Acta Cryst. (2009). E65, m1457 [ doi:10.1107/S1600536809043694 ]
In the title compound, [ZnBr2(C6H7N)2], the Zn atom (site symmetry 2) adopts a distorted tetrahedral ZnN2Br2 geometry. In the crystal, molecules are linked by N-H
Br hydrogen bonds, generating sheets containing R22(8) loops.
Zinc bromide (1.125 g, 5 mmol) was added to distilled water (20 ml). Aniline (0.93 g, 10 mmol) was added to the above solution and stirred at room temperature for 5 minutes. White precipitate formed was filtered off, washed with distilled water, dried and recrystallized in methanol to yield colourless blocks of (I).
All C-bonded H atoms were refined using a riding model, with C—H distances constrained to 0.93Å and with Uiso = 1.2Ueq(C). Amino H atoms were located in difference map and refined freely.
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./hb5146fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 30% probability level. [Symmety code: (iii) 1 - x, y, 3/2 - z.] |
![[Figure 2]](./hb5146fig2thm.gif)
| Fig. 2. Part of the crystal structure of the title compound, showing the formation of an R22(8) dimer along [010]. |
![[Figure 3]](./hb5146fig3thm.gif)
| Fig. 3. Part of the crystal structure of the title compound, showing the formation of an R22(8) dimer along [001]. Hydrogen bonds are indicated by dashed lines. H atoms not involved in these interactions have been omitted for clarity. (Symmetry codes as in Table 1.) |
| [ZnBr2(C6H7N)2] | Z = 4 |
| Mr = 411.44 | F(000) = 800 |
| Monoclinic, C2/c | Dx = 1.887 Mg m−3 |
| Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
| a = 25.7545 (16) Å | Cell parameters from 7092 reflections |
| b = 4.9415 (3) Å | µ = 7.19 mm−1 |
| c = 12.1919 (8) Å | T = 296 K |
| β = 111.035 (3)° | Block, colourless |
| V = 1448.21 (16) Å3 | 0.43 × 0.41 × 0.40 mm |
| Bruker APEXII CCD diffractometer | 1489 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.026 |
| graphite | θmax = 28.3°, θmin = 1.7° |
| φ and ω scans | h = −34→32 |
| 7092 measured reflections | k = −4→6 |
| 1796 independent reflections | l = −16→16 |
| 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.18 | w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3 |
| 1796 reflections | (Δ/σ)max = 0.001 |
| 86 parameters | Δρmax = 0.36 e Å−3 |
| 0 restraints | Δρmin = −0.60 e Å−3 |
| [ZnBr2(C6H7N)2] | V = 1448.21 (16) Å3 |
| Mr = 411.44 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 25.7545 (16) Å | µ = 7.19 mm−1 |
| b = 4.9415 (3) Å | T = 296 K |
| c = 12.1919 (8) Å | 0.43 × 0.41 × 0.40 mm |
| β = 111.035 (3)° |
| Bruker APEXII CCD diffractometer | 1489 reflections with I > 2σ(I) |
| 7092 measured reflections | Rint = 0.026 |
| 1796 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.068 | Δρmax = 0.36 e Å−3 |
| S = 1.18 | Δρmin = −0.60 e Å−3 |
| 1796 reflections | Absolute structure: ? |
| 86 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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.61172 (10) | −0.0453 (4) | 0.7448 (2) | 0.0332 (5) | |
| C2 | 0.65438 (13) | −0.1002 (6) | 0.8489 (3) | 0.0483 (7) | |
| H2 | 0.6498 | −0.2303 | 0.8998 | 0.058* | |
| C3 | 0.70386 (14) | 0.0379 (7) | 0.8775 (3) | 0.0618 (8) | |
| H3 | 0.7328 | −0.0013 | 0.9475 | 0.074* | |
| C4 | 0.71102 (14) | 0.2333 (7) | 0.8038 (3) | 0.0620 (9) | |
| H4 | 0.7445 | 0.3269 | 0.8240 | 0.074* | |
| C5 | 0.66823 (14) | 0.2887 (6) | 0.7000 (3) | 0.0543 (8) | |
| H5 | 0.6728 | 0.4200 | 0.6495 | 0.065* | |
| C6 | 0.61856 (12) | 0.1502 (5) | 0.6703 (2) | 0.0428 (6) | |
| H6 | 0.5897 | 0.1887 | 0.6001 | 0.051* | |
| N1 | 0.55851 (9) | −0.1809 (4) | 0.7147 (2) | 0.0350 (5) | |
| H1A | 0.5450 (13) | −0.231 (6) | 0.638 (3) | 0.052 (8)* | |
| H2A | 0.5592 (14) | −0.334 (6) | 0.750 (3) | 0.058 (9)* | |
| Zn1 | 0.5000 | 0.05076 (7) | 0.7500 | 0.03217 (12) | |
| Br1 | 0.546312 (11) | 0.32589 (5) | 0.91739 (2) | 0.04053 (11) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0370 (14) | 0.0280 (12) | 0.0384 (13) | 0.0019 (10) | 0.0181 (11) | −0.0068 (9) |
| C2 | 0.0499 (18) | 0.0449 (14) | 0.0472 (16) | 0.0039 (14) | 0.0136 (14) | 0.0063 (13) |
| C3 | 0.0452 (19) | 0.064 (2) | 0.063 (2) | 0.0048 (16) | 0.0033 (16) | −0.0045 (16) |
| C4 | 0.048 (2) | 0.0555 (18) | 0.085 (3) | −0.0135 (15) | 0.0271 (19) | −0.0186 (18) |
| C5 | 0.057 (2) | 0.0478 (16) | 0.069 (2) | −0.0092 (14) | 0.0348 (18) | −0.0008 (14) |
| C6 | 0.0466 (17) | 0.0427 (15) | 0.0412 (15) | −0.0038 (12) | 0.0184 (13) | −0.0023 (11) |
| N1 | 0.0406 (13) | 0.0297 (11) | 0.0374 (12) | −0.0024 (9) | 0.0176 (10) | −0.0032 (9) |
| Zn1 | 0.0379 (2) | 0.0308 (2) | 0.0310 (2) | 0.000 | 0.01626 (18) | 0.000 |
| Br1 | 0.0558 (2) | 0.03761 (16) | 0.02807 (15) | −0.00087 (11) | 0.01487 (12) | −0.00366 (9) |
| C1—C2 | 1.375 (4) | C5—C6 | 1.380 (4) |
| C1—C6 | 1.380 (3) | C5—H5 | 0.9300 |
| C1—N1 | 1.450 (3) | C6—H6 | 0.9300 |
| C2—C3 | 1.376 (4) | N1—H1A | 0.90 (3) |
| C2—H2 | 0.9300 | N1—H2A | 0.87 (3) |
| C3—C4 | 1.376 (5) | Zn1—N1 | 2.057 (2) |
| C3—H3 | 0.9300 | Zn1—N1i | 2.057 (2) |
| C4—C5 | 1.375 (5) | Zn1—Br1 | 2.3851 (3) |
| C4—H4 | 0.9300 | Zn1—Br1i | 2.3851 (3) |
| C2—C1—C6 | 119.8 (2) | C5—C6—C1 | 120.0 (3) |
| C2—C1—N1 | 120.8 (2) | C5—C6—H6 | 120.0 |
| C6—C1—N1 | 119.3 (2) | C1—C6—H6 | 120.0 |
| C1—C2—C3 | 119.8 (3) | C1—N1—Zn1 | 112.76 (14) |
| C1—C2—H2 | 120.1 | C1—N1—H1A | 111.5 (19) |
| C3—C2—H2 | 120.1 | Zn1—N1—H1A | 109 (2) |
| C2—C3—C4 | 120.8 (3) | C1—N1—H2A | 115 (2) |
| C2—C3—H3 | 119.6 | Zn1—N1—H2A | 106 (2) |
| C4—C3—H3 | 119.6 | H1A—N1—H2A | 102 (3) |
| C5—C4—C3 | 119.4 (3) | N1i—Zn1—N1 | 112.35 (13) |
| C5—C4—H4 | 120.3 | N1i—Zn1—Br1 | 108.50 (7) |
| C3—C4—H4 | 120.3 | N1—Zn1—Br1 | 108.50 (7) |
| C4—C5—C6 | 120.3 (3) | N1i—Zn1—Br1i | 108.50 (7) |
| C4—C5—H5 | 119.9 | N1—Zn1—Br1i | 108.50 (7) |
| C6—C5—H5 | 119.9 | Br1—Zn1—Br1i | 110.49 (5) |
| C6—C1—C2—C3 | −0.8 (4) | N1—C1—C6—C5 | 177.4 (2) |
| N1—C1—C2—C3 | −177.7 (2) | C2—C1—N1—Zn1 | 98.8 (2) |
| C1—C2—C3—C4 | 0.8 (5) | C6—C1—N1—Zn1 | −78.1 (2) |
| C2—C3—C4—C5 | −0.5 (5) | C1—N1—Zn1—N1i | −152.2 (2) |
| C3—C4—C5—C6 | 0.2 (5) | C1—N1—Zn1—Br1 | −32.26 (19) |
| C4—C5—C6—C1 | −0.2 (4) | C1—N1—Zn1—Br1i | 87.82 (17) |
| C2—C1—C6—C5 | 0.5 (4) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1ii | 0.90 (3) | 2.75 (3) | 3.597 (3) | 157 (2) |
| N1—H2A···Br1iii | 0.87 (3) | 2.76 (3) | 3.564 (3) | 156 (3) |
| Symmetry codes: (ii) x, −y, z−1/2; (iii) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···Br1i | 0.90 (3) | 2.75 (3) | 3.597 (3) | 157 (2) |
| N1—H2A···Br1ii | 0.87 (3) | 2.76 (3) | 3.564 (3) | 156 (3) |
| Symmetry codes: (i) x, −y, z−1/2; (ii) x, y−1, z. |
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Researches have worked on synthesis and X-ray studies of organo-zinc complexes for their applications in catalysis (Ibrahim et al., 2003, Park et al., 2008) and supramolecular chemistry (Nesterova et al., 2005). These complexes act as fluorescent probe for labeling proteins (Wu et al., 2008). Herein, we report the synthesis and crystal structure of the title compound, (I).
The molecular structure of (I) is presented in Fig. 1. The compound crystallizes in the space group C2/c with Z' = 1/2. The ZnII ion is located on a 2-fold axis and is coordinated by two Br atoms [Zn1—Br/Br1iii = 2.3851 (3) Å] and two amino N atoms from aniline ligands [Zn1—N1/N1iii = 2.057 (2) Å] [symmetry code: (iii) 1 - x, y, 3/2 - z]. The geometry around the ZnII ion is that of a tetrahedron. The benzene ring plane is approximately planar, with maximum deviation from the least-squares plane being 0.004 (2)Å for atom C2.
Molecules of the title compound are linked in to shetts by a combination of N—H···Br hydrogen bonds (Table 1). Amino atom N1 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via H2A, respectively, to atom Br1 in the molecule at (x, y - 1, z), so forming a C(4)[R22(8)] (Bernstein et al., 1995) chain of rings running parallel to the [010] direction (Fig. 2). Similarly, amino atom N1 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via H1A, respectively, to atom Br1 in the molecule at (x, -y, z - 1/2), so forming a C(4)[R22(8)] chain of rings running parallel to the [001] direction and centrosymmetric R22(8) ring centred at (1/2, 0, 1/2) (Fig. 3).