK, Shelxtl-Plus, Siemens, 1994' 
_computing_structure_solution     'SHELXS-97 (Sheldrick, 1990)' 
_computing_structure_refinement   'SHELXL-97 (Sheldrick, 1997)' 
_computing_molecular_graphics     'XP, Shelxtl-Plus, Siemens, 1994' 
_computing_publication_material   'XCIF, Shelxtl-Plus, Siemens, 1994'
 
_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. The methyl group of the 
 10-butyl chain was disordered and refined with two split positions. 
 Occupancies were determined by free refinement: C104a 0.65; C10d 0.35.
 Despite restraining the bond length the C103 C10d bond length remained 
at
 an unreasonably low value.
; 
 
_refine_ls_structure_factor_coef  Fsqd  
_refine_ls_matrix_type            full 
_refine_ls_weighting_scheme 
 'calc w=1/[\s^2^(Fo^2^)+(0.0780P)^2^+15.2512P] 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        n/d 
_refine_ls_number_reflns          3058 
_refine_ls_number_parameters      269 
_refine_ls_number_restraints      3 
_refine_ls_R_factor_all           0.0603 
_refine_ls_R_factor_gt            0.0552 
_refine_ls_wR_factor_ref          0.1469 
_refine_ls_wR_factor_gt           0.1430 
_refine_ls_goodness_of_fit_ref    1.097 
_refine_ls_restrained_S_all       1.101 
_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_calc_flag 
 _atom_site_refinement_flags 
 _atom_site_disorder_assembly 
 _atom_site_disorder_group 
Ni Ni 0.0000 0.59772(9) 0.2500 0.0106(2) Uani 1 d S . . 
N21 N 0.03085(10) 0.5961(3) 0.33232(10) 0.0131(6) Uani 1 d . . . 
N22 N 0.07480(10) 0.5940(3) 0.26022(11) 0.0143(6) Uani 1 d . . . 
C1 C 0.00561(12) 0.6667(4) 0.36266(13) 0.0127(7) Uani 1 d . . . 
C2 C 0.04358(13) 0.6395(4) 0.42560(13) 0.0148(7) Uani 1 d . . . 
C3 C 0.08980(12) 0.5421(4) 0.43200(13) 0.0134(7) Uani 1 d . . . 
C4 C 0.08224(12) 0.5178(4) 0.37289(13) 0.0127(7) Uani 1 d . . . 
C5 C 0.12267(12) 0.4506(4) 0.35801(13) 0.0133(7) Uani 1 d . . . 
C6 C 0.12195(12) 0.5107(4) 0.30638(13) 0.0120(7) Uani 1 d . . . 
C7 C 0.17013(13) 0.5192(4) 0.29490(13) 0.0142(7) Uani 1 d . . . 
C8 C 0.15218(13) 0.6175(4) 0.24448(13) 0.0146(7) Uani 1 d . . . 
C9 C 0.09157(12) 0.6586(4) 0.22209(13) 0.0132(7) Uani 1 d . . . 
C10 C 0.05244(13) 0.7267(4) 0.16581(13) 0.0150(7) Uani 1 d . . . 
C21 C 0.03582(14) 0.6946(5) 0.47716(14) 0.0218(7) Uani 1 d . . . 
H21A H 0.0534 0.6038 0.5086 0.026 Uiso 1 calc R . . 
H21B H -0.0060 0.7000 0.4639 0.026 Uiso 1 calc R . . 
C22 C 0.06314(15) 0.8735(5) 0.50294(16) 0.0350(10) Uani 1 d . . . 
H22A H 0.0569 0.9024 0.5362 0.053 Uiso 1 calc R . . 
H22B H 0.0453 0.9646 0.4723 0.053 Uiso 1 calc R . . 
H22C H 0.1048 0.8685 0.5169 0.053 Uiso 1 calc R . . 
C31 C 0.13995(13) 0.4873(4) 0.49090(13) 0.0195(7) Uani 1 d . . . 
H31A H 0.1468 0.5804 0.5205 0.023 Uiso 1 calc R . . 
H31B H 0.1751 0.4786 0.4871 0.023 Uiso 1 calc R . . 
C32 C 0.13080(16) 0.3116(5) 0.51381(15) 0.0283(8) Uani 1 d . . . 
H32A H 0.1649 0.2841 0.5520 0.042 Uiso 1 calc R . . 
H32B H 0.1249 0.2178 0.4853 0.042 Uiso 1 calc R . . 
H32C H 0.0967 0.3198 0.5188 0.042 Uiso 1 calc R . . 
C51 C 0.16340(13) 0.3039(4) 0.39416(13) 0.0170(7) Uani 1 d . . . 
H51A H 0.1593 0.2800 0.4294 0.020 Uiso 1 calc R . . 
H51B H 0.2039 0.3405 0.4080 0.020 Uiso 1 calc R . . 
C52 C 0.14973(14) 0.1351(4) 0.35650(14) 0.0213(7) Uani 1 d . . . 
H52A H 0.1090 0.1016 0.3424 0.026 Uiso 1 calc R . . 
H52B H 0.1534 0.1617 0.3212 0.026 Uiso 1 calc R . . 
C53 C 0.18837(15) -0.0227(5) 0.38876(15) 0.0266(8) Uani 1 d D . . 
H53A H 0.1785 -0.1211 0.3603 0.032 Uiso 1 calc R . . 
H53B H 0.2291 0.0105 0.4027 0.032 Uiso 1 calc R . . 
C54 C 0.18338(19) -0.0863(5) 0.44032(18) 0.0396(10) Uani 1 d D . . 
H54A H 0.2092 -0.1874 0.4585 0.059 Uiso 1 calc R . . 
H54B H 0.1434 -0.1224 0.4269 0.059 Uiso 1 calc R . . 
H54C H 0.1942 0.0090 0.4695 0.059 Uiso 1 calc R . . 
C71 C 0.23105(13) 0.4505(4) 0.33219(14) 0.0193(7) Uani 1 d . . . 
H71A H 0.2485 0.4327 0.3065 0.023 Uiso 1 calc R . . 
H71B H 0.2296 0.3341 0.3488 0.023 Uiso 1 calc R . . 
C72 C 0.26950(14) 0.5741(5) 0.38272(16) 0.0300(9) Uani 1 d . . . 
H72A H 0.3083 0.5231 0.4053 0.045 Uiso 1 calc R . . 
H72B H 0.2530 0.5900 0.4089 0.045 Uiso 1 calc R . . 
H72C H 0.2719 0.6889 0.3666 0.045 Uiso 1 calc R . . 
C81 C 0.18805(14) 0.6498(5) 0.21528(15) 0.0244(8) Uani 1 d . . . 
H81A H 0.2295 0.6534 0.2460 0.029 Uiso 1 calc R . . 
H81B H 0.1777 0.7663 0.1953 0.029 Uiso 1 calc R . . 
C82 C 0.17914(18) 0.5079(6) 0.17013(17) 0.0378(10) Uani 1 d . . . 
H82A H 0.2032 0.5343 0.1522 0.057 Uiso 1 calc R . . 
H82B H 0.1383 0.5053 0.1392 0.057 Uiso 1 calc R . . 
H82C H 0.1901 0.3926 0.1898 0.057 Uiso 1 calc R . . 
C101 C 0.07274(14) 0.8565(5) 0.13544(14) 0.0232(8) Uani 1 d . . . 
H10A H 0.0391 0.8945 0.0976 0.028 Uiso 1 calc R . . 
H10B H 0.1004 0.7963 0.1262 0.028 Uiso 1 calc R . . 
C102 C 0.10211(14) 1.0207(5) 0.17362(15) 0.0253(8) Uani 1 d . . . 
H10C H 0.1294 0.9810 0.2144 0.030 Uiso 1 calc R . . 
H10D H 0.1251 1.0790 0.1580 0.030 Uiso 1 calc R . . 
C103 C 0.0622(2) 1.1549(8) 0.1765(3) 0.0751(18) Uani 1 d D . . 
H10E H 0.0870 1.2489 0.2037 0.090 Uiso 1 calc R A 1 
H10F H 0.0408 1.2091 0.1367 0.090 Uiso 1 calc R A 1 
C104 C 0.0193(3) 1.1122(9) 0.1940(3) 0.043(2) Uani 0.646(11) d PD B 1 
H10G H -0.0017 1.2195 0.1930 0.065 Uiso 0.646(11) calc PR B 1 
H10H H 0.0388 1.0636 0.2343 0.065 Uiso 0.646(11) calc PR B 1 
H10I H -0.0079 1.0247 0.1666 0.065 Uiso 0.646(11) calc PR B 1 
C10D C 0.0078(5) 1.179(2) 0.1382(7) 0.068(6) Uani 0.354(11) d P B 2 
H10J H -0.0075 1.2758 0.1516 0.103 Uiso 0.354(11) calc PR B 2 
H10K H -0.0138 1.0708 0.1344 0.103 Uiso 0.354(11) calc PR B 2 
H10L H 0.0038 1.2098 0.0997 0.103 Uiso 0.354(11) calc PR B 2 
 
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 
Ni 0.0103(4) 0.0117(4) 0.0100(4) 0.000 0.0051(3) 0.000 
N21 0.0111(13) 0.0146(14) 0.0139(14) 0.0013(11) 0.0064(11) 0.0007(10) 
N22 0.0131(13) 0.0153(14) 0.0166(13) 0.0006(11) 0.0090(11) 0.0003(10) 
C1 0.0162(15) 0.0084(15) 0.0134(16) -0.0024(12) 0.0073(13) -0.0020(13) 
C2 0.0177(16) 0.0140(16) 0.0132(16) -0.0036(13) 0.0081(13) -0.0040(13) 
C3 0.0149(15) 0.0119(15) 0.0122(16) -0.0002(13) 0.0058(13) -0.0026(13) 
C4 0.0146(15) 0.0092(15) 0.0130(16) 0.0035(12) 0.0059(13) 0.0000(13) 
C5 0.0130(15) 0.0128(15) 0.0121(15) -0.0019(13) 0.0047(13) -0.0019(13) 
C6 0.0132(15) 0.0084(15) 0.0120(15) -0.0001(12) 0.0044(13) 0.0017(12) 
C7 0.0156(16) 0.0106(15) 0.0162(16) 0.0015(13) 0.0076(13) 0.0024(13) 
C8 0.0152(16) 0.0133(16) 0.0156(16) 0.0023(13) 0.0079(13) 0.0011(12) 
C9 0.0139(15) 0.0099(15) 0.0164(16) -0.0030(13) 0.0081(13) -0.0034(12) 
C10 0.0194(16) 0.0114(16) 0.0148(16) 0.0009(13) 0.0088(13) -0.0017(13) 
C21 0.0214(17) 0.0299(19) 0.0143(16) 0.0006(15) 0.0089(14) 0.0048(15) 
C22 0.0254(19) 0.045(2) 0.026(2) -0.0193(18) 0.0059(16) 0.0018(18) 
C31 0.0207(16) 0.0223(18) 0.0126(16) 0.0000(14) 0.0061(14) 0.0029(14) 
C32 0.037(2) 0.028(2) 0.0215(18) 0.0091(16) 0.0157(16) 0.0093(17) 
C51 0.0165(15) 0.0190(17) 0.0167(16) 0.0043(14) 0.0092(13) 0.0037(13) 
C52 0.0197(17) 0.0195(17) 0.0230(18) 0.0040(14) 0.0091(14) 0.0029(14) 
C53 0.0273(19) 0.0183(18) 0.032(2) -0.0008(16) 0.0128(16) 0.0060(15) 
C54 0.051(2) 0.021(2) 0.050(2) 0.0174(18) 0.028(2) 0.0128(18) 
C71 0.0159(16) 0.0203(17) 0.0252(18) 0.0075(15) 0.0128(14) 0.0057(14) 
C72 0.0158(17) 0.028(2) 0.034(2) 0.0097(17) 0.0025(15) 0.0018(15) 
C81 0.0197(17) 0.0304(19) 0.0303(19) 0.0076(16) 0.0179(15) 0.0037(15) 
C82 0.050(2) 0.043(2) 0.039(2) 0.0071(19) 0.036(2) 0.009(2) 
C101 0.0234(17) 0.0262(19) 0.0201(17) 0.0033(15) 0.0108(15) -0.0027(15) 
C102 0.0245(18) 0.0249(19) 0.0244(18) 0.0040(15) 0.0104(15) -0.0044(15) 
C103 0.044(3) 0.078(4) 0.090(4) -0.051(3) 0.023(3) -0.010(3) 
C104 0.034(4) 0.034(4) 0.061(5) -0.010(3) 0.023(3) -0.001(3) 
C10D 0.042(8) 0.054(9) 0.072(11) -0.024(8) 0.000(7) 0.030(7) 
 
_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 
Ni N22 1.872(2) . ? 
Ni N22 1.872(2) 2 ? 
Ni N21 1.873(3) 2 ? 
Ni N21 1.873(3) . ? 
N21 C1 1.371(4) . ? 
N21 C4 1.380(4) . ? 
N22 C9 1.362(4) . ? 
N22 C6 1.386(4) . ? 
C1 C10 1.416(4) 2 ? 
C1 C2 1.450(4) . ? 
C2 C3 1.370(4) . ? 
C2 C21 1.510(4) . ? 
C3 C4 1.458(4) . ? 
C3 C31 1.508(4) . ? 
C4 C5 1.405(4) . ? 
C5 C6 1.407(4) . ? 
C5 C51 1.510(4) . ? 
C6 C7 1.453(4) . ? 
C7 C8 1.370(4) . ? 
C7 C71 1.510(4) . ? 
C8 C9 1.451(4) . ? 
C8 C81 1.503(4) . ? 
C9 C10 1.407(4) . ? 
C10 C1 1.416(4) 2 ? 
C10 C101 1.516(4) . ? 
C21 C22 1.526(5) . ? 
C31 C32 1.524(5) . ? 
C51 C52 1.539(5) . ? 
C52 C53 1.527(5) . ? 
C53 C54 1.489(5) . ? 
C71 C72 1.522(5) . ? 
C81 C82 1.520(5) . ? 
C101 C102 1.540(5) . ? 
C102 C103 1.497(6) . ? 
C103 C10D 1.301(13) . ? 
C103 C104 1.456(6) . ? 
 
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 
N22 Ni N22 178.29(16) . 2 ? 
N22 Ni N21 89.82(11) . 2 ? 
N22 Ni N21 90.17(11) 2 2 ? 
N22 Ni N21 90.17(11) . . ? 
N22 Ni N21 89.82(11) 2 . ? 
N21 Ni N21 179.26(16) 2 . ? 
C1 N21 C4 108.0(2) . . ? 
C1 N21 Ni 126.2(2) . . ? 
C4 N21 Ni 125.7(2) . . ? 
C9 N22 C6 108.1(2) . . ? 
C9 N22 Ni 126.7(2) . . ? 
C6 N22 Ni 124.9(2) . . ? 
N21 C1 C10 122.8(3) . 2 ? 
N21 C1 C2 109.1(3) . . ? 
C10 C1 C2 127.3(3) 2 . ? 
C3 C2 C1 107.2(3) . . ? 
C3 C2 C21 123.2(3) . . ? 
C1 C2 C21 129.5(3) . . ? 
C2 C3 C4 106.9(3) . . ? 
C2 C3 C31 124.1(3) . . ? 
C4 C3 C31 128.8(3) . . ? 
N21 C4 C5 123.3(3) . . ? 
N21 C4 C3 108.6(3) . . ? 
C5 C4 C3 127.5(3) . . ? 
C4 C5 C6 119.6(3) . . ? 
C4 C5 C51 120.4(3) . . ? 
C6 C5 C51 119.8(3) . . ? 
N22 C6 C5 123.5(3) . . ? 
N22 C6 C7 108.3(2) . . ? 
C5 C6 C7 127.7(3) . . ? 
C8 C7 C6 107.1(3) . . ? 
C8 C7 C71 123.8(3) . . ? 
C6 C7 C71 128.9(3) . . ? 
C7 C8 C9 107.0(3) . . ? 
C7 C8 C81 124.2(3) . . ? 
C9 C8 C81 128.2(3) . . ? 
N22 C9 C10 123.2(3) . . ? 
N22 C9 C8 109.2(3) . . ? 
C10 C9 C8 126.8(3) . . ? 
C9 C10 C1 118.7(3) . 2 ? 
C9 C10 C101 120.5(3) . . ? 
C1 C10 C101 120.8(3) 2 . ? 
C2 C21 C22 112.9(3) . . ? 
C3 C31 C32 113.8(3) . . ? 
C5 C51 C52 110.1(2) . . ? 
C53 C52 C51 114.6(3) . . ? 
C54 C53 C52 114.3(3) . . ? 
C7 C71 C72 113.1(3) . . ? 
C8 C81 C82 112.3(3) . . ? 
C10 C101 C102 112.6(3) . . ? 
C103 C102 C101 115.7(3) . . ? 
C10D C103 C102 127.3(7) . . ? 
C104 C103 C102 123.2(5) . . ? 
 
_diffrn_measured_fraction_theta_max    0.457 
_diffrn_reflns_theta_full              57.08 
_diffrn_measured_fraction_theta_full   0.457 
_refine_diff_density_max    0.526 
_refine_diff_density_min   -0.706 
_refine_diff_density_rms    0.075