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The ZnII centre in the title compound, [ZnBr2(C12H9IN2)], is covalently bonded to two Br atoms and two N atoms of the diimine ligand in a distorted tetra­hedral geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051987/sj2380sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051987/sj2380Isup2.hkl
Contains datablock I

CCDC reference: 667236

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.017
  • wR factor = 0.045
  • Data-to-parameter ratio = 21.6

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT431_ALERT_2_C Short Inter HL..A Contact I1 .. Br1 .. 3.55 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.91
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Pyridinecarbaldehyde and its substituted derivatives condense with amines to give a range of diimine compounds; iminopyridine ligands have been used to give adducts with transition metals. Among such complexes whose structures have been described are, for example, complexes of CuI, (Dehghanpour et al., 2007), CoII, (Small et al., 2003) and FeII, (Britovsek et al., 1999). The title complex, (I), was prepared by the reaction of ZnBr2 with the bidentate ligand (4-iodo-phenyl)-pyridin-2-ylmethylene-amine.

Molecular structure of complex (I), as well as the atom-numbering scheme are shown in Fig. 1. A s one might expect for a four-coordinated zinc(II) complex, the metal center has a tetrahedral coordination. It shows signficant distortions mainly due to the presence of the 5-membered chelate cycle: the endocyclic N1—Zn1—N2 angle [80.87 (8)°] is much narrower than the ideal tetrahedral angle of 109.5°, whereas the N2—Zn1—Br1 angle [122.39 (6)°] is much wider than the ideal angle in the tetrahedron. The Zn1—Br1 and Zn1—Br2 bond lengths [2.3422 (7) and 2.3565 (7) Å respectively] are in good agreement with the Zn—Br distances in other tetrahedral zinc complexes, e.g. (Dehghanpour et al., 2007a,b).

Related literature top

For related literature, see: Britovsek et al. (1999); Dehghanpour & Mahmoudi (2007a, 2007b); Small et al. (1998).

Experimental top

To a solution of (4-iodo-phenyl)-pyridin-2-ylmethylene-amine (30.8 mg, 0.1 mmol) in 20 ml acetonitrile was added zinc bromide (22.5 mg, 0.1 mmol). The mixture was heated to dissolve the reactants. The solution was filtered and the volume of solvent removed under vacuum to about 5 ml. Diffusion of diethyl ether vapor into the solution gave yellow crystals. The crystals were collected and washed with diethylether-dichloromethane (9:1 v/v); yield 86%. Calc. for C12H9Br2IN2Zn: C 27.02, H 1.70, N 5.25%; found: C 27.01, H 1.72, N 5.26%.

Refinement top

The H(C) atom positions were calculated. All hydrogen atoms were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), for methyl groups equal to 1.5 Ueq(Cii), where U(Ci) and U(Cii) are respectively the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded.

Structure description top

Pyridinecarbaldehyde and its substituted derivatives condense with amines to give a range of diimine compounds; iminopyridine ligands have been used to give adducts with transition metals. Among such complexes whose structures have been described are, for example, complexes of CuI, (Dehghanpour et al., 2007), CoII, (Small et al., 2003) and FeII, (Britovsek et al., 1999). The title complex, (I), was prepared by the reaction of ZnBr2 with the bidentate ligand (4-iodo-phenyl)-pyridin-2-ylmethylene-amine.

Molecular structure of complex (I), as well as the atom-numbering scheme are shown in Fig. 1. A s one might expect for a four-coordinated zinc(II) complex, the metal center has a tetrahedral coordination. It shows signficant distortions mainly due to the presence of the 5-membered chelate cycle: the endocyclic N1—Zn1—N2 angle [80.87 (8)°] is much narrower than the ideal tetrahedral angle of 109.5°, whereas the N2—Zn1—Br1 angle [122.39 (6)°] is much wider than the ideal angle in the tetrahedron. The Zn1—Br1 and Zn1—Br2 bond lengths [2.3422 (7) and 2.3565 (7) Å respectively] are in good agreement with the Zn—Br distances in other tetrahedral zinc complexes, e.g. (Dehghanpour et al., 2007a,b).

For related literature, see: Britovsek et al. (1999); Dehghanpour & Mahmoudi (2007a, 2007b); Small et al. (1998).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing the atom-labelling scheme with thermal ellipsoids drawn at the 50% probability level.
Dibromido{2-[(4-iodophenyl)iminomethyl]pyridine-κ2N,N'}zinc(II) top
Crystal data top
[ZnBr2(C12H9IN2)]Z = 2
Mr = 533.30F(000) = 496
Triclinic, P1Dx = 2.421 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.750 (2) ÅCell parameters from 2531 reflections
b = 8.831 (2) Åθ = 3–29°
c = 11.270 (3) ŵ = 9.23 mm1
α = 89.44 (4)°T = 100 K
β = 71.66 (3)°Prism, yellow
γ = 87.81 (4)°0.4 × 0.3 × 0.2 mm
V = 731.5 (3) Å3
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
3520 independent reflections
Radiation source: fine-focus sealed tube3278 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 28.0°, θmin = 1.9°
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
h = 1010
Tmin = 0.047, Tmax = 0.160k = 1111
13887 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.045H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.026P)2 + 0.2955P]
where P = (Fo2 + 2Fc2)/3
3520 reflections(Δ/σ)max = 0.029
163 parametersΔρmax = 0.85 e Å3
0 restraintsΔρmin = 1.02 e Å3
Crystal data top
[ZnBr2(C12H9IN2)]γ = 87.81 (4)°
Mr = 533.30V = 731.5 (3) Å3
Triclinic, P1Z = 2
a = 7.750 (2) ÅMo Kα radiation
b = 8.831 (2) ŵ = 9.23 mm1
c = 11.270 (3) ÅT = 100 K
α = 89.44 (4)°0.4 × 0.3 × 0.2 mm
β = 71.66 (3)°
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer
3520 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
3278 reflections with I > 2σ(I)
Tmin = 0.047, Tmax = 0.160Rint = 0.026
13887 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.045H-atom parameters constrained
S = 1.00Δρmax = 0.85 e Å3
3520 reflectionsΔρmin = 1.02 e Å3
163 parameters
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
I11.162788 (19)0.189540 (15)0.037792 (12)0.01576 (5)
Br10.37752 (3)0.15813 (2)0.634148 (19)0.01502 (6)
Zn10.60460 (3)0.31017 (3)0.65953 (2)0.01325 (6)
Br20.81041 (3)0.17579 (3)0.74107 (2)0.02209 (6)
N20.5476 (3)0.5242 (2)0.74024 (17)0.0157 (4)
N10.7488 (2)0.4397 (2)0.50568 (16)0.0132 (3)
C41.0254 (3)0.2704 (2)0.14462 (18)0.0132 (4)
C70.7588 (3)0.5783 (2)0.53842 (19)0.0140 (4)
H70.83540.64430.48330.017*
C90.6424 (3)0.7819 (2)0.6999 (2)0.0159 (4)
H90.71150.85280.64570.019*
C51.0244 (3)0.4260 (2)0.1664 (2)0.0163 (4)
H51.08430.49040.10210.020*
C30.9352 (3)0.1728 (2)0.2394 (2)0.0152 (4)
H30.93520.06960.22360.018*
C10.8450 (3)0.3866 (2)0.38228 (19)0.0129 (4)
C120.4418 (3)0.5666 (3)0.8544 (2)0.0184 (4)
H120.37390.49400.90730.022*
C80.6478 (3)0.6307 (2)0.66368 (19)0.0134 (4)
C60.9332 (3)0.4841 (2)0.2848 (2)0.0157 (4)
H60.93070.58780.29930.019*
C20.8443 (3)0.2307 (2)0.35850 (19)0.0152 (4)
H20.78330.16600.42220.018*
C110.4295 (3)0.7156 (3)0.8972 (2)0.0201 (5)
H110.35430.74160.97700.024*
C100.5314 (3)0.8245 (3)0.8187 (2)0.0184 (4)
H100.52540.92450.84530.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01789 (8)0.01469 (8)0.01293 (7)0.00300 (5)0.00197 (5)0.00125 (5)
Br10.01511 (11)0.01407 (11)0.01579 (10)0.00331 (8)0.00439 (8)0.00009 (8)
Zn10.01469 (12)0.01014 (12)0.01407 (12)0.00238 (9)0.00313 (9)0.00119 (9)
Br20.02248 (12)0.01486 (11)0.03382 (13)0.00357 (9)0.01568 (10)0.00575 (9)
N20.0154 (9)0.0155 (9)0.0167 (9)0.0014 (7)0.0055 (7)0.0001 (7)
N10.0125 (8)0.0125 (9)0.0135 (8)0.0003 (7)0.0029 (7)0.0015 (7)
C40.0114 (9)0.0157 (10)0.0118 (9)0.0004 (8)0.0026 (8)0.0015 (7)
C70.0140 (10)0.0131 (10)0.0152 (10)0.0016 (8)0.0049 (8)0.0035 (8)
C90.0178 (11)0.0132 (10)0.0189 (10)0.0033 (8)0.0089 (8)0.0024 (8)
C50.0173 (11)0.0139 (10)0.0156 (10)0.0023 (8)0.0020 (8)0.0032 (8)
C30.0188 (11)0.0088 (10)0.0175 (10)0.0019 (8)0.0049 (8)0.0009 (8)
C10.0121 (10)0.0126 (10)0.0140 (9)0.0013 (8)0.0038 (8)0.0002 (7)
C120.0175 (11)0.0178 (11)0.0174 (10)0.0040 (9)0.0017 (8)0.0009 (8)
C80.0137 (10)0.0125 (10)0.0157 (10)0.0000 (8)0.0072 (8)0.0006 (8)
C60.0179 (11)0.0098 (10)0.0170 (10)0.0013 (8)0.0022 (8)0.0017 (8)
C20.0166 (10)0.0141 (10)0.0132 (9)0.0027 (8)0.0021 (8)0.0029 (8)
C110.0180 (11)0.0219 (12)0.0187 (11)0.0007 (9)0.0030 (9)0.0040 (9)
C100.0205 (11)0.0134 (10)0.0229 (11)0.0004 (9)0.0088 (9)0.0033 (8)
Geometric parameters (Å, º) top
Zn1—Br12.3422 (7)C9—H90.9300
Zn1—Br22.3565 (7)C5—C61.391 (3)
Zn1—N12.0985 (19)C5—H50.9300
Zn1—N22.076 (2)C3—C21.396 (3)
I1—C42.112 (2)C3—H30.9300
N2—C121.338 (3)C1—C61.404 (3)
N2—C81.360 (3)C1—C21.405 (3)
N1—C71.294 (3)C12—C111.395 (3)
N1—C11.430 (3)C12—H120.9300
C4—C31.389 (3)C6—H60.9300
C4—C51.398 (3)C2—H20.9300
C7—C81.471 (3)C11—C101.391 (3)
C7—H70.9300C11—H110.9300
C9—C101.391 (3)C10—H100.9300
C9—C81.395 (3)
N2—Zn1—N180.87 (8)C4—C3—C2119.6 (2)
N2—Zn1—Br1122.39 (6)C4—C3—H3120.2
N1—Zn1—Br1117.40 (5)C2—C3—H3120.2
N2—Zn1—Br2109.60 (6)C6—C1—C2119.60 (19)
N1—Zn1—Br2109.69 (5)C6—C1—N1122.62 (19)
Br1—Zn1—Br2112.81 (2)C2—C1—N1117.74 (18)
C12—N2—C8118.44 (19)N2—C12—C11122.6 (2)
C12—N2—Zn1130.10 (16)N2—C12—H12118.7
C8—N2—Zn1111.26 (14)C11—C12—H12118.7
C7—N1—C1121.34 (18)N2—C8—C9122.2 (2)
C7—N1—Zn1111.01 (14)N2—C8—C7116.11 (19)
C1—N1—Zn1127.26 (14)C9—C8—C7121.6 (2)
C3—C4—C5120.86 (19)C5—C6—C1120.1 (2)
C3—C4—I1121.24 (16)C5—C6—H6119.9
C5—C4—I1117.88 (16)C1—C6—H6119.9
N1—C7—C8119.40 (19)C3—C2—C1120.1 (2)
N1—C7—H7120.3C3—C2—H2119.9
C8—C7—H7120.3C1—C2—H2119.9
C10—C9—C8118.7 (2)C10—C11—C12118.9 (2)
C10—C9—H9120.6C10—C11—H11120.5
C8—C9—H9120.6C12—C11—H11120.5
C6—C5—C4119.7 (2)C11—C10—C9119.1 (2)
C6—C5—H5120.1C11—C10—H10120.5
C4—C5—H5120.1C9—C10—H10120.5
N1—Zn1—N2—C12176.7 (2)Zn1—N1—C1—C20.4 (3)
Br1—Zn1—N2—C1260.0 (2)C8—N2—C12—C110.6 (3)
Br2—Zn1—N2—C1275.5 (2)Zn1—N2—C12—C11174.89 (17)
N1—Zn1—N2—C88.61 (14)C12—N2—C8—C90.6 (3)
Br1—Zn1—N2—C8125.35 (13)Zn1—N2—C8—C9175.99 (16)
Br2—Zn1—N2—C899.15 (14)C12—N2—C8—C7178.84 (19)
N2—Zn1—N1—C710.45 (15)Zn1—N2—C8—C75.8 (2)
Br1—Zn1—N1—C7132.31 (14)C10—C9—C8—N20.4 (3)
Br2—Zn1—N1—C797.20 (15)C10—C9—C8—C7178.5 (2)
N2—Zn1—N1—C1176.65 (18)N1—C7—C8—N23.5 (3)
Br1—Zn1—N1—C154.80 (18)N1—C7—C8—C9174.7 (2)
Br2—Zn1—N1—C175.70 (17)C4—C5—C6—C11.0 (3)
C1—N1—C7—C8175.94 (18)C2—C1—C6—C52.1 (3)
Zn1—N1—C7—C810.7 (2)N1—C1—C6—C5179.8 (2)
C3—C4—C5—C60.6 (3)C4—C3—C2—C10.3 (3)
I1—C4—C5—C6179.06 (16)C6—C1—C2—C31.8 (3)
C5—C4—C3—C20.9 (3)N1—C1—C2—C3179.57 (19)
I1—C4—C3—C2179.36 (16)N2—C12—C11—C100.3 (4)
C7—N1—C1—C69.6 (3)C12—C11—C10—C90.1 (3)
Zn1—N1—C1—C6178.16 (16)C8—C9—C10—C110.1 (3)
C7—N1—C1—C2172.7 (2)

Experimental details

Crystal data
Chemical formula[ZnBr2(C12H9IN2)]
Mr533.30
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)7.750 (2), 8.831 (2), 11.270 (3)
α, β, γ (°)89.44 (4), 71.66 (3), 87.81 (4)
V3)731.5 (3)
Z2
Radiation typeMo Kα
µ (mm1)9.23
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerBruker SMART APEXII CCD area-detector
Absorption correctionMulti-scan
(APEX2; Bruker, 2005)
Tmin, Tmax0.047, 0.160
No. of measured, independent and
observed [I > 2σ(I)] reflections
13887, 3520, 3278
Rint0.026
(sin θ/λ)max1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.017, 0.045, 1.00
No. of reflections3520
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.85, 1.02

Computer programs: APEX2 (Bruker, 2005), SHELXTL (Sheldrick, 1998).

Selected geometric parameters (Å, º) top
Zn1—Br12.3422 (7)Zn1—N12.0985 (19)
Zn1—Br22.3565 (7)Zn1—N22.076 (2)
N2—Zn1—N180.87 (8)N2—Zn1—Br2109.60 (6)
N2—Zn1—Br1122.39 (6)N1—Zn1—Br2109.69 (5)
N1—Zn1—Br1117.40 (5)Br1—Zn1—Br2112.81 (2)
 

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