metal-organic compounds
[N-(1-Azanidyl-2,2,2-trichloroethylidene)-2,2,2-trichloroethanimidamide]copper(II)
aBaku State University, Z. Khalilov St 23, Baku AZ-1148, Azerbaijan, bChemistry Department, M.V. Lomonosov Moscow State University, Leninskie gory 1/3, Moscow 119991, Russian Federation, and cX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov St B-334, Moscow 119991, Russian Federation
*Correspondence e-mail: namiq155@yahoo.com
The title compound, [Cu(C4H2Cl6N3)2], was obtained by the reaction of CCl3CN with ammonia in presence of CuCl. The CuII atom is located about an inversion centre. The molecule consists of three planar units (one central square CuN4 and two C2N3 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-triazapentadienyl ligands by 0.246 (5) Å. The ipso-C atoms of the CCl3 substituents are slightly out of the 1,3,5-triazapentadienyl planes by 0.149 (6) and −0.106 (6) Å. The CCl3 groups of each 1,3,5-triazapentadienyl ligand are practically in the energetically favourable mutually eclipsed conformation. In the crystal, the molecules are packed in stacks along the a axis. The molecules in the stacks are held together by two additional axial Cu⋯Cl interactions of 3.354 (2) Å. Taking the axial Cu⋯Cl interactions into account, the CuII atom exhibits a distorted [4 + 2]-octahedral coordination environment. The stacks are bound to each other by weak intermolecular attractive Cl⋯Cl [3.505 (2)–3.592 (3) Å] interactions.
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
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Data collection: APEX2 (Bruker, 2005); cell 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.
Supporting information
10.1107/S1600536812036124/aa2069sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812036124/aa2069Isup2.hkl
A solution of trichloroacetonitrile (7.3 ml) in DMSO (15 ml) was dropped to a mixture of aqueous ammonia (5 ml) and freshly purified copper monochloride (0.3 g) during 3 min. upon keeping of the room temperature by the cooling on water-bath. The reaction mixture was stirred for 4 h. At the end of the reaction, the mixture was washed with water (150 ml) and filtered off. The formed product was re-crystallized from aqueous ethanol to give 1.47 g of red crystals of I. Yield is 73%. M.p. = 472–474 K.
The hydrogen atoms were placed in calculated positions with N–H = 0.86 Å and refined in the riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(N)].
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).[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 |
[Cu(C4H2Cl6N3)2] | γ = 103.662 (5)° |
Mr = 673.11 | V = 552.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.9317 (17) Å | Mo Kα radiation |
b = 9.078 (3) Å | µ = 2.45 mm−1 |
c = 10.831 (3) Å | T = 296 K |
α = 98.475 (5)° | 0.33 × 0.24 × 0.06 mm |
β = 97.525 (5)° |
Bruker APEXII CCD diffractometer | 2414 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2108 reflections with I > 2σ(I) |
Tmin = 0.499, Tmax = 0.867 | Rint = 0.029 |
5662 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.18 e Å−3 |
2414 reflections | Δρmin = −0.85 e Å−3 |
124 parameters |
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) |
Symmetry code: (i) −x+2, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C4H2Cl6N3)2] |
Mr | 673.11 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 5.9317 (17), 9.078 (3), 10.831 (3) |
α, β, γ (°) | 98.475 (5), 97.525 (5), 103.662 (5) |
V (Å3) | 552.1 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.45 |
Crystal size (mm) | 0.33 × 0.24 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.499, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5662, 2414, 2108 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.133, 1.00 |
No. of reflections | 2414 |
No. of parameters | 124 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.18, −0.85 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Recently we have discovered a new catalytic olefination reaction as a general method for the preparation of alkenes from polyhalogenated compounds and hydrazones (Fig. 1) (Shastin et al., 2001; Korotchenko et al., 2001; Nenajdenko et al., 2003, 2004a, 2004b, 2005, 2007).
During our study of the catalytic olefination reaction we have found that the reaction with trichloroacetonitrile demand the use of ethylenediamine as a base because in the case of ammonia no target alkene is formed (Nenajdenko et al., 2004c). We decided to study the reaction of CCl3CN with ammonia in presence of CuCl more thoroughly and found that the formation of the title copper (II) chelate complex takes place (Fig. 2). The formation of this complex can be explained by high electrophilicity of trichloroacetonitrile (Fig. 3). At the first stage, ammonia reacts with CN bond to form amidine A as an intermediate. The subsequent reaction of A with second molecule of trichloroacetonitrile gives B. And finally, B reacts with CuCl2 resulting in the copper(II) complex I in a high yield. We believe that Cu2+is formed by oxidation of Cu1+ with CCl3CN as it was confirmed previously for catalytic olefination reaction.
The structure of the title compound I, C8H4N6Cl12Cu, was unambigouosly established by X-ray diffraction study (Fig. 4). The compound I crystallizes in the triclinic space group P-1 and there is a crystallographically imposed inversion centre at the Cu atom of each molecule. The Cu atom has a square-planar coordination. The 1,3,5-triazapentadienyl ligands are also planar (r.m.s. deviation is 0.021 Å). However, the six-membered metallocycles deviate significantly from the planarity and have a sofa conformation with the Cu atom out of the plane of the 1,3,5-triazapentadienyl ligands by 0.246 (5) Å. Thus, the molecule of I consists of the three planar units adopting the staircase-like structure. The similar molecular conformation has been previously observed in the related compounds (Zhang et al., 2005; Igashira-Kamiyama et al., 2006; Figiel et al., 2010). Nevertheless, it is important to note that the analogous complexes can adopt the planar conformation also (Boča et al., 1996; Kajiwara et al., 2002; Zheng et al., 2007). The ipso-C atoms of the CCl3-substituents are slightly out of the 1,3,5-triazapentadienyl planes by 0.149 (6) and -0.106 (6) Å. The CCl3-groups of each 1,3,5-triazapentadienyl ligand are practically in the energetically favorable eclipsed mutual conformation.
In the crystal, the molecules are packed in stacks along the a axis (Fig. 5). The molecules in the stacks are held together by the two additional axial Cu···Cl [Cu1···Cl1i and Cu1···Cl1ii] interactions of 3.354 (2) Å. Taking the axial Cu···Cl interactions into account, the Cu atom attains the distorted [4 + 2]-octahedral coordination environment. The different stacks are bound to each other by weak intermolecular attractive interactions [Cu2···Cl2iii 3.505 (2), Cu2···Cl2iv 3.592 (3), Cu3···Cl4v 3.516 (2) and Cu3···Cl6vi 3.564 (2) Å] . Symmetry codes: (i) -x, -y + 2, -z + 2; (ii) x - 1, y, z; (iii) -x + 2, -y + 3, -z + 2; (iv) -x + 1, -y + 3, -z + 2; (v) x + 1, y + 1, z; (vi) -x, -y + 2, -z + 1.