{N,N′-Bis[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ4N,N′,N′′,N′′′}bis­(trifluoro­methane­sulfanato-κO)copper(II)

Coles, S.J.; Sengul, A.; Kurt, O.; Altin, S.

doi:10.1107/S1600536808033151

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1435

doi:10.1107/S1600536808033151

Open

access

{N,N′-Bis[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ⁴N,N′,N′′,N′′′}bis(trifluoromethanesulfanato-κO)copper(II)

Simon J. Coles,^a ^* Abdurrahman Sengul,^b ‡ Ozgur Kurt ^b and Safinaz Altin ^b

^aSchool of Chemistry, University of Southampton, Southampton SO17 1BJ, England, and ^bDepartment of Chemistry, Faculty of Arts and Sciences, Zonguldak Karaelmas University, 67100 Zonguldak, Turkey
^*Correspondence e-mail: s.j.coles@soton.ac.uk

(Received 12 August 2008; accepted 13 October 2008; online 18 October 2008)

A discrete neutral Cu^II complex, [Cu(CF₃SO₃)₂(C₁₆H₁₈N₄)], has been derived from the symmetrical tetradentate Schiff base, N,N′-bis[1-(pyridin-2-yl)ethylidene]ethane-1,2-diamine. The copper centre assumes a tetragonally distorted pseudo-octahedral geometry with the O atoms of two trifluoromethanesulfonate anions coordinated weakly in the axial positions. The Cu—N distances lie in the range 1.941 (3)–2.011 (3) Å and the Cu—O distances are 2.474 (3) and 2.564 (3) Å.

Related literature

For general background, see: Gourbatsis et al. (1999 ); Hamblin et al. (2002 ); Menteş et al. (2007 ); Szklarzewicz & Samotus (2002 ). For related synthesis, see: Hanack et al. (1988 ); Luo et al. (1993 ); Marks (1990 ). For related structural characteristics, see: Bowyer et al. (1998 ); Gourbatsis et al. (1998 ); Cremer & Pople (1975 ); Fielden et al. (2006 ); Haynes et al. (1988 ); Şengül & Büyükgüngör (2005 ).

Experimental

Crystal data

[Cu(CF₃SO₃)₂(C₁₆H₁₈N₄)]
M_r = 628.02
Monoclinic, P 2₁ /c
a = 9.2228 (4) Å
b = 25.5574 (13) Å
c = 9.8189 (5) Å
β = 94.961 (3)°
V = 2305.75 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 120 (2) K
0.35 × 0.2 × 0.06 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.78, T_max = 0.93
18769 measured reflections
5052 independent reflections
4062 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.118
S = 1.09
5052 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: DENZO (Otwinowski & Minor, 1997 ); cell refinement: DENZO and COLLECT (Nonius, 1998 ); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033151/bg2203sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033151/bg2203Isup2.hkl

checkCIF report

Comment top

Recently, the coordination chemistry of di-Schiff bases derived from 2-pyridyl ketones or aldehydes has generated a great deal of interest (Hamblin et al., 2002; Gourbatsis et al., 1998; Szklarzewicz & Samotus, 2002; Mentes et al., 2007). These studies have been mostly stimulated by an interest in modelling the enzyme, copper-zinc superoxide dismutase (SOD) (Luo et al., 1993) and also for the synthesis of metal containing polymers with interesting optical, magnetic and electrical properties (Hanack et al., 1988; Marks, 1990). It has also been found that such tetradentate Schiff base ligands may form complexes with different nuclearity according to the coordination preferences of the metal centre (Fielden et al., 2006).

Our interest in the ligand, L, (Scheme 2) was stimulated by the analogy between its donor set and that of the pyridylmethylketazine (L¹) and 2-pyridinealdazine (L²) system which form triple-stranded helical complexes with the formula [M₂(L)₃]⁴⁺ (M = Co, Fe and Ni). The helical complexes were shown to undergo exchange reactions on standing to form mono-nuclear complexes [M(L)₂]²⁺ in which the ligand twists to coordinate as tridentate with non-coordinated imine residue (Hamblin et al., 2002). Mononuclear species are favoured by coordination to octahedral metal centres whose equatorial sites are occupied by N4 donor set of the bis(axial) ligand, and their axial sites being occuppied by solvent molecules or counterions. In addition, dinuclear metal complexes are favoured by the four-coordinate tetrahedral metal centres whose ca 90° twist angle provides good geometric match for the bis(equatorial) ligand (Fielden et al., 2006).

Recently, the single-crystal X-ray analysis of L was reported (Mentes et al., 2007). The molecule adopts a centrosymmetric trans geometry and forms a dinuclear complex by reacting with Mo(CO)₆. The reaction of L with ZnX₂ (X = Cl or Br) in tetrahydrofuran yielded an octahedral complex [ZnX₂(L)] (Gourbatsis et al., 1999), whereas by reacting with a silver(I) cation the double-stranded helical complex [Ag₂(L)₂][BF₄]₂ (Bowyer et al., 1998) is formed. The synthesis of copper(II) complex by using Cu(NO₃)₂.3H₂O resulted in the tetragonally distorted octahedral complex, [Cu(L)(ONO₂)(OH₂)][NO₃] (Gourbatsis et al., 1998).

Herein we present the synthesis and structure of the complex [Cu(L)(OTf)₂], (where OTf = trifluoromethanesulfonate) with a molecular structure as illustrated in Scheme 1 and Figure 1. The crystal structure is composed of discrete neutral [Cu(L)(OTf)₂] units. The copper ion exhibits an elongated tetragonal octahedral CuN₄O₂ cromophore with four nitrogen atoms from the ligand occupying the equatorial plane and two axial oxygen atoms from the trans-coordinated unidentate trifluoromethanesulfonate anions. The four equatorial Cu–N distances [Cu1–N1 2.008 (3) Å, Cu1–N4 2.011 (3) Å, Cu1–N2 1.950 (2) Å, and Cu1–N3 1.944 (2) Å] are normal for this class of compounds and also very similar to those of Cu1–Npyridine 2.002 (4) and 2.022 (4) Å, and Cu1–Nimine 1.943 (4) and 1.938 (4) Å as found in [Cu(L)(ONO₂)(OH₂)][NO₃] (Gourbatsis et al., 1998). The bond lengths to the imine N atoms are slightly shorter than those to the pyridine N atoms (Table 1), which is presumably a consequence of the more effective σ donation or π back donation (Hamblin et al., 2002). The coordination is of the 4 + 2 type and thus belongs to the myriad of examples of such Jahn-Teller elongated pseudo-octahedral structures (Şengül & Büyükgüngör, 2005).

The structure contains unidentate trifluoromethanesulfonate anions which are semi-coordinated to the copper ion [Cu1–O2 2.568 (3) Å and Cu1–O4 2.476 (4) Å] in the axial positions with the angle of O2–Cu1–O4 177.9 (4)°. The bonding parameters for the trifluoromethanesulfonate anions are similar to those found for [Cu(pyridine)₄(CF₃SO₃)₂] (Haynes et al., 1988). For example, the trifluoromethanesulfonate anions adopt a staggered-ethane configuration about the S–C bond and the O–S–O angles [O3–S1–O1 116.01 (15)°, O3–S1–O2 113.97 (14)°, O1–S1–O2 114.93 (15)°] are greater than the C–S–O angles [C17–S1–O3 103.25 (15)°, C17–S1–O1 103.00 (15)°, and C17–S1–O2 103.25 (15)°]. The S–O bond lengths are also very similar to those found in [Cu(pyridine)₄(CF₃SO₃)₂], the S1–O2 1.450 (2) and S2–O4 1.446 (2) Å bonds involving the O atoms bound to copper being longer than those involving the terminally bound oxygen atoms [S1–O1 1.442 (2), S1–O3 1.440 (2) Å and S2–O5 1.441 (2), S2–O6 1.440 (2) Å].

The bite angles around the copper ion [N2–Cu1–N3 83.2 (2), N1–Cu1–N2 81.9 (7), N3–Cu1–N4 81.6 (7)°] are very similar to those found in [Cu(L)(ONO₂)(OH₂)][NO₃] with the corresponding angles of 83.2 (2), 80.6 (2) and 81.4 (2)°, respectively.

In the free ligand the pyridylimine units adopt a transoid configuration to minimize unfavourable electronic interactions between the lone pairs of pyridine nitrogen and imine nitrogen atoms. However, in the presence of a metal ion, the pyridine rings rotate by 180° with respect to the Aryl–C bond, positioning the two nitrogen atoms of each pyridylimine moiety on the same side of the ligand. Otherwise the geometric parameters in the free ligand are very similar to those of the coordinated moiety.

The pyridylimine units are not ideally planar due to a combined effect of the ring to the metal centre and a twist induced by the ethylene bridge [Cu1, N1, N2, C1>C6 and Cu1, N3, N4, C10, C12>C16 have devaitions from the mean plane of 0.088 (6) Å and 0.106 (6) Å for N2 and N3 respectively]. From puckering analysis (Cremer & Pople, 1975) the ring formed by the metal centre, the imine N atoms and the ethylene bridge has a Q value of 0.283 (3) Å and forms a twisted envelope conformation about the C8—C9 bond. This effect has the result of pushing the methyl groups out of the ring unit plane, with C7 deviating by 0.149 (5) Å and C11 by 0.167 (6) Å and accordingly the pyridylimine units are not coplanar, with the angle formed between these planes being 12.98 (9)°.

The crystal structure does not exhibit any classical hydrogen bonds and is primarily comprised of stacked undulating sheets formed by close packing and C—H···O interactions between the SO₃ group and pyridylimine ring H atoms.

Related literature top

Gourbatsis et al. (1998); Gourbatsis et al. (1999); Hamblin et al. (2002); Hanack et al. (1988); Luo et al. (1993); Mentes et al. (2007); Szklarzewicz & Samotus (2002). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that it said, for example, "For general background, see···. For related structures, see···; etc. Please revise this section as indicated.

For related literature, see: Bowyer et al. (1998); Cremer & Pople (1975); Fielden et al. (2006); Haynes et al. (1988); Marks (1990); Şengül & Büyükgüngör (2005).

Experimental top

The ligand, N,N'-bis-(1-pyridin-2-yl-ethylidene)-ethane-1,2-diamine (L) (0.213 g; 0.8 mmol) and Cu(CF3SO3)2 (0.297 g; 0.8 mmol) were dissolved in a minimum amount of methanol. The solution was stirred at room temperature for half an hour and filtered. The navy blue solution was poured into sample tubes and left for crystallization to yield very dark navy blue block crystals suitable for X-ray diffraction analysis. Anal. Calc.: C, 34.42; H, 2.89; N, 8.92. Found: C, 34.64; H, 3.07; N, 9.06%. ESI-MS (m/z) = 478.0 [Cu(L)(OTf)]⁺.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

Fig. 1. Molecular structure of the title compound (50% probability displacement ellipsoids).

{N,N'-Bis[1-(2-pyridyl)ethylidene]ethane-1,2-diamine- κ⁴N,N',N'',N'''}bis(trifluoromethanesulfanato- κO)copper(II) top

Crystal data top

[Cu(CF₃SO₃)₂(C₁₆H₁₈N₄)]	F(000) = 1268
M_r = 628.02	D_x = 1.809 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26348 reflections
a = 9.2228 (4) Å	θ = 2.9–27.5°
b = 25.5574 (13) Å	µ = 1.22 mm⁻¹
c = 9.8189 (5) Å	T = 120 K
β = 94.961 (3)°	Block, blue
V = 2305.75 (19) Å³	0.35 × 0.2 × 0.06 mm
Z = 4

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	4062 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.043
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	θ_max = 27.5°, θ_min = 3.0°
T_min = 0.78, T_max = 0.93	h = −11→11
18769 measured reflections	k = −30→33
5052 independent reflections	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.0383P)² + 4.934P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.118	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.43 e Å⁻³
5052 reflections	Δρ_min = −0.64 e Å⁻³
334 parameters

Crystal data top

[Cu(CF₃SO₃)₂(C₁₆H₁₈N₄)]	V = 2305.75 (19) Å³
M_r = 628.02	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.2228 (4) Å	µ = 1.22 mm⁻¹
b = 25.5574 (13) Å	T = 120 K
c = 9.8189 (5) Å	0.35 × 0.2 × 0.06 mm
β = 94.961 (3)°

Data collection top

Bruker–Nonius KappaCCD area-detector diffractometer	5052 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	4062 reflections with I > 2σ(I)
T_min = 0.78, T_max = 0.93	R_int = 0.043
18769 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.09	Δρ_max = 0.43 e Å⁻³
5052 reflections	Δρ_min = −0.64 e Å⁻³
334 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.36217 (4)	0.096617 (15)	0.13089 (4)	0.01732 (17)
S1	0.61344 (9)	0.13260 (3)	−0.13780 (9)	0.0201 (2)
S2	0.11834 (9)	0.11566 (4)	0.40390 (9)	0.0216 (2)
F1	0.6938 (2)	0.20219 (8)	0.0510 (2)	0.0335 (5)
F2	0.8673 (2)	0.15164 (8)	−0.0042 (2)	0.0339 (6)
F3	0.7879 (2)	0.21298 (8)	−0.1408 (3)	0.0395 (6)
F4	−0.1392 (2)	0.14451 (8)	0.2941 (2)	0.0329 (5)
F5	−0.0500 (3)	0.19350 (10)	0.4589 (3)	0.0529 (8)
F6	0.0325 (2)	0.19887 (9)	0.2612 (3)	0.0451 (7)
O1	0.5026 (3)	0.16759 (10)	−0.1968 (3)	0.0294 (6)
O2	0.5698 (3)	0.10044 (9)	−0.0264 (3)	0.0246 (6)
O3	0.6956 (3)	0.10514 (10)	−0.2337 (3)	0.0293 (6)
O4	0.1560 (3)	0.09377 (9)	0.2761 (3)	0.0260 (6)
O5	0.0389 (3)	0.08055 (11)	0.4852 (3)	0.0321 (6)
O6	0.2334 (3)	0.14490 (11)	0.4778 (3)	0.0349 (7)
N1	0.2386 (3)	0.05333 (10)	−0.0051 (3)	0.0169 (6)
N2	0.2689 (3)	0.15379 (10)	0.0252 (3)	0.0188 (6)
N3	0.4497 (3)	0.15332 (10)	0.2410 (3)	0.0177 (6)
N4	0.4951 (3)	0.05365 (10)	0.2608 (3)	0.0164 (6)
C1	0.2187 (4)	0.00137 (13)	−0.0122 (4)	0.0214 (7)
H1	0.2688	−0.0198	0.0531	0.026*
C2	0.1266 (4)	−0.02194 (14)	−0.1130 (4)	0.0252 (8)
H2	0.1149	−0.0581	−0.1155	0.030*
C3	0.0525 (4)	0.00934 (14)	−0.2097 (4)	0.0278 (8)
H3	−0.0091	−0.0055	−0.2791	0.033*
C4	0.0702 (4)	0.06320 (14)	−0.2027 (4)	0.0251 (8)
H4	0.0187	0.0848	−0.2659	0.030*
C5	0.1647 (4)	0.08421 (14)	−0.1013 (4)	0.0184 (7)
C6	0.1917 (4)	0.14160 (13)	−0.0857 (4)	0.0192 (7)
C7	0.1385 (4)	0.17828 (14)	−0.1956 (4)	0.0261 (8)
H7A	0.1495	0.2136	−0.1630	0.039*
H7B	0.0376	0.1714	−0.2219	0.039*
H7C	0.1939	0.1736	−0.2731	0.039*
C8	0.3222 (4)	0.20639 (12)	0.0623 (4)	0.0214 (7)
H8A	0.2428	0.2314	0.0514	0.026*
H8B	0.3961	0.2169	0.0032	0.026*
C9	0.3872 (4)	0.20533 (12)	0.2131 (4)	0.0212 (7)
H9A	0.4619	0.2319	0.2281	0.025*
H9B	0.3117	0.2123	0.2736	0.025*
C10	0.5278 (4)	0.14069 (13)	0.3512 (4)	0.0197 (7)
C11	0.5756 (4)	0.17735 (13)	0.4637 (4)	0.0258 (8)
H11A	0.5662	0.2127	0.4311	0.039*
H11B	0.6755	0.1705	0.4944	0.039*
H11C	0.5161	0.1725	0.5382	0.039*
C12	0.5645 (3)	0.08382 (13)	0.3585 (3)	0.0177 (7)
C13	0.6640 (4)	0.06293 (14)	0.4569 (4)	0.0231 (8)
H13	0.7115	0.0843	0.5233	0.028*
C14	0.6917 (4)	0.00970 (14)	0.4551 (4)	0.0240 (8)
H14	0.7586	−0.0050	0.5205	0.029*
C15	0.6207 (3)	−0.02138 (14)	0.3572 (4)	0.0228 (8)
H15	0.6378	−0.0572	0.3550	0.027*
C16	0.5222 (3)	0.00235 (13)	0.2610 (3)	0.0192 (7)
H16	0.4733	−0.0184	0.1940	0.023*
C17	0.7467 (4)	0.17719 (14)	−0.0524 (4)	0.0258 (8)
C18	−0.0166 (4)	0.16582 (14)	0.3522 (4)	0.0298 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0212 (17)	0.0175 (14)	0.0241 (18)	−0.0001 (12)	0.0006 (13)	0.0005 (12)
C2	0.0260 (18)	0.0214 (16)	0.0240 (19)	0.0052 (13)	0.0029 (15)	0.0050 (13)
C3	0.0282 (19)	0.0299 (18)	0.0200 (18)	0.0050 (14)	−0.0055 (15)	0.0042 (14)
C4	0.0235 (17)	0.0281 (17)	0.0171 (17)	0.0001 (13)	0.0009 (13)	−0.0007 (13)
C5	0.0176 (15)	0.0211 (15)	0.0154 (16)	−0.0013 (12)	0.0071 (12)	−0.0016 (12)
C6	0.0156 (15)	0.0198 (14)	0.0195 (17)	−0.0030 (11)	0.0057 (13)	−0.0021 (12)
C7	0.0258 (18)	0.0248 (16)	0.0249 (19)	−0.0026 (13)	−0.0012 (14)	−0.0059 (14)
C8	0.0268 (17)	0.0133 (14)	0.0228 (18)	−0.0011 (12)	0.0066 (14)	−0.0020 (12)
C9	0.0260 (17)	0.0154 (14)	0.0215 (17)	0.0012 (12)	0.0065 (14)	0.0028 (12)
C10	0.0176 (15)	0.0203 (15)	0.0183 (17)	0.0041 (12)	0.0056 (13)	0.0032 (12)
C11	0.0283 (18)	0.0226 (16)	0.0243 (18)	0.0036 (13)	0.0018 (15)	0.0098 (13)
C12	0.0154 (15)	0.0214 (15)	0.0152 (16)	0.0029 (11)	0.0043 (12)	0.0026 (12)
C13	0.0182 (16)	0.0294 (17)	0.0184 (17)	0.0028 (13)	0.0014 (13)	0.0028 (13)
C14	0.0168 (16)	0.0322 (18)	0.0208 (18)	−0.0048 (13)	−0.0013 (13)	−0.0027 (14)
C15	0.0178 (16)	0.0239 (16)	0.0255 (19)	−0.0032 (12)	0.0050 (14)	−0.0031 (13)
C16	0.0187 (16)	0.0192 (14)	0.0197 (17)	0.0005 (12)	0.0022 (13)	0.0009 (12)
C17	0.0249 (18)	0.0209 (15)	0.0288 (19)	−0.0019 (13)	0.0041 (15)	0.0001 (13)
C18	0.0267 (19)	0.0265 (17)	0.032 (2)	0.0015 (14)	0.0002 (16)	0.0033 (15)
N1	0.0178 (13)	0.0165 (12)	0.0148 (13)	0.0004 (10)	0.0011 (10)	0.0012 (10)
N2	0.0195 (13)	0.0152 (12)	0.0180 (14)	−0.0027 (10)	0.0041 (11)	−0.0002 (10)
N3	0.0171 (13)	0.0151 (12)	0.0186 (14)	0.0015 (10)	0.0032 (11)	0.0033 (10)
N4	0.0165 (13)	0.0174 (12)	0.0150 (13)	0.0008 (9)	0.0025 (10)	0.0004 (10)
O1	0.0240 (13)	0.0339 (13)	0.0252 (14)	−0.0048 (10)	−0.0015 (10)	−0.0036 (10)
O2	0.0260 (13)	0.0203 (11)	0.0262 (13)	−0.0004 (9)	0.0064 (10)	−0.0032 (9)
O3	0.0348 (14)	0.0297 (13)	0.0232 (13)	−0.0033 (10)	0.0076 (11)	0.0051 (10)
O4	0.0273 (13)	0.0284 (12)	0.0222 (13)	0.0030 (10)	0.0085 (10)	0.0059 (10)
O5	0.0302 (14)	0.0403 (14)	0.0255 (14)	−0.0047 (11)	0.0092 (11)	−0.0109 (11)
O6	0.0221 (13)	0.0544 (17)	0.0248 (14)	0.0007 (12)	−0.0011 (11)	0.0122 (12)
Cu1	0.0197 (2)	0.01299 (18)	0.0159 (2)	−0.00029 (14)	−0.00132 (15)	0.00080 (14)
S1	0.0213 (4)	0.0193 (4)	0.0172 (4)	−0.0013 (3)	0.0030 (3)	0.0007 (3)
S2	0.0184 (4)	0.0262 (4)	0.0175 (4)	−0.0022 (3)	0.0029 (3)	−0.0002 (3)
F1	0.0366 (12)	0.0300 (11)	0.0326 (12)	−0.0027 (9)	0.0002 (10)	0.0123 (9)
F2	0.0227 (11)	0.0352 (11)	0.0414 (13)	−0.0044 (8)	−0.0026 (10)	0.0015 (10)
F3	0.0382 (13)	0.0278 (11)	0.0511 (15)	0.0085 (9)	0.0084 (11)	−0.0106 (10)
F4	0.0203 (10)	0.0385 (12)	0.0369 (13)	0.0027 (8)	−0.0053 (9)	−0.0064 (9)
F5	0.0430 (14)	0.0500 (14)	0.0597 (17)	−0.0172 (11)	−0.0004 (13)	0.0275 (13)
F6	0.0374 (13)	0.0294 (11)	0.0646 (17)	0.0069 (10)	−0.0061 (12)	−0.0200 (11)

Geometric parameters (Å, º) top

Cu1—N3	1.941 (3)	C2—C3	1.376 (5)
Cu1—N2	1.949 (3)	C2—H2	0.9300
Cu1—N1	2.011 (3)	C3—C4	1.387 (5)
Cu1—N4	2.016 (3)	C3—H3	0.9300
Cu1—O4	2.474 (3)	C4—C5	1.375 (5)
Cu1—O2	2.564 (3)	C4—H4	0.9300
S1—O3	1.442 (3)	C5—C6	1.494 (5)
S1—O1	1.442 (3)	C6—C7	1.481 (5)
S1—O2	1.453 (3)	C7—H7A	0.9603
S1—C17	1.826 (4)	C7—H7B	0.9603
S2—O6	1.441 (3)	C7—H7C	0.9603
S2—O5	1.442 (3)	C8—C9	1.549 (5)
S2—O4	1.444 (3)	C8—H8A	0.9700
S2—C18	1.828 (4)	C8—H8B	0.9700
F1—C17	1.328 (4)	C9—H9A	0.9700
F2—C17	1.340 (4)	C9—H9B	0.9700
F3—C17	1.339 (4)	C10—C12	1.492 (4)
F4—C18	1.337 (4)	C10—C11	1.486 (5)
F5—C18	1.322 (4)	C11—H11A	0.9608
F6—C18	1.337 (4)	C11—H11B	0.9608
N1—C1	1.342 (4)	C11—H11C	0.9608
N1—C5	1.367 (4)	C12—C13	1.381 (5)
N2—C6	1.287 (4)	C13—C14	1.385 (5)
N2—C8	1.466 (4)	C13—H13	0.9300
N3—C10	1.288 (4)	C14—C15	1.369 (5)
N3—C9	1.465 (4)	C14—H14	0.9300
N4—C16	1.335 (4)	C15—C16	1.392 (5)
N4—C12	1.349 (4)	C15—H15	0.9300
C1—C2	1.383 (5)	C16—H16	0.9300
C1—H1	0.9300

N3—Cu1—N2	83.11 (12)	N2—C6—C5	113.5 (3)
N3—Cu1—N1	164.79 (11)	C7—C6—C5	120.4 (3)
N2—Cu1—N1	81.96 (11)	C6—C7—H7A	109.5
N3—Cu1—N4	81.59 (11)	C6—C7—H7B	109.5
N2—Cu1—N4	164.06 (11)	H7A—C7—H7B	109.4
N1—Cu1—N4	113.52 (12)	C6—C7—H7C	109.5
N3—Cu1—O4	90.25 (10)	H7A—C7—H7C	109.4
N2—Cu1—O4	90.19 (10)	H7B—C7—H7C	109.4
N1—Cu1—O4	86.96 (10)	N2—C8—C9	108.4 (2)
N4—Cu1—O4	94.30 (10)	N2—C8—H8A	110.1
N3—Cu1—O2	90.61 (10)	C9—C8—H8A	110.0
N2—Cu1—O2	88.21 (10)	N2—C8—H8B	110.0
N1—Cu1—O2	91.76 (10)	C9—C8—H8B	110.0
N4—Cu1—O2	87.53 (9)	H8A—C8—H8B	108.4
O4—Cu1—O2	178.07 (8)	N3—C9—C8	107.9 (2)
O3—S1—O1	115.72 (17)	N3—C9—H9A	110.1
O3—S1—O2	114.34 (16)	C8—C9—H9A	110.1
O1—S1—O2	114.89 (15)	N3—C9—H9B	110.2
O3—S1—C17	103.46 (16)	C8—C9—H9B	110.1
O1—S1—C17	102.90 (17)	H9A—C9—H9B	108.4
O2—S1—C17	103.10 (17)	N3—C10—C12	113.1 (3)
O6—S2—O5	115.54 (17)	N3—C10—C11	125.1 (3)
O6—S2—O4	114.61 (15)	C12—C10—C11	121.8 (3)
O5—S2—O4	114.34 (16)	C10—C11—H11A	109.6
O6—S2—C18	103.29 (17)	C10—C11—H11B	109.5
O5—S2—C18	102.91 (16)	H11A—C11—H11B	109.4
O4—S2—C18	103.87 (17)	C10—C11—H11C	109.5
S1—O2—Cu1	138.17 (14)	H11A—C11—H11C	109.4
S2—O4—Cu1	138.10 (15)	H11B—C11—H11C	109.4
C1—N1—C5	118.5 (3)	N4—C12—C13	121.5 (3)
C1—N1—Cu1	130.3 (2)	N4—C12—C10	115.5 (3)
C5—N1—Cu1	111.2 (2)	C13—C12—C10	123.0 (3)
C6—N2—C8	125.5 (3)	C12—C13—C14	118.9 (3)
C6—N2—Cu1	117.1 (2)	C12—C13—H13	120.6
C8—N2—Cu1	115.6 (2)	C14—C13—H13	120.6
C10—N3—C9	124.5 (3)	C15—C14—C13	120.1 (3)
C10—N3—Cu1	117.1 (2)	C15—C14—H14	119.9
C9—N3—Cu1	115.8 (2)	C13—C14—H14	120.0
C16—N4—C12	118.9 (3)	C14—C15—C16	117.9 (3)
C16—N4—Cu1	129.8 (2)	C14—C15—H15	121.1
C12—N4—Cu1	111.3 (2)	C16—C15—H15	121.0
N1—C1—C2	122.4 (3)	N4—C16—C15	122.7 (3)
N1—C1—H1	118.8	N4—C16—H16	118.7
C2—C1—H1	118.8	C15—C16—H16	118.6
C3—C2—C1	118.8 (3)	F1—C17—F2	108.2 (3)
C3—C2—H2	120.7	F1—C17—F3	108.1 (3)
C1—C2—H2	120.6	F2—C17—F3	106.8 (3)
C2—C3—C4	119.5 (3)	F1—C17—S1	112.0 (2)
C2—C3—H3	120.3	F2—C17—S1	111.3 (2)
C4—C3—H3	120.2	F3—C17—S1	110.2 (3)
C5—C4—C3	119.2 (3)	F5—C18—F4	108.1 (3)
C5—C4—H4	120.4	F5—C18—F6	107.9 (3)
C3—C4—H4	120.5	F4—C18—F6	107.1 (3)
N1—C5—C4	121.5 (3)	F5—C18—S2	110.8 (3)
N1—C5—C6	115.3 (3)	F4—C18—S2	111.3 (2)
C4—C5—C6	123.2 (3)	F6—C18—S2	111.5 (3)
N2—C6—C7	126.0 (3)

O3—S1—O2—Cu1	−150.8 (2)	C2—C3—C4—C5	1.7 (6)
O1—S1—O2—Cu1	−13.5 (3)	C1—N1—C5—C4	0.8 (5)
C17—S1—O2—Cu1	97.6 (2)	Cu1—N1—C5—C4	−178.2 (3)
N3—Cu1—O2—S1	−77.9 (2)	C1—N1—C5—C6	179.5 (3)
N2—Cu1—O2—S1	5.2 (2)	Cu1—N1—C5—C6	0.5 (3)
N1—Cu1—O2—S1	87.1 (2)	C3—C4—C5—N1	−1.7 (5)
N4—Cu1—O2—S1	−159.4 (2)	C3—C4—C5—C6	179.7 (3)
O6—S2—O4—Cu1	−5.8 (3)	C8—N2—C6—C7	−1.7 (6)
O5—S2—O4—Cu1	−142.5 (2)	Cu1—N2—C6—C7	−165.8 (3)
C18—S2—O4—Cu1	106.1 (2)	C8—N2—C6—C5	174.8 (3)
N3—Cu1—O4—S2	−10.5 (2)	Cu1—N2—C6—C5	10.7 (4)
N2—Cu1—O4—S2	−93.6 (2)	N1—C5—C6—N2	−7.2 (4)
N1—Cu1—O4—S2	−175.5 (2)	C4—C5—C6—N2	171.5 (3)
N4—Cu1—O4—S2	71.1 (2)	N1—C5—C6—C7	169.5 (3)
N3—Cu1—N1—C1	−164.2 (4)	C4—C5—C6—C7	−11.8 (5)
N2—Cu1—N1—C1	−175.1 (3)	C6—N2—C8—C9	170.5 (3)
N4—Cu1—N1—C1	8.9 (3)	Cu1—N2—C8—C9	−25.1 (3)
O4—Cu1—N1—C1	−84.5 (3)	C10—N3—C9—C8	171.4 (3)
O2—Cu1—N1—C1	97.0 (3)	Cu1—N3—C9—C8	−27.3 (3)
N3—Cu1—N1—C5	14.7 (6)	N2—C8—C9—N3	32.2 (4)
N2—Cu1—N1—C5	3.8 (2)	C9—N3—C10—C12	174.1 (3)
N4—Cu1—N1—C5	−172.2 (2)	Cu1—N3—C10—C12	13.1 (4)
O4—Cu1—N1—C5	94.4 (2)	C9—N3—C10—C11	−4.3 (5)
O2—Cu1—N1—C5	−84.2 (2)	Cu1—N3—C10—C11	−165.4 (3)
N3—Cu1—N2—C6	174.5 (3)	C16—N4—C12—C13	1.0 (5)
N1—Cu1—N2—C6	−8.4 (3)	Cu1—N4—C12—C13	−178.4 (2)
N4—Cu1—N2—C6	158.2 (4)	C16—N4—C12—C10	−179.9 (3)
O4—Cu1—N2—C6	−95.3 (3)	Cu1—N4—C12—C10	0.8 (3)
O2—Cu1—N2—C6	83.6 (3)	N3—C10—C12—N4	−8.9 (4)
N3—Cu1—N2—C8	8.7 (2)	C11—C10—C12—N4	169.6 (3)
N1—Cu1—N2—C8	−174.2 (2)	N3—C10—C12—C13	170.2 (3)
N4—Cu1—N2—C8	−7.6 (6)	C11—C10—C12—C13	−11.2 (5)
O4—Cu1—N2—C8	98.9 (2)	N4—C12—C13—C14	−0.5 (5)
O2—Cu1—N2—C8	−82.1 (2)	C10—C12—C13—C14	−179.6 (3)
N2—Cu1—N3—C10	174.2 (3)	C12—C13—C14—C15	−0.2 (5)
N1—Cu1—N3—C10	163.4 (4)	C13—C14—C15—C16	0.4 (5)
N4—Cu1—N3—C10	−10.2 (3)	C12—N4—C16—C15	−0.8 (5)
O4—Cu1—N3—C10	84.1 (3)	Cu1—N4—C16—C15	178.4 (2)
O2—Cu1—N3—C10	−97.6 (3)	C14—C15—C16—N4	0.1 (5)
N2—Cu1—N3—C9	11.5 (2)	O3—S1—C17—F1	−173.3 (2)
N1—Cu1—N3—C9	0.6 (6)	O1—S1—C17—F1	65.9 (3)
N4—Cu1—N3—C9	−173.0 (2)	O2—S1—C17—F1	−53.9 (3)
O4—Cu1—N3—C9	−78.6 (2)	O3—S1—C17—F2	−52.0 (3)
O2—Cu1—N3—C9	99.6 (2)	O1—S1—C17—F2	−172.8 (3)
N3—Cu1—N4—C16	−174.7 (3)	O2—S1—C17—F2	67.4 (3)
N2—Cu1—N4—C16	−158.3 (4)	O3—S1—C17—F3	66.3 (3)
N1—Cu1—N4—C16	7.1 (3)	O1—S1—C17—F3	−54.5 (3)
O4—Cu1—N4—C16	95.7 (3)	O2—S1—C17—F3	−174.3 (2)
O2—Cu1—N4—C16	−83.7 (3)	O6—S2—C18—F5	−53.1 (3)
N3—Cu1—N4—C12	4.5 (2)	O5—S2—C18—F5	67.5 (3)
N2—Cu1—N4—C12	20.9 (5)	O4—S2—C18—F5	−173.1 (3)
N1—Cu1—N4—C12	−173.6 (2)	O6—S2—C18—F4	−173.4 (3)
O4—Cu1—N4—C12	−85.1 (2)	O5—S2—C18—F4	−52.8 (3)
O2—Cu1—N4—C12	95.5 (2)	O4—S2—C18—F4	66.7 (3)
C5—N1—C1—C2	0.1 (5)	O6—S2—C18—F6	67.1 (3)
Cu1—N1—C1—C2	178.9 (2)	O5—S2—C18—F6	−172.4 (3)
N1—C1—C2—C3	0.0 (5)	O4—S2—C18—F6	−52.9 (3)
C1—C2—C3—C4	−0.9 (5)

Experimental details

Crystal data
Chemical formula	[Cu(CF₃SO₃)₂(C₁₆H₁₈N₄)]
M_r	628.02
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	9.2228 (4), 25.5574 (13), 9.8189 (5)
β (°)	94.961 (3)
V (Å³)	2305.75 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.35 × 0.2 × 0.06

Data collection
Diffractometer	Bruker–Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.78, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	18769, 5052, 4062
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.09
No. of reflections	5052
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.64

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), publCIF (Westrip, 2008).

Footnotes

‡Corresponding author for synthesis; e-mail: abdurrahmans2002@yahoo.co.uk.

Acknowledgements

This work was supported by the reserach project fund of Zonguldak Karaelmas University (grant Nos. 2007/2-13-02-12 and 2007/2-13-02-10) and the UK Engineering and Physical Sciences Research Council.

References

Bowyer, B. K., Porter, K. A., Rae, A. D., Willis, A. C. & Wild, S. B. (1998). J. Chem. Soc. Chem. Commun. 10, 1153–1154. CrossRef Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Fielden, J., Long, D.-L., Evans, C. & Cronin, L. (2006). Eur. J. Inorg. Chem. 2006, 3930–3935. Web of Science CSD CrossRef Google Scholar
Gourbatsis, S., Hadjiliadis, N., Perlepes, S. P., Garoufis, A. & Butler, I. S. (1998). Transition Met. Chem. 23, 599–604. Web of Science CSD CrossRef CAS Google Scholar
Gourbatsis, S., Perlepes, S. P., Butler, I. S. & Hadjiliadis, N. (1999). Polyhedron, 18, 2369–2375. Web of Science CSD CrossRef CAS Google Scholar
Hamblin, J., Jackson, A., Alcock, N. W. & Hannon, M. J. (2002). Dalton Trans. pp. 1635–1641. CrossRef Google Scholar
Hanack, M., Deger, S. & Lange, A. (1988). Coord. Chem. Rev. 83, 115–136. CrossRef CAS Web of Science Google Scholar
Haynes, J. S., Rettig, S. J., Sams, J. R., Trotter, J. & Thompson, R. C. (1988). Inorg. Chem. 27, 1237–1241. CSD CrossRef CAS Web of Science Google Scholar
Luo, Q., Lu, Q., Dai, A. & Huang, L. (1993). Inorg. Biochem. 51, 655–662. CrossRef CAS Web of Science Google Scholar
Marks, T. J. (1990). Angew. Chem. Int. Ed. Engl. 29, 857–879. CrossRef Web of Science Google Scholar
Menteş, A., Sezek, S., Hanhan, M. E. & Büyükgüngör, O. (2007). Turk. J. Chem. 31, 667–676. Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter, Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Şengül, A. & Büyükgüngör, O. (2005). Acta Cryst. C61, m119–m121. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2007). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Szklarzewicz, J. & Samotus, A. (2002). Transition Met. Chem. 27, 769–775. Web of Science CrossRef CAS Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar

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.