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_7017612
_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 H5 Mo5 O20 Ti 3-'
_chemical_formula_sum            'C55 H113 Mo5 N3 O20 Ti'
_chemical_formula_weight         1664.08
_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                   24.049(4)
_cell_length_b                   17.521(3)
_cell_length_c                   17.242(3)
_cell_measurement_reflns_used    32479
_cell_measurement_temperature    160(2)
_cell_measurement_theta_max      26.50
_cell_measurement_theta_min      2.30
_cell_volume                     7265(2)
_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 0.951
_diffrn_measured_fraction_theta_max 0.951
_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  0.1493
_diffrn_reflns_av_sigmaI/netI    0.1256
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            61909
_diffrn_reflns_theta_full        28.74
_diffrn_reflns_theta_max         28.74
_diffrn_reflns_theta_min         3.58
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  0.825
_exptl_absorpt_correction_T_min  0.750
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3424
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.003
_refine_diff_density_min         -0.881
_refine_diff_density_rms         0.160
_refine_ls_extinction_coef       0.0047(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         9237
_refine_ls_number_restraints     520
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.2085
_refine_ls_R_factor_gt           0.0748
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1193P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1667
_refine_ls_wR_factor_ref         0.2420
_reflns_number_gt                3755
_reflns_number_total             9237
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c1dt11256b.txt
_cod_data_source_block           rje286_salt_of_6
_cod_database_code               7017612
_computing_special_details
;
TITL rje286 in Pnma
CELL 0.71073 24.0494 17.5205 17.2421 90.000 90.000 90.000
ZERR 4.00 0.0037 0.0032 0.0029 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 220 452 12 80 4 20

SIZE 0.3 0.2 0.2
TEMP -113
SHEL 5.8 0

L.S. 24
ACTA
BOND $H
FMAP 2
PLAN 10

SIMU N1 > C35
DELU N1 > C35
CONN $MO $TI 6
SADI C8 C9 C9 C10 C10 C11
SADI C12 C13 C13 C14 C14 C15
SADI C16 C17 C17 C18 C18 C19
SADI C20 C21 C21 C22 C22 C23
SADI C24 C25 C25 C26 C26 C27
SADI C28 C29 C29 C30 C30 C31
SADI C32 C33 C33 C34 C34 C35

WGHT 0.119300
EXTI 0.004713
FVAR 0.03978
MO1 6 0.186770 0.344319 0.118541 11.00000 0.06767 0.05765 =
0.05128 0.00981 0.00390 0.01685
MO2 6 0.308761 0.344139 0.206840 11.00000 0.06398 0.05026 =
0.05249 -0.01011 0.00631 -0.01220
MO3 6 0.202803 0.250000 0.283584 10.50000 0.06090 0.05692 =
0.03700 0.00000 0.00922 0.00000
TI1 5 0.287644 0.250000 0.053605 10.50000 0.07161 0.04862 =
0.03761 0.00000 0.01454 0.00000
O1 4 0.341321 0.250000 -0.270412 10.50000 0.17329 0.16306 =
0.07069 0.00000 0.01592 0.00000
O2 4 0.327601 0.250000 -0.040799 10.50000 0.08031 0.08945 =
0.04230 0.00000 0.01888 0.00000
O3 4 0.149220 0.250000 0.093223 10.50000 0.06411 0.08087 =
0.05384 0.00000 -0.00466 0.00000
O4 4 0.141272 0.409994 0.087137 11.00000 0.09881 0.09764 =
0.08187 0.01321 -0.00272 0.03771
O5 4 0.352236 0.410607 0.242853 11.00000 0.09156 0.07443 =
0.09158 -0.02196 0.00872 -0.02537
O6 4 0.345235 0.250000 0.239462 10.50000 0.06160 0.07087 =
0.05296 0.00000 -0.00700 0.00000
O7 4 0.170204 0.250000 0.369524 10.50000 0.07863 0.10112 =
0.04384 0.00000 0.02577 0.00000
O8 4 0.258839 0.324776 0.294971 11.00000 0.07662 0.06608 =
0.04513 -0.02534 0.00669 -0.01074
O9 4 0.162482 0.324244 0.223938 11.00000 0.06633 0.06876 =
0.05178 0.00108 0.01117 0.02003
O10 4 0.233140 0.327418 0.033675 11.00000 0.08883 0.06051 =
0.04540 0.01404 0.00122 0.00535
O11 4 0.246538 0.403080 0.166195 11.00000 0.08947 0.03765 =
0.06869 -0.00741 0.01578 0.00048
O12 4 0.332539 0.327094 0.107650 11.00000 0.07206 0.05566 =
0.05564 0.00199 0.01917 -0.00854
O13 4 0.248756 0.250000 0.161005 10.50000 0.05056 0.03650 =
0.03606 0.00000 0.00359 0.00000
C1 1 0.377957 0.250000 -0.070473 10.50000 0.09036 0.04555 =
0.05198 0.00000 0.01744 0.00000
C2 1 0.425050 0.250000 -0.022117 10.50000 0.11335 0.10281 =
0.07597 0.00000 0.02483 0.00000
AFIX 43
H2 2 0.420437 0.250000 0.032604 10.50000 -1.20000
AFIX 0
C3 1 0.478468 0.250000 -0.053665 10.50000 0.08400 0.17103 =
0.10453 0.00000 0.02120 0.00000
AFIX 43
H3 2 0.510315 0.250000 -0.021067 10.50000 -1.20000
AFIX 0
C4 1 0.483989 0.250000 -0.133720 10.50000 0.09194 0.16543 =
0.10162 0.00000 0.05965 0.00000
AFIX 43
H4 2 0.520056 0.250000 -0.156192 10.50000 -1.20000
AFIX 0
C5 1 0.440034 0.250000 -0.178862 10.50000 0.15119 0.10560 =
0.06281 0.00000 0.04587 0.00000
AFIX 43
H5 2 0.445108 0.250000 -0.233504 10.50000 -1.20000
AFIX 0
C6 1 0.386161 0.250000 -0.149105 10.50000 0.10071 0.05436 =
0.04735 0.00000 0.03231 0.00000
C7 1 0.339123 0.250000 -0.201352 10.50000 0.15187 0.06331 =
0.04299 0.00000 0.02494 0.00000
AFIX 43
H7 2 0.303167 0.250000 -0.178536 10.50000 -1.20000
AFIX 0
SAME N1 C12 > C15
SAME N1 C16 > C19
SAME N1 C20 > C23
SAME N2 C24 > C27
SAME N2 C28 > C31
SAME N2 C32 > C35
N1 3 0.188957 0.503916 0.413363 11.00000 0.08791 0.05133 =
0.07484 -0.02410 0.00313 -0.00423
C8 1 0.152222 0.535878 0.476714 11.00000 0.08926 0.06857 =
0.06705 -0.02441 0.00227 0.00333
AFIX 23
H8A 2 0.176494 0.556393 0.518140 11.00000 -1.20000
H8B 2 0.131060 0.579345 0.454928 11.00000 -1.20000
AFIX 0
C9 1 0.111713 0.481842 0.513101 11.00000 0.09270 0.08581 =
0.09300 -0.02255 0.00760 -0.00877
AFIX 23
H9A 2 0.132447 0.439990 0.538631 11.00000 -1.20000
H9B 2 0.088224 0.459028 0.472040 11.00000 -1.20000
AFIX 0
C10 1 0.075111 0.520008 0.571656 11.00000 0.09544 0.14804 =
0.10168 -0.04616 0.01780 -0.03917
AFIX 23
H10A 2 0.099029 0.546734 0.609686 11.00000 -1.20000
H10B 2 0.052555 0.559188 0.544788 11.00000 -1.20000
AFIX 0
C11 1 0.037291 0.468933 0.614225 11.00000 0.09920 0.23102 =
0.13941 0.00663 0.02307 -0.04763
AFIX 33
H11A 2 0.014720 0.498955 0.650401 11.00000 -1.50000
H11B 2 0.059087 0.431248 0.643207 11.00000 -1.50000
H11C 2 0.012888 0.442592 0.577407 11.00000 -1.50000
AFIX 0
C12 1 0.154742 0.477539 0.344089 11.00000 0.10491 0.06191 =
0.06900 -0.02924 0.00020 -0.01410
AFIX 23
H12A 2 0.180270 0.454627 0.305528 11.00000 -1.20000
H12B 2 0.129120 0.436838 0.361671 11.00000 -1.20000
AFIX 0
C13 1 0.121460 0.537645 0.304764 11.00000 0.12185 0.09165 =
0.08787 -0.02511 -0.01467 0.00507
AFIX 23
H13A 2 0.146777 0.579716 0.289857 11.00000 -1.20000
H13B 2 0.094447 0.558509 0.342549 11.00000 -1.20000
AFIX 0
C14 1 0.090489 0.512849 0.234618 11.00000 0.18190 0.11039 =
0.09554 -0.03910 -0.03933 0.01706
AFIX 23
H14A 2 0.117351 0.489172 0.198368 11.00000 -1.20000
H14B 2 0.063868 0.472625 0.250349 11.00000 -1.20000
AFIX 0
C15 1 0.059527 0.571782 0.192013 11.00000 0.22952 0.13456 =
0.13300 -0.00082 -0.07832 0.00670
AFIX 33
H15A 2 0.040857 0.548564 0.147339 11.00000 -1.50000
H15B 2 0.085347 0.611236 0.173952 11.00000 -1.50000
H15C 2 0.031731 0.594842 0.226341 11.00000 -1.50000
AFIX 0
C16 1 0.220962 0.434905 0.442240 11.00000 0.09347 0.06023 =
0.08946 -0.02036 0.01196 0.00626
AFIX 23
H16A 2 0.193751 0.394113 0.453994 11.00000 -1.20000
H16B 2 0.244588 0.416321 0.399180 11.00000 -1.20000
AFIX 0
C17 1 0.257193 0.445080 0.511870 11.00000 0.12135 0.10277 =
0.09345 -0.02316 -0.00569 0.01168
AFIX 23
H17A 2 0.235526 0.468926 0.554253 11.00000 -1.20000
H17B 2 0.288600 0.479327 0.498956 11.00000 -1.20000
AFIX 0
C18 1 0.279313 0.368596 0.538317 11.00000 0.17234 0.13762 =
0.16916 0.03504 -0.06429 -0.00293
AFIX 23
H18A 2 0.247859 0.337375 0.557437 11.00000 -1.20000
H18B 2 0.295606 0.341857 0.493129 11.00000 -1.20000
AFIX 0
C19 1 0.321016 0.373519 0.598912 11.00000 0.31201 0.33847 =
0.26183 0.09194 -0.16383 -0.01045
AFIX 33
H19A 2 0.333855 0.322105 0.612343 11.00000 -1.50000
H19B 2 0.304827 0.397811 0.644861 11.00000 -1.50000
H19C 2 0.352537 0.403965 0.580462 11.00000 -1.50000
AFIX 0
C20 1 0.228448 0.567272 0.389212 11.00000 0.08920 0.06443 =
0.07814 -0.02283 0.00405 -0.01410
AFIX 23
H20A 2 0.205813 0.612207 0.374545 11.00000 -1.20000
H20B 2 0.250682 0.581902 0.435190 11.00000 -1.20000
AFIX 0
C21 1 0.267629 0.551206 0.324526 11.00000 0.11008 0.10189 =
0.08546 -0.02846 0.02062 -0.01482
AFIX 23
H21A 2 0.246639 0.531597 0.279330 11.00000 -1.20000
H21B 2 0.294390 0.511365 0.340789 11.00000 -1.20000
AFIX 0
C22 1 0.298759 0.622003 0.301537 11.00000 0.14167 0.11929 =
0.15572 -0.04514 0.06453 -0.04017
AFIX 23
H22A 2 0.271420 0.661674 0.286782 11.00000 -1.20000
H22B 2 0.319329 0.641033 0.347359 11.00000 -1.20000
AFIX 0
C23 1 0.338686 0.612303 0.236691 11.00000 0.18946 0.18635 =
0.15963 -0.00613 0.08704 -0.02230
AFIX 33
H23A 2 0.356617 0.661301 0.225463 11.00000 -1.50000
H23B 2 0.318812 0.594470 0.190499 11.00000 -1.50000
H23C 2 0.367004 0.574731 0.251277 11.00000 -1.50000
AFIX 0
N2 3 0.481792 0.250000 0.378213 10.50000 0.04527 0.17609 =
0.08635 0.00000 -0.00482 0.00000
C24 1 0.444141 0.318913 0.381472 11.00000 0.07630 0.20065 =
0.10738 0.01715 -0.00461 0.02201
AFIX 23
H24A 2 0.419276 0.317660 0.335730 11.00000 -1.20000
H24B 2 0.420455 0.314636 0.428230 11.00000 -1.20000
AFIX 0
C25 1 0.472577 0.394140 0.383307 11.00000 0.25627 0.17563 =
0.26286 0.04281 -0.05314 -0.00423
AFIX 23
H25A 2 0.493657 0.402784 0.334778 11.00000 -1.20000
H25B 2 0.498579 0.397083 0.427720 11.00000 -1.20000
AFIX 0
C26 1 0.427743 0.450688 0.391508 11.00000 0.31904 0.21254 =
0.32547 -0.03351 -0.18038 0.04409
AFIX 23
H26A 2 0.422425 0.472955 0.339260 11.00000 -1.20000
H26B 2 0.393649 0.421043 0.402819 11.00000 -1.20000
AFIX 0
C27 1 0.427225 0.512094 0.442839 11.00000 0.35032 0.38599 =
0.24394 -0.09751 0.10294 0.00215
AFIX 33
H27A 2 0.396196 0.546098 0.430051 11.00000 -1.50000
H27B 2 0.462318 0.540219 0.438610 11.00000 -1.50000
H27C 2 0.422797 0.493160 0.495963 11.00000 -1.50000
AFIX 0
C28 1 0.523026 0.250000 0.445564 10.50000 0.07582 0.17212 =
0.10124 0.00000 -0.02493 0.00000
AFIX 23
H28A 2 0.547132 0.204590 0.439473 10.50000 -1.20000
H28B 2 0.547132 0.295410 0.439473 10.50000 -1.20000
AFIX 0
C29 1 0.501972 0.250000 0.526436 10.50000 0.12487 0.25047 =
0.09381 0.00000 -0.01886 0.00000
AFIX 23
H29A 2 0.478887 0.204142 0.535851 10.50000 -1.20000
H29B 2 0.478887 0.295858 0.535851 10.50000 -1.20000
AFIX 0
C30 1 0.552253 0.250000 0.580145 10.50000 0.19218 0.32214 =
0.11409 0.00000 -0.06138 0.00000
AFIX 23
H30A 2 0.574960 0.204557 0.567441 10.50000 -1.20000
H30B 2 0.574960 0.295443 0.567441 10.50000 -1.20000
AFIX 0
C31 1 0.543035 0.250000 0.662808 10.50000 0.32514 0.52454 =
0.12287 0.00000 -0.07277 0.00000
AFIX 33
H31A 2 0.578910 0.250000 0.689764 10.50000 -1.50000
H31B 2 0.521966 0.204330 0.677410 10.50000 -1.50000
H31C 2 0.521966 0.295670 0.677410 10.50000 -1.50000
AFIX 0
PART -1
C32 1 0.516319 0.264004 0.304374 10.50000 0.05771 0.16653 =
0.09447 -0.00176 0.00000 -0.01984
AFIX 23
H32A 2 0.542161 0.306805 0.314666 10.50000 -1.20000
H32B 2 0.539213 0.218039 0.294601 10.50000 -1.20000
AFIX 0
C33 1 0.484631 0.281852 0.231906 10.50000 0.07360 0.13848 =
0.09649 0.01329 0.01422 0.00372
AFIX 23
H33A 2 0.469551 0.334347 0.234898 10.50000 -1.20000
H33B 2 0.453018 0.246052 0.226509 10.50000 -1.20000
AFIX 0
C34 1 0.521812 0.275018 0.163609 10.50000 0.06884 0.13237 =
0.09690 0.00718 0.01104 -0.00952
AFIX 23
H34A 2 0.502491 0.297717 0.118459 10.50000 -1.20000
H34B 2 0.555351 0.306284 0.173560 10.50000 -1.20000
AFIX 0
C35 1 0.540310 0.197100 0.141593 10.50000 0.09284 0.14896 =
0.09418 0.00183 -0.01194 0.02477
AFIX 33
H35A 2 0.567665 0.200541 0.099610 10.50000 -1.50000
H35B 2 0.508221 0.167266 0.124041 10.50000 -1.50000
H35C 2 0.557252 0.172079 0.186601 10.50000 -1.50000

HKLF 4

REM rje286 in Pnma
REM R1 = 0.0748 for 3755 Fo > 4sig(Fo) and 0.2085 for all 9237 data
REM 428 parameters refined using 520 restraints

END

WGHT 0.1209 0.0000
REM Highest difference peak 1.003, deepest hole -0.881, 1-sigma level 0.160
Q1 1 0.5800 0.2368 0.5988 11.00000 0.05 1.00
Q2 1 0.3176 0.3294 0.5187 11.00000 0.05 0.84
Q3 1 0.1939 0.3752 0.0796 11.00000 0.05 0.83
Q4 1 0.3002 0.3501 0.2568 11.00000 0.05 0.75
Q5 1 0.3294 0.4111 0.2036 11.00000 0.05 0.74
Q6 1 0.3573 0.3757 0.2066 11.00000 0.05 0.73
Q7 1 0.3367 0.3496 0.2599 11.00000 0.05 0.69
Q8 1 0.4128 0.5109 0.3961 11.00000 0.05 0.69
Q9 1 0.3207 0.2500 -0.0004 10.50000 0.05 0.68
Q10 1 0.2990 0.3141 0.2402 11.00000 0.05 0.68
;