Semiconducting single crystals comprising segregated arrays of complexes of c60.
Barnes, Jonathan C.; Dale, Edward J.; Prokofjevs, Aleksandrs; Narayanan, Ashwin; Gibbs-Hall, Ian C; Juríček, Michal; Stern, Charlotte L.; Sarjeant, Amy A.; Botros, Youssry Y.; Stupp, Samuel I.; Stoddart, J. Fraser; Journal of the American Chemical Society 137 (2015) 2392–2399; doi:10.1021/ja512959g

data_4123418
_publ_section_title
;
 Semiconducting single crystals comprising segregated arrays of complexes
 of c60.
;
_journal_issue                   6
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              2392
_journal_page_last               2399
_journal_paper_doi               10.1021/ja512959g
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety
'2(C60 H48 N4), 2(C3 H7 O0.5), 5.5(C20 H12), 8(F6 P)'
_chemical_formula_sum            'C236 H176 F48 N8 O P8'
_chemical_formula_weight         4299.60
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2013-09-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.8563(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.0809(5)
_cell_length_b                   23.1311(6)
_cell_length_c                   38.3125(9)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      62.43
_cell_measurement_theta_min      2.31
_cell_volume                     20381.1(8)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XM, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      99.99
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.873
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0521
_diffrn_reflns_av_unetI/netI     0.0622
_diffrn_reflns_Laue_measured_fraction_full 0.873
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            86658
_diffrn_reflns_point_group_measured_fraction_full 0.873
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         62.44
_diffrn_reflns_theta_min         1.16
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.530
_exptl_absorpt_correction_T_max  0.7522
_exptl_absorpt_correction_T_min  0.6641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0645 before and 0.0539 after correction.
The Ratio of minimum to maximum transmission is 0.8829.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             8832
_exptl_crystal_size_max          0.114
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.057
_refine_diff_density_max         2.440
_refine_diff_density_min         -0.964
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2910
_refine_ls_number_reflns         32209
_refine_ls_number_restraints     1731
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1376
_refine_ls_R_factor_gt           0.1038
_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^)+(0.1563P)^2^+75.4730P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2819
_refine_ls_wR_factor_ref         0.3033
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22374
_reflns_number_total             32209
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja512959g_si_003.cif
_cod_data_source_block           n3041
_cod_depositor_comments
'Adding full bibliography for 4123417--4123419.cif.'
_cod_database_code               4123418
_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
 F51-F53 \\sim F51-F54 \\sim F51-F52 \\sim F51-F50 \\sim F53-F52 \\sim F53-F49
 \\sim F53-F50 \\sim F54-F52
 \\sim F54-F49 \\sim F54-F50 \\sim F52-F49 \\sim F49-F50
 with sigma of 0.04
 P9-F51 \\sim P9-F53 \\sim P9-F54 \\sim P9-F52 \\sim P9-F49 \\sim P9-F50
 with sigma of 0.02
 F45-F47 \\sim F45-F48 \\sim F45-F46 \\sim F45-F44 \\sim F47-F46 \\sim F47-F43
 \\sim F47-F44 \\sim F48-F46
 \\sim F48-F43 \\sim F48-F44 \\sim F46-F43 \\sim F43-F44
 with sigma of 0.04
 P8-F45 \\sim P8-F47 \\sim P8-F48 \\sim P8-F46 \\sim P8-F43 \\sim P8-F44
 with sigma of 0.02
 F37-F38 \\sim F37-F41 \\sim F37-F42 \\sim F38-F39 \\sim F38-F41 \\sim F38-F42
 \\sim F40-F42
 with sigma of 0.04
 P7-F37 \\sim P7-F38 \\sim P7-F39 \\sim P7-F40 \\sim P7-F41 \\sim P7-F42
 with sigma of 0.02
 F37-F38 \\sim F37-F40 \\sim F37-F41 \\sim F37-F42 \\sim F38-F39 \\sim F38-F41
 \\sim F38-F42 \\sim F39-F41
 \\sim F40-F41 \\sim F40-F42
 with sigma of 0.04
 P7-F37 \\sim P7-F38 \\sim P7-F39 \\sim P7-F40 \\sim P7-F41 \\sim P7-F42
 with sigma of 0.02
 F37A-F38A \\sim F37A-F40A \\sim F37A-F41A \\sim F37A-F42A \\sim F38A-F39A
 \\sim F38A-F41A \\sim F38A-
 F42A \\sim F39A-F40A \\sim F39A-F41A \\sim F39A-F42A \\sim F40A-F41A 
 \\sim F40A-F42A
 with sigma of 0.04
 P7A-F37A \\sim P7A-F38A \\sim P7A-F39A \\sim P7A-F40A \\sim P7A-F41A 
 \\sim P7A-F42A
 with sigma of 0.02
 F31-F32 \\sim F31-F34 \\sim F31-F35 \\sim F31-F36 \\sim F32-F33 \\sim F32-F35
 \\sim F32-F36 \\sim F33-F34
 \\sim F33-F35 \\sim F33-F36 \\sim F34-F35 \\sim F34-F36
 with sigma of 0.04
 P6-F31 \\sim P6-F32 \\sim P6-F33 \\sim P6-F34 \\sim P6-F35 \\sim P6-F36
 with sigma of 0.02
 F31A-F32A \\sim F31A-F34A \\sim F31A-F35A \\sim F31A-F36A \\sim F32A-F33A 
 \\sim F32A-F35A \\sim F32A-
 F36A \\sim F33A-F34A \\sim F33A-F35A \\sim F33A-F36A \\sim F34A-F35A 
 \\sim F34A-F36A
 with sigma of 0.04
 P6A-F31A \\sim P6A-F32A \\sim P6A-F33A \\sim P6A-F34A \\sim P6A-F35A 
 \\sim P6A-F36A
 with sigma of 0.02
 C216-C215 \\sim C217-C216 \\sim C218-C217 \\sim C218-C213 \\sim C219-C213 
 \\sim C224-C219 \\sim C224-
 C223 \\sim C223-C222 \\sim C222-C221 \\sim C222_$1-C221 \\sim C223_$1-C222_$1 
 \\sim C224_$1-
 C223_$1 \\sim C224_$1-C219_$1 \\sim C219_$1-C213_$1 \\sim C218_$1-C213_$1 
 \\sim C218_$1-
 C217_$1 \\sim C217_$1-C216_$1 \\sim C216_$1-C215 \\sim C215-C214 
 \\sim C214-C213_$1 \\sim C214-
 C213 \\sim C220-C219 \\sim C220-C219_$1 \\sim C221-C220
 with sigma of 0.02
 C222-C224 \\sim C223-C219 \\sim C220-C213 \\sim C218-C216 \\sim C217-C215
 \\sim C216_$1-C218_$1 -
 C217_$1-C213_$1 \\sim C214-C219_$1 \\sim C224_$1-C222_$1 \\sim C223_$1-C221
 with sigma of 0.02
 C222-C219 \\sim C221-C224 \\sim C223-C220 \\sim C213-C219_$1 \\sim C214-C217
 \\sim C218-C215 -
 C216-C213 \\sim C216_$1-C213_$1 \\sim C215-C218_$1 \\sim C217_$1-C214 
 \\sim C219_$1-C222_$1 -
 C224_$1-C221 \\sim C220-C223_$1
 with sigma of 0.02
 C234-C233 \\sim C233-C232 \\sim C232-C231 \\sim C236-C231 \\sim C236-C235 
 \\sim C235-C234 \\sim C231-
 C225 \\sim C226-C225 \\sim C227-C226 \\sim C228-C227 \\sim C229-C228 
 \\sim C230-C229 \\sim C230-C225 -
 C235-C234_$1 \\sim C234_$1-C233_$1 \\sim C233_$1-C232_$1 \\sim C232_$1-C231_$1
 \\sim C236-
 C231_$1 \\sim C231_$1-C225_$1 \\sim C230-C225_$1 \\sim C226_$1-C225_$1
 \\sim C227_$1-C226_$1 -
 C228_$1-C227_$1 \\sim C229-C228_$1
 with sigma of 0.02
 C233-C231 \\sim C232-C234 \\sim C235-C233_$1 \\sim C234_$1-C232_$1
 \\sim C236-C225_$1 -
 C231_$1-C230 \\sim C225-C227 \\sim C226-C228 \\sim C229-C227_$1 
 \\sim C228_$1-C226_$1
 with sigma of 0.02
 C234-C231 \\sim C233-C236 \\sim C232-C235 \\sim C225-C228 \\sim C226-C229
 \\sim C227-C230 -
 C225_$1-C228_$1 \\sim C231_$1-C234_$1 \\sim C231-C225_$1 \\sim C231_$1-C225
 \\sim C236-C230 -
 C229-C226_$1 \\sim C232_$1-C235 \\sim C233_$1-C236 \\sim C234_$1-C231_$1 
 \\sim C227_$1-C230 -
 C228_$1-C225_$1
 with sigma of 0.02
 O2-C268 \\sim O2-C968 \\sim O2-C269 \\sim O2-C969
 with sigma of 0.02
 C270-C268 \\sim C271-C268 \\sim C971-C968 \\sim C970-C968 \\sim C973-C969
 \\sim C972-C969 \\sim C272-
 C269 \\sim C273-C269
 with sigma of 0.02
 C271-C270 \\sim C970-C971 \\sim C973-C972 \\sim C272-C273
 with sigma of 0.02
 C969-C968 \\sim C268-C269
 with sigma of 0.02
 O1-C249 \\sim O1-C252
 with sigma of 0.02
 C253-C252 \\sim C254-C252 \\sim C250-C249 \\sim C251-C249
 with sigma of 0.02
 C250-C251 \\sim C254-C253
 with sigma of 0.02
3. Rigid bond restraints
 P7A, F37A, F38A, F39A, F40A, F41A, F42A, F37, P7, F38, F39, F40, F41, F42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C971, O2, C268, C269, C969, C968, C270, C271, C272, C273, C973, C972, C970
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 F41, P7, F37, F38, F39, F40, F42, F39A, P7A, F37A, F38A, F40A, F41A, F42A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
P7A \\sim F37A \\sim F38A \\sim F39A \\sim F40A \\sim F41A \\sim F42A \\sim F42
 \\sim P7 \\sim F37 \\sim F38 \\sim F39 \\sim F40 \\sim F41: within 1.7A with 
 sigma of 0.04 and sigma for terminal atoms of 0.08
O2 \\sim C268 \\sim C269 \\sim C969 \\sim C968 \\sim C270 \\sim C271 \\sim C272
 \\sim C273 \\sim C973 \\sim C972 \\sim C970 \\sim C971: within 1.7A with sigma
 of 0.01 and sigma for terminal atoms of 0.02
F41 \\sim P7 \\sim F37 \\sim F38 \\sim F39 \\sim F40 \\sim F42 \\sim F39A
 \\sim P7A \\sim F37A \\sim F38A \\sim F40A \\sim F41A \\sim F42A: within 1.7A
 with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C215) = Uanis(C213) = Uanis(C218) = Uanis(C214) = Uanis(C219) = 
Uanis(C217) = Uanis(C224) = Uanis(C220) = Uanis(C216) = Uanis(C223) = 
Uanis(C221) = Uanis(C222)
Uanis(C228) = Uanis(C225) = Uanis(C226) = Uanis(C230) = Uanis(C231) = 
Uanis(C227) = Uanis(C229) = Uanis(C232) = Uanis(C236) = Uanis(C233) = 
Uanis(C235) = Uanis(C234)
5. Others
 Sof(C969)=Sof(H969)=Sof(C973)=Sof(H97A)=Sof(H97B)=Sof(H97C)=Sof(C972)=
 Sof(H97D)=Sof(H97E)=Sof(H97F)=Sof(C968)=Sof(H968)=Sof(C970)=Sof(H97G)=
 Sof(H97H)=Sof(H97I)=Sof(C971)=Sof(H97J)=Sof(H97K)=Sof(H97L)=0.5*(1-FVAR(2))
 Sof(C268)=Sof(H268)=Sof(C269)=Sof(H269)=Sof(C270)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C271)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C272)=Sof(H27G)=
 Sof(H27H)=Sof(H27I)=Sof(C273)=Sof(H27J)=Sof(H27K)=Sof(H27L)=0.5*FVAR(2)
 Sof(P6A)=Sof(F31A)=Sof(F32A)=Sof(F33A)=Sof(F34A)=Sof(F35A)=Sof(F36A)=1-FVAR(2)
 Sof(P6)=Sof(F31)=Sof(F32)=Sof(F33)=Sof(F34)=Sof(F35)=Sof(F36)=FVAR(2)
 Sof(P9)=Sof(F49)=Sof(F50)=Sof(F51)=Sof(F52)=Sof(F53)=Sof(F54)=1-FVAR(3)
 Sof(P8)=Sof(F43)=Sof(F44)=Sof(F45)=Sof(F46)=Sof(F47)=Sof(F48)=FVAR(3)
 Sof(P7A)=Sof(F37A)=Sof(F38A)=Sof(F39A)=Sof(F40A)=Sof(F41A)=Sof(F42A)=1-FVAR(4)
 Sof(P7)=Sof(F37)=Sof(F38)=Sof(F39)=Sof(F40)=Sof(F41)=Sof(F42)=FVAR(4)
 Fixed Sof: O2(0.5) O1(0.5) C249(0.5) H249(0.5) C250(0.5) H25A(0.5) H25B(0.5)
 H25C(0.5) C251(0.5) H25D(0.5) H25E(0.5) H25F(0.5) C252(0.5) H252(0.5)
 C253(0.5) H25G(0.5) H25H(0.5) H25I(0.5) C254(0.5) H25J(0.5) H25K(0.5) H25L(0.5)
 Fixed X: C229(1.25) C230(1.25) C235(1.25) C236(1.25) C214(1.25) C215(1.25)
 C220(1.25) C221(1.25)
 Fixed Z: C229(0.25) C230(0.25) C235(0.25) C236(0.25) C214(0.25) C215(0.25)
 C220(0.25) C221(0.25)
6.a Ternary CH refined with riding coordinates:
 C969(H969), C968(H968), C268(H268), C269(H269), C249(H249), C252(H252)
6.b Secondary CH2 refined with riding coordinates:
 C77(H77A,H77B), C90(H90A,H90B), C107(H10A,H10B), C120(H12A,H12B), C13(H13A,
 H13B), C30(H30A,H30B), C43(H43A,H43B), C60(H60A,H60B)
6.c Me refined with riding coordinates:
 C973(H97A,H97B,H97C), C972(H97D,H97E,H97F), C970(H97G,H97H,H97I), C971(H97J,
 H97K,H97L), C270(H27A,H27B,H27C), C271(H27D,H27E,H27F), C272(H27G,H27H,H27I),
 C273(H27J,H27K,H27L), C250(H25A,H25B,H25C), C251(H25D,H25E,H25F), C253(H25G,
 H25H,H25I), C254(H25J,H25K,H25L)
6.d Aromatic/amide H refined with riding coordinates:
 C61(H61), C62(H62), C64(H64), C65(H65), C67(H67), C68(H68), C70(H70),
 C71(H71), C73(H73), C74(H74), C75(H75), C76(H76), C79(H79), C80(H80), C82(H82),
  C83(H83), C85(H85), C86(H86), C88(H88), C89(H89), C91(H91), C92(H92),
 C94(H94), C95(H95), C97(H97), C98(H98), C100(H100), C101(H101), C103(H103),
 C104(H104), C105(H105), C106(H106), C109(H109), C110(H110), C112(H112),
 C113(H113), C115(H115), C116(H116), C118(H118), C119(H119), C2(H2), C3(H3),
 C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24), C26(H26), C27(H27),
  C28(H28), C29(H29), C32(H32), C33(H33), C35(H35), C36(H36), C38(H38),
 C39(H39), C41(H41), C42(H42), C44(H44), C45(H45), C47(H47), C48(H48), C50(H50),
  C51(H51), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
 C122(H122), C123(H123), C124(H124), C128(H128), C129(H129), C130(H130),
 C132(H132), C133(H133), C134(H134), C136(H136), C137(H137), C138(H138),
 C162(H162), C163(H163), C164(H164), C166(H166), C167(H167), C168(H168),
 C172(H172), C173(H173), C174(H174), C176(H176), C177(H177), C178(H178),
 C142(H142), C143(H143), C144(H144), C146(H146), C147(H147), C148(H148),
 C152(H152), C153(H153), C154(H154), C156(H156), C157(H157), C158(H158),
 C226(H226), C227(H227), C228(H228), C232(H232), C233(H233), C234(H234),
 C216(H216), C217(H217), C218(H218), C222(H222), C223(H223), C224(H224),
 C183(H183), C184(H184), C185(H185), C190(H190), C191(H191), C192(H192),
 C194(H194), C195(H195), C196(H196), C198(H198), C199(H199), C200(H200),
 C205(H205), C206(H206), C207(H207), C209(H209), C210(H210), C211(H211)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 952.1 Ang^3^ [4.7%]
Total electron count / cell = 278.9
;
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.845
_shelxl_version_number           2013-3