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In the title compound, [Cu(ClO4)2(C20H40N4)], the CuII ion has a tetra­gonally distorted octa­hedral environment, with the four N atoms of the macrocyclic ligand in equatorial positions and the O atoms of two perchlorate groups in axial positions. The CuII ion is situated on an inversion centre. The macrocyclic ligand adopts its most stable trans-III conformation. The long axial Cu—O bond is the result of the Jahn–Teller effect. The crystal structure is stabilized by intra­molecular hydrogen bonds between secondary N—H and the O atoms of the perchlorate groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048039/av3109sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048039/av3109Isup2.hkl
Contains datablock I

CCDC reference: 667125

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.051
  • wR factor = 0.102
  • Data-to-parameter ratio = 17.3

checkCIF/PLATON results

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Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 2.78 PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.69 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Cl1
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 2.784 Tmax scaled 0.801 Tmin scaled 0.617 PLAT793_ALERT_1_G Check the Absolute Configuration of N1 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of N2 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C1 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C6 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C9 = ... S PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 1.90
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

Comment top

Marcrocyclic complexes are involved in diverse application fields such as catalysis, enzyme mimics, chemical sensors, purification of waste water, selective metal ions recovery, pharmacology and therapy (Meyer et al., 1998, and references therein). Recently, metal-containing complexes of 14-membered cyclam and its derivatives have received a great deal of attention due to their highly potent and selective anti-HIV activity by specifically blocking the co-receptor CXCR4. It is found that the transition metal complexation to the cyclam ligands shows various antiviral activity in comparison to the marcrocycles alone (Liang & Sadler, 2004).

There are five configurational trans isomers of metal–cyclam complexes, which differ in the chirality of the N atoms. The configurations that are symmetrical about the diagonal also can fold to form cis isomers. The substitution on the ring of cyclam derivatives has a very important effect both on the chemical and the structural properties of complexes containing the macrocyclic ligands (Bakaj & Zimmer, 1999).

The crystal structures of copper(II) complexes containing ligand 5,16-dimethyl-2,6,13,17-tetraazatricyclo(14,4,01.18,07.12)docosane (L) have been reported previously (Choi et al., 1996; Choi, Suzuki & Kaizaki, 2006). The constrained ligand L containing two cyclohexane rings and methyl groups on the carbon atoms has often shown different coordination behaviors from those of the transition metal complexes with the cyclam.

The perchlorate ion, ClO4- also can coordinate to the transition metal ions as monodentate, chelating bidentate, and bridging bidentate ligand (Nakamoto, 1997).

The configuration of the macrocyclic ligand and orientation of the N—H bonds in the metal complexes are important factors for co-receptor recognition. Therefore, the understanding of binding affinity and configuration between perchlorato group and copper(II)-constrained cyclam has become extremely important in the improved design and development of new highly effective anti-HIV drugs that specially target alternative events in the HIV replicative cycle.

In this communication, we report the structure of the copper(II) complex, (I), with the 14-membered macrocycle (L) and perchlorato groups in order to determine the coordination mode of perchlorato group and the macrocyclic ring conformation.

The selected bond lengths and angles are listed in Table 1. A perspective drawing of the structure together with the atomic labeling is depicted in Fig. 1.

The coordination geometry around the copper(II) ion reveals a tetragonally distorted coordination environment with four N atoms from the macrocycle and two O atoms atoms of the perchlorato groups. The copper ion is situated on the centre of inversion. Two methyl groups on the six-membered chelate rings are anti with respect to the N4 plane. As usually observed, five-membered chelate rings adopt a gauche, and six-membered rings are in the chair conformations. The bond angles of five- and six-membered chelate rings around the copper(II) are the 85.04 (9) and 94.96 (9)°, respectively. The C—N and C—C distances in macrocyclic molecule are typical of macrocyclic tetramine complexes, 1.490 (3)–1.500 (3) Å and 1.517 (4)–1.533 (4) Å, respectively. The C—N—C and C—C—N angles are also typical (Choi, Clegg et al., 2006). The equatorial Cu—N1 [2.048 (2) Å] and Cu—N2 [2.005 (2) Å] bond distances are slightly different due to steric effect of the methyl group attached to the C9, and can be compared to corresponding bond lengths in other tetragonally elongated octahedral copper(II) complexes. However, the average bond length [2.027 Å] of Cu—N is in good agreement with those [2.028 Å and 2.025 Å] found in [Cu(L)(H2O)2]Cl2 and [Cu(L)(ONO2)2].3H2O, respectively (Choi et al., 1996; Choi, Suzuki & Kaizaki, 2006). In general, the Cu(II)–ligand bonds in the range of 2.5 and 2.9 Å may be considered as semi-coordinated bond (Karunakaran et al., 1999). The Cu1—O4 bond length of 2.623 (2) Å is the result of the Jahn–Teller effect. The Cl—O bond lengths in the perchlorate anion are in the range 1.419 (2)–1.442 (3) Å. The longer Cl1—O4 bond reflects that the O atom of perchlorato group is coordinated to the copper atom. The Cl1—O1 and Cl1—O3 bonds are slightly longer than Cl1—O2 bond, and the O—Cl—O angle deviating from the ideal value of 109° involves the O1 and O3 atoms linked to the cation by hydrogen bonds N1—H1···O1 and N2—H2···O3A. Thus the complex is stabilized by formation of the intramolecular hydrogen bond between the non-coordinated oxygen O1 and O3 of the perchlorato ligand and the secondary NH group of the macrocyclic ligand (Table 2).

Related literature top

For related literature, see: Bakaj & Zimmer (1999); Choi et al. (1996); Choi, Clegg et al. (2006); Choi, Suzuki & Kaizaki (2006); Kang et al. (1991); Karunakaran et al. (1999); Liang & Sadler (2004); Meyer et al. (1998); Nakamoto (1997).

Experimental top

The macrocyclicligand 5,16-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane (L) was prepared according to the literature method (Kang et al., 1991). A methanol suspension of Cu(OAc).H2O (0.95 g, 2.10 mmol) and the macrocyclic ligand (L) (1.0 g, 3 mmol) was heated to reflux for 30 min. The suspension mixture is refluxed for 30 min at 80 °C and cooled to room temperature. The HClO4 (60%, 0.66 ml) is added the reaction mixture and the solution is stored in the refrigerator. The product was filtered and air-dried. Recrystallization of the material from hot acetonitrile–water (1:2 v/v) mixture solution gave reddish violet crystals that were suitable for crystallographic analysis. Analysis calculated for C20H48Cl2CuN4O8: C, 40.10; H, 6.73; N, 9.35%; found: C, 40.15; H, 6.94; N, 9.31%.

Refinement top

The hydrogen atoms (H1 and H2) attached to nitrogen atoms were located in difference electron density maps, and refined isotropically. All the other hydrogen atoms were included in calculated positions and refined using a riding model, with C—H = 0.96–0.98 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(parent atom).

Structure description top

Marcrocyclic complexes are involved in diverse application fields such as catalysis, enzyme mimics, chemical sensors, purification of waste water, selective metal ions recovery, pharmacology and therapy (Meyer et al., 1998, and references therein). Recently, metal-containing complexes of 14-membered cyclam and its derivatives have received a great deal of attention due to their highly potent and selective anti-HIV activity by specifically blocking the co-receptor CXCR4. It is found that the transition metal complexation to the cyclam ligands shows various antiviral activity in comparison to the marcrocycles alone (Liang & Sadler, 2004).

There are five configurational trans isomers of metal–cyclam complexes, which differ in the chirality of the N atoms. The configurations that are symmetrical about the diagonal also can fold to form cis isomers. The substitution on the ring of cyclam derivatives has a very important effect both on the chemical and the structural properties of complexes containing the macrocyclic ligands (Bakaj & Zimmer, 1999).

The crystal structures of copper(II) complexes containing ligand 5,16-dimethyl-2,6,13,17-tetraazatricyclo(14,4,01.18,07.12)docosane (L) have been reported previously (Choi et al., 1996; Choi, Suzuki & Kaizaki, 2006). The constrained ligand L containing two cyclohexane rings and methyl groups on the carbon atoms has often shown different coordination behaviors from those of the transition metal complexes with the cyclam.

The perchlorate ion, ClO4- also can coordinate to the transition metal ions as monodentate, chelating bidentate, and bridging bidentate ligand (Nakamoto, 1997).

The configuration of the macrocyclic ligand and orientation of the N—H bonds in the metal complexes are important factors for co-receptor recognition. Therefore, the understanding of binding affinity and configuration between perchlorato group and copper(II)-constrained cyclam has become extremely important in the improved design and development of new highly effective anti-HIV drugs that specially target alternative events in the HIV replicative cycle.

In this communication, we report the structure of the copper(II) complex, (I), with the 14-membered macrocycle (L) and perchlorato groups in order to determine the coordination mode of perchlorato group and the macrocyclic ring conformation.

The selected bond lengths and angles are listed in Table 1. A perspective drawing of the structure together with the atomic labeling is depicted in Fig. 1.

The coordination geometry around the copper(II) ion reveals a tetragonally distorted coordination environment with four N atoms from the macrocycle and two O atoms atoms of the perchlorato groups. The copper ion is situated on the centre of inversion. Two methyl groups on the six-membered chelate rings are anti with respect to the N4 plane. As usually observed, five-membered chelate rings adopt a gauche, and six-membered rings are in the chair conformations. The bond angles of five- and six-membered chelate rings around the copper(II) are the 85.04 (9) and 94.96 (9)°, respectively. The C—N and C—C distances in macrocyclic molecule are typical of macrocyclic tetramine complexes, 1.490 (3)–1.500 (3) Å and 1.517 (4)–1.533 (4) Å, respectively. The C—N—C and C—C—N angles are also typical (Choi, Clegg et al., 2006). The equatorial Cu—N1 [2.048 (2) Å] and Cu—N2 [2.005 (2) Å] bond distances are slightly different due to steric effect of the methyl group attached to the C9, and can be compared to corresponding bond lengths in other tetragonally elongated octahedral copper(II) complexes. However, the average bond length [2.027 Å] of Cu—N is in good agreement with those [2.028 Å and 2.025 Å] found in [Cu(L)(H2O)2]Cl2 and [Cu(L)(ONO2)2].3H2O, respectively (Choi et al., 1996; Choi, Suzuki & Kaizaki, 2006). In general, the Cu(II)–ligand bonds in the range of 2.5 and 2.9 Å may be considered as semi-coordinated bond (Karunakaran et al., 1999). The Cu1—O4 bond length of 2.623 (2) Å is the result of the Jahn–Teller effect. The Cl—O bond lengths in the perchlorate anion are in the range 1.419 (2)–1.442 (3) Å. The longer Cl1—O4 bond reflects that the O atom of perchlorato group is coordinated to the copper atom. The Cl1—O1 and Cl1—O3 bonds are slightly longer than Cl1—O2 bond, and the O—Cl—O angle deviating from the ideal value of 109° involves the O1 and O3 atoms linked to the cation by hydrogen bonds N1—H1···O1 and N2—H2···O3A. Thus the complex is stabilized by formation of the intramolecular hydrogen bond between the non-coordinated oxygen O1 and O3 of the perchlorato ligand and the secondary NH group of the macrocyclic ligand (Table 2).

For related literature, see: Bakaj & Zimmer (1999); Choi et al. (1996); Choi, Clegg et al. (2006); Choi, Suzuki & Kaizaki (2006); Kang et al. (1991); Karunakaran et al. (1999); Liang & Sadler (2004); Meyer et al. (1998); Nakamoto (1997).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. A perspective view (50% probability level) of complex (I) with the atom-numbering scheme. Dashed lines indicate intramolecular hydrogen bonds.
(5,16-Dimethyl-2,6,13,17-tetraazatricyclo[14.4.01,18.07,12] docosane-κ4N)bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C20H40N4)]F(000) = 1260
Mr = 599.00Dx = 1.547 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4468 reflections
a = 18.8782 (12) Åθ = 2.2–28.2°
b = 8.0923 (5) ŵ = 1.11 mm1
c = 16.8906 (11) ÅT = 173 K
β = 94.741 (1)°Block, red-violet
V = 2571.5 (3) Å30.40 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2914 independent reflections
Radiation source: fine-focus sealed tube2627 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
φ and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
h = 2424
Tmin = 0.222, Tmax = 0.288k = 910
7765 measured reflectionsl = 2120
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.26 w = 1/[σ2(Fo2) + (0.0275P)2 + 8.4134P]
where P = (Fo2 + 2Fc2)/3
2914 reflections(Δ/σ)max = 0.001
168 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 1.02 e Å3
Crystal data top
[Cu(ClO4)2(C20H40N4)]V = 2571.5 (3) Å3
Mr = 599.00Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.8782 (12) ŵ = 1.11 mm1
b = 8.0923 (5) ÅT = 173 K
c = 16.8906 (11) Å0.40 × 0.30 × 0.20 mm
β = 94.741 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2914 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1999)
2627 reflections with I > 2σ(I)
Tmin = 0.222, Tmax = 0.288Rint = 0.026
7765 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.26Δρmax = 0.52 e Å3
2914 reflectionsΔρmin = 1.02 e Å3
168 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
xyzUiso*/Ueq
Cu10.50000.50000.50000.01430 (13)
Cl10.59889 (4)0.27519 (9)0.36069 (5)0.02685 (18)
O10.66514 (14)0.3277 (4)0.4016 (2)0.0628 (9)
O20.60819 (15)0.1267 (3)0.31806 (16)0.0448 (7)
O30.57461 (17)0.4046 (3)0.30745 (16)0.0507 (7)
O40.54793 (14)0.2534 (3)0.41891 (15)0.0410 (6)
N10.60523 (12)0.5385 (3)0.53479 (14)0.0155 (5)
H10.6243 (17)0.470 (4)0.5051 (19)0.020 (8)*
N20.50238 (12)0.3441 (3)0.59248 (14)0.0158 (5)
H20.4875 (16)0.396 (4)0.6259 (18)0.013 (8)*
C10.61957 (14)0.4670 (3)0.61637 (16)0.0176 (5)
H1A0.60090.54310.65470.021*
C20.69850 (15)0.4392 (4)0.63986 (18)0.0234 (6)
H2A0.72300.54460.64140.028*
H2B0.71850.37070.60020.028*
C30.71017 (15)0.3558 (4)0.72101 (18)0.0240 (6)
H3A0.76040.33390.73300.029*
H3B0.69470.42910.76160.029*
C40.66895 (16)0.1946 (4)0.72184 (18)0.0244 (6)
H4A0.67520.14630.77450.029*
H4B0.68770.11760.68480.029*
C50.58952 (15)0.2218 (4)0.69897 (17)0.0207 (6)
H5A0.56510.11630.69750.025*
H5B0.56960.29030.73870.025*
C60.57805 (14)0.3055 (3)0.61764 (16)0.0160 (5)
H60.59590.23120.57800.019*
C70.45702 (15)0.1938 (3)0.58195 (17)0.0198 (6)
H7A0.46160.12930.63050.024*
H7B0.47370.12640.53980.024*
C80.37895 (15)0.2367 (4)0.56167 (17)0.0219 (6)
H8A0.36560.32120.59840.026*
H8B0.35070.13930.57040.026*
C90.35957 (15)0.2981 (4)0.47688 (17)0.0219 (6)
H90.30810.31700.47140.026*
C100.37587 (19)0.1718 (4)0.41449 (19)0.0320 (7)
H10A0.36280.21580.36250.048*
H10B0.34930.07270.42200.048*
H10C0.42580.14710.41950.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0130 (2)0.0137 (2)0.0158 (2)0.00162 (19)0.00138 (16)0.00281 (19)
Cl10.0326 (4)0.0214 (4)0.0281 (4)0.0029 (3)0.0118 (3)0.0031 (3)
O10.0306 (14)0.081 (2)0.077 (2)0.0053 (15)0.0024 (14)0.0350 (19)
O20.0638 (18)0.0272 (13)0.0468 (16)0.0020 (12)0.0253 (13)0.0105 (11)
O30.083 (2)0.0344 (15)0.0368 (15)0.0139 (14)0.0160 (14)0.0071 (12)
O40.0563 (16)0.0321 (13)0.0384 (14)0.0093 (12)0.0264 (12)0.0074 (11)
N10.0175 (11)0.0126 (11)0.0162 (11)0.0016 (9)0.0004 (9)0.0008 (9)
N20.0147 (11)0.0144 (11)0.0181 (12)0.0006 (9)0.0012 (9)0.0003 (9)
C10.0196 (13)0.0152 (14)0.0176 (13)0.0007 (10)0.0002 (10)0.0015 (10)
C20.0156 (13)0.0272 (15)0.0263 (15)0.0019 (12)0.0042 (11)0.0046 (12)
C30.0200 (14)0.0283 (16)0.0224 (15)0.0020 (12)0.0055 (11)0.0033 (12)
C40.0244 (15)0.0251 (15)0.0224 (15)0.0040 (12)0.0055 (12)0.0040 (12)
C50.0219 (14)0.0198 (14)0.0200 (14)0.0008 (12)0.0009 (11)0.0038 (11)
C60.0151 (12)0.0150 (13)0.0177 (13)0.0022 (10)0.0002 (10)0.0011 (10)
C70.0222 (14)0.0135 (13)0.0233 (14)0.0022 (11)0.0004 (11)0.0030 (11)
C80.0198 (14)0.0221 (15)0.0234 (15)0.0068 (11)0.0014 (11)0.0068 (12)
C90.0175 (13)0.0216 (14)0.0259 (15)0.0055 (11)0.0025 (11)0.0056 (12)
C100.045 (2)0.0202 (15)0.0292 (17)0.0070 (14)0.0072 (14)0.0012 (13)
Geometric parameters (Å, º) top
Cu1—N22.005 (2)C3—H3A0.9700
Cu1—N2i2.005 (2)C3—H3B0.9700
Cu1—N12.048 (2)C4—C51.533 (4)
Cu1—N1i2.048 (2)C4—H4A0.9700
Cu1—O42.623 (2)C4—H4B0.9700
Cl1—O21.419 (2)C5—C61.531 (4)
Cl1—O31.431 (3)C5—H5A0.9700
Cl1—O11.442 (3)C5—H5B0.9700
Cl1—O41.442 (2)C6—H60.9800
N1—C11.499 (3)C7—C81.525 (4)
N1—C9i1.500 (3)C7—H7A0.9700
N1—H10.85 (3)C7—H7B0.9700
N2—C61.489 (3)C8—C91.531 (4)
N2—C71.490 (3)C8—H8A0.9700
N2—H20.77 (3)C8—H8B0.9700
C1—C61.525 (4)C9—N1i1.500 (3)
C1—C21.526 (4)C9—C101.517 (4)
C1—H1A0.9800C9—H90.9800
C2—C31.528 (4)C10—H10A0.9600
C2—H2A0.9700C10—H10B0.9600
C2—H2B0.9700C10—H10C0.9600
C3—C41.519 (4)
N2—Cu1—N2i180.000 (1)C2—C3—H3B109.5
N2—Cu1—N185.04 (9)H3A—C3—H3B108.1
N2i—Cu1—N194.96 (9)C3—C4—C5111.5 (2)
N2—Cu1—N1i94.96 (9)C3—C4—H4A109.3
N2i—Cu1—N1i85.04 (9)C5—C4—H4A109.3
N1—Cu1—N1i180.00 (4)C3—C4—H4B109.3
N2—Cu1—O486.65 (9)C5—C4—H4B109.3
N2i—Cu1—O493.35 (9)H4A—C4—H4B108.0
N1—Cu1—O484.11 (9)C6—C5—C4110.6 (2)
N1i—Cu1—O495.89 (9)C6—C5—H5A109.5
O2—Cl1—O3110.32 (16)C4—C5—H5A109.5
O2—Cl1—O1110.74 (17)C6—C5—H5B109.5
O3—Cl1—O1107.8 (2)C4—C5—H5B109.5
O2—Cl1—O4111.10 (15)H5A—C5—H5B108.1
O3—Cl1—O4108.71 (17)N2—C6—C1107.4 (2)
O1—Cl1—O4108.06 (18)N2—C6—C5114.2 (2)
Cl1—O4—Cu1122.78 (14)C1—C6—C5110.9 (2)
C1—N1—C9i114.4 (2)N2—C6—H6108.1
C1—N1—Cu1107.59 (16)C1—C6—H6108.1
C9i—N1—Cu1121.75 (17)C5—C6—H6108.1
C1—N1—H1104 (2)N2—C7—C8112.1 (2)
C9i—N1—H1107 (2)N2—C7—H7A109.2
Cu1—N1—H1100 (2)C8—C7—H7A109.2
C6—N2—C7113.0 (2)N2—C7—H7B109.2
C6—N2—Cu1108.26 (16)C8—C7—H7B109.2
C7—N2—Cu1116.42 (17)H7A—C7—H7B107.9
C6—N2—H2108 (2)C7—C8—C9115.8 (2)
C7—N2—H2107 (2)C7—C8—H8A108.3
Cu1—N2—H2104 (2)C9—C8—H8A108.3
N1—C1—C6106.9 (2)C7—C8—H8B108.3
N1—C1—C2113.2 (2)C9—C8—H8B108.3
C6—C1—C2111.2 (2)H8A—C8—H8B107.4
N1—C1—H1A108.5N1i—C9—C10112.6 (2)
C6—C1—H1A108.5N1i—C9—C8109.5 (2)
C2—C1—H1A108.5C10—C9—C8112.6 (3)
C1—C2—C3111.3 (2)N1i—C9—H9107.2
C1—C2—H2A109.4C10—C9—H9107.2
C3—C2—H2A109.4C8—C9—H9107.2
C1—C2—H2B109.4C9—C10—H10A109.5
C3—C2—H2B109.4C9—C10—H10B109.5
H2A—C2—H2B108.0H10A—C10—H10B109.5
C4—C3—C2110.6 (2)C9—C10—H10C109.5
C4—C3—H3A109.5H10A—C10—H10C109.5
C2—C3—H3A109.5H10B—C10—H10C109.5
C4—C3—H3B109.5
O2—Cl1—O4—Cu1171.89 (17)Cu1—N1—C1—C2162.54 (19)
O3—Cl1—O4—Cu150.3 (2)N1—C1—C2—C3176.2 (2)
O1—Cl1—O4—Cu166.4 (2)C6—C1—C2—C355.9 (3)
N2—Cu1—O4—Cl1142.5 (2)C1—C2—C3—C455.9 (3)
N2i—Cu1—O4—Cl137.5 (2)C2—C3—C4—C556.3 (3)
N1—Cu1—O4—Cl157.18 (19)C3—C4—C5—C656.4 (3)
N1i—Cu1—O4—Cl1122.82 (19)C7—N2—C6—C1173.3 (2)
N2—Cu1—N1—C113.38 (17)Cu1—N2—C6—C142.8 (2)
N2i—Cu1—N1—C1166.62 (17)C7—N2—C6—C563.3 (3)
O4—Cu1—N1—C1100.52 (17)Cu1—N2—C6—C5166.21 (19)
N2—Cu1—N1—C9i148.3 (2)N1—C1—C6—N254.8 (3)
N2i—Cu1—N1—C9i31.7 (2)C2—C1—C6—N2178.9 (2)
O4—Cu1—N1—C9i124.6 (2)N1—C1—C6—C5179.8 (2)
N1—Cu1—N2—C616.45 (17)C2—C1—C6—C555.7 (3)
N1i—Cu1—N2—C6163.55 (17)C4—C5—C6—N2177.1 (2)
O4—Cu1—N2—C667.92 (18)C4—C5—C6—C155.7 (3)
N1—Cu1—N2—C7145.1 (2)C6—N2—C7—C8176.1 (2)
N1i—Cu1—N2—C734.9 (2)Cu1—N2—C7—C857.6 (3)
O4—Cu1—N2—C760.68 (19)N2—C7—C8—C974.2 (3)
C9i—N1—C1—C6178.3 (2)C7—C8—C9—N1i65.9 (3)
Cu1—N1—C1—C639.7 (2)C7—C8—C9—C1060.2 (3)
C9i—N1—C1—C258.9 (3)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.85 (3)2.28 (3)3.110 (4)166 (2)
N2—H2···O3i0.77 (3)2.34 (3)3.084 (4)162 (3)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu(ClO4)2(C20H40N4)]
Mr599.00
Crystal system, space groupMonoclinic, C2/c
Temperature (K)173
a, b, c (Å)18.8782 (12), 8.0923 (5), 16.8906 (11)
β (°) 94.741 (1)
V3)2571.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.11
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1999)
Tmin, Tmax0.222, 0.288
No. of measured, independent and
observed [I > 2σ(I)] reflections
7765, 2914, 2627
Rint0.026
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.103, 1.26
No. of reflections2914
No. of parameters168
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.52, 1.02

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Selected geometric parameters (Å, º) top
Cu1—N22.005 (2)Cu1—O42.623 (2)
Cu1—N12.048 (2)
N2—Cu1—N185.04 (9)N1—Cu1—O484.11 (9)
N2—Cu1—O486.65 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.85 (3)2.28 (3)3.110 (4)166 (2)
N2—H2···O3i0.77 (3)2.34 (3)3.084 (4)162 (3)
Symmetry code: (i) x+1, y+1, z+1.
 

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