# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
# This journal is © the Owner Societies 2022

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_3
_database_code_depnum_ccdc_archive 'CCDC 2151777'
loop_
_audit_author_name
_audit_author_address
'Nicholas White'
;Australian National University
Australia
;
_audit_update_record             
;
2022-02-13 deposited with the CCDC.	2022-04-18 downloaded from the CCDC.
;

_exptl_special_details           
; 
 The crystal was 
placed in the cold stream of an Oxford 
Cryosystems open-flow nitrogen cryostat (Cosier & 
Glazer, 1986) with a nominal stability of 0.1K. 
 
Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107. 
;

_refine_special_details          
; 
The asymmetric unit cell contains one quarter of one tetraphenylsilane-based
molecule and two water molecules. Further investigation (both crystallographic
and using other chemical techniques) revealed that this is a H-bonded framework
between the tetra-carboxylate (4-) and the tetra-amidinium (4+) compounds.
As these have very similar geometries, they are in the same place 
crystallographically (i.e. all carbon atoms overlap, and the O/N atoms of the 
carboxylate/amidinium groups essentially overlap). Hydrogen atoms in sensible 
places for the amidinium NH2 groups are visible in the Fourier difference map.

The structure was modelled by having two half-occupancy oxygen atoms and
two half-occupancy nitrogen atoms (with attached hydrogen atoms). The C-N
and C-O bond lengths, and angles involving these atoms were restrained, 
as were the thermal and vibrational elliposid parameters for these atoms. 

C-H hydrogen atoms were  visible in the Fourier difference map and were 
initially refined with restraints on bond lengths and angles, after which the 
positions were used as the basis for a riding model.  There are two positions 
for the water hydrogen atoms (corresponding to different H-bonding networks 
with the H-bond accepting carboxylate oxygen atoms vs. the H-bond donating 
amidinium  nitrogen atoms). It was possible to resolve these sensibly by 
inserting the amidinium hydrogen atoms at geometric positions and the water 
hydrogen atoms at idealised H-bonding positions, and then refining the positions 
of  these atoms with restraints on N-H/O-H bond lengths and angles. 
;

_cell_length_a                   14.33058(3)
_cell_length_b                   14.33058(3)
_cell_length_c                   8.35856(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1716.560(8)

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'P 42/n '
_symmetry_space_group_name_Hall  '-P 4bc'

loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z
y+1/2,-x,z+1/2
-y+1/2,x,-z+1/2
x+1/2,y+1/2,-z
-x+1/2,-y+1/2,z
-y,x+1/2,z+1/2
y,-x+1/2,-z+1/2

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089
0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
Si 0.2541 0.3302 6.2915 2.4386 3.0353 32.3337 1.9891 0.6785 1.5410 81.6937
1.1407 'International Tables Vol C 4.2.6.8 and 6.1.1.4'

_cell_formula_units_Z            1

_chemical_formula_sum            'C56 H72 N8 O20 Si2'
_chemical_formula_moiety         'C28 H32 N8 Si, C28 H16 O8 Si, 12(H2 O)'
_chemical_compound_source        synthesized
_chemical_formula_weight         1233.40

_cell_measurement_reflns_used    3802
_cell_measurement_theta_min      6.00
_cell_measurement_theta_max      73.5
_cell_measurement_temperature    150

_exptl_crystal_description       shard
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.06
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_max          0.68

_exptl_crystal_density_diffrn    1.193
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000): 
_exptl_crystal_F_000             652
_exptl_absorpt_coefficient_mu    1.077

_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlisPro, (Agilent, 2011)'
_exptl_absorpt_correction_T_min  0.60
_exptl_absorpt_correction_T_max  1.00
_diffrn_measurement_device_type  'Oxford Diffraction Supernova'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_measurement_method       ω

_computing_data_collection       'CrysAlisPro, (Agilent, 2011'
_computing_cell_refinement       'CrysAlisPro, (Agilent, 2011)'
_computing_data_reduction        'CrysAlisPro, (Agilent, 2011)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        .

_diffrn_ambient_temperature      150
_diffrn_reflns_number            14784
_diffrn_reflns_av_unetI/netI     0.013
_reflns_number_total             1688
_diffrn_reflns_av_R_equivalents  0.093

_diffrn_reflns_theta_min         4.363
_diffrn_reflns_theta_max         73.539
_diffrn_measured_fraction_theta_max 0.972

_diffrn_reflns_theta_full        71.766
_diffrn_measured_fraction_theta_full 0.978

_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       7
_reflns_limit_h_min              -12
_reflns_limit_h_max              12
_reflns_limit_k_min              0
_reflns_limit_k_max              17
_reflns_limit_l_min              0
_reflns_limit_l_max              10

_oxford_diffrn_Wilson_B_factor   2.07
_oxford_diffrn_Wilson_scale      0.02

_atom_sites_solution_primary     other
_atom_sites_solution_hydrogens   difmap

_refine_diff_density_min         -0.44
_refine_diff_density_max         0.58

# The values actually used during refinement 
_oxford_refine_reflns_threshold_expression_ref I>-3.0\s(I)
_refine_ls_number_restraints     92
_refine_ls_number_parameters     132
_refine_ls_number_reflns         1393
_oxford_refine_ls_R_factor_ref   0.0845
_refine_ls_wR_factor_ref         0.1977
_refine_ls_goodness_of_fit_ref   1.0673
_refine_ls_shift/su_max          0.0000897
_refine_ls_shift/su_mean         0.0000147

# The values computed with all filters except I/sigma 
_oxford_reflns_number_all        1636
_refine_ls_R_factor_all          0.0955
_refine_ls_wR_factor_all         0.2334

# The values computed with a 2 sigma cutoff - a la SHELX 
_reflns_threshold_expression     I>2.0σ(I)
_reflns_number_gt                1582
_refine_ls_R_factor_gt           0.0938
_refine_ls_wR_factor_gt          0.2318


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
 Method= Modified Sheldrick 
 w=1/[σ²(F²) + ( 0.06P)² + 8.16P] 
 ,where P=(max(Fo²,0) + 2Fc²)/3 
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3
# Replace last . with number of unfound hydrogen atoms attached to an atom.
# ..._refinement_flags_... 
# . no refinement constraints           S special position constraint on site
# G rigid group refinement of site      R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond)  P partial occupancy constraint
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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
N1 N 0.5824(12) 1.0261(10) 0.8420(19) 0.0309 0.5000 Uani D U . . 1 .
N2 N 0.4866(12) 0.9009(10) 0.8822(17) 0.0346 0.5000 Uani D U . . 1 .
C3 C 0.5421(3) 0.9497(3) 0.7890(4) 0.0310 1.0000 Uani D U . . . .
C4 C 0.5813(3) 0.9037(3) 0.6438(4) 0.0267 1.0000 Uani D U . . . .
C5 C 0.6167(3) 0.9561(3) 0.5173(5) 0.0299 1.0000 Uani . . . . . .
C6 C 0.6613(3) 0.9109(3) 0.3915(4) 0.0284 1.0000 Uani . . . . . .
C7 C 0.6714(3) 0.8153(3) 0.3892(4) 0.0254 1.0000 Uani . . . . . .
C8 C 0.6319(3) 0.7641(3) 0.5145(5) 0.0310 1.0000 Uani . . . . . .
C9 C 0.5878(3) 0.8076(3) 0.6402(5) 0.0308 1.0000 Uani . . . . . .
Si10 Si 0.7500 0.7500 0.2500 0.0241 1.0000 Uani S T . . . .
O111 O 0.2500 0.7500 0.5274(5) 0.0507 1.0000 Uani S T . . . .
O101 O 0.3801(2) 0.7416(2) 0.7766(4) 0.0469 1.0000 Uani . . . . . .
O11 O 0.5675(10) 1.0322(7) 0.8227(16) 0.0325 0.5000 Uani D U . . 2 .
O12 O 0.4740(9) 0.9111(8) 0.8602(14) 0.0345 0.5000 Uani D U . . 2 .
H51 H 0.6103 1.0215 0.5168 0.0372 1.0000 Uiso R . . . . .
H61 H 0.6856 0.9463 0.3075 0.0351 1.0000 Uiso R . . . . .
H81 H 0.6365 0.6979 0.5129 0.0395 1.0000 Uiso R . . . . .
H91 H 0.5622 0.7720 0.7248 0.0386 1.0000 Uiso R . . . . .
H21 H 0.454(5) 0.856(5) 0.841(4) 0.0399(19) 0.5000 Uiso D . . . 1 .
H22 H 0.450(5) 0.930(2) 0.948(8) 0.0399(19) 0.5000 Uiso D . . . 1 .
H11 H 0.622(5) 1.055(4) 0.782(6) 0.0370(19) 0.5000 Uiso D . . . 1 .
H12 H 0.556(4) 1.059(4) 0.915(8) 0.0370(19) 0.5000 Uiso D . . . 1 .
H1011 H 0.3406 0.7441 0.7013 0.0565 0.5000 Uiso . . . . 1 .
H1113 H 0.2895 0.7475 0.6019 0.0595 0.5000 Uiso . . . . 2 .
H1111 H 0.2475 0.7104 0.4505 0.0600 0.5000 Uiso . . . . 1 .
H1012 H 0.3406 0.7442 0.8529 0.0565 0.5000 Uiso . . . . 1 .
H1013 H 0.4056 0.6909 0.7479 0.0565 0.5000 Uiso . . . . 2 .
H1014 H 0.4079 0.7920 0.8017 0.0565 0.5000 Uiso . . . . 2 .


_refine_ls_extinction_method     None
_oxford_refine_ls_scale          7.0(5)

loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
N1 . C3 . 1.314(8) yes
N1 . H11 . 0.855(19) no
N1 . H12 . 0.860(19) no
N2 . C3 . 1.314(8) yes
N2 . H21 . 0.867(19) no
N2 . H22 . 0.862(19) no
C3 . C4 . 1.491(5) yes
C4 . C5 . 1.391(5) yes
C4 . C9 . 1.382(6) yes
C5 . C6 . 1.390(5) yes
C5 . H51 . 0.942 no
C6 . C7 . 1.377(6) yes
C6 . H61 . 0.934 no
C7 . C8 . 1.399(5) yes
C7 . Si10 . 1.871(4) yes
C8 . C9 . 1.375(5) yes
C8 . H81 . 0.951 no
C9 . H91 . 0.946 no
O111 . H1111 6_565 0.858 no
O111 . H1111 . 0.858 no
O101 . H1011 . 0.847 no
O101 . H1012 . 0.853 no

loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C3 . N1 . H11 . 119.4(19) no
C3 . N1 . H12 . 120.0(19) no
H11 . N1 . H12 . 116(5) no
C3 . N2 . H21 . 119.2(19) no
C3 . N2 . H22 . 119.3(19) no
H21 . N2 . H22 . 106(7) no
N1 . C3 . N2 . 120.6(7) yes
N1 . C3 . C4 . 118.4(6) yes
N2 . C3 . C4 . 118.4(6) yes
C3 . C4 . C5 . 121.2(3) yes
C3 . C4 . C9 . 118.9(3) yes
C5 . C4 . C9 . 119.8(3) yes
C4 . C5 . C6 . 119.4(4) yes
C4 . C5 . H51 . 120.3 no
C6 . C5 . H51 . 120.3 no
C5 . C6 . C7 . 121.4(4) yes
C5 . C6 . H61 . 119.2 no
C7 . C6 . H61 . 119.3 no
C6 . C7 . C8 . 118.0(3) yes
C6 . C7 . Si10 . 124.7(3) yes
C8 . C7 . Si10 . 116.5(3) yes
C7 . C8 . C9 . 121.3(4) yes
C7 . C8 . H81 . 119.0 no
C9 . C8 . H81 . 119.7 no
C4 . C9 . C8 . 120.0(4) yes
C4 . C9 . H91 . 119.7 no
C8 . C9 . H91 . 120.3 no
C7 8_565 Si10 . C7 6_665 112.77(12) yes
C7 8_565 Si10 . C7 . 112.77(12) yes
C7 6_665 Si10 . C7 . 103.1(2) yes
C7 8_565 Si10 . C7 4_655 103.1(2) yes
C7 6_665 Si10 . C7 4_655 112.77(12) yes
C7 . Si10 . C7 4_655 112.77(12) yes
H1111 6_565 O111 . H1111 . 82.9 no
H1011 . O101 . H1012 . 96.4 no

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_site_symmetry_D
_geom_hbond_atom_site_label_H
_geom_hbond_site_symmetry_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_A
_geom_hbond_angle_DHA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_publ_flag
N2 . H21 . O101 . 171(6) 0.867 2.025 2.885(5) yes
O12 . H21 . O101 . 167(9) 0.854 2.025 2.863(5) yes
N2 . H22 . N1 2_677 152(9) 0.862 1.924 2.718(5) yes
N2 . H22 . O11 2_677 145(9) 0.862 2.009 2.758(5) yes
O12 . H22 . N1 2_677 171(9) 0.851 1.924 2.767(5) yes
O12 . H22 . O11 2_677 163(9) 0.851 2.009 2.835(5) yes
N1 . H11 . O101 8_566 157(7) 0.855 2.019 2.828(5) yes
O11 . H11 . O101 8_566 170(3) 0.904 2.019 2.914(5) yes
N1 . H12 . N2 2_677 161(9) 0.860 1.890 2.718(5) yes
O11 . H12 . N2 2_677 169(3) 0.878 1.890 2.758(5) yes
N1 . H12 . O12 2_677 153(9) 0.860 1.973 2.767(5) yes
O11 . H12 . O12 2_677 167(7) 0.878 1.973 2.835(5) yes
O101 . H1011 . O111 . 180 0.85 1.95 2.798(5) yes
O111 . H1113 . O101 . 179 0.84 1.96 2.798(5) yes
O111 . H1111 . O101 3_464 180 0.86 1.95 2.808(5) yes
O101 . H1012 . O111 3_465 180 0.85 1.95 2.808(5) yes
O101 . H1013 . N1 4_656 172 0.85 1.98 2.828(5) yes
O101 . H1013 . O11 4_656 180 0.85 2.07 2.914(5) yes
O101 . H1014 . N2 . 172 0.85 2.04 2.885(5) yes
O101 . H1014 . O12 . 180 0.85 2.01 2.863(5) yes


# looking for ARCHIVE-HKL.CIF 
# end of ARCHIVE-HKL.CIF 
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Water/ethanol'
