metal-organic compounds
Bis(2,4-dimethylpyridinium) tetrabromidomercurate(II)
aFaculty of Science and IT, Al-Balqa'a Applied University, Salt, Jordan, bDepartment of Chemistry, The University of Jordan, Amman 11942, Jordan, and cDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan
*Correspondence e-mail: bfali@aabu.edu.jo
The 7H10N)2[HgBr4], consists of one cation and one half-anion, bisected by a twofold rotation axis passing through the metal atom. The anion exhibits a distorted tetrahedral arrangement about the HgII atom. In the crystal, the cations and anions are linked by N—H⋯Br hydrogen-bonding interactions along [010]. Cation–cation π–π stacking and Br⋯Br intermolecular interactions are absent.
of the title compound, (CRelated literature
For intermolecular interactions, see: Desiraju (1997). For related structures, see: Al-Far & Ali (2007); Ali & Al-Far (2007); Ali et al. (2008). For structures containing the [HgBr4]2− anion, see: Gowda et al. (2009); Li et al. (2009). For standard bond lengths in the cation, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812046788/bx2429sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046788/bx2429Isup2.hkl
A warm solution (40°C) of HgCl2 (1.0 mmol) dissolved in ethanol (10 ml; 95%), was added drop wise to a stirred hot solution of 2,4-dimethylpyridine (1 mmol) dissolved in ethanol (10 ml; 95%) and HBr (60%, 1 ml). During reflux for 2 h, liquid Br2 (1 ml) was added to the mixture. The final mixture was allowed to stand undisturbed at room temperature. Colorless crystals of the title salt formed in two days, filtered off and one crystal suitable for diffraction measurements is used to collect data.
All H atoms were positioned geometrically and refined using a riding model, with N—H = 0.86 Å and C—H = 0.93 and 0.96 Å, for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(C methyl) or 1.2Ueq(N/C non-methyl).
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).(C7H10N)2[HgBr4] | F(000) = 1352 |
Mr = 736.51 | Dx = 2.288 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1281 reflections |
a = 20.022 (5) Å | θ = 2.9–29.1° |
b = 7.7985 (9) Å | µ = 14.67 mm−1 |
c = 17.651 (3) Å | T = 293 K |
β = 129.12 (3)° | Block, colourless |
V = 2138.1 (11) Å3 | 0.44 × 0.40 × 0.18 mm |
Z = 4 |
Agilent Xcalibur Eos diffractometer | 2895 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1454 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 16.0534 pixels mm-1 | θmax = 29.2°, θmin = 2.9° |
ω scans | h = −27→26 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −6→10 |
Tmin = 0.002, Tmax = 0.072 | l = −24→16 |
5366 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0354P)2] where P = (Fo2 + 2Fc2)/3 |
2895 reflections | (Δ/σ)max < 0.001 |
98 parameters | Δρmax = 1.45 e Å−3 |
0 restraints | Δρmin = −1.54 e Å−3 |
(C7H10N)2[HgBr4] | V = 2138.1 (11) Å3 |
Mr = 736.51 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.022 (5) Å | µ = 14.67 mm−1 |
b = 7.7985 (9) Å | T = 293 K |
c = 17.651 (3) Å | 0.44 × 0.40 × 0.18 mm |
β = 129.12 (3)° |
Agilent Xcalibur Eos diffractometer | 2895 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 1454 reflections with I > 2σ(I) |
Tmin = 0.002, Tmax = 0.072 | Rint = 0.036 |
5366 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.45 e Å−3 |
2895 reflections | Δρmin = −1.54 e Å−3 |
98 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 | 0.5000 | 0.17233 (6) | 0.7500 | 0.0544 (2) | |
Br1 | 0.54606 (6) | 0.33656 (12) | 0.90297 (6) | 0.0647 (3) | |
N1 | 0.3078 (5) | 0.0541 (10) | 0.9729 (5) | 0.066 (2) | |
H1A | 0.3343 | 0.0396 | 1.0342 | 0.080* | |
C1 | 0.3507 (5) | 0.1249 (10) | 0.9458 (6) | 0.050 (2) | |
Br2 | 0.36889 (6) | −0.01976 (14) | 0.69426 (7) | 0.0796 (4) | |
C2 | 0.3064 (5) | 0.1449 (10) | 0.8472 (6) | 0.053 (2) | |
H2A | 0.3348 | 0.1915 | 0.8260 | 0.064* | |
C3 | 0.2217 (6) | 0.0982 (11) | 0.7793 (6) | 0.054 (2) | |
C4 | 0.1817 (6) | 0.0263 (12) | 0.8122 (7) | 0.076 (3) | |
H4A | 0.1244 | −0.0076 | 0.7677 | 0.091* | |
C5 | 0.2249 (6) | 0.0046 (14) | 0.9087 (7) | 0.086 (3) | |
H5A | 0.1976 | −0.0443 | 0.9308 | 0.103* | |
C6 | 0.4414 (6) | 0.1759 (12) | 1.0245 (6) | 0.078 (3) | |
H6A | 0.4433 | 0.2624 | 1.0646 | 0.116* | |
H6B | 0.4658 | 0.2205 | 0.9961 | 0.116* | |
H6C | 0.4739 | 0.0777 | 1.0639 | 0.116* | |
C7 | 0.1732 (6) | 0.1298 (12) | 0.6723 (6) | 0.078 (3) | |
H7A | 0.1294 | 0.0438 | 0.6351 | 0.118* | |
H7B | 0.2122 | 0.1247 | 0.6581 | 0.118* | |
H7C | 0.1468 | 0.2411 | 0.6553 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0559 (3) | 0.0639 (4) | 0.0459 (3) | 0.000 | 0.0334 (2) | 0.000 |
Br1 | 0.0707 (6) | 0.0762 (8) | 0.0504 (5) | −0.0070 (5) | 0.0398 (5) | −0.0130 (5) |
N1 | 0.066 (5) | 0.079 (6) | 0.057 (5) | 0.005 (4) | 0.040 (4) | 0.015 (4) |
C1 | 0.058 (6) | 0.044 (6) | 0.055 (5) | 0.001 (4) | 0.039 (5) | −0.001 (4) |
Br2 | 0.0820 (7) | 0.1058 (9) | 0.0702 (6) | −0.0375 (6) | 0.0572 (6) | −0.0225 (6) |
C2 | 0.057 (6) | 0.056 (6) | 0.053 (5) | −0.003 (4) | 0.038 (5) | −0.002 (4) |
C3 | 0.059 (6) | 0.041 (5) | 0.052 (5) | 0.003 (4) | 0.030 (5) | 0.000 (4) |
C4 | 0.050 (6) | 0.084 (8) | 0.065 (6) | −0.012 (5) | 0.023 (5) | 0.011 (6) |
C5 | 0.058 (7) | 0.111 (10) | 0.087 (8) | 0.005 (6) | 0.046 (6) | 0.029 (7) |
C6 | 0.053 (6) | 0.100 (9) | 0.064 (6) | −0.012 (5) | 0.030 (5) | −0.003 (6) |
C7 | 0.078 (7) | 0.087 (8) | 0.053 (5) | 0.013 (6) | 0.033 (5) | 0.010 (5) |
Hg1—Br1 | 2.5767 (11) | C3—C4 | 1.372 (12) |
Hg1—Br1i | 2.5767 (10) | C3—C7 | 1.502 (11) |
Hg1—Br2 | 2.6160 (11) | C4—C5 | 1.349 (11) |
Hg1—Br2i | 2.6160 (11) | C4—H4A | 0.9300 |
N1—C1 | 1.338 (9) | C5—H5A | 0.9300 |
N1—C5 | 1.347 (10) | C6—H6A | 0.9600 |
N1—H1A | 0.8600 | C6—H6B | 0.9600 |
C1—C2 | 1.376 (10) | C6—H6C | 0.9600 |
C1—C6 | 1.485 (11) | C7—H7A | 0.9600 |
C2—C3 | 1.372 (10) | C7—H7B | 0.9600 |
C2—H2A | 0.9300 | C7—H7C | 0.9600 |
Br1—Hg1—Br1i | 120.39 (5) | C5—C4—C3 | 120.4 (9) |
Br1—Hg1—Br2 | 106.83 (4) | C5—C4—H4A | 119.8 |
Br1i—Hg1—Br2 | 106.25 (5) | C3—C4—H4A | 119.8 |
Br1—Hg1—Br2i | 106.25 (5) | N1—C5—C4 | 119.6 (9) |
Br1i—Hg1—Br2i | 106.83 (4) | N1—C5—H5A | 120.2 |
Br2—Hg1—Br2i | 110.13 (6) | C4—C5—H5A | 120.2 |
C1—N1—C5 | 123.1 (8) | C1—C6—H6A | 109.5 |
C1—N1—H1A | 118.5 | C1—C6—H6B | 109.5 |
C5—N1—H1A | 118.5 | H6A—C6—H6B | 109.5 |
N1—C1—C2 | 116.9 (8) | C1—C6—H6C | 109.5 |
N1—C1—C6 | 117.3 (8) | H6A—C6—H6C | 109.5 |
C2—C1—C6 | 125.8 (8) | H6B—C6—H6C | 109.5 |
C3—C2—C1 | 122.0 (8) | C3—C7—H7A | 109.5 |
C3—C2—H2A | 119.0 | C3—C7—H7B | 109.5 |
C1—C2—H2A | 119.0 | H7A—C7—H7B | 109.5 |
C2—C3—C4 | 118.0 (8) | C3—C7—H7C | 109.5 |
C2—C3—C7 | 121.2 (8) | H7A—C7—H7C | 109.5 |
C4—C3—C7 | 120.8 (9) | H7B—C7—H7C | 109.5 |
C5—N1—C1—C2 | −0.5 (13) | C1—C2—C3—C7 | 176.6 (7) |
C5—N1—C1—C6 | 179.1 (9) | C2—C3—C4—C5 | 0.6 (15) |
N1—C1—C2—C3 | 1.3 (12) | C7—C3—C4—C5 | −177.4 (9) |
C6—C1—C2—C3 | −178.3 (8) | C1—N1—C5—C4 | −0.1 (15) |
C1—C2—C3—C4 | −1.4 (13) | C3—C4—C5—N1 | 0.1 (16) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br2ii | 0.86 | 2.45 | 3.286 (7) | 163 |
Symmetry code: (ii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C7H10N)2[HgBr4] |
Mr | 736.51 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 20.022 (5), 7.7985 (9), 17.651 (3) |
β (°) | 129.12 (3) |
V (Å3) | 2138.1 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 14.67 |
Crystal size (mm) | 0.44 × 0.40 × 0.18 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.002, 0.072 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5366, 2895, 1454 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.686 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.102, 1.01 |
No. of reflections | 2895 |
No. of parameters | 98 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.45, −1.54 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br2i | 0.86 | 2.45 | 3.286 (7) | 163.3 |
Symmetry code: (i) x, −y, z+1/2. |
Acknowledgements
The structure was determined at the Hamdi Mango Center for Scientific Research at the University of Jordan, Amman, Jordan. RA-F would like to thank Al-Balqa'a Applied University (Jordan) for financial support (sabbatical leave).
References
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Noncovalent interactions play an important role in organizing structural units in both natural and artificial systems (Desiraju, 1997). In connection with ongoing studies (Al-Far & Ali 2007; Ali & Al-Far 2007; Ali et al., 2008) of the structural aspects of bromometal anions salts, we herein report the crystal structure of the title compound, (I).
In the title compound, Fig. 1, the asymmetric unit of the title compound, (C7H10N)2[HgBr4], consists of one cation and one half-anion, bisected by a twofold rotation axis passing through the metal center. The anion exhibits a distorted tetrahedral arrangement about the Hg atom (Table 1). The Hg—Br1 and the symmetry related one [2.5767 (11)Å] bonds are almost invariant and significantly shorter than Hg—Br2 and symmetry related one [2.6160 (11)Å]. These lengths fall within the range of Hg—Br distances reported previously for compounds containing [HgBr4]2- anions (Gowda et al., 2009; Li et al. 2009). It is noteworthy that the longer Hg—Br2 and the symmetry related bonds are involved in more and shorter interactions than the shorter bonds (Table 1). In the cation, the bond lengths and angles are in accordance with normal values (Allen et al., 1987). In the crystal structure the cations and anions are linked by N—H···Br hydrogen bonding interactions, Fig.2 along [010] direction. Cation···cation π···π stacking and Br···Br intermolecular interactions are absent.