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

Kim, D.-W.; Shin, J.W.; Moon, D.

doi:10.1107/S2056989014028047

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

doi:10.1107/S2056989014028047

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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

Dae-Woong Kim,^a Jong Won Shin ^a and Dohyun Moon ^a ^*

^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 Cu^II complex as the Cu^II 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.

Keywords: Crystal structure; azamacrocyclic ligand; Jahn–Teller distortion; synchrotron data; hydrogen bonds.

CCDC reference: 1040897

1. Chemical context

Coordination compounds with macrocyclic ligands have attracted considerable attention in chemistry, biological chemistry and materials science (Lehn, 1995 ). In particular, macrocyclic Cu^II 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, Cu^II 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 ) 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 Cu^II 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 Cu^II 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. 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 Cu^II 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).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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⋯O3^iv	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
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 ), 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.

Figure 2
View of the contacts made by an individual complex molecule with hydrogen bonds drawn as dashed lines.

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 ) indicated that 51 azamacrocyclic Cu^II 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 cyanido groups and carboxylic acid groups as ligands have also been investigated (Ko et al., 2002; Zhou et al., 2014 ). No corresponding azamacrocyclic Cu^II 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. 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 U_iso(H) values of 1.2 or 1.5 U_eq of the parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)₂(C₁₆H₃₈N₆)]
M_r	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)
V (Å³)	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 )
T_min, T_max	0.921, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	6292, 3195, 2536
R_int	0.025
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.86
Computer programs: PAL ADSC Quantum-210 ADX (Arvai & Nielsen, 1983 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014/4 and SHELXL2014/7 (Sheldrick, 2008 ), ORTEP-3 for Windows (Farrugia, 2012 )and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1040897

Crystal structure: contains datablock I. DOI: 10.1107/S2056989014028047/sj5435sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989014028047/sj5435Isup2.hkl

checkCIF report

Chemical context top

Coordination compounds with macrocyclic ligands have attracted considerable attention in chemistry, biological chemistry and materials science (Lehn, 1995). In particular, macrocyclic Cu^II 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, Cu^II 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 Cu^II 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 Cu^II 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 Cu^II 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 Cu^II 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 Cu^II 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 U_iso(H) values of 1.2 or 1.5 U_eq 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

	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.]
	Fig. 2. View of the contacts made by an individual complex molecule with hydrogen bonds drawn as dashed lines.
	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
M_r = 576.96	F(000) = 303
Triclinic, P1	D_x = 1.571 Mg m⁻³
a = 8.2230 (16) Å	Synchrotron radiation, λ = 0.62998 Å
b = 8.3600 (17) Å	Cell parameters from 16838 reflections
c = 10.039 (2) Å	θ = 0.4–33.6°
α = 92.87 (3)°	µ = 0.84 mm⁻¹
β = 96.12 (3)°	T = 100 K
γ = 116.60 (3)°	Plate, purple
V = 609.8 (3) Å³	0.10 × 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 magnet	R_int = 0.025
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
T_min = 0.921, T_max = 0.975	k = −11→11
6292 measured reflections	l = −13→13
3195 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0574P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3195 reflections	Δρ_max = 0.29 e Å⁻³
152 parameters	Δρ_min = −0.86 e Å⁻³

Crystal data top

[Cu(ClO₄)₂(C₁₆H₃₈N₆)]	γ = 116.60 (3)°
M_r = 576.96	V = 609.8 (3) Å³
Triclinic, P1	Z = 1
a = 8.2230 (16) Å	Synchrotron radiation, λ = 0.62998 Å
b = 8.3600 (17) Å	µ = 0.84 mm⁻¹
c = 10.039 (2) Å	T = 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)
T_min = 0.921, T_max = 0.975	R_int = 0.025
6292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.02	Δρ_max = 0.29 e Å⁻³
3195 reflections	Δρ_min = −0.86 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.01063 (10)
N1	0.7678 (2)	0.6261 (2)	0.57656 (16)	0.0119 (3)
H1	0.8221	0.5443	0.5535	0.014*
N2	0.4291 (2)	0.3507 (2)	0.65492 (16)	0.0123 (3)
H2	0.4599	0.2490	0.6389	0.015*
N3	0.7247 (2)	0.5222 (2)	0.80108 (16)	0.0152 (3)
C1	0.8525 (2)	0.7860 (2)	0.5034 (2)	0.0155 (4)
H1A	0.9876	0.8328	0.5156	0.019*
H1B	0.8242	0.8821	0.5385	0.019*
C2	0.8084 (3)	0.6731 (3)	0.7267 (2)	0.0164 (4)
H2A	0.9432	0.7303	0.7541	0.020*
H2B	0.7654	0.7626	0.7508	0.020*
C3	0.5278 (3)	0.4466 (3)	0.7910 (2)	0.0158 (4)
H3A	0.4948	0.5445	0.8119	0.019*
H3B	0.4855	0.3612	0.8594	0.019*
C4	0.2256 (2)	0.2705 (3)	0.6448 (2)	0.0156 (4)
H4A	0.1894	0.3598	0.6819	0.019*
H4B	0.1786	0.1649	0.6964	0.019*
C5	0.8000 (3)	0.3919 (3)	0.7910 (2)	0.0169 (4)
H5A	0.9359	0.4586	0.8041	0.020*
H5B	0.7593	0.3265	0.6992	0.020*
C6	0.7409 (3)	0.2567 (3)	0.8931 (2)	0.0177 (4)
H6A	0.6067	0.1782	0.8721	0.021*
H6B	0.7662	0.3217	0.9840	0.021*
C7	0.8401 (3)	0.1406 (3)	0.8937 (2)	0.0221 (4)
H7A	0.9723	0.2171	0.9266	0.026*
H7B	0.8289	0.0888	0.8003	0.026*
C8	0.7636 (3)	−0.0116 (3)	0.9822 (2)	0.0215 (4)
H8A	0.7749	0.0390	1.0749	0.032*
H8B	0.8328	−0.0812	0.9806	0.032*
H8C	0.6338	−0.0904	0.9481	0.032*
Cl1	0.32457 (6)	0.78356 (6)	0.65025 (4)	0.01406 (11)
O1	0.1610 (2)	0.6610 (2)	0.56090 (18)	0.0282 (4)
O2	0.48300 (19)	0.77847 (19)	0.60352 (16)	0.0221 (3)
O3	0.3102 (3)	0.7249 (2)	0.78200 (16)	0.0319 (4)
O4	0.3413 (2)	0.96148 (19)	0.65392 (18)	0.0285 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.00685 (15)	0.00798 (15)	0.01599 (17)	0.00179 (11)	0.00383 (11)	0.00327 (12)
N1	0.0092 (7)	0.0080 (6)	0.0180 (8)	0.0032 (5)	0.0030 (5)	0.0031 (6)
N2	0.0091 (6)	0.0114 (7)	0.0184 (8)	0.0053 (5)	0.0054 (6)	0.0044 (6)
N3	0.0152 (7)	0.0159 (8)	0.0170 (8)	0.0091 (6)	0.0028 (6)	0.0022 (6)
C1	0.0082 (8)	0.0091 (8)	0.0275 (10)	0.0015 (6)	0.0051 (7)	0.0069 (7)
C2	0.0143 (8)	0.0125 (8)	0.0208 (10)	0.0052 (7)	0.0009 (7)	0.0000 (7)
C3	0.0156 (9)	0.0176 (9)	0.0176 (9)	0.0100 (7)	0.0050 (7)	0.0034 (8)
C4	0.0094 (8)	0.0141 (8)	0.0253 (10)	0.0047 (7)	0.0096 (7)	0.0101 (8)
C5	0.0148 (8)	0.0199 (9)	0.0202 (9)	0.0112 (7)	0.0039 (7)	0.0046 (8)
C6	0.0197 (9)	0.0191 (9)	0.0194 (10)	0.0124 (8)	0.0057 (7)	0.0059 (8)
C7	0.0186 (9)	0.0242 (10)	0.0295 (11)	0.0133 (8)	0.0081 (8)	0.0100 (9)
C8	0.0242 (10)	0.0202 (10)	0.0244 (11)	0.0133 (8)	0.0050 (8)	0.0054 (8)
Cl1	0.0128 (2)	0.0121 (2)	0.0198 (2)	0.00762 (17)	0.00396 (16)	0.00067 (18)
O1	0.0152 (7)	0.0258 (8)	0.0420 (10)	0.0115 (6)	−0.0050 (6)	−0.0127 (7)
O2	0.0132 (6)	0.0216 (7)	0.0332 (8)	0.0088 (6)	0.0086 (6)	−0.0005 (6)
O3	0.0450 (10)	0.0412 (10)	0.0225 (8)	0.0280 (8)	0.0144 (7)	0.0124 (8)
O4	0.0297 (8)	0.0123 (7)	0.0490 (11)	0.0132 (6)	0.0101 (7)	0.0047 (7)

Geometric parameters (Å, º) top

Cu1—N1	2.0073 (17)	C4—C1ⁱ	1.518 (3)
Cu1—N1ⁱ	2.0073 (17)	C4—H4A	0.9900
Cu1—N2ⁱ	2.0131 (17)	C4—H4B	0.9900
Cu1—N2	2.0131 (17)	C5—C6	1.515 (3)
N1—C1	1.478 (2)	C5—H5A	0.9900
N1—C2	1.501 (3)	C5—H5B	0.9900
N1—H1	1.0000	C6—C7	1.522 (3)
N2—C4	1.487 (2)	C6—H6A	0.9900
N2—C3	1.496 (3)	C6—H6B	0.9900
N2—H2	1.0000	C7—C8	1.523 (3)
N3—C2	1.432 (2)	C7—H7A	0.9900
N3—C3	1.440 (2)	C7—H7B	0.9900
N3—C5	1.478 (2)	C8—H8A	0.9800
C1—C4ⁱ	1.518 (3)	C8—H8B	0.9800
C1—H1A	0.9900	C8—H8C	0.9800
C1—H1B	0.9900	Cl1—O4	1.4293 (15)
C2—H2A	0.9900	Cl1—O3	1.4318 (17)
C2—H2B	0.9900	Cl1—O1	1.4420 (17)
C3—H3A	0.9900	Cl1—O2	1.4481 (14)
C3—H3B	0.9900

N1—Cu1—N1ⁱ	180.00 (9)	H3A—C3—H3B	107.7
N1—Cu1—N2ⁱ	86.45 (7)	N2—C4—C1ⁱ	107.28 (15)
N1ⁱ—Cu1—N2ⁱ	93.55 (7)	N2—C4—H4A	110.3
N1—Cu1—N2	93.55 (7)	C1ⁱ—C4—H4A	110.3
N1ⁱ—Cu1—N2	86.45 (7)	N2—C4—H4B	110.3
N2ⁱ—Cu1—N2	180.0	C1ⁱ—C4—H4B	110.3
C1—N1—C2	112.37 (15)	H4A—C4—H4B	108.5
C1—N1—Cu1	106.33 (11)	N3—C5—C6	113.14 (15)
C2—N1—Cu1	115.28 (12)	N3—C5—H5A	109.0
C1—N1—H1	107.5	C6—C5—H5A	109.0
C2—N1—H1	107.5	N3—C5—H5B	109.0
Cu1—N1—H1	107.5	C6—C5—H5B	109.0
C4—N2—C3	113.49 (15)	H5A—C5—H5B	107.8
C4—N2—Cu1	106.73 (11)	C5—C6—C7	112.19 (16)
C3—N2—Cu1	115.29 (12)	C5—C6—H6A	109.2
C4—N2—H2	107.0	C7—C6—H6A	109.2
C3—N2—H2	107.0	C5—C6—H6B	109.2
Cu1—N2—H2	107.0	C7—C6—H6B	109.2
C2—N3—C3	114.81 (15)	H6A—C6—H6B	107.9
C2—N3—C5	114.08 (15)	C6—C7—C8	112.45 (16)
C3—N3—C5	116.15 (16)	C6—C7—H7A	109.1
N1—C1—C4ⁱ	107.87 (15)	C8—C7—H7A	109.1
N1—C1—H1A	110.1	C6—C7—H7B	109.1
C4ⁱ—C1—H1A	110.1	C8—C7—H7B	109.1
N1—C1—H1B	110.1	H7A—C7—H7B	107.8
C4ⁱ—C1—H1B	110.1	C7—C8—H8A	109.5
H1A—C1—H1B	108.4	C7—C8—H8B	109.5
N3—C2—N1	114.03 (15)	H8A—C8—H8B	109.5
N3—C2—H2A	108.7	C7—C8—H8C	109.5
N1—C2—H2A	108.7	H8A—C8—H8C	109.5
N3—C2—H2B	108.7	H8B—C8—H8C	109.5
N1—C2—H2B	108.7	O4—Cl1—O3	110.11 (11)
H2A—C2—H2B	107.6	O4—Cl1—O1	109.74 (10)
N3—C3—N2	113.39 (15)	O3—Cl1—O1	108.36 (11)
N3—C3—H3A	108.9	O4—Cl1—O2	110.65 (10)
N2—C3—H3A	108.9	O3—Cl1—O2	108.82 (10)
N3—C3—H3B	108.9	O1—Cl1—O2	109.12 (9)
N2—C3—H3B	108.9

C2—N1—C1—C4ⁱ	−169.53 (14)	C4—N2—C3—N3	179.24 (14)
Cu1—N1—C1—C4ⁱ	−42.53 (15)	Cu1—N2—C3—N3	−57.23 (18)
C3—N3—C2—N1	−69.8 (2)	C3—N2—C4—C1ⁱ	168.24 (15)
C5—N3—C2—N1	67.8 (2)	Cu1—N2—C4—C1ⁱ	40.14 (16)
C1—N1—C2—N3	178.48 (14)	C2—N3—C5—C6	167.34 (16)
Cu1—N1—C2—N3	56.43 (18)	C3—N3—C5—C6	−55.6 (2)
C2—N3—C3—N2	70.2 (2)	N3—C5—C6—C7	−172.24 (17)
C5—N3—C3—N2	−66.5 (2)	C5—C6—C7—C8	−172.38 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱⁱ	1.00	2.50	3.136 (2)	121
N2—H2···O4ⁱⁱⁱ	1.00	2.17	3.000 (2)	139
C1—H1A···O1ⁱⁱ	0.99	2.46	3.160 (2)	127
N1—H1···O1ⁱ	1.00	2.08	3.018 (2)	155
C6—H6B···O3^iv	0.99	2.50	3.338 (3)	142

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	1.00	2.50	3.136 (2)	121.3
N2—H2···O4ⁱⁱ	1.00	2.17	3.000 (2)	139.0
C1—H1A···O1ⁱ	0.99	2.46	3.160 (2)	127.1
N1—H1···O1ⁱⁱⁱ	1.00	2.08	3.018 (2)	154.9
C6—H6B···O3^iv	0.99	2.50	3.338 (3)	142.1

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.

Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)₂(C₁₆H₃₈N₆)]
M_r	576.96
Crystal system, space group	Triclinic, 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)
V (Å³)	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 diffractometer
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.921, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	6292, 3195, 2536
R_int	0.025
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	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

Arvai, A. J. & Nielsen, C. (1983). ADSC Quantum-210 ADX. Area Detector System Corporation, Poway, CA, USA. Google Scholar
Cho, J., Lough, A. J. & Kim, J. C. (2003). Inorg. Chim. Acta, 342, 305–310. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CrossRef CAS Google Scholar
Halcrow, M. A. (2013). Chem. Soc. Rev. 42, 1784–1795. Web of Science CrossRef CAS PubMed Google Scholar
Ko, J. W., Min, K. S. & Suh, M. P. (2002). Inorg. Chem. 41, 2151–2157. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kwak, C.-H., Jeong, J. & Kim, J. (2001). Inorg. Chem. Commun. 4, 264–268. Web of Science CSD CrossRef CAS Google Scholar
Lehn, J.-M. (1995). Supramolecular Chemistry; Concepts and Perspectives. Weinheim: VCH. Google Scholar
Min, K. S. & Suh, M. P. (2001). Chem. Eur. J. 7, 303–313. Web of Science CSD CrossRef PubMed CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. Academic Press, New York. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sowden, R. J., Trotter, K. D., Dunbar, L., Craig, G., Erdemli, O., Spickett, C. M. & Reglinski, J. (2013). Biometals, 26, 85–96. Google Scholar
Steed, J. W. & Atwood, J. L. (2009). Supramolecular Chemistry, 2nd ed. Chichester: John Wiley & Sons. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiang, H., Wang, S.-J., Jiang, L., Feng, X.-L. & Lu, T.-B. (2009). Eur. J. Inorg. Chem. pp. 2074–2082. Google Scholar
Zhou, H., Yan, J., Shen, X., Zhou, H. & Yuan, A. (2014). RSC Adv. 4, 61–70. Google Scholar

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

doi:10.1107/S2056989014028047

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