Download citation
Download citation
link to html
In the title complex, [ZnCl2(C12H9IN2)], the ZnII atom has a distorted tetra­hedral coordination. The organic ligand is bidentate, coordinating the ZnII atom via the two N atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051999/sj2381sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051999/sj2381Isup2.hkl
Contains datablock I

CCDC reference: 667237

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.061
  • wR factor = 0.144
  • Data-to-parameter ratio = 22.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.92
Author Response: the crystal is twinned and refined using TWIN/BASF (BASF 0.557)

Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for I1 - C10 .. 9.03 su
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 29.62 From the CIF: _diffrn_reflns_theta_full 29.62 From the CIF: _reflns_number_total 3470 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3778 Completeness (_total/calc) 91.85% PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.92 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT431_ALERT_2_C Short Inter HL..A Contact I1 .. Cl1 .. 3.45 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.922 Tmax scaled 0.508 Tmin scaled 0.318 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.93
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Metal complexes with diimines as ligands have played an important role in development of coordination chemistry (Yamada, 1999). Complexes of iminopyridines with late transition metals have recently found a renewal of interest (Small et al., 2003). The unexpected and recent discovery that such complexes, in particular iminopyridine iron(II) and cobalt (II) complexes, may act as active catalysts for olefin polymerization render them more attractive to chemists (Ittel et al., 2000; Britovsek et al., 1999). The title complex, (I), Fig. 1, was prepared by the reaction of ZnCl2 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 [80.22 (19)°] is much narrower than the ideal tetrahedral angle of 109.5°, whereas the N2—Zn1—Cl1 angle [119.49 (14)°] is much wider than the ideal angle in the tetrahedron. The Zn—Cl and Zn—N bond dimensions compare well with the values found in other tetrahedral diimine complexes of zinc chloride (Amirnasr et al., 2002).

Related literature top

For related literature, see: Amirnasr et al. (2002); Ittel et al. (2000); Yamada (1999).

For related literature, see: Britovsek et al. (1999); Small et al. (1998).

Experimental top

The title complex was prepared by the reaction of ZnCl2 with 4-iodo-phenyl)-pyridin-2-ylmethylene-amine (molar ratio 1:1) in acetonitrile at room temperature. The solution was then concentrated under vacuum, and diffusion of diethyl ether vapor into the concentrated solution gave colourless crystals of (I) in 78% yield. Calc. for C12H9Cl2IN2Zn: C 32.43, H 2.04, N 6.30%; found: C 32.42, H 2.05, N 6.33%.

Refinement top

The H(C) atom positions were calculated and were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci) where Ueq(Ci) are the equivalent thermal parameters of the atoms to which corresponding H atoms are bonded. There is a high positive residual density peak of 1.20 e Å-3 near the I1 center (distance 0.96%A) due to considerable absorption effects which could not be completely corrected.

Structure description top

Metal complexes with diimines as ligands have played an important role in development of coordination chemistry (Yamada, 1999). Complexes of iminopyridines with late transition metals have recently found a renewal of interest (Small et al., 2003). The unexpected and recent discovery that such complexes, in particular iminopyridine iron(II) and cobalt (II) complexes, may act as active catalysts for olefin polymerization render them more attractive to chemists (Ittel et al., 2000; Britovsek et al., 1999). The title complex, (I), Fig. 1, was prepared by the reaction of ZnCl2 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 [80.22 (19)°] is much narrower than the ideal tetrahedral angle of 109.5°, whereas the N2—Zn1—Cl1 angle [119.49 (14)°] is much wider than the ideal angle in the tetrahedron. The Zn—Cl and Zn—N bond dimensions compare well with the values found in other tetrahedral diimine complexes of zinc chloride (Amirnasr et al., 2002).

For related literature, see: Amirnasr et al. (2002); Ittel et al. (2000); Yamada (1999).

For related literature, see: Britovsek et al. (1999); 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.
Dichlorido{2-[(4-iodophenyl)iminomethyl]pyridine- κ2N,N'}zinc(II) top
Crystal data top
[ZnCl2(C12H9IN2)]Z = 2
Mr = 444.38F(000) = 424
Triclinic, P1Dx = 2.201 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5680 (6) ÅCell parameters from 3201 reflections
b = 8.5363 (6) Åθ = 2.4–31.9°
c = 10.8772 (8) ŵ = 4.51 mm1
α = 89.790 (2)°T = 296 K
β = 72.613 (2)°Plate, colourless
γ = 88.926 (2)°0.30 × 0.20 × 0.15 mm
V = 670.47 (9) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3470 independent reflections
Radiation source: fine-focus sealed tube2895 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
φ and ω scansθmax = 29.6°, θmin = 10.0°
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
h = 1010
Tmin = 0.345, Tmax = 0.551k = 1111
7690 measured reflectionsl = 1515
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)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0347P)2 + 10.4724P]
where P = (Fo2 + 2Fc2)/3
3470 reflections(Δ/σ)max < 0.001
152 parametersΔρmax = 1.20 e Å3
0 restraintsΔρmin = 1.12 e Å3
Crystal data top
[ZnCl2(C12H9IN2)]γ = 88.926 (2)°
Mr = 444.38V = 670.47 (9) Å3
Triclinic, P1Z = 2
a = 7.5680 (6) ÅMo Kα radiation
b = 8.5363 (6) ŵ = 4.51 mm1
c = 10.8772 (8) ÅT = 296 K
α = 89.790 (2)°0.30 × 0.20 × 0.15 mm
β = 72.613 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
3470 independent reflections
Absorption correction: multi-scan
(APEX2; Bruker, 2005)
2895 reflections with I > 2σ(I)
Tmin = 0.345, Tmax = 0.551Rint = 0.025
7690 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0347P)2 + 10.4724P]
where P = (Fo2 + 2Fc2)/3
3470 reflectionsΔρmax = 1.20 e Å3
152 parametersΔρmin = 1.12 e Å3
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
I10.34217 (8)0.81139 (7)1.53276 (6)0.04453 (19)
Zn10.89413 (9)0.69620 (7)0.84072 (6)0.01995 (17)
Cl11.1228 (2)0.84010 (16)0.85933 (14)0.0245 (3)
Cl20.6921 (2)0.82264 (17)0.76324 (17)0.0303 (3)
N10.7512 (7)0.5596 (6)0.9973 (5)0.0195 (9)
N20.9510 (7)0.4763 (6)0.7586 (5)0.0220 (9)
C11.0571 (8)0.4354 (7)0.6413 (6)0.0240 (11)
H1A1.12260.51290.58720.029*
C21.0743 (9)0.2816 (7)0.5963 (6)0.0260 (11)
H2A1.15060.25720.51410.031*
C30.9757 (9)0.1648 (7)0.6761 (6)0.0253 (11)
H3A0.98410.06120.64840.030*
C40.8634 (9)0.2074 (7)0.7993 (6)0.0242 (11)
H4A0.79590.13280.85570.029*
C50.8554 (8)0.3655 (7)0.8353 (6)0.0216 (10)
C60.7421 (8)0.4166 (7)0.9652 (6)0.0217 (10)
H6A0.66630.34681.02200.026*
C70.6558 (5)0.6143 (4)1.1248 (3)0.0192 (10)
C80.5653 (5)0.5138 (3)1.2234 (3)0.0230 (11)
H8A0.56740.40651.20840.028*
C90.4715 (5)0.5737 (4)1.3445 (3)0.0226 (10)
H9A0.41090.50651.41050.027*
C100.4684 (5)0.7341 (4)1.3669 (3)0.0214 (10)
C110.5589 (6)0.8346 (3)1.2683 (3)0.0234 (11)
H11A0.55680.94191.28330.028*
C120.6527 (5)0.7746 (4)1.1472 (3)0.0225 (10)
H12A0.71330.84181.08120.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0478 (3)0.0436 (3)0.0397 (3)0.0029 (2)0.0092 (2)0.0029 (2)
Zn10.0212 (3)0.0172 (3)0.0206 (3)0.0020 (2)0.0048 (2)0.0012 (2)
Cl10.0243 (6)0.0225 (6)0.0270 (6)0.0045 (5)0.0079 (5)0.0019 (5)
Cl20.0307 (7)0.0220 (6)0.0428 (8)0.0022 (5)0.0178 (6)0.0054 (6)
N10.019 (2)0.020 (2)0.020 (2)0.0002 (16)0.0063 (17)0.0007 (16)
N20.018 (2)0.023 (2)0.023 (2)0.0009 (17)0.0039 (18)0.0010 (18)
C10.024 (3)0.024 (3)0.022 (3)0.002 (2)0.003 (2)0.003 (2)
C20.026 (3)0.026 (3)0.023 (3)0.001 (2)0.004 (2)0.005 (2)
C30.029 (3)0.021 (3)0.026 (3)0.002 (2)0.008 (2)0.003 (2)
C40.030 (3)0.018 (2)0.025 (3)0.003 (2)0.008 (2)0.002 (2)
C50.022 (2)0.021 (2)0.023 (3)0.0023 (19)0.007 (2)0.001 (2)
C60.019 (2)0.022 (2)0.024 (3)0.0007 (19)0.006 (2)0.002 (2)
C70.018 (2)0.020 (2)0.018 (2)0.0002 (18)0.0026 (18)0.0013 (18)
C80.023 (3)0.019 (2)0.026 (3)0.001 (2)0.006 (2)0.003 (2)
C90.024 (3)0.018 (2)0.024 (3)0.0022 (19)0.005 (2)0.002 (2)
C100.020 (2)0.025 (3)0.018 (2)0.001 (2)0.0032 (19)0.0024 (19)
C110.025 (3)0.021 (2)0.024 (3)0.003 (2)0.006 (2)0.001 (2)
C120.024 (3)0.019 (2)0.023 (3)0.003 (2)0.004 (2)0.0026 (19)
Geometric parameters (Å, º) top
Zn1—N12.089 (5)C4—C51.402 (8)
Zn1—N22.064 (5)C4—H4A0.9300
Zn1—Cl12.1992 (15)C5—C61.480 (8)
Zn1—Cl22.2167 (17)C6—H6A0.9300
I1—C101.886 (3)C7—C81.3900
N1—C61.279 (8)C7—C121.3900
N1—C71.434 (5)C8—C91.3900
N2—C51.331 (8)C8—H8A0.9300
N2—C11.332 (8)C9—C101.3900
C1—C21.393 (9)C9—H9A0.9300
C1—H1A0.9300C10—C111.3900
C2—C31.392 (9)C11—C121.3900
C2—H2A0.9300C11—H11A0.9300
C3—C41.400 (9)C12—H12A0.9300
C3—H3A0.9300
N1—Zn1—N280.22 (19)N2—C5—C4123.1 (5)
N2—Zn1—Cl1119.49 (14)N2—C5—C6116.3 (5)
N1—Zn1—Cl1118.63 (14)C4—C5—C6120.5 (5)
N2—Zn1—Cl2110.03 (15)N1—C6—C5118.2 (5)
N1—Zn1—Cl2109.22 (14)N1—C6—H6A120.9
Cl1—Zn1—Cl2114.51 (6)C5—C6—H6A120.9
C6—N1—C7121.1 (5)C8—C7—C12120.0
C6—N1—Zn1112.0 (4)C8—C7—N1122.5 (3)
C7—N1—Zn1126.6 (3)C12—C7—N1117.5 (3)
C5—N2—C1118.4 (5)C9—C8—C7120.0
C5—N2—Zn1112.1 (4)C9—C8—H8A120.0
C1—N2—Zn1129.3 (4)C7—C8—H8A120.0
N2—C1—C2122.8 (6)C8—C9—C10120.0
N2—C1—H1A118.6C8—C9—H9A120.0
C2—C1—H1A118.6C10—C9—H9A120.0
C3—C2—C1119.1 (6)C11—C10—C9120.0
C3—C2—H2A120.4C11—C10—I1121.07 (19)
C1—C2—H2A120.4C9—C10—I1118.93 (19)
C2—C3—C4118.2 (5)C10—C11—C12120.0
C2—C3—H3A120.9C10—C11—H11A120.0
C4—C3—H3A120.9C12—C11—H11A120.0
C3—C4—C5118.2 (6)C11—C12—C7120.0
C3—C4—H4A120.9C11—C12—H12A120.0
C5—C4—H4A120.9C7—C12—H12A120.0
N2—Zn1—N1—C69.7 (4)C3—C4—C5—N20.8 (9)
Cl1—Zn1—N1—C6128.1 (4)C3—C4—C5—C6178.7 (6)
Cl2—Zn1—N1—C698.2 (4)C7—N1—C6—C5175.3 (5)
N2—Zn1—N1—C7176.1 (4)Zn1—N1—C6—C510.1 (6)
Cl1—Zn1—N1—C757.8 (4)N2—C5—C6—N13.8 (8)
Cl2—Zn1—N1—C775.9 (4)C4—C5—C6—N1174.3 (6)
N1—Zn1—N2—C57.7 (4)C6—N1—C7—C86.8 (6)
Cl1—Zn1—N2—C5125.1 (4)Zn1—N1—C7—C8179.5 (2)
Cl2—Zn1—N2—C599.4 (4)C6—N1—C7—C12171.8 (4)
N1—Zn1—N2—C1176.8 (6)Zn1—N1—C7—C121.9 (5)
Cl1—Zn1—N2—C159.3 (6)C12—C7—C8—C90.0
Cl2—Zn1—N2—C176.2 (5)N1—C7—C8—C9178.6 (4)
C5—N2—C1—C20.9 (9)C7—C8—C9—C100.0
Zn1—N2—C1—C2176.2 (5)C8—C9—C10—C110.0
N2—C1—C2—C30.6 (10)C8—C9—C10—I1179.3 (3)
C1—C2—C3—C40.3 (9)C9—C10—C11—C120.0
C2—C3—C4—C50.4 (9)I1—C10—C11—C12179.3 (3)
C1—N2—C5—C41.0 (9)C10—C11—C12—C70.0
Zn1—N2—C5—C4177.1 (5)C8—C7—C12—C110.0
C1—N2—C5—C6179.1 (5)N1—C7—C12—C11178.6 (4)
Zn1—N2—C5—C64.9 (6)

Experimental details

Crystal data
Chemical formula[ZnCl2(C12H9IN2)]
Mr444.38
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.5680 (6), 8.5363 (6), 10.8772 (8)
α, β, γ (°)89.790 (2), 72.613 (2), 88.926 (2)
V3)670.47 (9)
Z2
Radiation typeMo Kα
µ (mm1)4.51
Crystal size (mm)0.30 × 0.20 × 0.15
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(APEX2; Bruker, 2005)
Tmin, Tmax0.345, 0.551
No. of measured, independent and
observed [I > 2σ(I)] reflections
7690, 3470, 2895
Rint0.025
(sin θ/λ)max1)0.695
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.144, 0.97
No. of reflections3470
No. of parameters152
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0347P)2 + 10.4724P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.20, 1.12

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

Selected geometric parameters (Å, º) top
Zn1—N12.089 (5)Zn1—Cl12.1992 (15)
Zn1—N22.064 (5)Zn1—Cl22.2167 (17)
N1—Zn1—N280.22 (19)N2—Zn1—Cl2110.03 (15)
N2—Zn1—Cl1119.49 (14)N1—Zn1—Cl2109.22 (14)
N1—Zn1—Cl1118.63 (14)Cl1—Zn1—Cl2114.51 (6)
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds