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The title compound, (C4H14N2)[HgCl4], contains layers of tilted corner-sharing chloromercurate octahedra. Each HgII ion lies on a center of symmetry, and has four long bonds to the halide ions, forming puckered sheets parallel to the bc plane plus two short bonds to halide ions axial to the sheets, completing a tetragonally compressed octahedral coordination. Adjacent sheets have axial halide ions in an eclipsed conformation. The diammonium ions provide links between sheets, hydrogen bonding to the halides. The organic chains have the two ends of the diammonium ions equivalent by a center of symmetry, with C4 chains trans around the central bond and gauche for N versus C positioning around each terminal C-C bond. No phase transition before the decomposition temperature has been detected by differential scanning calorimetry.
Supporting information
CCDC reference: 189873
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.018 Å
- R factor = 0.036
- wR factor = 0.073
- Data-to-parameter ratio = 14.0
checkCIF results
No syntax errors found
Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575
Calculated sin(theta_max)/wavelength = 0.5599
| Author response: It is noticed that zero intensity was observed for the reflections at
higher angles, which is a characteristic behavior of this family of
organo-metallic compound (Spengler et al., 1998, Zouari et al.1998).
|
PLAT_112 Alert B ADDSYM Detects Additional (Pseudo) Symm. Elem. A
| Author response: The symmetry of these first layer of the structure taken alone is A2/m.
The 4DA chains building the second layer of the structure
have only the P21/c symmetry.
|
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 23.45
From the CIF: _reflns_number_total 741
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 802
Completeness (_total/calc) 92.39%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: local software (Huber, 2000); cell refinement: MACH3 in CAD-4 UNIX Software (Enraf-Nonius, 1998); data reduction: local software (Huber, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 1990).
Bis-buthanediammoniumchloride tetrachloromercurate
top
Crystal data top
(C4H14N2)[HgCl4] | F(000) = 400 |
Mr = 432.56 | Dx = 2.629 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.082 (2) Å | Cell parameters from 25 reflections |
b = 7.720 (5) Å | θ = 10–25° |
c = 7.996 (5) Å | µ = 15.01 mm−1 |
β = 102.907 (12)° | T = 293 K |
V = 546.5 (5) Å3 | Polyhedral, colorless |
Z = 2 | 0.40 × 0.32 × 0.25 mm |
Data collection top
Home-made (Huber, 2000) Image Plate diffractometer | 741 independent reflections |
Radiation source: fine-focus sealed tube | 571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
Detector resolution: Image Plate detector pixels mm-1 | θmax = 23.5°, θmin = 3.5° |
ω–scan | h = −10→9 |
Absorption correction: integration (local program; Hertlein, 1989) | k = 0→8 |
Tmin = 0.026, Tmax = 0.463 | l = 0→8 |
803 measured reflections | |
Refinement top
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
741 reflections | Δρmax = 1.46 e Å−3 |
53 parameters | Δρmin = −1.17 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: 0.111 (6) |
Special details top
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. Full experimental details are given in Table1. A colorless crystal of dimension
0.4x 0.3 x0.35 mm3 was used for X-ray scattering on a home made Image plate
diffractometer (Huber, T., 2000) using graphite-monochromated Mo Ka radiation
(λ = 0.70926 Å). The monoclinic lattice constants were obtained as a =
9.082 (2) b= 7.720 (5) c = 7.996 (5) β = 102.907 (12). For the data collection
61–121 data frames were collected by 3° steps in ω-scan with exposure time
of 500 second and crystal to detector distance of 12 cm. 8518 reflections were
measured. The intensity data were averaged in laue symmetry 2/m resulting in
741 independents reflections 571 reflections with I>2σ(I). The
analysis of the systematic absences showed the reflection condition to be
valid for a c glide perpendicular to the unique axis b, h0l: l =
2n and for a tow helicoidal axis parallel to b axis 0k0: k = 2n. The
space group compatible with these conditions is P21/c. The structure
refinement was performed using the program SHELXL97 (Sheldrick, 1997).
The refinement converge to a structure model with R(F) = 0.0360,
WR(F) = 0.0727. Patterson mapping found heavy atom positions. The C and
N atoms were found on difference Fourier maps and included in the
calculations. All the non-hydrogen atoms were anisotropically refined. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Hg | 0.0000 | 0.0000 | 0.0000 | 0.0255 (5) | |
Cl1 | 0.2697 (3) | 0.0551 (4) | 0.0535 (4) | 0.0362 (9) | |
Cl2 | −0.0399 (3) | 0.2326 (3) | −0.2742 (3) | 0.0350 (9) | |
N1 | 0.2203 (12) | 0.0275 (11) | 0.5684 (16) | 0.045 (3) | |
H1A | 0.1559 | 0.0159 | 0.6367 | 0.067* | |
H1B | 0.1799 | −0.0175 | 0.4659 | 0.067* | |
H1C | 0.2396 | 0.1394 | 0.5568 | 0.067* | |
C1 | 0.3626 (15) | −0.0643 (18) | 0.6443 (17) | 0.044 (3) | |
H1D | 0.3391 | −0.1785 | 0.6818 | 0.053* | |
H1E | 0.4164 | −0.0011 | 0.7442 | 0.053* | |
C2 | 0.4633 (14) | −0.0824 (17) | 0.5167 (14) | 0.037 (3) | |
H2A | 0.5412 | −0.1674 | 0.5600 | 0.045* | |
H2B | 0.4032 | −0.1259 | 0.4091 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Hg | 0.0223 (6) | 0.0259 (6) | 0.0291 (6) | −0.0044 (3) | 0.0077 (3) | 0.0002 (3) |
Cl1 | 0.0212 (17) | 0.0314 (18) | 0.055 (2) | −0.0034 (13) | 0.0065 (14) | 0.0043 (15) |
Cl2 | 0.0379 (19) | 0.0329 (18) | 0.0371 (17) | 0.0081 (15) | 0.0143 (14) | 0.0138 (16) |
N1 | 0.023 (6) | 0.035 (6) | 0.084 (9) | −0.006 (4) | 0.027 (6) | −0.014 (6) |
C1 | 0.038 (9) | 0.053 (7) | 0.047 (8) | 0.005 (7) | 0.017 (7) | 0.009 (7) |
C2 | 0.045 (8) | 0.029 (6) | 0.042 (8) | 0.011 (6) | 0.019 (6) | 0.007 (6) |
Geometric parameters (Å, º) top
Hg—Cl1 | 2.428 (3) | N1—H1B | 0.8900 |
Hg—Cl1i | 2.428 (3) | N1—H1C | 0.8900 |
Hg—Cl2i | 2.794 (3) | C1—C2 | 1.521 (17) |
Hg—Cl2 | 2.794 (3) | C1—H1D | 0.9700 |
Hg—Cl2ii | 2.819 (3) | C1—H1E | 0.9700 |
Hg—Cl2iii | 2.819 (3) | C2—C2v | 1.49 (3) |
Cl2—Hgiv | 2.819 (3) | C2—H2A | 0.9700 |
N1—C1 | 1.480 (17) | C2—H2B | 0.9700 |
N1—H1A | 0.8900 | | |
| | | |
Cl1—Hg—Cl1i | 180.00 (3) | C1—N1—H1B | 109.5 |
Cl1—Hg—Cl2i | 91.46 (10) | H1A—N1—H1B | 109.5 |
Cl1i—Hg—Cl2i | 88.54 (10) | C1—N1—H1C | 109.5 |
Cl1—Hg—Cl2 | 88.54 (10) | H1A—N1—H1C | 109.5 |
Cl1i—Hg—Cl2 | 91.46 (10) | H1B—N1—H1C | 109.5 |
Cl2i—Hg—Cl2 | 180.0 | N1—C1—C2 | 111.7 (10) |
Cl1—Hg—Cl2ii | 91.60 (10) | N1—C1—H1D | 109.3 |
Cl1i—Hg—Cl2ii | 88.40 (10) | C2—C1—H1D | 109.3 |
Cl2i—Hg—Cl2ii | 88.90 (5) | N1—C1—H1E | 109.3 |
Cl2—Hg—Cl2ii | 91.10 (5) | C2—C1—H1E | 109.3 |
Cl1—Hg—Cl2iii | 88.40 (10) | H1D—C1—H1E | 107.9 |
Cl1i—Hg—Cl2iii | 91.60 (10) | C2v—C2—C1 | 113.7 (14) |
Cl2i—Hg—Cl2iii | 91.10 (5) | C2v—C2—H2A | 108.8 |
Cl2—Hg—Cl2iii | 88.90 (5) | C1—C2—H2A | 108.8 |
Cl2ii—Hg—Cl2iii | 180.00 (8) | C2v—C2—H2B | 108.8 |
Hg—Cl2—Hgiv | 163.86 (13) | C1—C2—H2B | 108.8 |
C1—N1—H1A | 109.5 | H2A—C2—H2B | 107.7 |
| | | |
N1—C1—C2—C2v | 73.1 (13) | C1—C2—C2v—C1v | −180 |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z−1/2; (iv) −x, y+1/2, −z−1/2; (v) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2vi | 0.89 | 2.76 | 3.432 (11) | 133 |
N1—H1B···Cl2i | 0.89 | 2.42 | 3.245 (11) | 154 |
N1—H1C···Cl1ii | 0.89 | 2.38 | 3.259 (9) | 172 |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y+1/2, z+1/2; (vi) −x, y−1/2, −z+1/2. |
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