Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015337/bt6182sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015337/bt6182Isup2.hkl |
CCDC reference: 198296
1 mmol (0.1717 g) of tetraethylammonium bromide, (Et4)NBr, and 1 mmol (0.2715 g) of mercuric bromide HgBr2, were dissolved by stirring in 50 ml me thanol at 323 K until a clear solution was obtained. Single crystals were obtained when the solution was allowed to sit at room temperature for 2 d.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-STEP32 (Stoe & Cie, 2000); data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, Bonn, 1999); software used to prepare material for publication: SHELXL97.
(C8H20N)2[Hg2Br6] | F(000) = 1040 |
Mr = 1141.14 | Dx = 2.492 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 10530 reflections |
a = 9.1148 (16) Å | θ = 2.3–25.0° |
b = 10.8302 (13) Å | µ = 17.97 mm−1 |
c = 16.140 (4) Å | T = 293 K |
β = 107.377 (17)° | Prism, colorless |
V = 1520.5 (5) Å3 | 0.2 × 0.15 × 0.1 mm |
Z = 2 |
Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer | 2665 independent reflections |
Radiation source: fine-focus sealed tube | 1450 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.097 |
ϕ scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | h = −10→10 |
Tmin = 0.051, Tmax = 0.166 | k = −12→12 |
10530 measured reflections | l = −19→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.067 | w = 1/[σ2(Fo2) + (0.0161P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max = 0.001 |
2665 reflections | Δρmax = 0.66 e Å−3 |
119 parameters | Δρmin = −1.11 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00203 (12) |
(C8H20N)2[Hg2Br6] | V = 1520.5 (5) Å3 |
Mr = 1141.14 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.1148 (16) Å | µ = 17.97 mm−1 |
b = 10.8302 (13) Å | T = 293 K |
c = 16.140 (4) Å | 0.2 × 0.15 × 0.1 mm |
β = 107.377 (17)° |
Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer | 2665 independent reflections |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | 1450 reflections with I > 2σ(I) |
Tmin = 0.051, Tmax = 0.166 | Rint = 0.097 |
10530 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.66 e Å−3 |
2665 reflections | Δρmin = −1.11 e Å−3 |
119 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.14441 (5) | 0.37623 (4) | 0.06097 (3) | 0.06386 (18) | |
Br1 | 0.20423 (12) | 0.36463 (12) | 0.22440 (7) | 0.0669 (3) | |
Br2 | 0.26762 (15) | 0.23448 (10) | −0.02166 (9) | 0.0802 (4) | |
Br3 | 0.16792 (10) | 0.61764 (10) | 0.01128 (7) | 0.0567 (3) | |
N1 | 0.7227 (8) | 0.4212 (6) | 0.2792 (5) | 0.0400 (18) | |
C1 | 0.6627 (11) | 0.2912 (8) | 0.2543 (7) | 0.055 (3) | |
H1B | 0.5537 | 0.2962 | 0.2239 | 0.066* | |
H1A | 0.6742 | 0.2445 | 0.3071 | 0.066* | |
C2 | 0.8894 (10) | 0.4092 (9) | 0.3390 (7) | 0.057 (3) | |
H2B | 0.8904 | 0.3546 | 0.3869 | 0.069* | |
H2A | 0.9516 | 0.3713 | 0.3066 | 0.069* | |
C3 | 0.9623 (12) | 0.5320 (11) | 0.3758 (8) | 0.076 (3) | |
H3C | 1.0645 | 0.5177 | 0.4133 | 0.091* | |
H3B | 0.9017 | 0.5702 | 0.4082 | 0.091* | |
H3A | 0.9666 | 0.5852 | 0.3290 | 0.091* | |
C4 | 0.6094 (13) | 0.4214 (10) | 0.4075 (7) | 0.074 (3) | |
H4C | 0.5439 | 0.4690 | 0.4321 | 0.089* | |
H4B | 0.7097 | 0.4149 | 0.4489 | 0.089* | |
H4A | 0.5667 | 0.3404 | 0.3932 | 0.089* | |
C5 | 0.6221 (11) | 0.4847 (9) | 0.3258 (7) | 0.053 (3) | |
H5B | 0.6615 | 0.5675 | 0.3412 | 0.064* | |
H5A | 0.5195 | 0.4927 | 0.2855 | 0.064* | |
C6 | 0.7233 (11) | 0.4988 (9) | 0.1988 (6) | 0.050 (3) | |
H6B | 0.7579 | 0.5817 | 0.2177 | 0.061* | |
H6A | 0.7969 | 0.4631 | 0.1729 | 0.061* | |
C7 | 0.5707 (12) | 0.5068 (11) | 0.1310 (7) | 0.074 (3) | |
H7C | 0.5801 | 0.5558 | 0.0833 | 0.089* | |
H7B | 0.4976 | 0.5445 | 0.1554 | 0.089* | |
H7A | 0.5363 | 0.4254 | 0.1108 | 0.089* | |
C8 | 0.7398 (16) | 0.2204 (10) | 0.1983 (9) | 0.092 (4) | |
H8C | 0.6942 | 0.1400 | 0.1861 | 0.111* | |
H8B | 0.8474 | 0.2122 | 0.2283 | 0.111* | |
H8A | 0.7267 | 0.2641 | 0.1448 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0648 (3) | 0.0649 (3) | 0.0617 (3) | 0.0066 (3) | 0.0187 (2) | −0.0023 (3) |
Br1 | 0.0596 (7) | 0.0843 (8) | 0.0559 (6) | −0.0066 (7) | 0.0158 (5) | −0.0007 (7) |
Br2 | 0.0885 (9) | 0.0596 (7) | 0.1107 (10) | −0.0028 (6) | 0.0574 (8) | −0.0139 (7) |
Br3 | 0.0488 (6) | 0.0493 (5) | 0.0691 (7) | −0.0079 (5) | 0.0132 (5) | −0.0027 (6) |
N1 | 0.036 (4) | 0.040 (4) | 0.047 (5) | 0.006 (3) | 0.017 (4) | 0.008 (4) |
C1 | 0.053 (7) | 0.040 (5) | 0.076 (8) | −0.012 (5) | 0.025 (6) | −0.007 (5) |
C2 | 0.040 (6) | 0.067 (7) | 0.063 (6) | 0.014 (5) | 0.011 (5) | 0.021 (6) |
C3 | 0.057 (7) | 0.094 (9) | 0.069 (9) | −0.016 (6) | 0.007 (6) | 0.004 (7) |
C4 | 0.072 (8) | 0.094 (9) | 0.070 (8) | 0.006 (6) | 0.045 (6) | −0.004 (7) |
C5 | 0.042 (6) | 0.051 (6) | 0.074 (8) | 0.009 (5) | 0.029 (5) | 0.000 (6) |
C6 | 0.057 (7) | 0.052 (6) | 0.049 (7) | −0.009 (5) | 0.027 (6) | 0.009 (5) |
C7 | 0.066 (8) | 0.091 (8) | 0.053 (8) | −0.002 (7) | 0.001 (6) | 0.022 (6) |
C8 | 0.122 (11) | 0.057 (7) | 0.115 (11) | −0.003 (7) | 0.061 (10) | −0.020 (8) |
Hg1—Br2 | 2.5082 (12) | C3—H3A | 0.9600 |
Hg1—Br1 | 2.5322 (13) | C4—C5 | 1.521 (14) |
Hg1—Br3i | 2.7359 (11) | C4—H4C | 0.9600 |
Hg1—Br3 | 2.7618 (11) | C4—H4B | 0.9600 |
Br3—Hg1i | 2.7359 (11) | C4—H4A | 0.9600 |
N1—C5 | 1.514 (11) | C5—H5B | 0.9700 |
N1—C1 | 1.521 (11) | C5—H5A | 0.9700 |
N1—C6 | 1.547 (11) | C6—C7 | 1.493 (13) |
N1—C2 | 1.544 (11) | C6—H6B | 0.9700 |
C1—C8 | 1.509 (13) | C6—H6A | 0.9700 |
C1—H1B | 0.9700 | C7—H7C | 0.9600 |
C1—H1A | 0.9700 | C7—H7B | 0.9600 |
C2—C3 | 1.525 (14) | C7—H7A | 0.9600 |
C2—H2B | 0.9700 | C8—H8C | 0.9600 |
C2—H2A | 0.9700 | C8—H8B | 0.9600 |
C3—H3C | 0.9600 | C8—H8A | 0.9600 |
C3—H3B | 0.9600 | ||
Br2—Hg1—Br1 | 122.15 (5) | C5—C4—H4C | 109.5 |
Br2—Hg1—Br3i | 111.24 (4) | C5—C4—H4B | 109.5 |
Br1—Hg1—Br3i | 108.55 (4) | H4C—C4—H4B | 109.5 |
Br2—Hg1—Br3 | 109.82 (4) | C5—C4—H4A | 109.5 |
Br1—Hg1—Br3 | 109.77 (4) | H4C—C4—H4A | 109.5 |
Br3i—Hg1—Br3 | 90.82 (3) | H4B—C4—H4A | 109.5 |
Hg1i—Br3—Hg1 | 89.18 (3) | C4—C5—N1 | 116.1 (7) |
C5—N1—C1 | 109.2 (7) | C4—C5—H5B | 108.3 |
C5—N1—C6 | 108.9 (7) | N1—C5—H5B | 108.3 |
C1—N1—C6 | 111.9 (7) | C4—C5—H5A | 108.3 |
C5—N1—C2 | 110.9 (7) | N1—C5—H5A | 108.3 |
C1—N1—C2 | 107.2 (6) | H5B—C5—H5A | 107.4 |
C6—N1—C2 | 108.8 (7) | C7—C6—N1 | 114.2 (8) |
N1—C1—C8 | 115.7 (8) | C7—C6—H6B | 108.7 |
N1—C1—H1B | 108.4 | N1—C6—H6B | 108.7 |
C8—C1—H1B | 108.4 | C7—C6—H6A | 108.7 |
N1—C1—H1A | 108.4 | N1—C6—H6A | 108.7 |
C8—C1—H1A | 108.4 | H6B—C6—H6A | 107.6 |
H1B—C1—H1A | 107.4 | C6—C7—H7C | 109.5 |
C3—C2—N1 | 113.8 (8) | C6—C7—H7B | 109.5 |
C3—C2—H2B | 108.8 | H7C—C7—H7B | 109.5 |
N1—C2—H2B | 108.8 | C6—C7—H7A | 109.5 |
C3—C2—H2A | 108.8 | H7C—C7—H7A | 109.5 |
N1—C2—H2A | 108.8 | H7B—C7—H7A | 109.5 |
H2B—C2—H2A | 107.7 | C1—C8—H8C | 109.5 |
C2—C3—H3C | 109.5 | C1—C8—H8B | 109.5 |
C2—C3—H3B | 109.5 | H8C—C8—H8B | 109.5 |
H3C—C3—H3B | 109.5 | C1—C8—H8A | 109.5 |
C2—C3—H3A | 109.5 | H8C—C8—H8A | 109.5 |
H3C—C3—H3A | 109.5 | H8B—C8—H8A | 109.5 |
H3B—C3—H3A | 109.5 |
Symmetry code: (i) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C8H20N)2[Hg2Br6] |
Mr | 1141.14 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.1148 (16), 10.8302 (13), 16.140 (4) |
β (°) | 107.377 (17) |
V (Å3) | 1520.5 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 17.97 |
Crystal size (mm) | 0.2 × 0.15 × 0.1 |
Data collection | |
Diffractometer | Stoe Imaging Plate Diffraction System (IPDS-I) diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1998) |
Tmin, Tmax | 0.051, 0.166 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10530, 2665, 1450 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.067, 0.81 |
No. of reflections | 2665 |
No. of parameters | 119 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −1.11 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-STEP32 (Stoe & Cie, 2000), X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, Bonn, 1999), SHELXL97.
Hg1—Br2 | 2.5082 (12) | N1—C6 | 1.547 (11) |
Hg1—Br1 | 2.5322 (13) | N1—C2 | 1.544 (11) |
Hg1—Br3i | 2.7359 (11) | C1—C8 | 1.509 (13) |
Hg1—Br3 | 2.7618 (11) | C2—C3 | 1.525 (14) |
N1—C5 | 1.514 (11) | C4—C5 | 1.521 (14) |
N1—C1 | 1.521 (11) | C6—C7 | 1.493 (13) |
Br2—Hg1—Br1 | 122.15 (5) | C5—N1—C2 | 110.9 (7) |
Br2—Hg1—Br3 | 109.82 (4) | C1—N1—C2 | 107.2 (6) |
Br1—Hg1—Br3 | 109.77 (4) | C6—N1—C2 | 108.8 (7) |
Br3i—Hg1—Br3 | 90.82 (3) | N1—C1—C8 | 115.7 (8) |
Hg1i—Br3—Hg1 | 89.18 (3) | C3—C2—N1 | 113.8 (8) |
C5—N1—C1 | 109.2 (7) | C4—C5—N1 | 116.1 (7) |
C5—N1—C6 | 108.9 (7) | C7—C6—N1 | 114.2 (8) |
C1—N1—C6 | 111.9 (7) |
Symmetry code: (i) −x, −y+1, −z. |
The crystal structures of several trihalogenomercurate(II) salts have been reported and show a wide variety of stereochemical arrangements, as listed in a recent overview (Serezhkin et al., 2001). Many different types of halogenomercurate(II) anions were observed, dependent on the stoichiometry, as well as on the size and charge of the cation. With the smaller [Me4N]+ cation, for example, the structure consists of trigonal planar [HgBr3]− anions which are connected into infinite chains by long Hg···Cl contacts (White, 1963). The same anionic structure was found for (Et4N)[HgCl3] (Sandström & Liem, 1978).
The structure of (Et4N)2[Hg2Br6], (I), consists of isolated bitetrahedral [Hg2Br6]2− units consisting of two tetrahedra sharing one common edge. Two short bonds of 2.5085 (12) and 2.5319 (13) Å, and two long bonds to the bridging bromide ions of 2.7360 (11) and 2.7618 (11) Å are observed. This type of distorted tetrahedral coordination is also found in other complexes with discrete dimeric [Hg2X6]2− units (X = Cl, Br, I), e.g. in MgHg3Cl8·6H2O (Brodersen et al., 1983), (Ph3AsOH)2HgBr4 (Harris et al., 1967) and (NEt4)[HgI3] (Goggin et al., 1982). In (I), charge balance is achieved by ordered [Et4N]+ cations, which are quite remote from the anions although there are H atoms in the range 2.7–3.1 Å from Br−, with Br···H—C angles in the range 160–170°. A symmetry centre is located in the middle of the [Hg2Br6]2− units.