# Supplementary Material (ESI) for PCCP
# This journal is (c) the Owner Societies 2009

data_global
_journal_name_full               Phys.Chem.Chem.Phys.(PCCP)

_journal_coden_Cambridge         1326

_publ_contact_author_name        'Davide Barreca'
_publ_contact_author_email       DAVIDE.BARRECA@UNIPD.IT

_publ_section_title              
;
An integrated experimental and theoretical investigation
on Cu(hfa)2 TMEDA: structure, bonding and reactivity
;
loop_
_publ_author_name
'Davide Barreca'
'Giuliano Bandoli'
'Anjana Devi'
'Roland Fischer'
'Ettore Fois'
'Aldo Gamba'
;
A.Gasparotto
;
'Roberta Seraglia'
'Gloria Tabacchi'
'Eugenio Tondello'
'Manuela Winter'

# Attachment 'Cu_hfa_2_tmeda_revised.cif'

data_CU(hfa)2_tmeda_1
_database_code_depnum_ccdc_archive 'CCDC 722516'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H18 Cu F12 N2 O4'
_chemical_formula_weight         593.86

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Fdd2

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z'
'x+1/4, -y+1/4, z+1/4'
'-x+1/4, y+1/4, z+1/4'
'x, y+1/2, z+1/2'
'-x, -y+1/2, z+1/2'
'x+1/4, -y+3/4, z+3/4'
'-x+1/4, y+3/4, z+3/4'
'x+1/2, y, z+1/2'
'-x+1/2, -y, z+1/2'
'x+3/4, -y+1/4, z+3/4'
'-x+3/4, y+1/4, z+3/4'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'x+3/4, -y+3/4, z+1/4'
'-x+3/4, y+3/4, z+1/4'

_cell_length_a                   17.7404(6)
_cell_length_b                   26.0745(11)
_cell_length_c                   9.8300(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     4547.1(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    108(2)
_cell_measurement_reflns_used    1967
_cell_measurement_theta_min      2.588
_cell_measurement_theta_max      36.546

_exptl_crystal_description       prism
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.735
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2376
_exptl_absorpt_coefficient_mu    1.084
_exptl_absorpt_correction_type   'numeric analytical'
_exptl_absorpt_correction_T_min  0.7809
_exptl_absorpt_correction_T_max  0.8993
_exptl_absorpt_process_details   'Gaussian face-indexed'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      108(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'Enhance (Mo) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Sapphire2-CCD, Oxford Diffraction'
_diffrn_measurement_method       '407 images at 1.0 deg. in \w and 25 sec.'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6081
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_sigmaI/netI    0.0684
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.88
_diffrn_reflns_theta_max         27.59
_reflns_number_total             2606
_reflns_number_gt                1926
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'CrysAlis CCD 1.171.13, Oxford Diffraction'
_computing_cell_refinement       'CrysAlis RED 1.171.13, Oxford Diffraction'
_computing_data_reduction        'CrysAlis RED 1.171.13, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    SHELXS-97
_computing_publication_material  SHELXS-97

_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.
Restraints of respectively 1.32(0.01) and 1.51(0.005)\%A were used for the
C21-F22 and C1-C1_$1(-x,-y,z), the former being due to librational motion,
the latter due to disorder in a five-membered ring.
;

_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^)+(0.0495P)^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   0.018(18)
_refine_ls_number_reflns         2606
_refine_ls_number_parameters     161
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0583
_refine_ls_R_factor_gt           0.0417
_refine_ls_wR_factor_ref         0.0930
_refine_ls_wR_factor_gt          0.0900
_refine_ls_goodness_of_fit_ref   0.911
_refine_ls_restrained_S_all      0.917
_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
Cu1 Cu 0.0000 0.0000 0.30017(6) 0.02095(16) Uani 1 2 d S . .
N1 N -0.0089(2) 0.0527(2) 0.1502(5) 0.0402(12) Uani 1 1 d . . .
O1 O -0.12951(13) -0.00444(11) 0.3421(2) 0.0302(7) Uani 1 1 d . . .
C7 C -0.1535(2) 0.00953(17) 0.4543(4) 0.0332(10) Uani 1 1 d . . .
C21 C -0.2316(2) -0.00973(19) 0.4927(4) 0.0351(11) Uani 1 1 d D . .
F21 F -0.22806(15) -0.05004(12) 0.5761(4) 0.0701(11) Uani 1 1 d . . .
F22 F -0.27174(14) -0.02307(16) 0.3877(3) 0.0737(10) Uani 1 1 d D . .
F23 F -0.27213(13) 0.02462(12) 0.5601(4) 0.0604(8) Uani 1 1 d . . .
C8 C -0.11774(19) 0.04186(15) 0.5518(5) 0.0330(9) Uani 1 1 d . . .
H8 H -0.1443 0.0502 0.6327 0.040 Uiso 1 1 calc R . .
C9 C -0.0464(2) 0.06150(16) 0.5336(4) 0.0314(9) Uani 1 1 d . . .
C41 C -0.0146(2) 0.09799(17) 0.6423(4) 0.0342(10) Uani 1 1 d . . .
F41 F 0.04859(17) 0.08063(13) 0.6936(3) 0.0666(9) Uani 1 1 d . . .
F42 F -0.06055(15) 0.10536(12) 0.7459(3) 0.0586(8) Uani 1 1 d . . .
F43 F -0.00067(17) 0.14328(12) 0.5872(3) 0.0669(10) Uani 1 1 d . . .
O2 O -0.00075(14) 0.05477(13) 0.4392(3) 0.0282(9) Uani 1 1 d . . .
C51 C -0.0769(2) 0.0855(2) 0.1629(7) 0.0611(16) Uani 1 1 d . . .
H51A H -0.0783 0.1100 0.0874 0.092 Uiso 1 1 calc R . .
H51B H -0.0752 0.1042 0.2493 0.092 Uiso 1 1 calc R . .
H51C H -0.1222 0.0639 0.1602 0.092 Uiso 1 1 calc R . .
C52 C 0.0564(2) 0.0875(2) 0.1515(7) 0.0578(16) Uani 1 1 d . . .
H52A H 0.1029 0.0675 0.1441 0.087 Uiso 1 1 calc R . .
H52B H 0.0569 0.1070 0.2367 0.087 Uiso 1 1 calc R . .
H52C H 0.0529 0.1113 0.0744 0.087 Uiso 1 1 calc R . .
C1 C -0.0174(5) 0.02580(18) 0.0238(6) 0.119(3) Uani 1 1 d D . .
H1B H 0.0057 0.0465 -0.0497 0.143 Uiso 1 1 calc R . .
H1A H -0.0718 0.0223 0.0033 0.143 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
Cu1 0.0166(3) 0.0313(3) 0.0150(2) 0.000 0.000 -0.0008(4)
N1 0.046(3) 0.049(3) 0.026(2) 0.009(2) -0.0063(19) -0.005(2)
O1 0.0183(11) 0.0457(18) 0.0265(14) -0.0024(15) 0.0011(9) -0.0016(12)
C7 0.025(2) 0.041(3) 0.033(2) 0.0051(19) 0.0002(16) 0.0038(19)
C21 0.028(2) 0.039(3) 0.038(2) 0.007(2) 0.0079(18) -0.0012(19)
F21 0.061(2) 0.0530(18) 0.096(3) 0.0316(19) 0.0048(19) -0.0104(14)
F22 0.0266(13) 0.136(3) 0.059(2) -0.008(2) 0.0071(13) -0.0296(17)
F23 0.0404(16) 0.0655(19) 0.075(2) -0.004(2) 0.0296(18) 0.0048(13)
C8 0.033(2) 0.039(2) 0.0265(19) -0.001(2) 0.010(2) 0.0037(17)
C9 0.035(2) 0.028(2) 0.030(2) 0.002(2) 0.0004(19) 0.0036(17)
C41 0.043(3) 0.035(3) 0.025(2) -0.0043(19) 0.0031(18) 0.003(2)
F41 0.0483(17) 0.092(2) 0.0594(19) -0.0249(19) -0.0165(14) 0.0057(18)
F42 0.0562(16) 0.081(2) 0.0392(15) -0.0179(15) 0.0123(13) 0.0025(15)
F43 0.116(3) 0.0407(17) 0.0441(16) -0.0047(13) 0.0004(17) -0.0257(16)
O2 0.0252(17) 0.033(2) 0.0268(18) -0.0068(15) 0.0052(13) -0.0069(13)
C51 0.031(2) 0.063(4) 0.089(4) 0.040(3) -0.018(3) -0.003(2)
C52 0.029(2) 0.058(3) 0.086(4) 0.047(3) 0.013(3) -0.003(2)
C1 0.227(10) 0.109(6) 0.020(3) 0.015(3) -0.021(4) -0.006(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
Cu1 O2 1.977(3) . ?
Cu1 O2 1.977(3) 2 ?
Cu1 N1 2.021(5) . ?
Cu1 N1 2.021(5) 2 ?
Cu1 O1 2.337(2) 2 ?
Cu1 O1 2.337(2) . ?
N1 C1 1.435(7) . ?
N1 C52 1.472(6) . ?
N1 C51 1.484(7) . ?
O1 C7 1.236(5) . ?
C7 C8 1.425(6) . ?
C7 C21 1.522(6) . ?
C21 F22 1.302(5) . ?
C21 F23 1.326(5) . ?
C21 F21 1.334(5) . ?
C8 C9 1.377(5) . ?
C8 H8 0.9500 . ?
C9 O2 1.244(5) . ?
C9 C41 1.538(6) . ?
C41 F41 1.310(5) . ?
C41 F42 1.318(5) . ?
C41 F43 1.322(5) . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?
C51 H51C 0.9800 . ?
C52 H52A 0.9800 . ?
C52 H52B 0.9800 . ?
C52 H52C 0.9800 . ?
C1 C1 1.480(5) 2 ?
C1 H1B 0.9900 . ?
C1 H1A 0.9900 . ?

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 Cu1 O2 92.5(2) . 2 ?
O2 Cu1 N1 90.72(12) . . ?
O2 Cu1 N1 174.76(16) 2 . ?
O2 Cu1 N1 174.76(16) . 2 ?
O2 Cu1 N1 90.72(12) 2 2 ?
N1 Cu1 N1 86.4(3) . 2 ?
O2 Cu1 O1 81.30(10) . 2 ?
O2 Cu1 O1 84.67(10) 2 2 ?
N1 Cu1 O1 99.90(13) . 2 ?
N1 Cu1 O1 94.90(14) 2 2 ?
O2 Cu1 O1 84.67(10) . . ?
O2 Cu1 O1 81.30(10) 2 . ?
N1 Cu1 O1 94.90(14) . . ?
N1 Cu1 O1 99.90(13) 2 . ?
O1 Cu1 O1 159.66(12) 2 . ?
C1 N1 C52 113.0(5) . . ?
C1 N1 C51 105.6(5) . . ?
C52 N1 C51 106.5(4) . . ?
C1 N1 Cu1 107.9(3) . . ?
C52 N1 Cu1 110.6(3) . . ?
C51 N1 Cu1 113.2(3) . . ?
C7 O1 Cu1 118.7(2) . . ?
O1 C7 C8 128.4(4) . . ?
O1 C7 C21 115.9(4) . . ?
C8 C7 C21 115.7(4) . . ?
F22 C21 F23 106.3(4) . . ?
F22 C21 F21 107.6(4) . . ?
F23 C21 F21 104.5(4) . . ?
F22 C21 C7 112.9(4) . . ?
F23 C21 C7 113.3(4) . . ?
F21 C21 C7 111.7(4) . . ?
C9 C8 C7 122.8(4) . . ?
C9 C8 H8 118.6 . . ?
C7 C8 H8 118.6 . . ?
O2 C9 C8 130.0(4) . . ?
O2 C9 C41 111.5(3) . . ?
C8 C9 C41 118.5(4) . . ?
F41 C41 F42 106.4(3) . . ?
F41 C41 F43 107.8(4) . . ?
F42 C41 F43 107.6(4) . . ?
F41 C41 C9 111.6(3) . . ?
F42 C41 C9 113.6(3) . . ?
F43 C41 C9 109.7(4) . . ?
C9 O2 Cu1 128.5(3) . . ?
N1 C51 H51A 109.5 . . ?
N1 C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?
N1 C51 H51C 109.5 . . ?
H51A C51 H51C 109.5 . . ?
H51B C51 H51C 109.5 . . ?
N1 C52 H52A 109.5 . . ?
N1 C52 H52B 109.5 . . ?
H52A C52 H52B 109.5 . . ?
N1 C52 H52C 109.5 . . ?
H52A C52 H52C 109.5 . . ?
H52B C52 H52C 109.5 . . ?
N1 C1 C1 113.6(4) . 2 ?
N1 C1 H1B 108.8 . . ?
C1 C1 H1B 108.8 2 . ?
N1 C1 H1A 108.8 . . ?
C1 C1 H1A 108.8 2 . ?
H1B C1 H1A 107.7 . . ?

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
O2 Cu1 N1 C1 -174.7(5) . . . . ?
O2 Cu1 N1 C1 -47(2) 2 . . . ?
N1 Cu1 N1 C1 9.7(4) 2 . . . ?
O1 Cu1 N1 C1 104.0(5) 2 . . . ?
O1 Cu1 N1 C1 -90.0(5) . . . . ?
O2 Cu1 N1 C52 61.2(4) . . . . ?
O2 Cu1 N1 C52 -171(2) 2 . . . ?
N1 Cu1 N1 C52 -114.4(4) 2 . . . ?
O1 Cu1 N1 C52 -20.0(4) 2 . . . ?
O1 Cu1 N1 C52 146.0(4) . . . . ?
O2 Cu1 N1 C51 -58.2(4) . . . . ?
O2 Cu1 N1 C51 70(2) 2 . . . ?
N1 Cu1 N1 C51 126.2(4) 2 . . . ?
O1 Cu1 N1 C51 -139.5(4) 2 . . . ?
O1 Cu1 N1 C51 26.5(4) . . . . ?
O2 Cu1 O1 C7 -25.6(3) . . . . ?
O2 Cu1 O1 C7 67.7(3) 2 . . . ?
N1 Cu1 O1 C7 -115.9(3) . . . . ?
N1 Cu1 O1 C7 156.9(3) 2 . . . ?
O1 Cu1 O1 C7 20.8(3) 2 . . . ?
Cu1 O1 C7 C8 19.9(6) . . . . ?
Cu1 O1 C7 C21 -160.9(3) . . . . ?
O1 C7 C21 F22 -22.0(6) . . . . ?
C8 C7 C21 F22 157.4(4) . . . . ?
O1 C7 C21 F23 -142.8(4) . . . . ?
C8 C7 C21 F23 36.5(5) . . . . ?
O1 C7 C21 F21 99.5(5) . . . . ?
C8 C7 C21 F21 -81.2(5) . . . . ?
O1 C7 C8 C9 -2.3(7) . . . . ?
C21 C7 C8 C9 178.5(4) . . . . ?
C7 C8 C9 O2 -2.3(7) . . . . ?
C7 C8 C9 C41 177.3(4) . . . . ?
O2 C9 C41 F41 -58.4(5) . . . . ?
C8 C9 C41 F41 122.0(4) . . . . ?
O2 C9 C41 F42 -178.6(4) . . . . ?
C8 C9 C41 F42 1.8(6) . . . . ?
O2 C9 C41 F43 61.0(5) . . . . ?
C8 C9 C41 F43 -118.6(4) . . . . ?
C8 C9 O2 Cu1 -17.4(7) . . . . ?
C41 C9 O2 Cu1 163.0(3) . . . . ?
O2 Cu1 O2 C9 -56.1(4) 2 . . . ?
N1 Cu1 O2 C9 119.8(4) . . . . ?
N1 Cu1 O2 C9 176(2) 2 . . . ?
O1 Cu1 O2 C9 -140.3(4) 2 . . . ?
O1 Cu1 O2 C9 24.9(4) . . . . ?
C52 N1 C1 C1 95.2(10) . . . 2 ?
C51 N1 C1 C1 -148.8(9) . . . 2 ?
Cu1 N1 C1 C1 -27.4(11) . . . 2 ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        27.59
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.698
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.087