[N,N′-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine-κ2N,N′]iodidocopper(I)

Kia, R.; Fun, H.-K.; Kargar, H.

doi:10.1107/S160053680900107X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page m197

doi:10.1107/S160053680900107X

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[N,N′-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine-κ²N,N′]iodidocopper(I)

Reza Kia,^a Hoong-Kun Fun ^a ^* and Hadi Kargar ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, School of Science, Payame Noor University (PNU), Ardakan, Yazd, Iran
^*Correspondence e-mail: hkfun@usm.my

(Received 3 January 2009; accepted 9 January 2009; online 17 January 2009)

The molecule of the title compound, [CuI(C₁₉H₂₀Cl₂N₂)], lies across a crystallographic mirror plane. The coordination around the copper centre is distorted trigonal planar, with a bite angle of 94.40 (7)°. A six-membered chelate ring is formed by the coordination of iminic N atoms of the bidentate ligand to the Cu^I atom, adopting a chair conformation. This conformation is required if the local symmetry of the metal coordination site is in accordance with a mirror plane that passes through the metal atom normal to the line connecting the N atoms. The dihedral angle between the benzene rings is 78.66 (5)°. The crystal structure is stabilized by weak intermolecular C—H⋯π interactions, which link the molecules into chains along the b axis.

Related literature

For puckering parameters, see: Cremer & Pople (1975 ). For related literature and the catalytic applications, see, for example: Killian et al. (1996 ); Jung et al. (1996 ); Small et al. (1998 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

[CuI(C₁₉H₂₀Cl₂N₂)]
M_r = 537.71
Monoclinic, C 2/m
a = 16.2770 (1) Å
b = 12.2983 (1) Å
c = 10.6255 (1) Å
β = 92.249 (1)°
V = 2125.37 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 296 (2) K
0.44 × 0.31 × 0.28 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.334, T_max = 0.463
39802 measured reflections
4869 independent reflections
4157 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.067
S = 1.02
4869 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯Cg1ⁱ	0.97	2.92	3.7220 (19)	141
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ . Cg1 is the centroid of the C1–C6 benzene ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900107X/hk2609sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900107X/hk2609Isup2.hkl

checkCIF report

Comment top

In recent years, an increasing amount of research has been focused on the design and preparation of mono- or di-nuclear mixed ligand transition metal complexes containing neutral, chelating nitrogen ligands. Early and late transition metal complexes of this type have extensively been used as catalysts for a wide categories of reactions, including olefin polymerization (Killian et al., 1996) and oxygen activation (Jung et al., 1996). In this context, diverse chelating Schiff base type ligands, amines and pyridine derivatives (Small et al., 1998) have successfully been applied in the preparation of these homogeneous catalysts. Here we report the crystal structure of an aldimine Schiff base ligand with copper(I) iodide. To the best of our knowledge, the title compound is the first tricoordinate complex of an aldimine bis-Schiff base ligand with copper(I) iodide adopting triginal planar geometry.

The title compound, I, Fig. 1, lies across a crystallographic mirror plane. Atoms I1, Cu1, C9, C10 and C11 lies on this mirror plane. The asymmetric unit of (I) is composed of one-half of the molecule. The coordination geometry around copper has a distorted trigonal planar geometry. The deviation of the Cu atom from the N1/N1A/I1 plane is -0.1213 (8) Å. A six-membered chelate ring is formed in this case by the coordination of iminic nitrogen atoms of the bidentate ligand which adopts the chair conformation with the ring puckering paremeters (Cremer & Pople 1975) of Q = 0.7001 (14) Å, Θ = 7.72 (11)°, Φ = 0.0 (9)°. This conformation is required if the local symmetry of the metal coordination site is in accordance with a mirror plane that passed through the metal atom normal to the line connecting the nitrogen atoms. The dihedral angle between the phenyl rings is 78.66 (5)°. The crystal structure is stabilized by weak intermolecular C—H···π interactions (Cg1 is the centroid of the C1–C6 benzene ring) which link the molecules into chains along the b-axis (Fig. 2 and Table 1).

Related literature top

For puckering parameters, see: Cremer & Pople (1975). For related literature and the catalytic applications, see, for example: Killian et al. (1996); Jung et al. (1996); Small et al. (1998). For hydrogen-bond motifs, see: Bernstein et al. (1995). <t>Cg1 is the centroid of the C1–C6 benzene ring.

Experimental top

N,N'-Bis(4-chlorobenzylidene)-2,2-dimethylpropane (694 mg, 2 mmol) was added dropwise to a suspension of CuI (380 mg, 2.0 mmol) in 50 ml of THF. After 15 minutes a clear yellowish solution was obtained. The volume of the reaction mixture was reduced until the formation of a yellow precipitate occurred. Single crystals suitable for X-ray diffraction were grown from the acetonitrile solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids and the atomic numbering. Symmetry code for A atoms; X, -Y, Z.
	Fig. 2. The crystal packing of (I), viewed down the c-axis, showing C—H···π interactions linking the molecules into chains along the b-axis.

[N,N'-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine- κ²N,N']iodidocopper(I) top

Crystal data top

[CuI(C₁₉H₂₀Cl₂N₂)]	F(000) = 1056
M_r = 537.71	D_x = 1.674 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 9801 reflections
a = 16.2770 (1) Å	θ = 2.5–35.7°
b = 12.2983 (1) Å	µ = 2.74 mm⁻¹
c = 10.6255 (1) Å	T = 296 K
β = 92.249 (1)°	Block, yellow
V = 2125.37 (3) Å³	0.44 × 0.31 × 0.28 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4869 independent reflections
Radiation source: fine-focus sealed tube	4157 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 35.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −26→26
T_min = 0.334, T_max = 0.463	k = −19→19
39802 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.031P)² + 1.3061P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4869 reflections	Δρ_max = 0.74 e Å⁻³
122 parameters	Δρ_min = −0.55 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00458 (18)

Crystal data top

[CuI(C₁₉H₂₀Cl₂N₂)]	V = 2125.37 (3) Å³
M_r = 537.71	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 16.2770 (1) Å	µ = 2.74 mm⁻¹
b = 12.2983 (1) Å	T = 296 K
c = 10.6255 (1) Å	0.44 × 0.31 × 0.28 mm
β = 92.249 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4869 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4157 reflections with I > 2σ(I)
T_min = 0.334, T_max = 0.463	R_int = 0.026
39802 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.067	H-atom parameters constrained
S = 1.02	Δρ_max = 0.74 e Å⁻³
4869 reflections	Δρ_min = −0.55 e Å⁻³
122 parameters

Special details top

Experimental. The low-temperature data were collected with the Oxford Cyrosystem Cobra low-temperature attachment

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
I1	0.116357 (8)	0.0000	0.351624 (13)	0.04474 (5)
Cu1	0.250035 (16)	0.0000	0.46811 (2)	0.04325 (7)
Cl1	0.38586 (4)	0.32893 (7)	−0.03450 (5)	0.0900 (2)
N1	0.31811 (7)	0.11994 (10)	0.54747 (11)	0.0410 (2)
C1	0.32263 (11)	0.17020 (14)	0.27282 (15)	0.0515 (4)
H1A	0.2889	0.1119	0.2920	0.062*
C2	0.32963 (11)	0.20089 (16)	0.14902 (16)	0.0567 (4)
H2A	0.3009	0.1637	0.0851	0.068*
C3	0.37946 (11)	0.28682 (17)	0.12088 (16)	0.0545 (4)
C4	0.42404 (12)	0.34113 (16)	0.21435 (18)	0.0603 (4)
H4A	0.4593	0.3974	0.1940	0.072*
C5	0.41577 (11)	0.31124 (14)	0.33842 (16)	0.0519 (3)
H5A	0.4444	0.3493	0.4017	0.062*
C6	0.36540 (9)	0.22526 (11)	0.37029 (13)	0.0411 (3)
C7	0.35971 (9)	0.19805 (12)	0.50364 (14)	0.0440 (3)
H7A	0.3889	0.2415	0.5614	0.053*
C8	0.32286 (11)	0.10423 (13)	0.68508 (14)	0.0486 (3)
H8A	0.2675	0.1019	0.7156	0.058*
H8B	0.3505	0.1664	0.7237	0.058*
C9	0.36849 (14)	0.0000	0.72732 (19)	0.0456 (4)
C10	0.45648 (16)	0.0000	0.6822 (3)	0.0618 (6)
H10A	0.4554	0.0000	0.5918	0.093*
H10B	0.4847	−0.0637	0.7132	0.093*
C11	0.3698 (2)	0.0000	0.8725 (2)	0.0717 (8)
H11A	0.3144	0.0000	0.9003	0.108*
H11B	0.3978	0.0637	0.9038	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.03731 (7)	0.05062 (8)	0.04559 (8)	0.000	−0.00706 (5)	0.000
Cu1	0.03802 (12)	0.05125 (14)	0.04003 (12)	0.000	−0.00415 (9)	0.000
Cl1	0.0925 (4)	0.1280 (6)	0.0491 (2)	−0.0450 (4)	−0.0017 (2)	0.0181 (3)
N1	0.0443 (6)	0.0406 (5)	0.0381 (5)	0.0015 (4)	−0.0004 (4)	−0.0020 (4)
C1	0.0583 (9)	0.0507 (8)	0.0454 (7)	−0.0190 (7)	0.0027 (6)	−0.0049 (6)
C2	0.0583 (9)	0.0682 (10)	0.0433 (7)	−0.0221 (8)	0.0003 (6)	−0.0066 (7)
C3	0.0507 (8)	0.0683 (10)	0.0444 (7)	−0.0135 (7)	0.0022 (6)	0.0042 (7)
C4	0.0625 (10)	0.0636 (10)	0.0548 (9)	−0.0268 (8)	0.0007 (7)	0.0043 (8)
C5	0.0539 (8)	0.0520 (8)	0.0492 (8)	−0.0170 (7)	−0.0044 (6)	−0.0023 (6)
C6	0.0416 (6)	0.0381 (6)	0.0435 (6)	−0.0026 (5)	−0.0005 (5)	−0.0035 (5)
C7	0.0496 (7)	0.0396 (6)	0.0425 (6)	−0.0034 (5)	−0.0019 (5)	−0.0060 (5)
C8	0.0578 (8)	0.0509 (8)	0.0372 (6)	0.0027 (6)	0.0037 (6)	−0.0045 (6)
C9	0.0502 (11)	0.0543 (11)	0.0320 (8)	0.000	0.0000 (7)	0.000
C10	0.0463 (12)	0.0775 (17)	0.0611 (14)	0.000	−0.0050 (10)	0.000
C11	0.102 (2)	0.0794 (19)	0.0336 (10)	0.000	−0.0029 (12)	0.000

Geometric parameters (Å, º) top

I1—Cu1	2.4607 (3)	C5—C6	1.388 (2)
Cu1—N1	2.0104 (12)	C5—H5A	0.9300
Cu1—N1ⁱ	2.0104 (12)	C6—C7	1.462 (2)
Cl1—C3	1.7373 (17)	C7—H7A	0.9300
N1—C7	1.2739 (19)	C8—C9	1.540 (2)
N1—C8	1.4739 (18)	C8—H8A	0.9700
C1—C2	1.378 (2)	C8—H8B	0.9700
C1—C6	1.3998 (19)	C9—C10	1.528 (3)
C1—H1A	0.9300	C9—C8ⁱ	1.540 (2)
C2—C3	1.372 (2)	C9—C11	1.542 (3)
C2—H2A	0.9300	C10—H10A	0.9600
C3—C4	1.379 (2)	C10—H10B	0.9601
C4—C5	1.380 (2)	C11—H11A	0.9600
C4—H4A	0.9300	C11—H11B	0.9600

N1—Cu1—N1ⁱ	94.40 (7)	C1—C6—C7	123.89 (13)
N1—Cu1—I1	132.30 (3)	N1—C7—C6	125.56 (13)
N1ⁱ—Cu1—I1	132.30 (3)	N1—C7—H7A	117.2
C7—N1—C8	116.98 (13)	C6—C7—H7A	117.2
C7—N1—Cu1	133.79 (10)	N1—C8—C9	113.84 (13)
C8—N1—Cu1	109.06 (10)	N1—C8—H8A	108.8
C2—C1—C6	121.10 (14)	C9—C8—H8A	108.8
C2—C1—H1A	119.4	N1—C8—H8B	108.8
C6—C1—H1A	119.4	C9—C8—H8B	108.8
C3—C2—C1	119.40 (15)	H8A—C8—H8B	107.7
C3—C2—H2A	120.3	C10—C9—C8ⁱ	110.85 (12)
C1—C2—H2A	120.3	C10—C9—C8	110.85 (12)
C2—C3—C4	120.98 (16)	C8ⁱ—C9—C8	112.74 (19)
C2—C3—Cl1	119.64 (13)	C10—C9—C11	109.8 (2)
C4—C3—Cl1	119.38 (13)	C8ⁱ—C9—C11	106.21 (13)
C3—C4—C5	119.38 (15)	C8—C9—C11	106.21 (13)
C3—C4—H4A	120.3	C9—C10—H10A	109.5
C5—C4—H4A	120.3	C9—C10—H10B	109.5
C4—C5—C6	121.10 (14)	H10A—C10—H10B	109.5
C4—C5—H5A	119.5	C9—C11—H11A	109.4
C6—C5—H5A	119.5	C9—C11—H11B	109.5
C5—C6—C1	118.00 (14)	H11A—C11—H11B	109.5
C5—C6—C7	118.11 (13)

Symmetry code: (i) x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Cg1ⁱⁱ	0.97	2.92	3.7220 (19)	141

Symmetry code: (ii) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[CuI(C₁₉H₂₀Cl₂N₂)]
M_r	537.71
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	296
a, b, c (Å)	16.2770 (1), 12.2983 (1), 10.6255 (1)
β (°)	92.249 (1)
V (Å³)	2125.37 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.74
Crystal size (mm)	0.44 × 0.31 × 0.28

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.334, 0.463
No. of measured, independent and observed [I > 2σ(I)] reflections	39802, 4869, 4157
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.067, 1.02
No. of reflections	4869
No. of parameters	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.55

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Cg1ⁱ	0.97	2.92	3.7220 (19)	141

Symmetry code: (i) −x+1/2, −y+1/2, −z+1.

Acknowledgements

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant (No. 305/PFIZIK/613312). RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for financial support.

References

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