(11,13-Dimethyl-1,4,7,10-tetra­azacyclo­trideca-10,13-dienato)copper(II) per­chlorate

He, X.

doi:10.1107/S1600536809001664

metal-organic compounds

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doi:10.1107/S1600536809001664

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(11,13-Dimethyl-1,4,7,10-tetraazacyclotrideca-10,13-dienato)copper(II) perchlorate

Xiao-qiang He ^a ^*

^aChemical Technology & Medicine College, Jingchu University of Technology, Jingmen, Hubei 448000, People's Republic of China
^*Correspondence e-mail: jclghxq@126.com

(Received 12 January 2009; accepted 14 January 2009; online 17 January 2009)

The title complex, [Cu(C₁₁H₂₁N₄)]ClO₄, comprises [Cu^II(L)]⁺ (L = 11,13-dimethyl-1,4,7,10-tetraazacyclotrideca-10,12-dienate) cations and a perchlorate anion. The Cu atom is located on a twofold crystallographic symmetry axis and is coordinated by four N atoms in a slightly distorted square-planar geometry. Intermolecular N—H⋯O hydrogen bonds are present.

Related literature

For macrocyclic ligands containing four N atoms in a square-planar coordination geometry, see: Andrews et al. (1999 ); Kim et al. (2004 ); Richardson & Sievers (1972 ).

Experimental

Crystal data

[Cu(C₁₁H₂₁N₄)]ClO₄
M_r = 372.31
Orthorhombic, P b c n
a = 12.530 (5) Å
b = 14.469 (6) Å
c = 8.501 (4) Å
V = 1541.2 (11) Å³
Z = 4
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 293 (2) K
0.15 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.794, T_max = 0.843
6834 measured reflections
1349 independent reflections
950 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.216
S = 1.05
1349 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 1.10 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱⁱ	0.91	2.02	2.917 (8)	168
Symmetry codes: (i) x, y, z-1; (ii) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001664/hg2468sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001664/hg2468Isup2.hkl

checkCIF report

Comment top

Macrocyclic ligands containing four N atoms located in a square planar coordination geometry have been intensly studied during the past several decades (Richardson, et al., 1972; Andrews, et al., 1999; Kim, et al., 2004). Here,we report a macrocycle tetraaza copper(II) complex based on the condensation of triethylenetetraamine (trien) with acetylacetone in the presence of copper(II) perchlorate.

The geometry and labelling scheme for the crystal structure of the title complex are depicted in Figure 1. The coordination sphere for the Cu^II ion in the title complex, which coordinates to four N atoms from triethylenetetraamine, is square planar with a mean deviation from the plane formed by the Cu atom and four N atoms of 0.0929Å . The bond lengths of Cu1—N1 and Cu1—N2 are 1.809 (4) and 1.876 (4)Å , respectively, which are slightly shorter than the corresponding distances found in another macrocycle copper complex 13,14-benzo-2,4,9,11-tetramethyl- 1,5,8,12-tetraazacyclotetradeca-1,3,9,11-tetraenato(2-)copper(II) (Kim, et al., 2004).

Related literature top

For macrocyclic ligands containing four N atoms in a square-planar coordination geometry, see: Andrews et al. (1999); Kim et al. (2004); Richardson & Sievers (1972).

Experimental top

The title complex has been synthesized by the template method used commonly for synthesize metal complexes of macrocycle ligand. After the mixture, which is formed by acetylacetone, trien and Cu(ClO₄)₂.6H₂O with a molar ratio 1:1:1 in methanol/water(v:v, 1:1), has been stirred for 6 h at 323 K, it was filtered and the filtrate was allowed to partial evaporate in air for one week to produce crystals suitable for X-ray diffraction with a yield of about 45%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the cation of the title complex with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

(11,13-Dimethyl-1,4,7,10-tetraazacyclotrideca-10,13-dienato)copper(II) perchlorate top

Crystal data top

[Cu(C₁₁H₂₁N₄)]ClO₄	F(000) = 772
M_r = 372.31	D_x = 1.605 Mg m⁻³ D_m = 1.605 Mg m⁻³ D_m measured by not measured
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1838 reflections
a = 12.530 (5) Å	θ = 3.2–24.7°
b = 14.469 (6) Å	µ = 1.61 mm⁻¹
c = 8.501 (4) Å	T = 293 K
V = 1541.2 (11) Å³	Block, blue
Z = 4	0.15 × 0.13 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1349 independent reflections
Radiation source: fine-focus sealed tube	950 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −14→12
T_min = 0.794, T_max = 0.843	k = −15→17
6834 measured reflections	l = −9→10

Refinement top

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.216	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.144P)² + 0.9336P] where P = (F_o² + 2F_c²)/3
1349 reflections	(Δ/σ)_max < 0.001
98 parameters	Δρ_max = 1.10 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Cu(C₁₁H₂₁N₄)]ClO₄	V = 1541.2 (11) Å³
M_r = 372.31	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 12.530 (5) Å	µ = 1.61 mm⁻¹
b = 14.469 (6) Å	T = 293 K
c = 8.501 (4) Å	0.15 × 0.13 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1349 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	950 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.843	R_int = 0.064
6834 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.216	H-atom parameters constrained
S = 1.05	Δρ_max = 1.10 e Å⁻³
1349 reflections	Δρ_min = −0.59 e Å⁻³
98 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.

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.0000	0.32069 (5)	0.2500	0.0431 (4)
Cl1	0.0000	0.14239 (18)	0.7500	0.0660 (7)
O1	0.0525 (6)	0.2000 (6)	0.6429 (9)	0.139 (3)
O2	0.0806 (8)	0.0904 (4)	0.8238 (11)	0.160 (3)
N1	0.0904 (3)	0.4014 (3)	0.1568 (5)	0.0481 (11)
N2	0.0740 (3)	0.2278 (3)	0.1414 (5)	0.0476 (11)
H2	0.0427	0.2219	0.0453	0.057*
C1	0.0000	0.5334 (6)	0.2500	0.060 (2)
H1	0.0000	0.5976	0.2500	0.072*
C2	0.0803 (4)	0.4932 (3)	0.1651 (7)	0.0579 (15)
C3	0.1590 (5)	0.5506 (4)	0.0804 (9)	0.078 (2)
H3A	0.2298	0.5334	0.1122	0.117*
H3B	0.1471	0.6146	0.1047	0.117*
H3C	0.1513	0.5412	−0.0308	0.117*
C4	0.1727 (4)	0.3589 (4)	0.0637 (7)	0.0576 (14)
H4A	0.2396	0.3916	0.0780	0.069*
H4B	0.1537	0.3613	−0.0469	0.069*
C5	0.1840 (4)	0.2618 (4)	0.1151 (8)	0.0597 (14)
H5A	0.2253	0.2581	0.2114	0.072*
H5B	0.2193	0.2254	0.0347	0.072*
C6	0.0587 (5)	0.1407 (4)	0.2241 (7)	0.0574 (15)
H6A	0.1056	0.1369	0.3147	0.069*
H6B	0.0732	0.0888	0.1552	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0446 (7)	0.0320 (6)	0.0526 (7)	0.000	−0.0004 (3)	0.000
Cl1	0.0883 (17)	0.0572 (14)	0.0526 (13)	0.000	0.0019 (10)	0.000
O1	0.113 (5)	0.182 (6)	0.122 (6)	−0.012 (5)	−0.020 (4)	0.056 (5)
O2	0.244 (10)	0.106 (4)	0.130 (6)	0.077 (6)	−0.015 (7)	0.003 (5)
N1	0.045 (2)	0.039 (2)	0.060 (3)	−0.0019 (17)	−0.004 (2)	0.0077 (19)
N2	0.055 (3)	0.038 (2)	0.049 (2)	0.0060 (18)	0.0024 (19)	0.0023 (17)
C1	0.069 (5)	0.022 (3)	0.090 (7)	0.000	−0.026 (5)	0.000
C2	0.058 (3)	0.041 (3)	0.075 (4)	−0.011 (3)	−0.031 (3)	0.012 (3)
C3	0.078 (4)	0.051 (3)	0.104 (5)	−0.027 (3)	−0.026 (4)	0.020 (3)
C4	0.048 (3)	0.057 (3)	0.068 (4)	−0.002 (2)	0.006 (3)	0.011 (3)
C5	0.053 (3)	0.059 (3)	0.068 (4)	0.010 (2)	0.002 (3)	0.008 (3)
C6	0.070 (4)	0.034 (3)	0.068 (4)	0.007 (3)	0.002 (3)	0.004 (2)

Geometric parameters (Å, º) top

Cu1—N1ⁱ	1.809 (4)	C1—C2ⁱ	1.367 (7)
Cu1—N1	1.809 (4)	C1—H1	0.9300
Cu1—N2ⁱ	1.876 (4)	C2—C3	1.477 (8)
Cu1—N2	1.876 (4)	C3—H3A	0.9600
Cl1—O1ⁱⁱ	1.399 (8)	C3—H3B	0.9600
Cl1—O1	1.399 (8)	C3—H3C	0.9600
Cl1—O2	1.407 (8)	C4—C5	1.479 (8)
Cl1—O2ⁱⁱ	1.407 (8)	C4—H4A	0.9700
N1—C2	1.337 (6)	C4—H4B	0.9700
N1—C4	1.438 (7)	C5—H5A	0.9700
N2—C6	1.455 (7)	C5—H5B	0.9700
N2—C5	1.481 (7)	C6—C6ⁱ	1.535 (13)
N2—H2	0.9100	C6—H6A	0.9700
C1—C2	1.367 (7)	C6—H6B	0.9700

N1ⁱ—Cu1—N1	99.6 (3)	C1—C2—C3	120.7 (5)
N1ⁱ—Cu1—N2ⁱ	86.43 (19)	C2—C3—H3A	109.5
N1—Cu1—N2ⁱ	170.85 (17)	C2—C3—H3B	109.5
N1ⁱ—Cu1—N2	170.85 (17)	H3A—C3—H3B	109.5
N1—Cu1—N2	86.43 (19)	C2—C3—H3C	109.5
N2ⁱ—Cu1—N2	88.4 (2)	H3A—C3—H3C	109.5
O1ⁱⁱ—Cl1—O1	106.9 (7)	H3B—C3—H3C	109.5
O1ⁱⁱ—Cl1—O2	111.4 (5)	N1—C4—C5	108.2 (4)
O1—Cl1—O2	105.8 (5)	N1—C4—H4A	110.1
O1ⁱⁱ—Cl1—O2ⁱⁱ	105.8 (5)	C5—C4—H4A	110.1
O1—Cl1—O2ⁱⁱ	111.4 (5)	N1—C4—H4B	110.1
O2—Cl1—O2ⁱⁱ	115.3 (7)	C5—C4—H4B	110.1
C2—N1—C4	121.5 (4)	H4A—C4—H4B	108.4
C2—N1—Cu1	124.0 (4)	C4—C5—N2	105.8 (4)
C4—N1—Cu1	114.5 (3)	C4—C5—H5A	110.6
C6—N2—C5	118.9 (4)	N2—C5—H5A	110.6
C6—N2—Cu1	108.5 (3)	C4—C5—H5B	110.6
C5—N2—Cu1	107.2 (3)	N2—C5—H5B	110.6
C6—N2—H2	107.2	H5A—C5—H5B	108.7
C5—N2—H2	107.2	N2—C6—C6ⁱ	105.3 (4)
Cu1—N2—H2	107.2	N2—C6—H6A	110.7
C2—C1—C2ⁱ	129.7 (7)	C6ⁱ—C6—H6A	110.7
C2—C1—H1	115.1	N2—C6—H6B	110.7
C2ⁱ—C1—H1	115.1	C6ⁱ—C6—H6B	110.7
N1—C2—C1	121.3 (6)	H6A—C6—H6B	108.8
N1—C2—C3	118.0 (6)

Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱⁱⁱ	0.91	2.81	3.668 (5)	157
N2—H2···O1ⁱ	0.91	2.02	2.917 (8)	168

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₂₁N₄)]ClO₄
M_r	372.31
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	12.530 (5), 14.469 (6), 8.501 (4)
V (Å³)	1541.2 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.15 × 0.13 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.794, 0.843
No. of measured, independent and observed [I > 2σ(I)] reflections	6834, 1349, 950
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.216, 1.05
No. of reflections	1349
No. of parameters	98
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.10, −0.59

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1ⁱ	0.91	2.81	3.668 (5)	157.1
N2—H2···O1ⁱⁱ	0.91	2.02	2.917 (8)	168.4

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

References

Andrews, P. C., Atwood, J. L., Barbour, L. J., Croucher, P. D., Nichols, P. J., Smith, N. O., Skelton, B. W., White, A. H. & Raston, C. L. (1999). J. Chem. Soc. Dalton Trans. pp. 2927–2932. Web of Science CSD CrossRef Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kim, D. I., Kim, E. H., Bae, Z. U., Na, H. G., Choi, J. H. & Park, Y. C. (2004). J. Inclus. Phenom. Macrocycl. Chem. 49, 107–113. Web of Science CSD CrossRef CAS Google Scholar
Richardson, M. F. & Sievers, R. E. (1972). J. Am. Chem. Soc. 94, 4134–4139. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1998). XP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

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Volume 65| Part 2| February 2009| Page m205

doi:10.1107/S1600536809001664

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(11,13-Di­methyl-1,4,7,10-tetra­aza­cyclo­trideca-10,13-dienato)copper(II) per­chlorate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

(11,13-Dimethyl-1,4,7,10-tetraazacyclotrideca-10,13-dienato)copper(II) perchlorate