Precise peripheral design enables propeller-like squaraine dye with highly sensitive and wide-range piezochromism.
Guo, Weihan; Wang, Mingda; Si, Leilei; Wang, Yigang; Xia, Guomin; Wang, Hongming; Chemical science 14 (2023) 6348–6354; doi:10.1039/d3sc01730c

data_1569193
_publ_section_title
;
 Precise peripheral design enables propeller-like squaraine dye with
 highly sensitive and wide-range piezochromism.
;
_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              6348
_journal_page_last               6354
_journal_paper_doi               10.1039/d3sc01730c
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '11.001(C H2 Cl2), 8(C36 H40 N6 O2)'
_chemical_formula_sum            'C299 H342 Cl22 N48 O16'
_chemical_formula_weight         5644.09
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2fgn9w
_audit_creation_date             2023-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-14 deposited with the CCDC.	2023-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   8.5815(2)
_cell_length_b                   23.7567(5)
_cell_length_c                   38.1133(12)
_cell_measurement_reflns_used    8981
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      72.7120
_cell_measurement_theta_min      2.3390
_cell_volume                     7770.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.952
_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     43.00  82.00   0.50    0.80    --   63.04-124.00  33.00   78
  2  \w     59.00  91.00   0.50    0.80    --   76.80-124.00  33.00   64
  3  \w     37.00  62.00   0.50    0.80    --   72.79-124.00  33.00   50
  4  \w     51.00  94.00   0.50    0.80    --   72.79-125.00 -60.00   86
  5  \w     61.00 117.00   0.50    0.80    --   72.79  15.00 -90.00  112
  6  \w     52.00  97.00   0.50    0.80    --   63.04  15.00-180.00   90
  7  \w    -80.00 -53.00   0.50    0.80    --  -63.29 -15.00-120.00   54
  8  \w    -89.00 -62.00   0.50    0.80    --  -70.62 -15.00-180.00   54
  9  \w   -120.00 -70.00   0.50    0.80    --  -76.56 -15.00-120.00  100
 10  \w    -99.00 -67.00   0.50    0.80    --  -76.56 -15.00   0.00   64
 11  \w   -114.00 -73.00   0.50    0.80    --  -70.62 -15.00 150.00   82
 12  \w    -87.00 -60.00   0.50    0.80    --  -70.62 124.00 112.00   54
 13  \w    -55.00 -28.00   0.50    0.80    --  -70.62 124.00 112.00   54
 14  \w    -55.00 -21.00   0.50    0.80    --  -63.29 124.00 112.00   68
 15  \w    -99.00 -55.00   0.50    0.80    --  -81.16 124.00 112.00   88
 16  \w   -100.00 -42.00   0.50    0.80    --  -81.16 125.00 -90.00  116
 17  \w    -82.00 -56.00   0.50    0.80    --  -63.29 125.00-150.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0735406000
_diffrn_orient_matrix_UB_12      0.0559540000
_diffrn_orient_matrix_UB_13      -0.0119163000
_diffrn_orient_matrix_UB_21      0.0084817000
_diffrn_orient_matrix_UB_22      -0.0196810000
_diffrn_orient_matrix_UB_23      -0.0384733000
_diffrn_orient_matrix_UB_31      -0.1635694000
_diffrn_orient_matrix_UB_32      -0.0261996000
_diffrn_orient_matrix_UB_33      0.0033941000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0533
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            39616
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.569
_diffrn_reflns_theta_min         2.318
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.285
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92254
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             2974
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.546
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.081
_refine_ls_extinction_coef       0.00083(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     627
_refine_ls_number_reflns         7677
_refine_ls_number_restraints     655
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.1221
_refine_ls_R_factor_gt           0.0915
_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^)+(0.1223P)^2^+6.5600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2390
_refine_ls_wR_factor_ref         0.2588
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5629
_reflns_number_total             7677
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01730c2.cif
_cod_data_source_block           20230222-yxy-g2-200k
_cod_depositor_comments
'Adding full bibliography for 1569190--1569193.cif.'
_cod_database_code               1569193
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         CHON
_chemical_oxdiff_usercomment     CHO
_shelx_estimated_absorpt_t_max   0.771
_shelx_estimated_absorpt_t_min   0.726
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C4
 1.78 with sigma of 0.02
 Cl5-C4
 1.77 with sigma of 0.02
 Cl2-C4 = Cl5-C4
 1.771 with sigma of 0.01
 Cl6-Cl7
 2.916 with sigma of 0.03
 Cl2-Cl5
 2.916 with sigma of 0.03
 Cl6-C1
 1.78 with sigma of 0.02
 Cl7-C1
 1.77 with sigma of 0.02
 Cl6-C1 = Cl7-C1
 1.771 with sigma of 0.01
 Cl2-Cl5
 2.92 with sigma of 0.04
 Cl6-Cl7
 2.92 with sigma of 0.04
3. Restrained planarity
 C34, C30, C31, C33, C29, C32, N22, N35
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl3 \\sim C2 \\sim C2A \\sim Cl1A \\sim Cl3A \\sim C2B \\sim Cl1B
\\sim Cl3B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N35 \\sim C36A \\sim C31A \\sim C29 \\sim C29A \\sim C30 \\sim C33A \\sim C31
\\sim N35A \\sim C32 \\sim C30A \\sim C33 \\sim C32A \\sim C34 \\sim C34A \\sim
C36 \\sim C37A \\sim C37: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl2 \\sim Cl5 \\sim C4: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl6 \\sim Cl7 \\sim C1: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(Cl6) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(Cl7) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 N35, C37, C34, C29, C33, C30, C36, C31, C32, N22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C2B, Cl1B, Cl3B, C2A, Cl1A, Cl3A, C2, Cl1, Cl3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N35A, C37A, C34A, C29A, C33A, C30A, C36A, C31A, C32A, N22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl2, Cl5, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl6, Cl7, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{N35A, C29A, C30A, C31A, C32A, C33A, C34A, C36A, C37A} sigma for 1-2: 0.02,
1-3: 0.04
as in
{N35, C29, C30, C31, C32, C33, C34, C36, C37}
7. Others
 1*[Sof(Cl1)+Sof(Cl3)+Sof(C2)+Sof(H2A)+Sof(H2B)]+1*[Sof(C2A)+Sof(H2AA)+
 Sof(H2AB)+Sof(Cl1A)+Sof(Cl3A)]+1*[Sof(C2B)+Sof(H2BA)+Sof(H2BB)+Sof(Cl1B)+
 Sof(Cl3B)]=1 with esd of 0.0001
 Sof(N35A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(N35)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(C33)=
 Sof(H33)=Sof(C34)=Sof(H34)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(1)
 Sof(Cl1)=Sof(Cl3)=Sof(C2)=Sof(H2A)=Sof(H2B)=FVAR(2)
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(Cl1A)=Sof(Cl3A)=FVAR(3)
 Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(Cl1B)=Sof(Cl3B)=FVAR(4)
 Fixed Sof: Cl6(0.125) Cl7(0.125) C1(0.125) H1A(0.125) H1B(0.125) Cl2(0.25)
 Cl5(0.25) C4(0.25) H4A(0.25) H4B(0.25)
 Fixed Y: C37(0.615901)
8.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C1(H1A,H1B), C4(H4A,H4B), C2A(H2AA,H2AB), C2B(H2BA,H2BB)
8.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C16(H16), C17(H17),
 C24(H24), C25(H25), C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C34(H34),
  C30A(H30A), C31A(H31A), C33A(H33A), C34A(H34A)
8.c Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F)
;
_shelx_res_checksum              43965
_shelx_hkl_checksum              67371
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.566
_oxdiff_exptl_absorpt_empirical_full_min 0.385