(Acetato-κO)(2,5,5,7,9,12,12,14-octa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N,N′,N′′,N′′′)zinc perchlorate

Roy, T.G.; Hazari, S.K.S.; Barua, K.K.; Tiekink, E.R.T.

doi:10.1107/S1600536811045582

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1659-m1660

https://doi.org/10.1107/S1600536811045582

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(Acetato-κO)(2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N,N′,N′′,N′′′)zinc perchlorate

Tapashi G. Roy,^a ‡ Saroj K. S. Hazari,^a Kanak K. Barua ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, University of Chittagong, Chittagong 4331, Bangladesh, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 24 October 2011; accepted 30 October 2011; online 5 November 2011)

The Zn^II atom in the cation of the title salt, [Zn(C₂H₃O₂)(C₁₈H₄₀N₄)]ClO₄, is five-coordinated by the four N atoms of the macrocycle and the O atom of the monodentate acetate ligand. The N₄O donor set is based on a trigonal bipyramid with two N atoms occupying axial positions [N—Zn—N = 170.89 (16)°]. The perchlorate anions are associated with the cations via N—H⋯O hydrogen bonds; intramolecular N—H⋯O(acetate) interactions are also observed. The neutral aggregates are connected into an helical chain along the b axis via N—H⋯O(acetate) hydrogen bonds. The perchlorate anion was found to be disordered about a pseudo-threefold axis: the major component of the disorder had a site occupancy factor of 0.692 (11).

Related literature

For background to the synthesis, characterization, kinetic studies and biological activity of 14-membered methyl-substituted tetraazamacrocyclic ligands, their N-substituted derivatives and their metal complexes, see: Bembi et al. (1990 ); Roy et al. (2007 , 2011 ); Hazari et al. (2008 ). For additional geometric analysis, see: Addison et al. (1984 ).

Experimental

Crystal data

[Zn(C₂H₃O₂)(C₁₈H₄₀N₄)]ClO₄
M_r = 536.40
Orthorhombic, P b c a
a = 17.822 (6) Å
b = 12.995 (6) Å
c = 22.381 (7) Å
V = 5183 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 153 K
0.30 × 0.11 × 0.04 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.602, T_max = 1.000
23785 measured reflections
4534 independent reflections
4080 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.080
wR(F²) = 0.183
S = 1.29
4534 reflections
320 parameters
22 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn—O1	1.973 (4)
Zn—N1	2.124 (4)
Zn—N2	2.216 (4)
Zn—N3	2.095 (4)
Zn—N4	2.153 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O4	0.88 (4)	2.14 (5)	3.017 (10)	177 (5)
N2—H2n⋯O2ⁱ	0.88 (4)	2.60 (4)	3.375 (6)	147 (4)
N3—H3n⋯O5	0.88 (3)	2.42 (3)	3.228 (8)	153 (5)
N4—H4n⋯O2	0.88 (3)	2.25 (3)	2.978 (6)	140 (4)
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: https://doi.org/10.1107/S1600536811045582/hb6470sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045582/hb6470Isup2.hkl

checkCIF report

Comment top

In continuation of long-terms studies of the synthesis, characterization and biological activities of methyl substituted tetraazamacrocyclic ligands and their metal complexes (Bembi et al., 1990; Roy et al., 2007; Hazari et al., 2008; Roy et al., 2011), the synthesis and crystal structure of the title complex, (I), was investigated.

The asymmetric unit of (I) comprises a ZnL(O₂CMe) cation, Fig. 1, and a disordered perchlorate anion; L = 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetra-azacyclotetradecane. The Zn atom is five-coordinate, Table 1, within an N₄O donor set derived from the four N atoms of the macrocyclic ligand and an O atom of a monodentate acetate; the Zn···O2 separation is 3.132 (4) Å. Based on the value of τ = 0.71, compared with the values of t = 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal, respectively (Addison et al., 1984), the coordination geometry is distorted trigonal bipyramidal with the N2 and N4 atoms occupying axial positions; N2—Zn—N4 = 170.89 (16)°.

The cations in (I) are connected via weak N—H···O(acetate) hydrogen bonds, Table 1, which stabilize supramolecular helical chains along the b axis, Fig. 2; intramolecular N—H···O(acetate) hydrogen bonds are also present. The perchlorate anions associate with the chains via N—H···O interactions, also shown in Fig. 2.

Related literature top

For background to the synthesis, characterization, kinetic studies and biological activity of 14-membered methyl-substituted tetraazamacrocyclic ligands, their N-substituted derivatives and their metal complexes, see: Bembi et al. (1990); Roy et al. (2007, 2011); Hazari et al. (2008). For additional geometric analysis, see: Addison et al. (1984).

Experimental top

The title complex, (I), was prepared by the anion exchange reaction of [ZnL(O₂CMe)][O₂CMe] with perchlorate, where L is 2,5,5,7,9,12,12,14-octamethyl-1,4,8,11-tetra-azacyclotetradecane. Thus, [ZnL(O₂CMe)][O₂CMe] (0.495 g, 1.0 mmol) was dissolved in hot methanol (40 ml) and sodium perchlorate hexahydrate (0.460 g, 2.0 mmol) added. The reaction mixture was heated for 15 min. During heating a white product separated out. After cooling at room temperature for 30 min, the product, (I), was filtered off, washed with methanol followed by diethyl ether and dried in a desiccator over silica-gel. The yield was about 40%. Anal. Calc for C₂₀H₄₃ClN₄O₆Zn: C, 44.78; H, 7.46; N, 10.45; Zn, 12.20%. Found: C, 44.63; H, 7.32; N, 10.25; Zn, 12.01%. IR (cm^-1): 1599 ν(O₂C); 1129, 624 ν(ClO₄). Colourless prisms of (I) were obtained from slow evaporation of its methanol solution.

Structure description top

For background to the synthesis, characterization, kinetic studies and biological activity of 14-membered methyl-substituted tetraazamacrocyclic ligands, their N-substituted derivatives and their metal complexes, see: Bembi et al. (1990); Roy et al. (2007, 2011); Hazari et al. (2008). For additional geometric analysis, see: Addison et al. (1984).

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); 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 the atom-labelling scheme and displacement ellipsoids at the 50% probability level. The perchlorate counter-ion is omitted.
	Fig. 2. Helical supramolecular chains in (I) sustained by N—H···O(acetate) hydrogen bonds (blue dashed lines). Associated with these chains are the perchlorate anions held in place by N—H···O interactions (orange dashed lines).

(Acetato-κO)(2,5,5,7,9,12,12,14-octamethyl-1,4,8,11- tetraazacyclotetradecane-κ⁴N,N',N'',N''')zinc perchlorate top

Crystal data top

[Zn(C₂H₃O₂)(C₁₈H₄₀N₄)]ClO₄	F(000) = 2288
M_r = 536.40	D_x = 1.375 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7295 reflections
a = 17.822 (6) Å	θ = 2.9–30.3°
b = 12.995 (6) Å	µ = 1.09 mm⁻¹
c = 22.381 (7) Å	T = 153 K
V = 5183 (3) Å³	Prism, colourless
Z = 8	0.30 × 0.11 × 0.04 mm

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4534 independent reflections
Radiation source: fine-focus sealed tube	4080 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −20→19
T_min = 0.602, T_max = 1.000	k = −12→15
23785 measured reflections	l = −23→26

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.29	w = 1/[σ²(F_o²) + (0.0546P)² + 10.5654P] where P = (F_o² + 2F_c²)/3
4534 reflections	(Δ/σ)_max = 0.002
320 parameters	Δρ_max = 0.63 e Å⁻³
22 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Zn(C₂H₃O₂)(C₁₈H₄₀N₄)]ClO₄	V = 5183 (3) Å³
M_r = 536.40	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 17.822 (6) Å	µ = 1.09 mm⁻¹
b = 12.995 (6) Å	T = 153 K
c = 22.381 (7) Å	0.30 × 0.11 × 0.04 mm

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	4534 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4080 reflections with I > 2σ(I)
T_min = 0.602, T_max = 1.000	R_int = 0.069
23785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.080	22 restraints
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.29	w = 1/[σ²(F_o²) + (0.0546P)² + 10.5654P] where P = (F_o² + 2F_c²)/3
4534 reflections	Δρ_max = 0.63 e Å⁻³
320 parameters	Δρ_min = −0.48 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
Zn	1.01476 (3)	0.24442 (4)	0.65431 (3)	0.0345 (2)
O1	1.0503 (2)	0.2678 (3)	0.73667 (16)	0.0433 (9)
O2	1.0583 (2)	0.1015 (3)	0.76154 (16)	0.0491 (10)
N1	1.0563 (2)	0.3315 (3)	0.58108 (19)	0.0335 (9)
H1N	1.032 (3)	0.304 (4)	0.5507 (16)	0.040*
N2	0.9363 (2)	0.3757 (3)	0.6641 (2)	0.0392 (10)
H2N	0.952 (3)	0.419 (3)	0.6913 (19)	0.047*
N3	0.9287 (2)	0.1464 (3)	0.62552 (19)	0.0349 (10)
H3N	0.923 (3)	0.166 (4)	0.5881 (9)	0.042*
N4	1.0846 (2)	0.1156 (3)	0.63040 (19)	0.0351 (10)
H4N	1.093 (3)	0.086 (4)	0.6652 (12)	0.042*
C1	1.0292 (3)	0.4397 (4)	0.5913 (2)	0.0379 (12)
H1	1.0340	0.4792	0.5531	0.046*
C2	1.0757 (3)	0.4927 (4)	0.6390 (3)	0.0444 (14)
H2A	1.0825	0.4461	0.6730	0.067*
H2B	1.0498	0.5552	0.6524	0.067*
H2C	1.1248	0.5111	0.6225	0.067*
C3	0.9465 (3)	0.4332 (4)	0.6080 (2)	0.0404 (13)
H3A	0.9259	0.5035	0.6126	0.048*
H3B	0.9185	0.3985	0.5755	0.048*
C4	0.8573 (3)	0.3561 (5)	0.6842 (3)	0.0467 (14)
C5	0.8056 (4)	0.4482 (5)	0.6709 (4)	0.0645 (19)
H5A	0.8290	0.5115	0.6856	0.097*
H5B	0.7572	0.4380	0.6909	0.097*
H5C	0.7976	0.4535	0.6277	0.097*
C6	0.8606 (4)	0.3452 (5)	0.7522 (3)	0.0587 (17)
H6A	0.8995	0.2952	0.7629	0.088*
H6B	0.8119	0.3214	0.7670	0.088*
H6C	0.8725	0.4121	0.7701	0.088*
C7	0.8231 (3)	0.2632 (4)	0.6516 (3)	0.0477 (15)
H7A	0.8237	0.2799	0.6084	0.057*
H7B	0.7697	0.2597	0.6636	0.057*
C8	0.8554 (3)	0.1523 (4)	0.6580 (3)	0.0439 (13)
H8	0.8203	0.1065	0.6354	0.053*
C9	0.8603 (3)	0.1078 (5)	0.7196 (3)	0.0535 (16)
H9A	0.8657	0.0329	0.7169	0.080*
H9B	0.8146	0.1247	0.7418	0.080*
H9C	0.9039	0.1368	0.7403	0.080*
C10	0.9591 (3)	0.0393 (4)	0.6200 (2)	0.0369 (12)
H10	0.9632	0.0086	0.6608	0.044*
C11	0.9102 (3)	−0.0302 (4)	0.5816 (3)	0.0435 (13)
H11A	0.8634	−0.0454	0.6028	0.065*
H11B	0.9370	−0.0945	0.5734	0.065*
H11C	0.8987	0.0046	0.5438	0.065*
C12	1.0379 (3)	0.0472 (4)	0.5929 (2)	0.0372 (12)
H12A	1.0610	−0.0220	0.5907	0.045*
H12B	1.0347	0.0752	0.5518	0.045*
C13	1.1625 (3)	0.1373 (4)	0.6071 (2)	0.0397 (12)
C14	1.2063 (3)	0.1843 (5)	0.6585 (3)	0.0494 (15)
H14A	1.2567	0.2030	0.6448	0.074*
H14B	1.2101	0.1343	0.6911	0.074*
H14C	1.1802	0.2461	0.6728	0.074*
C15	1.2013 (3)	0.0373 (5)	0.5876 (3)	0.0500 (15)
H15A	1.2539	0.0515	0.5778	0.075*
H15B	1.1758	0.0094	0.5524	0.075*
H15C	1.1989	−0.0129	0.6202	0.075*
C16	1.1590 (3)	0.2100 (4)	0.5530 (2)	0.0359 (12)
H16A	1.1229	0.1803	0.5242	0.043*
H16B	1.2089	0.2089	0.5336	0.043*
C17	1.1374 (3)	0.3234 (4)	0.5624 (2)	0.0352 (12)
H17	1.1693	0.3523	0.5951	0.042*
C18	1.1531 (3)	0.3833 (4)	0.5052 (2)	0.0449 (13)
H18A	1.2058	0.3746	0.4940	0.067*
H18B	1.1426	0.4564	0.5118	0.067*
H18C	1.1209	0.3573	0.4731	0.067*
C19	1.0657 (3)	0.1956 (4)	0.7740 (2)	0.0390 (12)
C20	1.0900 (4)	0.2282 (5)	0.8341 (3)	0.0555 (16)
H20A	1.0463	0.2319	0.8606	0.083*
H20B	1.1137	0.2961	0.8316	0.083*
H20C	1.1260	0.1783	0.8500	0.083*
Cl	0.90070 (8)	0.24995 (10)	0.45914 (6)	0.0454 (4)	0.692 (11)
O3	0.8898 (3)	0.2216 (4)	0.39872 (16)	0.0672 (13)	0.692 (11)
O4	0.9752 (3)	0.2296 (10)	0.4786 (4)	0.102 (4)	0.692 (11)
O5	0.8516 (5)	0.1844 (6)	0.4969 (3)	0.081 (3)	0.692 (11)
O6	0.8776 (6)	0.3529 (4)	0.4698 (3)	0.074 (3)	0.692 (11)
Cl1	0.90070 (8)	0.24995 (10)	0.45914 (6)	0.0454 (4)	0.308 (11)
O13	0.8898 (3)	0.2216 (4)	0.39872 (16)	0.0672 (13)	0.308 (11)
O14	0.9755 (6)	0.2979 (15)	0.4630 (7)	0.102 (4)	0.308 (11)
O15	0.8985 (12)	0.1657 (9)	0.4985 (5)	0.081 (3)	0.308 (11)
O16	0.8483 (9)	0.3283 (11)	0.4765 (7)	0.074 (3)	0.308 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0378 (4)	0.0312 (4)	0.0344 (4)	−0.0006 (3)	0.0006 (2)	0.0000 (2)
O1	0.054 (2)	0.042 (2)	0.034 (2)	0.0042 (18)	−0.0023 (17)	−0.0004 (17)
O2	0.071 (3)	0.038 (2)	0.038 (2)	−0.006 (2)	−0.0047 (19)	0.0031 (18)
N1	0.036 (2)	0.029 (2)	0.035 (2)	0.0017 (19)	−0.0041 (18)	−0.0017 (18)
N2	0.039 (3)	0.036 (3)	0.042 (3)	0.003 (2)	0.001 (2)	−0.004 (2)
N3	0.036 (2)	0.032 (2)	0.037 (2)	0.0009 (18)	0.0018 (19)	−0.0004 (19)
N4	0.038 (2)	0.033 (2)	0.034 (2)	0.0042 (19)	−0.0036 (19)	0.0014 (19)
C1	0.053 (3)	0.025 (3)	0.036 (3)	0.004 (2)	0.004 (2)	0.000 (2)
C2	0.053 (4)	0.033 (3)	0.047 (3)	−0.008 (3)	0.012 (3)	−0.009 (2)
C3	0.044 (3)	0.037 (3)	0.041 (3)	0.008 (2)	−0.001 (2)	−0.005 (2)
C4	0.044 (3)	0.041 (3)	0.055 (4)	0.000 (3)	0.007 (3)	−0.008 (3)
C5	0.049 (4)	0.045 (4)	0.100 (5)	0.009 (3)	0.005 (4)	−0.014 (4)
C6	0.058 (4)	0.057 (4)	0.060 (4)	−0.013 (3)	0.024 (3)	−0.017 (3)
C7	0.034 (3)	0.050 (4)	0.059 (4)	0.000 (3)	0.004 (3)	−0.013 (3)
C8	0.044 (3)	0.034 (3)	0.053 (3)	−0.005 (2)	0.006 (3)	−0.009 (3)
C9	0.053 (4)	0.052 (4)	0.056 (4)	−0.008 (3)	0.014 (3)	−0.005 (3)
C10	0.044 (3)	0.028 (3)	0.038 (3)	0.001 (2)	−0.003 (2)	0.001 (2)
C11	0.051 (3)	0.032 (3)	0.047 (3)	−0.006 (3)	0.005 (3)	−0.003 (2)
C12	0.039 (3)	0.034 (3)	0.038 (3)	0.004 (2)	0.000 (2)	−0.005 (2)
C13	0.037 (3)	0.036 (3)	0.046 (3)	0.005 (2)	−0.003 (2)	−0.002 (2)
C14	0.046 (3)	0.054 (4)	0.048 (4)	−0.002 (3)	−0.006 (3)	0.004 (3)
C15	0.044 (3)	0.045 (3)	0.061 (4)	0.008 (3)	0.002 (3)	0.002 (3)
C16	0.034 (3)	0.035 (3)	0.039 (3)	0.001 (2)	0.000 (2)	−0.005 (2)
C17	0.038 (3)	0.035 (3)	0.032 (3)	−0.001 (2)	0.000 (2)	−0.004 (2)
C18	0.049 (3)	0.037 (3)	0.049 (3)	−0.003 (3)	0.005 (3)	0.002 (3)
C19	0.038 (3)	0.044 (3)	0.035 (3)	0.002 (2)	0.007 (2)	0.010 (2)
C20	0.076 (5)	0.046 (4)	0.045 (3)	−0.008 (3)	−0.006 (3)	0.001 (3)
Cl	0.0548 (9)	0.0363 (7)	0.0450 (8)	0.0057 (6)	−0.0117 (6)	−0.0036 (6)
O3	0.090 (4)	0.066 (3)	0.045 (3)	0.003 (3)	−0.022 (2)	−0.010 (2)
O4	0.060 (4)	0.161 (11)	0.085 (6)	0.047 (6)	−0.037 (4)	−0.066 (7)
O5	0.103 (8)	0.070 (5)	0.069 (4)	−0.023 (5)	−0.008 (5)	0.019 (3)
O6	0.122 (8)	0.025 (4)	0.076 (4)	0.008 (4)	−0.001 (4)	0.001 (3)
Cl1	0.0548 (9)	0.0363 (7)	0.0450 (8)	0.0057 (6)	−0.0117 (6)	−0.0036 (6)
O13	0.090 (4)	0.066 (3)	0.045 (3)	0.003 (3)	−0.022 (2)	−0.010 (2)
O14	0.060 (4)	0.161 (11)	0.085 (6)	0.047 (6)	−0.037 (4)	−0.066 (7)
O15	0.103 (8)	0.070 (5)	0.069 (4)	−0.023 (5)	−0.008 (5)	0.019 (3)
O16	0.122 (8)	0.025 (4)	0.076 (4)	0.008 (4)	−0.001 (4)	0.001 (3)

Geometric parameters (Å, º) top

Zn—O1	1.973 (4)	C9—H9A	0.9800
Zn—N1	2.124 (4)	C9—H9B	0.9800
Zn—N2	2.216 (4)	C9—H9C	0.9800
Zn—N3	2.095 (4)	C10—C11	1.521 (7)
Zn—N4	2.153 (4)	C10—C12	1.534 (7)
O1—C19	1.286 (6)	C10—H10	1.0000
O2—C19	1.261 (7)	C11—H11A	0.9800
N1—C1	1.504 (6)	C11—H11B	0.9800
N1—C17	1.508 (6)	C11—H11C	0.9800
N1—H1N	0.882 (10)	C12—H12A	0.9900
N2—C3	1.473 (7)	C12—H12B	0.9900
N2—C4	1.500 (7)	C13—C14	1.518 (8)
N2—H2N	0.878 (10)	C13—C16	1.537 (7)
N3—C8	1.497 (7)	C13—C15	1.535 (8)
N3—C10	1.499 (6)	C14—H14A	0.9800
N3—H3N	0.879 (10)	C14—H14B	0.9800
N4—C12	1.478 (7)	C14—H14C	0.9800
N4—C13	1.511 (7)	C15—H15A	0.9800
N4—H4N	0.880 (10)	C15—H15B	0.9800
C1—C2	1.518 (7)	C15—H15C	0.9800
C1—C3	1.523 (8)	C16—C17	1.537 (7)
C1—H1	1.0000	C16—H16A	0.9900
C2—H2A	0.9800	C16—H16B	0.9900
C2—H2B	0.9800	C17—C18	1.524 (7)
C2—H2C	0.9800	C17—H17	1.0000
C3—H3A	0.9900	C18—H18A	0.9800
C3—H3B	0.9900	C18—H18B	0.9800
C4—C6	1.528 (9)	C18—H18C	0.9800
C4—C7	1.537 (8)	C19—C20	1.476 (8)
C4—C5	1.540 (8)	C20—H20A	0.9800
C5—H5A	0.9800	C20—H20B	0.9800
C5—H5B	0.9800	C20—H20C	0.9800
C5—H5C	0.9800	Cl—O6	1.420 (5)
C6—H6A	0.9800	Cl—O3	1.415 (4)
C6—H6B	0.9800	Cl—O4	1.422 (5)
C6—H6C	0.9800	Cl—O5	1.484 (5)
C7—C8	1.559 (8)	Cl1—O15	1.405 (7)
C7—H7A	0.9900	Cl1—O16	1.435 (7)
C7—H7B	0.9900	Cl1—O13	1.415 (4)
C8—C9	1.497 (8)	Cl1—O14	1.474 (8)
C8—H8	1.0000

O1—Zn—N3	128.04 (17)	C7—C8—H8	105.8
O1—Zn—N1	121.79 (16)	C8—C9—H9A	109.5
N3—Zn—N1	109.96 (17)	C8—C9—H9B	109.5
O1—Zn—N4	99.58 (16)	H9A—C9—H9B	109.5
N3—Zn—N4	82.75 (16)	C8—C9—H9C	109.5
N1—Zn—N4	91.23 (16)	H9A—C9—H9C	109.5
O1—Zn—N2	89.52 (16)	H9B—C9—H9C	109.5
N3—Zn—N2	92.08 (17)	N3—C10—C11	113.0 (4)
N1—Zn—N2	83.46 (17)	N3—C10—C12	107.5 (4)
N4—Zn—N2	170.89 (16)	C11—C10—C12	109.9 (4)
C19—O1—Zn	124.3 (4)	N3—C10—H10	108.7
C1—N1—C17	114.5 (4)	C11—C10—H10	108.7
C1—N1—Zn	105.6 (3)	C12—C10—H10	108.7
C17—N1—Zn	120.6 (3)	C10—C11—H11A	109.5
C1—N1—H1N	109 (4)	C10—C11—H11B	109.5
C17—N1—H1N	104 (4)	H11A—C11—H11B	109.5
Zn—N1—H1N	102 (4)	C10—C11—H11C	109.5
C3—N2—C4	117.2 (4)	H11A—C11—H11C	109.5
C3—N2—Zn	103.2 (3)	H11B—C11—H11C	109.5
C4—N2—Zn	119.4 (3)	N4—C12—C10	109.3 (4)
C3—N2—H2N	103 (4)	N4—C12—H12A	109.8
C4—N2—H2N	102 (4)	C10—C12—H12A	109.8
Zn—N2—H2N	111 (4)	N4—C12—H12B	109.8
C8—N3—C10	113.7 (4)	C10—C12—H12B	109.8
C8—N3—Zn	117.3 (3)	H12A—C12—H12B	108.3
C10—N3—Zn	109.0 (3)	N4—C13—C14	106.6 (4)
C8—N3—H3N	110 (4)	N4—C13—C16	110.4 (4)
C10—N3—H3N	103 (4)	C14—C13—C16	111.8 (5)
Zn—N3—H3N	102 (4)	N4—C13—C15	110.7 (4)
C12—N4—C13	115.7 (4)	C14—C13—C15	109.0 (5)
C12—N4—Zn	106.5 (3)	C16—C13—C15	108.4 (4)
C13—N4—Zn	118.1 (3)	C13—C14—H14A	109.5
C12—N4—H4N	109 (4)	C13—C14—H14B	109.5
C13—N4—H4N	104 (4)	H14A—C14—H14B	109.5
Zn—N4—H4N	102 (4)	C13—C14—H14C	109.5
N1—C1—C2	110.9 (4)	H14A—C14—H14C	109.5
N1—C1—C3	107.2 (4)	H14B—C14—H14C	109.5
C2—C1—C3	112.4 (4)	C13—C15—H15A	109.5
N1—C1—H1	108.8	C13—C15—H15B	109.5
C2—C1—H1	108.8	H15A—C15—H15B	109.5
C3—C1—H1	108.8	C13—C15—H15C	109.5
C1—C2—H2A	109.5	H15A—C15—H15C	109.5
C1—C2—H2B	109.5	H15B—C15—H15C	109.5
H2A—C2—H2B	109.5	C13—C16—C17	119.5 (4)
C1—C2—H2C	109.5	C13—C16—H16A	107.5
H2A—C2—H2C	109.5	C17—C16—H16A	107.5
H2B—C2—H2C	109.5	C13—C16—H16B	107.5
N2—C3—C1	110.9 (4)	C17—C16—H16B	107.5
N2—C3—H3A	109.5	H16A—C16—H16B	107.0
C1—C3—H3A	109.5	N1—C17—C18	111.9 (4)
N2—C3—H3B	109.5	N1—C17—C16	110.2 (4)
C1—C3—H3B	109.5	C18—C17—C16	109.2 (4)
H3A—C3—H3B	108.1	N1—C17—H17	108.5
N2—C4—C6	106.2 (5)	C18—C17—H17	108.5
N2—C4—C7	111.3 (4)	C16—C17—H17	108.5
C6—C4—C7	114.6 (5)	C17—C18—H18A	109.5
N2—C4—C5	111.8 (5)	C17—C18—H18B	109.5
C6—C4—C5	106.7 (5)	H18A—C18—H18B	109.5
C7—C4—C5	106.3 (5)	C17—C18—H18C	109.5
C4—C5—H5A	109.5	H18A—C18—H18C	109.5
C4—C5—H5B	109.5	H18B—C18—H18C	109.5
H5A—C5—H5B	109.5	O2—C19—O1	122.8 (5)
C4—C5—H5C	109.5	O2—C19—C20	120.7 (5)
H5A—C5—H5C	109.5	O1—C19—C20	116.4 (5)
H5B—C5—H5C	109.5	C19—C20—H20A	109.5
C4—C6—H6A	109.5	C19—C20—H20B	109.5
C4—C6—H6B	109.5	H20A—C20—H20B	109.5
H6A—C6—H6B	109.5	C19—C20—H20C	109.5
C4—C6—H6C	109.5	H20A—C20—H20C	109.5
H6A—C6—H6C	109.5	H20B—C20—H20C	109.5
H6B—C6—H6C	109.5	O6—Cl—O3	111.5 (4)
C4—C7—C8	122.4 (5)	O6—Cl—O4	113.3 (4)
C4—C7—H7A	106.7	O3—Cl—O4	111.8 (4)
C8—C7—H7A	106.7	O6—Cl—O5	106.0 (4)
C4—C7—H7B	106.7	O3—Cl—O5	108.3 (4)
C8—C7—H7B	106.7	O4—Cl—O5	105.6 (4)
H7A—C7—H7B	106.6	O15—Cl1—O16	111.4 (7)
N3—C8—C9	112.1 (5)	O15—Cl1—O13	113.1 (6)
N3—C8—C7	108.9 (4)	O16—Cl1—O13	110.8 (6)
C9—C8—C7	117.6 (5)	O15—Cl1—O14	108.5 (6)
N3—C8—H8	105.8	O16—Cl1—O14	105.8 (6)
C9—C8—H8	105.8	O13—Cl1—O14	106.9 (6)

N3—Zn—O1—C19	48.1 (5)	C3—N2—C4—C6	−153.3 (5)
N1—Zn—O1—C19	−137.6 (4)	Zn—N2—C4—C6	80.8 (5)
N4—Zn—O1—C19	−40.2 (4)	C3—N2—C4—C7	81.4 (6)
N2—Zn—O1—C19	140.4 (4)	Zn—N2—C4—C7	−44.5 (6)
O1—Zn—N1—C1	−66.6 (4)	C3—N2—C4—C5	−37.3 (7)
N3—Zn—N1—C1	108.6 (3)	Zn—N2—C4—C5	−163.1 (4)
N4—Zn—N1—C1	−168.7 (3)	N2—C4—C7—C8	63.1 (7)
N2—Zn—N1—C1	18.7 (3)	C6—C4—C7—C8	−57.4 (7)
O1—Zn—N1—C17	65.2 (4)	C5—C4—C7—C8	−175.0 (5)
N3—Zn—N1—C17	−119.6 (4)	C10—N3—C8—C9	57.6 (6)
N4—Zn—N1—C17	−36.9 (4)	Zn—N3—C8—C9	−71.3 (5)
N2—Zn—N1—C17	150.5 (4)	C10—N3—C8—C7	−170.5 (4)
O1—Zn—N2—C3	134.4 (3)	Zn—N3—C8—C7	60.6 (5)
N3—Zn—N2—C3	−97.6 (3)	C4—C7—C8—N3	−71.8 (7)
N1—Zn—N2—C3	12.3 (3)	C4—C7—C8—C9	57.1 (8)
O1—Zn—N2—C4	−93.4 (4)	C8—N3—C10—C11	65.2 (6)
N3—Zn—N2—C4	34.7 (4)	Zn—N3—C10—C11	−161.8 (4)
N1—Zn—N2—C4	144.5 (4)	C8—N3—C10—C12	−173.3 (4)
O1—Zn—N3—C8	48.5 (4)	Zn—N3—C10—C12	−40.3 (5)
N1—Zn—N3—C8	−126.3 (4)	C13—N4—C12—C10	−175.8 (4)
N4—Zn—N3—C8	145.0 (4)	Zn—N4—C12—C10	−42.4 (5)
N2—Zn—N3—C8	−42.5 (4)	N3—C10—C12—N4	56.2 (5)
O1—Zn—N3—C10	−82.6 (4)	C11—C10—C12—N4	179.6 (4)
N1—Zn—N3—C10	102.6 (3)	C12—N4—C13—C14	−165.8 (4)
N4—Zn—N3—C10	13.9 (3)	Zn—N4—C13—C14	66.3 (5)
N2—Zn—N3—C10	−173.6 (3)	C12—N4—C13—C16	72.6 (5)
O1—Zn—N4—C12	143.2 (3)	Zn—N4—C13—C16	−55.3 (5)
N3—Zn—N4—C12	15.7 (3)	C12—N4—C13—C15	−47.5 (6)
N1—Zn—N4—C12	−94.3 (3)	Zn—N4—C13—C15	−175.3 (3)
O1—Zn—N4—C13	−84.7 (4)	N4—C13—C16—C17	70.6 (6)
N3—Zn—N4—C13	147.8 (4)	C14—C13—C16—C17	−47.8 (6)
N1—Zn—N4—C13	37.8 (4)	C15—C13—C16—C17	−167.9 (5)
C17—N1—C1—C2	−58.5 (5)	C1—N1—C17—C18	−58.2 (6)
Zn—N1—C1—C2	76.7 (4)	Zn—N1—C17—C18	174.0 (3)
C17—N1—C1—C3	178.5 (4)	C1—N1—C17—C16	−179.8 (4)
Zn—N1—C1—C3	−46.3 (4)	Zn—N1—C17—C16	52.3 (5)
C4—N2—C3—C1	−175.7 (4)	C13—C16—C17—N1	−68.1 (6)
Zn—N2—C3—C1	−42.2 (5)	C13—C16—C17—C18	168.7 (5)
N1—C1—C3—N2	62.6 (5)	Zn—O1—C19—O2	−1.1 (7)
C2—C1—C3—N2	−59.5 (6)	Zn—O1—C19—C20	−178.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O4	0.88 (4)	2.14 (5)	3.017 (10)	177 (5)
N2—H2n···O2ⁱ	0.88 (4)	2.60 (4)	3.375 (6)	147 (4)
N3—H3n···O5	0.88 (3)	2.42 (3)	3.228 (8)	153 (5)
N4—H4n···O2	0.88 (3)	2.25 (3)	2.978 (6)	140 (4)

Symmetry code: (i) −x+2, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₂H₃O₂)(C₁₈H₄₀N₄)]ClO₄
M_r	536.40
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	153
a, b, c (Å)	17.822 (6), 12.995 (6), 22.381 (7)
V (Å³)	5183 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.30 × 0.11 × 0.04

Data collection
Diffractometer	Rigaku AFC12K/SATURN724
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.602, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	23785, 4534, 4080
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.080, 0.183, 1.29
No. of reflections	4534
No. of parameters	320
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0546P)² + 10.5654P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.48

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Zn—O1	1.973 (4)	Zn—N3	2.095 (4)
Zn—N1	2.124 (4)	Zn—N4	2.153 (4)
Zn—N2	2.216 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O4	0.88 (4)	2.14 (5)	3.017 (10)	177 (5)
N2—H2n···O2ⁱ	0.88 (4)	2.60 (4)	3.375 (6)	147 (4)
N3—H3n···O5	0.88 (3)	2.42 (3)	3.228 (8)	153 (5)
N4—H4n···O2	0.88 (3)	2.25 (3)	2.978 (6)	140 (4)

Symmetry code: (i) −x+2, y+1/2, −z+3/2.

Footnotes

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

Acknowledgements

The authors are grateful to the Ministry of National Science, Information & Communication Technology (NSICT), Bangladesh, for the award of a research grant to TGR.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Bembi, R., Roy, T. G., Jhanji, A. K. & Maheswari, A. (1990). J. Chem. Soc. Dalton Trans. pp. 3531–3534. CrossRef Web of Science 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
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Roy, T. G., Hazari, S. K. S., Dey, B. K., Miah, H. A., Olbrich, F. & Rehder, D. (2007). Inorg. Chem. 46, 5372–5380. Web of Science CSD CrossRef PubMed CAS Google Scholar
Roy, T. G., Hazari, S. K. S., Dey, B. K., Nath, B. C., Dutta, A., Olbrich, F. & Rehder, D. (2011). Inorg. Chim. Acta, 371, 63–70. 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

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