[N-(1-Aza-nidyl-2,2,2-trichloro-ethyl-idene)-2,2,2-trichloro-ethanimidamide]-copper(II).

The title compound, [Cu(C(4)H(2)Cl(6)N(3))(2)], was obtained by the reaction of CCl(3)CN with ammonia in presence of CuCl. The Cu(II) atom is located about an inversion centre. The mol-ecule consists of three planar units (one central square CuN(4) and two C(2)N(3) fragments), adopting a staircase-like structure. The six-membered metallocycles have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triaza-penta-dienyl ligands by 0.246 (5) Å. The ipso-C atoms of the CCl(3) substituents are slightly out of the 1,3,5-triaza-penta-dienyl planes by 0.149 (6) and -0.106 (6) Å. The CCl(3) groups of each 1,3,5-triaza-penta-dienyl ligand are practically in the energetic-ally favourable mutually eclipsed conformation. In the crystal, the mol-ecules are packed in stacks along the a axis. The mol-ecules in the stacks are held together by two additional axial Cu⋯Cl inter-actions of 3.354 (2) Å. Taking the axial Cu⋯Cl inter-actions into account, the Cu(II) atom exhibits a distorted [4 + 2]-octa-hedral coordination environment. The stacks are bound to each other by weak inter-molecular attractive Cl⋯Cl [3.505 (2)-3.592 (3) Å] inter-actions.

Related literature

For a catalytic olefination reaction, see: Shastin et al. (2001 ▶); Korotchenko et al. (2001 ▶); Nenajdenko et al. (2003 ▶, 2004a ▶,b ▶,c ▶, 2005 ▶, 2007 ▶). For related compounds, see: Boča et al. (1996 ▶); Kajiwara et al. (2002 ▶); Zhang et al. (2005 ▶); Igashira-Kamiyama et al. (2006 ▶); Zheng et al. (2007 ▶); Figiel et al. (2010 ▶).

Experimental

Crystal data

[Cu(C4H2Cl6N3)2]

M = 673.11

Triclinic,

a = 5.9317 (17) Å

b = 9.078 (3) Å

c = 10.831 (3) Å

α = 98.475 (5)°

β = 97.525 (5)°

γ = 103.662 (5)°

V = 552.1 (3) Å3

Z = 1

Mo Kα radiation

μ = 2.45 mm−1

T = 296 K

0.33 × 0.24 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.499, T max = 0.867

5662 measured reflections

2414 independent reflections

2108 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.133

S = 1.00

2414 reflections

124 parameters

H-atom parameters constrained

Δρmax = 1.18 e Å−3

Δρmin = −0.85 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036124/aa2069sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036124/aa2069Isup2.hkl

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

[Cu(C4H2Cl6N3)2]	Z = 1
Mr = 673.11	F(000) = 327
Triclinic, P1	Dx = 2.024 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.9317 (17) Å	Cell parameters from 3874 reflections
b = 9.078 (3) Å	θ = 2.4–27.7°
c = 10.831 (3) Å	µ = 2.45 mm−1
α = 98.475 (5)°	T = 296 K
β = 97.525 (5)°	Plate, red
γ = 103.662 (5)°	0.33 × 0.24 × 0.06 mm
V = 552.1 (3) Å3

Bruker APEXII CCD diffractometer	2414 independent reflections
Radiation source: fine-focus sealed tube	2108 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.499, Tmax = 0.867	k = −11→11
5662 measured reflections	l = −13→13

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.076P)2 + 0.84P] where P = (Fo2 + 2Fc2)/3
2414 reflections	(Δ/σ)max < 0.001
124 parameters	Δρmax = 1.18 e Å−3
0 restraints	Δρmin = −0.85 e Å−3

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

	x	y	z	Uiso*/Ueq
Cu1	1.0000	1.0000	0.0000	0.03611 (19)
Cl1	0.20230 (19)	0.81177 (15)	0.21612 (13)	0.0696 (3)
Cl2	0.28874 (19)	0.61212 (13)	0.01081 (11)	0.0644 (3)
Cl3	0.5633 (2)	0.65213 (14)	0.25606 (12)	0.0677 (3)
Cl4	1.0465 (2)	1.42819 (12)	0.33037 (12)	0.0730 (4)
Cl5	0.5879 (2)	1.27757 (17)	0.35949 (16)	0.0868 (5)
Cl6	0.9881 (3)	1.18805 (17)	0.47247 (11)	0.0886 (5)
N1	0.7097 (5)	0.8671 (3)	0.0275 (3)	0.0437 (7)
H1	0.6365	0.7918	−0.0331	0.052*
C2	0.6169 (5)	0.8813 (4)	0.1278 (3)	0.0358 (6)
N3	0.6704 (5)	0.9993 (3)	0.2235 (3)	0.0441 (7)
C4	0.8405 (6)	1.1234 (4)	0.2244 (3)	0.0353 (6)
N5	0.9823 (6)	1.1456 (3)	0.1452 (3)	0.0446 (7)
H5	1.0802	1.2351	0.1582	0.054*
C6	0.4243 (6)	0.7471 (4)	0.1511 (4)	0.0421 (7)
C7	0.8629 (7)	1.2489 (4)	0.3416 (3)	0.0425 (7)

	U11	U22	U33	U12	U13	U23
Cu1	0.0386 (3)	0.0301 (3)	0.0377 (3)	0.0011 (2)	0.0172 (2)	0.0035 (2)
Cl1	0.0495 (6)	0.0725 (7)	0.0932 (9)	0.0109 (5)	0.0390 (6)	0.0205 (6)
Cl2	0.0505 (5)	0.0531 (6)	0.0697 (7)	−0.0144 (4)	0.0029 (5)	0.0011 (5)
Cl3	0.0586 (6)	0.0634 (7)	0.0806 (8)	0.0026 (5)	0.0025 (5)	0.0422 (6)
Cl4	0.0951 (9)	0.0370 (5)	0.0731 (7)	−0.0102 (5)	0.0382 (6)	−0.0097 (5)
Cl5	0.0568 (7)	0.0793 (8)	0.1141 (11)	0.0171 (6)	0.0303 (7)	−0.0268 (8)
Cl6	0.1405 (14)	0.0778 (9)	0.0422 (6)	0.0311 (9)	−0.0047 (7)	0.0076 (5)
N1	0.0425 (15)	0.0386 (15)	0.0407 (15)	−0.0039 (12)	0.0135 (12)	−0.0039 (12)
C2	0.0343 (15)	0.0320 (15)	0.0399 (16)	0.0027 (12)	0.0094 (12)	0.0099 (12)
N3	0.0496 (16)	0.0379 (15)	0.0401 (15)	−0.0022 (12)	0.0199 (13)	0.0035 (12)
C4	0.0397 (16)	0.0312 (15)	0.0346 (15)	0.0058 (12)	0.0109 (12)	0.0063 (12)
N5	0.0515 (17)	0.0300 (14)	0.0478 (16)	−0.0025 (12)	0.0241 (13)	0.0003 (12)
C6	0.0341 (16)	0.0409 (17)	0.0505 (19)	0.0028 (13)	0.0118 (14)	0.0136 (14)
C7	0.0497 (19)	0.0364 (17)	0.0394 (17)	0.0066 (14)	0.0158 (14)	0.0014 (13)

Cu1—N5	1.931 (3)	N1—C2	1.284 (4)
Cu1—N1	1.941 (3)	N1—H1	0.8600
Cl1—C6	1.749 (4)	C2—N3	1.322 (4)
Cl2—C6	1.767 (4)	C2—C6	1.537 (4)
Cl3—C6	1.759 (4)	N3—C4	1.321 (4)
Cl4—C7	1.762 (4)	C4—N5	1.282 (4)
Cl5—C7	1.742 (4)	C4—C7	1.544 (4)
Cl6—C7	1.736 (4)	N5—H5	0.8600
N5—Cu1—N1	87.83 (12)	Cu1—N5—H5	116.4
C2—N1—Cu1	126.0 (2)	C2—C6—Cl1	111.9 (2)
C2—N1—H1	117.0	C2—C6—Cl3	106.7 (2)
Cu1—N1—H1	117.0	Cl1—C6—Cl3	110.2 (2)
N1—C2—N3	128.5 (3)	C2—C6—Cl2	112.5 (2)
N1—C2—C6	120.3 (3)	Cl1—C6—Cl2	107.50 (19)
N3—C2—C6	111.2 (3)	Cl3—C6—Cl2	108.0 (2)
C4—N3—C2	120.5 (3)	C4—C7—Cl6	107.4 (2)
N5—C4—N3	128.3 (3)	C4—C7—Cl5	110.5 (2)
N5—C4—C7	120.3 (3)	Cl6—C7—Cl5	111.2 (2)
N3—C4—C7	111.4 (3)	C4—C7—Cl4	112.4 (2)
C4—N5—Cu1	127.1 (2)	Cl6—C7—Cl4	108.0 (2)
C4—N5—H5	116.4	Cl5—C7—Cl4	107.3 (2)
N5—Cu1—N1—C2	−14.1 (3)	N1—C2—C6—Cl1	−140.6 (3)
N5i—Cu1—N1—C2	165.9 (3)	N3—C2—C6—Cl1	41.9 (4)
Cu1—N1—C2—N3	12.6 (6)	N1—C2—C6—Cl3	98.8 (3)
Cu1—N1—C2—C6	−164.4 (2)	N3—C2—C6—Cl3	−78.7 (3)
N1—C2—N3—C4	−0.4 (6)	N1—C2—C6—Cl2	−19.5 (4)
C6—C2—N3—C4	176.7 (3)	N3—C2—C6—Cl2	163.0 (3)
C2—N3—C4—N5	−5.2 (6)	N5—C4—C7—Cl6	−105.0 (3)
C2—N3—C4—C7	177.1 (3)	N3—C4—C7—Cl6	72.9 (3)
N3—C4—N5—Cu1	−2.2 (6)	N5—C4—C7—Cl5	133.5 (3)
C7—C4—N5—Cu1	175.3 (2)	N3—C4—C7—Cl5	−48.6 (4)
N1—Cu1—N5—C4	9.6 (3)	N5—C4—C7—Cl4	13.7 (4)
N1i—Cu1—N5—C4	−170.4 (3)	N3—C4—C7—Cl4	−168.4 (3)