# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2011


data_global
_journal_name_full               'Dalton Trans.'
_journal_coden_cambridge         0222
#TrackingRef 'hmi.cif'

# 1. SUBMISSION DETAILS

_publ_contact_author             
;
'Gordon W. Driver'
;
_publ_contact_author_phone       ?
_publ_contact_author_fax         +35822154479
_publ_contact_author_email       Gordon.Driver@abo.fi
_publ_requested_coeditor_name    ?

_publ_contact_letter             
;
Please consider this CIF submission as an X-ray deposition file of a
compound coded HMI.
;

#=============================================================================

# 3. TITLE AND AUTHOR LIST

_publ_section_title              
;
The Complex Story of a Simple Br\/onsted Acid: Unusual Speciation of
HBr in an Ionic Liquid Medium.
;

loop_
_publ_author_name
_publ_author_address

'Gordon W. Driver'
; \%Abo Akademi University
Department of Chemical Engineering
Process Chemistry Centre
Biskopsgatan 8
20500, \%Abo
Finland
;
'Ilpo Mutikainen'
; University of Helsinki
Department of Chemistry
Laboratory of Inorganic Chemistry
FIN-00014 Helsinki
Finland
;

#=============================================================================

# 4. TEXT

_publ_section_abstract           
;

;
_publ_section_comment            
;

;
_publ_section_experimental       
;
A crystal was selected for
the X--ray measurements and mounted to the glass fiber using the oil drop
method (Kottke & Stalke, 1993) and data were collected at 173 K.
The intensity data were corrected for Lorentz and polarization
effects and for absorption.
The nonhydrogen atoms were refined anisotropically.
The H atoms of the 3-methylimidazolium cation were geometrically fixed
and allowed to ride on the attached atoms. The H atom of the bridging
Br2-anions was determined
in the difference map and refined isotropically with temperaure factor
riding with the BR2 temperature factor.
;
_publ_section_references         
;

Altomare, A., Burla, M.C., Camalli, M., Cascarano, G., Giacovazzo, C.,
Guagliardi, A., Moliterni, A.G.G., Polidori, G. & Spagna, R. (1999).
J. Appl. Cryst 32, 115-119.

Duisenberg, A.J.M., J. Appl. Cryst. 25 (1992) 92-96.

Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.

Kottke, T. and Stalke, D. (1993). J. Appl. Crystallogr. 26, 615--619.

Sheldrick, G.M. (1990). SHELXTL. University of G\"ottingen, Germany.

Sheldrick, G.M. (1996). SADABS. University of G\"ottingen, Germany.

Sheldrick, G.M. (1997). SHELX97. University of G\"ottingen, Germany.

;
_publ_section_figure_captions    
;

;
_publ_section_acknowledgements   
;

;
#=============================================================================

data_hmi
_database_code_depnum_ccdc_archive 'CCDC 812944'
#TrackingRef 'hmi.cif'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C12 H23 Br5 N6'
_chemical_formula_weight         650.91

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P-62c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+y, -x, -z+1/2'
'-y, x-y, z'
'x, y, -z+1/2'
'-x+y, -x, z'
'-y, x-y, -z+1/2'
'y, x, z+1/2'
'x-y, -y, -z'
'-x, -x+y, z+1/2'
'y, x, -z'
'x-y, -y, z+1/2'
'-x, -x+y, -z'

_cell_length_a                   13.2000(10)
_cell_length_b                   13.2000(10)
_cell_length_c                   7.1170(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     1073.93(19)
_cell_formula_units_Z            2
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    13151
_cell_measurement_theta_min      3.09
_cell_measurement_theta_max      25.05

_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    2.013
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             624
_exptl_absorpt_coefficient_mu    9.362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.2561
_exptl_absorpt_correction_T_max  0.2561
_exptl_absorpt_process_details   'SADABS (Sheldrick, 1996)'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       \f-scan
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13151
_diffrn_reflns_av_R_equivalents  0.0851
_diffrn_reflns_av_sigmaI/netI    0.0306
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         3.09
_diffrn_reflns_theta_max         25.05
_reflns_number_total             685
_reflns_number_gt                566
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'COLLECT (Nonius, 2002)'
_computing_cell_refinement       'DirAx (Duisenberg 1992)'
_computing_data_reduction        'COLLECT/EVAL (Nonius, 2002)'
_computing_structure_solution    'SHELXS97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 1990)'
_computing_publication_material  'SHELXTL (Sheldrick, 1990)'

_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^)+(0.0439P)^2^+2.2160P] 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    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.41(6)
_refine_ls_number_reflns         685
_refine_ls_number_parameters     50
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0364
_refine_ls_wR_factor_ref         0.0895
_refine_ls_wR_factor_gt          0.0789
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_restrained_S_all      1.211
_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
N1 N 0.3252(9) 0.3896(8) 0.7500 0.028(2) Uani 1 2 d S . .
C2 C 0.4167(10) 0.3797(13) 0.7500 0.043(3) Uani 1 2 d S . .
H2 H 0.4944 0.4440 0.7500 0.051 Uiso 1 2 calc SR . .
N3 N 0.3907(11) 0.2735(13) 0.7500 0.044(3) Uani 1 2 d S . .
H3 H 0.4399 0.2468 0.7500 0.053 Uiso 1 2 calc SR . .
C4 C 0.2762(19) 0.2111(14) 0.7500 0.095(6) Uani 1 2 d SU . .
H4 H 0.2311 0.1281 0.7500 0.114 Uiso 1 2 calc SR . .
C5 C 0.2334(12) 0.2849(14) 0.7500 0.065(5) Uani 1 2 d SU . .
H5 H 0.1536 0.2649 0.7500 0.078 Uiso 1 2 calc SR . .
C6 C 0.3190(11) 0.4990(10) 0.7500 0.045(3) Uani 1 2 d S . .
H6A H 0.3283 0.5288 0.8787 0.068 Uiso 0.50 1 calc PR . .
H6B H 0.2431 0.4827 0.7004 0.068 Uiso 0.50 1 calc PR . .
H6C H 0.3817 0.5577 0.6709 0.068 Uiso 0.50 1 calc PR . .
Br1 Br 0.6667 0.3333 0.7500 0.0362(5) Uani 1 6 d S . .
Br2 Br 0.64964(8) 0.64964(8) 0.0000 0.0368(3) Uani 1 2 d S . .
H7 H 0.646(19) 0.60(2) 0.2500 0.055 Uiso 0.66 2 d SP . .
Br3 Br 1.0000 0.0000 0.5000 0.0305(5) Uani 1 6 d S . .

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
N1 0.024(5) 0.020(5) 0.043(6) 0.000 0.000 0.014(5)
C2 0.028(6) 0.040(8) 0.073(9) 0.000 0.000 0.027(7)
N3 0.037(7) 0.050(7) 0.060(7) 0.000 0.000 0.033(6)
C4 0.075(12) 0.035(7) 0.185(17) 0.000 0.000 0.035(9)
C5 0.032(7) 0.034(7) 0.131(13) 0.000 0.000 0.019(6)
C6 0.041(6) 0.024(6) 0.080(9) 0.000 0.000 0.023(6)
Br1 0.0185(5) 0.0185(5) 0.0715(13) 0.000 0.000 0.0092(3)
Br2 0.0306(4) 0.0306(4) 0.0470(6) 0.0000(3) 0.0000(3) 0.0138(5)
Br3 0.0319(7) 0.0319(7) 0.0278(9) 0.000 0.000 0.0159(3)

_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
N1 C2 1.278(16) . ?
N1 C5 1.305(18) . ?
N1 C6 1.486(13) . ?
C2 N3 1.266(19) . ?
C2 H2 0.9500 . ?
N3 C4 1.31(2) . ?
N3 H3 0.8800 . ?
C4 C5 1.35(2) . ?
C4 H4 0.9500 . ?
C5 H5 0.9500 . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
Br2 H7 1.87(7) . ?

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
C2 N1 C5 108.4(11) . . ?
C2 N1 C6 127.8(11) . . ?
C5 N1 C6 123.8(10) . . ?
N3 C2 N1 111.5(12) . . ?
N3 C2 H2 124.3 . . ?
N1 C2 H2 124.3 . . ?
C2 N3 C4 106.6(11) . . ?
C2 N3 H3 126.7 . . ?
C4 N3 H3 126.7 . . ?
N3 C4 C5 108.3(14) . . ?
N3 C4 H4 125.9 . . ?
C5 C4 H4 125.9 . . ?
N1 C5 C4 105.3(13) . . ?
N1 C5 H5 127.4 . . ?
C4 C5 H5 127.4 . . ?
N1 C6 H6A 109.5 . . ?
N1 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
N1 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        25.05
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.659
_refine_diff_density_min         -0.791
_refine_diff_density_rms         0.134