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Acta Cryst. (2011). E67, m628    [ doi:10.1107/S1600536811014656 ]

Diiodido{2-(morpholin-4-yl)-N-[1-(2-pyridyl)ethylidene]ethanamine-[kappa]3N,N',N''}zinc

N. Suleiman Gwaram, H. Khaledi and H. Mohd Ali

Abstract top

In the title compound, [ZnI2(C13H19N3O)], the ZnII ion is five-coordinated in a distorted square-pyramidal geometry, in which the basal plane is defined by three N atoms from the Schiff base ligand and one iodide ion. A second iodide ligand, situated in the apical position, completes the coordination geometry. In the crystal structure, C-H...O hydrogen bonds link a pair of molecules around an inversion centre into a dimer.

Comment top

The title compound (Fig. 1) was obtained via the complexation of ZnII ion with the in situ prepared Schiff base, 2-morpholino-N-[1-(2-pyridyl)ethylidene]ethanamine, and two iodide ions. Similar to what was observed in an analogous ZnCl2 complex (Ikmal Hisham et al., 2011), the Schiff base acts as an N,N',N''-tridentate chelate ligand, along with two halide ligands, make a distorted square-pyramidal geometry around the metal ion (τ = 0.24, Addison et al., 1984). The Zn—I and Zn—N interatomic distances (Table 1) are comparable to the values reported for similar structures (Drew & Hollis, 1978; Yousefi, 2010). In the crystal, a pair of the molecules, related by a symmetry operation -x + 1, -y + 2, -z + 2, are linked through C—H···O hydrogen bonds into a centrosymmetric dimer (Table 2).

Related literature top

For the structure of an analogous ZnCl2 complex, see: Ikmal Hisham et al. (2011). For square-pyramidal ZnI2 complexes with N,N',N''-tridentate ligands, see: Drew & Hollis (1978); Yousefi (2010). For a description of the geometry of complexes with five-coordinated metal ions, see: Addison et al. (1984).

Experimental top

A mixture of 2-acetylpyridine (0.20 g, 1.65 mmol) and 4-(2-aminoethyl)morpholine (0.21 g, 1.65 mmol) in ethanol (20 ml) was refluxed for 2 h, followed by addition of a solution of zinc(II) acetate dihydrate (0.36 g, 1.65 mmol) and potassium iodide (0.54 g, 3.3 mmol) in a minimum amount of water. The resulting solution was refluxed for 30 min and then left at room temperature. Brown crystals of the title complex were obtained in a few days.

Refinement top

H atoms were placed at calculated positions and refined as riding atoms, with C—H = 0.95 (aryl), 0.98 (methyl) and 0.99 (methylene) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C).

Computing details top

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: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Diiodido{2-(morpholin-4-yl)-N-[1-(2-pyridyl)ethylidene]ethanamine- κ3N,N',N''}zinc top
Crystal data top
[ZnI2(C13H19N3O)]Z = 2
Mr = 552.48F(000) = 524
Triclinic, P1Dx = 2.260 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.8874 (3) ÅCell parameters from 6030 reflections
b = 10.3117 (4) Åθ = 2.3–30.4°
c = 10.3643 (4) ŵ = 5.31 mm−1
α = 68.8810 (18)°T = 100 K
β = 81.959 (2)°Block, brown
γ = 66.3990 (17)°0.17 × 0.13 × 0.09 mm
V = 811.91 (6) Å3
Data collection top
Bruker APEXII CCD
diffractometer		3517 independent reflections
Radiation source: fine-focus sealed tube3260 reflections with I > 2σ(I)
graphiteRint = 0.013
φ and ω scansθmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.465, Tmax = 0.646k = −13→13
7292 measured reflectionsl = −13→13
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)] = 0.018Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.045H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0197P)2 + 1.3278P]
where P = (Fo2 + 2Fc2)/3
3517 reflections(Δ/σ)max = 0.002
182 parametersΔρmax = 0.85 e Å−3
0 restraintsΔρmin = −1.23 e Å−3
Crystal data top
[ZnI2(C13H19N3O)]γ = 66.3990 (17)°
Mr = 552.48V = 811.91 (6) Å3
Triclinic, P1Z = 2
a = 8.8874 (3) ÅMo Kα radiation
b = 10.3117 (4) ŵ = 5.31 mm−1
c = 10.3643 (4) ÅT = 100 K
α = 68.8810 (18)°0.17 × 0.13 × 0.09 mm
β = 81.959 (2)°
Data collection top
Bruker APEXII CCD
diffractometer		3517 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3260 reflections with I > 2σ(I)
Tmin = 0.465, Tmax = 0.646Rint = 0.013
7292 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.018H-atom parameters constrained
wR(F2) = 0.045Δρmax = 0.85 e Å−3
S = 1.05Δρmin = −1.23 e Å−3
3517 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.77476 (4)0.81170 (3)0.66161 (3)0.01267 (7)
I10.64389 (2)1.103488 (18)0.584395 (17)0.01508 (5)
I21.05998 (2)0.694938 (19)0.791314 (17)0.01566 (5)
O10.3717 (2)0.8562 (2)1.0506 (2)0.0212 (4)
N10.8699 (3)0.8016 (2)0.4558 (2)0.0135 (4)
N20.7235 (3)0.6403 (2)0.6380 (2)0.0137 (4)
N30.6122 (3)0.7619 (2)0.8469 (2)0.0137 (4)
C10.9527 (3)0.8810 (3)0.3702 (3)0.0161 (5)
H10.96970.95370.39590.019*
C21.0153 (3)0.8615 (3)0.2446 (3)0.0181 (5)
H21.07670.91760.18680.022*
C30.9859 (3)0.7587 (3)0.2062 (3)0.0190 (6)
H31.02390.74550.11970.023*
C40.9002 (3)0.6744 (3)0.2951 (3)0.0165 (5)
H40.87970.60240.27090.020*
C50.8456 (3)0.6981 (3)0.4199 (3)0.0145 (5)
C60.7574 (3)0.6108 (3)0.5253 (3)0.0139 (5)
C70.7137 (3)0.5006 (3)0.4920 (3)0.0181 (5)
H7A0.67320.44120.57540.027*
H7B0.81120.43360.45820.027*
H7C0.62800.55470.42040.027*
C80.6366 (3)0.5663 (3)0.7513 (3)0.0161 (5)
H8A0.68370.45660.76930.019*
H8B0.51890.60520.72750.019*
C90.6557 (3)0.5993 (3)0.8785 (3)0.0150 (5)
H9A0.58390.56430.95310.018*
H9B0.77070.54350.91190.018*
C100.4339 (3)0.8512 (3)0.8159 (3)0.0157 (5)
H10A0.40080.82540.74400.019*
H10B0.41520.95940.77820.019*
C110.3273 (3)0.8231 (3)0.9429 (3)0.0177 (5)
H11A0.21070.88640.91740.021*
H11B0.33910.71660.97660.021*
C120.5400 (3)0.7684 (3)1.0885 (3)0.0188 (6)
H12A0.55610.66081.12760.023*
H12B0.56900.79601.16100.023*
C130.6531 (3)0.7918 (3)0.9652 (3)0.0168 (5)
H13A0.64660.89670.93380.020*
H13B0.76760.72470.99500.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01377 (14)0.01207 (14)0.01168 (14)−0.00432 (11)0.00086 (11)−0.00440 (11)
I10.01607 (9)0.01218 (8)0.01448 (9)−0.00349 (6)0.00078 (6)−0.00401 (6)
I20.01406 (9)0.01676 (9)0.01511 (9)−0.00421 (7)−0.00121 (6)−0.00553 (7)
O10.0184 (10)0.0264 (11)0.0200 (10)−0.0062 (8)0.0039 (8)−0.0130 (9)
N10.0131 (10)0.0134 (10)0.0120 (10)−0.0034 (8)0.0003 (8)−0.0039 (8)
N20.0130 (10)0.0110 (10)0.0147 (11)−0.0028 (8)−0.0011 (8)−0.0033 (8)
N30.0150 (11)0.0130 (10)0.0116 (10)−0.0047 (9)0.0001 (8)−0.0032 (8)
C10.0148 (12)0.0163 (12)0.0164 (13)−0.0051 (10)−0.0007 (10)−0.0051 (10)
C20.0142 (12)0.0194 (13)0.0178 (13)−0.0053 (11)0.0010 (10)−0.0047 (11)
C30.0171 (13)0.0214 (14)0.0138 (13)−0.0024 (11)0.0017 (10)−0.0067 (11)
C40.0153 (13)0.0178 (13)0.0160 (13)−0.0034 (10)−0.0007 (10)−0.0084 (11)
C50.0108 (12)0.0140 (12)0.0160 (13)−0.0014 (10)−0.0011 (9)−0.0053 (10)
C60.0116 (12)0.0123 (12)0.0159 (13)−0.0012 (10)−0.0012 (9)−0.0057 (10)
C70.0187 (13)0.0189 (13)0.0185 (14)−0.0070 (11)0.0010 (10)−0.0085 (11)
C80.0176 (13)0.0155 (12)0.0165 (13)−0.0077 (10)0.0038 (10)−0.0064 (10)
C90.0167 (13)0.0123 (12)0.0135 (13)−0.0048 (10)0.0009 (10)−0.0028 (10)
C100.0145 (12)0.0169 (12)0.0148 (13)−0.0042 (10)0.0003 (10)−0.0061 (10)
C110.0151 (13)0.0192 (13)0.0186 (14)−0.0055 (11)0.0020 (10)−0.0079 (11)
C120.0183 (13)0.0256 (14)0.0123 (13)−0.0071 (11)0.0008 (10)−0.0076 (11)
C130.0181 (13)0.0197 (13)0.0124 (13)−0.0064 (11)0.0018 (10)−0.0067 (10)
Geometric parameters (Å, °) top
Zn1—N12.205 (2)C4—H40.9500
Zn1—N22.093 (2)C5—C61.495 (4)
Zn1—N32.269 (2)C6—C71.495 (4)
Zn1—I12.6018 (4)C7—H7A0.9800
Zn1—I22.6506 (4)C7—H7B0.9800
O1—C111.423 (3)C7—H7C0.9800
O1—C121.426 (3)C8—C91.521 (4)
N1—C11.332 (3)C8—H8A0.9900
N1—C51.349 (3)C8—H8B0.9900
N2—C61.277 (3)C9—H9A0.9900
N2—C81.459 (3)C9—H9B0.9900
N3—C91.479 (3)C10—C111.521 (4)
N3—C131.490 (3)C10—H10A0.9900
N3—C101.491 (3)C10—H10B0.9900
C1—C21.394 (4)C11—H11A0.9900
C1—H10.9500C11—H11B0.9900
C2—C31.380 (4)C12—C131.521 (4)
C2—H20.9500C12—H12A0.9900
C3—C41.394 (4)C12—H12B0.9900
C3—H30.9500C13—H13A0.9900
C4—C51.387 (4)C13—H13B0.9900
N2—Zn1—N174.71 (8)C6—C7—H7B109.5
N2—Zn1—N378.31 (8)H7A—C7—H7B109.5
N1—Zn1—N3151.54 (8)C6—C7—H7C109.5
N2—Zn1—I1137.01 (6)H7A—C7—H7C109.5
N1—Zn1—I195.53 (6)H7B—C7—H7C109.5
N3—Zn1—I198.03 (6)N2—C8—C9107.5 (2)
N2—Zn1—I2109.52 (6)N2—C8—H8A110.2
N1—Zn1—I298.21 (6)C9—C8—H8A110.2
N3—Zn1—I299.18 (6)N2—C8—H8B110.2
I1—Zn1—I2113.325 (12)C9—C8—H8B110.2
C11—O1—C12110.8 (2)H8A—C8—H8B108.5
C1—N1—C5118.9 (2)N3—C9—C8111.1 (2)
C1—N1—Zn1126.70 (18)N3—C9—H9A109.4
C5—N1—Zn1114.34 (17)C8—C9—H9A109.4
C6—N2—C8122.6 (2)N3—C9—H9B109.4
C6—N2—Zn1120.65 (18)C8—C9—H9B109.4
C8—N2—Zn1116.61 (16)H9A—C9—H9B108.0
C9—N3—C13111.1 (2)N3—C10—C11112.5 (2)
C9—N3—C10112.5 (2)N3—C10—H10A109.1
C13—N3—C10107.4 (2)C11—C10—H10A109.1
C9—N3—Zn1100.98 (15)N3—C10—H10B109.1
C13—N3—Zn1111.80 (16)C11—C10—H10B109.1
C10—N3—Zn1113.10 (15)H10A—C10—H10B107.8
N1—C1—C2122.6 (3)O1—C11—C10111.4 (2)
N1—C1—H1118.7O1—C11—H11A109.3
C2—C1—H1118.7C10—C11—H11A109.3
C3—C2—C1118.3 (3)O1—C11—H11B109.3
C3—C2—H2120.8C10—C11—H11B109.3
C1—C2—H2120.8H11A—C11—H11B108.0
C2—C3—C4119.6 (3)O1—C12—C13111.7 (2)
C2—C3—H3120.2O1—C12—H12A109.3
C4—C3—H3120.2C13—C12—H12A109.3
C5—C4—C3118.4 (3)O1—C12—H12B109.3
C5—C4—H4120.8C13—C12—H12B109.3
C3—C4—H4120.8H12A—C12—H12B107.9
N1—C5—C4122.1 (2)N3—C13—C12113.3 (2)
N1—C5—C6114.8 (2)N3—C13—H13A108.9
C4—C5—C6123.1 (2)C12—C13—H13A108.9
N2—C6—C5115.4 (2)N3—C13—H13B108.9
N2—C6—C7125.4 (2)C12—C13—H13B108.9
C5—C6—C7119.2 (2)H13A—C13—H13B107.7
C6—C7—H7A109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1i0.992.553.491 (3)159
Symmetry codes: (i) −x+1, −y+2, −z+2.
Table 1
Selected geometric parameters (Å) top
Zn1—N12.205 (2)Zn1—I12.6018 (4)
Zn1—N22.093 (2)Zn1—I22.6506 (4)
Zn1—N32.269 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1i0.992.553.491 (3)159
Symmetry codes: (i) −x+1, −y+2, −z+2.
Acknowledgements top

The authors thank the University of Malaya for funding this study (FRGS grant No. FP004/2010B).

references
References top

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