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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 60| Part 6| June 2004| Pages m256-m257
doi:10.1107/S0108270104008765

(4,4,12,12-Tetra­methyl-5,8,11-tri­aza­penta-2,14-dione 2-oxime 14-oximato-κ5N)copper(II) perchlorate: a copper(II) compound with a pentadentate tri­amine–oxime–oximate ligand

CROSSMARK_Color_square_no_text.svg
Neil F. Curtis,a* Olga P. Gladkikh,a Keith R. Morgana and Sarah L. Heathb

aSchool of Chemical and Physical Sciences, Victoria University of Wellington, Box 600, Wellington, New Zealand, and bDepartment of Chemistry, University of Newcastle, Newcastle on Tyne NE1 7RU, England
*Correspondence e-mail: neil.curtis@vuw.ac.nz

(Received 23 February 2004; accepted 13 April 2004; online 22 May 2004)

The title compound, [Cu(C16H34N5O2)]ClO4, has discrete square-pyramidal (tri­amine–oxime–oximato)copper(II) cations and perchlorate anions. The cations have very approxi­mate mirror symmetry, with the oxime [Cu—N = 2.066 (2) Å], oximate [Cu—N = 2.087 (2) Å] and amine N atoms [Cu—N = 2.138 (2) and 2.095 (2) Å] in the tetrahedrally twisted basal plane, and the `central' amine N atom coordinated axially [Cu—N = 2.183 (2) Å]. The oxime and oximate groups are linked by an O—H⋯O hydrogen bond, forming a pseudo-cyclic pentadentate ligand, with an O⋯O distance of 2.395 (3) Å.

Comment

The structure of the title copper(II) compound, (I[link]), with a pentadentate tri­amino–oxime–oximate ligand, is reported. The ligand is the mono-deprotonated dioxime of the tri­amine–diketone 4,4,12,12-tetra­methyl-5,8,11-tri­aza­penta-2,14-dione, which is formed (as the di­hydro­perchlorate salt) by reaction of 3-aza­pentane-1,5-di­amine di­hydro­perchlorate with acetone (see scheme[link]) (Morgan et al., 1982[Morgan, K. R., Gainsford, G. J. & Curtis, N. F. (1982). Aust. J. Chem. 35, 1105-1117.]).

Compound (I[link]) has discrete cations, with CuII in a square-pyramidal coordination (Fig. 1[link]), and perchlorate anions. Oxime atom N2, oximate atom N14, and secondary amine atoms N5 and N11, are coordinated in the tetrahedrally twisted basal plane, with the bond to the axially coordinated secondary amine atom N8 being significantly longer. Displacements from the mean-square plane defined by atoms N2, N5, N11 and N14 are: N2 0.154, N5 −0.158, N11 0.158, N14 −0.154, Cu 0.100, N8 2.213, O2 0.793 and O14 0.082 Å (s.u. 0.003 Å), and the trans angles are N2—Cu—N11 = 175.75 (8)° and N14—Cu—N5 = 165.87 (8)°. The five-membered chelate rings both have asymmetrical gauche conformations [displacements of atoms from the Cu/N5/N8 plane: C6 0.145 and C7 0.697 Å; from the Cu/N8/N11 plane: C9 0.035 and C10 0.683 Å], while the six-membered chelate rings have `half-chair' conformations, with methyl substituents C41 and C121 axially oriented [displacements from the Cu/N2/N5 plane: C2 0.052, C3 0.445, C4 0.948, C41 −2.323 and C42 1.050 Å; from the Cu/N11/N14 plane: C12 0.984, C121 2.355, C122 1.039, C13 0.590 and C14 0.263 Å].

[Scheme 1]

Atom O2 of the oxime and O14 of the oximate group are linked by a short hydrogen bond (Table 2[link]), as is common for oxime–oximate compounds, forming a pseudo-macrocyclic ligand. The cations are linked into a one-dimensional chain, with base vector 001, by weak intramolecular hydrogen bonding. The perchlorate ion shows rotational disorder which was not modelled.

The structures of a number of copper(II) compounds with tetradentate di­aza–oxime–oximate ligands with short O—H⋯O hydrogen-bonded 14- to 16-membered pseudo-cyclic structures have been reported. These generally have square-pyramidal coordination, with water (Nunes et al., 1999[Nunes, F. S., Murta, P. D. M. L. & Da Cunha, C. J. (1999). J. Coord. Chem. 47, 251-267.]; Anderson & Packard, 1979[Anderson, O. P. & Packard, A. B. (1979). Inorg. Chem. 18, 1940-1947.]; Lee et al., 1990[Lee, T. J., Chang, Y., Chung, C. S. & Wang, Y. M. (1990). Acta Cryst. C46, 2360-2363.]; Pal et al., 1986[Pal, J., Murmann, R. K., Schlemper, E. O., Kay Fair, C. & Hussain, M. S. (1986). Inorg. Chim. Acta, 115, 153-161.]; Kiani et al., 2002[Kiani, S., Staples, R. J. & Packard, A. B. (2002). Acta Cryst. C58, m593-m596.]) or an anion (Tahirov et al., 1993,[Tahirov, T. H., Lu, T.-H., Luh, H. & Chung, C.-S. (1993). Acta Cryst. C49, 801-803.] 1995[Tahirov, T. H., Lu, T.-H., Luh, H., Lai, C.-Y. & Chung, C.-S. (1995). Acta Cryst. C51, 846-849.]; Jiang et al., 1993[Jiang, Z., Bai, L., Liao, D., Huang, J., Wang, G., Wang, H. & Yao, X. (1993). Polyhedron, 12, 523-525.]; Nunes et al., 1999[Nunes, F. S., Murta, P. D. M. L. & Da Cunha, C. J. (1999). J. Coord. Chem. 47, 251-267.]; Gavel & Schlemper, 1979[Gavel, D. P. & Schlemper, E. O. (1979). Inorg. Chem. 18, 283-286.]; Lee et al., 1991[Lee, T. J., Lee, T. Y., Chung, C. S. & Wang, Y. M. (1991). Acta Cryst. C47, 711-714.]; Liss et al., 1975[Liss, I. B. & Schlemper, E. O. (1975). Inorg. Chem. 14, 3035-3039.]; Schlemper et al., 1981[Schlemper, E. O., Hussain, M. S. & Murmann, R. K. (1981). Acta Cryst. B37, 234-237.]) coordinated axially, or have dinuclear (Tahirov et al., 1993[Tahirov, T. H., Lu, T.-H., Luh, H. & Chung, C.-S. (1993). Acta Cryst. C49, 801-803.]; Fraser et al., 1972[Fraser, J. W., Hedwig, G. R., Powell, H. K. J. & Robinson, W. T. (1972). Aust. J. Chem. 25, 747-759.]; Timmons et al., 1981[Timmons, J. H., Martin, J. W. L., Martell, A. E., Rudolf, P., Clearfield, A. & Buckley, R. C. (1981). Inorg. Chem. 20, 3056-3060.]; Kiani et al., 2002[Kiani, S., Staples, R. J. & Packard, A. B. (2002). Acta Cryst. C58, m593-m596.]; Pal et al., 1986[Pal, J., Murmann, R. K., Schlemper, E. O., Kay Fair, C. & Hussain, M. S. (1986). Inorg. Chim. Acta, 115, 153-161.]; Fun et al., 1993[Fun, H.-K., Lee, T. J., Tahirov, T., Lu, H., Luh, T. H. & Chung, C. S. (1993). J. Chin. Chem. Soc. (Taipei), 40, 429-435.]) or chain polymeric structures (Bertrand et al., 1977[Bertrand, J. A., Smith, J. H. & Van Derveer, D. G. (1977). Inorg. Chem. 16, 1484-1488.]) with an oximate O atom bridging to the axial site. The work presented here is the first report of a tri­aza–oxime–oximate compound in which the pentadentate ligand donor atoms occupy all five coordination sites about the copper(II).

[Figure 1]
Figure 1
The cation of (I[link]), drawn with displacement ellipsoids at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity, and H atoms bonded to N or O atoms are shown as circles of arbitrary radii.

Experimental

The starting material, 4,4,12,12-tetra­methyl-5,8,11-tri­aza­penta-2,14-dione di­hydro­perchlorate, was prepared by reaction of 3-aza­pentane-1,5-di­amine (diethyl­enetri­amine) di­hydro­perchlorate with acetone (Morgan et al., 1982[Morgan, K. R., Gainsford, G. J. & Curtis, N. F. (1982). Aust. J. Chem. 35, 1105-1117.]). The title compound was prepared by reaction of the starting material with [Cu(H2O)6](ClO4)2, hydroxylamine hydro­chloride and triethyl­amine in a 1:1:2:5 molar ratio in methanol. The green product which crystallized on addition of propan-2-ol was recrystallized by dissolving in methanol, adding propan-2-ol until just turbid, and allowing the solvent to evaporate.

Crystal data

  • [Cu(C16H34N5O2)]ClO4

  • Mr = 491.47

  • Monoclinic, P21/c

  • a = 10.8307 (7) Å

  • b = 23.9974 (15) Å

  • c = 8.6318 (6) Å

  • β = 90.058 (2)°

  • V = 2243.5 (3) Å3

  • Z = 4

  • Dx = 1.455 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 9707 reflections

  • θ = 2.1–28.4°

  • μ = 1.13 mm−1

  • T = 160 (2) K

  • Plate, green

  • 0.62 × 0.28 × 0.10 mm
Data collection

  • Siemens SMART CCD area-detector diffractometer

  • ω rotation scans with narrow frame

  • Absorption correction: multi-scan (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.540, Tmax = 0.895

  • 12 927 measured reflections

  • 4845 independent reflections

  • 4392 reflections with I > 2σ(I)

  • Rint = 0.035

  • θmax = 28.4°

  • h = −10 → 14

  • k = −26 → 30

  • l = −11 → 11
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.100

  • S = 1.12

  • 4845 reflections

  • 271 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • w = 1/[σ2(Fo2) + (0.0379P)2 + 3.1169P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.64 e Å−3

  • Δρmin = −0.70 e Å−3

Table 1
Selected geometric parameters (Å, °)

Cu1—N2 2.067 (2) 
Cu1—N14 2.088 (2)
Cu1—N11 2.096 (2)
Cu1—N5 2.138 (2)
Cu1—N8 2.182 (2)
N2—C2 1.285 (3)
N2—O2 1.420 (3)
C14—N14 1.292 (3)
N14—O14 1.426 (3)
N2—Cu1—N14 93.32 (9)
N2—Cu1—N11 175.79 (8)
N14—Cu1—N11 89.90 (8)
N2—Cu1—N5 89.33 (8)
N14—Cu1—N5 165.85 (8)
N11—Cu1—N5 88.20 (8)
N2—Cu1—N8 93.82 (8)
N14—Cu1—N8 110.13 (8)
N11—Cu1—N8 82.52 (8)
N5—Cu1—N8 83.53 (7)
C2—N2—O2 113.4 (2)
C2—N2—Cu1 130.4 (2)
O2—N2—Cu1 113.9 (2)
N2—C2—C3 122.7 (2)
C1—C2—C3 118.1 (2)
C2—C3—C4 121.8 (2)
C14—C13—C12 122.3 (2)
N14—C14—C15 118.9 (3)
N14—C14—C13 122.8 (2)
C15—C14—C13 118.2 (2)
C14—N14—O14 113.6 (2)
C14—N14—Cu1 129.3 (2)
O14—N14—Cu1 117.1 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2⋯O14 1.14 (4) 1.27 (4) 2.395 (3) 171 (4)
O2—H2⋯N14 1.14 (4) 2.16 (4) 3.044 (3) 132 (3)
N5—H5⋯O5 0.93 2.34 3.257 (4) 167
N8—H8⋯O14i 0.93 2.12 3.009 (3) 160
N11—H11⋯O4 0.93 2.58 3.437 (4) 154
Symmetry code: (i) [x,{\script{1\over 2}}-y,{\script{1\over 2}}+z].

For atom H2, the positional coordinates were refined, with Uiso = 1.5Ueq(O2). All other H atoms were treated as riding atoms, with N—H distances of 0.93 Å and C—H distances of 0.98 or 0.99 Å, and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(C).

Data collection: SMART (Siemens, 1995[Siemens (1995). SMART and SAINT. Versions 4.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: local programs; data reduction: SAINT (Siemens, 1995[Siemens (1995). SMART and SAINT. Versions 4.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S0108270104008765/gd1308sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104008765/gd1308Isup2.hkl


Comment top

The structure of the title copper(II) compound with a pentadentate triamino-oximo-oximato ligand, (I), is reported. The ligand is the mono-deprotonated dioxime of the triamine-diketone 4,4,12,12-tetramethyl-5,8,11-triazapenta-2,14-dione, which is formed (as the dihydroperchlorate salt) by reaction of 3-azapentane-1,5-diamine dihydroperchlorate with acetone (see scheme) (Morgan et al., 1982). \sch

Compound (I) has discrete cations, with CuII in a square-pyramidal coordination (Fig. 1), and perchlorate anions. The oximo atom N2, oximato atom N14, and secondary amine atoms N5 and N11, are coordinated in the tetrahedrally twisted basal plane, with the bond to the axially coordinated secondary amine atom N8 being significantly longer. Displacements from the mean square plane defined by atoms N2, N5, N11 and N14 are: N2 0.154, N5 − 0.158, N11 0.158, N14 − 0.154, Cu 0.100, N8 2.213, O2 0.793 and O14 0.082 Å (s.u. 0.003 Å), and trans-angles are N2—Cu—N11 175.75 (8)° and N14—Cu—N5 165.87 (8)°. The five-membered chelate rings both have asymmetrical gauche conformations [displacements of atoms from the Cu/N5/N8 plane: C6 0.145 and C7 0.697 Å; from the Cu/N8/N11 plane: C9 0.035 and C10 0.683 Å], while the six-membered chelate rings have `half-chair' conformations, with the methyl substituents C41 and C121 axially oriented [displacements from the Cu/N2/N5 plane: C2 0.052, C3 0.445, C4 0.948, C41 − 2.323 and C42 1.050 Å; from the Cu/N11/N14 plane: C12 0.984, C121 2.355, C122 1.039, C13 0.590 and C14 0.263 Å].

The atoms O2 of the oximo and O14 of the oximato group are linked by a short hydrogen bond (Table 2), as is common for oximo-oximato compounds, to form a pseudo-macrocyclic ligand. The cations are linked into a one-dimensional chain, with base vector 001, by weak intramolecular hydrogen bonding. The perchlorate ion shows rotational disorder which was not modelled.

Structures of a number of copper(II) compounds with tetradentate diaza-oximo-oximato ligands with short O—H···O hydrogen-bonded 14- to 16-membered pseudo-cyclic structures have been reported. These generally have square-pyramidal coordination, with water (Nunes et al., 1999; Anderson & Packard, 1979; Schlemper et al., 1981; Lee et al., 1990; Pal et al., 1986) or an anion (Tahirov et al., 1995; Jiang et al., 1993; Nunes et al., 1999; Gavel & Schlemper, 1979; Lee et al., 1991) coordinated axially, or have dinuclear (Tahirov et al., 1993; Fraser et al., 1972) or chain polymeric structures (Bertrand et al., 1977) with µ-oximato-O bridging to the axial site. The work presented here is the first report of a triaza-oximo-oximato compound in which the pentadentate ligand donor atoms occupy all five coordination sites about the copper(II).

Experimental top

(4,4,12,12-Tetramethyl-5,8,11-triazapenta-2,14-dione dihydroperchlorate was prepared by reaction of 3-azapentane-1,5-diamine (diethylenetriamine) dihydroperchlorate with acetone (Morgan et al., 1982). The title compound was prepared by reaction of this, [Cu(H2O)6](ClO4)2, hydroxylamine hydrochloride and triethylamine in a 1:1:2:5 molar ratio in methanol. The green product which crystallized on addition of propan-2-ol was recrystallized from methanol/propan-2-ol.

Refinement top

For atom H2, the positional coordinates were refined, with Uiso = 1.5Ueq(O2). All other H atoms were treated as riding atoms, with N—H distances of 0.93 Å and C—H distances of 0.98 or 0.99 Å, and with Uiso(H) = 1.2Ueq(N) or 1.5Ueq(C). Please check added text.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: local programs; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The cation of (I), drawn with displacement ellipsoids at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity and H atoms bonded to N or O atoms are shown as circles of arbitrary radii.
(4,4,12,12-Tetramethyl-5,8,11-triazapenta-2,14-dione 2-oxime 14-oximato-κ5N)copper(II) perchlorate top
Crystal data top
[Cu(C16H34N5O2)]ClO4F(000) = 1036
Mr = 491.47Dx = 1.455 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9707 reflections
a = 10.8307 (7) Åθ = 2.1–28.4°
b = 23.9974 (15) ŵ = 1.13 mm−1
c = 8.6318 (6) ÅT = 160 K
β = 90.058 (2)°Plate, green
V = 2243.5 (3) Å30.62 × 0.28 × 0.10 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer		4845 independent reflections
Radiation source: fine-focus sealed tube4392 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ω rotation with narrow frames scansθmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan
(Blessing, 1995)		h = −10→14
Tmin = 0.540, Tmax = 0.895k = −26→30
12927 measured reflectionsl = −11→11
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0379P)2 + 3.1169P]
where P = (Fo2 + 2Fc2)/3
4845 reflections(Δ/σ)max = 0.001
271 parametersΔρmax = 0.64 e Å−3
0 restraintsΔρmin = −0.70 e Å−3
Crystal data top
[Cu(C16H34N5O2)]ClO4V = 2243.5 (3) Å3
Mr = 491.47Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.8307 (7) ŵ = 1.13 mm−1
b = 23.9974 (15) ÅT = 160 K
c = 8.6318 (6) Å0.62 × 0.28 × 0.10 mm
β = 90.058 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		4845 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		4392 reflections with I > 2σ(I)
Tmin = 0.540, Tmax = 0.895Rint = 0.035
12927 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.64 e Å−3
4845 reflectionsΔρmin = −0.70 e Å−3
271 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 on F2 for ALL reflections except for 16 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor(obs.) 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.

H(2) located from difference syntheses and the position refined, other H atoms are riding in calculated positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.26542 (2)0.346322 (12)0.81688 (3)0.01749 (9)
N20.4077 (2)0.28900 (9)0.8262 (2)0.0238 (4)
O20.37197 (19)0.23610 (8)0.8847 (2)0.0346 (4)
H20.275 (3)0.2292 (15)0.838 (4)0.052*
C10.6098 (3)0.24921 (13)0.8809 (4)0.0403 (7)
H1A0.69580.26200.87980.060*
H1B0.60110.21680.81280.060*
H1C0.58660.23880.98680.060*
C20.5252 (2)0.29625 (11)0.8237 (3)0.0260 (5)
C30.5853 (2)0.35189 (11)0.7758 (3)0.0264 (5)
H3A0.64830.34300.69650.032*
H3B0.63040.36600.86760.032*
C40.5073 (2)0.40154 (10)0.7113 (3)0.0199 (5)
C410.4550 (2)0.38715 (11)0.5513 (3)0.0255 (5)
H4A0.52310.38210.47790.038*
H4B0.40160.41750.51560.038*
H4C0.40690.35260.55790.038*
C420.5873 (2)0.45630 (11)0.6981 (3)0.0281 (5)
H4D0.65100.45120.61880.042*
H4E0.62660.46410.79800.042*
H4F0.53390.48760.66920.042*
N50.39863 (17)0.41209 (8)0.8164 (2)0.0183 (4)
H50.35820.44280.77490.022*
C60.4288 (2)0.42768 (11)0.9806 (3)0.0237 (5)
H6A0.38520.46261.00740.028*
H6B0.51860.43470.98950.028*
C70.3911 (2)0.38126 (11)1.0982 (3)0.0250 (5)
H7A0.45040.35001.09140.030*
H7B0.39470.39641.20480.030*
N80.26537 (19)0.36052 (9)1.0665 (2)0.0226 (4)
H80.25030.32761.11990.027*
C90.1673 (2)0.40327 (12)1.1010 (3)0.0285 (6)
H9A0.20490.44081.10500.034*
H9B0.12980.39541.20320.034*
C100.0682 (2)0.40182 (12)0.9764 (3)0.0269 (5)
H10A0.02210.36630.98230.032*
H10B0.00910.43270.99260.032*
N110.12680 (17)0.40724 (9)0.8219 (2)0.0196 (4)
H110.16610.44170.81980.024*
C120.0397 (2)0.40594 (11)0.6866 (3)0.0241 (5)
C1210.1177 (2)0.40810 (13)0.5394 (3)0.0325 (6)
H12A0.06340.41100.44890.049*
H12B0.16740.37410.53160.049*
H12C0.17240.44060.54330.049*
C122−0.0472 (2)0.45843 (12)0.6906 (3)0.0320 (6)
H12D−0.09800.45930.59660.048*
H1DE0.00310.49230.69590.048*
H1DF−0.10080.45640.78180.048*
C13−0.0378 (2)0.35071 (12)0.6889 (3)0.0297 (6)
H13A−0.09910.35460.77320.036*
H14B−0.08500.34960.59070.036*
C140.0225 (2)0.29281 (12)0.7086 (3)0.0301 (6)
C15−0.0560 (3)0.24084 (15)0.6724 (5)0.0522 (9)
H15A−0.02570.22330.57720.078*
H15B−0.14240.25190.65850.078*
H15C−0.04970.21440.75850.078*
N140.13391 (19)0.28621 (9)0.7588 (2)0.0244 (4)
O140.16859 (18)0.22928 (8)0.7772 (2)0.0332 (4)
Cl10.24086 (5)0.57184 (3)0.78760 (7)0.02500 (14)
O30.1308 (2)0.59374 (10)0.7192 (3)0.0506 (6)
O40.2130 (2)0.53993 (12)0.9258 (3)0.0582 (7)
O50.2965 (4)0.53074 (15)0.6855 (4)0.0956 (13)
O60.3219 (3)0.61731 (13)0.8189 (5)0.0952 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01918 (15)0.01854 (16)0.01474 (14)0.00032 (11)0.00124 (10)−0.00069 (10)
N20.0294 (10)0.0197 (10)0.0224 (10)0.0034 (8)0.0008 (8)0.0003 (8)
O20.0387 (11)0.0239 (10)0.0413 (11)0.0000 (8)−0.0028 (9)0.0111 (8)
C10.0339 (15)0.0363 (16)0.0507 (18)0.0111 (13)−0.0039 (13)0.0069 (14)
C20.0280 (12)0.0275 (13)0.0227 (11)0.0079 (10)−0.0008 (9)−0.0017 (10)
C30.0198 (11)0.0309 (14)0.0285 (12)0.0048 (10)0.0010 (9)−0.0023 (10)
C40.0177 (10)0.0247 (12)0.0172 (10)−0.0002 (9)0.0030 (8)−0.0013 (9)
C410.0255 (12)0.0344 (14)0.0168 (11)−0.0013 (10)0.0047 (9)−0.0005 (10)
C420.0254 (12)0.0334 (14)0.0254 (12)−0.0056 (11)0.0053 (10)−0.0007 (11)
N50.0182 (9)0.0228 (10)0.0139 (8)0.0003 (7)0.0013 (7)0.0003 (7)
C60.0267 (12)0.0264 (13)0.0181 (11)−0.0037 (10)0.0013 (9)−0.0049 (9)
C70.0291 (12)0.0311 (14)0.0147 (10)0.0003 (10)−0.0017 (9)−0.0013 (9)
N80.0270 (10)0.0259 (11)0.0150 (9)−0.0018 (8)0.0024 (8)0.0021 (8)
C90.0293 (13)0.0379 (15)0.0182 (11)0.0019 (11)0.0072 (10)−0.0051 (10)
C100.0249 (12)0.0347 (15)0.0213 (11)0.0008 (10)0.0084 (9)−0.0021 (10)
N110.0184 (9)0.0232 (10)0.0172 (9)0.0001 (8)0.0015 (7)−0.0003 (8)
C120.0194 (11)0.0321 (14)0.0210 (11)0.0020 (10)0.0001 (9)0.0021 (10)
C1210.0255 (12)0.0510 (18)0.0209 (12)0.0069 (12)0.0005 (10)0.0068 (11)
C1220.0236 (12)0.0378 (16)0.0346 (14)0.0065 (11)−0.0008 (10)0.0037 (12)
C130.0201 (11)0.0388 (16)0.0304 (13)−0.0011 (11)−0.0024 (10)−0.0060 (11)
C140.0264 (12)0.0340 (15)0.0299 (13)−0.0049 (11)0.0025 (10)−0.0097 (11)
C150.0358 (16)0.0418 (19)0.079 (3)−0.0086 (14)−0.0065 (16)−0.0214 (18)
N140.0263 (10)0.0222 (11)0.0249 (10)−0.0010 (8)0.0031 (8)−0.0046 (8)
O140.0359 (10)0.0207 (10)0.0430 (11)−0.0020 (8)0.0031 (9)−0.0059 (8)
Cl10.0210 (3)0.0289 (3)0.0250 (3)0.0016 (2)−0.0004 (2)0.0049 (2)
O30.0359 (12)0.0545 (15)0.0613 (15)0.0046 (10)−0.0212 (11)0.0138 (12)
O40.0479 (13)0.0808 (19)0.0460 (13)0.0167 (13)0.0181 (11)0.0349 (13)
O50.137 (3)0.098 (3)0.0518 (17)0.078 (2)0.0264 (18)0.0059 (16)
O60.079 (2)0.068 (2)0.138 (3)−0.0430 (17)−0.067 (2)0.045 (2)
Geometric parameters (Å, º) top
Cu1—N22.067 (2)N8—C91.507 (3)
Cu1—N142.088 (2)N8—H80.9300
Cu1—N112.096 (2)C9—C101.519 (4)
Cu1—N52.138 (2)C9—H9A0.9900
Cu1—N82.1816 (19)C9—H9B0.9900
N2—C21.285 (3)C10—N111.483 (3)
N2—O21.420 (3)C10—H10A0.9900
O2—H21.14 (4)C10—H10B0.9900
C1—C21.535 (4)N11—C121.500 (3)
C1—H1A0.9800N11—H110.9300
C1—H1B0.9800C12—C1211.527 (3)
C1—H1C0.9800C12—C131.569 (4)
C2—C31.542 (4)C12—C1221.573 (4)
C3—C41.563 (3)C121—H12A0.9800
C3—H3A0.9900C121—H12B0.9800
C3—H3B0.9900C121—H12C0.9800
C4—N51.508 (3)C122—H12D0.9800
C4—C411.532 (3)C122—H1DE0.9800
C4—C421.578 (3)C122—H1DF0.9800
C41—H4A0.9800C13—C141.545 (4)
C41—H4B0.9800C13—H13A0.9900
C41—H4C0.9800C13—H14B0.9900
C42—H4D0.9800C14—N141.292 (3)
C42—H4E0.9800C14—C151.541 (4)
C42—H4F0.9800C15—H15A0.9800
N5—C61.501 (3)C15—H15B0.9800
N5—H50.9300C15—H15C0.9800
C6—C71.561 (3)N14—O141.426 (3)
C6—H6A0.9900O14—H21.27 (4)
C6—H6B0.9900Cl1—O61.426 (3)
C7—N81.475 (3)Cl1—O31.429 (2)
C7—H7A0.9900Cl1—O41.449 (2)
C7—H7B0.9900Cl1—O51.454 (3)
N2—Cu1—N1493.32 (9)C7—N8—Cu1103.58 (13)
N2—Cu1—N11175.79 (8)C9—N8—Cu1107.60 (14)
N14—Cu1—N1189.90 (8)C7—N8—H8110.9
N2—Cu1—N589.33 (8)C9—N8—H8110.9
N14—Cu1—N5165.85 (8)Cu1—N8—H8110.9
N11—Cu1—N588.20 (8)N8—C9—C10110.0 (2)
N2—Cu1—N893.82 (8)N8—C9—H9A109.7
N14—Cu1—N8110.13 (8)C10—C9—H9A109.7
N11—Cu1—N882.52 (8)N8—C9—H9B109.7
N5—Cu1—N883.53 (7)C10—C9—H9B109.7
C2—N2—O2113.4 (2)H9A—C9—H9B108.2
C2—N2—Cu1130.37 (18)N11—C10—C9109.4 (2)
O2—N2—Cu1113.90 (15)N11—C10—H10A109.8
N2—O2—H2104.9 (19)C9—C10—H10A109.8
C2—C1—H1A109.5N11—C10—H10B109.8
C2—C1—H1B109.5C9—C10—H10B109.8
H1A—C1—H1B109.5H10A—C10—H10B108.2
C2—C1—H1C109.5C10—N11—C12115.38 (18)
H1A—C1—H1C109.5C10—N11—Cu1105.33 (15)
H1B—C1—H1C109.5C12—N11—Cu1114.78 (15)
N2—C2—C1119.1 (2)C10—N11—H11106.9
N2—C2—C3122.7 (2)C12—N11—H11106.9
C1—C2—C3118.1 (2)Cu1—N11—H11106.9
C2—C3—C4121.8 (2)N11—C12—C121107.40 (19)
C2—C3—H3A106.9N11—C12—C13110.1 (2)
C4—C3—H3A106.9C121—C12—C13109.6 (2)
C2—C3—H3B106.9N11—C12—C122110.0 (2)
C4—C3—H3B106.9C121—C12—C122108.8 (2)
H3A—C3—H3B106.7C13—C12—C122110.8 (2)
N5—C4—C41107.01 (18)C12—C121—H12A109.5
N5—C4—C3109.59 (19)C12—C121—H12B109.5
C41—C4—C3110.4 (2)H12A—C121—H12B109.5
N5—C4—C42109.42 (19)C12—C121—H12C109.5
C41—C4—C42108.95 (19)H12A—C121—H12C109.5
C3—C4—C42111.35 (19)H12B—C121—H12C109.5
C4—C41—H4A109.5C12—C122—H12D109.5
C4—C41—H4B109.5C12—C122—H1DE109.5
H4A—C41—H4B109.5H12D—C122—H1DE109.5
C4—C41—H4C109.5C12—C122—H1DF109.5
H4A—C41—H4C109.5H12D—C122—H1DF109.5
H4B—C41—H4C109.5H1DE—C122—H1DF109.5
C4—C42—H4D109.5C14—C13—C12122.3 (2)
C4—C42—H4E109.5C14—C13—H13A106.7
H4D—C42—H4E109.5C12—C13—H13A106.7
C4—C42—H4F109.5C14—C13—H14B106.7
H4D—C42—H4F109.5C12—C13—H14B106.7
H4E—C42—H4F109.5H13A—C13—H14B106.6
C6—N5—C4116.16 (18)N14—C14—C15118.9 (3)
C6—N5—Cu1109.17 (14)N14—C14—C13122.8 (2)
C4—N5—Cu1113.83 (14)C15—C14—C13118.2 (2)
C6—N5—H5105.6C14—C15—H15A109.5
C4—N5—H5105.6C14—C15—H15B109.5
Cu1—N5—H5105.6H15A—C15—H15B109.5
N5—C6—C7112.28 (19)C14—C15—H15C109.5
N5—C6—H6A109.1H15A—C15—H15C109.5
C7—C6—H6A109.1H15B—C15—H15C109.5
N5—C6—H6B109.1C14—N14—O14113.6 (2)
C7—C6—H6B109.1C14—N14—Cu1129.26 (19)
H6A—C6—H6B107.9O14—N14—Cu1117.11 (15)
N8—C7—C6111.22 (19)N14—O14—H2106.7 (17)
N8—C7—H7A109.4O6—Cl1—O3108.03 (17)
C6—C7—H7A109.4O6—Cl1—O4112.1 (2)
N8—C7—H7B109.4O3—Cl1—O4111.10 (15)
C6—C7—H7B109.4O6—Cl1—O5112.3 (3)
H7A—C7—H7B108.0O3—Cl1—O5110.19 (19)
C7—N8—C9112.6 (2)O4—Cl1—O5103.13 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O141.14 (4)1.27 (4)2.395 (3)171 (4)
O2—H2···N141.14 (4)2.16 (4)3.044 (3)132 (3)
N5—H5···O50.932.343.257 (4)167
N8—H8···O14i0.932.123.009 (3)160
N11—H11···O40.932.583.437 (4)154
Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C16H34N5O2)]ClO4
Mr491.47
Crystal system, space groupMonoclinic, P21/c
Temperature (K)160
a, b, c (Å)10.8307 (7), 23.9974 (15), 8.6318 (6)
β (°) 90.058 (2)
V (Å3)2243.5 (3)
Z4
Radiation typeMo Kα
µ (mm−1)1.13
Crystal size (mm)0.62 × 0.28 × 0.10
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.540, 0.895
No. of measured, independent and
observed [I > 2σ(I)] reflections		12927, 4845, 4392
Rint0.035
(sin θ/λ)max (Å−1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.100, 1.12
No. of reflections4845
No. of parameters271
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.64, −0.70

Computer programs: SMART (Siemens, 1995), local programs, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—N22.067 (2)N2—C21.285 (3)
Cu1—N142.088 (2)N2—O21.420 (3)
Cu1—N112.096 (2)C14—N141.292 (3)
Cu1—N52.138 (2)N14—O141.426 (3)
Cu1—N82.1816 (19)
N2—Cu1—N1493.32 (9)O2—N2—Cu1113.90 (15)
N2—Cu1—N11175.79 (8)N2—C2—C3122.7 (2)
N14—Cu1—N1189.90 (8)C1—C2—C3118.1 (2)
N2—Cu1—N589.33 (8)C2—C3—C4121.8 (2)
N14—Cu1—N5165.85 (8)C14—C13—C12122.3 (2)
N11—Cu1—N588.20 (8)N14—C14—C15118.9 (3)
N2—Cu1—N893.82 (8)N14—C14—C13122.8 (2)
N14—Cu1—N8110.13 (8)C15—C14—C13118.2 (2)
N11—Cu1—N882.52 (8)C14—N14—O14113.6 (2)
N5—Cu1—N883.53 (7)C14—N14—Cu1129.26 (19)
C2—N2—O2113.4 (2)O14—N14—Cu1117.11 (15)
C2—N2—Cu1130.37 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O141.14 (4)1.27 (4)2.395 (3)171 (4)
O2—H2···N141.14 (4)2.16 (4)3.044 (3)132 (3)
N5—H5···O50.932.343.257 (4)167
N8—H8···O14i0.932.123.009 (3)160
N11—H11···O40.932.583.437 (4)154
Symmetry code: (i) x, −y+1/2, z+1/2.
 

Acknowledgements

The authors thank Professor W. Clegg, University of Newcastle, for the use of the diffractometer.

References

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 60| Part 6| June 2004| Pages m256-m257
doi:10.1107/S0108270104008765
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