#------------------------------------------------------------------------------
#$Date: 2016-03-23 03:47:51 +0200 (Wed, 23 Mar 2016) $
#$Revision: 179263 $
#$URL: svn://www.crystallography.net/cod/cif/4/31/83/4318356.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4318356
loop_
_publ_author_name
'Daniel L. Reger'
'Christine A. Little'
'Mark D. Smith'
'Gary J. Long'
_publ_section_title
;
 Solid-State Structural and Magnetic Investigations of
 {M[HC(3,5-Me2pz)3]2}(BF4)2 (M = Fe, Co, Ni, Cu): Observation of a
 Thermally Induced Solid-State Phase Change Controlling an Iron(II)
 Spin-State Crossover
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              4453
_journal_page_last               4460
_journal_paper_doi               10.1021/ic0112645
_journal_volume                  41
_journal_year                    2002
_chemical_formula_moiety
;
{[HC(C5H7N2)3]2Cu} [BF4]2
;
_chemical_formula_sum            'C32 H44 B2 Cu F8 N12'
_chemical_formula_weight         833.95
_chemical_name_systematic
;
  ?
;
_space_group_IT_number           15
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 112.6570(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.3890(14)
_cell_length_b                   10.3782(7)
_cell_length_c                   19.5811(14)
_cell_measurement_reflns_used    5366
_cell_measurement_temperature    220(2)
_cell_measurement_theta_max      28.226
_cell_measurement_theta_min      2.241
_cell_volume                     3823.6(5)
_computing_cell_refinement       'SAINT+ NT V6.02a (Bruker, 1998)'
_computing_data_collection       'SMART NT V5.619 (Bruker, 2000)'
_computing_data_reduction        'SAINT+ NT V6.02a'
_computing_molecular_graphics    'SHELXTL V5.1 (Sheldrick, 1997)'
_computing_publication_material  'SHELXTL V5.1'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      220(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker SMART APEX CCD diffractometer'
_diffrn_measurement_method       'omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_sigmaI/netI    0.0311
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            19861
_diffrn_reflns_theta_full        28.30
_diffrn_reflns_theta_max         28.30
_diffrn_reflns_theta_min         2.16
_diffrn_standards_decay_%        none
_exptl_absorpt_coefficient_mu    0.652
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            blue-green
_exptl_crystal_density_diffrn    1.449
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             1724
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.20
_refine_diff_density_max         0.414
_refine_diff_density_min         -0.343
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         4749
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0809P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1224
_refine_ls_wR_factor_ref         0.1266
_reflns_number_gt                3743
_reflns_number_total             4749
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic0112645_5.cif
_cod_data_source_block           cu220k
_cod_database_code               4318356
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'
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
Cu Cu 0.5000 0.0000 1.0000 0.02545(12) Uani 1 2 d S . .
C1 C 0.42517(9) 0.22213(16) 0.89191(9) 0.0261(3) Uani 1 1 d . . .
H1 H 0.3993(9) 0.2853(16) 0.8581(10) 0.017(4) Uiso 1 1 d . . .
C11 C 0.36522(10) 0.31726(18) 0.97140(10) 0.0350(4) Uani 1 1 d . . .
C12 C 0.36919(13) 0.2902(2) 1.04089(12) 0.0484(5) Uani 1 1 d . . .
H12 H 0.3443 0.3319 1.0662 0.058 Uiso 1 1 calc R . .
C13 C 0.41747(13) 0.1883(2) 1.06750(11) 0.0462(5) Uani 1 1 d . . .
C14 C 0.32230(13) 0.4160(2) 0.91757(12) 0.0488(5) Uani 1 1 d . . .
H14A H 0.3538 0.4746 0.9063 0.073 Uiso 1 1 calc R . .
H14B H 0.2939 0.4638 0.9389 0.073 Uiso 1 1 calc R . .
H14C H 0.2912 0.3738 0.8725 0.073 Uiso 1 1 calc R . .
C15 C 0.44123(18) 0.1259(3) 1.14244(14) 0.0755(9) Uani 1 1 d . . .
H15A H 0.4447 0.0334 1.1373 0.113 Uiso 1 1 calc R . .
H15B H 0.4070 0.1442 1.1645 0.113 Uiso 1 1 calc R . .
H15C H 0.4873 0.1597 1.1739 0.113 Uiso 1 1 calc R . .
C21 C 0.35925(9) 0.07381(19) 0.78550(10) 0.0325(4) Uani 1 1 d . . .
C22 C 0.35088(11) -0.0566(2) 0.78104(11) 0.0391(4) Uani 1 1 d . . .
H22 H 0.3244 -0.1041 0.7384 0.047 Uiso 1 1 calc R . .
C23 C 0.38884(11) -0.10655(18) 0.85137(11) 0.0391(5) Uani 1 1 d . . .
C24 C 0.33060(12) 0.1761(2) 0.72881(11) 0.0468(5) Uani 1 1 d . . .
H24A H 0.3044 0.2382 0.7454 0.070 Uiso 1 1 calc R . .
H24B H 0.2991 0.1378 0.6826 0.070 Uiso 1 1 calc R . .
H24C H 0.3695 0.2191 0.7213 0.070 Uiso 1 1 calc R . .
C25 C 0.39477(16) -0.2446(2) 0.87454(15) 0.0663(8) Uani 1 1 d . . .
H25A H 0.4297 -0.2527 0.9247 0.099 Uiso 1 1 calc R . .
H25B H 0.4095 -0.2959 0.8415 0.099 Uiso 1 1 calc R . .
H25C H 0.3490 -0.2748 0.8724 0.099 Uiso 1 1 calc R . .
C31 C 0.53218(10) 0.34353(18) 0.88886(11) 0.0369(4) Uani 1 1 d . . .
C32 C 0.60288(11) 0.3150(2) 0.91572(12) 0.0435(5) Uani 1 1 d . . .
H32 H 0.6394 0.3661 0.9120 0.052 Uiso 1 1 calc R . .
C33 C 0.61022(11) 0.1944(2) 0.95007(13) 0.0465(5) Uani 1 1 d . . .
C34 C 0.49235(14) 0.4588(3) 0.84842(19) 0.0656(8) Uani 1 1 d . . .
H34A H 0.4568 0.4323 0.8012 0.098 Uiso 1 1 calc R . .
H34B H 0.5251 0.5187 0.8402 0.098 Uiso 1 1 calc R . .
H34C H 0.4693 0.5004 0.8776 0.098 Uiso 1 1 calc R . .
C35 C 0.67652(12) 0.1179(3) 0.9883(2) 0.0789(10) Uani 1 1 d . . .
H35A H 0.7060 0.1611 1.0337 0.118 Uiso 1 1 calc R . .
H35B H 0.7025 0.1102 0.9561 0.118 Uiso 1 1 calc R . .
H35C H 0.6641 0.0327 0.9998 0.118 Uiso 1 1 calc R . .
N11 N 0.44258(9) 0.15251(15) 1.01650(8) 0.0355(4) Uani 1 1 d . . .
N12 N 0.41014(8) 0.23402(13) 0.95794(8) 0.0287(3) Uani 1 1 d . . .
N21 N 0.42121(9) -0.01185(13) 0.89839(9) 0.0323(4) Uani 1 1 d . . .
N22 N 0.40241(8) 0.09888(13) 0.85717(8) 0.0276(3) Uani 1 1 d . . .
N31 N 0.54739(8) 0.15014(16) 0.94558(10) 0.0416(4) Uani 1 1 d . . .
N32 N 0.49989(8) 0.24320(14) 0.90768(8) 0.0309(3) Uani 1 1 d . . .
B B 0.31431(13) 0.5692(2) 0.69449(13) 0.0400(5) Uani 1 1 d . . .
F1 F 0.31663(9) 0.50758(12) 0.75808(9) 0.0598(4) Uani 1 1 d . . .
F2 F 0.28992(13) 0.48754(18) 0.63595(11) 0.0944(7) Uani 1 1 d . . .
F3 F 0.38157(8) 0.61087(18) 0.70497(9) 0.0799(5) Uani 1 1 d . . .
F4 F 0.27005(9) 0.67318(15) 0.68108(10) 0.0793(5) Uani 1 1 d . . .
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'
B B 0.0013 0.0007 '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'
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'
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
N21 Cu N21 180.000(1) 5_657 . ?
N21 Cu N11 94.74(6) 5_657 . ?
N21 Cu N11 85.26(6) . . ?
N21 Cu N11 85.26(6) 5_657 5_657 ?
N21 Cu N11 94.74(6) . 5_657 ?
N11 Cu N11 180.000(1) . 5_657 ?
N21 Cu N31 84.36(6) 5_657 5_657 ?
N21 Cu N31 95.64(6) . 5_657 ?
N11 Cu N31 94.70(7) . 5_657 ?
N11 Cu N31 85.30(7) 5_657 5_657 ?
N21 Cu N31 95.64(6) 5_657 . ?
N21 Cu N31 84.36(6) . . ?
N11 Cu N31 85.30(7) . . ?
N11 Cu N31 94.70(7) 5_657 . ?
N31 Cu N31 180.000(1) 5_657 . ?
N22 C1 N12 110.98(14) . . ?
N22 C1 N32 110.84(14) . . ?
N12 C1 N32 111.37(14) . . ?
N12 C11 C12 106.16(17) . . ?
N12 C11 C14 123.87(17) . . ?
C12 C11 C14 129.97(18) . . ?
C11 C12 C13 106.87(18) . . ?
N11 C13 C12 110.35(18) . . ?
N11 C13 C15 122.5(2) . . ?
C12 C13 C15 127.2(2) . . ?
C22 C21 N22 105.70(15) . . ?
C22 C21 C24 131.23(17) . . ?
N22 C21 C24 123.07(17) . . ?
C21 C22 C23 107.31(16) . . ?
N21 C23 C22 110.29(17) . . ?
N21 C23 C25 122.43(18) . . ?
C22 C23 C25 127.28(19) . . ?
N32 C31 C32 106.29(17) . . ?
N32 C31 C34 122.56(18) . . ?
C32 C31 C34 131.13(19) . . ?
C31 C32 C33 106.28(18) . . ?
N31 C33 C32 110.75(18) . . ?
N31 C33 C35 120.7(2) . . ?
C32 C33 C35 128.5(2) . . ?
C13 N11 N12 104.63(15) . . ?
C13 N11 Cu 137.03(14) . . ?
N12 N11 Cu 117.46(11) . . ?
C11 N12 N11 111.99(14) . . ?
C11 N12 C1 128.33(15) . . ?
N11 N12 C1 119.67(14) . . ?
C23 N21 N22 105.03(16) . . ?
C23 N21 Cu 135.86(12) . . ?
N22 N21 Cu 117.65(11) . . ?
C21 N22 N21 111.66(14) . . ?
C21 N22 C1 128.22(15) . . ?
N21 N22 C1 120.03(14) . . ?
C33 N31 N32 104.75(16) . . ?
C33 N31 Cu 140.20(14) . . ?
N32 N31 Cu 113.20(11) . . ?
C31 N32 N31 111.92(15) . . ?
C31 N32 C1 129.64(15) . . ?
N31 N32 C1 118.41(14) . . ?
F2 B F4 109.3(2) . . ?
F2 B F3 110.0(2) . . ?
F4 B F3 109.1(2) . . ?
F2 B F1 110.3(2) . . ?
F4 B F1 109.20(19) . . ?
F3 B F1 108.93(19) . . ?
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
Cu N21 2.0229(16) 5_657 ?
Cu N21 2.0229(16) . ?
Cu N11 2.0668(16) . ?
Cu N11 2.0668(16) 5_657 ?
Cu N31 2.3001(17) 5_657 ?
Cu N31 2.3001(17) . ?
C1 N22 1.439(2) . ?
C1 N12 1.444(2) . ?
C1 N32 1.450(2) . ?
C11 N12 1.357(2) . ?
C11 C12 1.361(3) . ?
C11 C14 1.488(3) . ?
C12 C13 1.401(3) . ?
C13 N11 1.338(3) . ?
C13 C15 1.503(3) . ?
C21 C22 1.363(3) . ?
C21 N22 1.364(2) . ?
C21 C24 1.483(3) . ?
C22 C23 1.394(3) . ?
C23 N21 1.335(2) . ?
C23 C25 1.494(3) . ?
C31 N32 1.357(2) . ?
C31 C32 1.363(3) . ?
C31 C34 1.490(3) . ?
C32 C33 1.402(3) . ?
C33 N31 1.332(3) . ?
C33 C35 1.496(3) . ?
N11 N12 1.372(2) . ?
N21 N22 1.3714(19) . ?
N31 N32 1.367(2) . ?
B F2 1.356(3) . ?
B F4 1.366(3) . ?
B F3 1.376(3) . ?
B F1 1.384(3) . ?
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
Cu N11 N12 C11 170.22(13) . . . . ?
Cu N21 N22 C21 168.09(12) . . . . ?
Cu N31 N32 C31 167.73(13) . . . . ?
