Diaqua­[μ-11,23-di-tert-butyl-3,7,15,19-tetra­azatricyclo­[19.3.1.19,13]tetra­cosa-1(25),2,6,9,11,13(26),14,19,21,23-do­decaene-25,26-diolato-κ4N3,N7,O25,O26:κ4N15,N19,O25,O26]dicopper(II) bis­(perchlorate)

Xu, Q.; Wang, Z.; He, J.; Song, Z.; Chen, F.; Meng, J.; Hu, C.

doi:10.1107/S1600536812031248

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1060-m1061

https://doi.org/10.1107/S1600536812031248

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Diaqua[μ-11,23-di-tert-butyl-3,7,15,19-tetraazatricyclo[19.3.1.1^9,13]tetracosa-1(25),2,6,9,11,13(26),14,19,21,23-dodecaene-25,26-diolato-κ⁴N³,N⁷,O²⁵,O²⁶:κ⁴N¹⁵,N¹⁹,O²⁵,O²⁶]dicopper(II) bis(perchlorate)

Qiang Xu,^a ^* Zhaodong Wang,^a Jiahong He,^a Zhongrong Song,^a Fengming Chen,^a Jiangping Meng ^a and Chengbo Hu ^a

^aSchool of Materials and Chemical Engineering, Chongqing University of Arts and Sciences, Yongchuan, Chongqing 402160, People's Republic of China
^*Correspondence e-mail: xuq18@sina.com

(Received 12 June 2012; accepted 9 July 2012; online 14 July 2012)

In the dinuclear title complex, [Cu₂(C₃₀H₃₈N₄O₂)(H₂O)₂](ClO₄)₂, the coordination cation has crystallographically imposed twofold rotational symmetry. The Cu^II ion is five-coordinated by two N and two O atoms from the macrocylic ligand and one O atom from a water molecule, forming a square-pyramidal N₂O₃ geometry with the water molecule in the apical position. The distance between the two Cu^II atoms is 3.0930 (5) Å. Hydrogen bonds between water molecules and between water molecules and perchlorate anions assemble two cations and four anions into discrete supermolecules of S₄ symmetry. Intramolecular O—H⋯N hydrogen bonds are also observed. The perchlorate anion and the tert-butyl group are disordered over two positions, with occupancies of the major positions of 0.527 (11) and 0.592 (9), respectively.

Related literature

For the synthesis of the magnesium precursor, see: Mohanta et al. (1997 ). For the synthesis of 4-tert-butyl-2,6-diformylphenol, see: Lindoy et al. (1998 ). For similar copper(II) and nickel(II) complexes, see: Bai et al. (2007 ); Chen et al. (2005 ); Nanda et al. (1994 ). For the preparation of similar macrocyclic ligands, see: Thompson et al. (1996 ); Pilkington & Robson (1970 ); Zhou et al. (2005 ).

Experimental

Crystal data

[Cu₂(C₃₀H₃₈N₄O₂)(H₂O)₂](ClO₄)₂
M_r = 848.66
Tetragonal, $[P \overline 42_1 c ]$
a = 18.9013 (4) Å
c = 9.9174 (4) Å
V = 3543.08 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 296 K
0.38 × 0.36 × 0.32 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.615, T_max = 0.660
19006 measured reflections
3489 independent reflections
2942 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.115
S = 1.02
3489 reflections
298 parameters
125 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 1527 Friedel pairs
Flack parameter: 0.31 (3)

Table 1
Selected bond lengths (Å)

Cu1—N1	1.939 (4)
Cu1—N2	1.945 (4)
Cu1—O1ⁱ	1.954 (3)
Cu1—O1	1.964 (3)
Cu1—O2	2.707 (5)
Symmetry code: (i) -x, -y+2, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯O2ⁱⁱ	0.82 (2)	2.07 (4)	2.821 (6)	153 (8)
O2—H2A⋯O3	0.81 (2)	2.26 (3)	2.806 (8)	125 (2)
O2—H2A⋯O3′	0.81 (2)	2.49 (4)	2.947 (10)	117 (3)
O2—H2A⋯N1	0.81 (2)	2.55 (3)	3.197 (6)	138 (3)
Symmetry code: (ii) y-1, -x+1, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812031248/gk2504sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031248/gk2504Isup2.hkl

checkCIF report

Comment top

Dinuclear heterometallic and homometallic transition metal complexes have been well studied with a series of macrocyclic liagnds based on the first reported condensation reaction between 2,6-diformyl-4-R-phenol (R= CH₃, Cl, F, n-butyl) and alkylenediamine by stepwise template reaction (Thompson et al., 1996; Pilkington & Robson, 1970; Zhou et al., 2005). Several tetranuclear as well as trinuclear nickel(II) and copper(II) complexes have been structurally characterized (Mohanta et al.,1997; Nanda et al.,1994). In addition, Mohanta et al. (1997) reported a protonated macrocyclic magnesium compound of composition [Mg₂(L¹H₄)₂(NO₃)₂](NO₃)₂6H₂O by a template reaction. The transmetalation reaction of the magnesium precursor with copper(II) perchlorate in the presence of triethylamine resulted in the formation of a dinuclear copper(II) complex (Mohanta et al.,1997). Herein, we synthesized a similar magnesium precursor by a template reaction involving 4-tert-butyl-2,6-diformylphenol, 1,3-diaminopropane, magnesium acetate, and magnesium nitrate.The transmetalation reaction of the new magnesium precursor with copper(II) perchlorate leads to a new dinuclear copper(II) complex.

The structure of the cation the title compound is shown in Fig.1. In the cation, each copper(II) is coordinated by two O atoms and two N atoms from the macrocylic ligand and one O from water molecule, forming a square pyramidal {N₂O₃} geometry. In {N₂O₃}, the N₂O₂ donor sets from the macrocyclic ligand occupy the basal plane of the pyramid and the O atom from the water molecule locates in the apical position. The distance of the apical O atom and the copper atom [Cu1–O2: 2.707 (5) Å] is longer than the basal donors [ranging from 1.938 (4) to 1.964 (3) Å] due to the Jahn-Teller effect. Fig. 2 shows the crystal packing of the title compound along the b axis.

Related literature top

For the synthesis of the magnesium precursor, see: Mohanta et al.(1997). For the synthesis of 4-tert-butyl-2,6-diformylphenol, see: Lindoy et al. (1998). For similar copper(II) and nickel(II) complexes, see: Bai et al. (2007); Chen et al. (2005); Nanda et al. (1994). For the preparation of similar macrocyclic ligands, see: Thompson et al. (1996); Pilkington & Robson (1970); Zhou et al. (2005).

Experimental top

4-tert-Butyl-2,6-diformylphenol was synthesized according to the reported literature (Lindoy et al.,1998). The magnesium precursor was prepared according to the reported method by Mohanta (Mohanta et al.,1997). The title complex was obtained by the following procedures: Cu(ClO₄)₂6H₂O (0.185 g, 0.5 mmol) and magnesium precursor (0.136 g, 0.1 mmol) were dissolved in CH₃OH (15 ml) and the solution was filtered and left to stand at room temperature. Blue block single crystals suitable for X-ray analysis were obtained by slow evaporation over a period of two weeks.

Structure description top

For the synthesis of the magnesium precursor, see: Mohanta et al.(1997). For the synthesis of 4-tert-butyl-2,6-diformylphenol, see: Lindoy et al. (1998). For similar copper(II) and nickel(II) complexes, see: Bai et al. (2007); Chen et al. (2005); Nanda et al. (1994). For the preparation of similar macrocyclic ligands, see: Thompson et al. (1996); Pilkington & Robson (1970); Zhou et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. The H atoms attached to C atoms were omitted for clarity. Atoms with the A label are generated by the '-x, -y+2, z' symmetry operation. tert-Butyl group and perchlorate anion are disordered.
	Fig. 2. View of the crystal packing along the b axis. For the sake of clarity, H atoms and minor position of the disordered groups have been omitted.

Diaqua[µ-11,23-di-tert-butyl-3,7,15,19-tetraazatricyclo[19.3.1.1^9,13]tetracosa-1(25),2,6,9,11,13(26),14,19,21,23-dodecaene-25,26-diolato-κ⁴N³,N⁷,O²⁵,O²⁶:κ⁴N¹⁵,N¹⁹,O²⁵,O²⁶]dicopper(II) bis(perchlorate) top

Crystal data top

[Cu₂(C₃₀H₃₈N₄O₂)(H₂O)₂](ClO₄)₂	D_x = 1.591 Mg m⁻³
M_r = 848.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42₁c	Cell parameters from 7958 reflections
Hall symbol: P-42 n	θ = 2.3–29.4°
a = 18.9013 (4) Å	µ = 1.42 mm⁻¹
c = 9.9174 (4) Å	T = 296 K
V = 3543.08 (18) Å³	Block, blue
Z = 4	0.38 × 0.36 × 0.32 mm
F(000) = 1752

Data collection top

Bruker APEXII CCD diffractometer	3489 independent reflections
Radiation source: fine-focus sealed tube	2942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
phi and ω scans	θ_max = 26.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −18→23
T_min = 0.615, T_max = 0.660	k = −22→23
19006 measured reflections	l = −12→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0615P)² + 4.6836P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3489 reflections	Δρ_max = 0.47 e Å⁻³
298 parameters	Δρ_min = −0.33 e Å⁻³
125 restraints	Absolute structure: Flack (1983), 1527 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.31 (3)

Crystal data top

[Cu₂(C₃₀H₃₈N₄O₂)(H₂O)₂](ClO₄)₂	Z = 4
M_r = 848.66	Mo Kα radiation
Tetragonal, P42₁c	µ = 1.42 mm⁻¹
a = 18.9013 (4) Å	T = 296 K
c = 9.9174 (4) Å	0.38 × 0.36 × 0.32 mm
V = 3543.08 (18) Å³

Data collection top

Bruker APEXII CCD diffractometer	3489 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2942 reflections with I > 2σ(I)
T_min = 0.615, T_max = 0.660	R_int = 0.021
19006 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.115	Δρ_max = 0.47 e Å⁻³
S = 1.02	Δρ_min = −0.33 e Å⁻³
3489 reflections	Absolute structure: Flack (1983), 1527 Friedel pairs
298 parameters	Absolute structure parameter: 0.31 (3)
125 restraints

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	Occ. (<1)
Cu1	0.08182 (2)	0.99986 (3)	0.18030 (5)	0.03063 (16)
O1	−0.00045 (19)	0.93667 (12)	0.1690 (3)	0.0329 (6)
O2	0.0833 (2)	0.9539 (2)	0.4388 (5)	0.0614 (10)
N1	0.14955 (18)	0.92478 (19)	0.1474 (4)	0.0314 (9)
N2	0.14970 (19)	1.0758 (2)	0.2082 (4)	0.0389 (10)
C1	0.1312 (2)	1.1411 (2)	0.2233 (5)	0.0361 (10)
H1	0.1678	1.1728	0.2406	0.043*
C2	0.2279 (3)	1.0650 (3)	0.2171 (8)	0.0657 (19)
H2A'	0.2493	1.0819	0.1343	0.079*
H2B'	0.2461	1.0936	0.2904	0.079*
C3	0.2500 (2)	0.9908 (3)	0.2390 (6)	0.0504 (13)
H3A	0.2311	0.9744	0.3244	0.061*
H3B	0.3012	0.9889	0.2446	0.061*
C4	0.2254 (2)	0.9415 (3)	0.1278 (5)	0.0431 (11)
H4A	0.2322	0.9639	0.0408	0.052*
H4B	0.2530	0.8983	0.1296	0.052*
C5	0.1332 (2)	0.8591 (2)	0.1536 (5)	0.0347 (10)
H5	0.1698	0.8272	0.1384	0.042*
C6	0.0651 (2)	0.8288 (2)	0.1813 (5)	0.0318 (9)
C7	0.0649 (2)	0.7551 (2)	0.2042 (5)	0.0398 (11)
H7	0.1073	0.7305	0.1974	0.048*
C8	0.0046 (3)	0.71818 (19)	0.2360 (4)	0.0393 (9)
C9	−0.0578 (3)	0.7557 (2)	0.2404 (5)	0.0394 (11)
H9	−0.0995	0.7316	0.2599	0.047*
C10	−0.0611 (3)	0.8288 (2)	0.2168 (5)	0.0330 (11)
C11	0.0005 (3)	0.86673 (17)	0.1894 (4)	0.0297 (7)
C12	0.0062 (3)	0.6385 (2)	0.2598 (5)	0.0538 (12)
C13	0.0775 (4)	0.6074 (4)	0.2618 (11)	0.059 (3)	0.592 (9)
H13A	0.0741	0.5574	0.2771	0.089*	0.592 (9)
H13B	0.1047	0.6287	0.3328	0.089*	0.592 (9)
H13C	0.1004	0.6159	0.1768	0.089*	0.592 (9)
C14	−0.0277 (6)	0.6227 (6)	0.3911 (9)	0.085 (4)	0.592 (9)
H14A	−0.0269	0.5725	0.4067	0.127*	0.592 (9)
H14B	−0.0759	0.6389	0.3898	0.127*	0.592 (9)
H14C	−0.0024	0.6463	0.4619	0.127*	0.592 (9)
C15	−0.0368 (6)	0.6024 (6)	0.1554 (11)	0.086 (4)	0.592 (9)
H15A	−0.0357	0.5522	0.1705	0.129*	0.592 (9)
H15B	−0.0178	0.6127	0.0678	0.129*	0.592 (9)
H15C	−0.0848	0.6188	0.1603	0.129*	0.592 (9)
C13'	0.0409 (8)	0.6032 (9)	0.1429 (13)	0.084 (6)	0.408 (9)
H13D	0.0419	0.5530	0.1577	0.126*	0.408 (9)
H13E	0.0883	0.6206	0.1335	0.126*	0.408 (9)
H13F	0.0147	0.6132	0.0622	0.126*	0.408 (9)
C14'	0.0491 (8)	0.6226 (10)	0.3793 (13)	0.085 (6)	0.408 (9)
H14D	0.0500	0.5724	0.3938	0.127*	0.408 (9)
H14E	0.0289	0.6455	0.4567	0.127*	0.408 (9)
H14F	0.0964	0.6395	0.3657	0.127*	0.408 (9)
C15'	−0.0633 (5)	0.6048 (7)	0.2754 (15)	0.064 (4)	0.408 (9)
H15D	−0.0572	0.5550	0.2896	0.096*	0.408 (9)
H15E	−0.0908	0.6124	0.1953	0.096*	0.408 (9)
H15F	−0.0873	0.6251	0.3514	0.096*	0.408 (9)
Cl1	0.22950 (8)	0.78567 (9)	0.46056 (14)	0.0669 (4)
O3	0.1844 (6)	0.8458 (5)	0.4620 (12)	0.086 (4)	0.527 (11)
O4	0.2055 (8)	0.7328 (7)	0.5596 (13)	0.160 (7)	0.527 (11)
O5	0.2295 (6)	0.7511 (6)	0.3334 (8)	0.102 (4)	0.527 (11)
O6	0.2988 (5)	0.8071 (8)	0.4988 (16)	0.153 (6)	0.527 (11)
O3'	0.1632 (4)	0.8212 (7)	0.4726 (13)	0.082 (4)	0.473 (11)
O4'	0.2672 (7)	0.8119 (8)	0.3419 (11)	0.142 (7)	0.473 (11)
O5'	0.2189 (8)	0.7114 (4)	0.4411 (19)	0.164 (7)	0.473 (11)
O6'	0.2725 (5)	0.7960 (6)	0.5766 (10)	0.084 (4)	0.473 (11)
H2B	0.054 (4)	0.932 (4)	0.482 (8)	0.101*
H2A	0.115 (3)	0.937 (3)	0.395 (3)	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0211 (2)	0.0202 (2)	0.0506 (3)	0.0005 (3)	−0.00050 (19)	−0.0018 (3)
O1	0.0256 (12)	0.0176 (11)	0.0556 (16)	0.0010 (15)	0.002 (2)	0.0020 (10)
O2	0.051 (2)	0.056 (2)	0.078 (3)	0.0051 (18)	0.013 (2)	−0.008 (2)
N1	0.0249 (17)	0.0275 (18)	0.042 (2)	0.0022 (15)	0.0023 (15)	−0.0005 (15)
N2	0.0228 (17)	0.031 (2)	0.063 (3)	−0.0002 (15)	−0.0023 (17)	−0.0026 (18)
C1	0.030 (2)	0.027 (2)	0.052 (3)	−0.0061 (17)	−0.004 (2)	−0.0028 (19)
C2	0.026 (2)	0.037 (3)	0.134 (6)	0.001 (2)	−0.013 (3)	−0.016 (3)
C3	0.027 (2)	0.049 (3)	0.076 (3)	0.002 (2)	−0.009 (2)	−0.003 (3)
C4	0.030 (2)	0.033 (2)	0.066 (3)	0.0016 (19)	0.006 (2)	−0.006 (2)
C5	0.029 (2)	0.029 (2)	0.046 (3)	0.0074 (18)	0.0041 (19)	0.0023 (19)
C6	0.034 (2)	0.019 (2)	0.043 (2)	0.0015 (17)	−0.001 (2)	0.0013 (19)
C7	0.036 (2)	0.024 (2)	0.060 (3)	0.0062 (19)	−0.002 (2)	0.003 (2)
C8	0.046 (2)	0.0224 (17)	0.049 (2)	0.001 (2)	0.000 (2)	0.0035 (16)
C9	0.047 (3)	0.022 (2)	0.049 (3)	−0.006 (2)	0.004 (2)	0.0032 (19)
C10	0.034 (3)	0.022 (2)	0.043 (3)	−0.0023 (17)	0.0053 (19)	0.0008 (17)
C11	0.0305 (17)	0.0183 (15)	0.040 (2)	0.002 (2)	−0.004 (2)	0.0004 (14)
C12	0.054 (3)	0.0230 (18)	0.085 (3)	0.001 (2)	−0.005 (3)	0.010 (2)
C13	0.062 (4)	0.031 (4)	0.085 (5)	0.013 (3)	0.003 (4)	0.010 (3)
C14	0.097 (6)	0.066 (5)	0.091 (6)	0.013 (4)	0.012 (4)	0.020 (4)
C15	0.095 (6)	0.061 (5)	0.102 (6)	−0.006 (4)	−0.015 (5)	−0.001 (4)
C13'	0.092 (8)	0.068 (7)	0.092 (8)	−0.002 (5)	0.011 (5)	−0.008 (5)
C14'	0.088 (7)	0.075 (7)	0.091 (7)	−0.001 (5)	−0.008 (5)	0.015 (5)
C15'	0.070 (6)	0.048 (6)	0.075 (6)	−0.007 (4)	0.002 (5)	0.007 (4)
Cl1	0.0723 (9)	0.0795 (10)	0.0488 (7)	0.0325 (8)	−0.0097 (7)	−0.0036 (7)
O3	0.088 (5)	0.075 (5)	0.095 (5)	0.031 (4)	−0.004 (4)	0.003 (4)
O4	0.169 (8)	0.154 (8)	0.157 (8)	0.000 (5)	0.014 (5)	0.012 (5)
O5	0.105 (6)	0.110 (6)	0.091 (5)	0.033 (4)	0.002 (4)	−0.021 (4)
O6	0.142 (8)	0.159 (8)	0.157 (8)	−0.004 (5)	−0.012 (5)	0.004 (5)
O3'	0.076 (6)	0.082 (6)	0.087 (6)	0.019 (4)	0.002 (4)	−0.001 (4)
O4'	0.137 (8)	0.151 (8)	0.137 (8)	0.011 (5)	0.013 (5)	0.013 (5)
O5'	0.169 (9)	0.151 (8)	0.173 (9)	−0.002 (5)	0.002 (5)	−0.011 (5)
O6'	0.072 (5)	0.098 (6)	0.082 (5)	0.022 (4)	−0.026 (4)	−0.008 (4)

Geometric parameters (Å, º) top

Cu1—N1	1.939 (4)	C10—C1ⁱ	1.444 (6)
Cu1—N2	1.945 (4)	C12—C15'	1.467 (8)
Cu1—O1ⁱ	1.954 (3)	C12—C14'	1.468 (8)
Cu1—O1	1.964 (3)	C12—C13	1.471 (7)
Cu1—O2	2.707 (5)	C12—C14	1.482 (7)
O1—C11	1.338 (4)	C12—C15	1.482 (8)
O1—Cu1ⁱ	1.954 (3)	C12—C13'	1.489 (9)
O2—H2B	0.82 (2)	C13—H13A	0.9600
O2—H2A	0.81 (2)	C13—H13B	0.9600
N1—C5	1.282 (6)	C13—H13C	0.9600
N1—C4	1.481 (6)	C14—H14A	0.9600
N2—C1	1.291 (6)	C14—H14B	0.9600
N2—C2	1.494 (6)	C14—H14C	0.9600
C1—C10ⁱ	1.444 (6)	C15—H15A	0.9600
C1—H1	0.9300	C15—H15B	0.9600
C2—C3	1.480 (7)	C15—H15C	0.9600
C2—H2A'	0.9700	C13'—H13D	0.9600
C2—H2B'	0.9700	C13'—H13E	0.9600
C3—C4	1.516 (7)	C13'—H13F	0.9600
C3—H3A	0.9700	C14'—H14D	0.9600
C3—H3B	0.9700	C14'—H14E	0.9600
C4—H4A	0.9700	C14'—H14F	0.9600
C4—H4B	0.9700	C15'—H15D	0.9600
C5—C6	1.435 (6)	C15'—H15E	0.9600
C5—H5	0.9300	C15'—H15F	0.9600
C6—C7	1.411 (6)	Cl1—O5	1.421 (6)
C6—C11	1.418 (6)	Cl1—O3	1.421 (6)
C7—C8	1.372 (7)	Cl1—O6'	1.422 (7)
C7—H7	0.9300	Cl1—O6	1.422 (7)
C8—C9	1.378 (7)	Cl1—O3'	1.426 (7)
C8—C12	1.525 (5)	Cl1—O5'	1.431 (7)
C9—C10	1.403 (6)	Cl1—O4'	1.462 (8)
C9—H9	0.9300	Cl1—O4	1.472 (8)
C10—C11	1.395 (7)

N1—Cu1—N2	97.38 (14)	C13—C12—C14	107.7 (6)
N1—Cu1—O1ⁱ	163.64 (15)	C13—C12—C15	109.2 (6)
N2—Cu1—O1ⁱ	94.27 (13)	C14—C12—C15	106.5 (6)
N1—Cu1—O1	93.91 (13)	C15'—C12—C13'	106.4 (7)
N2—Cu1—O1	168.30 (15)	C14'—C12—C13'	107.1 (7)
O1ⁱ—Cu1—O1	75.33 (11)	C15'—C12—C8	115.3 (7)
C11—O1—Cu1ⁱ	127.5 (3)	C14'—C12—C8	109.8 (8)
C11—O1—Cu1	125.6 (3)	C13—C12—C8	114.4 (5)
Cu1ⁱ—O1—Cu1	104.28 (11)	C14—C12—C8	109.1 (6)
H2B—O2—H2A	125 (8)	C15—C12—C8	109.7 (6)
C5—N1—C4	116.5 (4)	C13'—C12—C8	109.3 (8)
C5—N1—Cu1	122.8 (3)	C12—C13—H13A	109.5
C4—N1—Cu1	120.3 (3)	C12—C13—H13B	109.5
C1—N2—C2	113.0 (4)	H13A—C13—H13B	109.5
C1—N2—Cu1	122.9 (3)	C12—C13—H13C	109.5
C2—N2—Cu1	124.1 (3)	H13A—C13—H13C	109.5
N2—C1—C10ⁱ	128.3 (4)	H13B—C13—H13C	109.5
N2—C1—H1	115.9	C12—C14—H14A	109.5
C10ⁱ—C1—H1	115.9	C12—C14—H14B	109.5
C3—C2—N2	114.7 (4)	H14A—C14—H14B	109.5
C3—C2—H2A'	108.6	C12—C14—H14C	109.5
N2—C2—H2A'	108.6	H14A—C14—H14C	109.5
C3—C2—H2B'	108.6	H14B—C14—H14C	109.5
N2—C2—H2B'	108.6	C12—C15—H15A	109.5
H2A'—C2—H2B'	107.6	C12—C15—H15B	109.5
C2—C3—C4	112.8 (5)	H15A—C15—H15B	109.5
C2—C3—H3A	109.0	C12—C15—H15C	109.5
C4—C3—H3A	109.0	H15A—C15—H15C	109.5
C2—C3—H3B	109.0	H15B—C15—H15C	109.5
C4—C3—H3B	109.0	C12—C13'—H13D	109.5
H3A—C3—H3B	107.8	C12—C13'—H13E	109.5
N1—C4—C3	109.5 (4)	H13D—C13'—H13E	109.5
N1—C4—H4A	109.8	C12—C13'—H13F	109.5
C3—C4—H4A	109.8	H13D—C13'—H13F	109.5
N1—C4—H4B	109.8	H13E—C13'—H13F	109.5
C3—C4—H4B	109.8	C12—C14'—H14D	109.5
H4A—C4—H4B	108.2	C12—C14'—H14E	109.5
N1—C5—C6	127.7 (4)	H14D—C14'—H14E	109.5
N1—C5—H5	116.1	C12—C14'—H14F	109.5
C6—C5—H5	116.1	H14D—C14'—H14F	109.5
C7—C6—C11	119.2 (4)	H14E—C14'—H14F	109.5
C7—C6—C5	115.3 (4)	C12—C15'—H15D	109.5
C11—C6—C5	125.6 (4)	C12—C15'—H15E	109.5
C8—C7—C6	122.8 (4)	H15D—C15'—H15E	109.5
C8—C7—H7	118.6	C12—C15'—H15F	109.5
C6—C7—H7	118.6	H15D—C15'—H15F	109.5
C7—C8—C9	117.2 (3)	H15E—C15'—H15F	109.5
C7—C8—C12	121.5 (5)	O5—Cl1—O3	112.1 (6)
C9—C8—C12	121.3 (5)	O5—Cl1—O6	111.6 (6)
C8—C9—C10	122.6 (4)	O3—Cl1—O6	108.8 (7)
C8—C9—H9	118.7	O6'—Cl1—O3'	111.6 (6)
C10—C9—H9	118.7	O6'—Cl1—O5'	108.9 (7)
C11—C10—C9	120.2 (4)	O3'—Cl1—O5'	110.5 (6)
C11—C10—C1ⁱ	124.9 (4)	O6'—Cl1—O4'	109.0 (6)
C9—C10—C1ⁱ	114.9 (4)	O3'—Cl1—O4'	109.7 (6)
O1—C11—C10	121.7 (4)	O5'—Cl1—O4'	107.0 (7)
O1—C11—C6	120.2 (4)	O5—Cl1—O4	106.3 (6)
C10—C11—C6	118.0 (3)	O3—Cl1—O4	110.5 (6)
C15'—C12—C14'	108.7 (7)	O6—Cl1—O4	107.4 (6)

N1—Cu1—O1—C11	23.1 (3)	C5—C6—C7—C8	178.0 (5)
N2—Cu1—O1—C11	−141.7 (7)	C6—C7—C8—C9	2.3 (7)
O1ⁱ—Cu1—O1—C11	−169.4 (3)	C6—C7—C8—C12	179.9 (5)
N1—Cu1—O1—Cu1ⁱ	−174.27 (14)	C7—C8—C9—C10	−1.4 (7)
N2—Cu1—O1—Cu1ⁱ	21.0 (8)	C12—C8—C9—C10	−178.9 (5)
O1ⁱ—Cu1—O1—Cu1ⁱ	−6.78 (17)	C8—C9—C10—C11	−0.9 (8)
N2—Cu1—N1—C5	163.2 (4)	C8—C9—C10—C1ⁱ	178.9 (4)
O1ⁱ—Cu1—N1—C5	−61.8 (7)	Cu1ⁱ—O1—C11—C10	3.0 (5)
O1—Cu1—N1—C5	−13.7 (4)	Cu1—O1—C11—C10	161.7 (3)
N2—Cu1—N1—C4	−10.2 (4)	Cu1ⁱ—O1—C11—C6	−177.9 (3)
O1ⁱ—Cu1—N1—C4	124.9 (5)	Cu1—O1—C11—C6	−19.3 (5)
O1—Cu1—N1—C4	172.9 (3)	C9—C10—C11—O1	−178.7 (4)
N1—Cu1—N2—C1	173.9 (4)	C1ⁱ—C10—C11—O1	1.5 (7)
O1ⁱ—Cu1—N2—C1	5.4 (4)	C9—C10—C11—C6	2.3 (6)
O1—Cu1—N2—C1	−21.5 (10)	C1ⁱ—C10—C11—C6	−177.5 (5)
N1—Cu1—N2—C2	−7.4 (5)	C7—C6—C11—O1	179.5 (4)
O1ⁱ—Cu1—N2—C2	−175.8 (5)	C5—C6—C11—O1	0.7 (7)
O1—Cu1—N2—C2	157.3 (7)	C7—C6—C11—C10	−1.4 (7)
C2—N2—C1—C10ⁱ	178.0 (5)	C5—C6—C11—C10	179.8 (5)
Cu1—N2—C1—C10ⁱ	−3.2 (7)	C7—C8—C12—C15'	−172.3 (8)
C1—N2—C2—C3	163.5 (5)	C9—C8—C12—C15'	5.1 (9)
Cu1—N2—C2—C3	−15.3 (8)	C7—C8—C12—C14'	64.5 (9)
N2—C2—C3—C4	59.5 (7)	C9—C8—C12—C14'	−118.0 (8)
C5—N1—C4—C3	−125.1 (4)	C7—C8—C12—C13	7.0 (8)
Cu1—N1—C4—C3	48.7 (5)	C9—C8—C12—C13	−175.5 (6)
C2—C3—C4—N1	−77.9 (6)	C7—C8—C12—C14	127.7 (7)
C4—N1—C5—C6	175.2 (5)	C9—C8—C12—C14	−54.8 (7)
Cu1—N1—C5—C6	1.6 (7)	C7—C8—C12—C15	−116.1 (7)
N1—C5—C6—C7	−169.8 (5)	C9—C8—C12—C15	61.4 (8)
N1—C5—C6—C11	9.0 (9)	C7—C8—C12—C13'	−52.6 (9)
C11—C6—C7—C8	−0.9 (8)	C9—C8—C12—C13'	124.9 (8)

Symmetry code: (i) −x, −y+2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O2ⁱⁱ	0.82 (2)	2.07 (4)	2.821 (6)	153 (8)
O2—H2A···O3	0.81 (2)	2.26 (3)	2.806 (8)	125 (2)
O2—H2A···O3′	0.81 (2)	2.49 (4)	2.947 (10)	117 (3)
O2—H2A···N1	0.81 (2)	2.55 (3)	3.197 (6)	138 (3)

Symmetry code: (ii) y−1, −x+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₃₀H₃₈N₄O₂)(H₂O)₂](ClO₄)₂
M_r	848.66
Crystal system, space group	Tetragonal, P42₁c
Temperature (K)	296
a, c (Å)	18.9013 (4), 9.9174 (4)
V (Å³)	3543.08 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.42
Crystal size (mm)	0.38 × 0.36 × 0.32

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.615, 0.660
No. of measured, independent and observed [I > 2σ(I)] reflections	19006, 3489, 2942
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.115, 1.02
No. of reflections	3489
No. of parameters	298
No. of restraints	125
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.33
Absolute structure	Flack (1983), 1527 Friedel pairs
Absolute structure parameter	0.31 (3)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.939 (4)	Cu1—O1	1.964 (3)
Cu1—N2	1.945 (4)	Cu1—O2	2.707 (5)
Cu1—O1ⁱ	1.954 (3)

Symmetry code: (i) −x, −y+2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O2ⁱⁱ	0.82 (2)	2.07 (4)	2.821 (6)	153 (8)
O2—H2A···O3	0.81 (2)	2.26 (3)	2.806 (8)	125 (2)
O2—H2A···O3'	0.81 (2)	2.49 (4)	2.947 (10)	117 (3)
O2—H2A···N1	0.81 (2)	2.55 (3)	3.197 (6)	138 (3)

Symmetry code: (ii) y−1, −x+1, −z+1.

Acknowledgements

The authors thank the Science and Technology Project of Chongqing Municipal Education Commission (KJ071208) for support.

References

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