# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2013

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_WOFOUR-1-Ni

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25.33 H22 N4.67 Ni O8.67 W'
_chemical_formula_weight         773.04

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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -5.4734 5.5774 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           trigonal
_symmetry_space_group_name_H-M   R32

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x-y, -y, -z'
'-x, -x+y, -z'
'y, x, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'y+1/3, x+2/3, -z+2/3'

_cell_length_a                   21.1295(3)
_cell_length_b                   21.1295(3)
_cell_length_c                   18.0194(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     6967.06(18)
_cell_formula_units_Z            9
_cell_measurement_temperature    228(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       rod
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3402
_exptl_absorpt_coefficient_mu    7.982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2850
_exptl_absorpt_correction_T_max  0.5024
_exptl_absorpt_process_details   'SADABS; (Sheldrick, 2003)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      228(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  'BRUKER SMART APEXII CCD'
_diffrn_measurement_method       'omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            15543
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_av_sigmaI/netI    0.0193
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         6.86
_diffrn_reflns_theta_max         68.68
_reflns_number_total             2841
_reflns_number_gt                2834
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2010)'
_computing_cell_refinement       'APEX2 (Bruker, 2010); SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009);XPREP(Sheldrick,2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008); OLEX2 (2009)'
_computing_molecular_graphics    ?
_computing_publication_material  'APEX2 (Bruker, 2010)'

_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^)+(0.0352P)^2^+3.4705P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(5)
_refine_ls_number_reflns         2841
_refine_ls_number_parameters     195
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0188
_refine_ls_R_factor_gt           0.0187
_refine_ls_wR_factor_ref         0.0488
_refine_ls_wR_factor_gt          0.0488
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_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
W1 W 0.0000 0.207146(8) 0.5000 0.01656(7) Uani 1 2 d S . .
Ni1 Ni 0.04860(3) 0.3333 0.3333 0.01192(14) Uani 1 2 d S . .
O2 O 0.01578(12) 0.26377(12) 0.42148(11) 0.0223(5) Uani 1 1 d . . .
N1 N 0.60851(15) 0.60474(17) 0.62043(12) 0.0196(5) Uani 1 1 d . . .
N2 N 0.15156(14) 0.39646(15) 0.38506(15) 0.0198(5) Uani 1 1 d . . .
C11 C 0.58562(19) 0.6371(2) 0.57200(17) 0.0237(6) Uani 1 1 d . . .
H11 H 0.6193 0.6844 0.5554 0.028 Uiso 1 1 calc R . .
C9 C 0.48797(19) 0.5007(2) 0.6184(2) 0.0298(7) Uani 1 1 d . . .
H9 H 0.4554 0.4536 0.6361 0.036 Uiso 1 1 calc R . .
C2 C 0.2453(2) 0.4001(2) 0.4631(2) 0.0372(9) Uani 1 1 d . . .
H2 H 0.2616 0.3744 0.4927 0.045 Uiso 1 1 calc R . .
C8 C 0.46451(19) 0.5338(2) 0.56706(18) 0.0285(7) Uani 1 1 d . . .
C1 C 0.1789(2) 0.3632(2) 0.4274(2) 0.0293(7) Uani 1 1 d . . .
H1 H 0.1512 0.3122 0.4327 0.035 Uiso 1 1 calc R . .
C5 C 0.1926(2) 0.4693(2) 0.3786(2) 0.0295(7) Uani 1 1 d . . .
H5 H 0.1748 0.4938 0.3493 0.035 Uiso 1 1 calc R . .
C3 C 0.2878(2) 0.4748(2) 0.4557(2) 0.0371(9) Uani 1 1 d . . .
C12 C 0.51517(19) 0.6045(2) 0.54532(19) 0.0291(7) Uani 1 1 d . . .
H12 H 0.5014 0.6300 0.5124 0.035 Uiso 1 1 calc R . .
O1 O -0.07715(17) 0.12021(15) 0.48292(17) 0.0420(7) Uani 1 1 d . . .
C7 C 0.3897(2) 0.4926(2) 0.5377(2) 0.0378(9) Uani 1 1 d . . .
H7 H 0.3599 0.4446 0.5550 0.045 Uiso 1 1 calc R . .
C6 C 0.3610(2) 0.5180(2) 0.4888(3) 0.0429(10) Uani 1 1 d . . .
H6 H 0.3894 0.5671 0.4742 0.051 Uiso 1 1 calc R . .
C4 C 0.2594(2) 0.5100(2) 0.4125(2) 0.0415(9) Uani 1 1 d . . .
H4 H 0.2857 0.5611 0.4069 0.050 Uiso 1 1 calc R . .
C10 C 0.55956(19) 0.53763(19) 0.64311(19) 0.0256(7) Uani 1 1 d . . .
H10 H 0.5744 0.5143 0.6776 0.031 Uiso 1 1 calc R . .
O3 O 0.3762(5) 0.5749(6) 0.3054(5) 0.058(3) Uani 0.33 1 d P . .
N5 N 0.3333 0.6667 0.5462(8) 0.137(5) Uani 1 3 d S . .
O6 O 0.3109(5) 0.3269(6) 0.6237(5) 0.081(3) Uiso 0.50 1 d P . .
O7 O 0.3685(8) 0.6487(8) 0.2732(7) 0.073(3) Uiso 0.33 1 d P . .
O8 O -0.2148(4) -0.0028(4) 0.4723(5) 0.066(2) Uiso 0.50 1 d P . .
O9 O 0.2426(7) 0.2433(7) 0.6268(7) 0.099(3) Uiso 0.50 1 d P . .
O4 O 0.3333 0.6071(9) 0.1667 0.075(5) Uiso 0.33 2 d SP . .
C13 C 0.3014(19) 0.6121(17) 0.5904(16) 0.110(8) Uiso 0.33 1 d P . .
C14 C 0.266(2) 0.548(2) 0.642(2) 0.162(14) Uiso 0.33 1 d P . .
H14A H 0.2660 0.5062 0.6196 0.244 Uiso 0.33 1 calc PR . .
H14B H 0.2158 0.5359 0.6515 0.244 Uiso 0.33 1 calc PR . .
H14C H 0.2926 0.5600 0.6885 0.244 Uiso 0.33 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
W1 0.02252(11) 0.01585(8) 0.01352(9) 0.00007(3) 0.00015(7) 0.01126(5)
Ni1 0.0113(3) 0.0167(3) 0.0096(3) -0.0016(2) -0.00081(12) 0.00833(16)
O2 0.0254(12) 0.0295(11) 0.0130(9) -0.0009(8) 0.0013(8) 0.0146(10)
N1 0.0145(13) 0.0274(15) 0.0176(10) -0.0055(11) -0.0048(11) 0.0110(10)
N2 0.0125(12) 0.0247(14) 0.0215(12) -0.0029(10) -0.0041(10) 0.0089(11)
C11 0.0215(17) 0.0280(18) 0.0223(14) 0.0000(14) -0.0038(13) 0.0127(14)
C9 0.0206(17) 0.0265(18) 0.0355(18) -0.0008(15) -0.0093(14) 0.0066(15)
C2 0.0274(19) 0.035(2) 0.048(2) 0.0016(17) -0.0189(18) 0.0150(17)
C8 0.0195(17) 0.0339(18) 0.0301(15) -0.0034(14) -0.0087(14) 0.0117(15)
C1 0.0200(16) 0.0240(17) 0.0392(18) 0.0020(14) -0.0097(14) 0.0076(14)
C5 0.0267(18) 0.0268(17) 0.0356(18) -0.0008(14) -0.0121(14) 0.0138(15)
C3 0.0236(19) 0.034(2) 0.048(2) -0.0036(17) -0.0167(17) 0.0104(16)
C12 0.0232(18) 0.0358(19) 0.0280(16) 0.0014(14) -0.0095(14) 0.0145(16)
O1 0.0483(17) 0.0231(13) 0.0490(15) -0.0040(12) -0.0043(13) 0.0137(13)
C7 0.0215(18) 0.038(2) 0.045(2) -0.0034(17) -0.0150(16) 0.0076(16)
C6 0.0260(19) 0.0320(19) 0.060(3) -0.0035(18) -0.0225(18) 0.0063(15)
C4 0.0293(19) 0.0254(18) 0.060(2) -0.0021(16) -0.0225(18) 0.0066(15)
C10 0.0233(17) 0.0277(17) 0.0253(16) 0.0022(14) -0.0075(14) 0.0123(15)
O3 0.046(5) 0.074(7) 0.047(5) 0.002(5) 0.020(4) 0.024(5)
N5 0.153(9) 0.153(9) 0.104(10) 0.000 0.000 0.077(4)

_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
W1 O1 1.770(3) 5_556 ?
W1 O1 1.770(3) . ?
W1 O2 1.774(2) . ?
W1 O2 1.774(2) 5_556 ?
Ni1 O2 2.036(2) . ?
Ni1 O2 2.036(2) 16 ?
Ni1 N2 2.116(3) . ?
Ni1 N2 2.117(3) 16 ?
Ni1 N1 2.131(3) 13_444 ?
Ni1 N1 2.131(3) 4_566 ?
N1 C10 1.334(5) . ?
N1 C11 1.339(4) . ?
N1 Ni1 2.131(3) 7 ?
N2 C5 1.341(5) . ?
N2 C1 1.347(5) . ?
C11 C12 1.377(5) . ?
C11 H11 0.9400 . ?
C9 C10 1.384(5) . ?
C9 C8 1.391(5) . ?
C9 H9 0.9400 . ?
C2 C3 1.378(6) . ?
C2 C1 1.378(5) . ?
C2 H2 0.9400 . ?
C8 C12 1.390(5) . ?
C8 C7 1.470(5) . ?
C1 H1 0.9400 . ?
C5 C4 1.375(5) . ?
C5 H5 0.9400 . ?
C3 C4 1.402(6) . ?
C3 C6 1.473(5) . ?
C12 H12 0.9400 . ?
C7 C6 1.326(6) . ?
C7 H7 0.9400 . ?
C6 H6 0.9400 . ?
C4 H4 0.9400 . ?
C10 H10 0.9400 . ?
O3 O7 1.747(18) . ?
N5 C13 1.28(3) . ?
N5 C13 1.28(3) 3_565 ?
N5 C13 1.28(3) 2_665 ?
O6 O9 1.631(16) . ?
O6 O6 1.753(19) 11_556 ?
O7 O7 1.71(2) 2_665 ?
O7 O7 1.71(2) 3_565 ?
O8 O8 1.004(17) 4_556 ?
C13 C14 1.50(5) . ?
C13 C13 1.74(5) 2_665 ?
C13 C13 1.74(5) 3_565 ?
C14 H14A 0.9700 . ?
C14 H14B 0.9700 . ?
C14 H14C 0.9700 . ?

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 W1 O1 109.5(2) 5_556 . ?
O1 W1 O2 110.13(13) 5_556 . ?
O1 W1 O2 109.05(12) . . ?
O1 W1 O2 109.05(12) 5_556 5_556 ?
O1 W1 O2 110.13(13) . 5_556 ?
O2 W1 O2 109.01(14) . 5_556 ?
O2 Ni1 O2 177.67(13) . 16 ?
O2 Ni1 N2 89.04(10) . . ?
O2 Ni1 N2 89.31(10) 16 . ?
O2 Ni1 N2 89.30(10) . 16 ?
O2 Ni1 N2 89.04(10) 16 16 ?
N2 Ni1 N2 89.07(15) . 16 ?
O2 Ni1 N1 89.30(10) . 13_444 ?
O2 Ni1 N1 92.45(10) 16 13_444 ?
N2 Ni1 N1 176.32(10) . 13_444 ?
N2 Ni1 N1 94.20(10) 16 13_444 ?
O2 Ni1 N1 92.45(10) . 4_566 ?
O2 Ni1 N1 89.30(9) 16 4_566 ?
N2 Ni1 N1 94.20(10) . 4_566 ?
N2 Ni1 N1 176.32(10) 16 4_566 ?
N1 Ni1 N1 82.59(13) 13_444 4_566 ?
W1 O2 Ni1 172.17(13) . . ?
C10 N1 C11 117.1(3) . . ?
C10 N1 Ni1 123.6(2) . 7 ?
C11 N1 Ni1 118.9(2) . 7 ?
C5 N2 C1 116.6(3) . . ?
C5 N2 Ni1 123.8(2) . . ?
C1 N2 Ni1 119.6(2) . . ?
N1 C11 C12 123.2(3) . . ?
N1 C11 H11 118.4 . . ?
C12 C11 H11 118.4 . . ?
C10 C9 C8 119.7(3) . . ?
C10 C9 H9 120.2 . . ?
C8 C9 H9 120.2 . . ?
C3 C2 C1 119.9(3) . . ?
C3 C2 H2 120.0 . . ?
C1 C2 H2 120.0 . . ?
C12 C8 C9 116.8(3) . . ?
C12 C8 C7 123.8(3) . . ?
C9 C8 C7 119.3(3) . . ?
N2 C1 C2 123.4(3) . . ?
N2 C1 H1 118.3 . . ?
C2 C1 H1 118.3 . . ?
N2 C5 C4 123.5(3) . . ?
N2 C5 H5 118.3 . . ?
C4 C5 H5 118.3 . . ?
C2 C3 C4 117.1(3) . . ?
C2 C3 C6 123.4(3) . . ?
C4 C3 C6 119.4(4) . . ?
C11 C12 C8 119.9(3) . . ?
C11 C12 H12 120.0 . . ?
C8 C12 H12 120.0 . . ?
C6 C7 C8 125.0(4) . . ?
C6 C7 H7 117.5 . . ?
C8 C7 H7 117.5 . . ?
C7 C6 C3 124.7(4) . . ?
C7 C6 H6 117.6 . . ?
C3 C6 H6 117.6 . . ?
C5 C4 C3 119.5(4) . . ?
C5 C4 H4 120.3 . . ?
C3 C4 H4 120.3 . . ?
N1 C10 C9 123.2(3) . . ?
N1 C10 H10 118.4 . . ?
C9 C10 H10 118.4 . . ?
C13 N5 C13 85(2) . 3_565 ?
C13 N5 C13 85(2) . 2_665 ?
C13 N5 C13 85(2) 3_565 2_665 ?
O9 O6 O6 109.1(8) . 11_556 ?
O7 O7 O7 60.003(4) 2_665 3_565 ?
O7 O7 O3 159.8(6) 2_665 . ?
O7 O7 O3 112.9(12) 3_565 . ?
N5 C13 C14 178(3) . . ?
N5 C13 C13 47.3(11) . 2_665 ?
C14 C13 C13 132(3) . 2_665 ?
N5 C13 C13 47.3(11) . 3_565 ?
C14 C13 C13 134(3) . 3_565 ?
C13 C13 C13 60.001(6) 2_665 3_565 ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?

_diffrn_measured_fraction_theta_max 0.989
_diffrn_reflns_theta_full        66.60
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.600
_refine_diff_density_min         -0.757
_refine_diff_density_rms         0.078
_database_code_depnum_ccdc_archive 'CCDC 946675'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_WOFOUR-1-Co

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H20 Co N4 O9.08 W'
_chemical_formula_weight         752.55

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'
Co Co -2.3653 3.6143 '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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -5.4734 5.5774 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           trigonal
_symmetry_space_group_name_H-M   R32

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x-y, -y, -z'
'-x, -x+y, -z'
'y, x, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'y+1/3, x+2/3, -z+2/3'

_cell_length_a                   21.3175(8)
_cell_length_b                   21.3175(8)
_cell_length_c                   17.9653(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     7070.3(5)
_cell_formula_units_Z            9
_cell_measurement_temperature    228(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       rod
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.591
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             3291
_exptl_absorpt_coefficient_mu    11.243
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2011
_exptl_absorpt_correction_T_max  0.6033
_exptl_absorpt_process_details   'SADABS; (Sheldrick, 2003)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      228(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  'BRUKER SMART APEXII CCD'
_diffrn_measurement_method       'omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17407
_diffrn_reflns_av_R_equivalents  0.0748
_diffrn_reflns_av_sigmaI/netI    0.0482
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         3.43
_diffrn_reflns_theta_max         68.22
_reflns_number_total             2866
_reflns_number_gt                2755
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2010)'
_computing_cell_refinement       'APEX2 (Bruker, 2010); SAINT (Bruker, 2009)'
_computing_data_reduction        'SAINT (Bruker, 2009);XPREP(Sheldrick,2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008); OLEX2 (2009)'
_computing_molecular_graphics    ?
_computing_publication_material  'APEX2 (Bruker, 2010)'
_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. 
 Disordered solvent refined as oxygen atoms. Water has been used during 
 synthesis
;

_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^)+(0.0286P)^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    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.074(8)
_refine_ls_number_reflns         2866
_refine_ls_number_parameters     212
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0286
_refine_ls_R_factor_gt           0.0271
_refine_ls_wR_factor_ref         0.0622
_refine_ls_wR_factor_gt          0.0617
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_restrained_S_all      0.999
_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
W1 W 0.3333 0.460015(13) 0.6667 0.01875(9) Uani 1 2 d S . .
Co1 Co 0.28334(5) 0.3333 0.8333 0.0142(2) Uani 1 2 d S . .
O1 O 0.3165(2) 0.40291(19) 0.74531(19) 0.0254(8) Uani 1 1 d . . .
O2 O 0.2569(3) 0.4698(3) 0.6477(3) 0.0458(11) Uani 1 1 d . . .
N1 N 0.3291(2) 0.2704(3) 0.7871(2) 0.0226(8) Uani 1 1 d . . .
N2 N 0.5757(2) 0.0641(2) 0.5532(3) 0.0231(10) Uani 1 1 d . . .
C4 C 0.3456(3) 0.1667(3) 0.7854(3) 0.0335(13) Uani 1 1 d . . .
H4 H 0.3309 0.1198 0.8029 0.040 Uiso 1 1 calc R . .
C1 C 0.3845(3) 0.3031(3) 0.7392(3) 0.0273(12) Uani 1 1 d . . .
H1 H 0.3982 0.3501 0.7228 0.033 Uiso 1 1 calc R . .
C8 C 0.5192(4) 0.1420(4) 0.6235(4) 0.0405(16) Uani 1 1 d . . .
C11 C 0.5177(3) 0.0314(3) 0.5969(4) 0.0332(14) Uani 1 1 d . . .
H11 H 0.4956 -0.0189 0.6037 0.040 Uiso 1 1 calc R . .
C9 C 0.5807(4) 0.1761(3) 0.5789(4) 0.0460(17) Uani 1 1 d . . .
H9 H 0.6045 0.2265 0.5718 0.055 Uiso 1 1 calc R . .
C2 C 0.4222(4) 0.2706(3) 0.7130(3) 0.0339(13) Uani 1 1 d . . .
H2 H 0.4613 0.2959 0.6802 0.041 Uiso 1 1 calc R . .
C3 C 0.4024(3) 0.2004(3) 0.7351(3) 0.0319(13) Uani 1 1 d . . .
C6 C 0.4364(4) 0.1596(4) 0.7061(4) 0.0424(16) Uani 1 1 d . . .
H6 H 0.4192 0.1125 0.7246 0.051 Uiso 1 1 calc R . .
C10 C 0.6066(3) 0.1352(3) 0.5449(4) 0.0343(14) Uani 1 1 d . . .
H10 H 0.6479 0.1589 0.5145 0.041 Uiso 1 1 calc R . .
C12 C 0.4884(4) 0.0682(4) 0.6330(4) 0.0399(16) Uani 1 1 d . . .
H12 H 0.4476 0.0430 0.6638 0.048 Uiso 1 1 calc R . .
C5 C 0.3110(3) 0.2036(3) 0.8095(3) 0.0277(12) Uani 1 1 d . . .
H5 H 0.2726 0.1803 0.8435 0.033 Uiso 1 1 calc R . .
C7 C 0.4886(4) 0.1838(4) 0.6568(4) 0.0477(18) Uani 1 1 d . . .
H7 H 0.5082 0.2321 0.6413 0.057 Uiso 1 1 calc R . .
O3 O 0.6834(13) 0.3006(12) 0.4366(11) 0.079(6) Uani 0.33 1 d P . .
O6 O 0.6589(7) 0.6818(7) 0.5434(9) 0.085(4) Uani 0.50 1 d P . .
O8 O 0.5449(7) 0.6642(8) 0.6380(8) 0.080(5) Uani 0.50 1 d P . .
O7 O 0.5770(11) 0.6665(10) 0.5405(10) 0.103(6) Uani 0.50 1 d P . .
O5 O 0.7247(10) 0.3333 0.3333 0.097(13) Uani 0.33 2 d SP . .
O4 O 0.7586(10) 0.2908(8) 0.4711(7) 0.056(4) Uani 0.33 1 d P . .
O10 O 0.3333 0.6667 0.278(3) 0.086(14) Uani 0.25 3 d SP . .
O9 O 0.352(4) 0.634(4) 0.234(3) 0.093(18) Uiso 0.13 1 d P . .

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
W1 0.02361(18) 0.01728(12) 0.01747(13) 0.00003(7) 0.00006(14) 0.01181(9)
Co1 0.0132(4) 0.0184(5) 0.0127(5) -0.0010(4) -0.0005(2) 0.0092(2)
O1 0.028(2) 0.0284(17) 0.0188(15) 0.0025(14) 0.0031(15) 0.0130(16)
O2 0.047(3) 0.046(3) 0.054(3) 0.002(2) -0.002(2) 0.030(2)
N1 0.0216(19) 0.031(3) 0.025(2) -0.005(2) 0.0012(16) 0.020(2)
N2 0.021(2) 0.027(2) 0.027(2) -0.0022(18) 0.0052(19) 0.0166(19)
C4 0.040(3) 0.031(3) 0.038(3) 0.002(3) 0.007(3) 0.023(3)
C1 0.027(3) 0.025(3) 0.030(3) -0.002(3) 0.007(2) 0.014(3)
C8 0.039(3) 0.038(3) 0.051(4) -0.006(3) 0.012(3) 0.024(3)
C11 0.030(3) 0.028(3) 0.043(3) 0.007(3) 0.013(3) 0.015(3)
C9 0.049(4) 0.031(3) 0.064(4) 0.000(3) 0.027(3) 0.025(3)
C2 0.037(3) 0.039(3) 0.032(3) 0.003(3) 0.012(3) 0.025(3)
C3 0.033(3) 0.033(3) 0.038(3) -0.008(2) 0.002(3) 0.023(3)
C6 0.047(4) 0.046(4) 0.049(4) -0.006(3) 0.009(3) 0.034(3)
C10 0.030(3) 0.029(3) 0.044(4) -0.001(3) 0.012(3) 0.015(3)
C12 0.035(3) 0.034(3) 0.055(4) 0.003(3) 0.025(3) 0.021(3)
C5 0.027(3) 0.028(3) 0.027(3) -0.003(2) 0.004(2) 0.014(2)
C7 0.050(4) 0.034(3) 0.069(5) -0.007(3) 0.019(4) 0.029(3)
O3 0.084(14) 0.079(14) 0.071(12) -0.034(11) -0.017(11) 0.038(12)
O6 0.059(8) 0.044(6) 0.139(13) 0.006(7) -0.009(8) 0.016(6)
O8 0.071(8) 0.042(6) 0.130(15) -0.011(11) -0.001(9) 0.030(7)
O7 0.131(16) 0.098(12) 0.087(11) 0.021(10) 0.040(11) 0.062(12)
O5 0.027(8) 0.023(10) 0.24(4) 0.001(16) 0.001(8) 0.011(5)
O4 0.077(11) 0.044(7) 0.038(7) -0.021(6) -0.001(8) 0.022(8)
O10 0.075(19) 0.075(19) 0.11(4) 0.000 0.000 0.037(9)

_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
W1 O2 1.777(5) . ?
W1 O2 1.777(5) 11_556 ?
W1 O1 1.780(3) 11_556 ?
W1 O1 1.780(3) . ?
Co1 O1 2.038(3) 16_556 ?
Co1 O1 2.038(3) . ?
Co1 N2 2.175(4) 10_456 ?
Co1 N2 2.175(4) 7_455 ?
Co1 N1 2.179(5) 16_556 ?
Co1 N1 2.179(5) . ?
N1 C5 1.337(8) . ?
N1 C1 1.342(7) . ?
N2 C10 1.324(8) . ?
N2 C11 1.331(8) . ?
N2 Co1 2.175(4) 13_544 ?
C4 C5 1.390(8) . ?
C4 C3 1.389(9) . ?
C4 H4 0.9400 . ?
C1 C2 1.380(8) . ?
C1 H1 0.9400 . ?
C8 C12 1.378(10) . ?
C8 C9 1.392(9) . ?
C8 C7 1.470(8) . ?
C11 C12 1.385(8) . ?
C11 H11 0.9400 . ?
C9 C10 1.386(8) . ?
C9 H9 0.9400 . ?
C2 C3 1.394(9) . ?
C2 H2 0.9400 . ?
C3 C6 1.477(8) . ?
C6 C7 1.310(10) . ?
C6 H6 0.9400 . ?
C10 H10 0.9400 . ?
C12 H12 0.9400 . ?
C5 H5 0.9400 . ?
C7 H7 0.9400 . ?
O3 O3 1.61(4) 3_665 ?
O3 O3 1.61(4) 2_655 ?
O6 O7 1.61(2) . ?
O6 O6 1.77(3) 6_556 ?
O8 O8 1.03(3) 10_566 ?
O10 O9 1.25(6) . ?
O10 O9 1.25(6) 3_565 ?
O10 O9 1.25(6) 2_665 ?
O9 O9 1.66(10) 2_665 ?
O9 O9 1.66(10) 3_565 ?

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
O2 W1 O2 109.6(3) . 11_556 ?
O2 W1 O1 108.8(2) . 11_556 ?
O2 W1 O1 110.4(2) 11_556 11_556 ?
O2 W1 O1 110.4(2) . . ?
O2 W1 O1 108.8(2) 11_556 . ?
O1 W1 O1 108.7(2) 11_556 . ?
O1 Co1 O1 178.0(2) 16_556 . ?
O1 Co1 N2 89.17(17) 16_556 10_456 ?
O1 Co1 N2 89.40(16) . 10_456 ?
O1 Co1 N2 89.40(16) 16_556 7_455 ?
O1 Co1 N2 89.17(16) . 7_455 ?
N2 Co1 N2 88.7(2) 10_456 7_455 ?
O1 Co1 N1 93.07(16) 16_556 16_556 ?
O1 Co1 N1 88.43(16) . 16_556 ?
N2 Co1 N1 175.89(16) 10_456 16_556 ?
N2 Co1 N1 94.77(16) 7_455 16_556 ?
O1 Co1 N1 88.43(16) 16_556 . ?
O1 Co1 N1 93.07(16) . . ?
N2 Co1 N1 94.77(16) 10_456 . ?
N2 Co1 N1 175.89(16) 7_455 . ?
N1 Co1 N1 81.9(2) 16_556 . ?
W1 O1 Co1 172.6(2) . . ?
C5 N1 C1 117.1(5) . . ?
C5 N1 Co1 124.1(3) . . ?
C1 N1 Co1 118.3(4) . . ?
C10 N2 C11 117.7(5) . . ?
C10 N2 Co1 122.9(4) . 13_544 ?
C11 N2 Co1 119.4(4) . 13_544 ?
C5 C4 C3 118.8(5) . . ?
C5 C4 H4 120.6 . . ?
C3 C4 H4 120.6 . . ?
N1 C1 C2 122.8(6) . . ?
N1 C1 H1 118.6 . . ?
C2 C1 H1 118.6 . . ?
C12 C8 C9 117.1(6) . . ?
C12 C8 C7 122.6(6) . . ?
C9 C8 C7 120.3(6) . . ?
N2 C11 C12 123.1(6) . . ?
N2 C11 H11 118.5 . . ?
C12 C11 H11 118.5 . . ?
C10 C9 C8 119.5(6) . . ?
C10 C9 H9 120.3 . . ?
C8 C9 H9 120.3 . . ?
C1 C2 C3 120.1(5) . . ?
C1 C2 H2 119.9 . . ?
C3 C2 H2 119.9 . . ?
C4 C3 C2 117.3(5) . . ?
C4 C3 C6 118.9(6) . . ?
C2 C3 C6 123.8(6) . . ?
C7 C6 C3 125.3(7) . . ?
C7 C6 H6 117.4 . . ?
C3 C6 H6 117.4 . . ?
N2 C10 C9 123.0(6) . . ?
N2 C10 H10 118.5 . . ?
C9 C10 H10 118.5 . . ?
C8 C12 C11 119.7(6) . . ?
C8 C12 H12 120.2 . . ?
C11 C12 H12 120.2 . . ?
N1 C5 C4 123.9(5) . . ?
N1 C5 H5 118.1 . . ?
C4 C5 H5 118.1 . . ?
C6 C7 C8 125.7(7) . . ?
C6 C7 H7 117.1 . . ?
C8 C7 H7 117.1 . . ?
O3 O3 O3 60.001(5) 3_665 2_655 ?
O7 O6 O6 109.6(13) . 6_556 ?
O9 O10 O9 84(5) . 3_565 ?
O9 O10 O9 84(5) . 2_665 ?
O9 O10 O9 84(5) 3_565 2_665 ?
O10 O9 O9 48(3) . 2_665 ?
O10 O9 O9 48(3) . 3_565 ?
O9 O9 O9 60.001(11) 2_665 3_565 ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        68.22
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.433
_refine_diff_density_min         -1.009
_refine_diff_density_rms         0.093
_database_code_depnum_ccdc_archive 'CCDC 946676'