# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_CaBH4THF_MONO_a
_database_code_depnum_ccdc_archive 'CCDC 1964638'
loop_
_audit_author_name
_audit_author_address
'Mark Rodriguez'
;Sandia National Laboratories
United States of America
;
_audit_update_record             
;
2019-11-08 deposited with the CCDC.	2020-03-23 downloaded from the CCDC.
;





_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        (THF)2Ca(BH4)2
_chemical_name_common            (THF)2Ca(BH4)2
_chemical_melting_point          ?
_chemical_formula_moiety         'C8 H24 B2 Ca O2'
_chemical_formula_sum            'C8 H24 B2 Ca O2'
_chemical_formula_weight         213.97

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'
Ca Ca 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   4.2819(9)
_cell_length_b                   18.053(4)
_cell_length_c                   8.0685(17)
_cell_angle_alpha                90
_cell_angle_beta                 90.142(9)
_cell_angle_gamma                90
_cell_volume                     623.7(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    190(2)
_cell_measurement_reflns_used    200
_cell_measurement_theta_min      2.00
_cell_measurement_theta_max      25.00

_exptl_crystal_description       irregular
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_F_000             236
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.150
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.473
_shelx_estimated_absorpt_T_min   0.932
_shelx_estimated_absorpt_T_max   0.963
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.91
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_process_details   'SADABS (Bruker, 2018)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      190(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX CCD'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5537
_diffrn_reflns_av_unetI/netI     0.0834
_diffrn_reflns_av_R_equivalents  0.0670
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.524
_diffrn_reflns_theta_max         26.512
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measured_fraction_theta_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.911
_diffrn_reflns_point_group_measured_fraction_full 0.951
_reflns_number_total             2372
_reflns_number_gt                2154
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.837
_reflns_Friedel_fraction_max     0.858
_reflns_Friedel_fraction_full    0.919

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.  Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'APEX 3  (Bruker, 2018)'
_computing_cell_refinement       'APEX 3  (Bruker, 2018)'
_computing_data_reduction        ?
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    'Mercury CSD 4.2.0 (CCDC, 2019)'
_computing_publication_material  ?

_refine_special_details          
;Structure refined as a 2-component inversion twin.

The atoms that made up the borohydride tetrahedra 
were not easily determined and refined to stable 
locations about the B atom based on the X-ray 
Diffraction data alone.  Instead, H positions were 
estimated in terms of location using observed Q 
peaks near the B atoms during refinement cycles 
of the X-ray Diffraction data, and then subsequently 
modeled via energy minimization via Density Functional 
Theory (DFT) models.  These modeled locations for the 
H atoms on the borohydride molecules were then fed back 
into the final X-ray structure and restrained in terms 
of bond distances and angles as dictated by the DFT 
output.  The Uiso values of the bound H atoms on the 
borohydride molecules were restrained to be identical 
for all eight of the H atoms that were present on the 
two different borohydride tetrahedra.  This was done 
to stabilize the isotropic atomic displacement 
parameters of the H atoms.,Twin
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1000P)²+0.7216P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.17(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.35(19)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2372
_refine_ls_number_parameters     145
_refine_ls_number_restraints     21
_refine_ls_R_factor_all          0.0893
_refine_ls_R_factor_gt           0.0802
_refine_ls_wR_factor_ref         0.2292
_refine_ls_wR_factor_gt          0.2231
_refine_ls_goodness_of_fit_ref   1.424
_refine_ls_restrained_S_all      1.417
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ca1 Ca 0.7015(3) 0.5004(2) 0.2500(2) 0.0178(6) Uani 1 1 d . . . . .
O1 O 0.7258(15) 0.3997(4) 0.0613(7) 0.0200(14) Uani 1 1 d . . . . .
C1 C 0.808(3) 0.3250(6) 0.1027(14) 0.033(2) Uani 1 1 d . . . . .
H1A H 0.690094 0.307973 0.200904 0.039 Uiso 1 1 calc R U . . .
H1B H 1.034381 0.321130 0.126878 0.039 Uiso 1 1 calc R U . . .
C2 C 0.724(3) 0.2795(6) -0.0474(13) 0.033(3) Uani 1 1 d . . . . .
H2A H 0.852925 0.234150 -0.054293 0.040 Uiso 1 1 calc R U . . .
H2B H 0.500332 0.265528 -0.046532 0.040 Uiso 1 1 calc R U . . .
C3 C 0.795(3) 0.3319(6) -0.1876(12) 0.032(2) Uani 1 1 d . . . . .
H3A H 0.664831 0.320548 -0.285938 0.039 Uiso 1 1 calc R U . . .
H3B H 1.018019 0.329053 -0.219111 0.039 Uiso 1 1 calc R U . . .
C4 C 0.717(3) 0.4072(6) -0.1183(12) 0.028(2) Uani 1 1 d . . . . .
H4A H 0.870716 0.444441 -0.155727 0.034 Uiso 1 1 calc R U . . .
H4B H 0.506171 0.422917 -0.155425 0.034 Uiso 1 1 calc R U . . .
O2 O 0.7245(15) 0.6016(4) 0.4401(7) 0.0191(14) Uani 1 1 d . . . . .
C5 C 0.717(3) 0.5937(6) 0.6180(12) 0.029(2) Uani 1 1 d . . . . .
H5A H 0.872204 0.556413 0.654682 0.034 Uiso 1 1 calc R U . . .
H5B H 0.507458 0.577634 0.654744 0.034 Uiso 1 1 calc R U . . .
C6 C 0.796(3) 0.6695(7) 0.6901(14) 0.035(3) Uani 1 1 d . . . . .
H6A H 1.019369 0.672777 0.721225 0.042 Uiso 1 1 calc R U . . .
H6B H 0.666217 0.680600 0.788371 0.042 Uiso 1 1 calc R U . . .
C7 C 0.719(3) 0.7217(6) 0.5461(14) 0.033(2) Uani 1 1 d . . . . .
H7A H 0.493564 0.734076 0.543789 0.039 Uiso 1 1 calc R U . . .
H7B H 0.841748 0.768003 0.553149 0.039 Uiso 1 1 calc R U . . .
C8 C 0.810(3) 0.6766(6) 0.3964(13) 0.030(2) Uani 1 1 d . . . . .
H8A H 0.695521 0.693337 0.296531 0.036 Uiso 1 1 calc R U . . .
H8B H 1.037467 0.680443 0.375284 0.036 Uiso 1 1 calc R U . . .
B1 B 0.210(2) 0.4363(6) 0.4421(12) 0.023(2) Uani 1 1 d D . . . .
B2 B 0.207(2) 0.5638(6) 0.0576(12) 0.021(2) Uani 1 1 d D . . . .
H1 H 0.366(14) 0.398(3) 0.346(7) 0.043(11) Uiso 1 1 d D . . . .
H2 H 0.241(16) 0.5021(10) 0.414(9) 0.043(11) Uiso 1 1 d D . . . .
H3 H 0.295(16) 0.424(4) 0.586(3) 0.043(11) Uiso 1 1 d D . . . .
H4 H -0.063(6) 0.417(4) 0.428(9) 0.043(11) Uiso 1 1 d D . . . .
H5 H 0.234(16) 0.4960(9) 0.078(9) 0.043(11) Uiso 1 1 d D . . . .
H6 H 0.293(16) 0.579(4) -0.082(4) 0.043(11) Uiso 1 1 d D . . . .
H7 H -0.067(6) 0.582(4) 0.075(9) 0.043(11) Uiso 1 1 d D . . . .
H8 H 0.362(14) 0.597(3) 0.162(7) 0.043(11) Uiso 1 1 d D . . . .


_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
Ca1 O1 2.374(7) . ?
Ca1 O2 2.387(7) . ?
Ca1 B1 2.859(11) . ?
Ca1 B2 2.861(10) . ?
Ca1 B2 2.903(10) 1_655 ?
Ca1 B1 2.910(10) 1_655 ?
Ca1 Ca1 4.2819(9) 1_655 ?
Ca1 Ca1 4.2819(9) 1_455 ?
Ca1 H1 2.46(7) . ?
Ca1 H2 2.38(7) . ?
Ca1 H5 2.43(7) . ?
Ca1 H8 2.38(7) . ?
O1 C1 1.433(12) . ?
O1 C4 1.456(11) . ?
C1 C2 1.506(15) . ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 C3 1.506(15) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C4 1.508(15) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
O2 C5 1.443(11) . ?
O2 C8 1.447(12) . ?
C5 C6 1.525(16) . ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 C7 1.531(16) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.509(15) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
B1 H1 1.230(6) . ?
B1 H2 1.216(6) . ?
B1 H3 1.239(6) . ?
B1 H4 1.226(6) . ?
B2 H5 1.240(6) . ?
B2 H6 1.215(6) . ?
B2 H7 1.227(6) . ?
B2 H8 1.230(6) . ?

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
O1 Ca1 O2 175.1(2) . . ?
O1 Ca1 B1 94.1(3) . . ?
O2 Ca1 B1 89.5(3) . . ?
O1 Ca1 B2 89.5(3) . . ?
O2 Ca1 B2 94.1(3) . . ?
B1 Ca1 B2 84.9(3) . . ?
O1 Ca1 B2 85.7(3) . 1_655 ?
O2 Ca1 B2 90.7(3) . 1_655 ?
B1 Ca1 B2 179.1(3) . 1_655 ?
B2 Ca1 B2 96.0(3) . 1_655 ?
O1 Ca1 B1 90.2(3) . 1_655 ?
O2 Ca1 B1 86.1(3) . 1_655 ?
B1 Ca1 B1 95.8(3) . 1_655 ?
B2 Ca1 B1 179.2(3) . 1_655 ?
B2 Ca1 B1 83.3(3) 1_655 1_655 ?
O1 Ca1 Ca1 87.40(15) . 1_655 ?
O2 Ca1 Ca1 87.73(15) . 1_655 ?
B1 Ca1 Ca1 137.5(2) . 1_655 ?
B2 Ca1 Ca1 137.6(2) . 1_655 ?
B2 Ca1 Ca1 41.6(2) 1_655 1_655 ?
B1 Ca1 Ca1 41.6(2) 1_655 1_655 ?
O1 Ca1 Ca1 92.60(15) . 1_455 ?
O2 Ca1 Ca1 92.27(15) . 1_455 ?
B1 Ca1 Ca1 42.5(2) . 1_455 ?
B2 Ca1 Ca1 42.4(2) . 1_455 ?
B2 Ca1 Ca1 138.4(2) 1_655 1_455 ?
B1 Ca1 Ca1 138.4(2) 1_655 1_455 ?
Ca1 Ca1 Ca1 180.00(9) 1_655 1_455 ?
O1 Ca1 H1 69.9(6) . . ?
O2 Ca1 H1 113.1(7) . . ?
B1 Ca1 H1 25.3(2) . . ?
B2 Ca1 H1 92.2(17) . . ?
B2 Ca1 H1 154.2(4) 1_655 . ?
B1 Ca1 H1 88.4(17) 1_655 . ?
Ca1 Ca1 H1 125.8(14) 1_655 . ?
Ca1 Ca1 H1 54.2(14) 1_455 . ?
O1 Ca1 H2 113.8(12) . . ?
O2 Ca1 H2 70.5(12) . . ?
B1 Ca1 H2 24.7(3) . . ?
B2 Ca1 H2 71.5(16) . . ?
B2 Ca1 H2 156.0(5) 1_655 . ?
B1 Ca1 H2 109.3(16) 1_655 . ?
Ca1 Ca1 H2 146.2(18) 1_655 . ?
Ca1 Ca1 H2 33.8(18) 1_455 . ?
H1 Ca1 H2 49.3(4) . . ?
O1 Ca1 H5 69.3(12) . . ?
O2 Ca1 H5 115.0(11) . . ?
B1 Ca1 H5 71.9(16) . . ?
B2 Ca1 H5 25.5(3) . . ?
B2 Ca1 H5 108.8(16) 1_655 . ?
B1 Ca1 H5 154.7(5) 1_655 . ?
Ca1 Ca1 H5 145.2(18) 1_655 . ?
Ca1 Ca1 H5 34.8(18) 1_455 . ?
H1 Ca1 H5 71(2) . . ?
H2 Ca1 H5 69(2) . . ?
O1 Ca1 H8 113.5(7) . . ?
O2 Ca1 H8 69.7(6) . . ?
B1 Ca1 H8 90.5(17) . . ?
B2 Ca1 H8 25.1(3) . . ?
B2 Ca1 H8 90.4(17) 1_655 . ?
B1 Ca1 H8 155.0(5) 1_655 . ?
Ca1 Ca1 H8 127.6(15) 1_655 . ?
Ca1 Ca1 H8 52.4(15) 1_455 . ?
H1 Ca1 H8 106.6(18) . . ?
H2 Ca1 H8 69(2) . . ?
H5 Ca1 H8 49.7(4) . . ?
C1 O1 C4 109.0(7) . . ?
C1 O1 Ca1 125.6(6) . . ?
C4 O1 Ca1 124.5(6) . . ?
O1 C1 C2 105.5(9) . . ?
O1 C1 H1A 110.6 . . ?
C2 C1 H1A 110.6 . . ?
O1 C1 H1B 110.6 . . ?
C2 C1 H1B 110.6 . . ?
H1A C1 H1B 108.8 . . ?
C3 C2 C1 102.3(9) . . ?
C3 C2 H2A 111.3 . . ?
C1 C2 H2A 111.3 . . ?
C3 C2 H2B 111.3 . . ?
C1 C2 H2B 111.3 . . ?
H2A C2 H2B 109.2 . . ?
C2 C3 C4 104.0(8) . . ?
C2 C3 H3A 111.0 . . ?
C4 C3 H3A 111.0 . . ?
C2 C3 H3B 111.0 . . ?
C4 C3 H3B 111.0 . . ?
H3A C3 H3B 109.0 . . ?
O1 C4 C3 106.2(8) . . ?
O1 C4 H4A 110.5 . . ?
C3 C4 H4A 110.5 . . ?
O1 C4 H4B 110.5 . . ?
C3 C4 H4B 110.5 . . ?
H4A C4 H4B 108.7 . . ?
C5 O2 C8 109.9(7) . . ?
C5 O2 Ca1 124.2(5) . . ?
C8 O2 Ca1 124.7(6) . . ?
O2 C5 C6 106.6(8) . . ?
O2 C5 H5A 110.4 . . ?
C6 C5 H5A 110.4 . . ?
O2 C5 H5B 110.4 . . ?
C6 C5 H5B 110.4 . . ?
H5A C5 H5B 108.6 . . ?
C5 C6 C7 102.4(9) . . ?
C5 C6 H6A 111.3 . . ?
C7 C6 H6A 111.3 . . ?
C5 C6 H6B 111.3 . . ?
C7 C6 H6B 111.3 . . ?
H6A C6 H6B 109.2 . . ?
C8 C7 C6 102.7(9) . . ?
C8 C7 H7A 111.2 . . ?
C6 C7 H7A 111.2 . . ?
C8 C7 H7B 111.2 . . ?
C6 C7 H7B 111.2 . . ?
H7A C7 H7B 109.1 . . ?
O2 C8 C7 104.0(8) . . ?
O2 C8 H8A 110.9 . . ?
C7 C8 H8A 110.9 . . ?
O2 C8 H8B 110.9 . . ?
C7 C8 H8B 110.9 . . ?
H8A C8 H8B 109.0 . . ?
Ca1 B1 Ca1 95.8(3) . 1_455 ?
Ca1 B1 H1 59(3) . . ?
Ca1 B1 H1 107(3) 1_455 . ?
Ca1 B1 H2 55(3) . . ?
Ca1 B1 H2 66(3) 1_455 . ?
H1 B1 H2 111.5(7) . . ?
Ca1 B1 H3 112(3) . . ?
Ca1 B1 H3 142(3) 1_455 . ?
H1 B1 H3 109.5(7) . . ?
H2 B1 H3 108.8(7) . . ?
Ca1 B1 H4 140(3) . . ?
Ca1 B1 H4 49(3) 1_455 . ?
H1 B1 H4 107.7(7) . . ?
H2 B1 H4 111.2(7) . . ?
H3 B1 H4 108.2(7) . . ?
Ca1 B2 Ca1 96.0(3) . 1_455 ?
Ca1 B2 H5 58(3) . . ?
Ca1 B2 H5 67(3) 1_455 . ?
Ca1 B2 H6 112(3) . . ?
Ca1 B2 H6 144(3) 1_455 . ?
H5 B2 H6 108.8(7) . . ?
Ca1 B2 H7 139(3) . . ?
Ca1 B2 H7 48(3) 1_455 . ?
H5 B2 H7 109.6(7) . . ?
H6 B2 H7 109.7(7) . . ?
Ca1 B2 H8 55(3) . . ?
Ca1 B2 H8 103(3) 1_455 . ?
H5 B2 H8 110.0(7) . . ?
H6 B2 H8 111.2(7) . . ?
H7 B2 H8 107.5(7) . . ?

_refine_diff_density_max         0.938
_refine_diff_density_min         -1.220
_refine_diff_density_rms         0.118


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_chemical_properties_physical    Air-sensitive,Oxygen-sensitive
