Supplementary Material (ESI) for Dalton Transactions
This journal is (C) The Royal Society of Chemistry 2011
data_global
_journal_name_full 'Dalton Trans.'
_journal_coden_Cambridge 0222
_journal_volume ?
_journal_page_first ?
_journal_year ?
_publ_contact_author_name 'Grochala, Wojciech'
_publ_contact_author_email wg22@cornell.edu
_publ_section_title
;
Na[Li(NH2BH3)2] - the first mixed-cation
amidoborane with unusual crystal structure
;
_publ_author_name W.Grochala
# Attachment '- C0JM03302B_ccdc_795163_cif.txt'
data_LiNaAB2
#TrackingRef '- C0JM03302B_ccdc_795163_cif.txt'
_database_code_depnum_ccdc_archive 'CCDC 795163'
#TrackingRef '- LiNaAB2_CSD-422190.cif'
_exptl_absorpt_process_details cylindical
#Added by publCIF
_refine_ls_R_Fsqd_factor ?
#Added by publCIF
_refine_ls_R_factor_all ?
#Added by publCIF
_pd_block_id LiNaAB2
# 15. CHEMICAL DATA
_chemical_name_systematic
;
Lithium Sodium diamidoborane
;
_chemical_name_common 'Lithium Sodium diamidoborane'
_chemical_formula_moiety '2(B H5 N), Na, Li'
_chemical_formula_structural 'Li Na BH3 NH2'
_chemical_formula_analytical ?
_chemical_formula_iupac 'Li Na BH3 NH2'
_chemical_formula_sum 'B2 H10 Li1 N2 Na1'
_chemical_formula_weight 89.65
_chemical_melting_point ?
_chemical_compound_source 'Synthesied in our laboratory'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Na Na ? ? 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N ? ? 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Li Li ? ? 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H ? ? 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
B B ? ? 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
#===============================================================================
# 16. POWDER SPECIMEN AND CRYSTAL DATA
_symmetry_cell_setting Triclinic
_symmetry_space_group_name_Hall '-P 1'
_symmetry_space_group_name_H-M 'P -1'
_symmetry_Int_Tables_number 2
loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 x,y,z
2 -x,-y,-z
_cell_length_a 5.0197(4)
_cell_length_b 7.1203(7)
_cell_length_c 8.9198(9)
_cell_angle_alpha 103.003(6)
_cell_angle_beta 102.200(5)
_cell_angle_gamma 103.575(5)
_cell_volume 289.98(5)
_cell_formula_units_Z 2
_cell_measurement_temperature 296
_cell_measurement_reflns_used ?
_cell_measurement_theta_min 3
_cell_measurement_theta_max 23.3
_cell_special_details
;
;
_pd_calibration_special_details
; The instrument has been allimented and centred using
the silicon powder NIST sample.
;
_exptl_crystal_density_diffrn 1.027
_exptl_crystal_density_method 'Not Measured'
_exptl_crystal_F_000 96
_exptl_absorpt_coefficient_mu ?
# The next three fields give the specimen dimensions in mm. The equatorial
# plane contains the incident and diffracted beam.
_pd_spec_size_axial 18 # perpendicular to
# equatorial plane
_pd_spec_size_equat 0.3 # parallel to
# scattering vector
# in transmission
_pd_spec_size_thick 0.3 # parallel to
# scattering vector
# in reflection
# The next five fields are character fields that describe the specimen.
_pd_spec_mounting 'quartz 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 powder
_pd_char_colour 'dark white' # 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_conditions
;at argone atmosphere
;
_pd_prep_pressure 101(1)
_pd_prep_temperature 296
#=======================================================================
# 17. EXPERIMENTAL DATA
# This 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
; ESRF France.
;
_diffrn_ambient_temperature 296
_diffrn_radiation_type synchrotron
_diffrn_radiation_source X-ray
_diffrn_radiation_wavelength 0.738080
_diffrn_measurement_device_type ESRF
_diffrn_detector two-dimensional
_diffrn_detector_type ?
_pd_meas_scan_method fixed # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
# The following six items are used for angular dispersive measurements only.
_diffrn_radiation_monochromator ?
# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.
#_pd_meas_number_of_points ?
#_pd_meas_2theta_range_min ?
#_pd_meas_2theta_range_max ?
_pd_meas_2theta_range_inc 0.0147512
# The following three items are used for time-of-flight measurements only.
_pd_instr_dist_src/spec ?
_pd_instr_dist_spec/detc ?
# The following fields are used to identify the programs used.
_computing_data_collection ?
_computing_cell_refinement 'TOPAS 4.2'
_computing_data_reduction fit2d
_computing_structure_solution ?
_computing_structure_refinement 'TOPAS 4.2'
_computing_molecular_graphics 'TOPAS Rigid-body editor & Mercury 2.3'
_computing_publication_material 'PLATON, publCIF, CrimsonEditor, Diamond 2.1d'
#==============================================================================
# 18. REFINEMENT DATA
# Use the next field to give any special details about the fitting of the
# powder pattern.
# The next three items are given as text
_pd_proc_ls_profile_function
;
The modified Thompson-Cox-Hastings pseudo-Voigt
;
_pd_proc_ls_pref_orient_corr
;
;
_pd_proc_ls_prof_R_factor 0.01913
_pd_proc_ls_prof_wR_factor 0.02505
_pd_proc_ls_prof_wR_expected 0.02040
_refine_special_details
;
There is a multi phase Rietvel refinement:
structure 1 LiNa(NH2BH3)2 - 94.8(1)%
structure 2 WC - 5.2(1)% P-6m2, a,b=2.906(3)A, c=2.8387(4)A, RBragg = 1.66%
phase 1: space group P-1, a=4.736(2), b=4.298(3), c=4.023(4),
alpha=87.3(7)deg., beta=112.7(3)deg., gamma=115.7(9)deg.
The z_matrix rigid body has been applied for both the NH2BH3 anions.
The angles and distaces were without restrains and has been refined
with the limitation of the lenght or angle.
The following Antibump penalty has been apllied:
H2 - H7 = 2.2A
Na* - H* = 2.6A
Na* - B* = 3.0A
Li* - Li* = 2.7A
Li* - B* = 2.6A
Li* - H* = 1.9A
Li* - N* = 1.9A
N* - N* = 2.9A
N* - B* = 1.34A
The maximum shift/s.u. ratio after final refinement cycle was not determined
and probably has little meaning in the context of TOPAS 4.x. For
example, TOPAS uses the Marquardt method and in the final cycles the change in
parameters are heavily damped according to min/max limits and a predictor
method for the Marquardt constant. For this reason the SHFSU_01 test was not
performed The Maximum and Minimum values of final difference map (e A-3) cant
be presented in the final CIF data, because of using the TOPAS 4.2 software,
that not displayed the Fourier Maps. For this reason the following tests
DIFMN_01, DIFMX_01,DIFMX_02, DIFMN_01,DIFMN_02 and DIFMN_03 will not be
performed during the IUCr PLATON/CheckCIF process.
;
_refine_ls_structure_factor_coef Inet
_refine_ls_matrix_type fullcycle
_refine_ls_weighting_scheme sigma
_refine_ls_weighting_details
'1/(\s(Y~o,m~)^2^), where \s(Y~o,m~) is the error in observed data'
_refine_ls_extinction_method none
_refine_ls_extinction_coef ?
_refine_ls_number_parameters 98
_refine_ls_number_restraints 0
_refine_ls_number_constraints 23 #rigid body
# The following item is the same as CHI, the square root of 'CHI squared'
_refine_ls_goodness_of_fit_all 1.228
_refine_ls_R_I_factor 0.02072
_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 2.9428394
_pd_proc_2theta_range_max 23.446833
_pd_proc_2theta_range_inc 0.0147512
_pd_proc_wavelength 0.738080
# Each refinement must be accompanied by a listing of the powder data
# in CIF format. Each listing should be sent as a separate file consisting
# of one data block containing a single powder profile. The value of
# _pd_block_diffractogram_id is used to associate each refinement with
# its corresponding powder profile, since it must match the value
# of _pd_block_id in the file containing the powder data.
_pd_block_diffractogram_id 2010-07-09T23:40|sample_7days|Filinchuk|ESRF
# Give appropriate details in the next two text fields.
_pd_proc_info_excluded_regions ?
_pd_proc_info_data_reduction ?
#==============================================================================
# 19. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_thermal_displace_type
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
_atom_site_calc_flag
_atom_site_refinement_flags
N1 N Uiso 0.999(4) 0.272(3) 0.378(2) 1.000 0.023(9) . .
B1 B Uiso 0.850(6) 0.201(3) 0.200(4) 1.000 0.037(14) . .
N2 N Uiso 0.707(5) 0.253(3) 0.655(2) 1.000 0.023(9) . .
B2 B Uiso 0.516(7) 0.353(3) 0.748(3) 1.000 0.037(14) . .
Na1 Na Uiso 0.677(3) 0.7686(14) 0.9764(14) 1.000 0.076(7) . .
Li1 Li Uiso 0.091(9) 0.450(7) 0.637(5) 1.000 0.028(11) . .
H1 H Uiso 1.11206 0.18064 0.40695 1.000 0.028(11) . .
H2 H Uiso 1.14093 0.40699 0.40159 1.000 0.028(11) . .
H3 H Uiso 0.86756 0.34294 0.14392 1.000 0.044(18) . .
H4 H Uiso 0.96628 0.09478 0.12701 1.000 0.044(18) . .
H5 H Uiso 0.60860 0.09283 0.17786 1.000 0.044(18) . .
H6 H Uiso 0.65361 0.10655 0.64775 1.000 0.028(11) . .
H7 H Uiso 0.65754 0.26355 0.54319 1.000 0.028(11) . .
H8 H Uiso 0.29311 0.22832 0.73503 1.000 0.044(18) . .
H9 H Uiso 0.64240 0.41235 0.89022 1.000 0.044(18) . .
H10 H Uiso 0.48747 0.50291 0.70982 1.000 0.044(18) . .
#===============================================================================
# 20. MOLECULAR GEOMETRY
_geom_special_details
;
Bond distances, angles etc. have been calculated using the
rounded fractional coordinates. All su's are estimated
from the variances of the (full) variance-covariance matrix.
The cell esds are taken into account in the estimation of
distances, angles and torsion angles
;
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
N1 B1 1.52(4) . . yes
N1 H1 1.0000 . . no
N1 H2 1.0000 . . no
N2 B2 1.58(4) . . yes
N2 H6 1.0000 . . no
N2 H7 1.0000 . . no
B1 H3 1.2200 . . no
B1 H4 1.2200 . . no
B1 H5 1.2200 . . no
B2 H8 1.2200 . . no
B2 H9 1.2200 . . no
B2 H10 1.2200 . . 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
B1 N1 H1 110.00 . . . no
B1 N1 H2 108.00 . . . no
H1 N1 H2 106.00 . . . no
B2 N2 H7 108.00 . . . no
H6 N2 H7 107.00 . . . no
B2 N2 H6 108.00 . . . no
N1 B1 H5 109.00 . . . no
H3 B1 H5 116.00 . . . no
H4 B1 H5 105.00 . . . no
H3 B1 H4 105.00 . . . no
N1 B1 H3 111.00 . . . no
N1 B1 H4 111.00 . . . no
N2 B2 H8 111.00 . . . no
N2 B2 H9 108.00 . . . no
N2 B2 H10 111.00 . . . no
H8 B2 H9 106.00 . . . no
H8 B2 H10 115.00 . . . no
H9 B2 H10 106.00 . . . no
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
#
#D H A D - H H...A D...A D - H...A symm(A)
#
N1 H2 N2 1.0000 2.5600 3.46(3) 150.00 2_766 yes
N2 H7 N1 1.0000 2.4800 3.14(3) 123.00 . yes
# Attachment '- LiNaAB2_CSD-422190.cif'