data_zach _publ_requested_journal 'Journal name' _publ_contact_author_name 'Klaas A. Zachariasse' _publ_contact_author_address ;Max-Planck-Institut f\"ur biophysikalische Chemie, Spektroskopie und Photochemische Kinetik D-37070 G\"ottingen Germany ; _publ_contact_author_email kzachar@gwdg.de _publ_contact_author_phone 49(551)201-1264 _publ_contact_author_fax 49(551)201-1501 loop_ _publ_author_name _publ_author_address 'Sergey I. Druzhinin' ;Max-Planck-Institut f\"ur biophysikalische Chemie, Spektroskopie und Photochemische Kinetik D-37070 G\"ottingen Germany ; 'Victor A. Galievsky' ;Max-Planck-Institut f\"ur biophysikalische Chemie, Spektroskopie und Photochemische Kinetik D-37070 G\"ottingen Germany ; 'Attila Demeter' ;Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences 1519 Budapest P.O.Box 286 Hungary ; 'Sergey A. Kovalenko' ;Institut für Chemie, Humboldt Universit\"at zu Berlin Brook-Taylor Strasse 2, D-12489 Berlin Germany ; 'Tamara Senyushkina' ;Max-Planck-Institut f\"ur biophysikalische Chemie, Spektroskopie und Photochemische Kinetik D-37070 G\"ottingen Germany ; 'Srinivas R. Dubbaka' ;Department Chemie und Biochemie Ludwig-Maximilians-Universit\"at Butenandtstrasse 5-13, Haus F, D-81377 M\"unchen Germany ; 'Paul Knochel' ;Department Chemie und Biochemie Ludwig-Maximilians-Universit\"at Butenandtstrasse 5-13, Haus F, D-81377 M\"unchen Germany ; 'Peter Mayer' ;Department Chemie und Biochemie Ludwig-Maximilians-Universit\"at Butenandtstrasse 5-13, Haus F, D-81377 M\"unchen Germany ; 'Gro\&se, Christian' ;Institut f\"ur Anorganische Chemie Georg-August Universit\"at Tammannstrasse 4 D-37077 G\"ottingen Germany ; 'Dietmar Stalke' ;Institut f\"ur Anorganische Chemie Georg-August Universit\"at Tammannstrasse 4 D-37077 G\"ottingen Germany ; 'Klaas A. Zachariasse' ;Max-Planck-Institut f\"ur biophysikalische Chemie, Spektroskopie und Photochemische Kinetik D-37070 G\"ottingen Germany ; _publ_section_title ; Two-State Intramolecular Charge Transfer (ICT) with 3,5-Dimethyl-4-(Dimethylamino)benzonitrile (MMD) and Its Meta-Isomer mMMD. Ground State Amino Twist Not Essential for ICT. ; _audit_creation_method SHELXL-97 _chemical_name_systematic 4-(di-tert-butylamino)benzonitrile _chemical_name_common DTABN _chemical_melting_point ? _chemical_formula_moiety 'C15 H22 N2' _chemical_formula_sum 'C15 H22 N2' _chemical_formula_weight 230.35 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21' _symmetry_int_tables_number 4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.4033(17) _cell_length_b 8.2068(16) _cell_length_c 10.092(2) _cell_angle_alpha 90.00 _cell_angle_beta 92.33(3) _cell_angle_gamma 90.00 _cell_volume 695.4(2) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 7508 _cell_measurement_theta_min 4.3845 _cell_measurement_theta_max 64.2225 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.100 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 252 _exptl_absorpt_coefficient_mu 0.491 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9081 _exptl_absorpt_correction_T_max 0.9081 _exptl_absorpt_process_details sadabs _exptl_special_details ; Intensities were measured with a SMART 6000 area detector ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_probe x-ray _diffrn_radiation_type CuK\a _diffrn_radiation_wavelength 1.54178 _diffrn_source 'rotating anode' _diffrn_source_type 'Bruker AXS' _diffrn_radiation_monochromator 'IMCOATEC multilayer optics' _diffrn_measurement_device_type 'Bruker three circle diffractometer' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean 5.602 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 7623 _diffrn_reflns_av_R_equivalents 0.0195 _diffrn_reflns_av_sigmaI/netI 0.0183 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 4.38 _diffrn_reflns_theta_max 64.57 _reflns_number_total 2062 _reflns_number_gt 2039 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Proteum2 (v 2.2-RC7, Bruker 2006)' _computing_cell_refinement 'Bruker AXS SAINT (v 7.40A, Bruker 2006)' _computing_data_reduction 'Bruker AXS SAINT (v 7.40A, Bruker 2006)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker AXS SHELXTL (v 6.12)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0496P)^2^+0.1018P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details ;Flack H D (1983), Acta Cryst. A39, 876-881. The Flack x parameter was calculated by SHELXL to 0.4(0.4). A new recalculation with Parsons' Q-values algorithm implimented in XPREP was carried out and gave the following values: Correlation coefficient 6.16, GooF 1.1931, Flack x 0.1194 ( 0.1527 ). ; _refine_ls_abs_structure_Flack 0.12(15) _refine_ls_number_reflns 2062 _refine_ls_number_parameters 160 _refine_ls_number_restraints 146 _refine_ls_R_factor_all 0.0297 _refine_ls_R_factor_gt 0.0294 _refine_ls_wR_factor_ref 0.0770 _refine_ls_wR_factor_gt 0.0768 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 0.989 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N9 N 0.10584(12) 0.32852(13) 0.21056(10) 0.0228(2) Uani 1 1 d U . . C7 C 0.57266(15) 0.82404(18) 0.28890(13) 0.0281(3) Uani 1 1 d U . . C2 C 0.27939(16) 0.49964(17) 0.36164(13) 0.0256(3) Uani 1 1 d U . . H2 H 0.2373 0.4481 0.4369 0.038 Uiso 1 1 calc R . . C14 C 0.17474(15) 0.15953(17) 0.22200(13) 0.0253(3) Uani 1 1 d U . . C5 C 0.40387(15) 0.65020(17) 0.14247(13) 0.0266(3) Uani 1 1 d U . . H5 H 0.4464 0.7014 0.0673 0.040 Uiso 1 1 calc R . . N8 N 0.66553(14) 0.92629(16) 0.30617(13) 0.0362(3) Uani 1 1 d U . . C4 C 0.45579(15) 0.69628(17) 0.26984(13) 0.0255(3) Uani 1 1 d U . . C3 C 0.39309(15) 0.62062(17) 0.37979(13) 0.0267(3) Uani 1 1 d U . . H3 H 0.4282 0.6519 0.4668 0.040 Uiso 1 1 calc R . . C6 C 0.28956(15) 0.52883(16) 0.12617(12) 0.0245(3) Uani 1 1 d U . . H6 H 0.2544 0.4977 0.0392 0.037 Uiso 1 1 calc R . . C1 C 0.22548(14) 0.45198(16) 0.23451(12) 0.0234(3) Uani 1 1 d U . . C16 C 0.24866(17) 0.11875(18) 0.36000(14) 0.0322(3) Uani 1 1 d U . . H16B H 0.1689 0.1346 0.4270 0.048 Uiso 1 1 calc R . . H16C H 0.3398 0.1906 0.3794 0.048 Uiso 1 1 calc R . . H16A H 0.2844 0.0051 0.3615 0.048 Uiso 1 1 calc R . . C15 C 0.30812(16) 0.14720(18) 0.12213(14) 0.0294(3) Uani 1 1 d U . . H15B H 0.3475 0.0349 0.1197 0.044 Uiso 1 1 calc R . . H15C H 0.3956 0.2203 0.1494 0.044 Uiso 1 1 calc R . . H15A H 0.2661 0.1785 0.0338 0.044 Uiso 1 1 calc R . . C17 C 0.05272(17) 0.02793(18) 0.18314(15) 0.0309(3) Uani 1 1 d U . . H17A H 0.0079 0.0501 0.0938 0.046 Uiso 1 1 calc R . . H17C H -0.0328 0.0282 0.2463 0.046 Uiso 1 1 calc R . . H17B H 0.1049 -0.0789 0.1844 0.046 Uiso 1 1 calc R . . C13 C -0.18666(15) 0.30847(19) 0.15771(14) 0.0304(3) Uani 1 1 d U . . H13B H -0.1548 0.3308 0.0672 0.046 Uiso 1 1 calc R . . H13C H -0.2879 0.3633 0.1730 0.046 Uiso 1 1 calc R . . H13A H -0.1995 0.1907 0.1696 0.046 Uiso 1 1 calc R . . C11 C -0.09455(16) 0.31208(19) 0.39686(13) 0.0306(3) Uani 1 1 d U . . H11B H -0.2021 0.3465 0.4185 0.046 Uiso 1 1 calc R . . H11C H -0.0171 0.3585 0.4615 0.046 Uiso 1 1 calc R . . H11A H -0.0879 0.1929 0.3996 0.046 Uiso 1 1 calc R . . C12 C -0.07440(16) 0.55893(18) 0.25544(15) 0.0306(3) Uani 1 1 d U . . H12A H -0.0472 0.6005 0.1682 0.046 Uiso 1 1 calc R . . H12C H -0.0022 0.6063 0.3237 0.046 Uiso 1 1 calc R . . H12B H -0.1844 0.5889 0.2732 0.046 Uiso 1 1 calc R . . C10 C -0.05778(15) 0.37220(17) 0.25725(13) 0.0259(3) Uani 1 1 d U . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 N9 0.0200(5) 0.0193(6) 0.0291(5) -0.0004(5) 0.0015(4) -0.0001(5) C7 0.0227(6) 0.0232(7) 0.0385(7) -0.0004(6) 0.0021(5) 0.0010(6) C2 0.0251(6) 0.0241(7) 0.0276(6) 0.0014(5) 0.0008(5) -0.0002(5) C14 0.0232(6) 0.0210(7) 0.0317(7) -0.0004(5) 0.0017(5) -0.0004(5) C5 0.0241(6) 0.0247(7) 0.0312(7) 0.0036(6) 0.0037(5) 0.0020(5) N8 0.0304(7) 0.0302(7) 0.0480(7) -0.0012(5) 0.0015(5) -0.0044(5) C4 0.0186(6) 0.0199(6) 0.0379(7) -0.0009(6) -0.0001(5) 0.0024(5) C3 0.0237(6) 0.0263(8) 0.0300(6) -0.0027(6) -0.0020(5) -0.0004(5) C6 0.0231(7) 0.0232(7) 0.0273(6) -0.0002(5) 0.0001(5) 0.0028(5) C1 0.0201(6) 0.0204(7) 0.0295(6) -0.0007(6) -0.0006(5) 0.0035(5) C16 0.0358(8) 0.0262(8) 0.0346(7) 0.0041(6) 0.0003(6) 0.0069(6) C15 0.0266(7) 0.0251(7) 0.0368(7) -0.0023(6) 0.0037(5) 0.0018(6) C17 0.0301(7) 0.0217(7) 0.0413(7) -0.0042(6) 0.0048(6) -0.0024(6) C13 0.0231(6) 0.0273(7) 0.0406(7) -0.0005(6) -0.0008(5) -0.0008(6) C11 0.0284(7) 0.0298(7) 0.0341(7) -0.0034(6) 0.0075(5) 0.0000(6) C12 0.0243(7) 0.0236(8) 0.0438(8) -0.0028(6) 0.0001(6) 0.0027(5) C10 0.0212(6) 0.0231(7) 0.0335(7) -0.0026(5) 0.0027(5) 0.0007(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag N9 C1 1.4408(16) . ? N9 C14 1.5055(18) . ? N9 C10 1.5145(16) . ? C7 N8 1.1543(19) . ? C7 C4 1.4442(19) . ? C2 C3 1.3849(19) . ? C2 C1 1.3990(18) . ? C2 H2 0.9500 . ? C14 C17 1.5294(19) . ? C14 C16 1.5386(19) . ? C14 C15 1.5408(19) . ? C5 C6 1.3889(19) . ? C5 C4 1.3929(19) . ? C5 H5 0.9500 . ? C4 C3 1.3936(19) . ? C3 H3 0.9500 . ? C6 C1 1.3897(19) . ? C6 H6 0.9500 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C16 H16A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C15 H15A 0.9800 . ? C17 H17A 0.9800 . ? C17 H17C 0.9800 . ? C17 H17B 0.9800 . ? C13 C10 1.539(2) . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C13 H13A 0.9800 . ? C11 C10 1.5361(18) . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C11 H11A 0.9800 . ? C12 C10 1.5389(19) . ? C12 H12A 0.9800 . ? C12 H12C 0.9800 . ? C12 H12B 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C1 N9 C14 111.80(9) . . ? C1 N9 C10 114.68(10) . . ? C14 N9 C10 123.05(10) . . ? N8 C7 C4 178.95(14) . . ? C3 C2 C1 121.18(12) . . ? C3 C2 H2 119.4 . . ? C1 C2 H2 119.4 . . ? N9 C14 C17 112.28(10) . . ? N9 C14 C16 114.19(11) . . ? C17 C14 C16 108.68(11) . . ? N9 C14 C15 107.34(10) . . ? C17 C14 C15 106.49(11) . . ? C16 C14 C15 107.47(11) . . ? C6 C5 C4 119.55(12) . . ? C6 C5 H5 120.2 . . ? C4 C5 H5 120.2 . . ? C3 C4 C5 119.97(12) . . ? C3 C4 C7 119.63(12) . . ? C5 C4 C7 120.39(12) . . ? C2 C3 C4 119.68(12) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C5 C6 C1 121.37(12) . . ? C5 C6 H6 119.3 . . ? C1 C6 H6 119.3 . . ? C6 C1 C2 118.25(12) . . ? C6 C1 N9 118.50(11) . . ? C2 C1 N9 123.25(11) . . ? C14 C16 H16B 109.5 . . ? C14 C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C14 C16 H16A 109.5 . . ? H16B C16 H16A 109.5 . . ? H16C C16 H16A 109.5 . . ? C14 C15 H15B 109.5 . . ? C14 C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C14 C15 H15A 109.5 . . ? H15B C15 H15A 109.5 . . ? H15C C15 H15A 109.5 . . ? C14 C17 H17A 109.5 . . ? C14 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? C14 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? H17C C17 H17B 109.5 . . ? C10 C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13A 109.5 . . ? H13B C13 H13A 109.5 . . ? H13C C13 H13A 109.5 . . ? C10 C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C11 H11A 109.5 . . ? H11B C11 H11A 109.5 . . ? H11C C11 H11A 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? H12C C12 H12B 109.5 . . ? N9 C10 C11 115.37(11) . . ? N9 C10 C13 109.89(10) . . ? C11 C10 C13 109.10(11) . . ? N9 C10 C12 108.36(10) . . ? C11 C10 C12 108.01(12) . . ? C13 C10 C12 105.64(11) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C1 N9 C14 C17 -174.22(11) . . . . ? C10 N9 C14 C17 42.98(15) . . . . ? C1 N9 C14 C16 61.48(13) . . . . ? C10 N9 C14 C16 -81.32(14) . . . . ? C1 N9 C14 C15 -57.53(13) . . . . ? C10 N9 C14 C15 159.67(11) . . . . ? C6 C5 C4 C3 0.03(19) . . . . ? C6 C5 C4 C7 -178.99(12) . . . . ? N8 C7 C4 C3 -13(8) . . . . ? N8 C7 C4 C5 166(8) . . . . ? C1 C2 C3 C4 -0.24(19) . . . . ? C5 C4 C3 C2 0.09(19) . . . . ? C7 C4 C3 C2 179.12(12) . . . . ? C4 C5 C6 C1 0.01(19) . . . . ? C5 C6 C1 C2 -0.16(19) . . . . ? C5 C6 C1 N9 179.22(11) . . . . ? C3 C2 C1 C6 0.28(19) . . . . ? C3 C2 C1 N9 -179.07(12) . . . . ? C14 N9 C1 C6 99.96(13) . . . . ? C10 N9 C1 C6 -113.93(13) . . . . ? C14 N9 C1 C2 -80.69(14) . . . . ? C10 N9 C1 C2 65.42(15) . . . . ? C1 N9 C10 C11 -94.06(14) . . . . ? C14 N9 C10 C11 47.80(16) . . . . ? C1 N9 C10 C13 142.12(11) . . . . ? C14 N9 C10 C13 -76.03(14) . . . . ? C1 N9 C10 C12 27.14(15) . . . . ? C14 N9 C10 C12 168.99(11) . . . . ? _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 64.57 _diffrn_measured_fraction_theta_full 0.985 _refine_diff_density_max 0.148 _refine_diff_density_min -0.132 _refine_diff_density_rms 0.035 _exptl_crystal_recrystallization_method 'at 188K, in toluene' # start Validation Reply Form _vrf_THETM01_zach ; PROBLEM: The value of sine(theta_max)/wavelength is less than 0.590 RESPONSE: Data were collected using Cu radiation. Highest resolution of collected data were used for structrure refinement. The final value of sine(theta_max)/wavelength is 0.5858 and close to 0.590. ; # end Validation Reply Form