Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'A. Downs' 'Timothy Greene' 'Hans-Jorg Himmel' 'Sarah Marchant' 'S. Parsons' 'Christina Y. Tang' _publ_contact_author_name 'Anthony Downs' _publ_contact_author_address ; Inorganic Chemistry Laboratory University of Oxford South Parks Road OXFORD OX1 3QR UNITED KINGDOM ; _publ_contact_author_email TONY.DOWNS@CHEM.OX.AC.UK _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Synthesis and structural characterisation of primary amine adducts of gallane, RH2N.GaH3, and of their decomposition products, [RHNGaH2]n (R = Me, n = 3; R = tBu, n = 2) ; data_menh2g _database_code_depnum_ccdc_archive 'CCDC 275758' #Compound #1 in paper _audit_creation_date 05-05-17 _audit_creation_method CRYSTALS_ver_12.80 _oxford_structure_analysis_title 'MENH2G in I2/a' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 12.351(3) _cell_length_b 4.9484(10) _cell_length_c 14.510(3) _cell_angle_alpha 90 _cell_angle_beta 92.552(3) _cell_angle_gamma 90 _cell_volume 885.9(3) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M I2/a _symmetry_space_group_name_Hall '-I 2ya' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z x+1/2,y+1/2,z+1/2 -x+1/2,-y+1/2,-z+1/2 -x+1/2,y,-z x+1/2,-y,z -x+1,y+1/2,-z+1/2 x+1,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ga 0.2307 1.6083 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.4135 1.7189 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 8 # Given Formula = C1 H8 Ga1 N1 # Dc = 1.56 Fooo = 416.00 Mu = 59.92 M = 103.80 # Found Formula = C1 H8 Ga1 N1 # Dc = 1.56 FOOO = 416.00 Mu = 59.92 M = 103.80 _chemical_formula_sum 'C1 H8 Ga1 N1' _chemical_formula_moiety 'C1 H8 Ga1 N1' _chemical_compound_source ? _chemical_formula_weight 103.80 _cell_measurement_reflns_used 2259 _cell_measurement_theta_min 3 _cell_measurement_theta_max 29 _cell_measurement_temperature 150 _exptl_crystal_description cylinder _exptl_crystal_colour colourless _exptl_crystal_size_min 0.53 _exptl_crystal_size_mid 0.53 _exptl_crystal_size_max 3.00 _exptl_crystal_density_diffrn 1.556 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 416 _exptl_absorpt_coefficient_mu 5.992 # Sheldrick geometric approximatio 0.04 0.04 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.004 _exptl_absorpt_correction_T_max 0.040 _diffrn_measurement_device_type 'Bruker SMART' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'SMART (Siemens, 1993)' _computing_data_reduction 'SAINT (Siemens ,1995)' _computing_cell_refinement 'SAINT (Siemens ,1995)' _computing_structure_solution 'DIRDIF-96 (Beurskens et al., 1996)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 3744 _reflns_number_total 1072 _diffrn_reflns_av_R_equivalents 0.034 # Number of reflections with Friedels Law is 1072 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 1163 _diffrn_reflns_theta_min 2.810 _diffrn_reflns_theta_max 28.862 _diffrn_measured_fraction_theta_max 0.922 _diffrn_reflns_theta_full 25.399 _diffrn_measured_fraction_theta_full 0.995 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 19 _reflns_limit_h_min -16 _reflns_limit_h_max 15 _reflns_limit_k_min 0 _reflns_limit_k_max 6 _reflns_limit_l_min 0 _reflns_limit_l_max 19 _oxford_diffrn_Wilson_B_factor 0.00 _oxford_diffrn_Wilson_scale 0.00 _atom_sites_solution_primary Patterson # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.32 _refine_diff_density_max 0.51 _refine_ls_number_reflns 1071 _refine_ls_number_restraints 9 _refine_ls_number_parameters 37 #_refine_ls_R_factor_ref 0.0254 _refine_ls_wR_factor_ref 0.0543 _refine_ls_goodness_of_fit_ref 0.9947 #_reflns_number_all 1071 _refine_ls_R_factor_all 0.0254 _refine_ls_wR_factor_all 0.0543 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 962 _refine_ls_R_factor_gt 0.0220 _refine_ls_wR_factor_gt 0.0534 _refine_ls_shift/su_max 0.000222 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment mixed # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; w=1/[\s^2^(F^2^) + 0.03 + 0.63P] where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; _publ_section_exptl_refinement ; H3GA-NH2Me is a liquid under normal conditions, with a mpt of 200 K. A crystal was grown in a capillary at 190K over the course of 30 min using an OHCD laser-assisted crystallisation device. The sample was cooled to 150 K for data collection. H-atoms were all located in a difference map. For consistency with other structures in this series the Ga-H distances were restrained to 1.50(1) Ang, and all H-Ga-H angles were restrained to be equal. A common U[iso] was refined for the H's attached to Ga. 063_ALERT_3_A Crystal Probably too Large for Beam Size ....... 3.00 mm This often happens with low-melting compounds, we have little experimental control over the length of a crystal grown in situ in a capillary. The method of growth also precludes measurement of crystal faces. Gorbitz has shown that use of a large crystal does not appear to matter. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090-1098 065_ALERT_3_A Crystal Requires Numerical Correction mu*tmid .. 3.18 The multiscan procedure appeared to have yielded a successful correction for absorption. 128_ALERT_4_C Non-standard setting of Space group C2/c .... I2/a No action. 415_ALERT_2_C Short Inter D-H..H-X H12 .. H21 .. 2.14 Ang. 420_ALERT_2_C D-H Without Acceptor N2 - H21 ... ? 420_ALERT_2_C D-H Without Acceptor N2 - H22 ... ? H...H bonding occurs here. 731_ALERT_1_C Bond Calc 1.50(2), Rep 1.503(9) ...... 2.22 su-Rat GA1 -H13 1.555 1.555 Distances involving H were subject to restraints (see above), and correct calculation of the s.u.s requires the full variance-covariance matrix. 911_ALERT_3_C # Missing FCF Refl. Between TH(Min) & STH/L=0.6 2 912_ALERT_3_C # Missing FCF Reflections Above STH/L=0.6 ...... 89 913_ALERT_3_C # Missing Very Strong Reflections in FCF ....... 1 No action necessary here. #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 0.998 463 462 1 23.01 0.550 0.998 618 617 1 25.24 0.600 0.997 796 794 2 #----------------------------------------------------------- ACTA Min. Res. ---- 27.51 0.650 0.987 1020 1007 13 28.86 0.679 0.922 1163 1072 91 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Beurskens, P.T., Beurskens, G., Bosman, W.P., de Gelder, R., Garcia Granda, S., Gould, R.O., Israel, R. and Smits J.M.M. (1996) University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands. Siemens Industrial Automation, Inc (1993) SMART: Area-Detector Software Package; Madison, WI. Siemens Industrial Automation, Inc (1995). SAINT: Area-Detector Integration Software.; Madison, WI. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1997). SHELXL-97. University of G\"ottingen, Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Ga1 Ga 0.069030(17) 0.15764(4) 0.122345(14) 0.0261 1.0000 Uani D . . . . . N2 N -0.07632(15) 0.3542(3) 0.11018(12) 0.0292 1.0000 Uani D . . . . . C3 C -0.17168(19) 0.1918(5) 0.1306(2) 0.0426 1.0000 Uani . . . . . . H11 H 0.0396(19) -0.123(2) 0.0898(17) 0.0500 1.0000 Uiso D . . . . . H12 H 0.1056(19) 0.185(4) 0.2214(7) 0.0500 1.0000 Uiso D . . . . . H13 H 0.1369(16) 0.310(4) 0.0563(13) 0.0500 1.0000 Uiso D . . . . . H21 H -0.0735 0.4973 0.1496 0.0350 1.0000 Uiso . . . . . . H22 H -0.0852 0.4151 0.0512 0.0350 1.0000 Uiso . . . . . . H31 H -0.2370 0.3033 0.1229 0.0642 1.0000 Uiso . . . . . . H32 H -0.1646 0.1261 0.1943 0.0642 1.0000 Uiso . . . . . . H33 H -0.1771 0.0376 0.0883 0.0642 1.0000 Uiso . . . . . . 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 Ga1 0.02474(14) 0.02686(15) 0.02644(15) 0.00107(8) -0.00037(9) -0.00058(8) N2 0.0293(9) 0.0289(9) 0.0292(9) 0.0027(6) 0.0013(7) 0.0001(6) C3 0.0267(11) 0.0420(13) 0.0596(16) 0.0060(11) 0.0076(10) -0.0003(9) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.12441(6) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga1 . N2 . 2.0424(18) yes Ga1 . H11 . 1.505(9) no Ga1 . H12 . 1.493(9) no Ga1 . H13 . 1.503(9) no N2 . C3 . 1.467(3) yes N2 . H21 . 0.910 no N2 . H22 . 0.910 no C3 . H31 . 0.980 no C3 . H32 . 0.980 no C3 . H33 . 0.980 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N2 . Ga1 . H11 . 102.3(9) no N2 . Ga1 . H12 . 105.5(9) no H11 . Ga1 . H12 . 116.3(12) no N2 . Ga1 . H13 . 102.6(9) no H11 . Ga1 . H13 . 113.3(12) no H12 . Ga1 . H13 . 114.5(12) no Ga1 . N2 . C3 . 115.61(13) yes Ga1 . N2 . H21 . 107.9 no C3 . N2 . H21 . 107.9 no Ga1 . N2 . H22 . 107.9 no C3 . N2 . H22 . 107.9 no H21 . N2 . H22 . 109.5 no N2 . C3 . H31 . 109.5 no N2 . C3 . H32 . 109.5 no H31 . C3 . H32 . 109.5 no N2 . C3 . H33 . 109.5 no H31 . C3 . H33 . 109.5 no H32 . C3 . H33 . 109.5 no data_gatbuh _database_code_depnum_ccdc_archive 'CCDC 275759' #Compound 2 in paper; see _publ_section_exptl_refinement for checkcif output. _audit_creation_date 05-05-06 _audit_creation_method CRYSTALS_ver_12.80 _oxford_structure_analysis_title 'GATBUH IN Pnma' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 16.223(2) _cell_length_b 7.9767(11) _cell_length_c 6.0427(10) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 781.96(19) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P n m a ' _symmetry_space_group_name_Hall '-P 2ac 2n' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x+1/2,y+1/2,z+1/2 x+1/2,-y+1/2,-z+1/2 x,-y+1/2,z -x,y+1/2,-z -x+1/2,-y,z+1/2 x+1/2,y,-z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ga 0.2307 1.6083 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.4135 1.7189 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C4 H9 Ga1 N1 # Dc = 1.20 Fooo = 304.00 Mu = 34.13 M = 70.42 # Found Formula = C4 H14 Ga1 N1 # Dc = 1.24 FOOO = 304.00 Mu = 34.14 M = 72.94 _chemical_formula_sum 'C4 H14 Ga1 N1' _chemical_formula_moiety 'C4 H14 Ga1 N1' _chemical_compound_source ? _chemical_formula_weight 145.88 _cell_measurement_reflns_used 1738 _cell_measurement_theta_min 2 _cell_measurement_theta_max 22 _cell_measurement_temperature 220 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_min 0.23 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_max 0.43 _exptl_crystal_density_diffrn 1.239 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 304 _exptl_absorpt_coefficient_mu 3.414 # Sheldrick geometric approximatio 0.40 0.46 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.29 _exptl_absorpt_correction_T_max 0.46 _diffrn_measurement_device_type 'Bruker SMART' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'SMART (Siemens, 1993)' _computing_data_reduction 'SAINT (Siemens ,1995)' _computing_cell_refinement 'SAINT (Siemens ,1995)' _computing_structure_solution 'DIRDIF-96 (Beurskens et al., 1996)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 220 _diffrn_reflns_number 6002 _reflns_number_total 565 _diffrn_reflns_av_R_equivalents 0.0673 # Number of reflections with Friedels Law is 565 # Number of reflections without Friedels Law is 1040 # Theoretical number of reflections is about 515 _diffrn_reflns_theta_min 2.511 _diffrn_reflns_theta_max 22.555 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 22.555 _diffrn_measured_fraction_theta_full 0.998 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 6 _reflns_limit_h_min 0 _reflns_limit_h_max 17 _reflns_limit_k_min 0 _reflns_limit_k_max 8 _reflns_limit_l_min 0 _reflns_limit_l_max 6 _oxford_diffrn_Wilson_B_factor 5.05 _oxford_diffrn_Wilson_scale 3.56 _atom_sites_solution_primary Patterson _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap/geom _refine_diff_density_min -0.54 _refine_diff_density_max 0.92 _refine_ls_number_reflns 564 _refine_ls_number_restraints 7 _refine_ls_number_parameters 39 #_refine_ls_R_factor_ref 0.0634 _refine_ls_wR_factor_ref 0.1212 _refine_ls_goodness_of_fit_ref 0.8755 #_reflns_number_all 564 _refine_ls_R_factor_all 0.0634 _refine_ls_wR_factor_all 0.1212 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 401 _refine_ls_R_factor_gt 0.0467 _refine_ls_wR_factor_gt 0.1174 _refine_ls_shift/su_max 0.000689 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment mixed # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; w=1/[\s^2^(F^2^) + 0.07 + 0.00P] where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; _publ_section_exptl_refinement ; H atoms placed geometrically after each cycle on C and N: The H's attached to Ga were located (tentatively)in a difference map and refined subject to explicit restraints on the GaH distances (r = 1.50(1) Ang) and similarity restraints on the HGaH and HGaN angles. U[iso] was fixed for H1 and H2 at 0.05 Ang**2. 023_ALERT_3_A Resolution (too) Low [sin(th)/Lambda < 0.6]..... 22.56 Deg. 027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 22.56 Deg. 911_ALERT_3_C # Missing FCF Refl. Between TH(Min) & STH/L=0.6 1 #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 1.000 441 441 0 22.55 0.540 0.998 566 565 1 There was little diffraction of any significance beyong about 45 deg in 2theta 341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9 This reflects the rather low crystal quality and the presence of a heavy atom. 420_ALERT_2_C D-H Without Acceptor N1 - H11 ... ? See text ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Beurskens, P.T., Beurskens, G., Bosman, W.P., de Gelder, R., Garcia Granda, S., Gould, R.O., Israel, R. and Smits J.M.M. (1996) University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands. Siemens Industrial Automation, Inc (1993) SMART: Area-Detector Software Package; Madison, WI. Siemens Industrial Automation, Inc (1995). SAINT: Area-Detector Integration Software.; Madison, WI. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1997). SHELXL-97. University of G\"ottingen, Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Ga1 Ga 0.28938(6) 0.7500 0.34167(19) 0.0779 1.0000 Uani DS T . . . . N1 N 0.1956(3) 0.7500 0.1123(9) 0.0498 1.0000 Uani DS T . . . . C2 C 0.1072(4) 0.7500 0.1785(13) 0.0510 1.0000 Uani S T . . . . C3 C 0.0553(5) 0.7500 -0.0336(15) 0.0727 1.0000 Uani S T . . . . C4 C 0.0901(4) 0.5938(8) 0.3139(10) 0.0742 1.0000 Uani . . . . . . H11 H 0.2031 0.8431 0.0285 0.0605 1.0000 Uiso . . . . . . H31 H -0.0035 0.7500 0.0040 0.1090 1.0000 Uiso . . . . . . H32 H 0.0679 0.8503 -0.1218 0.1090 1.0000 Uiso . . . . . . H41 H 0.0321 0.5925 0.3579 0.1115 1.0000 Uiso . . . . . . H42 H 0.1251 0.5941 0.4460 0.1115 1.0000 Uiso . . . . . . H43 H 0.1024 0.4944 0.2245 0.1115 1.0000 Uiso . . . . . . H1 H 0.2545(11) 0.7500 0.5733(13) 0.0500 1.0000 Uiso DS . . . . . H2 H 0.3425(6) 0.9028(6) 0.317(3) 0.0500 1.0000 Uiso D . . . . . 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 Ga1 0.0742(8) 0.0507(7) 0.1087(10) 0.0000 -0.0386(6) 0.0000 N1 0.052(4) 0.041(3) 0.056(4) 0.0000 0.003(3) 0.0000 C2 0.049(4) 0.051(4) 0.054(5) 0.0000 0.009(4) 0.0000 C3 0.050(5) 0.098(7) 0.070(6) 0.0000 -0.007(4) 0.0000 C4 0.077(4) 0.069(4) 0.076(4) 0.012(4) 0.011(3) -0.010(3) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.574(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga1 . H2 5_565 1.500(6) no Ga1 . N1 . 2.058(5) yes Ga1 . H1 . 1.509(9) no Ga1 . H2 . 1.500(6) no N1 . H11 5_565 0.907 no N1 . C2 . 1.488(9) yes N1 . H11 . 0.907 no C2 . C4 5_565 1.516(7) yes C2 . C3 . 1.534(11) yes C2 . C4 . 1.516(7) yes C3 . H32 5_565 0.983 no C3 . H31 . 0.981 no C3 . H32 . 0.983 no C4 . H41 . 0.977 no C4 . H42 . 0.980 no C4 . H43 . 0.981 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag H2 5_565 Ga1 . N1 . 110.9(5) no H2 5_565 Ga1 . H1 . 108.0(5) no N1 . Ga1 . H1 . 110.3(7) no H2 5_565 Ga1 . H2 . 108.6(8) no N1 . Ga1 . H2 . 110.9(5) no H1 . Ga1 . H2 . 108.0(5) no Ga1 . N1 . H11 5_565 106.1 no Ga1 . N1 . C2 . 122.1(5) yes H11 5_565 N1 . C2 . 106.2 no Ga1 . N1 . H11 . 106.1 no H11 5_565 N1 . H11 . 109.9 no C2 . N1 . H11 . 106.2 no C4 5_565 C2 . N1 . 108.8(4) yes C4 5_565 C2 . C3 . 110.5(4) yes N1 . C2 . C3 . 107.7(6) yes C4 5_565 C2 . C4 . 110.5(6) yes N1 . C2 . C4 . 108.8(4) yes C3 . C2 . C4 . 110.5(4) yes C2 . C3 . H32 5_565 109.8 no C2 . C3 . H31 . 109.9 no H32 5_565 C3 . H31 . 109.1 no C2 . C3 . H32 . 109.8 no H32 5_565 C3 . H32 . 109.0 no H31 . C3 . H32 . 109.1 no C2 . C4 . H41 . 109.4 no C2 . C4 . H42 . 109.3 no H41 . C4 . H42 . 109.7 no C2 . C4 . H43 . 109.3 no H41 . C4 . H43 . 109.7 no H42 . C4 . H43 . 109.4 no data_MENHGA _database_code_depnum_ccdc_archive 'CCDC 275760' #Compound #3 in paper _audit_creation_date 05-05-06 _audit_creation_method CRYSTALS_ver_12.80 _oxford_structure_analysis_title 'MENHGA in Pna2(1)' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 24.699(6) _cell_length_b 5.3158(13) _cell_length_c 8.711(2) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1143.7(5) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P n a 21 ' _symmetry_space_group_name_Hall 'P 2c -2n' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x+1/2,y+1/2,z+1/2 x+1/2,-y+1/2,z -x,-y,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0020 0.0020 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0040 0.0030 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ga 0.1630 1.6090 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.4135 1.7189 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C3 H18 Ga3 N3 # Dc = 1.77 Fooo = 600.00 Mu = 69.61 M = 305.36 # Found Formula = C3 H18 Ga3 N3 # Dc = 1.77 FOOO = 600.00 Mu = 69.61 M = 305.36 _chemical_formula_sum 'C3 H18 Ga3 N3' _chemical_formula_moiety 'C3 H18 Ga3 N3' _chemical_compound_source ? _chemical_formula_weight 305.36 _cell_measurement_reflns_used 4314 _cell_measurement_theta_min 2 _cell_measurement_theta_max 29 _cell_measurement_temperature 150 _exptl_crystal_description cylinder _exptl_crystal_colour colourless _exptl_crystal_size_min 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_max 1.00 _exptl_crystal_density_diffrn 1.773 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 600 _exptl_absorpt_coefficient_mu 6.961 # Sheldrick geometric approximatio 0.12 0.12 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.05 _exptl_absorpt_correction_T_max 0.12 _diffrn_measurement_device_type 'Bruker SMART' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method \w _computing_data_collection 'SMART (Siemens, 1993)' _computing_data_reduction 'SAINT (Siemens ,1995)' _computing_cell_refinement 'SAINT (Siemens ,1995)' _computing_structure_solution 'SHELXS 86 (Sheldrick, 1986)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 6999 _reflns_number_total 2427 _diffrn_reflns_av_R_equivalents 0.036 # Number of reflections with Friedels Law is 0 # Number of reflections without Friedels Law is 2427 # Theoretical number of reflections is about 2997 _diffrn_reflns_theta_min 1.649 _diffrn_reflns_theta_max 28.844 _diffrn_measured_fraction_theta_max 0.937 _diffrn_reflns_theta_full 26.825 _diffrn_measured_fraction_theta_full 0.996 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 11 _reflns_limit_h_min 0 _reflns_limit_h_max 33 _reflns_limit_k_min 0 _reflns_limit_k_max 7 _reflns_limit_l_min 0 _reflns_limit_l_max 11 _oxford_diffrn_Wilson_B_factor 0.00 _oxford_diffrn_Wilson_scale 0.00 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.91 _refine_diff_density_max 1.10 _refine_ls_number_reflns 2205 _refine_ls_number_restraints 1 _refine_ls_number_parameters 84 #_refine_ls_R_factor_ref 0.0394 _refine_ls_wR_factor_ref 0.0938 _refine_ls_goodness_of_fit_ref 1.0008 #_reflns_number_all 2205 _refine_ls_R_factor_all 0.0394 _refine_ls_wR_factor_all 0.0938 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 2077 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_gt 0.0929 _refine_ls_shift/su_max 0.000983 _refine_ls_abs_structure_Flack 0.37(9) _refine_ls_abs_structure_details 'Flack, 2427 Friedel-pairs' # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration ad _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; w=1/[\s^2^(F^2^) + 0.06 + 1.69P] where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; _publ_section_exptl_refinement ; H atoms placed geometrically after each cycle The compound is a liquid at room temperature, and the crystal was grown in a capillary using laser-assisted zone refinement carried out over the course of 14hr at 260K. It proved impossible to obtain a single crystal because the crystalline habit was needle-like. A number of methods were tested for treating the twinning, including simultaneous integration of up to four components (identified using CELL_NOW). The crystal contained more domains than this, but 4 is the upper limit available for simultaneous integration in Saint. In all cases R1 stuck at ca 5% with a highest difference max. of 4-5 e/Ang3. Refinement statistics obtained against data integrated as single-component using the orientation matrix of the major domain were not much worse than this (R1=6%, del(rho)max= 5 e/A3), but it was noted that all poorly-agreeing data had k=2n. The most satisfactory agreement indices were obtained by simply refining separate scale factors for the k=2n and k=2n+1 data. The k=2n scale = overall scale * 1.114(2). 063_ALERT_3_B Crystal Probably too Large for Beam Size ....... 1.00 mm This often happens with low-melting compounds, we have little experimental control over the length of a crystal grown in situ in a capillary. Note, though that the beam would never have passed through this length of sample because of the axial mount. Gorbitz has shown that use of a large crystal does not appear to matter. See C. H. Gorbitz Acta Cryst. (1999). B55, 1090-1098 033_ALERT_2_C Flack Parameter Value Deviates from Zero ....... 0.37 Presumably the crystal is an inversion twin; the s.u. on x is 0.09, so the value obtained is statistically meaningful. 415_ALERT_2_C Short Inter D-H..H-X H6 .. H52 .. 2.12 Ang. 420_ALERT_2_C D-H Without Acceptor N2 - H2 ... ? 420_ALERT_2_C D-H Without Acceptor N4 - H4 ... ? 420_ALERT_2_C D-H Without Acceptor N6 - H6 ... ? There is di-hydrogen bonding in this structure, see text. 911_ALERT_3_C # Missing FCF Refl. Between TH(Min) & STH/L=0.6 3 912_ALERT_3_C # Missing FCF Reflections Above STH/L=0.6 ...... 98 913_ALERT_3_C # Missing Very Strong Reflections in FCF ....... 1 No real problem here... #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 0.998 651 650 1 23.01 0.550 0.999 852 851 1 25.24 0.600 0.997 1117 1114 3 #----------------------------------------------------------- ACTA Min. Res. ---- 27.51 0.650 0.994 1398 1390 8 29.84 0.700 0.937 1596 1495 101 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Siemens Industrial Automation, Inc (1993) SMART: Area-Detector Software Package; Madison, WI. Siemens Industrial Automation, Inc (1995). SAINT: Area-Detector Integration Software.; Madison, WI. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1986). SHELXS86. Program for the solution of crystal structures. Univ. of G\"ottingen, Federal Republic of Germany. Sheldrick, G.M. (1997). SHELXL-97. University of G\"ottingen, Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Ga1 Ga 0.58161(2) 0.78179(11) 0.8204(2) 0.0290 1.0000 Uani . . . . . . N2 N 0.64459(17) 1.0049(9) 0.7865(7) 0.0271 1.0000 Uani . . . . . . C2 C 0.6738(3) 1.0563(14) 0.9332(9) 0.0437 1.0000 Uani . . . . . . Ga3 Ga 0.69507(2) 0.87036(16) 0.6278(2) 0.0365 1.0000 Uani . . . . . . N4 N 0.64260(17) 0.7300(9) 0.4751(7) 0.0276 1.0000 Uani . . . . . . C4 C 0.6694(2) 0.6815(14) 0.3257(11) 0.0447 1.0000 Uani . . . . . . Ga5 Ga 0.57744(2) 0.94159(11) 0.4505(2) 0.0277 1.0000 Uani . . . . . . N6 N 0.53609(16) 0.8576(9) 0.6379(9) 0.0293 1.0000 Uani . . . . . . C6 C 0.4968(2) 0.6449(11) 0.6142(12) 0.0412 1.0000 Uani . . . . . . H21 H 0.7048 1.1670 0.9130 0.0655 1.0000 Uiso . . . . . . H22 H 0.6868 0.8974 0.9770 0.0655 1.0000 Uiso . . . . . . H23 H 0.6492 1.1380 1.0059 0.0655 1.0000 Uiso . . . . . . H41 H 0.7015 0.5764 0.3419 0.0671 1.0000 Uiso . . . . . . H42 H 0.6802 0.8417 0.2793 0.0671 1.0000 Uiso . . . . . . H43 H 0.6441 0.5945 0.2572 0.0671 1.0000 Uiso . . . . . . H61 H 0.4741 0.6801 0.5245 0.0619 1.0000 Uiso . . . . . . H62 H 0.5169 0.4881 0.5975 0.0619 1.0000 Uiso . . . . . . H63 H 0.4738 0.6274 0.7054 0.0619 1.0000 Uiso . . . . . . H2 H 0.6317 1.1546 0.7512 0.0325 1.0000 Uiso . . . . . . H4 H 0.6314 0.5787 0.5120 0.0332 1.0000 Uiso . . . . . . H6 H 0.5161 0.9959 0.6619 0.0352 1.0000 Uiso . . . . . . H11 H 0.5527 0.8460 0.9668 0.0500 1.0000 Uiso . . . . . . H12 H 0.5982 0.5104 0.8236 0.0500 1.0000 Uiso . . . . . . H31 H 0.7291 1.0749 0.5589 0.0500 1.0000 Uiso . . . . . . H32 H 0.7311 0.6693 0.6922 0.0500 1.0000 Uiso . . . . . . H51 H 0.5917 1.2157 0.4456 0.0500 1.0000 Uiso . . . . . . H52 H 0.5466 0.8726 0.3083 0.0500 1.0000 Uiso . . . . . . 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 Ga1 0.0337(3) 0.0264(3) 0.0269(3) 0.0025(3) 0.0060(3) 0.0037(2) N2 0.027(2) 0.026(2) 0.028(3) -0.0008(19) -0.0031(19) 0.0021(16) C2 0.041(3) 0.058(4) 0.032(4) -0.005(3) -0.007(3) 0.004(3) Ga3 0.0234(3) 0.0542(4) 0.0318(3) -0.0090(3) 0.0004(3) -0.0001(3) N4 0.027(2) 0.032(2) 0.025(3) -0.003(2) 0.0041(19) -0.0016(16) C4 0.037(3) 0.063(4) 0.034(4) -0.019(4) 0.007(3) 0.000(3) Ga5 0.0308(3) 0.0264(3) 0.0259(3) 0.0001(2) -0.0028(3) 0.0027(2) N6 0.0260(19) 0.0230(18) 0.039(3) -0.0040(18) 0.001(2) 0.0020(17) C6 0.031(3) 0.030(3) 0.062(5) -0.004(3) -0.001(3) -0.006(2) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.2983(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga1 . N2 . 1.978(5) yes Ga1 . N6 . 1.988(7) yes Ga1 . H11 . 1.500 no Ga1 . H12 . 1.500 no N2 . C2 . 1.493(9) yes N2 . Ga3 . 1.994(6) yes N2 . H2 . 0.910 no C2 . H21 . 0.980 no C2 . H22 . 0.980 no C2 . H23 . 0.980 no Ga3 . N4 . 2.001(6) yes Ga3 . H31 . 1.500 no Ga3 . H32 . 1.500 no N4 . C4 . 1.482(9) yes N4 . Ga5 . 1.975(5) yes N4 . H4 . 0.910 no C4 . H41 . 0.980 no C4 . H42 . 0.980 no C4 . H43 . 0.980 no Ga5 . N6 . 1.977(8) yes Ga5 . H51 . 1.500 no Ga5 . H52 . 1.500 no N6 . C6 . 1.504(7) yes N6 . H6 . 0.910 no C6 . H61 . 0.979 no C6 . H62 . 0.980 no C6 . H63 . 0.981 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N2 . Ga1 . N6 . 101.7(3) yes N2 . Ga1 . H11 . 111.4 no N6 . Ga1 . H11 . 111.4 no N2 . Ga1 . H12 . 111.4 no N6 . Ga1 . H12 . 111.4 no H11 . Ga1 . H12 . 109.5 no Ga1 . N2 . C2 . 111.2(4) yes Ga1 . N2 . Ga3 . 112.3(3) yes C2 . N2 . Ga3 . 110.9(4) yes Ga1 . N2 . H2 . 107.4 no C2 . N2 . H2 . 107.4 no Ga3 . N2 . H2 . 107.4 no N2 . C2 . H21 . 109.5 no N2 . C2 . H22 . 109.4 no H21 . C2 . H22 . 109.5 no N2 . C2 . H23 . 109.5 no H21 . C2 . H23 . 109.5 no H22 . C2 . H23 . 109.4 no N2 . Ga3 . N4 . 100.92(17) yes N2 . Ga3 . H31 . 111.6 no N4 . Ga3 . H31 . 111.6 no N2 . Ga3 . H32 . 111.6 no N4 . Ga3 . H32 . 111.6 no H31 . Ga3 . H32 . 109.5 no Ga3 . N4 . C4 . 111.1(4) yes Ga3 . N4 . Ga5 . 112.8(3) yes C4 . N4 . Ga5 . 111.5(4) yes Ga3 . N4 . H4 . 107.0 no C4 . N4 . H4 . 107.0 no Ga5 . N4 . H4 . 107.0 no N4 . C4 . H41 . 109.5 no N4 . C4 . H42 . 109.4 no H41 . C4 . H42 . 109.5 no N4 . C4 . H43 . 109.5 no H41 . C4 . H43 . 109.5 no H42 . C4 . H43 . 109.5 no N4 . Ga5 . N6 . 101.7(3) yes N4 . Ga5 . H51 . 111.4 no N6 . Ga5 . H51 . 111.4 no N4 . Ga5 . H52 . 111.4 no N6 . Ga5 . H52 . 111.4 no H51 . Ga5 . H52 . 109.5 no Ga1 . N6 . Ga5 . 114.45(19) yes Ga1 . N6 . C6 . 108.8(5) yes Ga5 . N6 . C6 . 112.9(5) yes Ga1 . N6 . H6 . 106.7 no Ga5 . N6 . H6 . 106.7 no C6 . N6 . H6 . 106.7 no N6 . C6 . H61 . 109.6 no N6 . C6 . H62 . 109.5 no H61 . C6 . H62 . 109.5 no N6 . C6 . H63 . 109.5 no H61 . C6 . H63 . 109.5 no H62 . C6 . H63 . 109.4 no data_tbuga2 _database_code_depnum_ccdc_archive 'CCDC 275761' #Compound 4 in paper _audit_creation_date 05-05-06 _audit_creation_method CRYSTALS_ver_12.80 _oxford_structure_analysis_title 'TBUGA2 in Pccn' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 10.0630(15) _cell_length_b 16.964(2) _cell_length_c 7.9590(11) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1358.7(3) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P c c n ' _symmetry_space_group_name_Hall '-P 2ab 2ac' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x+1/2,y,z+1/2 x+1/2,-y,-z+1/2 x,-y+1/2,z+1/2 -x,y+1/2,-z+1/2 -x+1/2,-y+1/2,z x+1/2,y+1/2,-z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ga 0.1630 1.6090 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.4135 1.7189 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C8 H24 Ga2 N2 # Dc = 1.41 Fooo = 592.00 Mu = 39.29 M = 143.87 # Found Formula = C8 H24 Ga2 N2 # Dc = 1.41 FOOO = 592.00 Mu = 39.29 M = 143.87 _chemical_formula_sum 'C8 H24 Ga2 N2' _chemical_formula_moiety 'C8 H24 Ga2 N2' _chemical_compound_source ? _chemical_formula_weight 287.73 _cell_measurement_reflns_used 3025 _cell_measurement_theta_min 2 _cell_measurement_theta_max 29 _cell_measurement_temperature 150 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_min 0.16 _exptl_crystal_size_mid 0.28 _exptl_crystal_size_max 0.28 _exptl_crystal_density_diffrn 1.407 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 592 _exptl_absorpt_coefficient_mu 3.929 # Sheldrick geometric approximatio 0.33 0.53 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.42 _exptl_absorpt_correction_T_max 0.53 _diffrn_measurement_device_type 'Bruker SMART' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' _computing_data_collection 'SMART (Siemens, 1993)' _computing_data_reduction 'SAINT (Siemens ,1995)' _computing_cell_refinement 'SAINT (Siemens ,1995)' _computing_structure_solution 'DIRDIF-96 (Beurskens et al., 1996)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 8661 _reflns_number_total 1693 _diffrn_reflns_av_R_equivalents 0.023 # Number of reflections with Friedels Law is 1693 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 1787 _diffrn_reflns_theta_min 2.353 _diffrn_reflns_theta_max 28.888 _diffrn_measured_fraction_theta_max 0.942 _diffrn_reflns_theta_full 27.444 _diffrn_measured_fraction_theta_full 0.998 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 10 _reflns_limit_h_min 0 _reflns_limit_h_max 13 _reflns_limit_k_min 0 _reflns_limit_k_max 23 _reflns_limit_l_min 0 _reflns_limit_l_max 10 _oxford_diffrn_Wilson_B_factor 0.00 _oxford_diffrn_Wilson_scale 0.00 _atom_sites_solution_primary Patterson # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.41 _refine_diff_density_max 0.92 _refine_ls_number_reflns 1689 _refine_ls_number_restraints 3 _refine_ls_number_parameters 55 #_refine_ls_R_factor_ref 0.0767 _refine_ls_wR_factor_ref 0.1362 _refine_ls_goodness_of_fit_ref 1.0699 #_reflns_number_all 1689 _refine_ls_R_factor_all 0.0767 _refine_ls_wR_factor_all 0.1362 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 1346 _refine_ls_R_factor_gt 0.0604 _refine_ls_wR_factor_gt 0.1294 _refine_ls_shift/su_max 0.000038 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; w=1/[\s^2^(F^2^) + 0.05 + 3.53P] where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; _publ_section_exptl_refinement ; H atoms placed geometrically on C and N after each cycle. The H-atoms on Ga were located in a difference map and refined subject to the restraints that Ga-H = 1.50(1) Ang. Checkcif alerts: 912_ALERT_3_B # Missing FCF Reflections Above STH/L=0.6 ...... 105 Data were integrated to the edge of the detector, even though the highest resolution shells are incomplete. #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 1.000 708 708 0 23.01 0.550 1.000 947 947 0 25.24 0.600 1.000 1231 1231 0 #----------------------------------------------------------- ACTA Min. Res. ---- 27.51 0.650 0.999 1568 1566 2 29.84 0.700 0.942 1798 1693 105 060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.22 Sadabs corrects for all systematic errors that lead to disparities in the intensities of symmetry-equivalent data. These may include absorption by the mount, crystal decay etc. 222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.28 Ratio 242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 C1 is the pivot atom of a tBu group; this behaviour is normal. 341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8 No action taken. 415_ALERT_2_C Short Inter D-H..H-X H2 .. H3 .. 2.12 Ang. 420_ALERT_2_C D-H Without Acceptor N1 - H3 ... ? See text. ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Beurskens, P.T., Beurskens, G., Bosman, W.P., de Gelder, R., Garcia Granda, S., Gould, R.O., Israel, R. and Smits J.M.M. (1996) University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The Netherlands. Siemens Industrial Automation, Inc (1993) SMART: Area-Detector Software Package; Madison, WI. Siemens Industrial Automation, Inc (1995). SAINT: Area-Detector Integration Software.; Madison, WI. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1997). SHELXL-97. University of G\"ottingen, Germany. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Ga1 Ga 0.07843(7) 0.04164(3) 0.12290(7) 0.0471 1.0000 Uani D . . . . . N1 N 0.0376(3) 0.05347(19) -0.1204(4) 0.0263 1.0000 Uani D . . . . . C1 C -0.0044(4) 0.1298(3) -0.1959(6) 0.0305 1.0000 Uani . . . . . . C2 C -0.0239(7) 0.1175(4) -0.3846(8) 0.0571 1.0000 Uani . . . . . . C3 C -0.1308(6) 0.1585(4) -0.1145(10) 0.0690 1.0000 Uani . . . . . . C4 C 0.1056(5) 0.1898(3) -0.1682(7) 0.0416 1.0000 Uani . . . . . . H1 H 0.0293 0.1077 0.2317 0.0500 1.0000 Uiso D . . . . . H2 H 0.2217 0.0256 0.1619 0.0500 1.0000 Uiso D . . . . . H3 H 0.1131 0.0393 -0.1756 0.0316 1.0000 Uiso D . . . . . H21 H 0.0594 0.0989 -0.4346 0.0856 1.0000 Uiso . . . . . . H22 H -0.0497 0.1675 -0.4369 0.0856 1.0000 Uiso . . . . . . H23 H -0.0938 0.0782 -0.4033 0.0856 1.0000 Uiso . . . . . . H31 H -0.2015 0.1197 -0.1325 0.1035 1.0000 Uiso . . . . . . H32 H -0.1568 0.2089 -0.1646 0.1035 1.0000 Uiso . . . . . . H33 H -0.1161 0.1654 0.0063 0.1035 1.0000 Uiso . . . . . . H41 H 0.1186 0.1980 -0.0475 0.0623 1.0000 Uiso . . . . . . H42 H 0.0808 0.2399 -0.2212 0.0623 1.0000 Uiso . . . . . . H43 H 0.1883 0.1703 -0.2183 0.0623 1.0000 Uiso . . . . . . 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 Ga1 0.0733(5) 0.0411(3) 0.0269(3) 0.0030(3) -0.0159(3) -0.0320(3) N1 0.0302(17) 0.0248(16) 0.0240(16) 0.0013(15) 0.0036(15) -0.0015(13) C1 0.024(2) 0.026(2) 0.042(2) 0.0042(19) -0.0042(19) 0.0045(17) C2 0.077(4) 0.050(3) 0.044(3) 0.016(3) -0.023(3) -0.004(3) C3 0.036(3) 0.060(4) 0.110(6) -0.012(4) 0.011(4) 0.018(3) C4 0.047(3) 0.023(2) 0.055(3) 0.006(2) 0.000(2) -0.0041(19) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.2712(5) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga1 . N1 2_555 1.992(3) yes Ga1 . N1 . 1.989(4) yes Ga1 . H1 . 1.500 no Ga1 . H2 . 1.500 no N1 . C1 . 1.488(5) yes N1 . H3 . 0.910 no C1 . C2 . 1.529(7) yes C1 . C3 . 1.508(7) yes C1 . C4 . 1.520(6) yes C2 . H21 . 0.980 no C2 . H22 . 0.980 no C2 . H23 . 0.980 no C3 . H31 . 0.980 no C3 . H32 . 0.980 no C3 . H33 . 0.980 no C4 . H41 . 0.980 no C4 . H42 . 0.980 no C4 . H43 . 0.980 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag N1 2_555 Ga1 . N1 . 87.17(14) yes N1 2_555 Ga1 . H1 . 114.7 no N1 . Ga1 . H1 . 114.7 no N1 2_555 Ga1 . H2 . 114.7 no N1 . Ga1 . H2 . 114.7 no H1 . Ga1 . H2 . 109.5 no Ga1 2_555 N1 . Ga1 . 92.83(14) yes Ga1 2_555 N1 . C1 . 122.3(3) yes Ga1 . N1 . C1 . 122.6(3) yes Ga1 2_555 N1 . H3 . 105.7 no Ga1 . N1 . H3 . 105.7 no C1 . N1 . H3 . 105.7 no N1 . C1 . C2 . 108.3(4) yes N1 . C1 . C3 . 110.3(4) yes C2 . C1 . C3 . 111.0(5) yes N1 . C1 . C4 . 108.5(4) yes C2 . C1 . C4 . 109.1(4) yes C3 . C1 . C4 . 109.6(4) yes C1 . C2 . H21 . 109.5 no C1 . C2 . H22 . 109.5 no H21 . C2 . H22 . 109.5 no C1 . C2 . H23 . 109.5 no H21 . C2 . H23 . 109.5 no H22 . C2 . H23 . 109.5 no C1 . C3 . H31 . 109.4 no C1 . C3 . H32 . 109.5 no H31 . C3 . H32 . 109.5 no C1 . C3 . H33 . 109.5 no H31 . C3 . H33 . 109.5 no H32 . C3 . H33 . 109.5 no C1 . C4 . H41 . 109.5 no C1 . C4 . H42 . 109.5 no H41 . C4 . H42 . 109.5 no C1 . C4 . H43 . 109.5 no H41 . C4 . H43 . 109.5 no H42 . C4 . H43 . 109.5 no