Low temperature synthesis of ionic phosphates in dimethyl sulfoxide.
Mangstl, Martin; Celinski, Vinicius R.; Johansson, Sebastian; Weber, Johannes; An, Feng; Schmedt Auf der Günne, Jörn; Dalton transactions (Cambridge, England : 2003) 43 (2014) 10033–10039; doi:10.1039/c4dt00544a

data_7030864
_publ_contact_author
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Schmedt auf der G"unne, J"orn
Inorganic Materials Chemistry
University of Siegen
Adolf-Reichwein-Strasse 2
57068 Siegen
Germany 
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_publ_section_title
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 Low temperature synthesis of ionic phosphates in dimethyl sulfoxide.
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_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10033
_journal_page_last               10039
_journal_paper_doi               10.1039/c4dt00544a
_journal_volume                  43
_journal_year                    2014
_chemical_formula_moiety         '(N(CH3)4 1+)2 (P3O9H 1-)'
_chemical_formula_sum            'C8 H25 N2 O9 P3'
_chemical_formula_weight         386.213
_chemical_melting_point          486
_chemical_name_common
'Bistetramethylammonium hydrogencyclo-triphosphate'
_chemical_name_systematic
'Bistetramethylammonium hydrogencyclo-triphosphate'
_chemical_properties_physical
'air-sensitive, moisture-sensitive, hygroscopic'
_space_group_IT_number           61
_symmetry_cell_setting           orthorhombic
_symmetry_Int_Tables_number      61
_symmetry_space_group_name_Hall  '-P 2bc 2ac'
_symmetry_space_group_name_H-M   'P c a b'
_audit_creation_method           'TOPAS ACADEMIC 4.1 + PLATON'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.50568(14)
_cell_length_b                   10.98610(15)
_cell_length_c                   30.33966(42)
_cell_measurement_temperature    294
_cell_measurement_theta_max      66.99
_cell_measurement_theta_min      2.000
_cell_volume                     3501.70(8)
_computing_molecular_graphics    'Diamond 3.0'
_computing_publication_material  'TOPAS ACADEMIC 4.1'
_computing_structure_refinement  'TOPAS ACADEMIC 4.1'
_computing_structure_solution    'FOX 1.9.8'
_diffrn_ambient_pressure         1000
_diffrn_ambient_temperature      294(2)
_diffrn_measurement_device_type  'STOE Stadi P'
_diffrn_radiation_monochromator  Ge-111
_diffrn_radiation_polarisn_ratio 0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a1'
_diffrn_radiation_wavelength     1.540596
_diffrn_reflns_number            681
_diffrn_reflns_theta_max         66.99
_diffrn_source                   'sealed X-ray tube'
_exptl_absorpt_coefficient_mu    3.545
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details   '(A. Cohelo, TOPAS_Academic, Version 4.1)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.465
_exptl_crystal_description       microcrystalline
_exptl_crystal_F_000             1632
_exptl_crystal_recrystallization_method 'from DMSO/CH3CN '
_pd_calc_method                  'Rietveld Refinement'
_pd_char_colour                  colourless
_pd_char_particle_morphology     powder
_pd_meas_number_of_points        6500
_pd_proc_number_of_points        6500
_refine_ls_goodness_of_fit_all   1.194
_refine_ls_matrix_type           full
_refine_ls_number_constraints    90
_refine_ls_number_parameters     95
_refine_ls_number_restraints     0
_refine_ls_R_factor_gt           0.03296
_refine_ls_R_I_factor            0.995
_refine_ls_shift/su_max          0.00
_refine_ls_shift/su_mean         0.00
_refine_ls_wR_factor_ref         0.04483
_reflns_d_resolution_high        8.799
_reflns_d_resolution_low         1.424
_reflns_limit_h_max              7
_reflns_limit_h_min              0
_reflns_limit_k_max              7
_reflns_limit_k_min              0
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_total             681
_cod_data_source_file            c4dt00544a2.cif
_cod_data_source_block           '[N(CH3)4]2(P3O9H)'
_cod_depositor_comments          'Adding full bibliography for 7030864.cif.'
_cod_original_cell_volume        3501.695(81)
_cod_database_code               7030864
_solution_special_details
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The powder X-ray diffraction pattern of (TMA)2HP3O9 was recorded at
298 K on a STOE Stadi P powder diffractometer (STOE, Darmstadt,
Germany) in Debye Scherrer geometry (capillary inner diameter: 0.48mm)
by using Ge(111)-monochromated CuKa1 radiation (154.0596 pm) and a
position-sensitive detector.

Extraction of the peak positions and pattern indexing and Rietveld
refinement were carried out by using the TOPAS package (version 4.1,
Coelho Software, Brisbane, Australia, 2007). Indexing was performed
using the SVD method. Structure solution was done with parallel
tempering by using the program FOX (version 1.9.8, V. Favre-Nicolin,
J. Rohlicek, M. Husak, Grenoble, 2011) where the molecules were
restrained in different ways: Cyclic phosphate units with the
"flexibility model automatic from restraints, strict" and
tetramethylammonium (TMA) units with the "flexibility model rigid
bodies". The molecules chosen reflect the prior knowledge due to NMR
experiments. Rietveld refinement of the final structure model was
realized by applying the fundamental parameter approach implemented in
TOPAS (direct convolution of source emission profiles, axial
instrument contributions, and crystallite size and micro-strain
effects, using the rigid bodies for both TMA units as well as the
riding model for H97). All 24 N-C-H bonding angles of the TMA cation
were constrained to 108.4 deg, reflecting averaged values of a neutron
diffraction refinement of a similar TMA salt in F. A. Cotton et al.,
J. Am. Chem. Soc., 1984, 106, 117-120. The 16 dihedral angles
N-C(H)(H) between methyl hydrogen atoms inside the TMA units were
constrained to 240 and 120 degree, respectively. The 24 C-H atomic
distances were constrained to 96 pm as suggested by Sheldrick (SHELXL
User Guide, http://shelx.uni-ac.gwdg.de/SHELX/shelxl_user_guide.pdf,
link accessed 27.04.2014). The position of H97 was constrained to the
centre of the straight line between O7 and O9' from a neigbouring
cyclotriphosphate unit. Moreover the 25 isotropic atomic displacement
parameters (temperature factors) for H-atoms were constrained to
1.5*Beq of the heavy atoms at which the respective H-atoms were
bound. For H97 a Beq of 0.75*(Beq(O7)+Beq(O9)) was used.  
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