Inorganic acid influenced formation of Ti26 and Ti44 oxysulfates clusters with toroidal and capsule structures
Chintakrinda, Kalpana; Narayanam, Nagaraju; Chen, Guang-Hui; Wang, Fei; Zhang, Jian; Zhang, Lei; Dalton Transactions  (2022) –; doi:10.1039/D2DT00119E

data_7709838
_publ_section_title
;
 Inorganic acid influenced formation of Ti26 and Ti44 oxysulfates clusters
 with toroidal and capsule structures
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00119E
_journal_year                    2022
_chemical_formula_moiety         'O244 P8 S40 Ti44, 18(C6 H11 N2)'
_chemical_formula_sum            'C162 H297 N54 O244 P8 S40 Ti44'
_chemical_formula_weight         10543.28
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-03-20
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-03-22 deposited with the CCDC.	2022-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                92.297(3)
_cell_angle_beta                 98.803(3)
_cell_angle_gamma                117.541(3)
_cell_formula_units_Z            1
_cell_length_a                   19.0656(6)
_cell_length_b                   20.2491(7)
_cell_length_c                   27.7949(9)
_cell_measurement_reflns_used    12249
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      73.1270
_cell_measurement_theta_min      2.4100
_cell_volume                     9326.9(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector_area_resol_mean 10.3468
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -106.10 -17.00   0.90    1.67    --  -41.54 -38.00-150.00   99
  2  \w    -66.00  33.00   0.90    1.67    --  -41.54  38.00  30.00  110
  3  \w    -71.00  25.30   0.90    1.67    --  -41.54  77.00 120.00  107
  4  \w     26.00  58.40   0.90    1.67    --   41.54-125.00-150.00   36
  5  \w     65.00  96.50   0.90    1.67    --   41.54-125.00 -30.00   35
  6  \w     76.00 161.50   0.90    6.66    --  104.65  30.00 150.00   95
  7  \w     77.00 171.50   0.90    6.66    --  104.65  30.00  90.00  105
  8  \w     76.00 175.00   0.90    6.66    --  104.65  61.00   0.00  110
  9  \w     61.00 114.10   0.90    6.66    --  104.65-125.00 150.00   59
 10  \w     41.00 123.80   0.90    6.66    --  104.65 -45.00 -30.00   92
 11  \w     42.00 112.20   0.90    6.66    --  104.65-125.00 -30.00   78
 12  \w     33.00  71.70   0.90    6.66    --  104.65 -30.00 120.00   43
 13  \w     87.00 116.70   0.90    6.66    --  104.65-125.00-120.00   33
 14  \w     64.00  96.40   0.90    6.66    --  104.65 -94.00  30.00   36
 15  \w     50.00 119.30   0.90    6.66    --  104.65 -61.00 150.00   77
 16  \w    116.00 168.20   0.90    6.66    --  104.65 125.00 -90.00   58
 17  \w     99.00 132.30   0.90    6.66    --  104.65 -30.00 120.00   37
 18  \w     22.00 108.40   0.90    6.66    --  104.65 -94.00 -30.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0988
_diffrn_reflns_av_unetI/netI     0.1398
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            65751
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         2.481
_exptl_absorpt_coefficient_mu    11.019
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.768
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.877
_exptl_crystal_description       block
_exptl_crystal_F_000             5327
_exptl_crystal_size_max          0.223
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.039
_refine_diff_density_max         3.029
_refine_diff_density_min         -1.279
_refine_diff_density_rms         0.234
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2211
_refine_ls_number_reflns         32915
_refine_ls_number_restraints     4501
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1527
_refine_ls_R_factor_gt           0.1114
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2967
_refine_ls_wR_factor_ref         0.3467
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20885
_reflns_number_total             32915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00119e1.cif
_cod_data_source_block           kl6-45-2_sq
_cod_database_code               7709838
_shelx_shelxl_version_number     2018/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1AA-C17
 1.54 with sigma of 0.002
 N04O-C05J = N04H-C051 = N05G_$1-C06T_$1 = N05E_$1-C26_$1 = N04T-C05P = N04Q-
 C05I = N052_$2-C06L_$2 = N059_$2-C17_$2 = N056-C05V = N065-C077 = N053-C06B =
 N05C-C078 = N05D_$3-C13_$3 = N05Q_$3-C072_$3 = N04R-C06D = N04S-C06K
 1.46 with sigma of 0.002
 C2AA-C0AA
 2.45 with sigma of 0.002
 C078-C06Z = C060-C05P = C058-C051 = C07I-C06D = C26_$1-C06X_$1
 1.54 with sigma of 0.002
 C3AA-C2AA
 1.54 with sigma of 0.002
 C07E-C077
 1.54 with sigma of 0.002
 N05D-C061 = N05Q-C061
 1.35 with sigma of 0.002
 S1AB-O0
 1.5 with sigma of 0.01
 H06Y-H07O_$3
 2.2 with sigma of 0.001
 S1AB-O03J \\sim S1AB-O3B \\sim S1AB-O0 \\sim S1AB-O2
 with sigma of 0.02
 C07I-C06D \\sim C07J-C06D
 with sigma of 0.02
 S1AB-O3B \\sim S1AA-O3A \\sim S1AA-O1 \\sim S1AB-O0 \\sim S1AA-O2 \\sim
S1AB-O2 \\sim S1AB-O03J ~
 S1AA-O03J
 with sigma of 0.01
 O2-O0 \\sim O3B-O0 \\sim O03J-O0 \\sim O3B-O03J \\sim O2-O03J \\sim O3B-O2
 with sigma of 0.01
3. Rigid bond restraints
 N8, C2AA, C3AA
 with sigma for 1-2 distances of 0.0021 and sigma for 1-3 distances of 0.0041
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O0 \\sim S1AB \\sim O3B \\sim O2: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
O03R \\sim S17 \\sim O04N \\sim O04M: within 1.7A with sigma of 0.004 and sigma
for terminal atoms of 0.008 within 1.7A
S1AB \\sim S1AA \\sim O3B \\sim O3A \\sim O0 \\sim O1 \\sim O2 \\sim O03J:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C072) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C078) \\sim Ueq, Uanis(C06Z) \\sim Ueq: with sigma of 0.021 and sigma for
terminal atoms of 0.022
Uanis(N8) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C2AA)
\\sim Ueq, Uanis(C3AA) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O045) \\sim Ueq, Uanis(S19) \\sim Ueq, Uanis(O04F) \\sim Ueq, Uanis(O04I)
\\sim Ueq, Uanis(O04C) \\sim Ueq: with sigma of 0.021 and sigma for terminal
atoms of 0.042
Uanis(O03J) \\sim Ueq, Uanis(S1AB) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.004
Uanis(C06D) \\sim Ueq, Uanis(C07J) \\sim Ueq, Uanis(C07I) \\sim Ueq: with sigma
of 0.021 and sigma for terminal atoms of 0.02
Uanis(N059) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C1AA) \\sim Ueq: with sigma
of 0.021 and sigma for terminal atoms of 0.02
Uanis(C26) \\sim Ueq, Uanis(C06X) \\sim Ueq: with sigma of 0.021 and sigma for
terminal atoms of 0.02
Uanis(C077) \\sim Ueq, Uanis(C07E) \\sim Ueq: with sigma of 0.021 and sigma for
terminal atoms of 0.02
Uanis(N05D) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C33) \\sim Ueq: with sigma
of 0.021 and sigma for terminal atoms of 0.022
Uanis(N04O) \\sim Ueq, Uanis(C05J) \\sim Ueq: with sigma of 0.021 and sigma for
terminal atoms of 0.022
Uanis(N052) \\sim Ueq, Uanis(C06L) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N04S) \\sim Ueq, Uanis(C06K) \\sim Ueq: with sigma of 0.0021 and sigma
for terminal atoms of 0.0042
Uanis(S0S) \\sim Ueq, Uanis(O03F) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S14) \\sim Ueq, Uanis(O04K) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P18A) = Uanis(P18)
5. Rigid body (RIGU) restrains
 N05Q, N05D, C05K, C061, C13, C05Z, C33, C072
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C05U, N053, C06B, C074, N05C, C05Y, C078, C06Z
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 O0, S1AB, O3B, O2
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 O03R, S17, O04M, O04N
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C04X, N04H, C04U, C04W, C051, N04O, C058, C05J
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C050, N04R, C05X, C06D, N04S, C05F, C07I, C06K
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C04Z, C054, N059, N052, C05H, C17, C06L, C1AA
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 N056, C05R, C05V, C06F, N065, C05N, C077, C07E
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C057, N04Q, C04Y, C05I, N04T, C055, C05P, C060
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C05T, N05E, C06Q, C26, N05G, C064, C06X, C06T
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0002
 C06D, C07J, C07I
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O0, O1, O3B, O3A, S1AB, S1AA, O2, O03J
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O03F, Ti01, O01D, O01I, O01T, O029, O02M, O3B, O1, S0N, Ti02, Ti06, P18A, P18,
  S0P, S1AB, S1AA, O01Z, O02K, O02V, O01E, O01Y, O025, O02H, O032, O01B, O01L,
 O026, O02B, O01X, O02E, O024, O039, O0, O03J, O2, O3A, Ti03, Ti0F, Ti0A, S0T,
 Ti04, S0R, Ti07, Ti0D, Ti0C, S17, O03R, O046, O01G, O01U, O02Q, O02Y, O03K,
 Ti09, O01C, O01R, O020, O028, O02R, S0Z, O030, O03S, O01V, O02G, O02I, Ti0B,
 O01F, O01K, O01W, O02N, O022, O02U, O02W, O027, O02Z, O037, O038, O03A, O04M,
 O04N, Ti0H, S11, S13, Ti05, O01J, O02C, O02J, O035, P0O, S0S, O04A, O04E, Ti08,
  O01P, O01S, O02A, O02F, P0W, S0U, Ti0G, S15, S0Y, P0Q, Ti0K, Ti0M, O033, O03N,
  O03Q, O03U, O03T, O042, O047, O04G, O01M, O01O, O021, O023, Ti0E, Ti0J, O01N,
 O01Q, O02D, O02P, Ti0I, O01H, O031, O02L, O02T, O03I, O03O, O04J, O04L, O03L,
 O03X, O03B, O03H, O03P, O03Y, O036, O03C, O04F, S14, S0V, O02S, O02X, O03E,
 O03M, O03D, O045, O03W, O048, S0X, S16, Ti0L, S19, O041, O04K, O03G, S10, S12,
 O034, O03Z, O04B, O04D, O03V, O040, O049, O04C, O04I, O043, O044
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
6. Others
 Sof(H06C)=Sof(H06D)=Sof(C07J)=Sof(H07D)=Sof(H07E)=Sof(H07F)=1-FVAR(1)
 Sof(H06A)=Sof(H06B)=Sof(C07I)=Sof(H07A)=Sof(H07B)=Sof(H07C)=FVAR(1)
 Sof(P18A)=1-FVAR(2)
 Sof(P18)=FVAR(2)
 Sof(S1AB)=Sof(O0)=Sof(O3B)=1-FVAR(3)
 Sof(S1AA)=Sof(O3A)=Sof(O1)=FVAR(3)
7.a Riding coordinates:
 C06B(H06N,H06O,H06P), C06L(H06K,H06L,H06M), C06T(H06V,H06W,H06X), C07E(H07K,
 H07L,H07M), C07I(H07A,H07B,H07C), C1AA(H1AA,H1AB,H1AC), C33(H33A,H33B,H33C),
 C07J(H07D,H07E,H07F), C5(H5A,H5B,H5C)
7.b Secondary CH2 refined with riding coordinates:
 C051(H05A,H05B), C05P(H05M,H05N), C06D(H06A,H06B), C06D(H06C,H06D), C077(H07I,
 H07J), C078(H07G,H07H), C26(H26A,H26B), C17(H17A,H17B), C13(H13A,H13B),
 C2AA(H2AA,H2AB)
7.c Me refined with riding coordinates:
 C06Z(H06Q,H06R,H06S), C3AA(H3AA,H3AB,H3AC)
7.d Aromatic/amide H refined with riding coordinates:
 C04U(H04U), C04W(H04W), C04X(H04X), C04Y(H04Y), C04Z(H04Z), C050(H050),
 C054(H054), C055(H055), C057(H057), C05F(H05F), C05H(H05O), C05K(H05V),
 C05N(H05P), C05R(H05R), C05T(H05W), C05U(H05U), C05X(H05X), C05Y(H05Y),
 C05Z(H05Z), C061(H061), C064(H064), C06F(H06T), C06Q(H06U), C074(H074),
 C10(H10), C0AA(H0AA), C14(H14)
7.e Idealised Me refined as rotating group:
 C058(H05C,H05D,H05E), C05I(H05J,H05K,H05L), C05J(H05G,H05H,H05I), C05V(H05Q,
 H05S,H05T), C060(H06H,H06I,H06J), C06K(H06E,H06F,H06G), C06X(H06Y,H,HA),
 C072(H07N,H07O,H07P)
;
_shelx_res_checksum              45560
_shelx_fab_checksum              38695
_platon_squeeze_special_details
;
A solvent mask was calculated and 539 electrons were 
found in a volume of 1703\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
3[C6N2H11], 1C6N2H11], 0.5[C6N2H11] per Asymmetric Unit 
which account for 549 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;