# Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2003



data_global

_journal_coden_Cambridge         182
_journal_volume                  ?
_journal_year                    ?
_journal_page_first              ?

_publ_requested_journal          'Chemical Communications'

loop_
_publ_author_name
'Juan Campora'
'Ernesto Carmona'
'Claudia Graiff'
'Celia M. Maya'
'Pilar Palma'
'Antonio Tiripicchio'

_publ_contact_author_name        'Dr Juan Campora'
_publ_contact_author_address     
;
Instituto de Investigaciones Quimicas
Consejo Superior de Investigaciones Cientificas  
Universidad de Sevilla
c/ Americo Vespucio s/n
Sevilla
41092
SPAIN
;

_publ_contact_author_email       ' CAMPORA@IIQ.CSIC.ES'

_publ_section_title              
;
Addition Reactions of O-bound Cyclic Nickel Enolates to 
alpha,beta-Unsaturated Ketones.
;

data_r243f
_database_code_CSD               206759

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
? 
;
_chemical_name_common            ?
_chemical_formula_moiety         'C27 H46 Ni O2 P2'
_chemical_formula_sum            'C27 H46 Ni O2 P2'
_chemical_formula_weight         523.29

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 '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'
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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/c

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

_cell_length_a                   10.364(4)
_cell_length_b                   14.185(4)
_cell_length_c                   19.437(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 98.64(3)
_cell_angle_gamma                90.00
_cell_volume                     2825.1(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    24
_cell_measurement_theta_min      12
_cell_measurement_theta_max      19

_exptl_crystal_description       prismatic
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.19
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1128
_exptl_absorpt_coefficient_mu    0.820
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.804
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
; 
? 
;

_diffrn_ambient_temperature      293(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  'Philips PW 1100'
_diffrn_measurement_method       '\q/2\q scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         1
_diffrn_standards_interval_count 100
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8633
_diffrn_reflns_av_R_equivalents  0.0218
_diffrn_reflns_av_sigmaI/netI    0.0574
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         3.04
_diffrn_reflns_theta_max         30.01
_reflns_number_total             8236
_reflns_number_gt                5385
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_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 w==1/[\s^2^(Fo^2^)+(0.0461P)^2^+0.0000P] 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         8236
_refine_ls_number_parameters     304
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0695
_refine_ls_R_factor_gt           0.0371
_refine_ls_wR_factor_ref         0.0959
_refine_ls_wR_factor_gt          0.0865
_refine_ls_goodness_of_fit_ref   0.930
_refine_ls_restrained_S_all      0.930
_refine_ls_shift/su_max          0.048
_refine_ls_shift/su_mean         0.005

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
Ni1 Ni 0.13636(2) 0.163800(16) 0.836101(11) 0.02443(7) Uani 1 d . . .
P1 P 0.00251(5) 0.06700(3) 0.77683(3) 0.02806(11) Uani 1 d . . .
P2 P 0.29868(5) 0.07327(4) 0.81436(3) 0.03164(12) Uani 1 d . . .
O1 O 0.26582(12) 0.23638(9) 0.88592(7) 0.0328(3) Uani 1 d . . .
O2 O 0.28230(13) 0.39818(10) 0.89991(7) 0.0367(3) Uani 1 d . . .
C1 C 0.01470(17) 0.25064(13) 0.86822(9) 0.0264(4) Uani 1 d . . .
C2 C 0.08186(18) 0.32107(13) 0.90917(9) 0.0271(4) Uani 1 d . . .
C3 C 0.0181(2) 0.39266(14) 0.93892(10) 0.0380(5) Uani 1 d . . .
H3 H 0.0662 0.4395 0.9646 0.055(3) Uiso 1 calc R . .
C4 C -0.1170(2) 0.39480(16) 0.93065(11) 0.0424(5) Uani 1 d . . .
H4 H -0.1599 0.4428 0.9507 0.055(3) Uiso 1 calc R . .
C5 C -0.1868(2) 0.32503(15) 0.89240(11) 0.0398(5) Uani 1 d . . .
H5 H -0.2774 0.3246 0.8874 0.055(3) Uiso 1 calc R . .
C6 C -0.12160(18) 0.25539(14) 0.86131(10) 0.0346(4) Uani 1 d . . .
H6 H -0.1705 0.2098 0.8347 0.055(3) Uiso 1 calc R . .
C7 C 0.22830(18) 0.31012(13) 0.92343(9) 0.0274(4) Uani 1 d . . .
C8 C 0.28104(19) 0.29823(14) 1.00131(9) 0.0318(4) Uani 1 d . . .
H8 H 0.2604 0.3554 1.0258 0.030(5) Uiso 1 calc R . .
C9 C 0.4290(2) 0.28808(16) 1.00981(11) 0.0412(5) Uani 1 d . . .
H9A H 0.4654 0.2928 1.0587 0.051(5) Uiso 1 calc R . .
H9B H 0.4514 0.2267 0.9931 0.051(5) Uiso 1 calc R . .
C10 C 0.4850(2) 0.36333(16) 0.96987(11) 0.0431(5) Uani 1 d . . .
H10 H 0.5735 0.3770 0.9807 0.057(7) Uiso 1 calc R . .
C11 C 0.4142(2) 0.41128(15) 0.91979(11) 0.0389(5) Uani 1 d . . .
C12 C 0.2184(2) 0.21439(16) 1.03259(11) 0.0460(6) Uani 1 d . . .
H12A H 0.2526 0.2093 1.0812 0.062(4) Uiso 1 calc R . .
H12B H 0.2374 0.1577 1.0091 0.062(4) Uiso 1 calc R . .
H12C H 0.1256 0.2234 1.0272 0.062(4) Uiso 1 calc R . .
C13 C 0.4635(3) 0.48811(19) 0.87812(14) 0.0671(8) Uani 1 d . . .
H13A H 0.3928 0.5124 0.8453 0.282(17) Uiso 1 calc R . .
H13B H 0.5300 0.4635 0.8536 0.282(17) Uiso 1 calc R . .
H13C H 0.4994 0.5378 0.9086 0.282(17) Uiso 1 calc R . .
C14 C 0.0940(2) -0.04006(14) 0.75911(11) 0.0388(5) Uani 1 d . . .
H14A H 0.0903 -0.0853 0.7962 0.059(4) Uiso 1 calc R . .
H14B H 0.0523 -0.0684 0.7160 0.059(4) Uiso 1 calc R . .
C15 C 0.2364(2) -0.02004(15) 0.75335(11) 0.0417(5) Uani 1 d . . .
H15A H 0.2438 -0.0007 0.7062 0.059(4) Uiso 1 calc R . .
H15B H 0.2878 -0.0768 0.7637 0.059(4) Uiso 1 calc R . .
C16 C -0.1318(2) 0.01613(15) 0.81791(11) 0.0380(5) Uani 1 d . . .
H16 H -0.2021 0.0630 0.8129 0.040(6) Uiso 1 calc R . .
C17 C -0.0894(3) 0.00169(19) 0.89592(11) 0.0595(7) Uani 1 d . . .
H17A H -0.0542 0.0595 0.9165 0.061(3) Uiso 1 calc R . .
H17B H -0.0241 -0.0467 0.9032 0.061(3) Uiso 1 calc R . .
H17C H -0.1634 -0.0168 0.9171 0.061(3) Uiso 1 calc R . .
C18 C -0.1897(2) -0.07420(16) 0.78318(12) 0.0494(6) Uani 1 d . . .
H18A H -0.2161 -0.0631 0.7344 0.061(3) Uiso 1 calc R . .
H18B H -0.2642 -0.0929 0.8039 0.061(3) Uiso 1 calc R . .
H18C H -0.1254 -0.1233 0.7894 0.061(3) Uiso 1 calc R . .
C19 C -0.0789(2) 0.10227(16) 0.68902(10) 0.0396(5) Uani 1 d . . .
H19 H -0.1208 0.0459 0.6666 0.042(6) Uiso 1 calc R . .
C20 C 0.0206(3) 0.1366(2) 0.64442(12) 0.0620(7) Uani 1 d . . .
H20A H 0.0872 0.0896 0.6439 0.091(4) Uiso 1 calc R . .
H20B H 0.0595 0.1942 0.6634 0.091(4) Uiso 1 calc R . .
H20C H -0.0221 0.1475 0.5978 0.091(4) Uiso 1 calc R . .
C21 C -0.1838(3) 0.17644(19) 0.68972(14) 0.0642(8) Uani 1 d . . .
H21A H -0.2472 0.1546 0.7174 0.091(4) Uiso 1 calc R . .
H21B H -0.2258 0.1879 0.6430 0.091(4) Uiso 1 calc R . .
H21C H -0.1450 0.2338 0.7092 0.091(4) Uiso 1 calc R . .
C22 C 0.3822(2) 0.01384(19) 0.89340(12) 0.0517(6) Uani 1 d . . .
H22 H 0.4187 0.0639 0.9253 0.059(7) Uiso 1 calc R . .
C23 C 0.2879(3) -0.0400(2) 0.93038(14) 0.0719(8) Uani 1 d . . .
H23A H 0.2178 0.0008 0.9385 0.105(5) Uiso 1 calc R . .
H23B H 0.3324 -0.0629 0.9741 0.105(5) Uiso 1 calc R . .
H23C H 0.2533 -0.0924 0.9022 0.105(5) Uiso 1 calc R . .
C24 C 0.4965(3) -0.0484(2) 0.88100(17) 0.0927(11) Uani 1 d . . .
H24A H 0.5564 -0.0122 0.8585 0.105(5) Uiso 1 calc R . .
H24B H 0.4647 -0.1007 0.8520 0.105(5) Uiso 1 calc R . .
H24C H 0.5405 -0.0714 0.9248 0.105(5) Uiso 1 calc R . .
C25 C 0.4324(2) 0.12735(17) 0.77543(11) 0.0429(5) Uani 1 d . . .
H25 H 0.4846 0.0763 0.7597 0.042(6) Uiso 1 calc R . .
C26 C 0.3781(3) 0.1857(2) 0.71231(15) 0.0672(8) Uani 1 d . . .
H26A H 0.3222 0.1471 0.6799 0.110(5) Uiso 1 calc R . .
H26B H 0.4488 0.2092 0.6904 0.110(5) Uiso 1 calc R . .
H26C H 0.3291 0.2377 0.7266 0.110(5) Uiso 1 calc R . .
C27 C 0.5230(2) 0.1879(2) 0.82671(15) 0.0740(9) Uani 1 d . . .
H27A H 0.5582 0.1505 0.8662 0.110(5) Uiso 1 calc R . .
H27B H 0.4748 0.2399 0.8418 0.110(5) Uiso 1 calc R . .
H27C H 0.5930 0.2115 0.8044 0.110(5) Uiso 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
Ni1 0.02355(12) 0.02441(12) 0.02538(12) -0.00507(10) 0.00380(8) -0.00148(10)
P1 0.0288(2) 0.0254(2) 0.0298(2) -0.00468(19) 0.00386(19) -0.0047(2)
P2 0.0286(3) 0.0323(3) 0.0338(3) -0.0076(2) 0.0039(2) 0.0039(2)
O1 0.0239(6) 0.0364(8) 0.0376(7) -0.0143(6) 0.0032(6) -0.0028(6)
O2 0.0377(8) 0.0348(8) 0.0363(7) 0.0043(6) 0.0011(6) -0.0108(6)
C1 0.0272(9) 0.0240(9) 0.0286(9) -0.0019(7) 0.0067(7) -0.0019(7)
C2 0.0283(9) 0.0274(10) 0.0256(9) -0.0013(7) 0.0043(7) -0.0004(7)
C3 0.0386(11) 0.0331(11) 0.0410(11) -0.0132(9) 0.0016(9) 0.0011(9)
C4 0.0392(12) 0.0402(12) 0.0482(13) -0.0147(10) 0.0079(10) 0.0087(10)
C5 0.0289(10) 0.0403(12) 0.0514(13) -0.0081(10) 0.0093(9) 0.0027(9)
C6 0.0275(10) 0.0324(10) 0.0439(11) -0.0097(9) 0.0054(9) -0.0036(8)
C7 0.0280(9) 0.0265(9) 0.0278(9) -0.0040(7) 0.0049(7) -0.0049(7)
C8 0.0362(11) 0.0310(10) 0.0279(9) -0.0024(8) 0.0038(8) -0.0017(8)
C9 0.0374(11) 0.0484(13) 0.0349(11) 0.0001(10) -0.0036(9) -0.0011(10)
C10 0.0320(11) 0.0532(14) 0.0432(12) -0.0071(10) 0.0022(9) -0.0126(10)
C11 0.0377(11) 0.0410(12) 0.0383(11) -0.0043(9) 0.0067(9) -0.0174(10)
C12 0.0526(14) 0.0445(13) 0.0415(12) 0.0108(10) 0.0091(11) -0.0058(11)
C13 0.0690(18) 0.0682(18) 0.0648(17) 0.0153(14) 0.0124(14) -0.0352(15)
C14 0.0411(12) 0.0292(10) 0.0457(12) -0.0116(9) 0.0053(10) -0.0014(9)
C15 0.0415(12) 0.0360(11) 0.0480(12) -0.0160(10) 0.0081(10) 0.0019(10)
C16 0.0368(11) 0.0346(11) 0.0444(12) -0.0031(9) 0.0116(9) -0.0080(9)
C17 0.0731(18) 0.0626(17) 0.0457(14) 0.0016(12) 0.0179(12) -0.0239(15)
C18 0.0469(13) 0.0404(13) 0.0623(15) -0.0066(11) 0.0126(11) -0.0189(11)
C19 0.0407(12) 0.0423(12) 0.0337(11) -0.0030(9) -0.0013(9) -0.0058(10)
C20 0.0627(17) 0.082(2) 0.0414(13) 0.0132(13) 0.0073(12) -0.0119(15)
C21 0.0679(18) 0.0665(18) 0.0535(15) 0.0039(13) -0.0059(13) 0.0170(15)
C22 0.0468(14) 0.0585(16) 0.0463(13) 0.0002(12) -0.0047(11) 0.0157(12)
C23 0.084(2) 0.073(2) 0.0563(16) 0.0193(15) 0.0008(15) 0.0091(17)
C24 0.081(2) 0.105(3) 0.089(2) 0.016(2) 0.0030(18) 0.057(2)
C25 0.0310(11) 0.0505(14) 0.0497(13) -0.0147(11) 0.0144(10) 0.0009(10)
C26 0.0590(17) 0.0669(19) 0.081(2) 0.0158(16) 0.0262(15) -0.0062(14)
C27 0.0423(14) 0.101(2) 0.084(2) -0.0425(18) 0.0248(14) -0.0270(15)

_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 O1 1.8460(13) . ?
Ni1 C1 1.9322(18) . ?
Ni1 P1 2.1580(8) . ?
Ni1 P2 2.2071(8) . ?
P1 C14 1.850(2) . ?
P1 C16 1.852(2) . ?
P1 C19 1.855(2) . ?
P2 C15 1.829(2) . ?
P2 C25 1.843(2) . ?
P2 C22 1.849(2) . ?
O1 C7 1.365(2) . ?
O2 C11 1.377(2) . ?
O2 C7 1.469(2) . ?
C1 C2 1.396(2) . ?
C1 C6 1.400(3) . ?
C2 C3 1.385(3) . ?
C2 C7 1.509(3) . ?
C3 C4 1.385(3) . ?
C4 C5 1.376(3) . ?
C5 C6 1.386(3) . ?
C7 C8 1.539(3) . ?
C8 C12 1.525(3) . ?
C8 C9 1.524(3) . ?
C9 C10 1.488(3) . ?
C10 C11 1.317(3) . ?
C11 C13 1.493(3) . ?
C14 C15 1.523(3) . ?
C16 C17 1.528(3) . ?
C16 C18 1.528(3) . ?
C19 C21 1.515(3) . ?
C19 C20 1.523(3) . ?
C22 C23 1.505(4) . ?
C22 C24 1.526(3) . ?
C25 C26 1.516(3) . ?
C25 C27 1.527(3) . ?

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
O1 Ni1 C1 86.16(7) . . ?
O1 Ni1 P1 173.33(4) . . ?
C1 Ni1 P1 100.36(6) . . ?
O1 Ni1 P2 84.84(5) . . ?
C1 Ni1 P2 170.38(6) . . ?
P1 Ni1 P2 88.56(3) . . ?
C14 P1 C16 101.54(10) . . ?
C14 P1 C19 103.01(10) . . ?
C16 P1 C19 103.56(10) . . ?
C14 P1 Ni1 108.37(7) . . ?
C16 P1 Ni1 118.84(7) . . ?
C19 P1 Ni1 119.11(8) . . ?
C15 P2 C25 104.40(10) . . ?
C15 P2 C22 106.52(12) . . ?
C25 P2 C22 104.13(11) . . ?
C15 P2 Ni1 109.90(7) . . ?
C25 P2 Ni1 118.56(8) . . ?
C22 P2 Ni1 112.40(8) . . ?
C7 O1 Ni1 117.70(11) . . ?
C11 O2 C7 115.85(15) . . ?
C2 C1 C6 115.44(17) . . ?
C2 C1 Ni1 110.29(13) . . ?
C6 C1 Ni1 134.23(14) . . ?
C3 C2 C1 122.31(17) . . ?
C3 C2 C7 121.92(17) . . ?
C1 C2 C7 115.62(16) . . ?
C4 C3 C2 120.34(19) . . ?
C5 C4 C3 119.14(19) . . ?
C4 C5 C6 119.81(19) . . ?
C5 C6 C1 122.91(18) . . ?
O1 C7 O2 109.45(14) . . ?
O1 C7 C2 109.89(15) . . ?
O2 C7 C2 105.95(15) . . ?
O1 C7 C8 110.72(15) . . ?
O2 C7 C8 107.67(14) . . ?
C2 C7 C8 112.99(16) . . ?
C12 C8 C9 111.41(17) . . ?
C12 C8 C7 111.59(16) . . ?
C9 C8 C7 108.65(16) . . ?
C10 C9 C8 109.92(18) . . ?
C11 C10 C9 122.60(19) . . ?
C10 C11 O2 123.86(19) . . ?
C10 C11 C13 125.5(2) . . ?
O2 C11 C13 110.65(19) . . ?
C15 C14 P1 112.96(14) . . ?
C14 C15 P2 109.79(14) . . ?
C17 C16 C18 111.18(19) . . ?
C17 C16 P1 110.95(15) . . ?
C18 C16 P1 114.02(15) . . ?
C21 C19 C20 109.4(2) . . ?
C21 C19 P1 114.01(16) . . ?
C20 C19 P1 110.89(15) . . ?
C23 C22 C24 110.9(2) . . ?
C23 C22 P2 111.83(17) . . ?
C24 C22 P2 114.21(19) . . ?
C26 C25 C27 109.8(2) . . ?
C26 C25 P2 110.43(16) . . ?
C27 C25 P2 113.13(16) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        30.01
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.064
#======END