Bis­[N,N′-bis­(di­phenyl­methyl­ene)ethyl­enedi­amine-κ²N,N′]copper(I) di­chloro­cuprate(I)

The 1:1 adduct of N,N′-bis­(di­phenyl­methyl­ene)­ethyl­enedi­amine (bz₂en) with copper(I) chloride, viz. [Cu(C₂₈H₂₄N₂)₂][CuCl₂], has been synthesized. The structure contains cationic moieties of Cu^I ions (Cu on a twofold axis) coordinated to four N atoms of two bz₂en mol­ecules (in a distorted tetrahedron) and linear di­chloro­cuprate(I) anions (with Cu on an inversion centre). These cations and anions are packed in columns along b. The packing of the cation and anion columns involves a significant C—H...Cl interaction and four short intermolecular C—H...π contacts, two of which are between cation columns.

S1. Comment

The reaction of copper(I) halides, CuX, with nitrogen-based ligands (L) yields CuXL_n adducts. The number of ligands bound to the monovalent Cu ion is influenced greatly by both the chemical nature and the geometry of the ligand L and the type of halogen X (Zubieta et al., 1983; Kirchner et al., 1987; Alyea et al., 1990). In this context, we decided to examine the nature of the complex formed with an unconjugated diimine ligand. The title complex, (I), was prepared by reacting the bidentate ligand N,N'-bis(benzophenone)ethylenediimine (bz₂en) with CuCl. \sch

The structure determination of (I) is consistent with the stoichiometry of a 1:1 copper(I) chloride-ligand adduct. The atom disposition, however, is that of an ionic complex, the asymmetric unit of the structure comprising a bis(ligand) copper(I) cation and a dichlorocuprate(I) anion (Fig. 1). The Cu ion of the dichlorocopper(I) anion lies on a centre of symmetry, the anion thus being linear [Cu—Cl 2.0832 (8) Å]. The geometry of (I) (Table 1) is in good agreement with that of several other established examples (Kaiser et al., 1983; Engelhardt et al., 1984).

The Cu atom of the cation is on a twofold axis, coordinated to four N atoms belonging to two symmetry-related bz₂en molecules, in a distorted tetrahedral geometry. The N—Cu—N bond angles found in (I) [85.98 (8), 109.50 (8), 134.7 (1) and 140.0 (1)°] are similar to the corresponding data for ethylenediamine chelate rings (Engelhardt et al., 1984). The Cu—N bond lengths [2.030 (2) and 2.099 (3) Å] and angles are similar to those in the related bz₂en copper(I) perchlorate (2:1) complex, in which a perchlorate ion acts as counterion (Chowdhury et al., 2000). All the phenyl rings in (I) are planar, with a maximum out-of-plane deviation for atom C26 of 0.010 (2) Å. The acute angles made by the two rings connected to the same N atoms are 85.51 (9) and 80.26 (8)°.

The crystal packing of (I) involves columns of cations and anions packed along the b axis (Fig. 2). A significant interaction between the cation and anion columns is provided by a short C—H···Cl contact (Table 2). No short C—H···π interactions are found between rings belonging to the same N atom. There are, however, four short intramolecular C—H···π interactions (Table 2), two of which (involving atoms H4 and H12) are between different cation columns.

A calculation using PLATON (Spek, 1990) indicated four equivalent solvent-accessible voids of 26 ų. The final difference Fourier synthesis did not show any significant electron density in these areas.

Table 2. Hydrogen-bond parameters (Å, °). Cg1—Cg4 are the centroids of rings C1—C6, C8—C13, C19—C24 and C25—C30, respectively.

S2. Experimental

The title compound was prepared by the reaction of CuCl and bz₂en (molar ratio 1:1) in a mixed acetonitrile-tetrahydrofuran solution (Ratio?) at room temperature. The solution was then concentrated under vacuum. Red crystals of (I) were formed by vapour diffusion of ether into the concentrated solution.

S3. Refinement

H atoms were placed in calculated positions, with C—H distances of 0.95 Å, and treated as riding atoms, with U_iso(H) = 1.3U_eq(C).

Computing details

Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SIR (Burla et al., 1989); program(s) used to refine structure: LSFM in MolEN; molecular graphics: ORTEPII (Johnson, 1976; Farrugia, 1998); software used to prepare material for publication: BTABLE, PTABLE and CIF in MolEN.

Figures

	Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing in (I), viewed along the b axis, showing the columns of cations and anions.

Bis[N,N'-bis(diphenylmethylene)ethylenediamine-κ²N,N']copper(I) dichlorocuprate(I)

Crystal data

[Cu(C28H24N2)2][CuCl2]	F(000) = 2016
Mr = 975.02	Dx = 1.33 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 26.126 (9) Å	θ = 16–22.0°
b = 9.337 (5) Å	µ = 2.39 mm^−1
c = 23.649 (9) Å	T = 294 K
β = 122.48 (5)°	Block, red
V = 4867 (5) Å^3	0.40 × 0.30 × 0.30 mm
Z = 4.0

Data collection

Enraf-Nonius CAD-4 diffractometer	θmax = 75.0°
Radiation source: sealed X-ray tube	h = −32→32
ω scans	k = 0→11
10026 measured reflections	l = −29→29
5017 independent reflections	3 standard reflections every 60 min
3291 reflections with I > σ(I)	intensity decay: <0.5%
Rint = 0.038

Refinement

Refinement on F^2	w = 4Fo^2/[σ^2(Fo^2) + 0.0016Fo^4]
R[F^2 > 2σ(F^2)] = 0.053	(Δ/σ)max = 0.02
wR(F^2) = 0.137	Δρmax = 0.25 e Å^−3
S = 1.55	Δρmin = −0.29 e Å^−3
5017 reflections	Extinction correction: Zachariasen (1967)
292 parameters	Extinction coefficient: 0.14E-5
H-atom parameters constrained

Special details

Experimental. Data were collected in the ω scan mode (scan width (ω): 0.73 + 0.18 tanθ), using graphite monochromated Cu Kα radiation. The intensity data were corrected for Lorentz and polarization effects and for long time scale variation. No absorption correction was applied.

The structure was refined by full-matrix least-squares. Refinements (on F²) were made, using all reflections. All heavy atoms were refined with anisotropic thermal parameters. Hydrogen atoms were placed at calculated positions (C—H distance 0.95 Å, thermal parameters fixed at 1.3 U_iso of the parent atoms) and treated as riding atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.2142 (1)	0.2500	0.0915 (2)
Cu2	0.2500	0.2500	0.5000	0.1129 (3)
Cl3	0.20225 (4)	0.2287 (2)	0.39612 (4)	0.1422 (4)
N14	0.56393 (7)	0.2886 (3)	0.34231 (8)	0.0771 (7)
N17	0.57274 (7)	0.1275 (3)	0.24718 (8)	0.0788 (8)
C1	0.4697 (1)	0.5006 (5)	0.3109 (1)	0.110 (1)
C2	0.4187 (1)	0.5772 (5)	0.2955 (1)	0.114 (1)
C3	0.4002 (1)	0.5826 (4)	0.3388 (1)	0.083 (1)
C4	0.43277 (9)	0.5126 (3)	0.3985 (1)	0.0715 (8)
C5	0.48445 (9)	0.4364 (3)	0.41504 (9)	0.0613 (8)
C6	0.50342 (9)	0.4271 (3)	0.37060 (9)	0.0628 (8)
C7	0.55913 (9)	0.3469 (3)	0.38781 (9)	0.0630 (8)
C8	0.60783 (9)	0.3361 (3)	0.46062 (9)	0.0591 (7)
C9	0.6486 (1)	0.4455 (3)	0.4937 (1)	0.0718 (9)
C10	0.6938 (1)	0.4325 (4)	0.5614 (1)	0.080 (1)
C11	0.6973 (1)	0.3104 (4)	0.5947 (1)	0.083 (1)
C12	0.6569 (1)	0.2023 (4)	0.5625 (1)	0.087 (1)
C13	0.6126 (1)	0.2147 (3)	0.4955 (1)	0.0748 (9)
C15	0.6228 (1)	0.2196 (4)	0.3620 (1)	0.098 (1)
C16	0.62619 (9)	0.2060 (4)	0.2999 (1)	0.096 (1)
C18	0.57747 (8)	0.0578 (3)	0.20344 (9)	0.0628 (8)
C19	0.52606 (9)	−0.0268 (3)	0.1498 (1)	0.0664 (8)
C20	0.4777 (1)	−0.0689 (4)	0.1543 (1)	0.101 (1)
C21	0.4304 (1)	−0.1477 (5)	0.1039 (2)	0.121 (1)
C22	0.4303 (2)	−0.1843 (4)	0.0482 (2)	0.104 (1)
C23	0.4775 (1)	−0.1450 (4)	0.0425 (1)	0.088 (1)
C24	0.5254 (1)	−0.0681 (3)	0.0929 (1)	0.0715 (9)
C25	0.63429 (8)	0.0590 (3)	0.20248 (9)	0.0546 (7)
C26	0.64124 (9)	0.1593 (3)	0.1644 (1)	0.0665 (8)
C27	0.6919 (1)	0.1592 (3)	0.1601 (1)	0.0745 (9)
C28	0.73675 (9)	0.0607 (4)	0.1954 (1)	0.0771 (9)
C29	0.7317 (1)	−0.0371 (4)	0.2342 (1)	0.0756 (9)
C30	0.6802 (1)	−0.0406 (3)	0.2379 (1)	0.0672 (8)
H1	0.4820	0.4984	0.2796	0.143*
H2	0.3963	0.6265	0.2540	0.148*
H3	0.3648	0.6349	0.3278	0.108*
H4	0.4198	0.5160	0.4291	0.093*
H5	0.5071	0.3901	0.4573	0.080*
H9	0.6459	0.5306	0.4703	0.093*
H10	0.7219	0.5081	0.5840	0.103*
H11	0.7282	0.3006	0.6408	0.108*
H12	0.6593	0.1180	0.5863	0.113*
H13	0.5849	0.1380	0.4733	0.097*
H15A	0.6250	0.1273	0.3802	0.128*
H15B	0.6554	0.2769	0.3946	0.128*
H16A	0.6271	0.2988	0.2840	0.124*
H16B	0.6620	0.1554	0.3111	0.124*
H20	0.4769	−0.0432	0.1928	0.132*
H21	0.3977	−0.1764	0.1081	0.157*
H22	0.3973	−0.2373	0.0133	0.135*
H23	0.4775	−0.1707	0.0036	0.114*
H24	0.5585	−0.0430	0.0888	0.093*
H26	0.6107	0.2297	0.1407	0.086*
H27	0.6956	0.2274	0.1326	0.097*
H28	0.7717	0.0609	0.1927	0.100*
H29	0.7634	−0.1041	0.2591	0.098*
H30	0.6766	−0.1109	0.2646	0.087*
Cg1	0.45154 (4)	0.50608 (16)	0.35489 (4)	0.0*	0.0
Cg2	0.65284 (4)	0.32358 (14)	0.52807 (4)	0.0*	0.0
Cg3	0.47789 (5)	−0.10680 (16)	0.09860 (6)	0.0*	0.0
Cg4	0.68601 (4)	0.06008 (14)	0.19908 (4)	0.0*	0.0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0443 (2)	0.1900 (7)	0.0433 (2)	0.0000	0.0256 (1)	0.0000
Cu2	0.0998 (2)	0.1559 (7)	0.1195 (3)	−0.0056 (4)	0.0832 (2)	−0.0055 (4)
Cl3	0.1163 (4)	0.225 (1)	0.1187 (4)	−0.0021 (6)	0.0852 (2)	−0.0202 (6)
N14	0.0489 (7)	0.141 (2)	0.0427 (6)	0.017 (1)	0.0256 (5)	−0.002 (1)
N17	0.0491 (7)	0.143 (2)	0.0513 (7)	−0.007 (1)	0.0313 (5)	−0.019 (1)
C1	0.097 (1)	0.185 (3)	0.065 (1)	0.066 (2)	0.0551 (7)	0.045 (2)
C2	0.094 (1)	0.176 (3)	0.075 (1)	0.063 (2)	0.0469 (9)	0.041 (2)
C3	0.062 (1)	0.106 (2)	0.075 (1)	0.006 (1)	0.0332 (8)	−0.016 (1)
C4	0.0641 (9)	0.094 (2)	0.0679 (9)	−0.004 (1)	0.0428 (6)	−0.018 (1)
C5	0.0558 (9)	0.083 (2)	0.0472 (8)	−0.003 (1)	0.0290 (6)	−0.006 (1)
C6	0.0523 (8)	0.094 (2)	0.0452 (8)	0.006 (1)	0.0283 (5)	0.001 (1)
C7	0.0538 (8)	0.098 (2)	0.0412 (7)	0.008 (1)	0.0286 (5)	0.006 (1)
C8	0.0529 (8)	0.085 (2)	0.0418 (7)	0.003 (1)	0.0272 (5)	−0.001 (1)
C9	0.064 (1)	0.085 (2)	0.065 (1)	0.000 (1)	0.0344 (7)	0.002 (1)
C10	0.063 (1)	0.102 (2)	0.063 (1)	−0.011 (1)	0.0270 (8)	−0.015 (1)
C11	0.059 (1)	0.129 (3)	0.049 (1)	0.002 (2)	0.0208 (8)	0.001 (2)
C12	0.084 (1)	0.106 (2)	0.055 (1)	0.002 (2)	0.0266 (9)	0.018 (1)
C13	0.070 (1)	0.092 (2)	0.052 (1)	−0.012 (1)	0.0259 (8)	−0.000 (1)
C15	0.0460 (9)	0.188 (3)	0.054 (1)	0.020 (1)	0.0227 (6)	−0.025 (1)
C16	0.0463 (8)	0.178 (3)	0.066 (1)	−0.013 (1)	0.0321 (6)	−0.047 (1)
C18	0.0526 (8)	0.093 (2)	0.0503 (8)	0.002 (1)	0.0326 (5)	0.002 (1)
C19	0.0570 (9)	0.086 (2)	0.0565 (9)	−0.007 (1)	0.0306 (6)	0.001 (1)
C20	0.080 (1)	0.158 (3)	0.077 (1)	−0.033 (2)	0.0502 (7)	−0.009 (2)
C21	0.083 (1)	0.174 (3)	0.095 (2)	−0.058 (2)	0.041 (1)	−0.006 (2)
C22	0.096 (2)	0.096 (2)	0.085 (2)	−0.025 (2)	0.026 (1)	−0.004 (2)
C23	0.090 (2)	0.088 (2)	0.072 (1)	−0.012 (2)	0.035 (1)	−0.017 (2)
C24	0.068 (1)	0.083 (2)	0.062 (1)	0.000 (1)	0.0338 (7)	−0.005 (1)
C25	0.0497 (7)	0.071 (2)	0.0484 (7)	0.001 (1)	0.0300 (5)	−0.004 (1)
C26	0.0653 (9)	0.071 (2)	0.070 (1)	0.003 (1)	0.0411 (6)	0.006 (1)
C27	0.075 (1)	0.092 (2)	0.0704 (9)	−0.014 (1)	0.0486 (6)	−0.004 (1)
C28	0.0574 (9)	0.113 (2)	0.070 (1)	−0.012 (1)	0.0395 (6)	−0.024 (1)
C29	0.057 (1)	0.094 (2)	0.071 (1)	0.012 (1)	0.0314 (7)	−0.002 (1)
C30	0.063 (1)	0.080 (2)	0.0560 (9)	0.003 (1)	0.0309 (7)	0.008 (1)

Geometric parameters (Å, º)

Cu1—N14	2.030 (2)	C25—C26	1.378 (4)
Cu1—N17	2.099 (2)	C25—C30	1.388 (3)
Cu2—Cl3	2.0832 (8)	C26—C27	1.382 (4)
N14—C7	1.271 (3)	C27—C28	1.365 (4)
N14—C15	1.491 (4)	C28—C29	1.350 (4)
N17—C16	1.473 (3)	C29—C30	1.394 (4)
N17—C18	1.283 (4)	C1—H1	0.950
C1—C2	1.379 (5)	C2—H2	0.950
C1—C6	1.381 (3)	C3—H3	0.950
C2—C3	1.349 (5)	C4—H4	0.950
C3—C4	1.361 (3)	C5—H5	0.950
C4—C5	1.383 (4)	C9—H9	0.950
C5—C6	1.385 (4)	C10—H10	0.950
C6—C7	1.486 (3)	C11—H11	0.950
C7—C8	1.497 (2)	C12—H12	0.950
C8—C9	1.377 (4)	C13—H13	0.950
C8—C13	1.368 (4)	C15—H15A	0.950
C9—C10	1.392 (3)	C15—H15B	0.950
C10—C11	1.361 (5)	C16—H16A	0.950
C11—C12	1.359 (4)	C16—H16B	0.950
C12—C13	1.376 (3)	C20—H20	0.950
C15—C16	1.525 (4)	C21—H21	0.950
C18—C19	1.486 (3)	C22—H22	0.950
C18—C25	1.497 (3)	C23—H23	0.950
C19—C20	1.382 (4)	C24—H24	0.950
C19—C24	1.391 (4)	C26—H26	0.950
C20—C21	1.381 (4)	C27—H27	0.950
C21—C22	1.361 (6)	C28—H28	0.950
C22—C23	1.362 (6)	C29—H29	0.950
C23—C24	1.378 (3)	C30—H30	0.950
N14—Cu1—N14^i	140.0 (1)	C2—C1—H1	119.3
N14—Cu1—N17	85.98 (8)	C6—C1—H1	119.3
N14—Cu1—N17^i	109.50 (8)	C1—C2—H2	119.7
N17—Cu1—N17^i	134.7 (1)	C3—C2—H2	119.7
Cl3—Cu2—Cl3^ii	180 (1)	C2—C3—H3	120.3
Cu1—N14—C7	131.2 (2)	C4—C3—H3	120.3
Cu1—N14—C15	107.7 (2)	C3—C4—H4	119.6
C7—N14—C15	118.3 (2)	C5—C4—H4	119.6
Cu1—N17—C16	104.2 (2)	C4—C5—H5	119.7
Cu1—N17—C18	134.6 (1)	C6—C5—H5	119.7
C16—N17—C18	118.5 (2)	C8—C9—H9	119.7
C2—C1—C6	121.5 (3)	C10—C9—H9	119.7
C1—C2—C3	120.7 (3)	C9—C10—H10	120.3
C2—C3—C4	119.3 (3)	C11—C10—H10	120.3
C3—C4—C5	120.8 (3)	C10—C11—H11	119.8
C4—C5—C6	120.7 (2)	C12—C11—H11	119.8
C1—C6—C5	117.0 (2)	C11—C12—H12	119.9
C1—C6—C7	121.5 (3)	C13—C12—H12	119.9
C5—C6—C7	121.4 (2)	C8—C13—H13	119.6
N14—C7—C6	120.8 (2)	C12—C13—H13	119.6
N14—C7—C8	122.4 (2)	N14—C15—H15A	109.7
C6—C7—C8	116.8 (2)	N14—C15—H15B	109.7
C7—C8—C9	121.6 (2)	C16—C15—H15A	109.7
C7—C8—C13	119.7 (2)	C16—C15—H15B	109.7
C9—C8—C13	118.7 (2)	H15A—C15—H15B	109.5
C8—C9—C10	120.5 (3)	N17—C16—H16A	109.4
C9—C10—C11	119.4 (3)	N17—C16—H16B	109.4
C10—C11—C12	120.4 (2)	C15—C16—H16A	109.4
C11—C12—C13	120.2 (3)	C15—C16—H16B	109.4
C8—C13—C12	120.8 (3)	H16A—C16—H16B	109.5
N14—C15—C16	108.6 (2)	C19—C20—H20	119.5
N17—C16—C15	109.7 (2)	C21—C20—H20	119.5
N17—C18—C19	121.6 (2)	C20—C21—H21	119.8
N17—C18—C25	122.3 (2)	C22—C21—H21	119.8
C19—C18—C25	116.1 (2)	C21—C22—H22	120.1
C18—C19—C20	122.0 (2)	C23—C22—H22	120.1
C18—C19—C24	120.6 (2)	C22—C23—H23	119.9
C20—C19—C24	117.3 (2)	C24—C23—H23	119.9
C19—C20—C21	121.1 (3)	C19—C24—H24	119.5
C20—C21—C22	120.4 (4)	C23—C24—H24	119.5
C21—C22—C23	119.9 (3)	C25—C26—H26	119.5
C22—C23—C24	120.2 (3)	C27—C26—H26	119.5
C19—C24—C23	121.1 (3)	C26—C27—H27	120.1
C18—C25—C26	119.7 (2)	C28—C27—H27	120.1
C18—C25—C30	121.9 (2)	C27—C28—H28	119.8
C26—C25—C30	118.4 (2)	C29—C28—H28	119.8
C25—C26—C27	121.1 (2)	C28—C29—H29	119.7
C26—C27—C28	119.7 (3)	C30—C29—H29	119.7
C27—C28—C29	120.4 (3)	C25—C30—H30	120.1
C28—C29—C30	120.6 (2)	C29—C30—H30	120.1
C25—C30—C29	119.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···Cl3^iii	0.95	2.71	3.652 (4)	173
C26—H26···Cg1^i	0.95	3.08	3.922 (4)	148
C4—H4···Cg2^iv	0.95	2.99	3.812 (4)	146
C13—H13···Cg3^i	0.95	2.79	3.729 (4)	167
C12—H12···Cg4^v	0.95	2.89	3.791 (4)	158

Symmetry codes: (i) −x+1, y, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z+1; (v) x, −y, z+1/2.