##############################################################################
###                                                                        ###
###           Full Paper (Acta Crystallographica Section C)                ###
###                                                                        ###
##############################################################################
#                                                                            #
# This CIF contains the data in a paper accepted for publication in Acta     #
# Crystallographica Section C. It conforms to the editorial and technical    #
# requirements of Notes for Authors for Section C, and has been peer         #
# reviewed under the auspices of the IUCr Commission on Journals.            #
#                                                                            #
# Full details of the Crystallographic Information File format               #
# are given in the paper "The Crystallographic Information File (CIF):       #
# a New Standard Archive File for Crystallography" by S. R. Hall, F. H.      #
# Allen and I. D. Brown [Acta Cryst. (1991), A47, 655-685].                  #
#                                                                            #
# The current version of the core CIF dictionary is obtainable from          #
# ftp://ftp.iucr.org/pub/cif_core.dic. The current version number is 2.1.    #
#                                                                            #
# Software is freely available for graphical display of the structure(s) in  #
# this CIF.  For information consult the CIF home page http://www.iucr.org/  #
# cif/home.html                                                              #
#                                                                            #
#            Copyright International Union of Crystallography                #
#                                                                            #
##############################################################################
data_I
_audit_creation_method     SHELXL97
_chemical_name_systematic
;
copper cobalt nickel tetraselenide
;
_chemical_name_common     tyrrellite
_chemical_formula_moiety     'Co1.36 Cu Ni0.64 Se4'
_chemical_formula_sum     'Co1.36 Cu Ni0.64 Se4'
_chemical_formula_weight     497.06
_chemical_melting_point     ?
_symmetry_cell_setting     cubic
_symmetry_space_group_name_H-M     'F d -3 m'
_symmetry_space_group_name_Hall     '-F 4vw 2vw'
loop_
    _symmetry_equiv_pos_as_xyz
    'x, y, z'
    '-x+3/4, -y+1/4, z+1/2'
    '-x+1/4, y+1/2, -z+3/4'
    'x+1/2, -y+3/4, -z+1/4'
    'z, x, y'
    'z+1/2, -x+3/4, -y+1/4'
    '-z+3/4, -x+1/4, y+1/2'
    '-z+1/4, x+1/2, -y+3/4'
    'y, z, x'
    '-y+1/4, z+1/2, -x+3/4'
    'y+1/2, -z+3/4, -x+1/4'
    '-y+3/4, -z+1/4, x+1/2'
    'y+3/4, x+1/4, -z+1/2'
    '-y, -x, -z'
    'y+1/4, -x+1/2, z+3/4'
    '-y+1/2, x+3/4, z+1/4'
    'x+3/4, z+1/4, -y+1/2'
    '-x+1/2, z+3/4, y+1/4'
    '-x, -z, -y'
    'x+1/4, -z+1/2, y+3/4'
    'z+3/4, y+1/4, -x+1/2'
    'z+1/4, -y+1/2, x+3/4'
    '-z+1/2, y+3/4, x+1/4'
    '-z, -y, -x'
    'x, y+1/2, z+1/2'
    '-x+3/4, -y+3/4, z+1'
    '-x+1/4, y+1, -z+5/4'
    'x+1/2, -y+5/4, -z+3/4'
    'z, x+1/2, y+1/2'
    'z+1/2, -x+5/4, -y+3/4'
    '-z+3/4, -x+3/4, y+1'
    '-z+1/4, x+1, -y+5/4'
    'y, z+1/2, x+1/2'
    '-y+1/4, z+1, -x+5/4'
    'y+1/2, -z+5/4, -x+3/4'
    '-y+3/4, -z+3/4, x+1'
    'y+3/4, x+3/4, -z+1'
    '-y, -x+1/2, -z+1/2'
    'y+1/4, -x+1, z+5/4'
    '-y+1/2, x+5/4, z+3/4'
    'x+3/4, z+3/4, -y+1'
    '-x+1/2, z+5/4, y+3/4'
    '-x, -z+1/2, -y+1/2'
    'x+1/4, -z+1, y+5/4'
    'z+3/4, y+3/4, -x+1'
    'z+1/4, -y+1, x+5/4'
    '-z+1/2, y+5/4, x+3/4'
    '-z, -y+1/2, -x+1/2'
    'x+1/2, y, z+1/2'
    '-x+5/4, -y+1/4, z+1'
    '-x+3/4, y+1/2, -z+5/4'
    'x+1, -y+3/4, -z+3/4'
    'z+1/2, x, y+1/2'
    'z+1, -x+3/4, -y+3/4'
    '-z+5/4, -x+1/4, y+1'
    '-z+3/4, x+1/2, -y+5/4'
    'y+1/2, z, x+1/2'
    '-y+3/4, z+1/2, -x+5/4'
    'y+1, -z+3/4, -x+3/4'
    '-y+5/4, -z+1/4, x+1'
    'y+5/4, x+1/4, -z+1'
    '-y+1/2, -x, -z+1/2'
    'y+3/4, -x+1/2, z+5/4'
    '-y+1, x+3/4, z+3/4'
    'x+5/4, z+1/4, -y+1'
    '-x+1, z+3/4, y+3/4'
    '-x+1/2, -z, -y+1/2'
    'x+3/4, -z+1/2, y+5/4'
    'z+5/4, y+1/4, -x+1'
    'z+3/4, -y+1/2, x+5/4'
    '-z+1, y+3/4, x+3/4'
    '-z+1/2, -y, -x+1/2'
    'x+1/2, y+1/2, z'
    '-x+5/4, -y+3/4, z+1/2'
    '-x+3/4, y+1, -z+3/4'
    'x+1, -y+5/4, -z+1/4'
    'z+1/2, x+1/2, y'
    'z+1, -x+5/4, -y+1/4'
    '-z+5/4, -x+3/4, y+1/2'
    '-z+3/4, x+1, -y+3/4'
    'y+1/2, z+1/2, x'
    '-y+3/4, z+1, -x+3/4'
    'y+1, -z+5/4, -x+1/4'
    '-y+5/4, -z+3/4, x+1/2'
    'y+5/4, x+3/4, -z+1/2'
    '-y+1/2, -x+1/2, -z'
    'y+3/4, -x+1, z+3/4'
    '-y+1, x+5/4, z+1/4'
    'x+5/4, z+3/4, -y+1/2'
    '-x+1, z+5/4, y+1/4'
    '-x+1/2, -z+1/2, -y'
    'x+3/4, -z+1, y+3/4'
    'z+5/4, y+3/4, -x+1/2'
    'z+3/4, -y+1, x+3/4'
    '-z+1, y+5/4, x+1/4'
    '-z+1/2, -y+1/2, -x'
    '-x, -y, -z'
    'x-3/4, y-1/4, -z-1/2'
    'x-1/4, -y-1/2, z-3/4'
    '-x-1/2, y-3/4, z-1/4'
    '-z, -x, -y'
    '-z-1/2, x-3/4, y-1/4'
    'z-3/4, x-1/4, -y-1/2'
    'z-1/4, -x-1/2, y-3/4'
    '-y, -z, -x'
    'y-1/4, -z-1/2, x-3/4'
    '-y-1/2, z-3/4, x-1/4'
    'y-3/4, z-1/4, -x-1/2'
    '-y-3/4, -x-1/4, z-1/2'
    'y, x, z'
    '-y-1/4, x-1/2, -z-3/4'
    'y-1/2, -x-3/4, -z-1/4'
    '-x-3/4, -z-1/4, y-1/2'
    'x-1/2, -z-3/4, -y-1/4'
    'x, z, y'
    '-x-1/4, z-1/2, -y-3/4'
    '-z-3/4, -y-1/4, x-1/2'
    '-z-1/4, y-1/2, -x-3/4'
    'z-1/2, -y-3/4, -x-1/4'
    'z, y, x'
    '-x, -y+1/2, -z+1/2'
    'x-3/4, y+1/4, -z'
    'x-1/4, -y, z-1/4'
    '-x-1/2, y-1/4, z+1/4'
    '-z, -x+1/2, -y+1/2'
    '-z-1/2, x-1/4, y+1/4'
    'z-3/4, x+1/4, -y'
    'z-1/4, -x, y-1/4'
    '-y, -z+1/2, -x+1/2'
    'y-1/4, -z, x-1/4'
    '-y-1/2, z-1/4, x+1/4'
    'y-3/4, z+1/4, -x'
    '-y-3/4, -x+1/4, z'
    'y, x+1/2, z+1/2'
    '-y-1/4, x, -z-1/4'
    'y-1/2, -x-1/4, -z+1/4'
    '-x-3/4, -z+1/4, y'
    'x-1/2, -z-1/4, -y+1/4'
    'x, z+1/2, y+1/2'
    '-x-1/4, z, -y-1/4'
    '-z-3/4, -y+1/4, x'
    '-z-1/4, y, -x-1/4'
    'z-1/2, -y-1/4, -x+1/4'
    'z, y+1/2, x+1/2'
    '-x+1/2, -y, -z+1/2'
    'x-1/4, y-1/4, -z'
    'x+1/4, -y-1/2, z-1/4'
    '-x, y-3/4, z+1/4'
    '-z+1/2, -x, -y+1/2'
    '-z, x-3/4, y+1/4'
    'z-1/4, x-1/4, -y'
    'z+1/4, -x-1/2, y-1/4'
    '-y+1/2, -z, -x+1/2'
    'y+1/4, -z-1/2, x-1/4'
    '-y, z-3/4, x+1/4'
    'y-1/4, z-1/4, -x'
    '-y-1/4, -x-1/4, z'
    'y+1/2, x, z+1/2'
    '-y+1/4, x-1/2, -z-1/4'
    'y, -x-3/4, -z+1/4'
    '-x-1/4, -z-1/4, y'
    'x, -z-3/4, -y+1/4'
    'x+1/2, z, y+1/2'
    '-x+1/4, z-1/2, -y-1/4'
    '-z-1/4, -y-1/4, x'
    '-z+1/4, y-1/2, -x-1/4'
    'z, -y-3/4, -x+1/4'
    'z+1/2, y, x+1/2'
    '-x+1/2, -y+1/2, -z'
    'x-1/4, y+1/4, -z-1/2'
    'x+1/4, -y, z-3/4'
    '-x, y-1/4, z-1/4'
    '-z+1/2, -x+1/2, -y'
    '-z, x-1/4, y-1/4'
    'z-1/4, x+1/4, -y-1/2'
    'z+1/4, -x, y-3/4'
    '-y+1/2, -z+1/2, -x'
    'y+1/4, -z, x-3/4'
    '-y, z-1/4, x-1/4'
    'y-1/4, z+1/4, -x-1/2'
    '-y-1/4, -x+1/4, z-1/2'
    'y+1/2, x+1/2, z'
    '-y+1/4, x, -z-3/4'
    'y, -x-1/4, -z-1/4'
    '-x-1/4, -z+1/4, y-1/2'
    'x, -z-1/4, -y-1/4'
    'x+1/2, z+1/2, y'
    '-x+1/4, z, -y-3/4'
    '-z-1/4, -y+1/4, x-1/2'
    '-z+1/4, y, -x-3/4'
    'z, -y-1/4, -x-1/4'
    'z+1/2, y+1/2, x'
_cell_length_a     9.98850(10)
_cell_length_b     9.98850(10)
_cell_length_c     9.98850(10)
_cell_angle_alpha     90.00
_cell_angle_beta     90.00
_cell_angle_gamma     90.00
_cell_volume     996.55(2)
_cell_formula_units_Z     8
_cell_measurement_reflns_used     1008
_cell_measurement_theta_min     3.54
_cell_measurement_theta_max     44.13
_cell_measurement_temperature     293(2)
_exptl_crystal_description     block
_exptl_crystal_colour     black
_exptl_crystal_size_max     0.07
_exptl_crystal_size_mid     0.07
_exptl_crystal_size_min     0.06
_exptl_crystal_density_diffrn     6.627
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000     1757
_exptl_absorpt_coefficient_mu     40.123
_exptl_absorpt_correction_type     multi-scan
_exptl_absorpt_process_details     '(SADABS; Sheldrick, 2005)'
_exptl_absorpt_correction_T_min     0.1229
_exptl_absorpt_correction_T_max     0.1416
_exptl_special_details
;
 ?
;
_diffrn_ambient_temperature     293(2)
_diffrn_radiation_type     MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_source     'fine-focus sealed tube'
_diffrn_radiation_monochromator     graphite
_diffrn_measurement_device_type     'Bruker APEXII CCD area-detector'
_diffrn_measurement_method     'π and ω'
_diffrn_detector_area_resol_mean     ?
_diffrn_reflns_number     2566
_diffrn_reflns_av_R_equivalents     0.0304
_diffrn_reflns_av_sigmaI/netI     0.0169
_diffrn_reflns_theta_min     3.53
_diffrn_reflns_theta_max     44.78
_diffrn_reflns_theta_full     44.78
_diffrn_measured_fraction_theta_max     0.991
_diffrn_measured_fraction_theta_full     0.991
_diffrn_reflns_limit_h_min     -18
_diffrn_reflns_limit_h_max     19
_diffrn_reflns_limit_k_min     -18
_diffrn_reflns_limit_k_max     12
_diffrn_reflns_limit_l_min     -17
_diffrn_reflns_limit_l_max     11
_diffrn_standards_number     ?
_diffrn_standards_interval_count     ?
_diffrn_standards_interval_time     ?
_diffrn_standards_decay_%     ?
_refine_special_details
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_reflns_number_total     227
_reflns_number_gt     206
_reflns_threshold_expression     I>2σ(I)
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all     0.0169
_refine_ls_R_factor_gt     0.0139
_refine_ls_wR_factor_gt     0.0270
_refine_ls_wR_factor_ref     0.0275
_refine_ls_goodness_of_fit_ref     1.115
_refine_ls_restrained_S_all     1.115
_refine_ls_number_reflns     227
_refine_ls_number_parameters     9
_refine_ls_number_restraints     0
_refine_ls_weighting_scheme     calc
_refine_ls_weighting_details
       'calc w = 1/[σ²(Fo²)+(0.0086P)²+2.3104P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary     difmap
_refine_ls_shift/su_max     0.001
_refine_ls_shift/su_mean     0.000
_refine_diff_density_max     0.788
_refine_diff_density_min     -1.269
_refine_ls_extinction_method     'SHELXL97 (Sheldrick, 1997)'
_refine_ls_extinction_coef     0.00182(6)
_refine_ls_extinction_expression
                                  'Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^'
loop_
    _atom_type_symbol
    _atom_type_description
    _atom_type_scat_dispersion_real
    _atom_type_scat_dispersion_imag
    _atom_type_scat_source
    'Co' 'Co' 0.3494 0.9721
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'Ni' 'Ni' 0.3393 1.1124
                         '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'
    'Se' 'Se' -0.0929 2.2259
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_computing_data_collection     'APEX2 (Bruker, 2003)'
_computing_cell_refinement     'SAINT (Bruker, 2005)'
_computing_data_reduction     SAINT
_computing_structure_solution     'SHELXS97 (Sheldrick, 1997)'
_computing_structure_refinement     'SHELXL97 (Sheldrick, 1997)'
_computing_molecular_graphics     'Please provide missing information'
_computing_publication_material     'SHELXTL (Bruker, 1997)'
loop_
    _atom_site_type_symbol
    _atom_site_label
    _atom_site_fract_x
    _atom_site_fract_y
    _atom_site_fract_z
    _atom_site_U_iso_or_equiv
    _atom_site_adp_type
    _atom_site_calc_flag
    _atom_site_refinement_flags
    _atom_site_occupancy
    _atom_site_disorder_assembly
    _atom_site_disorder_group
    Cu Cu1 0.1250 0.1250 0.1250 0.01020(11) Uani d S 1 . .
    Co Co1 0.5000 0.0000 0.0000 0.00624(11) Uani d SP 0.68(6) . .
    Ni Ni1 0.5000 0.0000 0.0000 0.00624(11) Uani d SP 0.32(6) . .
    Se Se1 0.261923(14) -0.011923(14) -0.011923(14) 0.00705(6) Uani d S 1 . .
loop_
    _atom_site_aniso_label
    _atom_site_aniso_U_11
    _atom_site_aniso_U_22
    _atom_site_aniso_U_33
    _atom_site_aniso_U_12
    _atom_site_aniso_U_13
    _atom_site_aniso_U_23
    Cu1 0.01020(11) 0.01020(11) 0.01020(11) 0.000 0.000 0.000
    Co1 0.00624(11) 0.00624(11) 0.00624(11) -0.00031(6) -0.00031(6) -0.00031(6)
    Ni1 0.00624(11) 0.00624(11) 0.00624(11) -0.00031(6) -0.00031(6) -0.00031(6)
    Se1 0.00705(6) 0.00705(6) 0.00705(6) 0.00027(4) 0.00027(4) -0.00027(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_site_symmetry_2
    _geom_bond_distance
    _geom_bond_publ_flag
    Cu1 Se1 27_544 2.3688(2) ?
    Cu1 Se1 50_454 2.3688(2) ?
    Cu1 Se1 76_445 2.3688(2) ?
    Cu1 Se1 . 2.3688(2) ?
    Co1 Se1 75_544 2.38399(13) ?
    Co1 Se1 26_544 2.38399(13) ?
    Co1 Se1 . 2.38399(13) ?
    Co1 Se1 171_556 2.38399(13) ?
    Co1 Se1 122_655 2.38399(13) ?
    Co1 Se1 97_655 2.38399(13) ?
loop_
    _geom_angle_atom_site_label_1
    _geom_angle_atom_site_label_2
    _geom_angle_atom_site_label_3
    _geom_angle_site_symmetry_1
    _geom_angle_site_symmetry_3
    _geom_angle
    _geom_angle_publ_flag
    Se1 Cu1 Se1 27_544 50_454 109.5 ?
    Se1 Cu1 Se1 27_544 76_445 109.5 ?
    Se1 Cu1 Se1 50_454 76_445 109.5 ?
    Se1 Cu1 Se1 27_544 . 109.5 ?
    Se1 Cu1 Se1 50_454 . 109.5 ?
    Se1 Cu1 Se1 76_445 . 109.5 ?
    Se1 Co1 Se1 75_544 26_544 84.137(7) ?
    Se1 Co1 Se1 75_544 . 84.137(7) ?
    Se1 Co1 Se1 26_544 . 84.137(7) ?
    Se1 Co1 Se1 75_544 171_556 180.0 ?
    Se1 Co1 Se1 26_544 171_556 95.863(7) ?
    Se1 Co1 Se1 . 171_556 95.863(7) ?
    Se1 Co1 Se1 75_544 122_655 95.863(7) ?
    Se1 Co1 Se1 26_544 122_655 180.0 ?
    Se1 Co1 Se1 . 122_655 95.863(7) ?
    Se1 Co1 Se1 171_556 122_655 84.137(7) ?
    Se1 Co1 Se1 75_544 97_655 95.863(7) ?
    Se1 Co1 Se1 26_544 97_655 95.863(7) ?
    Se1 Co1 Se1 . 97_655 180.0 ?
    Se1 Co1 Se1 171_556 97_655 84.137(7) ?
    Se1 Co1 Se1 122_655 97_655 84.137(7) ?
    Cu1 Se1 Ni1 . 75_544 121.213(5) ?
    Cu1 Se1 Ni1 . 26_544 121.213(5) ?
    Ni1 Se1 Ni1 75_544 26_544 95.576(7) ?
    Cu1 Se1 Co1 . 75_544 121.213(5) ?
    Ni1 Se1 Co1 75_544 75_544 0.0 ?
    Ni1 Se1 Co1 26_544 75_544 95.576(7) ?
    Cu1 Se1 Co1 . 26_544 121.213(5) ?
    Ni1 Se1 Co1 75_544 26_544 95.576(7) ?
    Ni1 Se1 Co1 26_544 26_544 0.0 ?
    Co1 Se1 Co1 75_544 26_544 95.576(7) ?
    Cu1 Se1 Co1 . . 121.213(5) ?
    Ni1 Se1 Co1 75_544 . 95.576(7) ?
    Ni1 Se1 Co1 26_544 . 95.576(7) ?
    Co1 Se1 Co1 75_544 . 95.576(7) ?
    Co1 Se1 Co1 26_544 . 95.576(7) ?
data_global
_journal_date_recd_electronic     2007-05-11
_journal_date_accepted     2007-06-22
_journal_name_full     'Acta Crystallographica, Section C'
_journal_year     2007
_journal_volume     63
_journal_issue      8
_journal_page_first     i73
_journal_page_last     i74
_journal_paper_category     FI
_journal_coeditor_code     BC3052
_publ_contact_author_name     'Yang, Hexiong'
_publ_contact_author_address
;
Department of Geosciences
Gould-Simpson Building
University of Arizona
1040 East 4th Street
Tucson
AZ 85721-0077
USA
;
_publ_contact_author_email     hyang@u.arizona.edu
_publ_contact_author_fax     520-621-2672
_publ_contact_author_phone     520-621-9993
_publ_section_title
;
Tyrrellite, Cu(Co~0.68~Ni~0.32~2)₂Se₄, isostructural with spinel
;
loop_
    _publ_author_name
    _publ_author_address
    'Yang, Hexiong'
;
Department of Geosciences
University of Arizona
1040 East 4th Street
Tucson
AZ 85721-0077
USA
;
    'Hubler, David K.'
;
Department of Geosciences
University of Arizona
1040 East 4th Street
Tucson
AZ 85721-0077
USA
;
    'Lavina, Barbara'
;
GSECARS-APS Building 434A
Argonne National Loboratory
9700 South Cass Avenue
Argonne
IL 60439
USA
;
    'Downs, Robert T.'
;
Department of Geosciences
University of Arizona
1040 East 4th Street
Tucson
AZ 85721-0077
USA
;
    'Costin, Gelu'
;
Department of Geosciences
University of Arizona
1040 East 4th Street
Tucson
AZ 85721-0077
USA
;
_publ_section_synopsis
;
Tyrrellite, Cu(Co,Ni)₂Se₄, is a normal spinel containing Cu in a
tetrahedral coordination.
;
