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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): m197.
Published online 2009 January 17. doi:  10.1107/S160053680900107X
PMCID: PMC2968316

[N,N′-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine-κ2 N,N′]iodidocopper(I)

Abstract

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 CuI 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 [triangle]). For related literature and the catalytic applications, see, for example: Killian et al. (1996 [triangle]); Jung et al. (1996 [triangle]); Small et al. (1998 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m197-scheme1.jpg

Experimental

Crystal data

  • [CuI(C19H20Cl2N2)]
  • M r = 537.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m197-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.067
  • S = 1.02
  • 4869 reflections
  • 122 parameters
  • H-atom parameters constrained
  • Δρmax = 0.74 e Å−3
  • Δρmin = −0.55 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were positioned geometrically with C—H = 0.93 Å (aromatic), 0.96 Å (methyl), and 0.97 Å (methylene) and refined in the riding model approximation with Uiso(H) = 1.2 or 1.5 Ueq(C). The highest peak (0.74 e. Å-3) is located 0.60 Å from I1 and the deepest hole (-0.55 e. Å-3 is located 0.59 Å from I1.

Figures

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.

Crystal data

[CuI(C19H20Cl2N2)]F(000) = 1056
Mr = 537.71Dx = 1.674 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 9801 reflections
a = 16.2770 (1) Åθ = 2.5–35.7°
b = 12.2983 (1) ŵ = 2.74 mm1
c = 10.6255 (1) ÅT = 296 K
β = 92.249 (1)°Block, yellow
V = 2125.37 (3) Å30.44 × 0.31 × 0.28 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer4869 independent reflections
Radiation source: fine-focus sealed tube4157 reflections with I > 2σ(I)
graphiteRint = 0.026
[var phi] and ω scansθmax = 35.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −26→26
Tmin = 0.334, Tmax = 0.463k = −19→19
39802 measured reflectionsl = −17→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.067w = 1/[σ2(Fo2) + (0.031P)2 + 1.3061P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
4869 reflectionsΔρmax = 0.74 e Å3
122 parametersΔρmin = −0.55 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00458 (18)

Special details

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)

xyzUiso*/Ueq
I10.116357 (8)0.00000.351624 (13)0.04474 (5)
Cu10.250035 (16)0.00000.46811 (2)0.04325 (7)
Cl10.38586 (4)0.32893 (7)−0.03450 (5)0.0900 (2)
N10.31811 (7)0.11994 (10)0.54747 (11)0.0410 (2)
C10.32263 (11)0.17020 (14)0.27282 (15)0.0515 (4)
H1A0.28890.11190.29200.062*
C20.32963 (11)0.20089 (16)0.14902 (16)0.0567 (4)
H2A0.30090.16370.08510.068*
C30.37946 (11)0.28682 (17)0.12088 (16)0.0545 (4)
C40.42404 (12)0.34113 (16)0.21435 (18)0.0603 (4)
H4A0.45930.39740.19400.072*
C50.41577 (11)0.31124 (14)0.33842 (16)0.0519 (3)
H5A0.44440.34930.40170.062*
C60.36540 (9)0.22526 (11)0.37029 (13)0.0411 (3)
C70.35971 (9)0.19805 (12)0.50364 (14)0.0440 (3)
H7A0.38890.24150.56140.053*
C80.32286 (11)0.10423 (13)0.68508 (14)0.0486 (3)
H8A0.26750.10190.71560.058*
H8B0.35050.16640.72370.058*
C90.36849 (14)0.00000.72732 (19)0.0456 (4)
C100.45648 (16)0.00000.6822 (3)0.0618 (6)
H10A0.45540.00000.59180.093*
H10B0.4847−0.06370.71320.093*
C110.3698 (2)0.00000.8725 (2)0.0717 (8)
H11A0.31440.00000.90030.108*
H11B0.39780.06370.90380.108*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.03731 (7)0.05062 (8)0.04559 (8)0.000−0.00706 (5)0.000
Cu10.03802 (12)0.05125 (14)0.04003 (12)0.000−0.00415 (9)0.000
Cl10.0925 (4)0.1280 (6)0.0491 (2)−0.0450 (4)−0.0017 (2)0.0181 (3)
N10.0443 (6)0.0406 (5)0.0381 (5)0.0015 (4)−0.0004 (4)−0.0020 (4)
C10.0583 (9)0.0507 (8)0.0454 (7)−0.0190 (7)0.0027 (6)−0.0049 (6)
C20.0583 (9)0.0682 (10)0.0433 (7)−0.0221 (8)0.0003 (6)−0.0066 (7)
C30.0507 (8)0.0683 (10)0.0444 (7)−0.0135 (7)0.0022 (6)0.0042 (7)
C40.0625 (10)0.0636 (10)0.0548 (9)−0.0268 (8)0.0007 (7)0.0043 (8)
C50.0539 (8)0.0520 (8)0.0492 (8)−0.0170 (7)−0.0044 (6)−0.0023 (6)
C60.0416 (6)0.0381 (6)0.0435 (6)−0.0026 (5)−0.0005 (5)−0.0035 (5)
C70.0496 (7)0.0396 (6)0.0425 (6)−0.0034 (5)−0.0019 (5)−0.0060 (5)
C80.0578 (8)0.0509 (8)0.0372 (6)0.0027 (6)0.0037 (6)−0.0045 (6)
C90.0502 (11)0.0543 (11)0.0320 (8)0.0000.0000 (7)0.000
C100.0463 (12)0.0775 (17)0.0611 (14)0.000−0.0050 (10)0.000
C110.102 (2)0.0794 (19)0.0336 (10)0.000−0.0029 (12)0.000

Geometric parameters (Å, °)

I1—Cu12.4607 (3)C5—C61.388 (2)
Cu1—N12.0104 (12)C5—H5A0.9300
Cu1—N1i2.0104 (12)C6—C71.462 (2)
Cl1—C31.7373 (17)C7—H7A0.9300
N1—C71.2739 (19)C8—C91.540 (2)
N1—C81.4739 (18)C8—H8A0.9700
C1—C21.378 (2)C8—H8B0.9700
C1—C61.3998 (19)C9—C101.528 (3)
C1—H1A0.9300C9—C8i1.540 (2)
C2—C31.372 (2)C9—C111.542 (3)
C2—H2A0.9300C10—H10A0.9600
C3—C41.379 (2)C10—H10B0.9601
C4—C51.380 (2)C11—H11A0.9600
C4—H4A0.9300C11—H11B0.9600
N1—Cu1—N1i94.40 (7)C1—C6—C7123.89 (13)
N1—Cu1—I1132.30 (3)N1—C7—C6125.56 (13)
N1i—Cu1—I1132.30 (3)N1—C7—H7A117.2
C7—N1—C8116.98 (13)C6—C7—H7A117.2
C7—N1—Cu1133.79 (10)N1—C8—C9113.84 (13)
C8—N1—Cu1109.06 (10)N1—C8—H8A108.8
C2—C1—C6121.10 (14)C9—C8—H8A108.8
C2—C1—H1A119.4N1—C8—H8B108.8
C6—C1—H1A119.4C9—C8—H8B108.8
C3—C2—C1119.40 (15)H8A—C8—H8B107.7
C3—C2—H2A120.3C10—C9—C8i110.85 (12)
C1—C2—H2A120.3C10—C9—C8110.85 (12)
C2—C3—C4120.98 (16)C8i—C9—C8112.74 (19)
C2—C3—Cl1119.64 (13)C10—C9—C11109.8 (2)
C4—C3—Cl1119.38 (13)C8i—C9—C11106.21 (13)
C3—C4—C5119.38 (15)C8—C9—C11106.21 (13)
C3—C4—H4A120.3C9—C10—H10A109.5
C5—C4—H4A120.3C9—C10—H10B109.5
C4—C5—C6121.10 (14)H10A—C10—H10B109.5
C4—C5—H5A119.5C9—C11—H11A109.4
C6—C5—H5A119.5C9—C11—H11B109.5
C5—C6—C1118.00 (14)H11A—C11—H11B109.5
C5—C6—C7118.11 (13)

Symmetry codes: (i) x, −y, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8A···Cg1ii0.972.923.7220 (19)141

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2609).

References

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  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Jung, B., Karlin, K. D. & Zuberbühler, A. D. (1996). J. Am. Chem. Soc., 118, 3763–3768.
  • Killian, C. M., Tempel, D. J., Johnson, L. K. & Brookhart, M. (1996). J. Am. Chem. Soc.118, 11664–11670.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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