Poly[[bis­{μ3-tris­[2-(1H-tetra­zol-1-yl)eth­yl]amine}copper(II)] bis­(perchlorate)]

Werner, F.; Tokuno, K.; Hasegawa, M.; Linert, W.; Mereiter, K.

doi:10.1107/S1600536810008998

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m399-m400

doi:10.1107/S1600536810008998

Open

access

Poly[[bis{μ₃-tris[2-(1H-tetrazol-1-yl)ethyl]amine}copper(II)] bis(perchlorate)]

Franz Werner,^a ‡ Kenji Tokuno,^a Miki Hasegawa,^a ^* Wolfgang Linert ^b and Kurt Mereiter ^c ^*

^aAoyama-Gakuin University, College of Science and Engineering, Department of Chemistry and Biological Science, 5-10-1 Fuchinobe, Sagamihara, Kanagawa 229-8558, Japan, ^bVienna University of Technology, Institute of Applied Synthetic Chemistry, Getreidemarkt 9/163, 1060 Vienna, Austria, and ^cVienna University of Technology, Institute of Chemical Technologies and Analytics, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: hasemiki@chem.aoyama.ac.jp, kurt.mereiter@tuwien.ac.at

(Received 10 February 2010; accepted 9 March 2010; online 13 March 2010)

In the title compound, {[Cu(C₉H₁₅N₁₃)₂](ClO₄)₂}_n, the Cu²⁺ cation lies on an inversion center and is coordinated by the tetrazole N⁴ atoms of six symmetry-equivalent tris[2-(1H-tetrazol-1-yl)ethyl]amine ligands (t³z) in the form of a Jahn–Teller-distorted octahedron with Cu—N bond distances of 2.0210 (8), 2.0259 (8) and 2.4098 (8) Å. The tertiary amine N atom is stereochemically inactive. The cationic part of the structure, viz. [Cu(t³z)₂]²⁺, forms an infinite two-dimensional network parallel to (100), in pockets of which the perchlorate anions reside. The individual networks are partially interlocked and held together by C—H⋯O interactions to the perchlorate anions and C—H⋯N interactions to tetrazole N atoms.

Related literature

For a general procedure for the synthesis of tetrazoles, see: Kamiya & Saito (1973 ). For the crystal structures of the t³z ligand and its complex with Cu(NO₃)₂, see: Hartdegen et al. (2009 ). For supramolecular compounds made up of di-tetrazolylalkanes, see: Liu et al. (2008 ); Yu et al. (2008 ). For Fe²⁺ spin-crossover complexes based on di-tetrazolylalkanes, see: Grunert et al. (2004 ); Absmeier et al. (2006 ); Quesada et al. (2007 ); Bialonska et al. (2008 ). For a related structure, see: Werner et al. (2009 ).

Experimental

Crystal data

[Cu(C₉H₁₅N₁₃)₂](ClO₄)₂
M_r = 873.12
Triclinic, $[P \overline 1]$
a = 8.5902 (3) Å
b = 9.4932 (4) Å
c = 11.8446 (5) Å
α = 69.233 (1)°
β = 74.652 (1)°
γ = 71.602 (1)°
V = 844.19 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 100 K
0.60 × 0.38 × 0.35 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.86, T_max = 1.00
18905 measured reflections
5317 independent reflections
5160 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.072
S = 1.07
5317 reflections
250 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N10ⁱ	0.99	2.60	3.366 (2)	134
C4—H4⋯O2	0.95	2.33	3.191 (2)	151
C5—H5B⋯O1	0.99	2.58	3.557 (2)	168
C6—H6A⋯O4ⁱⁱ	0.99	2.54	3.459 (2)	154
C7—H7⋯O3ⁱⁱ	0.95	2.41	3.305 (2)	157
C8—H8A⋯N2ⁱⁱⁱ	0.99	2.47	3.361 (2)	149
C8—H8B⋯O4ⁱⁱ	0.99	2.50	3.440 (2)	159
C8—H8B⋯O4^iv	0.99	2.59	3.136 (2)	115
Symmetry codes: (i) -x, -y, -z+1; (ii) x, y-1, z; (iii) x-1, y, z; (iv) -x, -y+1, -z.

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008998/bq2196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008998/bq2196Isup2.hkl

checkCIF report

Comment top

Polyfunctional molecules containing two or more 1H-tetrazol-1-yl groups linked by flexible spacer moieties are of considerable interest in supramolecular chemistry (e.g. Liu et al. 2008; Yu et al., 2008) and in the construction of new Fe²⁺-based spin-crossover complexes (e.g. Grunert et al., 2004; Absmeier et al., 2006; Quesada et al., 2007; Bialonska et al., 2008). In continuation of previous studies (Werner et al., 2009) the tris(2-(1H-tetrazol-1-yl)ethyl)-amine ligand (t³z) and the title compound were synthesized as described in the experimental section.

The title compound crystallizes in the triclinic space group P1 with one formula unit, [Cu(C₉H₁₅N₁₃)₂](ClO₄)₂, per unit cell. Copper lies on an inversion center (we selected x,y,z = 1/2, 1/2, 1/2 for Cu) and is coordinated by six symmetry equivalent t³z ligands via their 1H-tetrazole N4 atoms. The coordination figure about Cu (Fig. 1) is a Jahn-Teller distorted octahedron with four short Cu—N bonds (N4: 2 × 2.0259 (8) Å; N8: 2 × 2.0210 (8) Å) and two long Cu—N bonds (N12: 2 × 2.4098 (8) Å). The N—Cu—N angles are either 180° or deviate only by up to 2.20 (3)° from 90°. A view of the three-armed ligand with the three copper atoms bonded to it is shown in Fig. 2. The ligand adopts an unsymmetrical conformation with two ethyl groups in trans and one in gauche configuration (N1—C2—C3—N13 = 176.71 (8)°, N5—C5—C6—N13 = 170.74 (7)°, N9—C8—C9—N13 = 66.24 (10)°). It is obvious that the ligand is not chelating a copper atom but forms exclusively bridging links between each three of them. This is not unexpected because 1-alkyl-1H-tetrazoles coordinate transition metals generally via their N4 atoms (i.e. N4, N8 and N12 in the title compound) and the spacer length of four carbon plus one nitrogen atoms between two rigid tetrazole rings is too short to permit a reasonable chelation of a single metal centre. With this in mind it is clear that the structure of the title compound should be a coordination polymer. Instead of an expected three-dimensional network, the cationic part of the structure is an infinite two-dimensional coordination polymer extending parallel to (100), as shown in Figs. 3 and 4. The ClO₄ anions are residing in pockets of this coordination polymer and are anchored via intra- as well as inter-layer C—H···O interactions (Table 1). Two of these interactions are depicted in Fig. 2.

Interestingly, the title compound turned out to be isostructural with [Cu(t³z)₂](NO₃)₂ recently described by Hartdegen et al. (2009). This compound crystallizes similar to (I) in the triclinic space group P1 with a = 8.5850 (5) Å, b = 8.9606 (5) Å, c = 11.9532 (7) Å, α = 70.215 (5) Å, β = 76.919 (5)°, γ = 69.639 (5)°, V = 805.02 (8) Å³, and Z = 2 at T = 200 K. A view of this structure is presented in Fig. 5. After suitable origin selection the atomic coordinates of equivalent atomic positions of the [Cu(t³z)₂] layers in the ClO₄ and the NO₃ salt differ for non-hydrogen atoms between 0 and 0.40 Å and on the average by 0.22 Å. The flat NO₃ group is close in location to Cl1, O1, O2, and O3 in (I).

Related literature top

For a general procedure for the synthesis of tetrazoles, see: Kamiya & Saito (1973). For the crystal structures of the t³z ligand and its complex with Cu(NO₃)₂, see: Hartdegen et al. (2009). For supramolecular compounds made up of di-tetrazolylalkanes, see: Liu et al. (2008); Yu et al. (2008). For Fe²⁺ spin-crossover complexes based on di-tetrazolylalkanes, see: Grunert et al. (2004); Absmeier et al. (2006); Quesada et al. (2007); Bialonska et al. (2008). For a related structure, see: Werner et al. (2009).

Experimental top

CAUTION! Tetrazoles and perchlorates are energetic compounds sensitive towards heat and impact. Proper precautions and care should be applied. The ligand tris(2-(1H-tetrazol-1-yl)ethyl)-amine, t³z, was prepared according to the general procedure of Kamiya & Saito (1973). A solution of 2.0 g tris(2-aminoethyl)-amine (13.7 mmol, Aldrich, 96%), 3.07 g sodium azide (47.2 mmol, Wako, min. 98.0%) and 9.12 g triethyl orthoformate (61.5 mmol, Sigma-Aldrich, 98%) in 120 ml glacial acetic acid (Kanto Chemical, 99.5%), was stirred for 3 h at a temperature of 343 - 353 K. After cooling to rt overnight the solvent was removed under reduced pressure. The solid residue was dissolved in 20 ml H₂O, the solution was made alkaline (pH>11) by adding 100 ml of aqueous 4 N NaOH, and was then extracted with ethyl acetate. The combined organic layers were dried with sodium sulphate and the solvent was distilled off. The raw product was recrystallised from methanol yielding 178 mg (4.3%) of t³z. Elemental analysis (Micro Corder JM10, J-Science Lab): C (calculated 35.41%/found 35.85%), H (4.95/4.94), N (59.64/59.37). NMR (JEOL JNM-ECP 500): ¹H(DMSO-d₆) δ 3.01 (t, 6 H, CH₂), 4.42 (t, 6H, CH₂), 9.15 (s, 3 H, CH); ¹³C (DMSO-d₆) δ 45.3 (CH₂), 52.1 (CH₂), 144.6 (CH).

Single crystals of the title complex, [Cu(t³z)₂](ClO₄)₂, developed overnight from the combined solutions of 15.5 mg of Cu(ClO₄)₂^.6H₂O (0.041 mmol, Kanto Chemical) in 2.5 ml H₂O and of 25.1 mg of t³z (0.082 mmol) in 5 ml H₂O. Yield 28.2 mg (79%), blue needles (Fig. 6). Elemental analysis: C (calculated 24.76%/found 24.96%), H(3.46/3.52), N (41.71/42.62).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The coordination octahedron of Cu in (I) with incomplete t³z ligands. Displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. Symmetry codes for the t³z fragments are given in italics.
	Fig. 2. Asymmetric unit of (I) viewed along approximately perpendicular to the plane C3—C6—C9 of the t³z ligand. Displacement ellipsoids drawn at the 50% probability level. Symmetry codes of Cu atoms in italics. Two C—H···O hydrogen bonds shown as red broken lines.
	Fig. 3. The two-dimensional coordination polymer in (I) extending parallel to (100) in a projection down the a-axis. H-atoms omitted for clarity.
	Fig. 4. The two-dimensional coordination polymer in (I) extending parallel to (100) in a projection along the b-axis. H-atoms omitted for clarity.
	Fig. 5. The structure of [Cu(t³z)₂](NO₃)₂ (Hartdegen et al., 2009) in a view corresponding to Fig. 4 after shifting the coordinates by x' = x+1/2.
	Fig. 6. Crystals of [Cu(t³z)₂](ClO₄)₂, as-grown from water.

Poly[[bis{µ₃-tris[2-(1H-tetrazol-1-yl)ethyl]amine}copper(II)] bis(perchlorate)] top

Crystal data top

[Cu(C₉H₁₅N₁₃)₂](ClO₄)₂	Z = 1
M_r = 873.12	F(000) = 447
Triclinic, P1	D_x = 1.717 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5902 (3) Å	Cell parameters from 7355 reflections
b = 9.4932 (4) Å	θ = 2.4–31.0°
c = 11.8446 (5) Å	µ = 0.89 mm⁻¹
α = 69.233 (1)°	T = 100 K
β = 74.652 (1)°	Prism, blue
γ = 71.602 (1)°	0.60 × 0.38 × 0.35 mm
V = 844.19 (6) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	5317 independent reflections
Radiation source: normal-focus sealed tube	5160 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 31.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −12→12
T_min = 0.86, T_max = 1.00	k = −13→13
18905 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0428P)² + 0.303P] where P = (F_o² + 2F_c²)/3
5317 reflections	(Δ/σ)_max = 0.001
250 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Cu(C₉H₁₅N₁₃)₂](ClO₄)₂	γ = 71.602 (1)°
M_r = 873.12	V = 844.19 (6) Å³
Triclinic, P1	Z = 1
a = 8.5902 (3) Å	Mo Kα radiation
b = 9.4932 (4) Å	µ = 0.89 mm⁻¹
c = 11.8446 (5) Å	T = 100 K
α = 69.233 (1)°	0.60 × 0.38 × 0.35 mm
β = 74.652 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	5317 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	5160 reflections with I > 2σ(I)
T_min = 0.86, T_max = 1.00	R_int = 0.015
18905 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	Δρ_max = 0.53 e Å⁻³
5317 reflections	Δρ_min = −0.36 e Å⁻³
250 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cu1	0.5000	0.5000	0.5000	0.01041 (5)
N1	0.42188 (10)	0.17443 (9)	0.37722 (7)	0.01129 (14)
N2	0.58575 (11)	0.11927 (10)	0.38325 (8)	0.01522 (16)
N3	0.62835 (11)	0.21526 (10)	0.41688 (8)	0.01499 (15)
N4	0.49368 (10)	0.33358 (9)	0.43272 (7)	0.01173 (14)
N5	0.23080 (11)	0.34128 (10)	−0.15509 (8)	0.01398 (15)
N6	0.19378 (16)	0.26607 (14)	−0.21840 (9)	0.0293 (2)
N7	0.27560 (15)	0.30387 (14)	−0.32835 (9)	0.0271 (2)
N8	0.36562 (11)	0.40410 (10)	−0.33836 (8)	0.01278 (15)
N9	0.05800 (10)	−0.15980 (9)	0.33579 (7)	0.01167 (14)
N10	−0.01294 (11)	−0.20876 (10)	0.45440 (8)	0.01605 (16)
N11	0.09776 (11)	−0.32341 (11)	0.50942 (8)	0.01675 (16)
N12	0.24167 (11)	−0.35052 (10)	0.42864 (8)	0.01439 (15)
N13	0.19387 (10)	0.11244 (9)	0.17899 (7)	0.01133 (14)
C1	0.36653 (12)	0.30591 (11)	0.40781 (9)	0.01306 (16)
H1	0.2557	0.3687	0.4112	0.016*
C2	0.33577 (12)	0.09397 (11)	0.33747 (9)	0.01269 (16)
H2A	0.2419	0.0650	0.4026	0.015*
H2B	0.4136	−0.0025	0.3230	0.015*
C3	0.27031 (12)	0.19884 (11)	0.22024 (9)	0.01354 (16)
H3A	0.1870	0.2925	0.2357	0.016*
H3B	0.3629	0.2327	0.1562	0.016*
C4	0.33503 (12)	0.42623 (11)	−0.22978 (8)	0.01214 (16)
H4	0.3797	0.4914	−0.2088	0.015*
C5	0.16668 (12)	0.31649 (11)	−0.02381 (9)	0.01354 (16)
H5A	0.0434	0.3462	−0.0095	0.016*
H5B	0.2054	0.3823	0.0063	0.016*
C6	0.22876 (12)	0.14415 (11)	0.04621 (9)	0.01244 (16)
H6A	0.1755	0.0811	0.0243	0.015*
H6B	0.3505	0.1111	0.0195	0.015*
C7	0.21343 (12)	−0.24693 (11)	0.32171 (9)	0.01360 (16)
H7	0.2912	−0.2365	0.2472	0.016*
C8	−0.02967 (11)	−0.02595 (11)	0.24720 (9)	0.01210 (16)
H8A	−0.1514	−0.0119	0.2749	0.015*
H8B	−0.0011	−0.0455	0.1665	0.015*
C9	0.01822 (12)	0.12133 (11)	0.23426 (9)	0.01177 (15)
H9A	−0.0525	0.2122	0.1825	0.014*
H9B	−0.0021	0.1360	0.3161	0.014*
Cl1	0.29526 (3)	0.69679 (3)	0.01464 (2)	0.01452 (6)
O1	0.24265 (13)	0.56699 (11)	0.10773 (11)	0.0356 (2)
O2	0.35608 (12)	0.66142 (13)	−0.10061 (10)	0.0316 (2)
O3	0.42605 (10)	0.72936 (10)	0.04944 (8)	0.02103 (16)
O4	0.15606 (10)	0.83116 (9)	0.00141 (8)	0.02162 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01374 (8)	0.01175 (8)	0.00772 (8)	−0.00612 (6)	−0.00085 (5)	−0.00332 (5)
N1	0.0123 (3)	0.0121 (3)	0.0110 (3)	−0.0033 (3)	−0.0029 (3)	−0.0042 (3)
N2	0.0129 (4)	0.0158 (4)	0.0190 (4)	−0.0018 (3)	−0.0050 (3)	−0.0074 (3)
N3	0.0136 (4)	0.0153 (4)	0.0181 (4)	−0.0028 (3)	−0.0040 (3)	−0.0070 (3)
N4	0.0125 (3)	0.0134 (3)	0.0104 (3)	−0.0041 (3)	−0.0019 (3)	−0.0041 (3)
N5	0.0185 (4)	0.0172 (4)	0.0095 (3)	−0.0102 (3)	−0.0011 (3)	−0.0035 (3)
N6	0.0471 (7)	0.0421 (6)	0.0132 (4)	−0.0352 (5)	0.0045 (4)	−0.0111 (4)
N7	0.0437 (6)	0.0366 (5)	0.0132 (4)	−0.0315 (5)	0.0040 (4)	−0.0091 (4)
N8	0.0164 (4)	0.0140 (3)	0.0101 (3)	−0.0072 (3)	−0.0023 (3)	−0.0031 (3)
N9	0.0117 (3)	0.0124 (3)	0.0110 (3)	−0.0044 (3)	−0.0009 (3)	−0.0029 (3)
N10	0.0147 (4)	0.0186 (4)	0.0122 (4)	−0.0052 (3)	0.0001 (3)	−0.0022 (3)
N11	0.0160 (4)	0.0192 (4)	0.0129 (4)	−0.0049 (3)	−0.0015 (3)	−0.0026 (3)
N12	0.0149 (4)	0.0151 (4)	0.0128 (4)	−0.0031 (3)	−0.0029 (3)	−0.0040 (3)
N13	0.0128 (3)	0.0144 (3)	0.0091 (3)	−0.0069 (3)	−0.0012 (3)	−0.0036 (3)
C1	0.0133 (4)	0.0136 (4)	0.0144 (4)	−0.0036 (3)	−0.0026 (3)	−0.0063 (3)
C2	0.0162 (4)	0.0120 (4)	0.0126 (4)	−0.0052 (3)	−0.0049 (3)	−0.0037 (3)
C3	0.0180 (4)	0.0141 (4)	0.0117 (4)	−0.0083 (3)	−0.0051 (3)	−0.0019 (3)
C4	0.0144 (4)	0.0132 (4)	0.0099 (4)	−0.0059 (3)	−0.0017 (3)	−0.0029 (3)
C5	0.0174 (4)	0.0154 (4)	0.0083 (4)	−0.0066 (3)	0.0001 (3)	−0.0035 (3)
C6	0.0148 (4)	0.0138 (4)	0.0096 (4)	−0.0055 (3)	−0.0006 (3)	−0.0038 (3)
C7	0.0134 (4)	0.0141 (4)	0.0128 (4)	−0.0025 (3)	−0.0017 (3)	−0.0045 (3)
C8	0.0114 (4)	0.0120 (4)	0.0130 (4)	−0.0036 (3)	−0.0035 (3)	−0.0022 (3)
C9	0.0126 (4)	0.0120 (4)	0.0111 (4)	−0.0043 (3)	−0.0009 (3)	−0.0036 (3)
Cl1	0.01424 (10)	0.01325 (10)	0.01848 (11)	−0.00314 (7)	−0.00498 (8)	−0.00616 (8)
O1	0.0351 (5)	0.0191 (4)	0.0465 (6)	−0.0144 (4)	−0.0063 (4)	0.0039 (4)
O2	0.0295 (5)	0.0418 (5)	0.0332 (5)	0.0009 (4)	−0.0087 (4)	−0.0285 (4)
O3	0.0167 (3)	0.0320 (4)	0.0204 (4)	−0.0103 (3)	−0.0048 (3)	−0.0099 (3)
O4	0.0195 (4)	0.0178 (3)	0.0286 (4)	0.0029 (3)	−0.0097 (3)	−0.0106 (3)

Geometric parameters (Å, º) top

Cu1—N8ⁱ	2.0210 (8)	N13—C6	1.4579 (12)
Cu1—N8ⁱⁱ	2.0210 (8)	N13—C3	1.4617 (12)
Cu1—N4	2.0259 (8)	N13—C9	1.4656 (12)
Cu1—N4ⁱⁱⁱ	2.0259 (8)	C1—H1	0.9500
Cu1—N12^iv	2.4098 (8)	C2—C3	1.5215 (13)
Cu1—N12^v	2.4098 (8)	C2—H2A	0.9900
N1—C1	1.3305 (12)	C2—H2B	0.9900
N1—N2	1.3500 (11)	C3—H3A	0.9900
N1—C2	1.4657 (12)	C3—H3B	0.9900
N2—N3	1.2915 (12)	C4—H4	0.9500
N3—N4	1.3599 (12)	C5—C6	1.5395 (13)
N4—C1	1.3249 (12)	C5—H5A	0.9900
N5—C4	1.3286 (12)	C5—H5B	0.9900
N5—N6	1.3500 (12)	C6—H6A	0.9900
N5—C5	1.4649 (12)	C6—H6B	0.9900
N6—N7	1.2892 (13)	C7—H7	0.9500
N7—N8	1.3614 (12)	C8—H8A	0.9900
N8—C4	1.3210 (12)	C8—H8B	0.9900
N8—Cu1^vi	2.0209 (8)	C9—C8	1.5248 (13)
N9—C7	1.3332 (12)	C9—H9A	0.9900
N9—N10	1.3505 (11)	C9—H9B	0.9900
N9—C8	1.4668 (12)	Cl1—O1	1.4362 (9)
N10—N11	1.2982 (12)	Cl1—O4	1.4409 (8)
N11—N12	1.3630 (12)	Cl1—O3	1.4430 (8)
N12—C7	1.3262 (12)	Cl1—O2	1.4442 (10)
N12—Cu1^vii	2.4098 (8)

N8ⁱ—Cu1—N8ⁱⁱ	180.0	C3—C2—H2A	109.7
N8ⁱ—Cu1—N4	89.54 (3)	N1—C2—H2B	109.7
N8ⁱⁱ—Cu1—N4	90.46 (3)	C3—C2—H2B	109.7
N8ⁱ—Cu1—N4ⁱⁱⁱ	90.46 (3)	H2A—C2—H2B	108.2
N8ⁱⁱ—Cu1—N4ⁱⁱⁱ	89.54 (3)	N13—C3—C2	108.77 (7)
N4—Cu1—N4ⁱⁱⁱ	180.0	N13—C3—H3A	109.9
N8ⁱ—Cu1—N12^iv	88.33 (3)	C2—C3—H3A	109.9
N8ⁱⁱ—Cu1—N12^iv	91.67 (3)	N13—C3—H3B	109.9
N4—Cu1—N12^iv	92.20 (3)	C2—C3—H3B	109.9
N4ⁱⁱⁱ—Cu1—N12^iv	87.80 (3)	H3A—C3—H3B	108.3
N8ⁱ—Cu1—N12^v	91.67 (3)	N8—C4—N5	108.02 (8)
N8ⁱⁱ—Cu1—N12^v	88.33 (3)	N8—C4—H4	126.0
N4—Cu1—N12^v	87.80 (3)	N5—C4—H4	126.0
N4ⁱⁱⁱ—Cu1—N12^v	92.20 (3)	N5—C5—C6	109.51 (8)
N12^iv—Cu1—N12^v	180.0	N5—C5—H5A	109.8
C1—N1—N2	108.62 (8)	C6—C5—H5A	109.8
C1—N1—C2	130.53 (8)	N5—C5—H5B	109.8
N2—N1—C2	120.81 (8)	C6—C5—H5B	109.8
N3—N2—N1	107.19 (8)	H5A—C5—H5B	108.2
N2—N3—N4	109.54 (8)	N13—C6—C5	113.54 (8)
C1—N4—N3	106.88 (8)	N13—C6—H6A	108.9
C1—N4—Cu1	130.20 (7)	C5—C6—H6A	108.9
N3—N4—Cu1	122.61 (6)	N13—C6—H6B	108.9
C4—N5—N6	108.65 (8)	C5—C6—H6B	108.9
C4—N5—C5	129.94 (8)	H6A—C6—H6B	107.7
N6—N5—C5	121.31 (8)	N12—C7—N9	108.87 (9)
N7—N6—N5	106.93 (9)	N12—C7—H7	125.6
N6—N7—N8	109.82 (9)	N9—C7—H7	125.6
C4—N8—N7	106.58 (8)	N9—C8—C9	110.61 (7)
C4—N8—Cu1^vi	131.67 (7)	N9—C8—H8A	109.5
N7—N8—Cu1^vi	121.62 (7)	C9—C8—H8A	109.5
C7—N9—N10	108.17 (8)	N9—C8—H8B	109.5
C7—N9—C8	129.90 (8)	C9—C8—H8B	109.5
N10—N9—C8	121.83 (8)	H8A—C8—H8B	108.1
N11—N10—N9	106.94 (8)	N13—C9—C8	111.13 (8)
N10—N11—N12	110.25 (8)	N13—C9—H9A	109.4
C7—N12—N11	105.77 (8)	C8—C9—H9A	109.4
C7—N12—Cu1^vii	130.45 (7)	N13—C9—H9B	109.4
N11—N12—Cu1^vii	120.86 (6)	C8—C9—H9B	109.4
C6—N13—C3	112.76 (7)	H9A—C9—H9B	108.0
C6—N13—C9	114.58 (7)	O1—Cl1—O4	109.30 (6)
C3—N13—C9	113.41 (8)	O1—Cl1—O3	109.62 (6)
N4—C1—N1	107.78 (8)	O4—Cl1—O3	109.26 (5)
N4—C1—H1	126.1	O1—Cl1—O2	109.78 (7)
N1—C1—H1	126.1	O4—Cl1—O2	109.38 (6)
N1—C2—C3	110.04 (7)	O3—Cl1—O2	109.49 (6)
N1—C2—H2A	109.7

C1—N1—N2—N3	0.07 (11)	N2—N1—C1—N4	0.06 (11)
C2—N1—N2—N3	178.01 (8)	C2—N1—C1—N4	−177.61 (9)
N1—N2—N3—N4	−0.17 (11)	C1—N1—C2—C3	60.09 (13)
N2—N3—N4—C1	0.21 (11)	N2—N1—C2—C3	−117.34 (9)
N2—N3—N4—Cu1	174.39 (7)	C6—N13—C3—C2	−140.77 (8)
N8ⁱ—Cu1—N4—C1	−113.40 (9)	C9—N13—C3—C2	86.92 (10)
N8ⁱⁱ—Cu1—N4—C1	66.60 (9)	N1—C2—C3—N13	176.71 (8)
N12^iv—Cu1—N4—C1	158.29 (9)	N7—N8—C4—N5	0.55 (12)
N12^v—Cu1—N4—C1	−21.71 (9)	Cu1^vi—N8—C4—N5	176.20 (7)
N8ⁱ—Cu1—N4—N3	73.91 (8)	N6—N5—C4—N8	−0.77 (12)
N8ⁱⁱ—Cu1—N4—N3	−106.09 (8)	C5—N5—C4—N8	175.60 (9)
N12^iv—Cu1—N4—N3	−14.40 (8)	C4—N5—C5—C6	−115.73 (11)
N12^v—Cu1—N4—N3	165.60 (8)	N6—N5—C5—C6	60.24 (13)
C4—N5—N6—N7	0.68 (15)	C3—N13—C6—C5	−59.54 (10)
C5—N5—N6—N7	−176.05 (11)	C9—N13—C6—C5	72.20 (10)
N5—N6—N7—N8	−0.34 (16)	N5—C5—C6—N13	170.74 (7)
N6—N7—N8—C4	−0.13 (14)	C6—N13—C9—C8	79.11 (9)
N6—N7—N8—Cu1^vi	−176.32 (9)	C3—N13—C9—C8	−149.46 (8)
C7—N9—N10—N11	−0.45 (11)	C7—N9—C8—C9	−80.18 (12)
C8—N9—N10—N11	−177.15 (8)	N10—N9—C8—C9	95.73 (10)
N9—N10—N11—N12	0.29 (11)	N13—C9—C8—N9	66.24 (10)
N10—N11—N12—C7	−0.02 (11)	N11—N12—C7—N9	−0.27 (11)
N10—N11—N12—Cu1^vii	162.54 (7)	Cu1^vii—N12—C7—N9	−160.50 (7)
N3—N4—C1—N1	−0.17 (11)	N10—N9—C7—N12	0.45 (11)
Cu1—N4—C1—N1	−173.74 (6)	C8—N9—C7—N12	176.79 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N10^viii	0.99	2.60	3.366 (2)	134
C4—H4···O2	0.95	2.33	3.191 (2)	151
C5—H5B···O1	0.99	2.58	3.557 (2)	168
C6—H6A···O4^vii	0.99	2.54	3.459 (2)	154
C7—H7···O3^vii	0.95	2.41	3.305 (2)	157
C8—H8A···N2^ix	0.99	2.47	3.361 (2)	149
C8—H8B···O4^vii	0.99	2.50	3.440 (2)	159
C8—H8B···O4^x	0.99	2.59	3.136 (2)	115

Symmetry codes: (vii) x, y−1, z; (viii) −x, −y, −z+1; (ix) x−1, y, z; (x) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Cu(C₉H₁₅N₁₃)₂](ClO₄)₂
M_r	873.12
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.5902 (3), 9.4932 (4), 11.8446 (5)
α, β, γ (°)	69.233 (1), 74.652 (1), 71.602 (1)
V (Å³)	844.19 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.60 × 0.38 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.86, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	18905, 5317, 5160
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.724

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.072, 1.07
No. of reflections	5317
No. of parameters	250
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.36

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SADABS and XPREP (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N10ⁱ	0.99	2.60	3.366 (2)	133.8
C4—H4···O2	0.95	2.33	3.191 (2)	151.2
C5—H5B···O1	0.99	2.58	3.557 (2)	168.0
C6—H6A···O4ⁱⁱ	0.99	2.54	3.459 (2)	153.9
C7—H7···O3ⁱⁱ	0.95	2.41	3.305 (2)	157.3
C8—H8A···N2ⁱⁱⁱ	0.99	2.47	3.361 (2)	148.8
C8—H8B···O4ⁱⁱ	0.99	2.50	3.440 (2)	158.6
C8—H8B···O4^iv	0.99	2.59	3.136 (2)	115.0

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

Footnotes

‡Present address: Tallinn University of Technology, Department of Chemistry, Chair of Organic Chemistry, Akadeemia tee 15, 12618 Tallinn, Estonia.

Acknowledgements

The authors wish to thank Ms Yuki Inagaki (Aoyama-Gakuin University) for her assistance during the preparation of the complex. FW is grateful to the Japan Society for the Promotion of Science for financial support through a fellowship. MH acknowledges support from a grant-in-aid for Young Scientists A (No. 20685011) and a High-Tech Research Center project for private universities with the matching fund subsidy of MEXT in Japan.

References

Absmeier, A., Bartel, M., Carbonera, C., Jameson, G. N. L., Weinberger, P., Caneschi, A., Mereiter, K., Létard, J.-F. & Linert, W. (2006). Chem. Eur. J. 12, 2235–2243. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bialonska, A., Bronisz, R. & Weselski, M. (2008). Inorg. Chem. 47, 4436–4438. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (2003). SMART, SAINT, SADABS and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Grunert, M., Schweifer, J., Weinberger, P., Linert, W., Mereiter, K., Hilscher, G., Müller, M., Wiesinger, G. & van Koningsbruggen, P. J. (2004). Inorg. Chem. 43, 155–165. Web of Science CSD CrossRef PubMed CAS Google Scholar
Hartdegen, V., Klapötke, T. M. & Sproll, S. M. (2009). Z. Naturforsch. Teil B, 64, 1535–1541. CAS Google Scholar
Kamiya, T. & Saito, Y. (1973). Offenlegungsschrift 2147023 (Patent). Google Scholar
Liu, P.-P., Cheng, A.-L., Yue, Q., Liu, N., Sun, W.-W. & Gao, E.-Q. (2008). Cryst. Growth Des. 8, 1668–1674. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Quesada, M., Kooijman, H., Gamez, P., Sanchez Costa, J., van Koningsbruggen, P. J., Weinberger, P., Reissner, M., Spek, A. L., Haasnoot, J. G. & Reedijk, J. (2007). Dalton Trans. pp. 5434–5440. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Werner, F., Mereiter, K., Tokuno, K., Inagaki, Y. & Hasegawa, M. (2009). Acta Cryst. E65, o2726–o2727. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar
Yu, J.-H., Mereiter, K., Hassan, N., Feldgitscher, C. & Linert, W. (2008). Cryst. Growth Des. 8, 1535–1540. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.