Diiodido{2-(morpholin-4-yl)-N-[1-(2-pyrid­yl)ethyl­idene]ethanamine-κ3N,N′,N′′}zinc

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

doi:10.1107/S1600536811014656

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m628

doi:10.1107/S1600536811014656

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Diiodido{2-(morpholin-4-yl)-N-[1-(2-pyridyl)ethylidene]ethanamine-κ³N,N′,N′′}zinc

Nura Suleiman Gwaram,^a Hamid Khaledi ^a ^* and Hapipah Mohd Ali ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: khaledi@siswa.um.edu.my

(Received 14 April 2011; accepted 19 April 2011; online 22 April 2011)

In the title compound, [ZnI₂(C₁₃H₁₉N₃O)], the Zn^II 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.

Related literature

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

Crystal data

[ZnI₂(C₁₃H₁₉N₃O)]
M_r = 552.48
Triclinic, $[P \overline 1]$
a = 8.8874 (3) Å
b = 10.3117 (4) Å
c = 10.3643 (4) Å
α = 68.8810 (18)°
β = 81.959 (2)°
γ = 66.3990 (17)°
V = 811.91 (6) Å³
Z = 2
Mo Kα radiation
μ = 5.31 mm⁻¹
T = 100 K
0.17 × 0.13 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.465, T_max = 0.646
7292 measured reflections
3517 independent reflections
3260 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.045
S = 1.05
3517 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.85 e Å⁻³
Δρ_min = −1.23 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N1	2.205 (2)
Zn1—N2	2.093 (2)
Zn1—N3	2.269 (2)
Zn1—I1	2.6018 (4)
Zn1—I2	2.6506 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13A⋯O1ⁱ	0.99	2.55	3.491 (3)	159
Symmetry code: (i) -x+1, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014656/hy2422sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014656/hy2422Isup2.hkl

checkCIF report

Comment top

The title compound (Fig. 1) was obtained via the complexation of Zn^II 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.

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

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
M_r = 552.48	F(000) = 524
Triclinic, P1	D_x = 2.260 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8874 (3) Å	Cell parameters from 6030 reflections
b = 10.3117 (4) Å	θ = 2.3–30.4°
c = 10.3643 (4) Å	µ = 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 tube	3260 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.465, T_max = 0.646	k = −13→13
7292 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.045	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0197P)² + 1.3278P] where P = (F_o² + 2F_c²)/3
3517 reflections	(Δ/σ)_max = 0.002
182 parameters	Δρ_max = 0.85 e Å⁻³
0 restraints	Δρ_min = −1.23 e Å⁻³

Crystal data top

[ZnI₂(C₁₃H₁₉N₃O)]	γ = 66.3990 (17)°
M_r = 552.48	V = 811.91 (6) Å³
Triclinic, P1	Z = 2
a = 8.8874 (3) Å	Mo Kα radiation
b = 10.3117 (4) Å	µ = 5.31 mm⁻¹
c = 10.3643 (4) Å	T = 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)
T_min = 0.465, T_max = 0.646	R_int = 0.013
7292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.05	Δρ_max = 0.85 e Å⁻³
3517 reflections	Δρ_min = −1.23 e Å⁻³
182 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.77476 (4)	0.81170 (3)	0.66161 (3)	0.01267 (7)
I1	0.64389 (2)	1.103488 (18)	0.584395 (17)	0.01508 (5)
I2	1.05998 (2)	0.694938 (19)	0.791314 (17)	0.01566 (5)
O1	0.3717 (2)	0.8562 (2)	1.0506 (2)	0.0212 (4)
N1	0.8699 (3)	0.8016 (2)	0.4558 (2)	0.0135 (4)
N2	0.7235 (3)	0.6403 (2)	0.6380 (2)	0.0137 (4)
N3	0.6122 (3)	0.7619 (2)	0.8469 (2)	0.0137 (4)
C1	0.9527 (3)	0.8810 (3)	0.3702 (3)	0.0161 (5)
H1	0.9697	0.9537	0.3959	0.019*
C2	1.0153 (3)	0.8615 (3)	0.2446 (3)	0.0181 (5)
H2	1.0767	0.9176	0.1868	0.022*
C3	0.9859 (3)	0.7587 (3)	0.2062 (3)	0.0190 (6)
H3	1.0239	0.7455	0.1197	0.023*
C4	0.9002 (3)	0.6744 (3)	0.2951 (3)	0.0165 (5)
H4	0.8797	0.6024	0.2709	0.020*
C5	0.8456 (3)	0.6981 (3)	0.4199 (3)	0.0145 (5)
C6	0.7574 (3)	0.6108 (3)	0.5253 (3)	0.0139 (5)
C7	0.7137 (3)	0.5006 (3)	0.4920 (3)	0.0181 (5)
H7A	0.6732	0.4412	0.5754	0.027*
H7B	0.8112	0.4336	0.4582	0.027*
H7C	0.6280	0.5547	0.4204	0.027*
C8	0.6366 (3)	0.5663 (3)	0.7513 (3)	0.0161 (5)
H8A	0.6837	0.4566	0.7693	0.019*
H8B	0.5189	0.6052	0.7275	0.019*
C9	0.6557 (3)	0.5993 (3)	0.8785 (3)	0.0150 (5)
H9A	0.5839	0.5643	0.9531	0.018*
H9B	0.7707	0.5435	0.9119	0.018*
C10	0.4339 (3)	0.8512 (3)	0.8159 (3)	0.0157 (5)
H10A	0.4008	0.8254	0.7440	0.019*
H10B	0.4152	0.9594	0.7782	0.019*
C11	0.3273 (3)	0.8231 (3)	0.9429 (3)	0.0177 (5)
H11A	0.2107	0.8864	0.9174	0.021*
H11B	0.3391	0.7166	0.9766	0.021*
C12	0.5400 (3)	0.7684 (3)	1.0885 (3)	0.0188 (6)
H12A	0.5561	0.6608	1.1276	0.023*
H12B	0.5690	0.7960	1.1610	0.023*
C13	0.6531 (3)	0.7918 (3)	0.9652 (3)	0.0168 (5)
H13A	0.6466	0.8967	0.9338	0.020*
H13B	0.7676	0.7247	0.9950	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01377 (14)	0.01207 (14)	0.01168 (14)	−0.00432 (11)	0.00086 (11)	−0.00440 (11)
I1	0.01607 (9)	0.01218 (8)	0.01448 (9)	−0.00349 (6)	0.00078 (6)	−0.00401 (6)
I2	0.01406 (9)	0.01676 (9)	0.01511 (9)	−0.00421 (7)	−0.00121 (6)	−0.00553 (7)
O1	0.0184 (10)	0.0264 (11)	0.0200 (10)	−0.0062 (8)	0.0039 (8)	−0.0130 (9)
N1	0.0131 (10)	0.0134 (10)	0.0120 (10)	−0.0034 (8)	0.0003 (8)	−0.0039 (8)
N2	0.0130 (10)	0.0110 (10)	0.0147 (11)	−0.0028 (8)	−0.0011 (8)	−0.0033 (8)
N3	0.0150 (11)	0.0130 (10)	0.0116 (10)	−0.0047 (9)	0.0001 (8)	−0.0032 (8)
C1	0.0148 (12)	0.0163 (12)	0.0164 (13)	−0.0051 (10)	−0.0007 (10)	−0.0051 (10)
C2	0.0142 (12)	0.0194 (13)	0.0178 (13)	−0.0053 (11)	0.0010 (10)	−0.0047 (11)
C3	0.0171 (13)	0.0214 (14)	0.0138 (13)	−0.0024 (11)	0.0017 (10)	−0.0067 (11)
C4	0.0153 (13)	0.0178 (13)	0.0160 (13)	−0.0034 (10)	−0.0007 (10)	−0.0084 (11)
C5	0.0108 (12)	0.0140 (12)	0.0160 (13)	−0.0014 (10)	−0.0011 (9)	−0.0053 (10)
C6	0.0116 (12)	0.0123 (12)	0.0159 (13)	−0.0012 (10)	−0.0012 (9)	−0.0057 (10)
C7	0.0187 (13)	0.0189 (13)	0.0185 (14)	−0.0070 (11)	0.0010 (10)	−0.0085 (11)
C8	0.0176 (13)	0.0155 (12)	0.0165 (13)	−0.0077 (10)	0.0038 (10)	−0.0064 (10)
C9	0.0167 (13)	0.0123 (12)	0.0135 (13)	−0.0048 (10)	0.0009 (10)	−0.0028 (10)
C10	0.0145 (12)	0.0169 (12)	0.0148 (13)	−0.0042 (10)	0.0003 (10)	−0.0061 (10)
C11	0.0151 (13)	0.0192 (13)	0.0186 (14)	−0.0055 (11)	0.0020 (10)	−0.0079 (11)
C12	0.0183 (13)	0.0256 (14)	0.0123 (13)	−0.0071 (11)	0.0008 (10)	−0.0076 (11)
C13	0.0181 (13)	0.0197 (13)	0.0124 (13)	−0.0064 (11)	0.0018 (10)	−0.0067 (10)

Geometric parameters (Å, º) top

Zn1—N1	2.205 (2)	C4—H4	0.9500
Zn1—N2	2.093 (2)	C5—C6	1.495 (4)
Zn1—N3	2.269 (2)	C6—C7	1.495 (4)
Zn1—I1	2.6018 (4)	C7—H7A	0.9800
Zn1—I2	2.6506 (4)	C7—H7B	0.9800
O1—C11	1.423 (3)	C7—H7C	0.9800
O1—C12	1.426 (3)	C8—C9	1.521 (4)
N1—C1	1.332 (3)	C8—H8A	0.9900
N1—C5	1.349 (3)	C8—H8B	0.9900
N2—C6	1.277 (3)	C9—H9A	0.9900
N2—C8	1.459 (3)	C9—H9B	0.9900
N3—C9	1.479 (3)	C10—C11	1.521 (4)
N3—C13	1.490 (3)	C10—H10A	0.9900
N3—C10	1.491 (3)	C10—H10B	0.9900
C1—C2	1.394 (4)	C11—H11A	0.9900
C1—H1	0.9500	C11—H11B	0.9900
C2—C3	1.380 (4)	C12—C13	1.521 (4)
C2—H2	0.9500	C12—H12A	0.9900
C3—C4	1.394 (4)	C12—H12B	0.9900
C3—H3	0.9500	C13—H13A	0.9900
C4—C5	1.387 (4)	C13—H13B	0.9900

N2—Zn1—N1	74.71 (8)	C6—C7—H7B	109.5
N2—Zn1—N3	78.31 (8)	H7A—C7—H7B	109.5
N1—Zn1—N3	151.54 (8)	C6—C7—H7C	109.5
N2—Zn1—I1	137.01 (6)	H7A—C7—H7C	109.5
N1—Zn1—I1	95.53 (6)	H7B—C7—H7C	109.5
N3—Zn1—I1	98.03 (6)	N2—C8—C9	107.5 (2)
N2—Zn1—I2	109.52 (6)	N2—C8—H8A	110.2
N1—Zn1—I2	98.21 (6)	C9—C8—H8A	110.2
N3—Zn1—I2	99.18 (6)	N2—C8—H8B	110.2
I1—Zn1—I2	113.325 (12)	C9—C8—H8B	110.2
C11—O1—C12	110.8 (2)	H8A—C8—H8B	108.5
C1—N1—C5	118.9 (2)	N3—C9—C8	111.1 (2)
C1—N1—Zn1	126.70 (18)	N3—C9—H9A	109.4
C5—N1—Zn1	114.34 (17)	C8—C9—H9A	109.4
C6—N2—C8	122.6 (2)	N3—C9—H9B	109.4
C6—N2—Zn1	120.65 (18)	C8—C9—H9B	109.4
C8—N2—Zn1	116.61 (16)	H9A—C9—H9B	108.0
C9—N3—C13	111.1 (2)	N3—C10—C11	112.5 (2)
C9—N3—C10	112.5 (2)	N3—C10—H10A	109.1
C13—N3—C10	107.4 (2)	C11—C10—H10A	109.1
C9—N3—Zn1	100.98 (15)	N3—C10—H10B	109.1
C13—N3—Zn1	111.80 (16)	C11—C10—H10B	109.1
C10—N3—Zn1	113.10 (15)	H10A—C10—H10B	107.8
N1—C1—C2	122.6 (3)	O1—C11—C10	111.4 (2)
N1—C1—H1	118.7	O1—C11—H11A	109.3
C2—C1—H1	118.7	C10—C11—H11A	109.3
C3—C2—C1	118.3 (3)	O1—C11—H11B	109.3
C3—C2—H2	120.8	C10—C11—H11B	109.3
C1—C2—H2	120.8	H11A—C11—H11B	108.0
C2—C3—C4	119.6 (3)	O1—C12—C13	111.7 (2)
C2—C3—H3	120.2	O1—C12—H12A	109.3
C4—C3—H3	120.2	C13—C12—H12A	109.3
C5—C4—C3	118.4 (3)	O1—C12—H12B	109.3
C5—C4—H4	120.8	C13—C12—H12B	109.3
C3—C4—H4	120.8	H12A—C12—H12B	107.9
N1—C5—C4	122.1 (2)	N3—C13—C12	113.3 (2)
N1—C5—C6	114.8 (2)	N3—C13—H13A	108.9
C4—C5—C6	123.1 (2)	C12—C13—H13A	108.9
N2—C6—C5	115.4 (2)	N3—C13—H13B	108.9
N2—C6—C7	125.4 (2)	C12—C13—H13B	108.9
C5—C6—C7	119.2 (2)	H13A—C13—H13B	107.7
C6—C7—H7A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1ⁱ	0.99	2.55	3.491 (3)	159

Symmetry code: (i) −x+1, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	[ZnI₂(C₁₃H₁₉N₃O)]
M_r	552.48
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.8874 (3), 10.3117 (4), 10.3643 (4)
α, β, γ (°)	68.8810 (18), 81.959 (2), 66.3990 (17)
V (Å³)	811.91 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.31
Crystal size (mm)	0.17 × 0.13 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.465, 0.646
No. of measured, independent and observed [I > 2σ(I)] reflections	7292, 3517, 3260
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.05
No. of reflections	3517
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.85, −1.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn1—N1	2.205 (2)	Zn1—I1	2.6018 (4)
Zn1—N2	2.093 (2)	Zn1—I2	2.6506 (4)
Zn1—N3	2.269 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O1ⁱ	0.99	2.55	3.491 (3)	159

Symmetry code: (i) −x+1, −y+2, −z+2.

Acknowledgements

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

References

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