Acta Cryst. (2009). E65, m581-m582 [ doi:10.1107/S1600536809015219 ]
In the crystal structure of the title compound, (C7H10N)2[ZnBr4], the coordination geometry of the anion is approximately tetrahedral and a twofold rotation axis passes through the Zn atom. The Zn-Br bond lengths range from 2.400 (2) to 2.408 (3) Å and the Br-Zn-Br angles range from 108.14 (6) to 115.15 (15)°. In the crystal structure, the [ZnBr4]2- anion is connected to two cations through N-H
Br and H2C-HBr hydrogen bonds, forming two-dimensional cation-anion-cation layers normal to the b axis. No significant BrBr interactions [the shortest being 4.423 (4) Å] are observed in the structure.
Warm solution of ZnCl2 (1.0 mmol) dissolved in absolute ethanol (10 ml) and HBr (60%, 5 ml), was mixed with a stirred hot solution of 2,6-dimethylpyridine (2 mmol) dissolved in ethanol (10 ml). The mixture was then refluxed for 2 h, and then allowed to evaporate undisturbed at room temperature. The salt crystallized over 3 d as nice colourless crystals.
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).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 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).
![[Figure 1]](./at2771fig1thm.gif)
| Fig. 1. A view of the asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry operation A: -x + 1, y, -z + 1/2]. |
![[Figure 2]](./at2771fig2thm.gif)
| Fig. 2. A packing diagram of (I), shows alternating stacks of anions and cations. C,N—H···Br—Zn interactions are shown as dashed lines. |
| (C7H10N)2[ZnBr4] | F(000) = 1152 |
| Mr = 601.33 | Dx = 1.860 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 250 reflections |
| a = 17.237 (2) Å | θ = 3.2–18.0° |
| b = 9.0754 (17) Å | µ = 8.58 mm−1 |
| c = 13.7302 (14) Å | T = 293 K |
| V = 2147.9 (5) Å3 | Plate, colourless |
| Z = 4 | 0.30 × 0.20 × 0.20 mm |
| Bruker P4 diffractometer | 1850 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.086 |
| graphite | θmax = 25.5°, θmin = 2.5° |
| ω scans | h = −1→20 |
| Absorption correction: numerical (SADABS; Bruker 2001) | k = −1→10 |
| Tmin = 0.183, Tmax = 0.279 | l = −1→16 |
| 2020 measured reflections | 3 standard reflections every 97 reflections |
| 1987 independent reflections | intensity decay: 0.01% |
| 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)] = 0.088 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.177 | H-atom parameters constrained |
| S = 0.98 | w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3 |
| 1980 reflections | (Δ/σ)max < 0.001 |
| 98 parameters | Δρmax = 0.60 e Å−3 |
| 0 restraints | Δρmin = −0.48 e Å−3 |
| (C7H10N)2[ZnBr4] | V = 2147.9 (5) Å3 |
| Mr = 601.33 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 17.237 (2) Å | µ = 8.58 mm−1 |
| b = 9.0754 (17) Å | T = 293 K |
| c = 13.7302 (14) Å | 0.30 × 0.20 × 0.20 mm |
| Bruker P4 diffractometer | 1850 reflections with I > 2σ(I) |
| Absorption correction: numerical (SADABS; Bruker 2001) | Rint = 0.086 |
| Tmin = 0.183, Tmax = 0.279 | θmax = 25.5° |
| 2020 measured reflections | 3 standard reflections every 97 reflections |
| 1987 independent reflections | intensity decay: 0.01% |
| R[F2 > 2σ(F2)] = 0.088 | H-atom parameters constrained |
| wR(F2) = 0.177 | Δρmax = 0.60 e Å−3 |
| S = 0.98 | Δρmin = −0.48 e Å−3 |
| 1980 reflections | Absolute structure: ? |
| 98 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. 7 reflections were rejected based on high deviation from observed ones |
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.5000 | 0.7858 (3) | 0.2500 | 0.0644 (10) | |
| Br1 | 0.60634 (9) | 0.9276 (2) | 0.18715 (12) | 0.0652 (6) | |
| N1 | 0.3780 (7) | 0.6538 (15) | 0.4943 (10) | 0.057 (4) | |
| H1 | 0.4205 | 0.6422 | 0.4626 | 0.068* | |
| Br2 | 0.54864 (10) | 0.6305 (2) | 0.37844 (13) | 0.0812 (7) | |
| C2 | 0.3794 (11) | 0.736 (2) | 0.5723 (14) | 0.062 (5) | |
| C3 | 0.3122 (13) | 0.747 (2) | 0.6241 (14) | 0.087 (6) | |
| H3 | 0.3123 | 0.8001 | 0.6818 | 0.105* | |
| C4 | 0.2454 (14) | 0.683 (3) | 0.5953 (19) | 0.105 (9) | |
| H4 | 0.1999 | 0.6943 | 0.6308 | 0.126* | |
| C5 | 0.2470 (11) | 0.599 (2) | 0.5103 (15) | 0.093 (7) | |
| H5 | 0.2025 | 0.5519 | 0.4879 | 0.112* | |
| C6 | 0.3146 (12) | 0.586 (2) | 0.4611 (11) | 0.065 (5) | |
| C7 | 0.4534 (12) | 0.819 (2) | 0.5998 (14) | 0.134 (9) | |
| H7A | 0.4741 | 0.8668 | 0.5431 | 0.200* | |
| H7B | 0.4908 | 0.7507 | 0.6250 | 0.200* | |
| H7C | 0.4416 | 0.8915 | 0.6485 | 0.200* | |
| C8 | 0.3264 (10) | 0.498 (2) | 0.3707 (13) | 0.102 (7) | |
| H8A | 0.3733 | 0.4416 | 0.3764 | 0.153* | |
| H8B | 0.3302 | 0.5628 | 0.3157 | 0.153* | |
| H8C | 0.2833 | 0.4323 | 0.3618 | 0.153* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0466 (16) | 0.079 (2) | 0.0675 (17) | 0.000 | 0.0036 (16) | 0.000 |
| Br1 | 0.0502 (10) | 0.0731 (13) | 0.0722 (11) | −0.0146 (10) | 0.0135 (10) | −0.0024 (12) |
| N1 | 0.041 (8) | 0.073 (11) | 0.057 (9) | −0.007 (8) | 0.001 (8) | −0.013 (9) |
| Br2 | 0.0493 (10) | 0.1111 (17) | 0.0831 (12) | 0.0147 (12) | 0.0050 (11) | 0.0377 (13) |
| C2 | 0.065 (13) | 0.060 (13) | 0.061 (12) | −0.004 (11) | 0.009 (11) | 0.010 (11) |
| C3 | 0.090 (15) | 0.097 (17) | 0.075 (13) | 0.007 (15) | 0.012 (15) | −0.012 (14) |
| C4 | 0.069 (15) | 0.11 (2) | 0.14 (2) | 0.034 (15) | 0.052 (16) | 0.023 (19) |
| C5 | 0.043 (11) | 0.12 (2) | 0.116 (17) | 0.005 (13) | 0.017 (13) | 0.018 (18) |
| C6 | 0.074 (13) | 0.085 (15) | 0.037 (10) | 0.014 (13) | −0.021 (10) | 0.011 (12) |
| C7 | 0.107 (18) | 0.17 (2) | 0.125 (18) | −0.016 (18) | −0.024 (15) | −0.080 (18) |
| C8 | 0.069 (12) | 0.14 (2) | 0.094 (15) | −0.031 (14) | 0.008 (13) | −0.011 (16) |
| Zn1—Br1 | 2.400 (2) | C4—C5 | 1.39 (3) |
| Zn1—Br1i | 2.400 (2) | C4—H4 | 0.9300 |
| Zn1—Br2i | 2.408 (3) | C5—C6 | 1.35 (2) |
| Zn1—Br2 | 2.408 (3) | C5—H5 | 0.9300 |
| N1—C2 | 1.31 (2) | C6—C8 | 1.49 (2) |
| N1—C6 | 1.333 (19) | C7—H7A | 0.9600 |
| N1—H1 | 0.8600 | C7—H7B | 0.9600 |
| C2—C3 | 1.36 (2) | C7—H7C | 0.9600 |
| C2—C7 | 1.53 (2) | C8—H8A | 0.9600 |
| C3—C4 | 1.35 (3) | C8—H8B | 0.9600 |
| C3—H3 | 0.9300 | C8—H8C | 0.9600 |
| Br1—Zn1—Br1i | 115.15 (15) | C6—C5—C4 | 119 (2) |
| Br1—Zn1—Br2i | 108.45 (6) | C6—C5—H5 | 120.6 |
| Br1i—Zn1—Br2i | 108.14 (6) | C4—C5—H5 | 120.6 |
| Br1—Zn1—Br2 | 108.14 (6) | N1—C6—C5 | 119.8 (17) |
| Br1i—Zn1—Br2 | 108.45 (6) | N1—C6—C8 | 114.9 (17) |
| Br2i—Zn1—Br2 | 108.35 (16) | C5—C6—C8 | 125 (2) |
| C2—N1—C6 | 124.1 (15) | C2—C7—H7A | 109.5 |
| C2—N1—H1 | 118.0 | C2—C7—H7B | 109.5 |
| C6—N1—H1 | 118.0 | H7A—C7—H7B | 109.5 |
| N1—C2—C3 | 116.7 (18) | C2—C7—H7C | 109.5 |
| N1—C2—C7 | 120.0 (16) | H7A—C7—H7C | 109.5 |
| C3—C2—C7 | 123 (2) | H7B—C7—H7C | 109.5 |
| C4—C3—C2 | 123 (2) | C6—C8—H8A | 109.5 |
| C4—C3—H3 | 118.5 | C6—C8—H8B | 109.5 |
| C2—C3—H3 | 118.5 | H8A—C8—H8B | 109.5 |
| C3—C4—C5 | 118 (2) | C6—C8—H8C | 109.5 |
| C3—C4—H4 | 121.2 | H8A—C8—H8C | 109.5 |
| C5—C4—H4 | 121.2 | H8B—C8—H8C | 109.5 |
| C6—N1—C2—C3 | 3(2) | C3—C4—C5—C6 | 0(3) |
| C6—N1—C2—C7 | −175.0 (17) | C2—N1—C6—C5 | −2(3) |
| N1—C2—C3—C4 | −4(3) | C2—N1—C6—C8 | 179.9 (15) |
| C7—C2—C3—C4 | 175 (2) | C4—C5—C6—N1 | 0(3) |
| C2—C3—C4—C5 | 2(3) | C4—C5—C6—C8 | 178.4 (19) |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Br2 | 0.86 | 2.49 | 3.351 (12) | 175 |
| C7—H7C···Br1ii | 0.96 | 2.91 | 3.861 (18) | 171 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1. |
| Zn1—Br1 | 2.400 (2) | Zn1—Br2 | 2.408 (3) |
| Br1—Zn1—Br1i | 115.15 (15) | Br1—Zn1—Br2 | 108.14 (6) |
| Br1—Zn1—Br2i | 108.45 (6) | Br2i—Zn1—Br2 | 108.35 (16) |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Br2 | 0.86 | 2.49 | 3.351 (12) | 175 |
| C7—H7C···Br1ii | 0.96 | 2.91 | 3.861 (18) | 171 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1. |
Al al-Bayt University and Al-Balqa'a Applied University are thanked for supporting this work. We also thank Professor S. F. Haddad for helpful discussions.
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Non-covalent interactions play an important role in organizing structural units in both natural and artificial systems (Desiraju, 1997). 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 (Al-Far & Ali, 2007; Ali & Al-Far, 2007; Ali et al., 2008; Al-Far & Ali, 2009) of the structural aspects of halo-metal anion salts, we herein report the crystal structure of title compound (I).
The asymmetric unit in (I), contains half an anion and one cation (Fig. 1). The geometry of ZnBr42- anions is approximately tetrahedral and a twofold rotation axis passes through the ZnII ion (Table 1). The Zn—Br bonds range from 2.400 (2) to 2.408 (3) Å and the Br—Zn—Br angles range from 108.14 (6) to 115.15 (15)°. The bond distances and angles fall in the range of those reported previously for compounds containing Zn—Br anions (Gao et al., 2007). In the cation, the bond lengths and angles are within normal range (Allen et al., 1987).
The packing of the structure (Fig. 2) can be regarded as alternating stacks of anions and stacks of cations. The anion stacks are parallel to the cation stacks, with no significant inter- and intra-stack halogen···halogen interactions [shortest Br···Br interactions being 4.4233 (35) Å]. The anions and cations are interacting significantly through extensive N—H···Br and C—H···Br hydrogen bonding involving Br- anions and N—H and CH3 groups (Table 2). These interactions link anions and cations into two-dimensional cation···anion···cation layers normal to the crystallographic b axis (Fig. 2).
The N—H···Br and C—H···Br hydrogen bonding are potential building blocks for this stable supramolecular lattice. The stability of this lattice is evident in the isostructurality with the reported analogue (Ali et al., 2008).