[(4E,11E)-5,7,12,14-Tetra­benzyl-7,14-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene]copper(II) bis(per­chlorate)

Roy, T.G.; Hazari, S.K.S.; Nath, B.C.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811042796

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1581-m1582

doi:10.1107/S1600536811042796

Open

access

[(4E,11E)-5,7,12,14-Tetrabenzyl-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene]copper(II) bis(perchlorate)

Tapashi G. Roy,^a ‡ Saroj K. S. Hazari,^a Babul C. Nath,^a Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, University of Chittagong, Chittagong-4331, Bangladesh, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 13 October 2011; accepted 15 October 2011; online 22 October 2011)

The complete cation in the title compound, [Cu(C₄₀H₄₈N₄)](ClO₄)₂, is generated by the operation of a crystallographic centre of inversion. The Cu^II ion exists in a tetragonally distorted trans-N₄O₂ coordination geometry defined by the four N atoms of the macrocyclic ligand and two weakly bound perchlorate-O atoms from two anions. The N—H atoms form intramolecular N—H⋯O(perchlorate) hydrogen bonds. Disorder was resolved in the –CH₂–NH– portion of the macrocycle with the major component having a site-occupancy factor of 0.570 (6).

Related literature

For background to the synthesis, characterization, kinetic studies and biological activities of 14-membered methyl-substituted tetraazamacrocyclic ligands, their N-substituted derivatives and their metal complexes, see: Hazari et al. (2008 ).

Experimental

Crystal data

[Cu(C₄₀H₄₈N₄)](ClO₄)₂
M_r = 847.26
Monoclinic, P 2₁ /n
a = 10.1170 (3) Å
b = 16.6017 (4) Å
c = 11.9910 (3) Å
β = 108.818 (3)°
V = 1906.35 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.792, T_max = 1.000
9806 measured reflections
4253 independent reflections
3707 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.145
S = 1.08
4253 reflections
251 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu—N1	2.032 (4)
Cu—N2	1.977 (2)
Cu—O1	2.662 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.88	2.39	2.940 (5)	121
N1′—H1′⋯O2	0.88	2.29	3.104 (4)	153
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811042796/hb6449sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042796/hb6449Isup2.hkl

checkCIF report

Comment top

The title complex, (I), was investigated in continuation of studies of the synthesis, characterization and biological activities of methyl substituted tetraazamacrocyclic ligands and their metal complexes (Hazari et al., 2008).

The structure of (I), Fig. 1, features a tetragonally distorted N₄O₂ donor set about a Cu^II atom, Table 1. The N-donor atoms are derived from the (4E,11E)-5,7,12,14-tetrabenzyl-7,14-dimethyl- 1,4,8,11-tetraazacyclotetradeca-4,11-diene macrocyclic ligand, and the O-donors are derived from two perchlorate anions. The complex is centrosymmetric. A C-meso, N-meso configuration is found in (I). With reference to the six-membered chelate ring, the benzyl and methyl groups equatorially and axially orientated, respectively. The dihedral angle formed between the benzene rings is 44.22 (16) Å. Each N—H atom of the disordered —CH₂—NH— residue forms an intramolecular N—H···O hydrogen bond with a perchlorate-O atom, Table 2, i.e. to either side of the CuN₄ plane. The competition between the formation of these alternate hydrogen bonds provides a rationale for the observed disorder.

Related literature top

Experimental top

The macrocyclic ligand as its hydroperchloric acid salt (0.783 g, 1.0 mmol) was suspended in methanol (20 ml). Copper(II) perchlorate hexahydrate (0.370 g, 1.0 mmol) was dissolved in methanol (30 ml) and then was mixed with the suspension of the ligand salt. The mixture was refluxed for 3 h and a clear violet solution evolved. The solution was filtered and kept at room temperature. After 24 h, violet crystals of the complex were observed. The crystals were separated by filtration, washed with dry ethanol, followed by diethylether and dried in a vacuum desiccator over silica gel. M.pt. 510–512 K. Yield 45%. Anal. Calc. for [Cu(C₄₀H₄₈N₄)](ClO₄)₂ C, 56.77; H, 5.56; N, 6.62; Cu, 7.51%. Found: C, 56.56; H, 5.53; N, 6.75; Cu, 7.35%. FT—IR (KBr, cm^-1) 3220 ν(N—H), 3028 ν(Ar—H), 2980 ν(C—H), 1650 ν(C═N), 1375 ν(CH₃), 1185 ν(C—C), 1126 ν(ClO₄), 710 ν(ArC—H)), 488 ν(Cu—N). The light-purple prisms were prepared by slow evaporation of a methanol solution of the complex.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level. Only the major component of the disordered residue is shown. Unlabelled atoms are generated by the symmetry operation (1–x, 1–y, 1–z).

[(4E,11E)-5,7,12,14-Tetrabenzyl-7,14-dimethyl- 1,4,8,11-tetraazacyclotetradeca-4,11-diene]copper(II) bis(perchlorate) top

Crystal data top

[Cu(C₄₀H₄₈N₄)](ClO₄)₂	F(000) = 886
M_r = 847.26	D_x = 1.476 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4647 reflections
a = 10.1170 (3) Å	θ = 2.3–29.3°
b = 16.6017 (4) Å	µ = 0.77 mm⁻¹
c = 11.9910 (3) Å	T = 100 K
β = 108.818 (3)°	Prism, light-purple
V = 1906.35 (9) Å³	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	4253 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	3707 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.3°
ω scan	h = −11→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −21→16
T_min = 0.792, T_max = 1.000	l = −15→15
9806 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0495P)² + 4.3222P] where P = (F_o² + 2F_c²)/3
4253 reflections	(Δ/σ)_max < 0.001
251 parameters	Δρ_max = 0.64 e Å⁻³
15 restraints	Δρ_min = −1.08 e Å⁻³

Crystal data top

[Cu(C₄₀H₄₈N₄)](ClO₄)₂	V = 1906.35 (9) Å³
M_r = 847.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1170 (3) Å	µ = 0.77 mm⁻¹
b = 16.6017 (4) Å	T = 100 K
c = 11.9910 (3) Å	0.30 × 0.25 × 0.20 mm
β = 108.818 (3)°

Data collection top

Agilent Technologies SuperNova Dual diffractometer with Atlas detector	4253 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	3707 reflections with I > 2σ(I)
T_min = 0.792, T_max = 1.000	R_int = 0.024
9806 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	15 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.08	Δρ_max = 0.64 e Å⁻³
4253 reflections	Δρ_min = −1.08 e Å⁻³
251 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.

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	Occ. (<1)
Cu	0.5000	0.5000	0.5000	0.0368 (2)
Cl1	0.85496 (8)	0.59569 (5)	0.64594 (7)	0.0320 (2)
O1	0.7221 (2)	0.59629 (15)	0.5522 (2)	0.0349 (6)
O2	0.8616 (3)	0.52613 (18)	0.7184 (3)	0.0520 (8)
O3	0.9641 (3)	0.5963 (2)	0.5963 (3)	0.0660 (10)
O4	0.8647 (3)	0.66693 (18)	0.7171 (2)	0.0492 (7)
N1	0.4748 (5)	0.4782 (3)	0.6587 (3)	0.0245 (10)	0.570 (6)
H1	0.4019	0.4462	0.6445	0.029*	0.570 (6)
N2	0.6240 (3)	0.40479 (15)	0.5342 (2)	0.0239 (5)
C1	0.6015 (5)	0.4282 (3)	0.7295 (4)	0.0277 (11)	0.570 (6)
H1A	0.6845	0.4631	0.7610	0.033*	0.570 (6)
H1B	0.5825	0.4011	0.7964	0.033*	0.570 (6)
C2	0.6264 (3)	0.36629 (19)	0.6456 (3)	0.0261 (7)
H2A	0.7181	0.3401	0.6825	0.031*	0.570 (6)
H2B	0.5533	0.3242	0.6294	0.031*	0.570 (6)
H2C	0.7195	0.3726	0.7058	0.031*	0.430 (6)
H2D	0.6056	0.3081	0.6334	0.031*	0.430 (6)
C3	0.7012 (3)	0.3815 (2)	0.4734 (3)	0.0257 (6)
C4	0.7948 (3)	0.3080 (2)	0.4994 (3)	0.0282 (7)
H4A	0.8072	0.2883	0.5800	0.034*
H4B	0.8878	0.3221	0.4943	0.034*
C5	0.7277 (3)	0.2425 (2)	0.4096 (3)	0.0281 (7)
C6	0.6296 (4)	0.1915 (2)	0.4294 (3)	0.0352 (8)
H6	0.6083	0.1955	0.5008	0.042*
C7	0.5617 (4)	0.1344 (2)	0.3456 (4)	0.0399 (9)
H7	0.4942	0.0999	0.3601	0.048*
C8	0.5919 (4)	0.1277 (2)	0.2413 (3)	0.0379 (8)
H8	0.5445	0.0892	0.1836	0.045*
C9	0.6922 (4)	0.1776 (2)	0.2218 (3)	0.0374 (8)
H9	0.7144	0.1728	0.1510	0.045*
C10	0.7604 (3)	0.2349 (2)	0.3059 (3)	0.0309 (7)
H10	0.8294	0.2687	0.2923	0.037*
C11	0.7003 (4)	0.4281 (2)	0.3652 (3)	0.0316 (7)
H11A	0.7518	0.3964	0.3226	0.038*
H11B	0.7527	0.4789	0.3911	0.038*
C12	0.5570 (4)	0.4493 (2)	0.2784 (3)	0.0303 (7)
C13	0.5729 (4)	0.4799 (2)	0.1621 (3)	0.0354 (8)
H13A	0.4791	0.4937	0.1074	0.042*
H13B	0.6288	0.5301	0.1784	0.042*
C14	0.4581 (3)	0.3778 (3)	0.2546 (3)	0.0391 (9)
H14A	0.3668	0.3939	0.2004	0.059*
H14B	0.4477	0.3591	0.3288	0.059*
H14C	0.4962	0.3341	0.2191	0.059*
C15	0.6410 (4)	0.42125 (19)	0.1011 (3)	0.0280 (7)
C16	0.5637 (3)	0.36046 (19)	0.0285 (3)	0.0268 (7)
H16	0.4664	0.3561	0.0163	0.032*
C17	0.6273 (3)	0.3066 (2)	−0.0260 (3)	0.0287 (7)
H17	0.5736	0.2650	−0.0742	0.034*
C18	0.7686 (4)	0.3126 (2)	−0.0109 (3)	0.0316 (7)
H18	0.8120	0.2756	−0.0485	0.038*
C19	0.8455 (4)	0.3731 (2)	0.0598 (3)	0.0366 (8)
H19	0.9421	0.3784	0.0698	0.044*
C20	0.7815 (3)	0.42676 (17)	0.1166 (2)	0.0331 (8)
H20	0.8358	0.4674	0.1665	0.040*
N1'	0.5452 (3)	0.49931 (17)	0.6741 (2)	0.0245 (10)	0.43
H1'	0.6332	0.5119	0.7103	0.029*	0.430 (6)
C1'	0.5178 (3)	0.40711 (17)	0.6846 (2)	0.0277 (11)	0.43
H1'1	0.5276	0.3925	0.7670	0.033*	0.430 (6)
H1'2	0.4230	0.3922	0.6333	0.033*	0.430 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0564 (4)	0.0281 (3)	0.0199 (3)	0.0258 (3)	0.0039 (3)	0.0029 (2)
Cl1	0.0177 (4)	0.0351 (4)	0.0413 (4)	−0.0034 (3)	0.0068 (3)	0.0122 (4)
O1	0.0232 (12)	0.0389 (14)	0.0379 (13)	0.0015 (10)	0.0034 (10)	−0.0016 (11)
O2	0.0465 (17)	0.0398 (15)	0.0623 (19)	−0.0023 (13)	0.0074 (14)	0.0250 (14)
O3	0.0303 (15)	0.092 (3)	0.087 (2)	−0.0031 (16)	0.0339 (16)	0.013 (2)
O4	0.0510 (17)	0.0442 (16)	0.0411 (15)	−0.0104 (13)	−0.0008 (13)	0.0021 (13)
N1	0.023 (2)	0.022 (2)	0.0222 (18)	0.0091 (17)	−0.0004 (19)	0.0010 (15)
N2	0.0225 (12)	0.0202 (12)	0.0252 (12)	0.0015 (10)	0.0024 (10)	0.0019 (10)
C1	0.025 (2)	0.034 (3)	0.026 (2)	0.013 (2)	0.0118 (18)	0.012 (2)
C2	0.0249 (15)	0.0244 (15)	0.0294 (16)	0.0057 (12)	0.0091 (13)	0.0081 (13)
C3	0.0182 (14)	0.0273 (16)	0.0282 (15)	−0.0013 (12)	0.0030 (12)	0.0037 (13)
C4	0.0182 (14)	0.0398 (18)	0.0266 (15)	0.0081 (13)	0.0075 (12)	0.0064 (14)
C5	0.0245 (15)	0.0303 (17)	0.0304 (16)	0.0158 (13)	0.0100 (13)	0.0096 (14)
C6	0.0354 (19)	0.0325 (18)	0.0418 (19)	0.0103 (15)	0.0183 (16)	0.0068 (16)
C7	0.038 (2)	0.0305 (18)	0.054 (2)	0.0072 (15)	0.0194 (18)	0.0029 (17)
C8	0.039 (2)	0.0277 (17)	0.042 (2)	0.0112 (15)	0.0063 (16)	0.0020 (16)
C9	0.042 (2)	0.039 (2)	0.0307 (17)	0.0218 (16)	0.0109 (15)	0.0106 (16)
C10	0.0245 (16)	0.0341 (18)	0.0361 (17)	0.0140 (13)	0.0127 (13)	0.0116 (15)
C11	0.0306 (17)	0.0320 (17)	0.0278 (16)	−0.0083 (14)	0.0033 (13)	0.0067 (14)
C12	0.0353 (18)	0.0277 (16)	0.0266 (15)	0.0127 (14)	0.0081 (13)	0.0019 (13)
C13	0.051 (2)	0.0247 (16)	0.0234 (16)	0.0058 (15)	0.0021 (15)	0.0004 (13)
C14	0.0204 (16)	0.066 (3)	0.0304 (17)	−0.0019 (16)	0.0080 (13)	−0.0073 (18)
C15	0.0372 (18)	0.0224 (15)	0.0204 (14)	0.0005 (13)	0.0035 (13)	0.0043 (12)
C16	0.0258 (15)	0.0268 (16)	0.0243 (15)	−0.0018 (13)	0.0030 (12)	0.0009 (13)
C17	0.0320 (17)	0.0268 (16)	0.0258 (15)	−0.0046 (13)	0.0072 (13)	−0.0018 (13)
C18	0.0318 (17)	0.0381 (19)	0.0268 (16)	−0.0006 (15)	0.0120 (14)	0.0002 (15)
C19	0.0298 (17)	0.051 (2)	0.0269 (16)	−0.0090 (16)	0.0058 (14)	−0.0010 (16)
C20	0.0376 (19)	0.0343 (18)	0.0235 (15)	−0.0129 (15)	0.0046 (14)	−0.0011 (14)
N1'	0.023 (2)	0.022 (2)	0.0222 (18)	0.0091 (17)	−0.0004 (19)	0.0010 (15)
C1'	0.025 (2)	0.034 (3)	0.026 (2)	0.013 (2)	0.0118 (18)	0.012 (2)

Geometric parameters (Å, º) top

Cu—N1	2.032 (4)	C7—H7	0.9500
Cu—N2	1.977 (2)	C8—C9	1.386 (6)
Cu—N2ⁱ	1.977 (2)	C8—H8	0.9500
Cu—N1'ⁱ	1.988 (2)	C9—C10	1.396 (5)
Cu—N1'	1.988 (2)	C9—H9	0.9500
Cu—N1ⁱ	2.032 (4)	C10—H10	0.9500
Cu—O1ⁱ	2.662 (2)	C11—C12	1.528 (5)
Cu—O1	2.662 (2)	C11—H11A	0.9900
Cl1—O3	1.413 (3)	C11—H11B	0.9900
Cl1—O2	1.433 (3)	C12—N1ⁱ	1.510 (5)
Cl1—O4	1.443 (3)	C12—C14	1.519 (5)
Cl1—O1	1.447 (2)	C12—C13	1.541 (5)
N1—C12ⁱ	1.510 (5)	C12—N1'ⁱ	1.582 (4)
N1—C1	1.534 (4)	C13—C15	1.511 (5)
N1—H1	0.8800	C13—H13A	0.9900
N2—C3	1.287 (4)	C13—H13B	0.9900
N2—C2	1.475 (4)	C14—H14A	0.9800
C1—C2	1.515 (5)	C14—H14B	0.9800
C1—H1A	0.9900	C14—H14C	0.9800
C1—H1B	0.9900	C15—C20	1.376 (4)
C2—C1'	1.489 (4)	C15—C16	1.396 (4)
C2—H2A	0.9900	C16—C17	1.383 (5)
C2—H2B	0.9900	C16—H16	0.9500
C2—H2C	0.9900	C17—C18	1.385 (5)
C2—H2D	0.9900	C17—H17	0.9500
C3—C4	1.514 (4)	C18—C19	1.381 (5)
C3—C11	1.509 (4)	C18—H18	0.9500
C4—C5	1.527 (5)	C19—C20	1.400 (5)
C4—H4A	0.9900	C19—H19	0.9500
C4—H4B	0.9900	C20—H20	0.9500
C5—C6	1.383 (5)	N1'—C1'	1.5679
C5—C10	1.392 (4)	N1'—C12ⁱ	1.582 (4)
C6—C7	1.390 (5)	N1'—H1'	0.8800
C6—H6	0.9500	C1'—H1'1	0.9900
C7—C8	1.385 (5)	C1'—H1'2	0.9900

O1—Cu—N1	103.76 (15)	H4A—C4—H4B	108.3
O1—Cu—N2	90.01 (9)	C6—C5—C10	119.3 (3)
N2—Cu—N2ⁱ	180	C6—C5—C4	119.7 (3)
N2—Cu—N1'ⁱ	97.92 (11)	C10—C5—C4	121.0 (3)
N2ⁱ—Cu—N1'ⁱ	82.08 (11)	C5—C6—C7	120.5 (3)
N2—Cu—N1'	82.08 (11)	C5—C6—H6	119.7
N2ⁱ—Cu—N1'	97.92 (11)	C7—C6—H6	119.7
N1'ⁱ—Cu—N1'	180	C8—C7—C6	120.4 (4)
N2—Cu—N1ⁱ	94.20 (14)	C8—C7—H7	119.8
N2ⁱ—Cu—N1ⁱ	85.80 (14)	C6—C7—H7	119.8
N1'ⁱ—Cu—N1ⁱ	21.80 (14)	C7—C8—C9	119.3 (4)
N1'—Cu—N1ⁱ	158.20 (15)	C7—C8—H8	120.3
N1—Cu—N2	85.80 (14)	C9—C8—H8	120.3
N2ⁱ—Cu—N1	94.20 (14)	C10—C9—C8	120.3 (3)
N1'ⁱ—Cu—N1	158.20 (15)	C10—C9—H9	119.9
N1'—Cu—N1	21.80 (14)	C8—C9—H9	119.9
N1ⁱ—Cu—N1	180	C9—C10—C5	120.1 (3)
N2—Cu—O1ⁱ	89.99 (9)	C9—C10—H10	119.9
N2ⁱ—Cu—O1ⁱ	90.01 (9)	C5—C10—H10	119.9
N1'ⁱ—Cu—O1ⁱ	82.27 (10)	C3—C11—C12	116.4 (3)
N1'—Cu—O1ⁱ	97.73 (10)	C3—C11—H11A	108.2
N1ⁱ—Cu—O1ⁱ	103.76 (15)	C12—C11—H11A	108.2
N1—Cu—O1ⁱ	76.24 (15)	C3—C11—H11B	108.2
N2ⁱ—Cu—O1	89.99 (9)	C12—C11—H11B	108.2
N1'ⁱ—Cu—O1	97.73 (10)	H11A—C11—H11B	107.3
N1'—Cu—O1	82.27 (10)	N1ⁱ—C12—C14	118.9 (3)
N1ⁱ—Cu—O1	76.24 (15)	N1ⁱ—C12—C11	98.7 (3)
O1ⁱ—Cu—O1	180.0	C14—C12—C11	111.8 (3)
O3—Cl1—O2	111.7 (2)	N1ⁱ—C12—C13	106.9 (3)
O3—Cl1—O4	109.3 (2)	C14—C12—C13	110.0 (3)
O2—Cl1—O4	108.75 (18)	C11—C12—C13	109.8 (3)
O3—Cl1—O1	109.20 (19)	C14—C12—N1'ⁱ	91.3 (3)
O2—Cl1—O1	109.04 (16)	C11—C12—N1'ⁱ	117.8 (3)
O4—Cl1—O1	108.80 (16)	C13—C12—N1'ⁱ	114.8 (3)
Cl1—O1—Cu	132.88 (15)	C15—C13—C12	115.0 (3)
C12ⁱ—N1—C1	115.5 (3)	C15—C13—H13A	108.5
C12ⁱ—N1—Cu	115.9 (3)	C12—C13—H13A	108.5
C1—N1—Cu	106.3 (3)	C15—C13—H13B	108.5
C12ⁱ—N1—H1	106.1	C12—C13—H13B	108.5
C1—N1—H1	106.1	H13A—C13—H13B	107.5
Cu—N1—H1	106.1	C12—C14—H14A	109.5
C3—N2—C2	123.2 (3)	C12—C14—H14B	109.5
C3—N2—Cu	125.7 (2)	H14A—C14—H14B	109.5
C2—N2—Cu	110.97 (19)	C12—C14—H14C	109.5
C2—C1—N1	106.7 (3)	H14A—C14—H14C	109.5
C2—C1—H1A	110.4	H14B—C14—H14C	109.5
N1—C1—H1A	110.4	C20—C15—C16	118.6 (3)
C2—C1—H1B	110.4	C20—C15—C13	120.3 (3)
N1—C1—H1B	110.4	C16—C15—C13	121.1 (3)
H1A—C1—H1B	108.6	C17—C16—C15	120.6 (3)
N2—C2—C1'	106.8 (2)	C17—C16—H16	119.7
N2—C2—C1	110.5 (3)	C15—C16—H16	119.7
N2—C2—H2A	109.5	C16—C17—C18	120.6 (3)
C1'—C2—H2A	137.7	C16—C17—H17	119.7
C1—C2—H2A	109.5	C18—C17—H17	119.7
N2—C2—H2B	109.5	C19—C18—C17	119.1 (3)
C1'—C2—H2B	78.6	C19—C18—H18	120.5
C1—C2—H2B	109.5	C17—C18—H18	120.5
H2A—C2—H2B	108.1	C18—C19—C20	120.3 (3)
N2—C2—H2C	110.4	C18—C19—H19	119.9
C1'—C2—H2C	110.4	C20—C19—H19	119.9
C1—C2—H2C	76.6	C15—C20—C19	120.7 (3)
H2B—C2—H2C	133.9	C15—C20—H20	119.6
N2—C2—H2D	110.4	C19—C20—H20	119.6
C1'—C2—H2D	110.4	C1'—N1'—C12ⁱ	110.16 (17)
C1—C2—H2D	133.4	C1'—N1'—Cu	95.92 (8)
H2A—C2—H2D	76.1	C12ⁱ—N1'—Cu	114.78 (19)
H2C—C2—H2D	108.6	C1'—N1'—H1'	111.7
N2—C3—C4	125.4 (3)	C12ⁱ—N1'—H1'	111.7
N2—C3—C11	119.8 (3)	Cu—N1'—H1'	111.7
C4—C3—C11	114.8 (3)	C2—C1'—N1'	104.57 (17)
C3—C4—C5	108.8 (2)	C2—C1'—H1'1	110.8
C3—C4—H4A	109.9	N1'—C1'—H1'1	110.8
C5—C4—H4A	109.9	C2—C1'—H1'2	110.8
C3—C4—H4B	109.9	N1'—C1'—H1'2	110.8
C5—C4—H4B	109.9	H1'1—C1'—H1'2	108.9

O3—Cl1—O1—Cu	124.9 (2)	C3—C4—C5—C6	−85.3 (4)
O2—Cl1—O1—Cu	2.5 (3)	C3—C4—C5—C10	92.6 (3)
O4—Cl1—O1—Cu	−115.9 (2)	C10—C5—C6—C7	−1.5 (5)
N2—Cu—O1—Cl1	−43.1 (2)	C4—C5—C6—C7	176.4 (3)
N2ⁱ—Cu—O1—Cl1	136.9 (2)	C5—C6—C7—C8	0.3 (5)
N1'ⁱ—Cu—O1—Cl1	−141.1 (2)	C6—C7—C8—C9	0.9 (5)
N1'—Cu—O1—Cl1	38.9 (2)	C7—C8—C9—C10	−0.9 (5)
N1ⁱ—Cu—O1—Cl1	−137.4 (2)	C8—C9—C10—C5	−0.3 (5)
N1—Cu—O1—Cl1	42.6 (2)	C6—C5—C10—C9	1.5 (5)
N2—Cu—N1—C12ⁱ	151.7 (3)	C4—C5—C10—C9	−176.4 (3)
N2ⁱ—Cu—N1—C12ⁱ	−28.3 (3)	N2—C3—C11—C12	−48.0 (4)
N1'ⁱ—Cu—N1—C12ⁱ	−107.5 (5)	C4—C3—C11—C12	130.8 (3)
N1'—Cu—N1—C12ⁱ	72.5 (5)	C3—C11—C12—N1ⁱ	80.6 (4)
O1ⁱ—Cu—N1—C12ⁱ	−117.3 (3)	C3—C11—C12—C14	−45.5 (4)
O1—Cu—N1—C12ⁱ	62.7 (3)	C3—C11—C12—C13	−167.9 (3)
N2—Cu—N1—C1	21.9 (3)	C3—C11—C12—N1'ⁱ	58.3 (4)
N2ⁱ—Cu—N1—C1	−158.1 (3)	N1ⁱ—C12—C13—C15	164.9 (3)
N1'ⁱ—Cu—N1—C1	122.7 (4)	C14—C12—C13—C15	−64.7 (4)
N1'—Cu—N1—C1	−57.3 (4)	C11—C12—C13—C15	58.7 (4)
O1ⁱ—Cu—N1—C1	112.9 (3)	N1'ⁱ—C12—C13—C15	−165.9 (3)
O1—Cu—N1—C1	−67.1 (3)	C12—C13—C15—C20	−96.7 (4)
N1'ⁱ—Cu—N2—C3	30.0 (3)	C12—C13—C15—C16	83.1 (4)
N1'—Cu—N2—C3	−150.0 (3)	C20—C15—C16—C17	0.5 (5)
N1ⁱ—Cu—N2—C3	8.4 (3)	C13—C15—C16—C17	−179.3 (3)
N1—Cu—N2—C3	−171.6 (3)	C15—C16—C17—C18	−0.9 (5)
O1ⁱ—Cu—N2—C3	112.2 (3)	C16—C17—C18—C19	0.2 (5)
O1—Cu—N2—C3	−67.8 (3)	C17—C18—C19—C20	1.0 (5)
N1'ⁱ—Cu—N2—C2	−154.7 (2)	C16—C15—C20—C19	0.7 (4)
N1'—Cu—N2—C2	25.3 (2)	C13—C15—C20—C19	−179.5 (3)
N1ⁱ—Cu—N2—C2	−176.3 (2)	C18—C19—C20—C15	−1.5 (5)
N1—Cu—N2—C2	3.7 (2)	N2—Cu—N1'—C1'	−47.47 (8)
O1ⁱ—Cu—N2—C2	−72.5 (2)	N2ⁱ—Cu—N1'—C1'	132.53 (8)
O1—Cu—N2—C2	107.5 (2)	N1ⁱ—Cu—N1'—C1'	−128.9 (4)
C12ⁱ—N1—C1—C2	−172.4 (4)	N1—Cu—N1'—C1'	51.1 (4)
Cu—N1—C1—C2	−42.3 (4)	O1ⁱ—Cu—N1'—C1'	41.44 (6)
C3—N2—C2—C1'	−176.9 (3)	O1—Cu—N1'—C1'	−138.56 (6)
Cu—N2—C2—C1'	7.7 (3)	N2—Cu—N1'—C12ⁱ	−162.9 (2)
C3—N2—C2—C1	145.9 (3)	N2ⁱ—Cu—N1'—C12ⁱ	17.1 (2)
Cu—N2—C2—C1	−29.6 (3)	N1ⁱ—Cu—N1'—C12ⁱ	115.6 (4)
N1—C1—C2—N2	47.6 (5)	N1—Cu—N1'—C12ⁱ	−64.4 (4)
N1—C1—C2—C1'	−42.7 (3)	O1ⁱ—Cu—N1'—C12ⁱ	−74.0 (2)
C2—N2—C3—C4	5.9 (5)	O1—Cu—N1'—C12ⁱ	106.0 (2)
Cu—N2—C3—C4	−179.3 (2)	N2—C2—C1'—N1'	−48.2 (2)
C2—N2—C3—C11	−175.4 (3)	C1—C2—C1'—N1'	53.7 (4)
Cu—N2—C3—C11	−0.6 (4)	C12ⁱ—N1'—C1'—C2	−176.1 (3)
N2—C3—C4—C5	106.0 (4)	Cu—N1'—C1'—C2	64.78 (16)
C11—C3—C4—C5	−72.8 (3)

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···O1ⁱ	0.88	2.39	2.940 (5)	121
N1′—H1′···O2	0.88	2.29	3.104 (4)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₄₀H₄₈N₄)](ClO₄)₂
M_r	847.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.1170 (3), 16.6017 (4), 11.9910 (3)
β (°)	108.818 (3)
V (Å³)	1906.35 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.792, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9806, 4253, 3707
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.145, 1.08
No. of reflections	4253
No. of parameters	251
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −1.08

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu—N1	2.032 (4)	Cu—O1	2.662 (2)
Cu—N2	1.977 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.88	2.39	2.940 (5)	121
N1'—H1'···O2	0.88	2.29	3.104 (4)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author, e-mail: tapashir@yahoo.com.

Acknowledgements

The authors are grateful to the Bangladesh Ministry of Science, and Information and Communication Technology, Bangladesh, for awarding a research grant to TGR and to the University of Malaya for support of the crystallographic facility.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hazari, S. K. S., Roy, S. K. S., Barua, K. K. & Tiekink, E. R. T. (2008). J. Chem. Crystallogr. 38, 1–8. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals 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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1581-m1582

doi:10.1107/S1600536811042796

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

[(4E,11E)-5,7,12,14-Tetra­benzyl-7,14-di­methyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene]copper(II) bis­(per­chlorate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

metal-organic compounds

[(4E,11E)-5,7,12,14-Tetrabenzyl-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene]copper(II) bis(perchlorate)