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

The Zn^II 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.

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

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S1. Comment

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 Cu^I, (Dehghanpour et al., 2007), Co^II, (Small et al., 2003) and Fe^II, (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

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

S2. Experimental

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%.

S3. Refinement

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

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.

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

Crystal data

[ZnBr2(C12H9IN2)]	Z = 2
Mr = 533.30	F(000) = 496
Triclinic, P1	Dx = 2.421 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.750 (2) Å	Cell parameters from 2531 reflections
b = 8.831 (2) Å	θ = 3–29°
c = 11.270 (3) Å	µ = 9.23 mm^−1
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) Å^3

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	3520 independent reflections
Radiation source: fine-focus sealed tube	3278 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 28.0°, θmin = 1.9°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −10→10
Tmin = 0.047, Tmax = 0.160	k = −11→11
13887 measured reflections	l = −14→14

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.045	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.026P)^2 + 0.2955P] where P = (Fo^2 + 2Fc^2)/3
3520 reflections	(Δ/σ)max = 0.029
163 parameters	Δρmax = 0.85 e Å^−3
0 restraints	Δρmin = −1.02 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	1.162788 (19)	0.189540 (15)	−0.037792 (12)	0.01576 (5)
Br1	0.37752 (3)	0.15813 (2)	0.634148 (19)	0.01502 (6)
Zn1	0.60460 (3)	0.31017 (3)	0.65953 (2)	0.01325 (6)
Br2	0.81041 (3)	0.17579 (3)	0.74107 (2)	0.02209 (6)
N2	0.5476 (3)	0.5242 (2)	0.74024 (17)	0.0157 (4)
N1	0.7488 (2)	0.4397 (2)	0.50568 (16)	0.0132 (3)
C4	1.0254 (3)	0.2704 (2)	0.14462 (18)	0.0132 (4)
C7	0.7588 (3)	0.5783 (2)	0.53842 (19)	0.0140 (4)
H7	0.8354	0.6443	0.4833	0.017*
C9	0.6424 (3)	0.7819 (2)	0.6999 (2)	0.0159 (4)
H9	0.7115	0.8528	0.6457	0.019*
C5	1.0244 (3)	0.4260 (2)	0.1664 (2)	0.0163 (4)
H5	1.0843	0.4904	0.1021	0.020*
C3	0.9352 (3)	0.1728 (2)	0.2394 (2)	0.0152 (4)
H3	0.9352	0.0696	0.2236	0.018*
C1	0.8450 (3)	0.3866 (2)	0.38228 (19)	0.0129 (4)
C12	0.4418 (3)	0.5666 (3)	0.8544 (2)	0.0184 (4)
H12	0.3739	0.4940	0.9073	0.022*
C8	0.6478 (3)	0.6307 (2)	0.66368 (19)	0.0134 (4)
C6	0.9332 (3)	0.4841 (2)	0.2848 (2)	0.0157 (4)
H6	0.9307	0.5878	0.2993	0.019*
C2	0.8443 (3)	0.2307 (2)	0.35850 (19)	0.0152 (4)
H2	0.7833	0.1660	0.4222	0.018*
C11	0.4295 (3)	0.7156 (3)	0.8972 (2)	0.0201 (5)
H11	0.3543	0.7416	0.9770	0.024*
C10	0.5314 (3)	0.8245 (3)	0.8187 (2)	0.0184 (4)
H10	0.5254	0.9245	0.8453	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.01789 (8)	0.01469 (8)	0.01293 (7)	−0.00300 (5)	−0.00197 (5)	−0.00125 (5)
Br1	0.01511 (11)	0.01407 (11)	0.01579 (10)	−0.00331 (8)	−0.00439 (8)	−0.00009 (8)
Zn1	0.01469 (12)	0.01014 (12)	0.01407 (12)	−0.00238 (9)	−0.00313 (9)	0.00119 (9)
Br2	0.02248 (12)	0.01486 (11)	0.03382 (13)	−0.00357 (9)	−0.01568 (10)	0.00575 (9)
N2	0.0154 (9)	0.0155 (9)	0.0167 (9)	−0.0014 (7)	−0.0055 (7)	0.0001 (7)
N1	0.0125 (8)	0.0125 (9)	0.0135 (8)	0.0003 (7)	−0.0029 (7)	0.0015 (7)
C4	0.0114 (9)	0.0157 (10)	0.0118 (9)	−0.0004 (8)	−0.0026 (8)	−0.0015 (7)
C7	0.0140 (10)	0.0131 (10)	0.0152 (10)	−0.0016 (8)	−0.0049 (8)	0.0035 (8)
C9	0.0178 (11)	0.0132 (10)	0.0189 (10)	−0.0033 (8)	−0.0089 (8)	0.0024 (8)
C5	0.0173 (11)	0.0139 (10)	0.0156 (10)	−0.0023 (8)	−0.0020 (8)	0.0032 (8)
C3	0.0188 (11)	0.0088 (10)	0.0175 (10)	−0.0019 (8)	−0.0049 (8)	−0.0009 (8)
C1	0.0121 (10)	0.0126 (10)	0.0140 (9)	−0.0013 (8)	−0.0038 (8)	0.0002 (7)
C12	0.0175 (11)	0.0178 (11)	0.0174 (10)	−0.0040 (9)	−0.0017 (8)	−0.0009 (8)
C8	0.0137 (10)	0.0125 (10)	0.0157 (10)	0.0000 (8)	−0.0072 (8)	0.0006 (8)
C6	0.0179 (11)	0.0098 (10)	0.0170 (10)	−0.0013 (8)	−0.0022 (8)	0.0017 (8)
C2	0.0166 (10)	0.0141 (10)	0.0132 (9)	−0.0027 (8)	−0.0021 (8)	0.0029 (8)
C11	0.0180 (11)	0.0219 (12)	0.0187 (11)	−0.0007 (9)	−0.0030 (9)	−0.0040 (9)
C10	0.0205 (11)	0.0134 (10)	0.0229 (11)	0.0004 (9)	−0.0088 (9)	−0.0033 (8)

Geometric parameters (Å, º)

Zn1—Br1	2.3422 (7)	C9—H9	0.9300
Zn1—Br2	2.3565 (7)	C5—C6	1.391 (3)
Zn1—N1	2.0985 (19)	C5—H5	0.9300
Zn1—N2	2.076 (2)	C3—C2	1.396 (3)
I1—C4	2.112 (2)	C3—H3	0.9300
N2—C12	1.338 (3)	C1—C6	1.404 (3)
N2—C8	1.360 (3)	C1—C2	1.405 (3)
N1—C7	1.294 (3)	C12—C11	1.395 (3)
N1—C1	1.430 (3)	C12—H12	0.9300
C4—C3	1.389 (3)	C6—H6	0.9300
C4—C5	1.398 (3)	C2—H2	0.9300
C7—C8	1.471 (3)	C11—C10	1.391 (3)
C7—H7	0.9300	C11—H11	0.9300
C9—C10	1.391 (3)	C10—H10	0.9300
C9—C8	1.395 (3)
N2—Zn1—N1	80.87 (8)	C4—C3—C2	119.6 (2)
N2—Zn1—Br1	122.39 (6)	C4—C3—H3	120.2
N1—Zn1—Br1	117.40 (5)	C2—C3—H3	120.2
N2—Zn1—Br2	109.60 (6)	C6—C1—C2	119.60 (19)
N1—Zn1—Br2	109.69 (5)	C6—C1—N1	122.62 (19)
Br1—Zn1—Br2	112.81 (2)	C2—C1—N1	117.74 (18)
C12—N2—C8	118.44 (19)	N2—C12—C11	122.6 (2)
C12—N2—Zn1	130.10 (16)	N2—C12—H12	118.7
C8—N2—Zn1	111.26 (14)	C11—C12—H12	118.7
C7—N1—C1	121.34 (18)	N2—C8—C9	122.2 (2)
C7—N1—Zn1	111.01 (14)	N2—C8—C7	116.11 (19)
C1—N1—Zn1	127.26 (14)	C9—C8—C7	121.6 (2)
C3—C4—C5	120.86 (19)	C5—C6—C1	120.1 (2)
C3—C4—I1	121.24 (16)	C5—C6—H6	119.9
C5—C4—I1	117.88 (16)	C1—C6—H6	119.9
N1—C7—C8	119.40 (19)	C3—C2—C1	120.1 (2)
N1—C7—H7	120.3	C3—C2—H2	119.9
C8—C7—H7	120.3	C1—C2—H2	119.9
C10—C9—C8	118.7 (2)	C10—C11—C12	118.9 (2)
C10—C9—H9	120.6	C10—C11—H11	120.5
C8—C9—H9	120.6	C12—C11—H11	120.5
C6—C5—C4	119.7 (2)	C11—C10—C9	119.1 (2)
C6—C5—H5	120.1	C11—C10—H10	120.5
C4—C5—H5	120.1	C9—C10—H10	120.5
N1—Zn1—N2—C12	176.7 (2)	Zn1—N1—C1—C2	0.4 (3)
Br1—Zn1—N2—C12	60.0 (2)	C8—N2—C12—C11	0.6 (3)
Br2—Zn1—N2—C12	−75.5 (2)	Zn1—N2—C12—C11	174.89 (17)
N1—Zn1—N2—C8	−8.61 (14)	C12—N2—C8—C9	−0.6 (3)
Br1—Zn1—N2—C8	−125.35 (13)	Zn1—N2—C8—C9	−175.99 (16)
Br2—Zn1—N2—C8	99.15 (14)	C12—N2—C8—C7	−178.84 (19)
N2—Zn1—N1—C7	10.45 (15)	Zn1—N2—C8—C7	5.8 (2)
Br1—Zn1—N1—C7	132.31 (14)	C10—C9—C8—N2	0.4 (3)
Br2—Zn1—N1—C7	−97.20 (15)	C10—C9—C8—C7	178.5 (2)
N2—Zn1—N1—C1	−176.65 (18)	N1—C7—C8—N2	3.5 (3)
Br1—Zn1—N1—C1	−54.80 (18)	N1—C7—C8—C9	−174.7 (2)
Br2—Zn1—N1—C1	75.70 (17)	C4—C5—C6—C1	1.0 (3)
C1—N1—C7—C8	175.94 (18)	C2—C1—C6—C5	−2.1 (3)
Zn1—N1—C7—C8	−10.7 (2)	N1—C1—C6—C5	−179.8 (2)
C3—C4—C5—C6	0.6 (3)	C4—C3—C2—C1	−0.3 (3)
I1—C4—C5—C6	179.06 (16)	C6—C1—C2—C3	1.8 (3)
C5—C4—C3—C2	−0.9 (3)	N1—C1—C2—C3	179.57 (19)
I1—C4—C3—C2	−179.36 (16)	N2—C12—C11—C10	−0.3 (4)
C7—N1—C1—C6	−9.6 (3)	C12—C11—C10—C9	0.1 (3)
Zn1—N1—C1—C6	178.16 (16)	C8—C9—C10—C11	−0.1 (3)
C7—N1—C1—C2	172.7 (2)