organic compounds
Bis(2,6-dimethylpyridinium) dibromoiodate bromide
aFaculty of Science and IT, Al-Balqa'a Applied University, Salt, Jordan, bDepartment of Chemistry, Al al-Bayt University, Mafraq 25113, Jordan, and cDepartment of Chemistry, The University of Jordan, Amman 11942, Jordan
*Correspondence e-mail: bfali@aabu.edu.jo
In the title salt, 2C7H10N+·IBr2−·Br−, each of the anions, viz. [IBr2]− and Br−, lie on a twofold axis. The IBr2− anion is almost linear, with a Br—I—Br angle of 178.25 (3)°. The cation is essentially planar (r.m.s. deviation = 0.0067 Å). In the crystal, each Br− anion links two cations via N—H⋯Br⋯H—N hydrogen-bonding interactions.
Related literature
For background to this study, see: Kochel (2006). For comparison bond lengths and angles, see: Gardberg et al. (2002); Ahmadi et al. (2008).
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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812035702/pv2580sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035702/pv2580Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035702/pv2580Isup3.cml
A solution of CdI2 (0.37 g, 1 mmol) dissolved in 95% EtOH (10 ml) and 2 ml 60% HBr solution was added to a mixture of 2,6-dimethylpyridine (0.11 g, 1 mmol) dissolved in 95% EtOH (10 ml), 60% HBr (2 ml) and molecular bromine (2 ml). The resulting mixture was refluxed for 2 hr. On cooling few reddish crystals of the title complex were found mixed in the bulk of the precipitate formed which proved to be mainly 2,6-dimethylpyridinium bromide.
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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Molecular configuration and atom naming scheme for I. Displacement ellipsoids are drawn at the 30% probability level. A stands for the symmetry operation: -x + 1, y, -z + 1/2 Packing diagram of I, down crystallographic c axis. Interspecies hydrogen bonds are shown as dashed lines. |
2C7H10N+·Br2I−·Br− | F(000) = 1104 |
Mr = 582.92 | Dx = 1.870 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1414 reflections |
a = 13.8627 (16) Å | θ = 3.0–29.4° |
b = 11.3622 (9) Å | µ = 7.33 mm−1 |
c = 13.8957 (15) Å | T = 293 K |
β = 108.885 (13)° | Block, orange |
V = 2070.9 (4) Å3 | 0.34 × 0.28 × 0.15 mm |
Z = 4 |
Agilent Xcalibur Eos diffractometer | 1834 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 16.0534 pixels mm-1 | θmax = 25.0°, θmin = 3.1° |
ω scans | h = −16→12 |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011) | k = −12→13 |
Tmin = 0.578, Tmax = 0.733 | l = −16→16 |
4417 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0423P)2 + 1.4129P] where P = (Fo2 + 2Fc2)/3 |
1834 reflections | (Δ/σ)max = 0.001 |
92 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
2C7H10N+·Br2I−·Br− | V = 2070.9 (4) Å3 |
Mr = 582.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.8627 (16) Å | µ = 7.33 mm−1 |
b = 11.3622 (9) Å | T = 293 K |
c = 13.8957 (15) Å | 0.34 × 0.28 × 0.15 mm |
β = 108.885 (13)° |
Agilent Xcalibur Eos diffractometer | 1834 independent reflections |
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011) | 1280 reflections with I > 2σ(I) |
Tmin = 0.578, Tmax = 0.733 | Rint = 0.034 |
4417 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.52 e Å−3 |
1834 reflections | Δρmin = −0.58 e Å−3 |
92 parameters |
Geometry. 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. |
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 | ||
I1 | 0.5000 | 0.56444 (5) | 0.2500 | 0.0633 (2) | |
Br1 | 0.31439 (6) | 0.56808 (6) | 0.10417 (6) | 0.0846 (3) | |
Br2 | 0.0000 | 0.55587 (7) | 0.2500 | 0.0665 (3) | |
N1 | 0.1116 (3) | 0.3483 (4) | 0.1556 (3) | 0.0529 (11) | |
H1A | 0.0824 | 0.4027 | 0.1793 | 0.064* | |
C6 | 0.2531 (5) | 0.3799 (6) | 0.3092 (5) | 0.081 (2) | |
H6A | 0.2058 | 0.4369 | 0.3186 | 0.122* | |
H6B | 0.3145 | 0.4188 | 0.3090 | 0.122* | |
H6C | 0.2688 | 0.3237 | 0.3637 | 0.122* | |
C1 | 0.2069 (5) | 0.3183 (5) | 0.2109 (5) | 0.0614 (16) | |
C5 | 0.0574 (5) | 0.2992 (5) | 0.0649 (5) | 0.0654 (17) | |
C2 | 0.2529 (6) | 0.2305 (6) | 0.1722 (6) | 0.085 (2) | |
H2A | 0.3183 | 0.2057 | 0.2091 | 0.101* | |
C7 | −0.0487 (5) | 0.3421 (7) | 0.0149 (5) | 0.093 (2) | |
H7A | −0.0643 | 0.4021 | 0.0563 | 0.140* | |
H7B | −0.0955 | 0.2778 | 0.0069 | 0.140* | |
H7C | −0.0544 | 0.3742 | −0.0506 | 0.140* | |
C4 | 0.1058 (8) | 0.2137 (6) | 0.0278 (6) | 0.090 (2) | |
H4A | 0.0720 | 0.1780 | −0.0341 | 0.108* | |
C3 | 0.2038 (8) | 0.1805 (6) | 0.0814 (7) | 0.098 (3) | |
H3A | 0.2363 | 0.1235 | 0.0550 | 0.117* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0866 (5) | 0.0525 (4) | 0.0601 (4) | 0.000 | 0.0366 (3) | 0.000 |
Br1 | 0.0928 (6) | 0.0837 (5) | 0.0703 (5) | 0.0069 (4) | 0.0166 (4) | −0.0037 (4) |
Br2 | 0.0573 (5) | 0.0564 (5) | 0.0949 (7) | 0.000 | 0.0371 (5) | 0.000 |
N1 | 0.059 (3) | 0.046 (3) | 0.059 (3) | 0.006 (2) | 0.026 (2) | 0.005 (2) |
C6 | 0.065 (4) | 0.083 (5) | 0.082 (5) | 0.005 (4) | 0.005 (4) | −0.001 (4) |
C1 | 0.058 (4) | 0.056 (4) | 0.074 (4) | 0.010 (3) | 0.028 (3) | 0.023 (3) |
C5 | 0.088 (5) | 0.058 (4) | 0.058 (4) | −0.014 (4) | 0.034 (4) | −0.002 (3) |
C2 | 0.098 (6) | 0.068 (5) | 0.107 (6) | 0.035 (4) | 0.061 (5) | 0.032 (4) |
C7 | 0.076 (5) | 0.116 (6) | 0.078 (5) | −0.017 (5) | 0.012 (4) | 0.001 (4) |
C4 | 0.152 (8) | 0.063 (5) | 0.068 (5) | −0.018 (5) | 0.054 (5) | −0.014 (4) |
C3 | 0.151 (8) | 0.066 (5) | 0.101 (6) | 0.031 (5) | 0.076 (6) | 0.011 (5) |
I1—Br1 | 2.7117 (9) | C1—C2 | 1.383 (9) |
I1—Br1i | 2.7117 (9) | C5—C4 | 1.372 (9) |
Br2—Br2ii | 0.0000 | C5—C7 | 1.490 (9) |
Br2—Br2 | 0.0000 | C2—C3 | 1.350 (10) |
N1—C1 | 1.340 (7) | C2—H2A | 0.9300 |
N1—C5 | 1.361 (7) | C7—H7A | 0.9600 |
N1—H1A | 0.8600 | C7—H7B | 0.9600 |
C6—C1 | 1.483 (8) | C7—H7C | 0.9600 |
C6—H6A | 0.9600 | C4—C3 | 1.373 (10) |
C6—H6B | 0.9600 | C4—H4A | 0.9300 |
C6—H6C | 0.9600 | C3—H3A | 0.9300 |
Br1—I1—Br1i | 178.25 (3) | C4—C5—C7 | 125.8 (7) |
Br2ii—Br2—Br2 | 0 (10) | C3—C2—C1 | 120.7 (7) |
C1—N1—C5 | 125.0 (5) | C3—C2—H2A | 119.6 |
C1—N1—H1A | 117.5 | C1—C2—H2A | 119.6 |
C5—N1—H1A | 117.5 | C5—C7—H7A | 109.5 |
C1—C6—H6A | 109.5 | C5—C7—H7B | 109.5 |
C1—C6—H6B | 109.5 | H7A—C7—H7B | 109.5 |
H6A—C6—H6B | 109.5 | C5—C7—H7C | 109.5 |
C1—C6—H6C | 109.5 | H7A—C7—H7C | 109.5 |
H6A—C6—H6C | 109.5 | H7B—C7—H7C | 109.5 |
H6B—C6—H6C | 109.5 | C5—C4—C3 | 120.6 (7) |
N1—C1—C2 | 117.0 (6) | C5—C4—H4A | 119.7 |
N1—C1—C6 | 117.4 (5) | C3—C4—H4A | 119.7 |
C2—C1—C6 | 125.6 (6) | C2—C3—C4 | 120.1 (7) |
N1—C5—C4 | 116.6 (6) | C2—C3—H3A | 119.9 |
N1—C5—C7 | 117.6 (6) | C4—C3—H3A | 119.9 |
C5—N1—C1—C2 | −0.2 (9) | C6—C1—C2—C3 | −179.9 (7) |
C5—N1—C1—C6 | −178.7 (5) | N1—C5—C4—C3 | 0.4 (9) |
C1—N1—C5—C4 | −0.9 (9) | C7—C5—C4—C3 | −179.4 (7) |
C1—N1—C5—C7 | 178.9 (5) | C1—C2—C3—C4 | −2.2 (11) |
N1—C1—C2—C3 | 1.8 (9) | C5—C4—C3—C2 | 1.1 (11) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | 2C7H10N+·Br2I−·Br− |
Mr | 582.92 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.8627 (16), 11.3622 (9), 13.8957 (15) |
β (°) | 108.885 (13) |
V (Å3) | 2070.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.33 |
Crystal size (mm) | 0.34 × 0.28 × 0.15 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos diffractometer |
Absorption correction | Analytical (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.578, 0.733 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4417, 1834, 1280 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.104, 1.05 |
No. of reflections | 1834 |
No. of parameters | 92 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.52, −0.58 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Footnotes
‡Cuurrent address: Qassim University, Faculty of Science, Chemistry Department, Qassim, Saudi Arabia.
Acknowledgements
The structure was determined at the Hamdi Mango Center for Scientific Research of the University of Jordan.
References
Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Ahmadi, R., Dehghan, L., Amani, V. & Khavasi, H. R. (2008). Acta Cryst. E64, m1237. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gardberg, A. S., Yang, S., Hoffman, B. M. & Ibers, J. A. (2002). Inorg. Chem. 41, 1778–1781. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kochel, A. (2006). Acta Cryst. E62, o5605–o5606. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Polyhalides display a variety of structures. Various compounds with interesting structures were found when protonated aromatic nitrogen bases were combined with polyhalides (Kochel, 2006). Herein, we report the crystal structure of [(C7H10N)+]2. [IBr2] –. Br-, (I). Few crystals of (I) were found as an unexpected product from reaction mixture of CdI2, HBr, 2,6-dimethylpyridine and Br2 upon attempting to formulate [(C7H10N)]2 [CdBr4] salt of 2,6-dimethylpyrinium.
The title salt is depicted in Fig. 1. The IBr2– anion is symmetrical and almost linear, Br1—I—Br1i angle of 178.25 (3) °; (i) –x + 1, y, -z + 1/2], with I—Br1 distance of 2.7117 (9) Å. These values are in agreement with the values reported in the literature (Gardberg et al., 2002). The molecular dimensions of the cation are as expected (Ahmadi et al., 2008).
The cations are arranged as zigzag stacks parallel to the c-axis (Fig. 2). Moreover, alternating Br- and IBr2- anions form stacks that separate the cations. Each bromide anion is hydrogen bonded via N1—H1A···Br2 with two cations along the b-axis (Table 1). There are no significant Br···Br or aryl···aryl interactions in the crystal structure; the shortest Br···Br separation is just greater than 5.0 Å and the shortest distance between the ring centroids is over 4.8 Å.