#------------------------------------------------------------------------------
#$Date: 2016-03-23 03:47:51 +0200 (Wed, 23 Mar 2016) $
#$Revision: 179263 $
#$URL: svn://www.crystallography.net/cod/cif/4/31/83/4318354.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_4318354
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_sum            'C32 H44 B2 F8 N12 Ni'
_chemical_formula_weight         829.12
_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                 111.965(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   20.316(3)
_cell_length_b                   10.2919(15)
_cell_length_c                   19.622(3)
_cell_measurement_reflns_used    3842
_cell_measurement_temperature    220(2)
_cell_measurement_theta_max      25.110
_cell_measurement_theta_min      2.238
_cell_volume                     3805.0(10)
_computing_cell_refinement       'SAINT+ NT V6.02a (Bruker, 1998)'
_computing_data_collection       'SMART NT V5.624 (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  0.0499
_diffrn_reflns_av_sigmaI/netI    0.0629
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            10790
_diffrn_reflns_theta_full        25.11
_diffrn_reflns_theta_max         25.11
_diffrn_reflns_theta_min         2.16
_diffrn_standards_decay_%        none
_exptl_absorpt_coefficient_mu    0.591
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.447
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1720
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.438
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     260
_refine_ls_number_reflns         3395
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0422
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0255P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0791
_refine_ls_wR_factor_ref         0.0838
_reflns_number_gt                2366
_reflns_number_total             3395
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic0112645_3.cif
_cod_data_source_block           ni220k
_cod_original_cell_volume        3804.9(10)
_cod_database_code               4318354
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
Ni Ni 0.5000 0.0000 1.0000 0.02724(15) Uani 1 2 d S . .
C1 C 0.42137(15) 0.2163(3) 0.89320(15) 0.0276(7) Uani 1 1 d . . .
H1 H 0.3955(12) 0.284(2) 0.8599(12) 0.016(6) Uiso 1 1 d . . .
C11 C 0.35917(15) 0.3138(3) 0.97151(15) 0.0335(7) Uani 1 1 d . . .
C12 C 0.36415(17) 0.2872(3) 1.04112(16) 0.0463(8) Uani 1 1 d . . .
H12 H 0.3395 0.3295 1.0668 0.056 Uiso 1 1 calc R . .
C13 C 0.41240(17) 0.1859(3) 1.06732(16) 0.0416(8) Uani 1 1 d . . .
C14 C 0.31621(16) 0.4108(3) 0.91775(16) 0.0456(8) Uani 1 1 d . . .
H14A H 0.3470 0.4633 0.9012 0.068 Uiso 1 1 calc R . .
H14B H 0.2918 0.4662 0.9407 0.068 Uiso 1 1 calc R . .
H14C H 0.2816 0.3665 0.8761 0.068 Uiso 1 1 calc R . .
C15 C 0.4361(2) 0.1231(3) 1.14155(17) 0.0702(12) Uani 1 1 d . . .
H15A H 0.4742 0.0624 1.1468 0.105 Uiso 1 1 calc R . .
H15B H 0.3965 0.0770 1.1466 0.105 Uiso 1 1 calc R . .
H15C H 0.4529 0.1893 1.1793 0.105 Uiso 1 1 calc R . .
C21 C 0.35622(15) 0.0694(3) 0.78614(15) 0.0306(7) Uani 1 1 d . . .
C22 C 0.35075(15) -0.0632(3) 0.78080(15) 0.0379(8) Uani 1 1 d . . .
H22 H 0.3251 -0.1111 0.7384 0.046 Uiso 1 1 calc R . .
C23 C 0.39004(16) -0.1134(3) 0.84967(16) 0.0377(8) Uani 1 1 d . . .
C24 C 0.32608(16) 0.1728(3) 0.73046(15) 0.0446(8) Uani 1 1 d . . .
H24A H 0.3002 0.2345 0.7484 0.067 Uiso 1 1 calc R . .
H24B H 0.2941 0.1343 0.6850 0.067 Uiso 1 1 calc R . .
H24C H 0.3642 0.2172 0.7216 0.067 Uiso 1 1 calc R . .
C25 C 0.39928(19) -0.2530(3) 0.87159(18) 0.0666(11) Uani 1 1 d . . .
H25A H 0.4381 -0.2616 0.9188 0.100 Uiso 1 1 calc R . .
H25B H 0.4098 -0.3027 0.8349 0.100 Uiso 1 1 calc R . .
H25C H 0.3559 -0.2854 0.8754 0.100 Uiso 1 1 calc R . .
C31 C 0.53042(16) 0.3317(3) 0.89070(16) 0.0362(7) Uani 1 1 d . . .
C32 C 0.60057(16) 0.3003(3) 0.91959(17) 0.0434(8) Uani 1 1 d . . .
H32 H 0.6380 0.3485 0.9149 0.052 Uiso 1 1 calc R . .
C33 C 0.60663(17) 0.1841(3) 0.95714(16) 0.0426(8) Uani 1 1 d . . .
C34 C 0.49249(17) 0.4447(3) 0.84590(19) 0.0603(10) Uani 1 1 d . . .
H34A H 0.4592 0.4144 0.7988 0.091 Uiso 1 1 calc R . .
H34B H 0.5266 0.5029 0.8381 0.091 Uiso 1 1 calc R . .
H34C H 0.4670 0.4907 0.8716 0.091 Uiso 1 1 calc R . .
C35 C 0.67312(17) 0.1111(3) 0.9989(2) 0.0685(11) Uani 1 1 d . . .
H35A H 0.6619 0.0372 1.0233 0.103 Uiso 1 1 calc R . .
H35B H 0.7060 0.1678 1.0353 0.103 Uiso 1 1 calc R . .
H35C H 0.6947 0.0807 0.9653 0.103 Uiso 1 1 calc R . .
N11 N 0.43720(12) 0.1491(2) 1.01643(12) 0.0333(6) Uani 1 1 d . . .
N12 N 0.40413(11) 0.2286(2) 0.95778(11) 0.0282(5) Uani 1 1 d . . .
N21 N 0.42019(12) -0.0183(2) 0.89681(11) 0.0331(6) Uani 1 1 d . . .
N22 N 0.39860(11) 0.0934(2) 0.85717(12) 0.0278(5) Uani 1 1 d . . .
N31 N 0.54274(12) 0.1426(2) 0.95295(12) 0.0347(6) Uani 1 1 d . . .
N32 N 0.49657(11) 0.2348(2) 0.91119(12) 0.0291(5) Uani 1 1 d . . .
B B 0.3184(2) 0.5588(4) 0.6956(2) 0.0403(9) Uani 1 1 d . . .
F1 F 0.31832(9) 0.50239(17) 0.75956(8) 0.0527(5) Uani 1 1 d . . .
F2 F 0.29861(12) 0.47103(19) 0.64026(10) 0.0839(7) Uani 1 1 d . . .
F3 F 0.38591(10) 0.6033(2) 0.70699(10) 0.0767(7) Uani 1 1 d . . .
F4 F 0.27313(11) 0.66254(18) 0.67663(11) 0.0730(6) 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'
Ni Ni 0.3393 1.1124 '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 Ni N21 180.000(1) . 5_657 ?
N21 Ni N31 86.26(9) . . ?
N21 Ni N31 93.74(9) 5_657 . ?
N21 Ni N31 93.74(9) . 5_657 ?
N21 Ni N31 86.26(9) 5_657 5_657 ?
N31 Ni N31 180.00(11) . 5_657 ?
N21 Ni N11 94.70(9) . 5_657 ?
N21 Ni N11 85.30(9) 5_657 5_657 ?
N31 Ni N11 93.95(8) . 5_657 ?
N31 Ni N11 86.05(8) 5_657 5_657 ?
N21 Ni N11 85.30(9) . . ?
N21 Ni N11 94.70(9) 5_657 . ?
N31 Ni N11 86.05(8) . . ?
N31 Ni N11 93.95(8) 5_657 . ?
N11 Ni N11 180.00(12) 5_657 . ?
N22 C1 N12 111.7(2) . . ?
N22 C1 N32 110.6(2) . . ?
N12 C1 N32 110.8(2) . . ?
C12 C11 N12 105.4(2) . . ?
C12 C11 C14 131.0(3) . . ?
N12 C11 C14 123.6(2) . . ?
C11 C12 C13 107.4(3) . . ?
N11 C13 C12 110.4(2) . . ?
N11 C13 C15 122.2(3) . . ?
C12 C13 C15 127.4(3) . . ?
N22 C21 C22 105.2(3) . . ?
N22 C21 C24 123.6(2) . . ?
C22 C21 C24 131.2(3) . . ?
C21 C22 C23 107.2(3) . . ?
N21 C23 C22 110.5(2) . . ?
N21 C23 C25 122.2(3) . . ?
C22 C23 C25 127.2(3) . . ?
N32 C31 C32 105.7(2) . . ?
N32 C31 C34 122.9(3) . . ?
C32 C31 C34 131.5(3) . . ?
C31 C32 C33 107.3(3) . . ?
N31 C33 C32 110.5(3) . . ?
N31 C33 C35 122.0(3) . . ?
C32 C33 C35 127.4(3) . . ?
C13 N11 N12 104.9(2) . . ?
C13 N11 Ni 138.30(19) . . ?
N12 N11 Ni 116.41(15) . . ?
C11 N12 N11 111.9(2) . . ?
C11 N12 C1 129.2(2) . . ?
N11 N12 C1 118.9(2) . . ?
C23 N21 N22 104.9(2) . . ?
C23 N21 Ni 137.26(18) . . ?
N22 N21 Ni 116.54(16) . . ?
C21 N22 N21 112.1(2) . . ?
C21 N22 C1 128.9(2) . . ?
N21 N22 C1 119.0(2) . . ?
C33 N31 N32 104.3(2) . . ?
C33 N31 Ni 138.6(2) . . ?
N32 N31 Ni 116.51(16) . . ?
C31 N32 N31 112.2(2) . . ?
C31 N32 C1 129.2(2) . . ?
N31 N32 C1 118.6(2) . . ?
F2 B F4 109.6(3) . . ?
F2 B F3 109.4(3) . . ?
F4 B F3 108.1(3) . . ?
F2 B F1 110.3(3) . . ?
F4 B F1 110.1(3) . . ?
F3 B F1 109.3(3) . . ?
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
Ni N21 2.076(2) . ?
Ni N21 2.076(2) 5_657 ?
Ni N31 2.088(2) . ?
Ni N31 2.088(2) 5_657 ?
Ni N11 2.096(2) 5_657 ?
Ni N11 2.096(2) . ?
C1 N22 1.438(3) . ?
C1 N12 1.441(3) . ?
C1 N32 1.446(3) . ?
C11 C12 1.359(4) . ?
C11 N12 1.363(3) . ?
C11 C14 1.477(4) . ?
C12 C13 1.391(4) . ?
C13 N11 1.331(3) . ?
C13 C15 1.499(4) . ?
C21 N22 1.359(3) . ?
C21 C22 1.369(3) . ?
C21 C24 1.484(4) . ?
C22 C23 1.387(4) . ?
C23 N21 1.329(3) . ?
C23 C25 1.491(4) . ?
C31 N32 1.355(3) . ?
C31 C32 1.361(4) . ?
C31 C34 1.488(4) . ?
C32 C33 1.386(4) . ?
C33 N31 1.339(3) . ?
C33 C35 1.495(4) . ?
N11 N12 1.367(3) . ?
N21 N22 1.365(3) . ?
N31 N32 1.370(3) . ?
B F2 1.352(4) . ?
B F4 1.367(4) . ?
B F3 1.382(4) . ?
B F1 1.384(4) . ?
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
N12 C11 C12 C13 0.0(3) . . . . ?
C14 C11 C12 C13 179.8(3) . . . . ?
C11 C12 C13 N11 -0.1(4) . . . . ?
C11 C12 C13 C15 179.4(3) . . . . ?
N22 C21 C22 C23 0.4(3) . . . . ?
C24 C21 C22 C23 179.5(3) . . . . ?
C21 C22 C23 N21 -0.9(4) . . . . ?
C21 C22 C23 C25 179.0(3) . . . . ?
N32 C31 C32 C33 -0.1(3) . . . . ?
C34 C31 C32 C33 179.6(3) . . . . ?
C31 C32 C33 N31 -0.4(4) . . . . ?
C31 C32 C33 C35 -179.1(3) . . . . ?
C12 C13 N11 N12 0.1(3) . . . . ?
C15 C13 N11 N12 -179.4(3) . . . . ?
C12 C13 N11 Ni -171.8(2) . . . . ?
C15 C13 N11 Ni 8.7(5) . . . . ?
N21 Ni N11 C13 131.8(3) . . . . ?
N21 Ni N11 C13 -48.2(3) 5_657 . . . ?
N31 Ni N11 C13 -141.6(3) . . . . ?
N31 Ni N11 C13 38.4(3) 5_657 . . . ?
N11 Ni N11 C13 -109(100) 5_657 . . . ?
N21 Ni N11 N12 -39.43(18) . . . . ?
N21 Ni N11 N12 140.57(18) 5_657 . . . ?
N31 Ni N11 N12 47.13(18) . . . . ?
N31 Ni N11 N12 -132.87(18) 5_657 . . . ?
N11 Ni N11 N12 80(100) 5_657 . . . ?
C12 C11 N12 N11 0.1(3) . . . . ?
C14 C11 N12 N11 -179.7(3) . . . . ?
C12 C11 N12 C1 -177.9(3) . . . . ?
C14 C11 N12 C1 2.3(4) . . . . ?
C13 N11 N12 C11 -0.1(3) . . . . ?
Ni N11 N12 C11 173.87(17) . . . . y
C13 N11 N12 C1 178.1(2) . . . . ?
Ni N11 N12 C1 -7.9(3) . . . . ?
N22 C1 N12 C11 -115.7(3) . . . . ?
N32 C1 N12 C11 120.4(3) . . . . ?
N22 C1 N12 N11 66.4(3) . . . . ?
N32 C1 N12 N11 -57.4(3) . . . . ?
C22 C23 N21 N22 0.9(3) . . . . ?
C25 C23 N21 N22 -179.0(3) . . . . ?
C22 C23 N21 Ni -165.0(2) . . . . ?
C25 C23 N21 Ni 15.2(5) . . . . ?
N21 Ni N21 C23 -178(100) 5_657 . . . ?
N31 Ni N21 C23 128.1(3) . . . . ?
N31 Ni N21 C23 -51.9(3) 5_657 . . . ?
N11 Ni N21 C23 34.4(3) 5_657 . . . ?
N11 Ni N21 C23 -145.6(3) . . . . ?
N21 Ni N21 N22 18(100) 5_657 . . . ?
N31 Ni N21 N22 -36.62(17) . . . . ?
N31 Ni N21 N22 143.38(17) 5_657 . . . ?
N11 Ni N21 N22 -130.29(17) 5_657 . . . ?
N11 Ni N21 N22 49.71(17) . . . . ?
C22 C21 N22 N21 0.1(3) . . . . ?
C24 C21 N22 N21 -179.0(2) . . . . ?
C22 C21 N22 C1 -179.3(2) . . . . ?
C24 C21 N22 C1 1.5(4) . . . . ?
C23 N21 N22 C21 -0.6(3) . . . . ?
Ni N21 N22 C21 168.69(17) . . . . y
C23 N21 N22 C1 178.9(2) . . . . ?
Ni N21 N22 C1 -11.8(3) . . . . ?
N12 C1 N22 C21 125.1(3) . . . . ?
N32 C1 N22 C21 -110.9(3) . . . . ?
N12 C1 N22 N21 -54.3(3) . . . . ?
N32 C1 N22 N21 69.7(3) . . . . ?
C32 C33 N31 N32 0.7(3) . . . . ?
C35 C33 N31 N32 179.5(3) . . . . ?
C32 C33 N31 Ni -169.9(2) . . . . ?
C35 C33 N31 Ni 8.9(5) . . . . ?
N21 Ni N31 C33 -142.5(3) . . . . ?
N21 Ni N31 C33 37.5(3) 5_657 . . . ?
N31 Ni N31 C33 177(88) 5_657 . . . ?
N11 Ni N31 C33 -48.0(3) 5_657 . . . ?
N11 Ni N31 C33 132.0(3) . . . . ?
N21 Ni N31 N32 47.63(18) . . . . ?
N21 Ni N31 N32 -132.37(18) 5_657 . . . ?
N31 Ni N31 N32 7(73) 5_657 . . . ?
N11 Ni N31 N32 142.08(18) 5_657 . . . ?
N11 Ni N31 N32 -37.92(18) . . . . ?
C32 C31 N32 N31 0.6(3) . . . . ?
C34 C31 N32 N31 -179.2(3) . . . . ?
C32 C31 N32 C1 -177.4(3) . . . . ?
C34 C31 N32 C1 2.9(4) . . . . ?
C33 N31 N32 C31 -0.8(3) . . . . ?
Ni N31 N32 C31 172.30(18) . . . . y
C33 N31 N32 C1 177.4(2) . . . . ?
Ni N31 N32 C1 -9.5(3) . . . . ?
N22 C1 N32 C31 122.0(3) . . . . ?
N12 C1 N32 C31 -113.5(3) . . . . ?
N22 C1 N32 N31 -55.8(3) . . . . ?
N12 C1 N32 N31 68.7(3) . . . . ?
