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Acta Cryst. (2007). E63, m2377    [ doi:10.1107/S1600536807039670 ]

Di-[mu]-iodido-bis[(N-morpholino-2-pyridylmethanimine-[kappa]2N,N')copper(I)] acetonitrile solvate

S. Dehghanpour, F. Rominger and S. W. Ng

Abstract top

In the crystal structure of the title compound, [Cu2I2(C10H13N3O)2]·CH3CN, the Schiff base chelates the CuI atom, which is linked to two I atoms in a tetrahedral geometry; the covalent Cu-I bond is only marginally shorter than the dative Cu-I bond. The dinuclear molecule lies about a centre of inversion and the solvent molecule on a twofold rotation axis.

Comment top

Copper(I) iodide forms a large number of adducts with Schiff bases. However, there are no structural studies on the morpholine-2-pyridyl-methanimine. In the title compound, the Schiff base chelates to the copper(I) atom, which is linked to two iodine atoms in a tetrahedral geometry; the covalent Cu–I bond is only marginally shorter than the dative Cu–I bond (Table 1) in the crystal structure of (C10H13N3O)2(CuI)2.CH3CN. The dinuclear molecule lies about a center-of-inversion whereas the solvent molecule lies on a twofold rotation axis.

Related literature top

For the synthesis of the Schiff base ligand, see Wiley et al. (1959). There are only two reports of metal adducts (not crystallographic studies): see Nasser-Eddine et al. (2004) for the copper(I) bromide adduct, and Nikolcheva et al. (2003) for the platinum(II) dichloride adduct.

Experimental top

Copper(I) iodide (1 mmol) and morpholine-2-pyridylmethanimine (1 mmol) were dissolved in acetonitrile under a nitrogen atmosphere. The solvent was partially removed and diethyl ether vapor diffused into the concentrated solution. Orange crystals were obtained in 90% yield. Calc. for C20H26Cu2I2N6O2:C 31.47, H 3.43, N 11.01%. Found: C 31.45, H 3.40, N 11.06%.

Refinement top

The carbon-bound hydrogen atoms were placed at calculated positions (C–H 0.93 – 0.99 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2 – 1.5 Ueq(C). The methyl group of the acetonitrile molecule is disordered over two equally occupied sites. The final difference Fourier map had a large peak/hole in the vicinity of the iodine atom.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of (C10H13N3O)2(CuI)2.CH3CN drawn at the 70% probability level; hydrogen atoms are shown as spheres of arbitrary radius. Symmetry code (i): 1 – x, 1 – y, 1 – z.
Di-µ-iodido-bis[(N-morpholino-2-pyridylmethanimine-κ2N,N')copper(I)] acetonitrile solvate top
Crystal data top
[Cu2I2(C10H13N3O)2]·C2H3NF000 = 1560
Mr = 804.40Dx = 1.893 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8192 reflections
a = 16.0206 (2) Åθ = 2.4–27.5º
b = 10.2820 (1) ŵ = 3.73 mm−1
c = 17.2086 (1) ÅT = 200 (2) K
β = 95.329 (1)ºPolyhedron, orange
V = 2822.41 (5) Å30.24 × 0.18 × 0.05 mm
Z = 4
Data collection top
Bruker SMART area-detector
diffractometer		3247 independent reflections
Radiation source: fine-focus sealed tube2897 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.050
T = 200(2) Kθmax = 27.5º
φ and ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→20
Tmin = 0.468, Tmax = 0.836k = −13→13
13511 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.080  w = 1/[σ2(Fo2) + (0.0356P)2 + 6.1582P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3247 reflectionsΔρmax = 1.01 e Å−3
161 parametersΔρmin = −1.03 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2I2(C10H13N3O)2]·C2H3NV = 2822.41 (5) Å3
Mr = 804.40Z = 4
Monoclinic, C2/cMo Kα
a = 16.0206 (2) ŵ = 3.73 mm−1
b = 10.2820 (1) ÅT = 200 (2) K
c = 17.2086 (1) Å0.24 × 0.18 × 0.05 mm
β = 95.329 (1)º
Data collection top
Bruker SMART area-detector
diffractometer		3247 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2897 reflections with I > 2σ(I)
Tmin = 0.468, Tmax = 0.836Rint = 0.050
13511 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030161 parameters
wR(F2) = 0.080H-atom parameters constrained
S = 1.04Δρmax = 1.01 e Å−3
3247 reflectionsΔρmin = −1.03 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.55574 (2)0.41824 (4)0.48182 (2)0.03299 (11)
I10.600440 (12)0.60525 (2)0.576912 (13)0.03845 (9)
O10.69807 (18)0.6939 (3)0.24161 (16)0.0525 (7)
N10.59867 (15)0.2310 (2)0.50200 (15)0.0302 (5)
N20.64685 (15)0.4059 (2)0.39882 (14)0.0274 (5)
N30.67489 (16)0.5071 (2)0.35742 (15)0.0309 (5)
N40.50000.9807 (8)0.25000.135 (4)
C10.5713 (2)0.1401 (3)0.5497 (2)0.0395 (7)
H10.53060.16430.58380.047*
C20.5995 (2)0.0129 (3)0.5513 (2)0.0433 (8)
H20.5778−0.04890.58530.052*
C30.6595 (2)−0.0229 (3)0.5030 (2)0.0421 (8)
H30.6803−0.10940.50340.051*
C40.6886 (2)0.0692 (3)0.45417 (19)0.0348 (7)
H40.73030.04700.42070.042*
C50.65638 (17)0.1957 (3)0.45415 (16)0.0271 (6)
C60.68527 (18)0.2951 (3)0.40212 (17)0.0278 (6)
H60.73070.27890.37170.033*
C70.7327 (2)0.4817 (3)0.29850 (18)0.0342 (6)
H7A0.70360.43320.25420.041*
H7B0.78030.42840.32110.041*
C80.7643 (2)0.6107 (3)0.2703 (2)0.0456 (8)
H8A0.79790.65440.31390.055*
H8B0.80140.59460.22840.055*
C90.6470 (3)0.7216 (4)0.3030 (3)0.0560 (10)
H9A0.60200.78280.28390.067*
H9B0.68140.76390.34660.067*
C100.6084 (2)0.5989 (3)0.3320 (2)0.0453 (9)
H10A0.57520.61970.37610.054*
H10B0.57040.55970.28970.054*
C110.50001.0891 (7)0.25000.0634 (17)
C120.50001.2277 (6)0.25000.0564 (14)
H12A0.44211.25950.24740.085*0.50
H12B0.52671.25950.20470.085*0.50
H12C0.53111.25950.29800.085*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0308 (2)0.02673 (19)0.0425 (2)0.00814 (14)0.00937 (16)−0.00119 (15)
I10.03060 (13)0.03548 (13)0.04833 (15)0.00547 (8)−0.00136 (9)−0.01112 (8)
O10.0623 (16)0.0444 (14)0.0523 (15)−0.0009 (12)0.0136 (13)0.0198 (12)
N10.0269 (12)0.0278 (12)0.0356 (13)0.0044 (9)0.0018 (10)0.0041 (10)
N20.0281 (12)0.0240 (11)0.0303 (12)0.0011 (9)0.0040 (10)0.0011 (9)
N30.0345 (13)0.0273 (12)0.0317 (12)0.0028 (10)0.0077 (10)0.0042 (10)
N40.110 (6)0.059 (5)0.239 (12)0.0000.024 (7)0.000
C10.0387 (17)0.0377 (17)0.0425 (18)0.0016 (14)0.0058 (14)0.0101 (14)
C20.0465 (19)0.0343 (17)0.0476 (19)−0.0028 (14)−0.0036 (15)0.0134 (15)
C30.0484 (19)0.0254 (15)0.0499 (19)0.0067 (14)−0.0098 (15)0.0039 (13)
C40.0342 (16)0.0285 (14)0.0403 (17)0.0102 (12)−0.0027 (13)−0.0026 (12)
C50.0261 (13)0.0239 (13)0.0300 (14)0.0041 (10)−0.0039 (11)−0.0025 (10)
C60.0278 (13)0.0258 (13)0.0299 (14)0.0032 (11)0.0036 (11)−0.0049 (11)
C70.0384 (16)0.0348 (16)0.0306 (15)0.0002 (13)0.0103 (12)−0.0009 (12)
C80.049 (2)0.046 (2)0.0441 (19)−0.0056 (15)0.0149 (16)0.0072 (15)
C90.064 (2)0.0336 (18)0.073 (3)0.0077 (17)0.020 (2)0.0157 (18)
C100.0424 (19)0.0364 (18)0.059 (2)0.0099 (14)0.0142 (17)0.0162 (15)
C110.044 (3)0.056 (4)0.091 (5)0.0000.015 (3)0.000
C120.064 (4)0.055 (3)0.052 (3)0.0000.013 (3)0.000
Geometric parameters (Å, °) top
Cu1—N12.063 (2)C3—H30.9500
Cu1—N22.139 (2)C4—C51.399 (4)
Cu1—Cu1i2.5719 (7)C4—H40.9500
Cu1—I12.5827 (4)C5—C61.462 (4)
Cu1—I1i2.6211 (4)C6—H60.9500
I1—Cu1i2.6211 (4)C7—C81.516 (4)
O1—C81.415 (5)C7—H7A0.9900
O1—C91.423 (5)C7—H7B0.9900
N1—C51.344 (4)C8—H8A0.9900
N1—C11.345 (4)C8—H8B0.9900
N2—C61.293 (4)C9—C101.510 (5)
N2—N31.361 (3)C9—H9A0.9900
N3—C71.459 (4)C9—H9B0.9900
N3—C101.459 (4)C10—H10A0.9900
N4—C111.114 (9)C10—H10B0.9900
C1—C21.383 (5)C11—C121.425 (9)
C1—H10.9500C12—H12A0.9800
C2—C31.378 (5)C12—H12B0.9800
C2—H20.9500C12—H12C0.9800
C3—C41.376 (5)
N1—Cu1—N279.59 (9)C4—C5—C6120.8 (3)
N1—Cu1—Cu1i142.87 (8)N2—C6—C5117.8 (3)
N2—Cu1—Cu1i137.20 (7)N2—C6—H6121.1
N1—Cu1—I1121.31 (7)C5—C6—H6121.1
N2—Cu1—I1107.53 (7)N3—C7—C8108.6 (3)
Cu1i—Cu1—I161.128 (16)N3—C7—H7A110.0
N1—Cu1—I1i105.69 (7)C8—C7—H7A110.0
N2—Cu1—I1i115.04 (7)N3—C7—H7B110.0
Cu1i—Cu1—I1i59.638 (16)C8—C7—H7B110.0
I1—Cu1—I1i120.766 (14)H7A—C7—H7B108.4
Cu1—I1—Cu1i59.234 (14)O1—C8—C7112.2 (3)
C8—O1—C9109.0 (3)O1—C8—H8A109.2
C5—N1—C1117.9 (3)C7—C8—H8A109.2
C5—N1—Cu1112.77 (19)O1—C8—H8B109.2
C1—N1—Cu1129.0 (2)C7—C8—H8B109.2
C6—N2—N3121.2 (3)H8A—C8—H8B107.9
C6—N2—Cu1112.01 (19)O1—C9—C10111.1 (3)
N3—N2—Cu1125.65 (18)O1—C9—H9A109.4
N2—N3—C7119.2 (2)C10—C9—H9A109.4
N2—N3—C10112.6 (2)O1—C9—H9B109.4
C7—N3—C10113.6 (3)C10—C9—H9B109.4
N1—C1—C2123.1 (3)H9A—C9—H9B108.0
N1—C1—H1118.5N3—C10—C9109.2 (3)
C2—C1—H1118.5N3—C10—H10A109.8
C3—C2—C1119.0 (3)C9—C10—H10A109.8
C3—C2—H2120.5N3—C10—H10B109.8
C1—C2—H2120.5C9—C10—H10B109.8
C4—C3—C2118.7 (3)H10A—C10—H10B108.3
C4—C3—H3120.7N4—C11—C12180.000 (3)
C2—C3—H3120.7C11—C12—H12A109.5
C3—C4—C5119.6 (3)C11—C12—H12B109.5
C3—C4—H4120.2H12A—C12—H12B109.5
C5—C4—H4120.2C11—C12—H12C109.5
N1—C5—C4121.7 (3)H12A—C12—H12C109.5
N1—C5—C6117.4 (2)H12B—C12—H12C109.5
N1—Cu1—I1—Cu1i−136.91 (9)C5—N1—C1—C2−0.2 (5)
N2—Cu1—I1—Cu1i134.79 (7)Cu1—N1—C1—C2172.5 (3)
I1i—Cu1—I1—Cu1i0.0N1—C1—C2—C31.1 (5)
N2—Cu1—N1—C5−2.1 (2)C1—C2—C3—C4−0.7 (5)
Cu1i—Cu1—N1—C5171.24 (14)C2—C3—C4—C5−0.5 (5)
I1—Cu1—N1—C5−106.40 (19)C1—N1—C5—C4−1.1 (4)
I1i—Cu1—N1—C5111.17 (19)Cu1—N1—C5—C4−174.9 (2)
N2—Cu1—N1—C1−175.1 (3)C1—N1—C5—C6179.5 (3)
Cu1i—Cu1—N1—C1−1.8 (4)Cu1—N1—C5—C65.7 (3)
I1—Cu1—N1—C180.6 (3)C3—C4—C5—N11.5 (5)
I1i—Cu1—N1—C1−61.8 (3)C3—C4—C5—C6−179.2 (3)
N1—Cu1—N2—C6−2.0 (2)N3—N2—C6—C5173.9 (2)
Cu1i—Cu1—N2—C6−176.06 (16)Cu1—N2—C6—C55.5 (3)
I1—Cu1—N2—C6117.78 (19)N1—C5—C6—N2−7.8 (4)
I1i—Cu1—N2—C6−104.5 (2)C4—C5—C6—N2172.8 (3)
N1—Cu1—N2—N3−169.6 (2)N2—N3—C7—C8−171.4 (3)
Cu1i—Cu1—N2—N316.3 (3)C10—N3—C7—C852.2 (4)
I1—Cu1—N2—N3−49.9 (2)C9—O1—C8—C761.5 (4)
I1i—Cu1—N2—N387.8 (2)N3—C7—C8—O1−56.1 (4)
C6—N2—N3—C718.0 (4)C8—O1—C9—C10−61.5 (4)
Cu1—N2—N3—C7−175.4 (2)N2—N3—C10—C9167.4 (3)
C6—N2—N3—C10154.8 (3)C7—N3—C10—C9−53.2 (4)
Cu1—N2—N3—C10−38.6 (4)O1—C9—C10—N357.0 (5)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the Alzahra University Research Council, the University of Heidelberg and the University of Malaya for supporting this study.

references
References top

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