# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2012


data_global
_journal_name_full               'Dalton Trans.'
_journal_coden_cambridge         0222
_journal_year                    ?
_journal_volume                  ?
_journal_page_first              ?
loop_
_publ_author_name
_publ_author_address
M.Grzywa Grzywa
D.Denysenko Dmytro
J.Hanss
;
Institute of Physics,
Chair of Solid State and Material Science
Augsburg University
Universitaetsstrasse 1,
D-86135 Augsburg,
Germany
;
E.-W.Scheidt Hanss
W.Scherer Ernst-Wilhelm
M.Weil Wolfgang
D.Volkmer
;
Institute of Physics,
Chair of Chemical Physics,
Augsburg University,
Universitaetsstrasse 1,
D-86135 Augsburg,
Germany
;
_publ_contact_author_address     
;
Institute of Physics,
Chair of Solid State and Material Science
Augsburg University
Universitaetsstrasse 1,
D-86135 Augsburg,
Germany
;
_publ_contact_author_email       dirk.volkmer@physik.uni-augsburg.de
_publ_contact_author_fax         '+49 (0)821 598 5955'
_publ_contact_author_phone       '+49 (0)821 598 3006'
#TrackingRef '- CCDC 853111_revised.cif'

_publ_contact_author_name        'Professor Dirk Volkmer'

_publ_section_title              
;
CuN6 Jahn-Teller centers in coordination frameworks comprising
fully condensed Kuratowski-type secondary building units:
phase transitions and magneto-structural correlations'
;

data_alpha-Cu(ta)2
_database_code_depnum_ccdc_archive 'CCDC 853111'

_publ_section_references         
;
Bruker (2008). <i>APEX2, SAINT</i> and <i>SADABS</i>.
Bruker AXS Inc., Madison, Wisconsin, USA.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P.,
Taylor, R., Towler, M. & van de Streek, J. (2006). <i>J. Appl. Cryst.</i>
<b>39</b>, 453--457.

Sheldrick, G. M. (2008). <i>Acta Cryst.</i> A<b>64</b>, 112--122.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'Cu (C2 N3 H2)2'
_chemical_formula_sum            'C4 H4 Cu N6'
_chemical_melting_point          ?

_exptl_crystal_description       'distorted octahedral'
_exptl_crystal_colour            blue

_diffrn_ambient_temperature      295(2)
_chemical_formula_weight         199.67

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'I 41/a m d'
_symmetry_space_group_name_Hall  '-I 4bd 2'

_symmetry_int_tables_number      141
_chemical_absolute_configuration ?

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-y+1/4, x+3/4, z+1/4'
'y+1/4, -x+1/4, z+3/4'
'-x+1/2, y, -z+1/2'
'x, -y, -z'
'y+1/4, x+3/4, -z+1/4'
'-y+1/4, -x+1/4, -z+3/4'
'x+1/2, y+1/2, z+1/2'
'-x+1, -y+1/2, z+1'
'-y+3/4, x+5/4, z+3/4'
'y+3/4, -x+3/4, z+5/4'
'-x+1, y+1/2, -z+1'
'x+1/2, -y+1/2, -z+1/2'
'y+3/4, x+5/4, -z+3/4'
'-y+3/4, -x+3/4, -z+5/4'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'y-1/4, -x-3/4, -z-1/4'
'-y-1/4, x-1/4, -z-3/4'
'x-1/2, -y, z-1/2'
'-x, y, z'
'-y-1/4, -x-3/4, z-1/4'
'y-1/4, x-1/4, z-3/4'
'-x+1/2, -y+1/2, -z+1/2'
'x, y+1/2, -z'
'y+1/4, -x-1/4, -z+1/4'
'-y+1/4, x+1/4, -z-1/4'
'x, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'
'-y+1/4, -x-1/4, z+1/4'
'y+1/4, x+1/4, z-1/4'

_cell_length_a                   11.8447(7)
_cell_length_b                   11.8447(7)
_cell_length_c                   18.9782(13)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2662.6(3)
_cell_formula_units_Z            12
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    8954
_cell_measurement_theta_min      3.25
_cell_measurement_theta_max      26.42
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1188
_exptl_absorpt_coefficient_mu    2.409
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9183
_exptl_absorpt_correction_T_max  0.9717
_exptl_absorpt_process_details   '(<i>SADABS</i>, Bruker, 2008)'

_exptl_special_details           
;
?
;
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEXII CCD'
_diffrn_measurement_method       '\w- and \f-scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_interval_time  .
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            20893
_diffrn_reflns_av_R_equivalents  0.1713
_diffrn_reflns_av_sigmaI/netI    0.0836
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         3.24
_diffrn_reflns_theta_max         28.54
_reflns_number_total             928
_reflns_number_gt                616
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX2 (Bruker, 2008)'
_computing_cell_refinement       'SAINT (Bruker, 2008)'
_computing_data_reduction        'SAINT (Bruker, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'MERCURY (Macrae et al., 2006)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'

_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^)+(0.0000P)^2^+15.1859P] 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     SHELXL
_refine_ls_extinction_coef       0.0005(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         928
_refine_ls_number_parameters     47
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0475
_refine_ls_wR_factor_ref         0.1040
_refine_ls_wR_factor_gt          0.0908
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_restrained_S_all      1.088
_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
Cu2 Cu 0.0000 0.7500 0.1250 0.0148(4) Uani 1 8 d S . .
Cu1 Cu 0.0000 0.5000 0.0000 0.0201(3) Uani 1 4 d S . .
N4 N 0.0000 0.7500 0.0013(3) 0.0203(15) Uani 1 4 d S . .
N2 N 0.1218(3) 0.6282(3) 0.1250 0.0265(11) Uani 1 2 d S . .
N3 N 0.0000 0.3415(4) 0.0394(2) 0.0231(11) Uani 1 2 d S . .
N1 N 0.1284(3) 0.5447(3) 0.0779(2) 0.0345(10) Uani 1 1 d . . .
C1 C 0.0000 0.3070(5) 0.1062(3) 0.0356(17) Uani 1 2 d S . .
H1 H 0.0000 0.3533 0.1458 0.043 Uiso 1 2 calc SR . .
C2 C 0.2194(4) 0.4835(4) 0.0961(3) 0.0521(15) Uani 1 1 d . . .
H2 H 0.2455 0.4196 0.0728 0.063 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
Cu2 0.0137(5) 0.0137(5) 0.0170(7) 0.000 0.000 0.000
Cu1 0.0271(6) 0.0137(6) 0.0195(5) -0.0042(4) 0.000 0.000
N4 0.028(4) 0.011(3) 0.022(3) 0.000 0.000 0.000
N2 0.0270(17) 0.0270(17) 0.026(2) 0.0052(17) 0.0052(17) 0.011(2)
N3 0.033(3) 0.017(3) 0.019(2) -0.008(2) 0.000 0.000
N1 0.035(2) 0.025(2) 0.044(2) 0.0018(18) 0.0117(18) 0.0092(17)
C1 0.062(5) 0.024(3) 0.021(3) -0.002(3) 0.000 0.000
C2 0.037(3) 0.031(3) 0.088(4) -0.002(3) 0.008(3) 0.014(2)

_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
Cu2 N2 2.040(4) 20_666 ?
Cu2 N2 2.040(4) 27_465 ?
Cu2 N2 2.040(4) 10_464 ?
Cu2 N2 2.040(4) . ?
Cu2 N4 2.348(6) 27_465 ?
Cu2 N4 2.348(6) . ?
Cu1 N3 2.021(5) . ?
Cu1 N3 2.021(5) 17_565 ?
Cu1 N1 2.186(4) 17_565 ?
Cu1 N1 2.186(4) 6_565 ?
Cu1 N1 2.186(4) . ?
Cu1 N1 2.186(4) 22 ?
N4 N3 1.330(5) 17_565 ?
N4 N3 1.330(5) 26 ?
N2 N1 1.336(4) 16_554 ?
N2 N1 1.336(4) . ?
N3 N4 1.330(5) 17_565 ?
N3 C1 1.333(7) . ?
N1 C2 1.343(6) . ?
C1 C1 1.351(12) 10_454 ?
C1 H1 0.9300 . ?
C2 C2 1.352(11) 16_554 ?
C2 H2 0.9300 . ?

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
N2 Cu2 N2 180.0 20_666 27_465 ?
N2 Cu2 N2 90.0 20_666 10_464 ?
N2 Cu2 N2 90.0 27_465 10_464 ?
N2 Cu2 N2 90.0 20_666 . ?
N2 Cu2 N2 90.0 27_465 . ?
N2 Cu2 N2 180.000(1) 10_464 . ?
N2 Cu2 N4 90.0 20_666 27_465 ?
N2 Cu2 N4 90.0 27_465 27_465 ?
N2 Cu2 N4 90.0 10_464 27_465 ?
N2 Cu2 N4 90.0 . 27_465 ?
N2 Cu2 N4 90.0 20_666 . ?
N2 Cu2 N4 90.0 27_465 . ?
N2 Cu2 N4 90.0 10_464 . ?
N2 Cu2 N4 90.0 . . ?
N4 Cu2 N4 180.0 27_465 . ?
N3 Cu1 N3 180.0(3) . 17_565 ?
N3 Cu1 N1 91.43(13) . 17_565 ?
N3 Cu1 N1 88.57(13) 17_565 17_565 ?
N3 Cu1 N1 91.43(13) . 6_565 ?
N3 Cu1 N1 88.57(13) 17_565 6_565 ?
N1 Cu1 N1 88.20(19) 17_565 6_565 ?
N3 Cu1 N1 88.57(13) . . ?
N3 Cu1 N1 91.43(13) 17_565 . ?
N1 Cu1 N1 180.00(15) 17_565 . ?
N1 Cu1 N1 91.80(19) 6_565 . ?
N3 Cu1 N1 88.57(13) . 22 ?
N3 Cu1 N1 91.43(13) 17_565 22 ?
N1 Cu1 N1 91.80(19) 17_565 22 ?
N1 Cu1 N1 180.0 6_565 22 ?
N1 Cu1 N1 88.20(19) . 22 ?
N3 N4 N3 109.1(6) 17_565 26 ?
N3 N4 Cu2 125.4(3) 17_565 . ?
N3 N4 Cu2 125.4(3) 26 . ?
N1 N2 N1 111.2(5) 16_554 . ?
N1 N2 Cu2 124.4(2) 16_554 . ?
N1 N2 Cu2 124.4(2) . . ?
N4 N3 C1 107.6(5) 17_565 . ?
N4 N3 Cu1 122.9(4) 17_565 . ?
C1 N3 Cu1 129.5(4) . . ?
N2 N1 C2 105.9(4) . . ?
N2 N1 Cu1 126.2(3) . . ?
C2 N1 Cu1 127.0(3) . . ?
N3 C1 C1 107.8(3) . 10_454 ?
N3 C1 H1 126.1 . . ?
C1 C1 H1 126.1 10_454 . ?
N1 C2 C2 108.5(3) . 16_554 ?
N1 C2 H2 125.8 . . ?
C2 C2 H2 125.8 16_554 . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        28.54
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.507
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.117