supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

at2561 scheme

Acta Cryst. (2008). E64, m689-m690    [ doi:10.1107/S1600536808010647 ]

Bis(2-amino-6-methylpyridinium) tetrabromidocuprate(II)

R. H. Al-Far, B. F. Ali and S. F. Haddad

Abstract top

In the crystal structure of the title compound, (C6H9N2)2[CuBr4], the geometry around the Cu atom is intermediate between tetrahedral (Td) and square planar (D4h). Each [CuBr4]2- anion is connected non-symmetrically to four surrounding cations through N-H...X (pyridine and amine proton) hydrogen bonds, forming chains of the ladder-type running parallel to the crystallographic b axis. These layers are further connected by means of offset face-to-face interactions (parallel to the a axis), giving a three-dimensional network. Cation [pi]-[pi] stacking [centroid separations of 3.69 (9) and 3.71 (1) Å] and Br...aryl interactions [3.72 (2) and 4.04 (6) Å] are present in the crystal structure. There are no intermolecular Br...Br interactions.

Comment top

Non-covalent interactions play an important role in organizing structural units in both natural and artificial systems. They exercise important effects on the organization and properties of many materials in areas such as biology (Hunter 1994; Desiraju & Steiner 1999), crystal engineering (see for example: Allen et al.,1997; Dolling et al., 2001) and material science (Panunto et al., 1987; Robinson et al., 2000). The interactions governing the crystal organization are expected to affect the packing and then the specific properties of solids. In connection with ongoing studies (Ali & Al-Far, 2008; Ali & Al-Far, 2007; Al-Far & Ali, 2007a,b) of the structural aspects of halo-metal anion salts, we herein report the crystal structure of title compound (I) along with its crystal supramolecularity.

The asymmetric unit in (I) contains one anion and two cations (Fig. 1). The Cu—Br distances are similar, but Cu—Br2 that is engaged in longest hydrogen bonding is shorter than the others (Table 2). The Cu—Br bond distances fall in the range of bond distances reported previously for compounds containing Cu—Br anions (Luque et al., 2001; Raithby et al., 2000; Haddad et al., 2006). The bond angles are present in two distinguished sets. The first contains four angles in the range 98.36 (6) - 101.27 (6)° which are much lower than the other set which contains two angles 129.74 (7) and 132.23 (7)°. Accordingly the geometry of CuBr42- anion is an intermediate between regular tetrahedral (Td) and square planar (D4h) (Table 2).

The cation bond lengths and angles are within expected range (Allen et al. 1987), with the cations (type A contains N1 and type B contains N8) being of course planar.

In the structure (Fig. 2), each anion is connected nonsymmetrically to four cations interacting via N—H···Br and HN—H···Br hydrogen bonding, Table 3, forming chains of the ladder type run approximately parallel to the crystallographic b-axis. The cations type A represnt the rungs while both cations type B and anions represent the rails of a ladder (Fig. 3).

There are no Br···Br interactions were observed (shortest being 4.6651 (17) Å). Cations π···π stacking (in a-ditrection) is observed, with significant ones being X1A···X1A [2 - x, 2 - y, 2 - z] and X1B···X1B [- x, 1 - y, 1 - z] of 3.69 (9) and 3.71 (1), respectively. Also Br···aryl interactions present by the unusually short Br(1) [-x, 2 - y, 1 - z]···X1B contact of 3.72 (2) Å and the longer Br(3)···X1A of 4.04 (6) Å contact.

Related literature top

For related literature, see: Al-Far & Ali (2007a,b); Ali & Al-Far (2007, 2008); Allen et al. (1987, 1997); Desiraju & Steiner (1999); Dolling et al. (2001); Haddad et al. (2006); Hunter (1994); Panunto et al. (1987); Raithby et al. (2000); Robinson et al. (2000); Luque et al. (2001).

Experimental top

To a warm solution of 2-amino-6-methylpyridine (2 mmol) dissolved in 10 ml absolute ethanol acidified with 3 ml 60% HBr, CuBr2 (1 mmol) dissolved in 10 ml absolute ethanol was added. The resulting solution was then treated with 2 ml of Br2 (l). The mixture was refluxed for 2 h. The mixture was then allowed to stand and evaporate slowly at room temperature. In two days time, block blue crystals were formed and filtered (yield, 86.5%). A single-crystal suitable for diffraction measurements were chosen and used for data collection.

Refinement top

H atoms bound to carbon and nitrogen were placed at idealized positions [C—H = 0.93 and 0.96 Å and N—H = 0.86 Å] and allowed to ride on their parent atoms with Uiso fixed at 1.2 or 1.5 Ueq(C,N).

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: SHELXTL (Sheldrick, 2008); 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).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Anion···cation intermolecular interactions between one anion and four surrounding cations. N—H···Br—Cu intermolecular interactions are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding omitted for clarity.
[Figure 3] Fig. 3. A packing diagram of (I), shows chains of the ladder type run approximately parallel to the crystallographic b-axis. Hydrogen atoms omitted for clarity.
bis(2-amino-6-methylpyridinium) tetrabromidocuprate(II) top
Crystal data top
(C6H9N2)2[CuBr4]Z = 2
Mr = 601.45F000 = 574
Triclinic, P1Dx = 2.056 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.9238 (9) ÅCell parameters from 298 reflections
b = 8.2521 (11) Åθ = 2.2–27.5º
c = 15.2916 (18) ŵ = 9.35 mm−1
α = 78.472 (11)ºT = 293 (2) K
β = 82.839 (10)ºBlock, blue
γ = 89.947 (14)º0.20 × 0.15 × 0.10 mm
V = 971.8 (2) Å3
Data collection top
Bruker P4
diffractometer		3567 independent reflections
Radiation source: fine-focus sealed tube2018 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
Detector resolution: 3 pixels mm-1θmax = 25.5º
T = 293(2) Kθmin = 2.5º
ω scansh = −9→1
Absorption correction: ψ scan
(PROGRAM; REF (YEAR)		k = −9→9
Tmin = 0.199, Tmax = 0.392l = −18→18
4381 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.153  w = 1/[σ2(Fo2) + (0.0724P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
3567 reflectionsΔρmax = 0.57 e Å−3
190 parametersΔρmin = −0.65 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C6H9N2)2[CuBr4]γ = 89.947 (14)º
Mr = 601.45V = 971.8 (2) Å3
Triclinic, P1Z = 2
a = 7.9238 (9) ÅMo Kα
b = 8.2521 (11) ŵ = 9.35 mm−1
c = 15.2916 (18) ÅT = 293 (2) K
α = 78.472 (11)º0.20 × 0.15 × 0.10 mm
β = 82.839 (10)º
Data collection top
Bruker P4
diffractometer		3567 independent reflections
Absorption correction: ψ scan
(PROGRAM; REF (YEAR)		2018 reflections with I > 2σ(I)
Tmin = 0.199, Tmax = 0.392Rint = 0.053
4381 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058190 parameters
wR(F2) = 0.153H-atom parameters constrained
S = 1.00Δρmax = 0.57 e Å−3
3567 reflectionsΔρmin = −0.65 e Å−3
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. 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
xyzUiso*/Ueq
Br10.18757 (14)0.94944 (11)0.69574 (7)0.0597 (3)
Cu10.32354 (14)0.69646 (13)0.74711 (8)0.0442 (3)
N10.6876 (10)1.0718 (9)1.0416 (6)0.052 (2)
H10.62921.11201.08320.062*
Br20.08231 (15)0.54289 (13)0.82710 (9)0.0745 (4)
N20.6864 (13)0.8282 (10)1.1440 (6)0.074 (3)
H2A0.62680.87501.18250.089*
H2B0.71430.72661.15910.089*
C20.7347 (13)0.9116 (12)1.0624 (7)0.052 (3)
Br30.56567 (13)0.80573 (15)0.79499 (8)0.0679 (4)
C30.8257 (13)0.8462 (13)0.9938 (8)0.060 (3)
H30.85940.73681.00490.072*
Br40.45192 (14)0.50445 (13)0.66438 (8)0.0650 (4)
C40.8653 (14)0.9439 (17)0.9100 (8)0.073 (4)
H40.92390.90060.86360.087*
C50.8171 (15)1.1093 (15)0.8947 (7)0.070 (3)
H50.84871.17610.83840.084*
C60.7270 (14)1.1742 (12)0.9585 (7)0.058 (3)
C70.6683 (17)1.3493 (13)0.9503 (9)0.089 (4)
H7C0.70281.40970.89020.134*
H7B0.71801.40070.99230.134*
H7A0.54651.34910.96300.134*
N80.0896 (10)0.7845 (9)0.5235 (5)0.049 (2)
H80.12790.82420.56530.059*
C9−0.0722 (12)0.7230 (11)0.5402 (7)0.049 (2)
N9−0.1600 (12)0.7226 (11)0.6204 (7)0.080 (3)
H9A−0.11370.76080.66030.095*
H9B−0.26290.68410.63220.095*
C10−0.1360 (13)0.6650 (11)0.4711 (8)0.057 (3)
H10−0.24730.62390.47880.068*
C11−0.0343 (14)0.6690 (12)0.3923 (8)0.057 (3)
H11−0.07710.63020.34610.069*
C120.1301 (15)0.7289 (12)0.3794 (7)0.062 (3)
H120.19680.72900.32490.074*
C130.1985 (13)0.7888 (11)0.4451 (7)0.052 (3)
C140.3706 (14)0.8601 (14)0.4410 (8)0.075 (3)
H14A0.38230.89230.49690.112*
H14B0.38780.95530.39290.112*
H14C0.45380.77920.43060.112*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0758 (8)0.0456 (6)0.0583 (7)0.0137 (5)−0.0121 (6)−0.0101 (5)
Cu10.0410 (7)0.0451 (6)0.0453 (7)0.0029 (5)0.0001 (5)−0.0096 (5)
N10.049 (5)0.058 (5)0.050 (6)−0.003 (4)0.005 (4)−0.023 (4)
Br20.0557 (7)0.0607 (7)0.0916 (10)−0.0022 (5)0.0223 (7)0.0021 (6)
N20.116 (9)0.060 (5)0.045 (6)0.010 (5)−0.009 (6)−0.003 (5)
C20.067 (7)0.050 (6)0.046 (7)0.015 (5)−0.013 (6)−0.018 (5)
Br30.0443 (6)0.1028 (9)0.0670 (8)−0.0010 (6)−0.0037 (6)−0.0441 (7)
C30.052 (7)0.067 (7)0.071 (9)0.000 (5)−0.013 (6)−0.034 (7)
Br40.0553 (7)0.0640 (7)0.0793 (9)0.0006 (5)0.0101 (6)−0.0345 (6)
C40.050 (7)0.125 (11)0.061 (9)0.010 (7)−0.010 (6)−0.060 (8)
C50.076 (8)0.100 (9)0.035 (7)0.001 (7)−0.010 (6)−0.013 (6)
C60.063 (7)0.063 (6)0.044 (7)−0.002 (5)−0.010 (6)−0.003 (5)
C70.091 (10)0.069 (8)0.098 (11)0.009 (7)0.000 (8)0.001 (7)
N80.050 (5)0.055 (5)0.045 (5)0.008 (4)−0.009 (4)−0.014 (4)
C90.037 (6)0.049 (5)0.059 (7)0.009 (4)−0.002 (5)−0.010 (5)
N90.058 (6)0.108 (8)0.080 (8)−0.007 (5)0.009 (6)−0.048 (6)
C100.048 (6)0.053 (6)0.069 (8)0.010 (5)−0.020 (6)−0.001 (6)
C110.057 (7)0.070 (7)0.049 (7)0.007 (6)−0.022 (6)−0.011 (5)
C120.079 (9)0.070 (7)0.035 (6)0.017 (6)−0.005 (6)−0.005 (5)
C130.055 (6)0.042 (5)0.053 (7)0.003 (5)0.002 (6)0.001 (5)
C140.050 (7)0.091 (8)0.075 (9)−0.006 (6)0.008 (6)−0.006 (7)
Geometric parameters (Å, °) top
Br1—Cu12.3848 (14)C7—H7B0.9600
Cu1—Br22.3575 (16)C7—H7A0.9600
Cu1—Br42.3713 (14)N8—C91.355 (12)
Cu1—Br32.3765 (16)N8—C131.382 (12)
N1—C21.360 (11)N8—H80.8600
N1—C61.377 (13)C9—N91.331 (13)
N1—H10.8600C9—C101.391 (14)
N2—C21.310 (13)N9—H9A0.8600
N2—H2A0.8600N9—H9B0.8600
N2—H2B0.8600C10—C111.359 (14)
C2—C31.396 (13)C10—H100.9300
C3—C41.371 (16)C11—C121.370 (15)
C3—H30.9300C11—H110.9300
C4—C51.399 (15)C12—C131.371 (14)
C4—H40.9300C12—H120.9300
C5—C61.335 (14)C13—C141.475 (14)
C5—H50.9300C14—H14A0.9600
C6—C71.504 (13)C14—H14B0.9600
C7—H7C0.9600C14—H14C0.9600
Br2—Cu1—Br4101.27 (6)C6—C7—H7A109.5
Br2—Cu1—Br3132.23 (7)H7C—C7—H7A109.5
Br4—Cu1—Br3100.99 (6)H7B—C7—H7A109.5
Br2—Cu1—Br198.36 (6)C9—N8—C13125.5 (9)
Br4—Cu1—Br1129.74 (7)C9—N8—H8117.2
Br3—Cu1—Br198.93 (6)C13—N8—H8117.2
C2—N1—C6124.6 (8)N9—C9—N8118.6 (10)
C2—N1—H1117.7N9—C9—C10124.3 (10)
C6—N1—H1117.7N8—C9—C10117.1 (9)
C2—N2—H2A120.0C9—N9—H9A120.0
C2—N2—H2B120.0C9—N9—H9B120.0
H2A—N2—H2B120.0H9A—N9—H9B120.0
N2—C2—N1117.9 (9)C11—C10—C9119.4 (10)
N2—C2—C3124.8 (9)C11—C10—H10120.3
N1—C2—C3117.3 (10)C9—C10—H10120.3
C4—C3—C2119.8 (10)C10—C11—C12121.3 (10)
C4—C3—H3120.1C10—C11—H11119.4
C2—C3—H3120.1C12—C11—H11119.4
C3—C4—C5119.5 (10)C11—C12—C13121.6 (10)
C3—C4—H4120.3C11—C12—H12119.2
C5—C4—H4120.3C13—C12—H12119.2
C6—C5—C4122.0 (11)C12—C13—N8115.1 (10)
C6—C5—H5119.0C12—C13—C14128.1 (11)
C4—C5—H5119.0N8—C13—C14116.8 (10)
C5—C6—N1116.8 (10)C13—C14—H14A109.5
C5—C6—C7126.9 (11)C13—C14—H14B109.5
N1—C6—C7116.3 (9)H14A—C14—H14B109.5
C6—C7—H7C109.5C13—C14—H14C109.5
C6—C7—H7B109.5H14A—C14—H14C109.5
H7C—C7—H7B109.5H14B—C14—H14C109.5
C6—N1—C2—N2−179.2 (10)C13—N8—C9—N9177.8 (9)
C6—N1—C2—C3−1.6 (15)C13—N8—C9—C10−2.5 (13)
N2—C2—C3—C4178.1 (11)N9—C9—C10—C11−179.0 (10)
N1—C2—C3—C40.7 (15)N8—C9—C10—C111.4 (13)
C2—C3—C4—C51.4 (16)C9—C10—C11—C120.1 (15)
C3—C4—C5—C6−2.8 (17)C10—C11—C12—C13−0.6 (16)
C4—C5—C6—N11.9 (17)C11—C12—C13—N8−0.3 (14)
C4—C5—C6—C7179.9 (11)C11—C12—C13—C14−178.6 (10)
C2—N1—C6—C50.3 (16)C9—N8—C13—C122.0 (14)
C2—N1—C6—C7−177.9 (9)C9—N8—C13—C14−179.5 (9)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br3i0.862.473.324 (7)172
N8—H8···Br10.862.523.367 (8)170
N9—H9B···Br4ii0.862.643.487 (10)168
N2—H2B···Br2iii0.862.733.547 (9)158
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Br1—Cu12.3848 (14)Cu1—Br42.3713 (14)
Cu1—Br22.3575 (16)Cu1—Br32.3765 (16)
Br2—Cu1—Br4101.27 (6)Br2—Cu1—Br198.36 (6)
Br2—Cu1—Br3132.23 (7)Br4—Cu1—Br1129.74 (7)
Br4—Cu1—Br3100.99 (6)Br3—Cu1—Br198.93 (6)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br3i0.862.473.324 (7)172
N8—H8···Br10.862.523.367 (8)170
N9—H9B···Br4ii0.862.643.487 (10)168
N2—H2B···Br2iii0.862.733.547 (9)158
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+2.
Acknowledgements top

Al al-Bayt University and Al-Balqa'a Applied University are thanked for financial support.

references
References top

Al-Far, R. & Ali, B. F. (2007a). Acta Cryst. C63, m137–m139.

Al-Far, R. & Ali, B. F. (2007b). J. Chem. Cryst. 37, 333–341.

Ali, B. F. & Al-Far, R. (2007). Acta Cryst. C63, m451–m453.

Ali, B. F. & Al-Far, R. (2008). J. Chem. Cryst. (Submitted).

Allen, F. H., Hoy, V. J., Howard, J. A. K., Thalladi, V. R., Desiraju, G. R., Wilson, C. C. & McIntyre, G. J. (1997). J. Am. Chem. Soc. 119, 3477–3480.

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Bruker (1996). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA.

Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford University Press.

Dolling, B., Gillon, A. L., Orpen, A. G., Starbuck, J. & Wang, X.-M. (2001). Chem. Commun. pp. 567–568.

Haddad, S. F., AlDaamen, M. A. & Willett, R. D. (2006). Inorg. Chim. Acta, 359, 424–432.

Hunter, C. A. (1994). Chem. Soc. Rev. 2, 101–109.

Luque, A., Sertucha, J., Castillo, O. & Román, P. (2001). New J. Chem. 25, 1208–1214.

Panunto, T. W., Urbanczyk-Lipkowska, Z., Johnson, R. & Etter, M. C. (1987). J. Am. Chem. Soc. 109, 7786–7797.

Raithby, P. R., Shields, G. P., Allen, F. H. & Motherwell, W. D. S. (2000). Acta Cryst. B56, 444–454.

Robinson, J. M. A., Philp, D., Harris, K. D. M. & Kariuki, B. M. (2000). New J. Chem. 10, 799–806.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.