[μ-N,N,N′,N′-Tetra­kis(pyridin-2-ylmeth­yl)butane-1,4-di­amine]­bis­[(di­methanol-κO)(perchlorato-κO)copper(II)] bis­(perchlorate)

Zhu, X.-H.; Li, P.; Chen, X.-W.; Ke, W.-S.; Chen, F.; Zhang, H.-X.

doi:10.1107/S2414314616003448

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160344

doi:10.1107/S2414314616003448

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[μ-N,N,N′,N′-Tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine]bis[(dimethanol-κO)(perchlorato-κO)copper(II)] bis(perchlorate)

Xian-Hong Zhu,^a Peng Li,^a Xiao-Wei Chen,^a Wen-Shan Ke,^a Fei Chen ^a and Hua-Xin Zhang ^a,^b ^*

^aSchool of Chemistry and Chemical Engineering, Guangxi University, No. 100 Daxue East Road, Nanning, Guangxi 530004, People's Republic of China, and ^bGuangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development, Nanning 530004, People's Republic of China
^*Correspondence e-mail: zhanghx@gxu.edu.cn

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 10 February 2016; accepted 28 February 2016; online 4 March 2016)

The binuclear cation of the title compound, [Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₃OH)₄](ClO₄)₂, is located on an inversion centre. The Cu^II atom adopts a distorted octahedral coordination geometry due to the Jahn–Teller effect. The equatorial plane consists of one methanol molecule and three N atoms from the N,N,N′,N′-tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine ligand. The Cu—N bond lengths are in the range 1.975 (3)–2.041 (2) Å and the Cu—O bond length is 2.008 (2) Å. The axial coordination sites of the Cu^II atom are occupied by the O atoms of one methanol molecule and one perchlorate anion, with Cu—O bond lengths of 2.385 (3) and 2.565 (3) Å, respectively. In the crystal, the cations and the perchlorate anions are connected via O—H⋯O hydrogen bonds. In addition, weak C—H⋯O interactions stabilize the structure.

Keywords: crystal structure; copper(II) complex; hydrogen bonds.

CCDC reference: 1439047

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Chemical scheme

Structure description

Transition metal complexes of tetrakis(pyridin-2-yl-methyl)alkyldiamine ligands have attracted much attention recently (Mambanda et al., 2010 ; Bartholomä et al., 2009 ). We report herein the crystal structure of the title complex [Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₃OH)₄](ClO₄)₂ (Fig. 1).

Figure 1
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) −x, −y + 1, −z + 1.]

Crystal structures of some dicopper(II) and dicadmium(II) complexes closely related to the title compound have been reported (Bartholomä et al., 2010a ,b ,c ,d ,e ; Tahsini et al., 2012 ). The copper(II) atoms in the previously reported dicopper(II) complexes adopt a distorted square-pyramidal or a pseudotetrahedral coordination geometry. Polymeric coordination compounds based on copper complexes of diamine ligands have been synthesized (Bartholomä et al., 2011 ; Khullar & Mandal, 2014 ). The oxygen reduction reaction activity of copper complexes of diamine ligands has also been studied (Tse et al., 2014 ).

In the crystal, the cations and the perchlorate anions are connected via O—H⋯O hydrogen bonds (Table 1). In addition, weak C—H⋯O interactions stabilize the structure. These interactions give rise to a two-dimensional network parallel to (101).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O7ⁱ	0.83 (1)	2.01 (2)	2.819 (4)	163 (4)
O1—H1A⋯O10	0.84 (1)	2.76 (5)	3.340 (7)	128 (5)
O1—H1A⋯O7	0.84 (1)	2.28 (2)	3.102 (5)	169 (6)
C2—H2⋯O10ⁱⁱ	0.93	2.52	3.189 (7)	129
C4—H4⋯O8ⁱⁱⁱ	0.93	2.55	3.153 (7)	123
C13—H13B⋯O5^iv	0.96	2.56	3.325 (5)	136
C15—H15A⋯O10	0.97	2.38	3.326 (5)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) -x, -y+1, -z+1; (iv) -x+1, -y, -z+1.

Synthesis and crystallization

The ligand μ-N,N,N′,N′-tetrakis(pyrid-2-ylmethyl)butane-1,4-diamine (45.3 mg, 0.10 mmol) was dissolved in 10 ml CH₃OH to form a clear solution, to which was added a CH₃OH solution (6 ml) of Cu(ClO₄)₂·6H₂O (74.1 mg, 0.20 mmol). The solution turned deep blue immediately and a small amount of precipitate appeared. The mixture was stirred at room temperature for 24 h. A cloudy blue solution was obtained and filtered. The filtrate was diffused by diethyl ether and blue block-shaped crystals were obtained after one week. Yield: 83 mg (75%). Analysis found: C, 34.57; H. 4.24; N, 7.45. Calculated for C₃₂H₄₈Cl₄Cu₂N₆O₂₀: C, 34.76; H, 4.38; N, 7.60%. IR (KBr pellet, cm⁻¹): 3432, 3033, 2911, 2856, 1614, 1418, 1083 (vs), 771, 637.

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₄O)₄](ClO₄)₂
M_r	1105.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	15.262 (6), 9.355 (4), 15.832 (6)
β (°)	92.858 (4)
V (Å³)	2257.6 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.26
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick,1996 )
T_min, T_max	0.833, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	10866, 4092, 3585
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.05
No. of reflections	4092
No. of parameters	299
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.51
Computer programs: SMART (Siemens, 1996 ), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008).

Structural data

CCDC reference: 1439047

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616003448/bt4002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616003448/bt4002Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616003448/bt4002Isup3.mol

Supporting information file. DOI: 10.1107/S2414314616003448/bt4002Isup4.mol

Supporting information file. DOI: 10.1107/S2414314616003448/bt4002Isup5.mol

checkCIF report

Comment top

The transition metal complexes of the tetrakis(pyridin-2-yl-methyl)-alkyl-diamine ligands have recently attracted much attention (Mambanda et al., 2010; Bartholomä et al., 2009). We report herein the crystal structure of the title complex [Cu₂(C₂₈H₃₂N₆)(CH₃OH)₄(ClO₄)₂]²⁺(ClO₄)⁻₂ (Fig. 1).

Crystal structures of some dicopper(II) and dicadmium(II) complexes closely related to the title compound have been reported (Bartholomä et al., 2010a,b,c,d,e; Tahsini, et al., 2012). The copper (II) centres in the previously reported dicopper(II) complexes take a distorted square-pyramidal or a pseudotetrahedral coordination geometry. Polymeric coordination compounds based on the copper complexes of the diamine ligands have been synthesized (Bartholomä et al., 2011; Khullar, et al., 2014). The oxygen reduction reaction activity of the copper complexes of the diamine ligands has also been studied (Tse, et al., 2014).

Experimental top

The ligand µ-N,N,N',N'–tetrakis(2-pyridylmethyl)-butane-1,4-diamine (45.3 mg, 0.10 mmol) was dissolved in 10 ml CH₃OH to form a clear solution, to which was added a CH₃OH solution (6 ml) of Cu(ClO₄)₂·6H₂O (74.1 mg, 0.20 mmol). The solution turned deep blue immediately and a small amount of precipitate appeared. The mixture was stirred at room temperature for 24 h. A cloudy blue solution was obtained and filtered. The filtrate was diffused by diethyl ether and blue block-shaped crystals were obtained after one week. Yield: 83 mg (75%). Analysis found: C, 34.57; H. 4.24; N, 7.45. Calculated for C₃₂H₄₈Cl₄Cu₂N₆O₂₀: C, 34.76; H, 4.38; N, 7.60%. IR (KBr pellet, cm⁻¹): 3432, 3033, 2911, 2856, 1614, 1418, 1083 (vs), 771, 637.

Structure description top

Transition metal complexes of tetrakis(pyridin-2-yl-methyl)alkyldiamine ligands have attracted much attention recently (Mambanda et al., 2010; Bartholomä et al., 2009). We report herein the crystal structure of the title complex [Cu₂(C₂₈H₃₂N₆)(CH₃OH)₄(ClO₄)₂]²⁺(ClO₄)⁻₂ (Fig. 1).

Crystal structures of some dicopper(II) and dicadmium(II) complexes closely related to the title compound have been reported (Bartholomä et al., 2010a,b,c,d,e; Tahsini, et al., 2012). The copper(II) atoms in the previously reported dicopper(II) complexes adopt a distorted square-pyramidal or a pseudotetrahedral coordination geometry. Polymeric coordination compounds based on copper complexes of diamine ligands have been synthesized (Bartholomä et al., 2011; Khullar, et al., 2014). The oxygen reduction reaction activity of copper complexes of diamine ligands has also been studied (Tse et al., 2014).

In the crystal, the cations and the perchlorate anions are connected via O—H···O hydrogen bonds (Table 1). In addition, weak C—H···O interactions stabilize the structure. These interactions give rise to a two-dimensional network parallel to (101).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) −x, −y + 1, −z + 1.]

[µ-N,N,N',N'-Tetrakis(pyridin-2-ylmethyl)butane-1,4-diamine]bis[(dimethanol-κO)(perchlorato-κO)copper(II)] bis(perchlorate) top

Crystal data top

[Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₄O)₄](ClO₄)₂	F(000) = 1136
M_r = 1105.64	D_x = 1.626 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.262 (6) Å	Cell parameters from 10866 reflections
b = 9.355 (4) Å	θ = 2.5–25.4°
c = 15.832 (6) Å	µ = 1.26 mm⁻¹
β = 92.858 (4)°	T = 296 K
V = 2257.6 (16) Å³	Cuboid, blue
Z = 2	0.15 × 0.12 × 0.10 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	3585 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
phi and ω scans	θ_max = 25.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	h = −18→18
T_min = 0.833, T_max = 0.884	k = −10→11
10866 measured reflections	l = −19→16
4092 independent reflections

Refinement top

Refinement on F²	22 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0693P)² + 2.3032P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4092 reflections	Δρ_max = 0.96 e Å⁻³
299 parameters	Δρ_min = −0.51 e Å⁻³

Crystal data top

[Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₄O)₄](ClO₄)₂	V = 2257.6 (16) Å³
M_r = 1105.64	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.262 (6) Å	µ = 1.26 mm⁻¹
b = 9.355 (4) Å	T = 296 K
c = 15.832 (6) Å	0.15 × 0.12 × 0.10 mm
β = 92.858 (4)°

Data collection top

Siemens SMART CCD area-detector diffractometer	4092 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	3585 reflections with I > 2σ(I)
T_min = 0.833, T_max = 0.884	R_int = 0.022
10866 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	22 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.96 e Å⁻³
4092 reflections	Δρ_min = −0.51 e Å⁻³
299 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
C1	0.1455 (2)	0.0368 (3)	0.5044 (2)	0.0440 (8)
H1	0.1648	0.0170	0.4509	0.053*
C2	0.0999 (3)	−0.0655 (4)	0.5452 (3)	0.0620 (11)
H2	0.0883	−0.1536	0.5197	0.074*
C3	0.0714 (3)	−0.0365 (4)	0.6244 (3)	0.0644 (11)
H3	0.0414	−0.1058	0.6537	0.077*
C4	0.0875 (2)	0.0954 (4)	0.6600 (2)	0.0505 (9)
H4	0.0671	0.1177	0.7127	0.061*
C5	0.13469 (18)	0.1947 (3)	0.61593 (19)	0.0344 (7)
C6	0.1599 (2)	0.3373 (3)	0.65356 (18)	0.0358 (7)
H6A	0.1100	0.3784	0.6805	0.043*
H6B	0.2069	0.3246	0.6964	0.043*
C7	0.2619 (2)	0.5306 (4)	0.6191 (2)	0.0391 (7)
H7A	0.2967	0.4812	0.6629	0.047*
H7B	0.2378	0.6160	0.6437	0.047*
C8	0.31903 (19)	0.5715 (3)	0.5488 (2)	0.0368 (7)
C9	0.3711 (3)	0.6939 (4)	0.5513 (3)	0.0555 (10)
H9	0.3684	0.7588	0.5956	0.067*
C10	0.4271 (3)	0.7166 (5)	0.4864 (3)	0.0673 (12)
H10	0.4634	0.7964	0.4872	0.081*
C11	0.4287 (3)	0.6211 (5)	0.4211 (3)	0.0628 (11)
H11	0.4660	0.6357	0.3772	0.075*
C12	0.3750 (2)	0.5037 (4)	0.4209 (2)	0.0490 (8)
H12	0.3754	0.4400	0.3758	0.059*
C13	0.3553 (3)	0.0668 (5)	0.4236 (3)	0.0731 (13)
H13A	0.3653	0.0485	0.4829	0.110*
H13B	0.4099	0.0895	0.3992	0.110*
H13C	0.3302	−0.0165	0.3965	0.110*
C14	0.1120 (3)	0.3258 (6)	0.3058 (3)	0.0769 (14)
H14A	0.1070	0.2258	0.3182	0.115*
H14B	0.1309	0.3376	0.2493	0.115*
H14C	0.0561	0.3712	0.3107	0.115*
C15	0.11512 (18)	0.5284 (3)	0.55231 (19)	0.0325 (6)
H15A	0.1368	0.5876	0.5076	0.039*
H15B	0.0972	0.5917	0.5968	0.039*
C16	0.03470 (18)	0.4473 (3)	0.51735 (19)	0.0343 (6)
H16A	0.0107	0.3901	0.5618	0.041*
H16B	0.0513	0.3834	0.4726	0.041*
Cl1	0.37875 (5)	0.12281 (9)	0.66713 (5)	0.0410 (2)
Cl2	0.15310 (9)	0.76483 (12)	0.30737 (7)	0.0715 (3)
Cu1	0.24114 (2)	0.31381 (4)	0.49533 (2)	0.02964 (14)
N1	0.16344 (16)	0.1652 (3)	0.53909 (16)	0.0329 (5)
N2	0.32171 (15)	0.4784 (3)	0.48422 (16)	0.0357 (6)
N3	0.18915 (14)	0.4362 (3)	0.58710 (14)	0.0294 (5)
O1	0.17400 (17)	0.3889 (3)	0.36349 (16)	0.0527 (6)
H1A	0.190 (4)	0.465 (4)	0.342 (4)	0.12 (2)*
O2	0.29635 (17)	0.1842 (3)	0.41199 (15)	0.0472 (6)
H2A	0.287 (3)	0.194 (4)	0.3599 (8)	0.057 (12)*
O3	0.3075 (2)	0.0238 (4)	0.6663 (2)	0.0861 (11)
O4	0.36000 (16)	0.2327 (3)	0.60525 (16)	0.0563 (7)
O5	0.4561 (2)	0.0499 (4)	0.6471 (2)	0.0976 (12)
O6	0.3892 (3)	0.1839 (4)	0.7486 (2)	0.1032 (13)
O7	0.2095 (3)	0.6690 (4)	0.2660 (2)	0.0938 (11)
O8	0.0697 (4)	0.7308 (12)	0.2688 (9)	0.373 (10)
O9	0.1657 (5)	0.9069 (4)	0.2901 (3)	0.169 (3)
O10	0.1527 (8)	0.7413 (7)	0.3898 (3)	0.286 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0466 (17)	0.0288 (16)	0.056 (2)	−0.0009 (14)	0.0012 (15)	−0.0048 (14)
C2	0.063 (2)	0.0303 (19)	0.093 (3)	−0.0080 (17)	0.003 (2)	0.0013 (19)
C3	0.059 (2)	0.045 (2)	0.090 (3)	−0.0126 (18)	0.013 (2)	0.024 (2)
C4	0.0485 (19)	0.051 (2)	0.053 (2)	−0.0015 (16)	0.0116 (15)	0.0169 (17)
C5	0.0295 (14)	0.0351 (16)	0.0387 (16)	0.0057 (12)	0.0015 (12)	0.0104 (12)
C6	0.0405 (16)	0.0399 (17)	0.0273 (15)	0.0044 (13)	0.0046 (12)	0.0033 (12)
C7	0.0389 (15)	0.0385 (17)	0.0393 (17)	−0.0040 (13)	−0.0028 (13)	−0.0097 (13)
C8	0.0345 (15)	0.0308 (16)	0.0444 (17)	−0.0011 (12)	−0.0059 (12)	0.0012 (13)
C9	0.056 (2)	0.038 (2)	0.072 (3)	−0.0118 (16)	−0.0053 (19)	−0.0039 (17)
C10	0.057 (2)	0.050 (2)	0.095 (3)	−0.0224 (19)	0.000 (2)	0.017 (2)
C11	0.056 (2)	0.064 (3)	0.069 (3)	−0.016 (2)	0.0145 (19)	0.020 (2)
C12	0.0479 (18)	0.056 (2)	0.0436 (19)	−0.0082 (17)	0.0092 (14)	0.0059 (16)
C13	0.078 (3)	0.076 (3)	0.064 (3)	0.043 (2)	−0.003 (2)	−0.017 (2)
C14	0.057 (2)	0.118 (4)	0.055 (3)	−0.019 (3)	−0.0119 (19)	−0.001 (2)
C15	0.0348 (14)	0.0268 (15)	0.0358 (15)	0.0064 (12)	0.0021 (12)	0.0015 (11)
C16	0.0325 (14)	0.0317 (16)	0.0387 (16)	0.0053 (12)	0.0031 (12)	0.0026 (12)
Cl1	0.0359 (4)	0.0506 (5)	0.0363 (4)	0.0061 (3)	−0.0019 (3)	0.0082 (3)
Cl2	0.0999 (8)	0.0561 (6)	0.0623 (6)	−0.0027 (6)	0.0418 (6)	−0.0047 (5)
Cu1	0.0313 (2)	0.0263 (2)	0.0317 (2)	−0.00060 (13)	0.00539 (14)	−0.00210 (13)
N1	0.0324 (12)	0.0268 (13)	0.0395 (14)	0.0013 (10)	0.0012 (10)	0.0017 (10)
N2	0.0330 (12)	0.0357 (14)	0.0384 (14)	−0.0037 (10)	0.0016 (10)	0.0039 (11)
N3	0.0314 (12)	0.0275 (12)	0.0293 (12)	0.0012 (10)	0.0002 (9)	−0.0011 (9)
O1	0.0553 (15)	0.0547 (17)	0.0468 (14)	−0.0034 (13)	−0.0105 (11)	0.0086 (12)
O2	0.0603 (15)	0.0469 (14)	0.0348 (13)	0.0181 (11)	0.0072 (11)	−0.0012 (10)
O3	0.0678 (18)	0.082 (2)	0.106 (3)	−0.0239 (17)	−0.0199 (17)	0.043 (2)
O4	0.0545 (15)	0.0567 (16)	0.0568 (15)	0.0015 (12)	−0.0068 (12)	0.0217 (13)
O5	0.0637 (19)	0.109 (3)	0.122 (3)	0.046 (2)	0.0188 (19)	0.022 (2)
O6	0.139 (3)	0.125 (3)	0.0444 (18)	−0.008 (3)	−0.0083 (19)	−0.0154 (18)
O7	0.098 (3)	0.106 (3)	0.080 (2)	0.018 (2)	0.027 (2)	−0.013 (2)
O8	0.111 (5)	0.333 (13)	0.68 (2)	0.000 (7)	0.087 (9)	−0.317 (16)
O9	0.310 (8)	0.074 (3)	0.128 (4)	0.013 (4)	0.067 (5)	0.035 (3)
O10	0.661 (19)	0.120 (4)	0.095 (4)	0.099 (8)	0.187 (7)	0.044 (3)

Geometric parameters (Å, º) top

C1—N1	1.343 (4)	C13—H13B	0.9600
C1—C2	1.364 (5)	C13—H13C	0.9600
C1—H1	0.9300	C14—O1	1.411 (5)
C2—C3	1.375 (6)	C14—H14A	0.9600
C2—H2	0.9300	C14—H14B	0.9600
C3—C4	1.374 (6)	C14—H14C	0.9600
C3—H3	0.9300	C15—N3	1.504 (3)
C4—C5	1.385 (4)	C15—C16	1.524 (4)
C4—H4	0.9300	C15—H15A	0.9700
C5—N1	1.342 (4)	C15—H15B	0.9700
C5—C6	1.503 (4)	C16—C16ⁱ	1.529 (5)
C6—N3	1.486 (4)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700
C6—H6B	0.9700	Cl1—O6	1.412 (3)
C7—N3	1.487 (4)	Cl1—O5	1.413 (3)
C7—C8	1.498 (4)	Cl1—O3	1.427 (3)
C7—H7A	0.9700	Cl1—O4	1.439 (2)
C7—H7B	0.9700	Cl2—O10	1.323 (4)
C8—N2	1.344 (4)	Cl2—O9	1.372 (4)
C8—C9	1.393 (5)	Cl2—O8	1.419 (6)
C9—C10	1.385 (6)	Cl2—O7	1.424 (3)
C9—H9	0.9300	Cu1—N1	1.975 (3)
C10—C11	1.367 (7)	Cu1—N2	1.984 (3)
C10—H10	0.9300	Cu1—O2	2.008 (2)
C11—C12	1.371 (5)	Cu1—N3	2.041 (2)
C11—H11	0.9300	Cu1—O1	2.385 (3)
C12—N2	1.342 (4)	Cu1—O4	2.565 (3)
C12—H12	0.9300	O1—H1A	0.835 (10)
C13—O2	1.425 (4)	O2—H2A	0.834 (10)
C13—H13A	0.9600

N1—C1—C2	122.2 (4)	H14B—C14—H14C	109.5
N1—C1—H1	118.9	N3—C15—C16	115.1 (2)
C2—C1—H1	118.9	N3—C15—H15A	108.5
C1—C2—C3	119.0 (4)	C16—C15—H15A	108.5
C1—C2—H2	120.5	N3—C15—H15B	108.5
C3—C2—H2	120.5	C16—C15—H15B	108.5
C4—C3—C2	119.5 (3)	H15A—C15—H15B	107.5
C4—C3—H3	120.2	C15—C16—C16ⁱ	109.9 (3)
C2—C3—H3	120.2	C15—C16—H16A	109.7
C3—C4—C5	118.9 (4)	C16ⁱ—C16—H16A	109.7
C3—C4—H4	120.5	C15—C16—H16B	109.7
C5—C4—H4	120.5	C16ⁱ—C16—H16B	109.7
N1—C5—C4	121.3 (3)	H16A—C16—H16B	108.2
N1—C5—C6	116.9 (3)	O6—Cl1—O5	110.0 (3)
C4—C5—C6	121.7 (3)	O6—Cl1—O3	108.8 (2)
N3—C6—C5	110.6 (2)	O5—Cl1—O3	109.2 (2)
N3—C6—H6A	109.5	O6—Cl1—O4	110.0 (2)
C5—C6—H6A	109.5	O5—Cl1—O4	109.4 (2)
N3—C6—H6B	109.5	O3—Cl1—O4	109.37 (17)
C5—C6—H6B	109.5	O10—Cl2—O9	111.4 (4)
H6A—C6—H6B	108.1	O10—Cl2—O8	109.8 (7)
N3—C7—C8	110.6 (2)	O9—Cl2—O8	105.3 (6)
N3—C7—H7A	109.5	O10—Cl2—O7	112.4 (4)
C8—C7—H7A	109.5	O9—Cl2—O7	115.1 (3)
N3—C7—H7B	109.5	O8—Cl2—O7	102.2 (3)
C8—C7—H7B	109.5	N1—Cu1—N2	164.38 (11)
H7A—C7—H7B	108.1	N1—Cu1—O2	94.85 (11)
N2—C8—C9	121.0 (3)	N2—Cu1—O2	97.37 (11)
N2—C8—C7	116.1 (3)	N1—Cu1—N3	83.31 (10)
C9—C8—C7	122.7 (3)	N2—Cu1—N3	83.82 (10)
C10—C9—C8	118.4 (4)	O2—Cu1—N3	175.70 (9)
C10—C9—H9	120.8	N1—Cu1—O1	105.97 (10)
C8—C9—H9	120.8	N2—Cu1—O1	86.27 (10)
C11—C10—C9	119.7 (4)	O2—Cu1—O1	77.22 (10)
C11—C10—H10	120.1	N3—Cu1—O1	107.01 (10)
C9—C10—H10	120.1	C5—N1—C1	119.0 (3)
C10—C11—C12	119.5 (4)	C5—N1—Cu1	113.7 (2)
C10—C11—H11	120.3	C1—N1—Cu1	126.9 (2)
C12—C11—H11	120.3	C12—N2—C8	119.7 (3)
N2—C12—C11	121.6 (4)	C12—N2—Cu1	127.2 (2)
N2—C12—H12	119.2	C8—N2—Cu1	113.1 (2)
C11—C12—H12	119.2	C6—N3—C7	112.0 (2)
O2—C13—H13A	109.5	C6—N3—C15	111.7 (2)
O2—C13—H13B	109.5	C7—N3—C15	108.6 (2)
H13A—C13—H13B	109.5	C6—N3—Cu1	107.21 (18)
O2—C13—H13C	109.5	C7—N3—Cu1	105.37 (17)
H13A—C13—H13C	109.5	C15—N3—Cu1	111.88 (17)
H13B—C13—H13C	109.5	C14—O1—Cu1	133.5 (3)
O1—C14—H14A	109.5	C14—O1—H1A	107 (4)
O1—C14—H14B	109.5	Cu1—O1—H1A	119 (4)
H14A—C14—H14B	109.5	C13—O2—Cu1	131.6 (2)
O1—C14—H14C	109.5	C13—O2—H2A	106 (3)
H14A—C14—H14C	109.5	Cu1—O2—H2A	122 (3)

N1—C1—C2—C3	−0.1 (6)	C6—C5—N1—Cu1	4.2 (3)
C1—C2—C3—C4	1.5 (6)	C2—C1—N1—C5	−0.8 (5)
C2—C3—C4—C5	−2.0 (6)	C2—C1—N1—Cu1	171.4 (3)
C3—C4—C5—N1	1.1 (5)	C11—C12—N2—C8	1.5 (5)
C3—C4—C5—C6	−175.8 (3)	C11—C12—N2—Cu1	−179.1 (3)
N1—C5—C6—N3	17.5 (3)	C9—C8—N2—C12	−0.4 (5)
C4—C5—C6—N3	−165.5 (3)	C7—C8—N2—C12	−176.5 (3)
N3—C7—C8—N2	−27.3 (4)	C9—C8—N2—Cu1	−179.8 (3)
N3—C7—C8—C9	156.7 (3)	C7—C8—N2—Cu1	4.1 (3)
N2—C8—C9—C10	−1.0 (5)	C5—C6—N3—C7	−144.0 (2)
C7—C8—C9—C10	174.9 (3)	C5—C6—N3—C15	94.0 (3)
C8—C9—C10—C11	1.3 (6)	C5—C6—N3—Cu1	−28.9 (3)
C9—C10—C11—C12	−0.2 (7)	C8—C7—N3—C6	151.1 (2)
C10—C11—C12—N2	−1.3 (6)	C8—C7—N3—C15	−85.1 (3)
N3—C15—C16—C16ⁱ	−179.0 (3)	C8—C7—N3—Cu1	34.9 (3)
C4—C5—N1—C1	0.3 (4)	C16—C15—N3—C6	−55.7 (3)
C6—C5—N1—C1	177.3 (3)	C16—C15—N3—C7	−179.6 (2)
C4—C5—N1—Cu1	−172.9 (2)	C16—C15—N3—Cu1	64.5 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O7ⁱⁱ	0.83 (1)	2.01 (2)	2.819 (4)	163 (4)
O1—H1A···O10	0.84 (1)	2.76 (5)	3.340 (7)	128 (5)
O1—H1A···O7	0.84 (1)	2.28 (2)	3.102 (5)	169 (6)
C2—H2···O10ⁱⁱⁱ	0.93	2.52	3.189 (7)	129
C4—H4···O8ⁱ	0.93	2.55	3.153 (7)	123
C13—H13B···O5^iv	0.96	2.56	3.325 (5)	136
C15—H15A···O10	0.97	2.38	3.326 (5)	166

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O7ⁱ	0.834 (10)	2.011 (16)	2.819 (4)	163 (4)
O1—H1A···O10	0.835 (10)	2.76 (5)	3.340 (7)	128 (5)
O1—H1A···O7	0.835 (10)	2.280 (17)	3.102 (5)	169 (6)
C2—H2···O10ⁱⁱ	0.93	2.52	3.189 (7)	128.6
C4—H4···O8ⁱⁱⁱ	0.93	2.55	3.153 (7)	122.7
C13—H13B···O5^iv	0.96	2.56	3.325 (5)	136.4
C15—H15A···O10	0.97	2.38	3.326 (5)	165.9

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

Experimental details

Crystal data
Chemical formula	[Cu₂(ClO₄)₂(C₂₈H₃₂N₆)(CH₄O)₄](ClO₄)₂
M_r	1105.64
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	15.262 (6), 9.355 (4), 15.832 (6)
β (°)	92.858 (4)
V (Å³)	2257.6 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.833, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	10866, 4092, 3585
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.05
No. of reflections	4092
No. of parameters	299
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.51

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), SHELXTL (Sheldrick, 2008).

Acknowledgements

The project was sponsored by the Scientific Research Foundation of Guangxi University (grant No. XDZ140116), the Natural Science Foundation of Guangxi (grant No. 2015GXNSFCB139003) and the National Natural Science Foundation of China (grant No. 21561003).

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