Protonolysis of [((i)PrO)TiMo5O18]3-: access to a family of TiMo5 Lindqvist type polyoxometalates.
Coyle, Laura; Middleton, Paul S.; Murphy, Christopher J.; Clegg, William; Harrington, Ross W.; Errington, R. John; Dalton transactions (Cambridge, England : 2003) 41 (2012) 971–981; doi:10.1039/c1dt11256b

data_7017611
_publ_section_title
;
 Protonolysis of [((i)PrO)TiMo5O18]3-: access to a family of TiMo5
 Lindqvist type polyoxometalates.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              971
_journal_page_last               981
_journal_paper_doi               10.1039/c1dt11256b
_journal_volume                  41
_journal_year                    2012
_chemical_formula_moiety         '3 C16 H36 N +,C7 H7 Mo5 O19 Ti 3-'
_chemical_formula_sum            'C55 H115 Mo5 N3 O19 Ti'
_chemical_formula_weight         1650.10
_chemical_name_systematic
;
?
;
_space_group_IT_number           62
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   23.8573(14)
_cell_length_b                   16.9901(10)
_cell_length_c                   17.3090(10)
_cell_measurement_reflns_used    20087
_cell_measurement_temperature    160(2)
_cell_measurement_theta_max      28.25
_cell_measurement_theta_min      2.39
_cell_volume                     7016.0(7)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      160(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.928
_diffrn_measurement_device_type  'Bruker SMART 1K CCD diffractometer'
_diffrn_measurement_method       'thin-slice \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0513
_diffrn_reflns_av_sigmaI/netI    0.0394
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            50872
_diffrn_reflns_theta_full        26.00
_diffrn_reflns_theta_max         28.25
_diffrn_reflns_theta_min         1.68
_exptl_absorpt_coefficient_mu    1.040
_exptl_absorpt_correction_T_max  0.820
_exptl_absorpt_correction_T_min  0.625
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'rectangular prism'
_exptl_crystal_F_000             3400
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.591
_refine_diff_density_min         -1.691
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.334
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     421
_refine_ls_number_reflns         8322
_refine_ls_number_restraints     117
_refine_ls_restrained_S_all      1.336
_refine_ls_R_factor_all          0.1081
_refine_ls_R_factor_gt           0.0964
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+107.4965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1801
_refine_ls_wR_factor_ref         0.1843
_reflns_number_gt                7184
_reflns_number_total             8322
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c1dt11256b.txt
_cod_data_source_block           rje270_salt_of_5
_cod_database_code               7017611
_computing_special_details
;
TITL rje270 in Pnma
CELL 0.71073 23.8573 16.9901 17.3090 90.000 90.000 90.000
ZERR 4.00 0.0014 0.0010 0.0010 0.000 0.000 0.000
LATT 1
SYMM 0.5-X, -Y, 0.5+Z
SYMM -X, 0.5+Y, -Z
SYMM 0.5+X, 0.5-Y, 0.5-Z
SFAC C H N O TI MO
UNIT 220 460 12 76 4 20

SIZE 0.5 0.32 0.2
TEMP -113

CONN $TI $MO 6
L.S. 8
ACTA 52
BOND $H
FMAP 2
PLAN 10

DELU N2 > C234
SIMU N2 > C234

REM EXTI insignificant
WGHT 0.000000 107.496498
FVAR 0.10074
MO1 6 0.305307 0.250000 0.776702 10.50000 0.02054 0.02213 =
0.01416 0.00000 -0.00586 0.00000
MO2 6 0.198463 0.152910 0.699666 11.00000 0.03348 0.03402 =
0.02657 0.01440 -0.01078 -0.01972
MO3 6 0.321949 0.152452 0.612817 11.00000 0.03317 0.03359 =
0.02478 -0.01119 -0.01086 0.02177
TI1 5 0.221051 0.250000 0.546363 10.50000 0.02093 0.01506 =
0.01381 0.00000 -0.00642 0.00000
O10 4 0.337490 0.250000 0.863591 10.50000 0.02966 0.04584 =
0.01952 0.00000 -0.00634 0.00000
O12 4 0.249005 0.172134 0.787618 11.00000 0.02800 0.03385 =
0.02000 0.01379 -0.00680 -0.00542
O13 4 0.346324 0.172921 0.717198 11.00000 0.02430 0.03443 =
0.02347 0.00103 -0.00581 0.01149
O20 4 0.154070 0.083498 0.735397 11.00000 0.05419 0.06386 =
0.05511 0.03647 -0.01558 -0.04227
O22 4 0.162328 0.250000 0.732755 10.50000 0.01603 0.04846 =
0.02283 0.00000 0.00398 0.00000
O23 4 0.261549 0.091104 0.659861 11.00000 0.04935 0.01091 =
0.03691 0.00444 -0.01656 0.00591
O24 4 0.174762 0.170626 0.600645 11.00000 0.02741 0.02167 =
0.02511 -0.00022 -0.01080 -0.00478
O30 4 0.368157 0.083759 0.582301 11.00000 0.05390 0.07086 =
0.04278 -0.02410 -0.01339 0.05330
O33 4 0.360644 0.250000 0.586945 10.50000 0.01883 0.05796 =
0.01825 0.00000 -0.00253 0.00000
O34 4 0.275574 0.169828 0.527303 11.00000 0.03057 0.02668 =
0.02098 -0.00773 -0.00611 0.00465
O40 4 0.259886 0.250000 0.655030 10.50000 0.01518 0.01357 =
0.00979 0.00000 -0.00736 0.00000
O1 4 0.180447 0.250000 0.454593 10.50000 0.02721 0.02446 =
0.01909 0.00000 -0.00994 0.00000
C1 1 0.127284 0.250000 0.427450 10.50000 0.03674 0.00610 =
0.02457 0.00000 -0.01286 0.00000
C2 1 0.081637 0.250000 0.475669 10.50000 0.03046 0.03534 =
0.02922 0.00000 -0.00882 0.00000
AFIX 43
H2 2 0.086912 0.250000 0.530070 10.50000 -1.20000
AFIX 0
C3 1 0.027751 0.250000 0.445295 10.50000 0.01844 0.04168 =
0.05417 0.00000 -0.00544 0.00000
AFIX 43
H3 2 -0.003299 0.250000 0.479658 10.50000 -1.20000
AFIX 0
C4 1 0.017912 0.250000 0.366508 10.50000 0.03861 0.03056 =
0.05133 0.00000 -0.02500 0.00000
C5 1 0.063988 0.250000 0.319430 10.50000 0.05589 0.02221 =
0.03627 0.00000 -0.02635 0.00000
AFIX 43
H5 2 0.058376 0.250000 0.265093 10.50000 -1.20000
AFIX 0
C6 1 0.118383 0.250000 0.347231 10.50000 0.03283 0.01800 =
0.03126 0.00000 -0.01322 0.00000
AFIX 43
H6 2 0.149253 0.250000 0.312561 10.50000 -1.20000
AFIX 0
C7 1 -0.041032 0.250000 0.334242 10.50000 0.04064 0.06649 =
0.08147 0.00000 -0.03347 0.00000
AFIX 123
H7A 2 -0.068052 0.250000 0.376887 10.25000 -1.50000
H7B 2 -0.046610 0.202904 0.302471 10.25000 -1.50000
H7C 2 -0.046610 0.297096 0.302471 10.25000 -1.50000
H7D 2 -0.039463 0.250000 0.277666 10.25000 -1.50000
H7E 2 -0.060905 0.297096 0.352082 10.25000 -1.50000
H7F 2 -0.060905 0.202904 0.352082 10.25000 -1.50000
AFIX 0
N1 3 0.317017 -0.003775 0.908609 11.00000 0.02986 0.01648 =
0.03147 0.01572 -0.00769 -0.00536
C111 1 0.284068 0.067597 0.935405 11.00000 0.03693 0.01944 =
0.03469 0.00842 -0.00231 -0.00287
AFIX 23
H11A 2 0.260684 0.086169 0.891814 11.00000 -1.20000
H11B 2 0.310973 0.110104 0.947865 11.00000 -1.20000
AFIX 0
C112 1 0.246042 0.055121 1.005350 11.00000 0.03860 0.03509 =
0.03539 0.01079 0.00211 -0.00245
AFIX 23
H11C 2 0.215674 0.017797 0.992042 11.00000 -1.20000
H11D 2 0.267947 0.032494 1.048554 11.00000 -1.20000
AFIX 0
C113 1 0.221116 0.133371 1.029543 11.00000 0.08142 0.05074 =
0.06376 0.00448 0.02481 -0.00313
AFIX 23
H11E 2 0.200973 0.156806 0.985143 11.00000 -1.20000
H11F 2 0.251739 0.169717 1.044276 11.00000 -1.20000
AFIX 0
C114 1 0.180824 0.124717 1.097079 11.00000 0.09792 0.05882 =
0.07915 0.00549 0.03585 -0.00142
AFIX 33
H11G 2 0.165948 0.176532 1.111165 11.00000 -1.50000
H11H 2 0.200701 0.102071 1.141361 11.00000 -1.50000
H11I 2 0.149854 0.089971 1.082237 11.00000 -1.50000
AFIX 0
C121 1 0.278419 -0.070472 0.884158 11.00000 0.03798 0.02145 =
0.03614 0.01507 -0.00504 -0.01240
AFIX 23
H12A 2 0.301761 -0.117113 0.872313 11.00000 -1.20000
H12B 2 0.254231 -0.084298 0.928607 11.00000 -1.20000
AFIX 0
C122 1 0.241151 -0.054180 0.815231 11.00000 0.03077 0.04063 =
0.03613 0.01015 -0.01093 -0.00635
AFIX 23
H12C 2 0.263739 -0.033510 0.771752 11.00000 -1.20000
H12D 2 0.212387 -0.014528 0.828822 11.00000 -1.20000
AFIX 0
C123 1 0.212890 -0.132211 0.791927 11.00000 0.05375 0.05164 =
0.05968 0.00136 -0.02010 -0.02241
AFIX 23
H12E 2 0.242078 -0.171095 0.777926 11.00000 -1.20000
H12F 2 0.191722 -0.153305 0.836552 11.00000 -1.20000
AFIX 0
C124 1 0.172877 -0.121104 0.723387 11.00000 0.05540 0.08508 =
0.08045 -0.01739 -0.02650 -0.01961
AFIX 33
H12G 2 0.155868 -0.171785 0.709929 11.00000 -1.50000
H12H 2 0.193812 -0.100822 0.678927 11.00000 -1.50000
H12I 2 0.143396 -0.083610 0.737529 11.00000 -1.50000
AFIX 0
C131 1 0.352866 0.023987 0.841201 11.00000 0.03425 0.02652 =
0.02619 0.00941 -0.00436 -0.00877
AFIX 23
H13A 2 0.379117 0.064834 0.860034 11.00000 -1.20000
H13B 2 0.328178 0.048784 0.802201 11.00000 -1.20000
AFIX 0
C132 1 0.386748 -0.041404 0.801991 11.00000 0.02946 0.03294 =
0.03845 0.01374 -0.00308 -0.00352
AFIX 23
H13C 2 0.412916 -0.065079 0.839811 11.00000 -1.20000
H13D 2 0.361034 -0.083184 0.783733 11.00000 -1.20000
AFIX 0
C133 1 0.419751 -0.008729 0.733822 11.00000 0.05279 0.04507 =
0.03985 0.01126 0.00585 0.01104
AFIX 23
H13E 2 0.444790 0.033798 0.752200 11.00000 -1.20000
H13F 2 0.393370 0.014350 0.695926 11.00000 -1.20000
AFIX 0
C134 1 0.454823 -0.072151 0.694059 11.00000 0.06008 0.04989 =
0.04932 -0.00207 0.01042 0.01331
AFIX 33
H13G 2 0.475985 -0.048584 0.651402 11.00000 -1.50000
H13H 2 0.430041 -0.113290 0.673854 11.00000 -1.50000
H13I 2 0.480936 -0.095255 0.731421 11.00000 -1.50000
AFIX 0
C141 1 0.352965 -0.037312 0.973116 11.00000 0.03566 0.03212 =
0.02596 0.01692 -0.00942 -0.00077
AFIX 23
H14A 2 0.327725 -0.060160 1.012589 11.00000 -1.20000
H14B 2 0.375544 -0.080978 0.951536 11.00000 -1.20000
AFIX 0
C142 1 0.392457 0.019407 1.013246 11.00000 0.03227 0.03216 =
0.04176 -0.00049 -0.00871 -0.00520
AFIX 23
H14C 2 0.370708 0.060075 1.041161 11.00000 -1.20000
H14D 2 0.416530 0.046001 0.974658 11.00000 -1.20000
AFIX 0
C143 1 0.428623 -0.026832 1.070015 11.00000 0.03546 0.06059 =
0.03701 0.00724 -0.00718 -0.00714
AFIX 23
H14E 2 0.403944 -0.057677 1.104623 11.00000 -1.20000
H14F 2 0.452257 -0.064411 1.040866 11.00000 -1.20000
AFIX 0
C144 1 0.465318 0.024561 1.117611 11.00000 0.05612 0.08650 =
0.05118 -0.00259 -0.01009 -0.00830
AFIX 33
H14G 2 0.487720 -0.007990 1.152701 11.00000 -1.50000
H14H 2 0.442130 0.060922 1.147782 11.00000 -1.50000
H14I 2 0.490308 0.054650 1.083744 11.00000 -1.50000
AFIX 0
SAME N2 C221 > C224
SAME N2 C231 > C234
N2 3 0.527400 0.250000 0.613269 10.50000 0.01577 0.09775 =
0.04404 0.00000 0.00388 0.00000
C211 1 0.486274 0.250000 0.547018 10.50000 0.02783 0.06561 =
0.03530 0.00000 0.00043 0.00000
AFIX 23
H21A 2 0.461981 0.296973 0.551944 10.50000 -1.20000
H21B 2 0.461981 0.203027 0.551944 10.50000 -1.20000
AFIX 0
C212 1 0.512356 0.250000 0.465560 10.50000 0.03729 0.10576 =
0.04371 0.00000 0.00959 0.00000
AFIX 23
H21C 2 0.546892 0.217696 0.465491 10.50000 -1.20000
H21D 2 0.522585 0.304406 0.450705 10.50000 -1.20000
AFIX 0
PART -1
C213 1 0.469092 0.215446 0.405443 10.50000 0.08405 0.09174 =
0.03466 -0.01015 -0.00346 0.01971
AFIX 23
H21E 2 0.487518 0.215428 0.354195 10.50000 -1.20000
H21F 2 0.462316 0.159765 0.419476 10.50000 -1.20000
AFIX 0
PART 0
C214 1 0.419126 0.250000 0.397184 10.50000 0.05138 0.20985 =
0.04509 0.00000 -0.00597 0.00000
AFIX 33
H21G 2 0.397039 0.221244 0.358685 10.50000 -1.50000
H21H 2 0.424372 0.304471 0.380020 10.50000 -1.50000
H21I 2 0.399326 0.249623 0.446789 10.50000 -1.50000
AFIX 0
C221 1 0.491728 0.250000 0.686117 10.50000 0.01774 0.13529 =
0.03314 0.00000 -0.00186 0.00000
AFIX 23
H22A 2 0.456716 0.220456 0.676041 10.50000 -1.20000
H22B 2 0.481335 0.304878 0.698943 10.50000 -1.20000
AFIX 0
PART -1
C222 1 0.522649 0.212130 0.757473 10.50000 0.03566 0.06359 =
0.05226 0.00759 -0.00985 -0.00242
AFIX 23
H22C 2 0.558840 0.239031 0.766735 10.50000 -1.20000
H22D 2 0.530113 0.155671 0.747759 10.50000 -1.20000
AFIX 0
C223 1 0.482473 0.222204 0.830381 10.50000 0.06108 0.04325 =
0.04466 0.00472 -0.01275 0.00160
AFIX 23
H22E 2 0.446338 0.195708 0.819692 10.50000 -1.20000
H22F 2 0.499764 0.196022 0.875580 10.50000 -1.20000
AFIX 0
C224 1 0.472416 0.300318 0.848223 10.50000 0.05914 0.03745 =
0.05971 -0.00645 -0.03041 -0.00619
AFIX 33
H22G 2 0.447351 0.303389 0.892978 10.50000 -1.50000
H22H 2 0.454836 0.326402 0.803919 10.50000 -1.50000
H22I 2 0.507937 0.326491 0.860411 10.50000 -1.50000
AFIX 0
PART 0
C231 1 0.565594 0.178357 0.610814 11.00000 0.05954 0.18332 =
0.10660 0.06505 0.04350 0.07609
AFIX 23
H23A 2 0.590532 0.179482 0.656516 11.00000 -1.20000
H23B 2 0.589522 0.181704 0.564200 11.00000 -1.20000
AFIX 0
C232 1 0.533936 0.099416 0.609641 11.00000 0.25632 0.10987 =
0.22994 0.08441 0.13123 0.08540
AFIX 23
H23C 2 0.495816 0.108311 0.588798 11.00000 -1.20000
H23D 2 0.529924 0.080192 0.663350 11.00000 -1.20000
AFIX 0
C233 1 0.564031 0.033008 0.559351 11.00000 0.27002 0.14899 =
0.20038 0.09563 0.09823 0.14933
AFIX 23
H23E 2 0.535174 -0.002615 0.537748 11.00000 -1.20000
H23F 2 0.583728 0.058239 0.515523 11.00000 -1.20000
AFIX 0
C234 1 0.600824 -0.009469 0.599995 11.00000 0.07979 0.17750 =
0.08710 -0.02093 0.00417 0.03396
AFIX 33
H23G 2 0.618677 -0.048263 0.566082 11.00000 -1.50000
H23H 2 0.581287 -0.036724 0.642004 11.00000 -1.50000
H23I 2 0.629487 0.025433 0.621700 11.00000 -1.50000

HKLF 4

REM rje270 in Pnma
REM R1 = 0.0964 for 7184 Fo > 4sig(Fo) and 0.1081 for all 8322 data
REM 421 parameters refined using 117 restraints

END

WGHT 0.0000 104.8252
REM Highest difference peak 1.591, deepest hole -1.691, 1-sigma level 0.170
Q1 1 0.6139 0.0678 0.5898 11.00000 0.05 1.59
Q2 1 0.5158 0.0885 0.5805 11.00000 0.05 1.32
Q3 1 0.2817 0.2112 0.7780 11.00000 0.05 1.23
Q4 1 0.5490 0.1223 0.6626 11.00000 0.05 1.19
Q5 1 0.2113 0.2007 0.7041 11.00000 0.05 1.15
Q6 1 0.3367 0.1061 0.6050 11.00000 0.05 1.06
Q7 1 0.3307 0.2107 0.7731 11.00000 0.05 1.02
Q8 1 0.2690 0.2500 0.7748 10.50000 0.05 1.00
Q9 1 0.5489 0.0259 0.5449 11.00000 0.05 0.99
Q10 1 0.3626 0.1444 0.6069 11.00000 0.05 0.99
;