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


data_global

_journal_coden_Cambridge         222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

loop_
_publ_author_name
'Manson, Jamie'
'Carreiro, Kimberly'
'Lapidus, Saul'
'Stephens, Peter'
'Goddard, Paul'
'Del Sesto, Rico'
'Bendix, Jesper'
'Ghannadzadeh, Saman'
'Franke, Isabel'
'Singleton, John'
'Lancaster, Tom'
'Moeller, Johannes'
'Baker, Peter'
'Pratt, Francis'
'Blundell, Stephen'
'Kang, Jinhee'
'Lee, Changhoon'
'Whangbo, Myung-Hwan'

_publ_contact_author_name        'Dr Manson, Jamie '
_publ_contact_author_email       jmanson@ewu.edu

_publ_section_title              
;
Influence of HF<sub>2</sub><sup>-</sup>
geometry on magnetic interactions elucidated from polymorphs
of the bifluoride-pillared metal-organic framework
[Ni(HF<sub>2</sub>)(pyz)<sub>2</sub>]PF<sub>6</sub> (pyz = pyrazine)

;

# Attachment '- KEC01-025b_295K_pub.cif'

#TrackingRef '- KEC01-025b_295K_pub.cif'

#
data_KEC-01-025
_database_code_depnum_ccdc_archive 'CCDC 863843'
#TrackingRef '- KEC01-025b_295K_pub.cif'

# 5. CHEMICAL DATA

_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_formula_moiety         'C8 H9 F2 N4 Ni, F6 P'
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_formula_sum            'C8 H9 F8 N4 Ni P'
_chemical_formula_weight         402.85
_chemical_melting_point          ?
_chemical_compound_source        ? # for minerals and
# natural products

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
_atom_type_scat_length_neutron # include if applicable
? ? ? ? ? ?

#==============================================================================

# 6. POWDER SPECIMEN AND CRYSTAL DATA

_symmetry_cell_setting           Tetragonal
_symmetry_space_group_name_Hall  'P 4ab 2ab -1ab'
_symmetry_space_group_name_H-M   'P 4/n m m:1'
_symmetry_Int_Tables_number      129

loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 x,y,z
2 1/2-y,1/2+x,z
3 -x,-y,z
4 1/2+y,1/2-x,z
5 1/2+x,1/2-y,-z
6 y,x,-z
7 1/2-x,1/2+y,-z
8 -y,-x,-z
9 1/2-x,1/2-y,-z
10 y,-x,-z
11 1/2+x,1/2+y,-z
12 -y,x,-z
13 -x,y,z
14 1/2-y,1/2-x,z
15 x,-y,z
16 1/2+y,1/2+x,z

_cell_length_a                   9.9197(3)
_cell_length_b                   9.9197(3)
_cell_length_c                   6.3434(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     624.195(33)
_cell_formula_units_Z            2
_cell_measurement_temperature    300

_cell_special_details            
; ?
;

# The next three fields give the specimen dimensions in mm. The equatorial
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              ? # perpendicular to
# equatorial plane

_pd_spec_size_equat              ? # parallel to
# scattering vector
# in transmission

_pd_spec_size_thick              ? # parallel to
# scattering vector
# in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                
# This field should be
# used to give details of the
# container.
;
capillary
;
_pd_spec_mount_mode              transmission # options are 'reflection'
# or 'transmission'

_pd_spec_shape                   cylinder # options are 'cylinder'
# 'flat_sheet' or 'irregular'

_pd_char_particle_morphology     ?
_pd_char_colour                  ? # use ICDD colour descriptions

# The following three fields describe the preparation of the specimen.
# The cooling rate is in K/min. The pressure at which the sample was
# prepared is in kPa. The temperature of preparation is in K.

_pd_prep_cool_rate               ?
_pd_prep_pressure                ?
_pd_prep_temperature             ?

# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu    ? # include if applicable
_exptl_absorpt_correction_type   ? # include if applicable
_exptl_absorpt_process_details   ? # include if applicable
_exptl_absorpt_correction_T_min  ? # include if applicable
_exptl_absorpt_correction_T_max  ? # include if applicable

#==============================================================================

# 7. EXPERIMENTAL DATA

_exptl_special_details           
; ?
;

# The following item is used to identify the equipment used to record
# the powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location               
;
X16C, National Synchrotron Light Source, Brookhaven National Laboratory
;
_pd_calibration_special_details  
# description of the method used
# to calibrate the instrument
;
NIST standard reference material 1976(sintered plate of Al2O3)
Well-isolated 7 reflections were used to calibrate wavelength and detector zero.
;

_diffrn_ambient_temperature      300
_diffrn_source                   synchrotron
_diffrn_source_target            ?
_diffrn_source_type              ?
_diffrn_radiation_type           synchrotron
_diffrn_measurement_device_type  'Huber diffractometer'
_diffrn_detector                 'NaI scintillation counter'
_diffrn_detector_type            ? # make or model of detector

_pd_meas_scan_method             step # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
_pd_meas_special_details         
; ?
;

# The following six items are used for angular dispersive measurements only.

_diffrn_radiation_wavelength     0.699455
_diffrn_radiation_monochromator  'Si(111) channel cut'

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        7401
_pd_meas_2theta_range_min        5.0
_pd_meas_2theta_range_max        42.0
_pd_meas_2theta_range_inc        0.005

# The following three items are used for time-of-flight measurements only.

_pd_instr_dist_src/spec          ?
_pd_instr_dist_spec/detc         ?
_pd_meas_2theta_fixed            ?

#==============================================================================

# 8. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
;
Molecules are defined as rigid bodies using the z-matrix function
implemented in TOPAS-Academic. The same isotropic displacement parameters are
assigned to all of the molecules.
;

# The next three items are given as text.

_pd_proc_ls_profile_function     
;
Simple_Axial_model function with Rp=9999,Rs=330 in TOPAS-Academic
;
_pd_proc_ls_background_function  
;
1 Pearson-Voight peaks and Chebyshev polynomial with 9 coefficients
;
_pd_proc_ls_pref_orient_corr     
;
none
;

_pd_proc_ls_prof_R_factor        0.04821 # 4.821(%)
_pd_proc_ls_prof_wR_factor       0.0617 # 6.170(%)
_pd_proc_ls_prof_wR_expected     0.02764 # 2.764(%)
_refine_ls_R_I_factor            ?
_refine_ls_R_Fsqd_factor         ?
_refine_ls_R_factor_all          ?

_refine_special_details          
; ?
;

_refine_ls_matrix_type           ?
_refine_ls_weighting_scheme      
sigma # options are 'sigma'(based on measured su's)
# or 'calc' (calculated weights)
_refine_ls_weighting_details     1/(sigma*sigma)
_refine_ls_extinction_coef       ?
_refine_ls_number_parameters     43
_refine_ls_number_restraints     ?
_refine_ls_number_constraints    ?

# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all   2.232

_refine_ls_restrained_S_all      ?
_refine_ls_shift/su_max          ?
_refine_ls_shift/su_mean         ?

# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        5.0
_pd_proc_2theta_range_max        42.0
_pd_proc_2theta_range_inc        0.005
_pd_proc_wavelength              0.699455

_pd_block_diffractogram_id       KEC-01-025
# The id used for the block containing
# the powder pattern profile (section 11).

# Give appropriate details in the next two text fields.

_pd_proc_info_excluded_regions   ?
_pd_proc_info_data_reduction     ?

# The following items are used to identify the programs used.

_computing_data_collection       SPEC
_computing_cell_refinement       TOPAS-Academic
_computing_data_reduction        TOPAS-Academic
_computing_structure_solution    TOPAS-Academic
_computing_structure_refinement  TOPAS-Academic
_computing_molecular_graphics    ?
_computing_publication_material  ?

#==============================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv

Ni1 Ni 2 0 0 0 1 0.960(32)
F3 F 4 0 0 0.32578(41) 1 2.724(47)
N1 N 8 0.15047(19) 0.15047(19) 0 1 2.724(47)
P P 2 0 0.5 0.39102(46) 1 3.464(88)
F1 F 8 0.00000 0.3404(2) 0.4015(3) 1 5.164(66)
F2 F 2 0 0.5 0.64008(88) 1 5.164(66)
F4 F 2 0 0.5 0.14707(68) 1 2.724(47)
C1 C 16 0.22268(24) 0.17520(21) 0.16735(38) 1 2.724(47)
H1 H 4 0.20153 0.1225 0.290239 1 2.724(47)
H2 H 2 0 0 0.5 1 2.724(47)

#===============================================================================

# 10. MOLECULAR GEOMETRY

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ni1 F3 2.067(3) . . yes
Ni1 N1 2.1109(19) . . yes
Ni1 N1 2.1109(19) . 3_555 yes
Ni1 F3 2.067(3) . 6_555 yes
Ni1 N1 2.1109(19) . 10_555 yes
Ni1 N1 2.1109(19) . 12_555 yes
P F4 1.547(5) . . yes
P F1 1.585(2) . 2_555 yes
P F1 1.585(2) . 3_565 yes
P F1 1.585(2) . 4_455 yes
P F1 1.585(2) . . yes
P F2 1.580(7) . . yes
F3 H2 1.1100 . . no
N1 C1 1.304(3) . . yes
N1 C1 1.304(3) . 6_555 yes
C1 C1 1.432(3) . 14_555 no
C1 H1 0.9600 . . no

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_2
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
F3 Ni1 N1 90.00 . . . yes
F3 Ni1 N1 90.00 . . 3_555 yes
F3 Ni1 F3 180.00 . . 6_555 yes
F3 Ni1 N1 90.00 . . 10_555 yes
F3 Ni1 N1 90.00 . . 12_555 yes
N1 Ni1 N1 180.00 . . 3_555 yes
F3 Ni1 N1 90.00 6_555 . . yes
N1 Ni1 N1 90.00(7) . . 10_555 yes
N1 Ni1 N1 90.00(7) . . 12_555 yes
F3 Ni1 N1 90.00 6_555 . 3_555 yes
N1 Ni1 N1 90.00(7) 3_555 . 10_555 yes
N1 Ni1 N1 90.00(7) 3_555 . 12_555 yes
F3 Ni1 N1 90.00 6_555 . 10_555 yes
F3 Ni1 N1 90.00 6_555 . 12_555 yes
N1 Ni1 N1 180.00 10_555 . 12_555 yes
F1 P F2 87.59(13) 4_455 . . yes
F1 P F4 92.41(13) 2_555 . . yes
F1 P F4 92.41(13) 3_565 . . yes
F1 P F4 92.41(13) 4_455 . . yes
F1 P F1 89.90(1) 2_555 . 3_565 yes
F1 P F1 175.2(2) 2_555 . 4_455 yes
F1 P F1 89.90(1) 3_565 . 4_455 yes
F1 P F2 87.59(13) . . . yes
F1 P F4 92.41(13) . . . yes
F1 P F1 89.90(1) . . 2_555 yes
F1 P F1 175.2(2) . . 3_565 yes
F1 P F1 89.90(1) . . 4_455 yes
F2 P F4 180.00(2) . . . yes
F1 P F2 87.59(13) 2_555 . . yes
F1 P F2 87.59(13) 3_565 . . yes
Ni1 F3 H2 180.00 . . . no
Ni1 N1 C1 121.43(12) . . . yes
C1 N1 C1 117.14(19) . . 6_555 yes
Ni1 N1 C1 121.43(12) . . 6_555 yes
N1 C1 C1 121.4(2) . . 14_555 yes
N1 C1 H1 116.00 . . . no
C1 C1 H1 123.00 14_555 . . no

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
F3 Ni1 N1 C1 17.42(16) . . . . no
Ni1 N1 C1 C1 180.00(14) . . . 14_555 no