Dichlorido{2-[(4-iodo­phen­yl)imino­methyl]pyridine-κ²N,N′}zinc(II)

In the title complex, [ZnCl₂(C₁₂H₉IN₂)], the Zn^II atom has a distorted tetra­hedral coordination. The organic ligand is bidentate, coordinating the Zn^II atom via the two N atoms.

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

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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

The H(C) atom positions were calculated and were refined in isotropic approximation in riding model with the U_iso(H) parameters equal to 1.2 U_eq(Ci) where U_eq(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.

Computing details

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

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)

Crystal data

[ZnCl2(C12H9IN2)]	Z = 2
Mr = 444.38	F(000) = 424
Triclinic, P1	Dx = 2.201 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5680 (6) Å	Cell parameters from 3201 reflections
b = 8.5363 (6) Å	θ = 2.4–31.9°
c = 10.8772 (8) Å	µ = 4.51 mm^−1
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) Å^3

Data collection

Bruker APEXII CCD area-detector diffractometer	3470 independent reflections
Radiation source: fine-focus sealed tube	2895 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 29.6°, θmin = 10.0°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −10→10
Tmin = 0.345, Tmax = 0.551	k = −11→11
7690 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0347P)^2 + 10.4724P] where P = (Fo^2 + 2Fc^2)/3
3470 reflections	(Δ/σ)max < 0.001
152 parameters	Δρmax = 1.20 e Å^−3
0 restraints	Δρmin = −1.12 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.34217 (8)	0.81139 (7)	1.53276 (6)	0.04453 (19)
Zn1	0.89413 (9)	0.69620 (7)	0.84072 (6)	0.01995 (17)
Cl1	1.1228 (2)	0.84010 (16)	0.85933 (14)	0.0245 (3)
Cl2	0.6921 (2)	0.82264 (17)	0.76324 (17)	0.0303 (3)
N1	0.7512 (7)	0.5596 (6)	0.9973 (5)	0.0195 (9)
N2	0.9510 (7)	0.4763 (6)	0.7586 (5)	0.0220 (9)
C1	1.0571 (8)	0.4354 (7)	0.6413 (6)	0.0240 (11)
H1A	1.1226	0.5129	0.5872	0.029*
C2	1.0743 (9)	0.2816 (7)	0.5963 (6)	0.0260 (11)
H2A	1.1506	0.2572	0.5141	0.031*
C3	0.9757 (9)	0.1648 (7)	0.6761 (6)	0.0253 (11)
H3A	0.9841	0.0612	0.6484	0.030*
C4	0.8634 (9)	0.2074 (7)	0.7993 (6)	0.0242 (11)
H4A	0.7959	0.1328	0.8557	0.029*
C5	0.8554 (8)	0.3655 (7)	0.8353 (6)	0.0216 (10)
C6	0.7421 (8)	0.4166 (7)	0.9652 (6)	0.0217 (10)
H6A	0.6663	0.3468	1.0220	0.026*
C7	0.6558 (5)	0.6143 (4)	1.1248 (3)	0.0192 (10)
C8	0.5653 (5)	0.5138 (3)	1.2234 (3)	0.0230 (11)
H8A	0.5674	0.4065	1.2084	0.028*
C9	0.4715 (5)	0.5737 (4)	1.3445 (3)	0.0226 (10)
H9A	0.4109	0.5065	1.4105	0.027*
C10	0.4684 (5)	0.7341 (4)	1.3669 (3)	0.0214 (10)
C11	0.5589 (6)	0.8346 (3)	1.2683 (3)	0.0234 (11)
H11A	0.5568	0.9419	1.2833	0.028*
C12	0.6527 (5)	0.7746 (4)	1.1472 (3)	0.0225 (10)
H12A	0.7133	0.8418	1.0812	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0478 (3)	0.0436 (3)	0.0397 (3)	−0.0029 (2)	−0.0092 (2)	−0.0029 (2)
Zn1	0.0212 (3)	0.0172 (3)	0.0206 (3)	−0.0020 (2)	−0.0048 (2)	0.0012 (2)
Cl1	0.0243 (6)	0.0225 (6)	0.0270 (6)	−0.0045 (5)	−0.0079 (5)	0.0019 (5)
Cl2	0.0307 (7)	0.0220 (6)	0.0428 (8)	−0.0022 (5)	−0.0178 (6)	0.0054 (6)
N1	0.019 (2)	0.020 (2)	0.020 (2)	−0.0002 (16)	−0.0063 (17)	0.0007 (16)
N2	0.018 (2)	0.023 (2)	0.023 (2)	−0.0009 (17)	−0.0039 (18)	−0.0010 (18)
C1	0.024 (3)	0.024 (3)	0.022 (3)	−0.002 (2)	−0.003 (2)	0.003 (2)
C2	0.026 (3)	0.026 (3)	0.023 (3)	−0.001 (2)	−0.004 (2)	−0.005 (2)
C3	0.029 (3)	0.021 (3)	0.026 (3)	0.002 (2)	−0.008 (2)	−0.003 (2)
C4	0.030 (3)	0.018 (2)	0.025 (3)	−0.003 (2)	−0.008 (2)	0.002 (2)
C5	0.022 (2)	0.021 (2)	0.023 (3)	0.0023 (19)	−0.007 (2)	−0.001 (2)
C6	0.019 (2)	0.022 (2)	0.024 (3)	−0.0007 (19)	−0.006 (2)	0.002 (2)
C7	0.018 (2)	0.020 (2)	0.018 (2)	0.0002 (18)	−0.0026 (18)	0.0013 (18)
C8	0.023 (3)	0.019 (2)	0.026 (3)	−0.001 (2)	−0.006 (2)	0.003 (2)
C9	0.024 (3)	0.018 (2)	0.024 (3)	−0.0022 (19)	−0.005 (2)	0.002 (2)
C10	0.020 (2)	0.025 (3)	0.018 (2)	0.001 (2)	−0.0032 (19)	−0.0024 (19)
C11	0.025 (3)	0.021 (2)	0.024 (3)	−0.003 (2)	−0.006 (2)	0.001 (2)
C12	0.024 (3)	0.019 (2)	0.023 (3)	−0.003 (2)	−0.004 (2)	0.0026 (19)

Geometric parameters (Å, º)

Zn1—N1	2.089 (5)	C4—C5	1.402 (8)
Zn1—N2	2.064 (5)	C4—H4A	0.9300
Zn1—Cl1	2.1992 (15)	C5—C6	1.480 (8)
Zn1—Cl2	2.2167 (17)	C6—H6A	0.9300
I1—C10	1.886 (3)	C7—C8	1.3900
N1—C6	1.279 (8)	C7—C12	1.3900
N1—C7	1.434 (5)	C8—C9	1.3900
N2—C5	1.331 (8)	C8—H8A	0.9300
N2—C1	1.332 (8)	C9—C10	1.3900
C1—C2	1.393 (9)	C9—H9A	0.9300
C1—H1A	0.9300	C10—C11	1.3900
C2—C3	1.392 (9)	C11—C12	1.3900
C2—H2A	0.9300	C11—H11A	0.9300
C3—C4	1.400 (9)	C12—H12A	0.9300
C3—H3A	0.9300
N1—Zn1—N2	80.22 (19)	N2—C5—C4	123.1 (5)
N2—Zn1—Cl1	119.49 (14)	N2—C5—C6	116.3 (5)
N1—Zn1—Cl1	118.63 (14)	C4—C5—C6	120.5 (5)
N2—Zn1—Cl2	110.03 (15)	N1—C6—C5	118.2 (5)
N1—Zn1—Cl2	109.22 (14)	N1—C6—H6A	120.9
Cl1—Zn1—Cl2	114.51 (6)	C5—C6—H6A	120.9
C6—N1—C7	121.1 (5)	C8—C7—C12	120.0
C6—N1—Zn1	112.0 (4)	C8—C7—N1	122.5 (3)
C7—N1—Zn1	126.6 (3)	C12—C7—N1	117.5 (3)
C5—N2—C1	118.4 (5)	C9—C8—C7	120.0
C5—N2—Zn1	112.1 (4)	C9—C8—H8A	120.0
C1—N2—Zn1	129.3 (4)	C7—C8—H8A	120.0
N2—C1—C2	122.8 (6)	C8—C9—C10	120.0
N2—C1—H1A	118.6	C8—C9—H9A	120.0
C2—C1—H1A	118.6	C10—C9—H9A	120.0
C3—C2—C1	119.1 (6)	C11—C10—C9	120.0
C3—C2—H2A	120.4	C11—C10—I1	121.07 (19)
C1—C2—H2A	120.4	C9—C10—I1	118.93 (19)
C2—C3—C4	118.2 (5)	C10—C11—C12	120.0
C2—C3—H3A	120.9	C10—C11—H11A	120.0
C4—C3—H3A	120.9	C12—C11—H11A	120.0
C3—C4—C5	118.2 (6)	C11—C12—C7	120.0
C3—C4—H4A	120.9	C11—C12—H12A	120.0
C5—C4—H4A	120.9	C7—C12—H12A	120.0
N2—Zn1—N1—C6	−9.7 (4)	C3—C4—C5—N2	−0.8 (9)
Cl1—Zn1—N1—C6	−128.1 (4)	C3—C4—C5—C6	−178.7 (6)
Cl2—Zn1—N1—C6	98.2 (4)	C7—N1—C6—C5	−175.3 (5)
N2—Zn1—N1—C7	176.1 (4)	Zn1—N1—C6—C5	10.1 (6)
Cl1—Zn1—N1—C7	57.8 (4)	N2—C5—C6—N1	−3.8 (8)
Cl2—Zn1—N1—C7	−75.9 (4)	C4—C5—C6—N1	174.3 (6)
N1—Zn1—N2—C5	7.7 (4)	C6—N1—C7—C8	6.8 (6)
Cl1—Zn1—N2—C5	125.1 (4)	Zn1—N1—C7—C8	−179.5 (2)
Cl2—Zn1—N2—C5	−99.4 (4)	C6—N1—C7—C12	−171.8 (4)
N1—Zn1—N2—C1	−176.8 (6)	Zn1—N1—C7—C12	1.9 (5)
Cl1—Zn1—N2—C1	−59.3 (6)	C12—C7—C8—C9	0.0
Cl2—Zn1—N2—C1	76.2 (5)	N1—C7—C8—C9	−178.6 (4)
C5—N2—C1—C2	−0.9 (9)	C7—C8—C9—C10	0.0
Zn1—N2—C1—C2	−176.2 (5)	C8—C9—C10—C11	0.0
N2—C1—C2—C3	0.6 (10)	C8—C9—C10—I1	−179.3 (3)
C1—C2—C3—C4	−0.3 (9)	C9—C10—C11—C12	0.0
C2—C3—C4—C5	0.4 (9)	I1—C10—C11—C12	179.3 (3)
C1—N2—C5—C4	1.0 (9)	C10—C11—C12—C7	0.0
Zn1—N2—C5—C4	177.1 (5)	C8—C7—C12—C11	0.0
C1—N2—C5—C6	179.1 (5)	N1—C7—C12—C11	178.6 (4)
Zn1—N2—C5—C6	−4.9 (6)