# Supplementary Material (ESI) for New Journal of Chemistry
# This journal is © The Royal Society of Chemistry and 
# The Centre National de la Recherche Scientifique, 2011

data_global
_journal_name_full               'New J.Chem.'

_journal_coden_Cambridge         0440

_publ_contact_author_name        'Bousseksou, Azzedine'
_publ_contact_author_email       boussek@lcc-toulouse.fr

_publ_section_title              
;
Thermal and Pressure - Induced Spin Crossover
in a Novel Three-Dimensional Hoffman-like Chathrate Complex
;
loop_
_publ_author_name
L.Salmon
A.Bousseksou
G.Molnar

# Attachment 'exp-268-corr2.cif'

data_Fe(bpac)Ag(CN)2
_database_code_depnum_ccdc_archive 'CCDC 799275'
#TrackingRef 'exp-268-corr2.cif'

_audit_creation_date             2010-11-29
_audit_creation_method           
;
Olex2 1.1-beta
(compiled 2010.09.30 svn.r1450, GUI svn.r3284)
;
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.25(C56 H32 Ag4 Fe2 N16)'
_chemical_formula_sum            'C14 H8 Ag Fe0.50 N4'
_chemical_formula_weight         368.04
_chemical_melting_point          ?
_chemical_oxdiff_usercomment     220K
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'
Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 'x, y, z'
2 '-x+1/2, y+1/2, -z+1/2'
3 '-x, -y, -z'
4 'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   9.6204(4)
_cell_length_b                   10.8948(5)
_cell_length_c                   13.3105(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 95.411(4)
_cell_angle_gamma                90.00
_cell_volume                     1388.89(10)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2158
_cell_measurement_temperature    220
_cell_measurement_theta_max      29.0122
_cell_measurement_theta_min      3.5632
_exptl_absorpt_coefficient_mu    1.944
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97777
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.760
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       irregular
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_exptl_special_details           ?
_diffrn_reflns_av_R_equivalents  0.0292
_diffrn_reflns_av_unetI/netI     0.0792
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            5937
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         29.0122
_diffrn_reflns_theta_min         3.5632
_diffrn_ambient_temperature      220.0
_diffrn_detector_area_resol_mean 16.1978
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.850
_diffrn_measurement_details      
;
#__ type_ start__ end____ width___ exp.time_
1 omega -90.00 23.00 1.0000 50.0000
omega____ theta____ kappa____ phi______ frames
- -18.3269 0.0000 -30.0000 113

#__ type_ start__ end____ width___ exp.time_
2 omega -90.00 -64.00 1.0000 50.0000
omega____ theta____ kappa____ phi______ frames
- -18.3269 179.0000 -90.0000 26

#__ type_ start__ end____ width___ exp.time_
3 omega -40.00 -15.00 1.0000 50.0000
omega____ theta____ kappa____ phi______ frames
- -18.3269 -37.0000 -120.0000 25

#__ type_ start__ end____ width___ exp.time_
4 omega -12.00 38.00 1.0000 50.0000
omega____ theta____ kappa____ phi______ frames
- 18.5612 84.0000 -128.0000 50
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0127488000
_diffrn_orient_matrix_UB_12      0.0566904000
_diffrn_orient_matrix_UB_13      0.0255021000
_diffrn_orient_matrix_UB_21      -0.0609368000
_diffrn_orient_matrix_UB_22      -0.0084323000
_diffrn_orient_matrix_UB_23      0.0252227000
_diffrn_orient_matrix_UB_31      0.0399843000
_diffrn_orient_matrix_UB_32      -0.0309310000
_diffrn_orient_matrix_UB_33      0.0397813000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'Enhance (Mo) X-ray Source'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.7107
_diffrn_standards_decay_%        ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_number         ?
_reflns_number_gt                1910
_reflns_number_total             3161
_reflns_odcompleteness_completeness 99.57
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_reflns_threshold_expression     >2sigma(I)
_computing_cell_refinement       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_data_collection       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_data_reduction        
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
;
_computing_molecular_graphics    
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material  
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'A short history of SHELX (Sheldrick, 2007)'
_refine_diff_density_max         2.579
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.133
_refine_ls_extinction_coef       ?
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.905
_refine_ls_hydrogen_treatment    riding
_refine_ls_matrix_type           full
_refine_ls_number_parameters     178
_refine_ls_number_reflns         3161
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0803
_refine_ls_R_factor_gt           0.0458
_refine_ls_restrained_S_all      0.905
_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/[\s^2^(Fo^2^)+(0.0722P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1190
_refine_ls_wR_factor_ref         0.1264
_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.
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap

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
Ag Ag 0.24039(5) -0.33496(5) 0.68018(3) 0.03852(17) Uani 1 1 d . . .
C1 C 0.3644(6) -0.2481(6) 0.5810(4) 0.0365(14) Uani 1 1 d . . .
C2 C 0.3374(6) 0.0963(6) 0.6905(4) 0.0342(13) Uani 1 1 d . . .
C3 C 0.1852(6) -0.0067(7) 0.4127(4) 0.0444(16) Uani 1 1 d . . .
H3 H 0.1770 -0.0460 0.4747 0.053 Uiso 1 1 calc R . .
C4 C 0.0662(6) 0.0073(7) 0.3472(5) 0.0460(17) Uani 1 1 d . . .
H4 H -0.0198 -0.0238 0.3639 0.055 Uiso 1 1 calc R . .
C5 C 0.0750(6) 0.0670(6) 0.2576(4) 0.0372(14) Uani 1 1 d . . .
C6 C 0.2048(6) 0.1100(7) 0.2358(4) 0.0459(17) Uani 1 1 d . . .
H6 H 0.2149 0.1523 0.1754 0.055 Uiso 1 1 calc R . .
C7 C 0.3193(6) 0.0890(7) 0.3055(4) 0.0440(16) Uani 1 1 d . . .
H7 H 0.4074 0.1164 0.2899 0.053 Uiso 1 1 calc R . .
C8 C -0.3865(6) 0.1457(7) -0.1047(5) 0.0454(17) Uani 1 1 d . . .
H8 H -0.3839 0.1430 -0.1751 0.054 Uiso 1 1 calc R . .
C9 C -0.2619(6) 0.1272(6) -0.0431(5) 0.0443(16) Uani 1 1 d . . .
H9 H -0.1773 0.1141 -0.0715 0.053 Uiso 1 1 calc R . .
C10 C -0.2667(6) 0.1285(5) 0.0605(4) 0.0361(14) Uani 1 1 d . . .
C11 C -0.3926(6) 0.1499(6) 0.0978(5) 0.0474(17) Uani 1 1 d . . .
H11 H -0.3996 0.1507 0.1677 0.057 Uiso 1 1 calc R . .
C12 C -0.5100(7) 0.1703(7) 0.0302(5) 0.0491(17) Uani 1 1 d . . .
H12 H -0.5952 0.1874 0.0565 0.059 Uiso 1 1 calc R . .
C13 C -0.0455(6) 0.0866(6) 0.1849(5) 0.0421(15) Uani 1 1 d . . .
C14 C -0.1431(6) 0.1066(6) 0.1266(5) 0.0391(14) Uani 1 1 d . . .
Fe Fe 0.5000 0.0000 0.5000 0.0284(3) Uani 1 2 d S . .
N1 N 0.3931(5) 0.0652(5) 0.6215(4) 0.0377(12) Uani 1 1 d . . .
N2 N 0.4236(5) -0.1816(5) 0.5338(4) 0.0387(12) Uani 1 1 d . . .
N3 N 0.3104(5) 0.0320(5) 0.3931(3) 0.0336(11) Uani 1 1 d . . .
N4 N -0.5077(5) 0.1670(5) -0.0684(4) 0.0435(13) Uani 1 1 d . . .

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
Ag 0.0394(3) 0.0390(3) 0.0373(3) 0.0060(2) 0.00461(18) -0.0077(2)
C1 0.034(3) 0.038(4) 0.038(3) 0.002(3) 0.004(3) -0.005(3)
C2 0.031(3) 0.039(4) 0.032(3) 0.004(3) 0.001(2) 0.002(3)
C3 0.038(4) 0.056(4) 0.039(3) 0.019(3) 0.005(3) 0.001(3)
C4 0.027(3) 0.060(5) 0.050(4) 0.003(4) -0.004(3) -0.006(3)
C5 0.032(3) 0.040(4) 0.039(3) -0.004(3) -0.002(3) 0.005(3)
C6 0.042(3) 0.063(5) 0.032(3) 0.007(3) -0.001(3) 0.004(3)
C7 0.030(3) 0.069(5) 0.034(3) 0.007(3) 0.005(2) 0.000(3)
C8 0.040(3) 0.061(5) 0.033(3) -0.002(3) -0.005(3) 0.002(3)
C9 0.032(3) 0.053(4) 0.047(4) 0.004(3) 0.001(3) 0.004(3)
C10 0.033(3) 0.031(3) 0.042(3) -0.001(3) -0.009(3) -0.001(3)
C11 0.040(3) 0.067(5) 0.034(3) -0.006(3) -0.003(3) -0.001(3)
C12 0.034(3) 0.065(5) 0.047(4) -0.011(4) 0.000(3) 0.002(3)
C13 0.039(3) 0.036(4) 0.049(4) 0.005(3) -0.005(3) 0.002(3)
C14 0.041(3) 0.031(3) 0.044(3) 0.001(3) -0.005(3) -0.004(3)
Fe 0.0241(5) 0.0354(7) 0.0261(5) 0.0050(5) 0.0049(4) -0.0006(5)
N1 0.035(3) 0.041(3) 0.036(3) -0.001(2) -0.001(2) 0.003(2)
N2 0.036(3) 0.042(3) 0.038(3) 0.006(3) 0.003(2) 0.005(2)
N3 0.027(2) 0.044(3) 0.030(2) 0.004(2) 0.0028(19) 0.001(2)
N4 0.031(3) 0.055(4) 0.042(3) -0.007(3) -0.006(2) 0.005(3)

_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
Ag C2 2.080(6) 2_546 ?
Ag C1 2.087(6) . ?
Ag N4 2.569(4) 2_445 ?
C1 N2 1.146(7) . ?
C2 N1 1.158(7) . ?
C2 Ag 2.080(6) 2_556 ?
C3 N3 1.324(7) . ?
C3 C4 1.381(7) . ?
C3 H3 0.9400 . ?
C4 C5 1.369(8) . ?
C4 H4 0.9400 . ?
C5 C6 1.389(9) . ?
C5 C13 1.454(8) . ?
C6 C7 1.390(8) . ?
C6 H6 0.9400 . ?
C7 N3 1.331(7) . ?
C7 H7 0.9400 . ?
C8 N4 1.323(8) . ?
C8 C9 1.402(8) . ?
C8 H8 0.9400 . ?
C9 C10 1.384(8) . ?
C9 H9 0.9400 . ?
C10 C11 1.372(9) . ?
C10 C14 1.431(8) . ?
C11 C12 1.393(9) . ?
C11 H11 0.9400 . ?
C12 N4 1.315(8) . ?
C12 H12 0.9400 . ?
C13 C14 1.181(8) . ?
Fe N1 2.119(5) 3_656 ?
Fe N1 2.119(5) . ?
Fe N2 2.172(5) 3_656 ?
Fe N2 2.172(5) . ?
Fe N3 2.233(4) 3_656 ?
Fe N3 2.233(4) . ?
N4 Ag 2.569(4) 2_455 ?

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
C2 Ag C1 163.4(2) 2_546 . ?
C2 Ag N4 96.90(19) 2_546 2_445 ?
C1 Ag N4 98.6(2) . 2_445 ?
N2 C1 Ag 167.7(6) . . ?
N1 C2 Ag 172.8(5) . 2_556 ?
N3 C3 C4 123.8(5) . . ?
N3 C3 H3 118.1 . . ?
C4 C3 H3 118.1 . . ?
C5 C4 C3 119.1(6) . . ?
C5 C4 H4 120.4 . . ?
C3 C4 H4 120.4 . . ?
C4 C5 C6 118.2(5) . . ?
C4 C5 C13 122.6(6) . . ?
C6 C5 C13 119.2(6) . . ?
C5 C6 C7 118.5(6) . . ?
C5 C6 H6 120.8 . . ?
C7 C6 H6 120.8 . . ?
N3 C7 C6 123.3(6) . . ?
N3 C7 H7 118.4 . . ?
C6 C7 H7 118.4 . . ?
N4 C8 C9 123.1(6) . . ?
N4 C8 H8 118.5 . . ?
C9 C8 H8 118.5 . . ?
C10 C9 C8 118.3(6) . . ?
C10 C9 H9 120.8 . . ?
C8 C9 H9 120.8 . . ?
C11 C10 C9 118.4(5) . . ?
C11 C10 C14 121.1(6) . . ?
C9 C10 C14 120.5(6) . . ?
C10 C11 C12 118.9(6) . . ?
C10 C11 H11 120.6 . . ?
C12 C11 H11 120.6 . . ?
N4 C12 C11 123.4(6) . . ?
N4 C12 H12 118.3 . . ?
C11 C12 H12 118.3 . . ?
C14 C13 C5 177.8(7) . . ?
C13 C14 C10 176.5(7) . . ?
N1 Fe N1 179.999(1) 3_656 . ?
N1 Fe N2 87.1(2) 3_656 3_656 ?
N1 Fe N2 92.9(2) . 3_656 ?
N1 Fe N2 92.9(2) 3_656 . ?
N1 Fe N2 87.1(2) . . ?
N2 Fe N2 180.0 3_656 . ?
N1 Fe N3 90.44(17) 3_656 3_656 ?
N1 Fe N3 89.56(17) . 3_656 ?
N2 Fe N3 90.12(18) 3_656 3_656 ?
N2 Fe N3 89.88(18) . 3_656 ?
N1 Fe N3 89.56(17) 3_656 . ?
N1 Fe N3 90.44(17) . . ?
N2 Fe N3 89.88(18) 3_656 . ?
N2 Fe N3 90.12(18) . . ?
N3 Fe N3 180.00(14) 3_656 . ?
C2 N1 Fe 176.8(5) . . ?
C1 N2 Fe 152.2(5) . . ?
C3 N3 C7 117.1(5) . . ?
C3 N3 Fe 121.9(4) . . ?
C7 N3 Fe 121.0(4) . . ?
C12 N4 C8 117.9(5) . . ?
C12 N4 Ag 118.9(4) . 2_455 ?
C8 N4 Ag 122.4(4) . 2_455 ?