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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 2| February 2015| Pages 136-138

Crystal structure of trans-(1,8-di­butyl-1,3,6,8,10,13-hexa­aza­cyclo­tetra­decane-κ4N3,N6,N10,N13)bis­­(perchlorato-κO)copper(II) from synchrotron data

aBeamline Department, Pohang Accelerator Laboratory/POSTECH 80, Pohang 790-784, South Korea
*Correspondence e-mail: dmoon@postech.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 16 December 2014; accepted 24 December 2014; online 10 January 2015)

The structure of the title compound, [Cu(ClO4)2(C16H38N6)] has been determined from synchrotron data, λ = 0.62988 Å. The asymmetric unit comprises one half of the CuII complex as the CuII cation lies on an inversion center. It is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutually trans O atoms of the two perchlorate ions in a tetra­gonally distorted octa­hedral geometry. The average equatorial Cu—N bond length is significantly shorter than the average axial Cu—O bond length [2.010 (4) and 2.569 (1) Å, respectively]. Intra­molecular N—H⋯O hydrogen bonds between the macrocyclic ligand and uncoordinating O atoms of the perchlorate ligand stabilize the mol­ecular structure. In the crystal structure, an extensive series of inter­molecular N—H⋯O and C—H⋯O hydrogen bonds generate a three-dimensional network.

1. Chemical context

Coordination compounds with macrocyclic ligands have attracted considerable attention in chemistry, biological chemistry and materials science (Lehn, 1995[Lehn, J.-M. (1995). Supramolecular Chemistry; Concepts and Perspectives. Weinheim: VCH.]). In particular, macrocyclic CuII complexes with vacant sites in the axial positions are good building blocks for assembling multi-dimensional frameworks (Ko et al., 2002[Ko, J. W., Min, K. S. & Suh, M. P. (2002). Inorg. Chem. 41, 2151-2157.]), with potential applications as metal extractants, radiotherapeutic materials and as medical imaging agents (Sowen et al., 2013[Sowden, R. J., Trotter, K. D., Dunbar, L., Craig, G., Erdemli, O., Spickett, C. M. & Reglinski, J. (2013). Biometals, 26, 85-96.]). For example, CuII complexes with tetra-aza­macrocyclic ligands have been studied with various auxiliary anionic ligands such as ferricyanide and hexacyanidochromate and their biological redox-sensing and magnetic properties (Xiang et al., 2009[Xiang, H., Wang, S.-J., Jiang, L., Feng, X.-L. & Lu, T.-B. (2009). Eur. J. Inorg. Chem. pp. 2074-2082.]) have been investigated. Moreover, the perchlorate ion is a versatile anion which can easily bridge two transition metal complexes, allowing the assembly of multi-dimensional compounds (Kwak et al., 2001[Kwak, C.-H., Jeong, J. & Kim, J. (2001). Inorg. Chem. Commun. 4, 264-268.]).

[Scheme 1]

Here, we report the synthesis and crystal structure of a CuII aza­macrocyclic complex, trans-(1,8-dibutyl-1,3,6,8,10,13-hexaaza­cyclo­tetra­decane-κ4N3,N6,N10,N13)bis­(perchlorato-κO)copper(II), which has two perchlorate ions coordinating in the axial positions of the overall six-coordinate complex.

2. Structural commentary

In the title compound, the coordination environment around the CuII ion, which lies on an inversion center, is tetra­gonally distorted octa­hedral. The copper(II) ion binds to the four secondary N atoms of the aza­macrocyclic ligand in a square-planar fashion in the equatorial plane, with two O atoms from the perchlorate anions in axial positions as shown in Fig. 1[link]. The bonds to the two axially located perchlorate anions are significantly longer than those to the donor N atoms in the equatorial plane. This can be attributed either to a rather large Jahn–Teller distortion of the CuII ion and/or to a considerable ring contraction of the aza­macrocyclic ligand (Halcrow, 2013[Halcrow, M. A. (2013). Chem. Soc. Rev. 42, 1784-1795.]). The six-membered chelate rings adopt chair conformations and the five-membered chelate rings assume gauche conformations (Min & Suh, 2001[Min, K. S. & Suh, M. P. (2001). Chem. Eur. J. 7, 303-313.]). Intra­molecular N—H⋯O hydrogen bonds between the secondary amine groups of the aza­macrocyclic ligand and an O atom of each perchlorate ion contribute to the mol­ecular conformation (Fig. 1[link] and Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 1.00 2.50 3.136 (2) 121
N2—H2⋯O4ii 1.00 2.17 3.000 (2) 139
C1—H1A⋯O1i 0.99 2.46 3.160 (2) 127
N1—H1⋯O1iii 1.00 2.08 3.018 (2) 155
C6—H6B⋯O3iv 0.99 2.50 3.338 (3) 142
Symmetry codes: (i) x+1, y, z; (ii) x, y-1, z; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z+2.
[Figure 1]
Figure 1
View of the mol­ecular structure of the title compound, showing the atom labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. Intra­molecular N—H⋯O hydrogen bonds are shown as black dashed lines. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

3. Supra­molecular features

Each complex mol­ecule forms three N—H⋯O and two C—H⋯O hydrogen bonds (Steed & Atwood, 2009[Steed, J. W. & Atwood, J. L. (2009). Supramolecular Chemistry, 2nd ed. Chichester: John Wiley & Sons.]), as shown in Table 1[link], Fig. 2[link]. Sheets of complex mol­ecules form in the ab plane, Fig. 3[link], and additional C6—H6B⋯O3 contacts link these sheets into a three-dimensional network.

[Figure 2]
Figure 2
View of the contacts made by an individual complex mol­ecule with hydrogen bonds drawn as dashed lines.
[Figure 3]
Figure 3
Sheets of complex mol­ecules in the ab plane. Hydrogen-bonding interactions are shown as dashed lines.

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, May 2014 with three updates; Groom & Allen 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) indicated that 51 aza­macrocyclic CuII complexes with pendant alkyl groups had been reported previously. These complexes have been studied as good building blocks for supra­molecular chemistry and contain a variety of pendant alkyl groups (Cho et al., 2003[Cho, J., Lough, A. J. & Kim, J. C. (2003). Inorg. Chim. Acta, 342, 305-310.]). Their magnetic properties and guest-exchange effects with cyanido groups and carb­oxy­lic acid groups as ligands have also been investigated (Ko et al., 2002[Ko, J. W., Min, K. S. & Suh, M. P. (2002). Inorg. Chem. 41, 2151-2157.]; Zhou et al., 2014[Zhou, H., Yan, J., Shen, X., Zhou, H. & Yuan, A. (2014). RSC Adv. 4, 61-70.]). No corresponding aza­macrocyclic CuII complex with pendant butyl groups has been reported and the title compound was newly synthesized for this research.

5. Synthesis and crystallization

The title compound was prepared as follows. Ethyl­enedi­amine (3.4 mL, 0.05 mol), paraformaldehyde (3.0 g, 0.10 mol), and butyl­amine (3.7 g, 0.05 mol) were slowly added to a stirred solution of CuCl2·2H2O (4.26 g, 0.025 mol) in MeOH (50 mL). The mixture was heated to reflux for 1 day. The solution was filtered and cooled at room temperature. HClO4 (70%, 15 mL) was added to the purple solution. A bright-purple precipitate formed and was filtered off, washed with H2O, MeOH, and diethyl ether, and dried in air. Purple crystals of the title compound were obtained by diffusion of diethyl ether into the purple solution over several days. Yield: 2.38g (17%). FT–IR (ATR, cm−1): 3240, 2936, 1443, 1053, 995, 962, 746.

Safety note: Although we have experienced no problems with the compound reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98–0.99 Å and an N—H distance of 1.0 Å with Uiso(H) values of 1.2 or 1.5 Ueq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula [Cu(ClO4)2(C16H38N6)]
Mr 576.96
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 100
a, b, c (Å) 8.2230 (16), 8.3600 (17), 10.039 (2)
α, β, γ (°) 92.87 (3), 96.12 (3), 116.60 (3)
V3) 609.8 (3)
Z 1
Radiation type Synchrotron, λ = 0.62998 Å
μ (mm−1) 0.84
Crystal size (mm) 0.10 × 0.10 × 0.03
 
Data collection
Diffractometer ADSC Q210 CCD area detector
Absorption correction Empirical (using intensity measurements) HKL3000sm SCALEPACK (Otwinowski & Minor, 1997[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. Academic Press, New York.])
Tmin, Tmax 0.921, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections 6292, 3195, 2536
Rint 0.025
(sin θ/λ)max−1) 0.696
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.091, 1.02
No. of reflections 3195
No. of parameters 152
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.29, −0.86
Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983[Arvai, A. J. & Nielsen, C. (1983). ADSC Quantum-210 ADX. Area Detector System Corporation, Poway, CA, USA.]), HKL3000sm (Otwinowski & Minor, 1997[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. Academic Press, New York.]), SHELXT2014/4 and SHELXL2014/7 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.])and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Chemical context top

Coordination compounds with macrocyclic ligands have attracted considerable attention in chemistry, biological chemistry and materials science (Lehn, 1995). In particular, macrocyclic CuII complexes with vacant sites in the axial positions are good building blocks for assembling multi-dimensional frameworks (Ko et al., 2002), with potential applications as metal extra­cta­nts, radiotherapeutic materials and as medical imaging agents (Sowen et al., 2013). For example, CuII complexes with tetra-aza­macrocyclic ligands have been studied with various auxiliary anionic ligands such as ferricyanide and hexa­cyano­chromate and their biological redox-sensing and magnetic properties (Xiang et al., 2009) have been investigated. Moreover, the perchlorate ion is a versatile anion which can easily bridge two transition metal complexes, allowing the assembly of multi-dimensional compounds (Kwak et al., 2001). Here, we report the synthesis and crystal structure of a CuII aza­macrocyclic complex, trans-diperchlorato(1,8-di­butyl-1,3,6,8,10,13-hexa­aza­cyclo­tetra­decane)­copper(II), which has two perchlorate ions coordinated in the axial positions in the six-coordinate complex.

Structural commentary top

In the title compound, the coordination environment around the CuII ion, which lies on an inversion centre, is tetra­gonally distorted o­cta­hedral. The copper(II) ion binds to the four secondary N atoms of the aza­macrocyclic ligand in a square-planar fashion in the equatorial plane, with two O atoms from the perchlorate anions in axial positions as shown in Fig. 1. The bonds to the two axially located perchlorate anions are significantly longer than those to the donor N atoms in the equatorial plane. This can be attributed either to a rather large Jahn–Teller distortion of the CuII ion and/or to a considerable ring contraction of the aza­macrocyclic ligand (Halcrow, 2013). The six-membered chelate rings adopt chair conformations and the five-membered chelate rings assume gauche conformations (Min & Suh, 2001). Intra­molecular N—H···O hydrogen bonds between the secondary amine groups of the aza­macrocyclic ligand and an O atom of each perchlorate ion contribute to the molecular conformation (Fig. 1 and Table 1).

Supra­molecular features top

Each complex molecule forms three N—H···O and two C—H···O hydrogen bonds (Steed & Atwood, 2009), as shown in Table 1, Fig. 2. Sheets of complex molecules form in the ab plane, Fig. 3, and additional C6—H6B···O3 contacts link these sheets into a three-dimensional network.

Database survey top

A search of the Cambridge Structural Database (Version 5.35, May 2014 with three updates; Groom & Allen 2014) indicated that 51 aza­macrocyclic CuII complexes with pendant alkyl groups had been reported previously. These complexes have been studied as good building blocks for supra­molecular chemistry and contain a variety of pendant alkyl groups (Cho et al., 2003). Their magnetic properties and guest-exchange effects with cyano groups and carb­oxy­lic acid groups as ligands have also been investigated (Ko et al., 2002; Zhou et al., 2014). No corresponding aza­macrocyclic CuII complex with pendant butyl groups has been reported and the title compound was newly synthesized for this research.

Synthesis and crystallization top

The title compound was prepared as follows. Ethyl­enedi­amine (3.4 ml, 0.05 mol), paraformaldehyde (3.0 g, 0.10 mol), and butyl­amine (3.7 g, 0.05 mol) were slowly added to a stirred solution of CuCl2·2H2O (4.26 g, 0.025 mol) in MeOH (50 ml). The mixture was heated to reflux for 1 day. The solution was filtered and cooled at room temperature. HClO4 (70%, 15 ml) was added to the purple solution. A bright-purple precipitate formed and was filtered off, washed with H2O, MeOH, and di­ethyl ether, and dried in air. Purple crystals of the title compound were obtained by diffusion of di­ethyl ether into the purple solution over several days. Yield: 2.38g (17%). FT–IR (ATR, cm-1): 3240, 2936, 1443, 1053, 995, 962, 746. Safety note: Although we have experienced no problems with the compound reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.98–0.99 Å and an N—H distance of 1.0 Å with Uiso(H) values of 1.2 or 1.5 Ueq of the parent atoms.

Related literature top

For related literature, see: Cho et al. (2003); Groom & Allen (2014); Halcrow (2013); Ko et al. (2002); Kwak et al. (2001); Lehn (1995); Min & Suh (2001); Sowen et al. (2013); Steed & Atwood (2009); Zhou et al. (2014).

Computing details top

Data collection: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H···O hydrogen bonds are shown as black dashed lines. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 2] Fig. 2. View of the contacts made by an individual complex molecule with hydrogen bonds drawn as dashed lines.
[Figure 3] Fig. 3. Sheets of complex molecules in the ab plane.
trans-(1,8-Dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ4N3,N6,N10,N13)bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C16H38N6)]Z = 1
Mr = 576.96F(000) = 303
Triclinic, P1Dx = 1.571 Mg m3
a = 8.2230 (16) ÅSynchrotron radiation, λ = 0.62998 Å
b = 8.3600 (17) ÅCell parameters from 16838 reflections
c = 10.039 (2) Åθ = 0.4–33.6°
α = 92.87 (3)°µ = 0.84 mm1
β = 96.12 (3)°T = 100 K
γ = 116.60 (3)°Plate, purple
V = 609.8 (3) Å30.10 × 0.10 × 0.03 mm
Data collection top
ADSC Q210 CCD area-detector
diffractometer
2536 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnetRint = 0.025
ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: empirical (using intensity measurements)
(HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
h = 1111
Tmin = 0.921, Tmax = 0.975k = 1111
6292 measured reflectionsl = 1313
3195 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(Fo2) + (0.0574P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3195 reflectionsΔρmax = 0.29 e Å3
152 parametersΔρmin = 0.86 e Å3
Crystal data top
[Cu(ClO4)2(C16H38N6)]γ = 116.60 (3)°
Mr = 576.96V = 609.8 (3) Å3
Triclinic, P1Z = 1
a = 8.2230 (16) ÅSynchrotron radiation, λ = 0.62998 Å
b = 8.3600 (17) ŵ = 0.84 mm1
c = 10.039 (2) ÅT = 100 K
α = 92.87 (3)°0.10 × 0.10 × 0.03 mm
β = 96.12 (3)°
Data collection top
ADSC Q210 CCD area-detector
diffractometer
3195 independent reflections
Absorption correction: empirical (using intensity measurements)
(HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
2536 reflections with I > 2σ(I)
Tmin = 0.921, Tmax = 0.975Rint = 0.025
6292 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 1.02Δρmax = 0.29 e Å3
3195 reflectionsΔρmin = 0.86 e Å3
152 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
xyzUiso*/Ueq
Cu10.50000.50000.50000.01063 (10)
N10.7678 (2)0.6261 (2)0.57656 (16)0.0119 (3)
H10.82210.54430.55350.014*
N20.4291 (2)0.3507 (2)0.65492 (16)0.0123 (3)
H20.45990.24900.63890.015*
N30.7247 (2)0.5222 (2)0.80108 (16)0.0152 (3)
C10.8525 (2)0.7860 (2)0.5034 (2)0.0155 (4)
H1A0.98760.83280.51560.019*
H1B0.82420.88210.53850.019*
C20.8084 (3)0.6731 (3)0.7267 (2)0.0164 (4)
H2A0.94320.73030.75410.020*
H2B0.76540.76260.75080.020*
C30.5278 (3)0.4466 (3)0.7910 (2)0.0158 (4)
H3A0.49480.54450.81190.019*
H3B0.48550.36120.85940.019*
C40.2256 (2)0.2705 (3)0.6448 (2)0.0156 (4)
H4A0.18940.35980.68190.019*
H4B0.17860.16490.69640.019*
C50.8000 (3)0.3919 (3)0.7910 (2)0.0169 (4)
H5A0.93590.45860.80410.020*
H5B0.75930.32650.69920.020*
C60.7409 (3)0.2567 (3)0.8931 (2)0.0177 (4)
H6A0.60670.17820.87210.021*
H6B0.76620.32170.98400.021*
C70.8401 (3)0.1406 (3)0.8937 (2)0.0221 (4)
H7A0.97230.21710.92660.026*
H7B0.82890.08880.80030.026*
C80.7636 (3)0.0116 (3)0.9822 (2)0.0215 (4)
H8A0.77490.03901.07490.032*
H8B0.83280.08120.98060.032*
H8C0.63380.09040.94810.032*
Cl10.32457 (6)0.78356 (6)0.65025 (4)0.01406 (11)
O10.1610 (2)0.6610 (2)0.56090 (18)0.0282 (4)
O20.48300 (19)0.77847 (19)0.60352 (16)0.0221 (3)
O30.3102 (3)0.7249 (2)0.78200 (16)0.0319 (4)
O40.3413 (2)0.96148 (19)0.65392 (18)0.0285 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.00685 (15)0.00798 (15)0.01599 (17)0.00179 (11)0.00383 (11)0.00327 (12)
N10.0092 (7)0.0080 (6)0.0180 (8)0.0032 (5)0.0030 (5)0.0031 (6)
N20.0091 (6)0.0114 (7)0.0184 (8)0.0053 (5)0.0054 (6)0.0044 (6)
N30.0152 (7)0.0159 (8)0.0170 (8)0.0091 (6)0.0028 (6)0.0022 (6)
C10.0082 (8)0.0091 (8)0.0275 (10)0.0015 (6)0.0051 (7)0.0069 (7)
C20.0143 (8)0.0125 (8)0.0208 (10)0.0052 (7)0.0009 (7)0.0000 (7)
C30.0156 (9)0.0176 (9)0.0176 (9)0.0100 (7)0.0050 (7)0.0034 (8)
C40.0094 (8)0.0141 (8)0.0253 (10)0.0047 (7)0.0096 (7)0.0101 (8)
C50.0148 (8)0.0199 (9)0.0202 (9)0.0112 (7)0.0039 (7)0.0046 (8)
C60.0197 (9)0.0191 (9)0.0194 (10)0.0124 (8)0.0057 (7)0.0059 (8)
C70.0186 (9)0.0242 (10)0.0295 (11)0.0133 (8)0.0081 (8)0.0100 (9)
C80.0242 (10)0.0202 (10)0.0244 (11)0.0133 (8)0.0050 (8)0.0054 (8)
Cl10.0128 (2)0.0121 (2)0.0198 (2)0.00762 (17)0.00396 (16)0.00067 (18)
O10.0152 (7)0.0258 (8)0.0420 (10)0.0115 (6)0.0050 (6)0.0127 (7)
O20.0132 (6)0.0216 (7)0.0332 (8)0.0088 (6)0.0086 (6)0.0005 (6)
O30.0450 (10)0.0412 (10)0.0225 (8)0.0280 (8)0.0144 (7)0.0124 (8)
O40.0297 (8)0.0123 (7)0.0490 (11)0.0132 (6)0.0101 (7)0.0047 (7)
Geometric parameters (Å, º) top
Cu1—N12.0073 (17)C4—C1i1.518 (3)
Cu1—N1i2.0073 (17)C4—H4A0.9900
Cu1—N2i2.0131 (17)C4—H4B0.9900
Cu1—N22.0131 (17)C5—C61.515 (3)
N1—C11.478 (2)C5—H5A0.9900
N1—C21.501 (3)C5—H5B0.9900
N1—H11.0000C6—C71.522 (3)
N2—C41.487 (2)C6—H6A0.9900
N2—C31.496 (3)C6—H6B0.9900
N2—H21.0000C7—C81.523 (3)
N3—C21.432 (2)C7—H7A0.9900
N3—C31.440 (2)C7—H7B0.9900
N3—C51.478 (2)C8—H8A0.9800
C1—C4i1.518 (3)C8—H8B0.9800
C1—H1A0.9900C8—H8C0.9800
C1—H1B0.9900Cl1—O41.4293 (15)
C2—H2A0.9900Cl1—O31.4318 (17)
C2—H2B0.9900Cl1—O11.4420 (17)
C3—H3A0.9900Cl1—O21.4481 (14)
C3—H3B0.9900
N1—Cu1—N1i180.00 (9)H3A—C3—H3B107.7
N1—Cu1—N2i86.45 (7)N2—C4—C1i107.28 (15)
N1i—Cu1—N2i93.55 (7)N2—C4—H4A110.3
N1—Cu1—N293.55 (7)C1i—C4—H4A110.3
N1i—Cu1—N286.45 (7)N2—C4—H4B110.3
N2i—Cu1—N2180.0C1i—C4—H4B110.3
C1—N1—C2112.37 (15)H4A—C4—H4B108.5
C1—N1—Cu1106.33 (11)N3—C5—C6113.14 (15)
C2—N1—Cu1115.28 (12)N3—C5—H5A109.0
C1—N1—H1107.5C6—C5—H5A109.0
C2—N1—H1107.5N3—C5—H5B109.0
Cu1—N1—H1107.5C6—C5—H5B109.0
C4—N2—C3113.49 (15)H5A—C5—H5B107.8
C4—N2—Cu1106.73 (11)C5—C6—C7112.19 (16)
C3—N2—Cu1115.29 (12)C5—C6—H6A109.2
C4—N2—H2107.0C7—C6—H6A109.2
C3—N2—H2107.0C5—C6—H6B109.2
Cu1—N2—H2107.0C7—C6—H6B109.2
C2—N3—C3114.81 (15)H6A—C6—H6B107.9
C2—N3—C5114.08 (15)C6—C7—C8112.45 (16)
C3—N3—C5116.15 (16)C6—C7—H7A109.1
N1—C1—C4i107.87 (15)C8—C7—H7A109.1
N1—C1—H1A110.1C6—C7—H7B109.1
C4i—C1—H1A110.1C8—C7—H7B109.1
N1—C1—H1B110.1H7A—C7—H7B107.8
C4i—C1—H1B110.1C7—C8—H8A109.5
H1A—C1—H1B108.4C7—C8—H8B109.5
N3—C2—N1114.03 (15)H8A—C8—H8B109.5
N3—C2—H2A108.7C7—C8—H8C109.5
N1—C2—H2A108.7H8A—C8—H8C109.5
N3—C2—H2B108.7H8B—C8—H8C109.5
N1—C2—H2B108.7O4—Cl1—O3110.11 (11)
H2A—C2—H2B107.6O4—Cl1—O1109.74 (10)
N3—C3—N2113.39 (15)O3—Cl1—O1108.36 (11)
N3—C3—H3A108.9O4—Cl1—O2110.65 (10)
N2—C3—H3A108.9O3—Cl1—O2108.82 (10)
N3—C3—H3B108.9O1—Cl1—O2109.12 (9)
N2—C3—H3B108.9
C2—N1—C1—C4i169.53 (14)C4—N2—C3—N3179.24 (14)
Cu1—N1—C1—C4i42.53 (15)Cu1—N2—C3—N357.23 (18)
C3—N3—C2—N169.8 (2)C3—N2—C4—C1i168.24 (15)
C5—N3—C2—N167.8 (2)Cu1—N2—C4—C1i40.14 (16)
C1—N1—C2—N3178.48 (14)C2—N3—C5—C6167.34 (16)
Cu1—N1—C2—N356.43 (18)C3—N3—C5—C655.6 (2)
C2—N3—C3—N270.2 (2)N3—C5—C6—C7172.24 (17)
C5—N3—C3—N266.5 (2)C5—C6—C7—C8172.38 (18)
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···O1ii1.002.503.136 (2)121
N2—H2···O4iii1.002.173.000 (2)139
C1—H1A···O1ii0.992.463.160 (2)127
N1—H1···O1i1.002.083.018 (2)155
C6—H6B···O3iv0.992.503.338 (3)142
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x, y1, z; (iv) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i1.002.503.136 (2)121.3
N2—H2···O4ii1.002.173.000 (2)139.0
C1—H1A···O1i0.992.463.160 (2)127.1
N1—H1···O1iii1.002.083.018 (2)154.9
C6—H6B···O3iv0.992.503.338 (3)142.1
Symmetry codes: (i) x+1, y, z; (ii) x, y1, z; (iii) x+1, y+1, z+1; (iv) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formula[Cu(ClO4)2(C16H38N6)]
Mr576.96
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)8.2230 (16), 8.3600 (17), 10.039 (2)
α, β, γ (°)92.87 (3), 96.12 (3), 116.60 (3)
V3)609.8 (3)
Z1
Radiation typeSynchrotron, λ = 0.62998 Å
µ (mm1)0.84
Crystal size (mm)0.10 × 0.10 × 0.03
Data collection
DiffractometerADSC Q210 CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.921, 0.975
No. of measured, independent and
observed [I > 2σ(I)] reflections
6292, 3195, 2536
Rint0.025
(sin θ/λ)max1)0.696
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.091, 1.02
No. of reflections3195
No. of parameters152
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.86

Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), publCIF (Westrip, 2010).

 

Acknowledgements

This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2012R1A1A2002507 and NRF-2014R1A1A2058815). The X-ray crystallography 2D-SMC beamline and the FT–IR experiment at PLS-II are supported in part by MSIP and POSTECH.

References

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Volume 71| Part 2| February 2015| Pages 136-138
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