[μ-(4S,5S,15S,16S)-10,21-Di-tert-butyl-4,5,15,16-tetra­phenyl-3,6,14,17-tetra­aza­tricyclo­[17.3.1.18,12]tetra­cosa-1(23),8,10,12(24),19,21-hexa­ene-23,24-diolato-κ8N3,N6,O23,O24:N14N17,O23,O24]bis­[(acetato-κO)zinc(II)] ethanol disolvate

Fan, L.-J.; Ma, J.-F.; Liu, J.

doi:10.1107/S1600536809021990

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages m777-m778

doi:10.1107/S1600536809021990

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[μ-(4S,5S,15S,16S)-10,21-Di-tert-butyl-4,5,15,16-tetraphenyl-3,6,14,17-tetraazatricyclo[17.3.1.1^8,12]tetracosa-1(23),8,10,12(24),19,21-hexaene-23,24-diolato-κ⁸N³,N⁶,O²³,O²⁴:N¹⁴N¹⁷,O²³,O²⁴]bis[(acetato-κO)zinc(II)] ethanol disolvate

Li-Jing Fan,^a ^* Jian-Fang Ma ^a and Jie Liu ^a

^aDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China
^*Correspondence e-mail: majf247nenu@yahoo.com.cn

(Received 28 April 2009; accepted 10 June 2009; online 17 June 2009)

In the title compound, [Zn₂(C₃₆H₄₂N₄O₂)(CH₃COO)₂]·2CH₃CH₂OH, a centrosymmetric dinuclear zinc macrocyclic complex is accompanied by two half-occupied ethanol solvent molecues resulting in a 1:2 macrocycle–solvent composition. The Zn^II atom has a square-pyramidal geometry arising from an N₂O₃ donor set, being coordinated by two N atoms and two O atoms from the macrocyclic ligand in the equatorial sites and one O atom from an acetate anion in the apical site. The two Zn^II atoms are linked by two phenolate O atoms, generating a four-membered Zn₂O₂ ring at the centre of the macrocycle. The tert-butyl group shows rotational disorder over two sets of sites in a 0.552 (12):0.448 (12) ratio. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds are seen and a short intramolecular C—H⋯O contact occurs.

Related literature

For background to the biochemistry of zinc compounds, see: Lipscomb & Straeter (1996 ); Burley et al. (1990 ); Roderick & Mathews (1993 ); Bazzicalupi et al. (1997 ). For related structures, see: Dutta et al. (2005 ); Liu et al. (2007 ). For further synthetic details, see: Tian et al. (1999 ).

Experimental

Crystal data

[Zn₂(C₃₆H₄₂N₄O₂)(C₂H₃O₂)₂]·2C₂H₆O
M_r = 903.70
Triclinic, $[P \overline 1]$
a = 9.0566 (3) Å
b = 10.8410 (5) Å
c = 14.2828 (5) Å
α = 71.246 (4)°
β = 86.514 (3)°
γ = 78.362 (3)°
V = 1300.56 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 293 K
0.45 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Gemini R Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.748, T_max = 0.824
11846 measured reflections
6368 independent reflections
4133 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.253
S = 1.05
6368 reflections
285 parameters
655 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.15 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.025 (5)
Zn1—O3	2.033 (4)
Zn1—O3ⁱ	2.043 (4)
Zn1—N2	2.100 (5)
Zn1—N1	2.104 (5)
Symmetry code: (i) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O2	0.97	2.45	3.246 (10)	139
N1—H1N⋯O4	0.86 (7)	2.23 (7)	2.952 (9)	141 (6)
N2—H2N⋯O5ⁱⁱ	0.87 (4)	2.13 (4)	2.999 (9)	175 (4)
O4—H4⋯O2ⁱⁱⁱ	0.82	2.06	2.768 (10)	145
O5—H5⋯O1^iv	0.82	1.92	2.700 (9)	159
Symmetry codes: (ii) -x+1, -y, -z+1; (iii) -x, -y+1, -z+1; (iv) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021990/hb2961sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021990/hb2961Isup2.hkl

checkCIF report

Comment top

Zinc is an essential element for all forms of life and plays a critical role in various functions, both structural and catalytic, in proteins and enzymes (Lipscomb et al.,1996; Burley et al.,1990; Roderick & Mathews, 1993). In addition, some synthetic dinuclear zinc(II) compounds appears to have functions in dephosphorylation (Bazzicalupi et al.,1997). As part of out studies in this area, the title compound, (I), a new dinuclear zinc(II) compound has been synthesized, and its structure is reported here (Fig. 1).

The complete macrocycle is generated by a crystallographic inversion centre The coordination environment around zinc is a square-pyramid with two N atoms and two O atoms from the macrocyclic (C₃₆H₄₄N₄O₂) ligand occupying the basal positions and one O atom from a acetate anion occupying the apical position. The two zinc atoms are bridged by two phenolate O atoms to generate a four-membered Zn₂O₂ring. The Zn—O and Zn—N distances are normal (Dutta et al., 2005).

Related literature top

For background to the biochemistry of zinc compounds, see: Lipscomb & Straeter (1996); Burley et al. (1990); Roderick & Mathews (1993); Bazzicalupi et al. (1997). For related structures, see: Dutta et al. (2005); Liu et al. (2007). For further synthetic details, see: Tian et al. (1999).

Experimental top

To a stirred methanol (30 ml) suspension of the schiff base C₃₆H₄₀N₄O₂ (0.5 mmol), which was synthesized by the methods reported previously (Tian et al., 1999), was added solid NaBH₄ (0.5 g, 13 mmol) in small portions. Over a period of 0.5 h when the red solid material gradually went into solution, and eventually an amorphous yellow mass precipitated. After 1 h, the formed yellow powder products (H₂L) were filtrated off and washed thoroughly with water and ethanol, and dried in avacuum (yield 54%).

The title compound was prepared by reaction between the ligand (H₂L) and zinc acetate. A mixture of H₂L (0.108 g, 0.2 mmol) and Zn(OAc)₂.6H₂O (0.117 g, 0.4 mmol) in ethanol (20 ml) was heated with stirring to yield a clear pale yellow solution. Filtration and cooling to room temperature resulted in formation of a crystalline precipitate. Recrystallization by slow evaporation of an ethanol solution of the compound resulted in well-formed yellow blocks of (I) (yield 46%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLEASE PROVIDE PROGRAM NAME AND REFERENCE; software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I). Displaceement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

[µ-(4S,5S,15S,16S)-10,21-Di-tert-butyl- 4,5,15,16-tetraphenyl-3,6,14,17-tetraazatricyclo[17.3.1.1^8,12]tetracosa- 1(23),8,10,12 (24),19,21-hexaene-23,24-diolato- κ⁸N³,N⁶,O²³,O²⁴: N¹⁴N¹⁷,O²³,O²⁴]bis[(acetato- κO)zinc(II)] ethanol disolvate top

Crystal data top

[Zn₂(C₃₆H₄₂N₄O₂)(C₂H₃O₂)₂]·2C₂H₆O	Z = 1
M_r = 903.70	F(000) = 476
Triclinic, P1	D_x = 1.154 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0566 (3) Å	Cell parameters from 2131 reflections
b = 10.8410 (5) Å	θ = 3.1–26.5°
c = 14.2828 (5) Å	µ = 0.97 mm⁻¹
α = 71.246 (4)°	T = 293 K
β = 86.514 (3)°	Block, yellow
γ = 78.362 (3)°	0.45 × 0.25 × 0.20 mm
V = 1300.56 (9) Å³

Data collection top

Oxford Diffraction Gemini R Ultra diffractometer	6368 independent reflections
Radiation source: fine-focus sealed tube	4133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 10.0 pixels mm^-1	θ_max = 29.8°, θ_min = 4.4°
ω scans	h = −11→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −14→14
T_min = 0.748, T_max = 0.824	l = −18→19
11846 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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.253	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1644P)²] where P = (F_o² + 2F_c²)/3
6368 reflections	(Δ/σ)_max < 0.001
285 parameters	Δρ_max = 1.15 e Å⁻³
655 restraints	Δρ_min = −0.77 e Å⁻³

Crystal data top

[Zn₂(C₃₆H₄₂N₄O₂)(C₂H₃O₂)₂]·2C₂H₆O	γ = 78.362 (3)°
M_r = 903.70	V = 1300.56 (9) Å³
Triclinic, P1	Z = 1
a = 9.0566 (3) Å	Mo Kα radiation
b = 10.8410 (5) Å	µ = 0.97 mm⁻¹
c = 14.2828 (5) Å	T = 293 K
α = 71.246 (4)°	0.45 × 0.25 × 0.20 mm
β = 86.514 (3)°

Data collection top

Oxford Diffraction Gemini R Ultra diffractometer	6368 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	4133 reflections with I > 2σ(I)
T_min = 0.748, T_max = 0.824	R_int = 0.035
11846 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	655 restraints
wR(F²) = 0.253	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.15 e Å⁻³
6368 reflections	Δρ_min = −0.77 e Å⁻³
285 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)
Zn1	0.05562 (7)	0.12433 (7)	0.50054 (5)	0.0340 (3)
C1	−0.1270 (7)	−0.0328 (6)	0.6667 (4)	0.0348 (12)
C2	−0.0490 (7)	−0.0070 (7)	0.7384 (5)	0.0393 (13)
C3	−0.0831 (8)	−0.0639 (8)	0.8383 (5)	0.0466 (15)
H3	−0.0290	−0.0493	0.8858	0.056*
C4	0.0649 (7)	0.0818 (7)	0.7131 (5)	0.0414 (13)
H4A	0.0126	0.1736	0.6901	0.050*
H4B	0.1207	0.0693	0.7724	0.050*
C5	0.3043 (7)	0.1208 (6)	0.6217 (5)	0.0378 (12)
C6	0.3920 (8)	0.1117 (7)	0.7007 (6)	0.0465 (14)
H6	0.3657	0.0661	0.7646	0.056*
C7	0.5162 (8)	0.1685 (8)	0.6863 (6)	0.0509 (15)
H7	0.5743	0.1609	0.7401	0.061*
C8	0.5554 (8)	0.2371 (8)	0.5923 (6)	0.0489 (15)
H8	0.6404	0.2755	0.5821	0.059*
C9	0.4671 (7)	0.2484 (7)	0.5129 (6)	0.0454 (14)
H9	0.4931	0.2953	0.4493	0.055*
C10	0.3420 (7)	0.1915 (6)	0.5269 (5)	0.0375 (12)
C11	0.3368 (7)	0.1223 (7)	0.3804 (5)	0.0397 (13)
H11A	0.3798	0.0336	0.4223	0.048*
H11B	0.4192	0.1649	0.3484	0.048*
C12	0.2376 (7)	0.1125 (7)	0.3023 (5)	0.0397 (13)
C13	0.2679 (8)	0.1641 (8)	0.2016 (5)	0.0513 (15)
H13	0.3412	0.2163	0.1820	0.062*
C14	0.1915 (9)	0.1397 (8)	0.1302 (5)	0.0530 (16)
C15	0.2210 (10)	0.2038 (10)	0.0195 (6)	0.070 (2)
C16	0.0903 (18)	0.274 (2)	−0.0392 (19)	0.106 (6)*	0.448 (12)
H16A	0.0088	0.2276	−0.0169	0.159*	0.448 (12)
H16B	0.1117	0.2812	−0.1072	0.159*	0.448 (12)
H16C	0.0625	0.3617	−0.0331	0.159*	0.448 (12)
C17	0.3466 (18)	0.269 (2)	−0.0069 (17)	0.078 (5)*	0.448 (12)
H17A	0.4286	0.2207	0.0380	0.117*	0.448 (12)
H17B	0.3183	0.3576	−0.0035	0.117*	0.448 (12)
H17C	0.3774	0.2721	−0.0730	0.117*	0.448 (12)
C18	0.276 (3)	0.084 (2)	−0.022 (2)	0.101 (6)*	0.448 (12)
H18A	0.3649	0.0287	0.0136	0.151*	0.448 (12)
H18B	0.2996	0.1178	−0.0908	0.151*	0.448 (12)
H18C	0.1983	0.0336	−0.0136	0.151*	0.448 (12)
C16'	0.146 (3)	0.3448 (14)	−0.0045 (17)	0.106 (5)*	0.552 (12)
H16D	0.0426	0.3503	0.0157	0.158*	0.552 (12)
H16E	0.1510	0.3878	−0.0745	0.158*	0.552 (12)
H16F	0.1963	0.3879	0.0297	0.158*	0.552 (12)
C17'	0.373 (3)	0.163 (3)	0.0001 (18)	0.106 (5)*	0.552 (12)
H17D	0.3988	0.0676	0.0228	0.160*	0.552 (12)
H17E	0.4347	0.1978	0.0340	0.160*	0.552 (12)
H17F	0.3908	0.1950	−0.0697	0.160*	0.552 (12)
C18'	0.154 (2)	0.1537 (17)	−0.0493 (15)	0.083 (4)*	0.552 (12)
H18D	0.0463	0.1770	−0.0471	0.124*	0.552 (12)
H18E	0.1845	0.0589	−0.0303	0.124*	0.552 (12)
H18F	0.1882	0.1926	−0.1152	0.124*	0.552 (12)
C19	−0.1180 (8)	0.3676 (7)	0.4525 (7)	0.0524 (18)
C20	−0.2183 (11)	0.4959 (9)	0.3983 (7)	0.074 (3)
H20A	−0.2489	0.4915	0.3365	0.110*
H20B	−0.1644	0.5672	0.3861	0.110*
H20C	−0.3057	0.5112	0.4376	0.110*
C21	0.192 (3)	0.573 (3)	0.260 (2)	0.107 (7)*	0.50
H21A	0.2097	0.6567	0.2627	0.129*	0.50
H21B	0.0950	0.5895	0.2286	0.129*	0.50
C22	0.308 (3)	0.525 (3)	0.197 (2)	0.117 (7)*	0.50
H22A	0.3097	0.5925	0.1341	0.176*	0.50
H22B	0.2863	0.4467	0.1867	0.176*	0.50
H22C	0.4052	0.5031	0.2281	0.176*	0.50
C23	0.690 (2)	0.287 (2)	0.1224 (14)	0.081 (5)	0.50
H23A	0.7180	0.3421	0.0591	0.121*	0.50
H23B	0.5824	0.3020	0.1279	0.121*	0.50
H23C	0.7284	0.1956	0.1289	0.121*	0.50
C24	0.7513 (19)	0.3194 (16)	0.1974 (12)	0.058 (4)	0.50
H24A	0.7141	0.4124	0.1901	0.070*	0.50
H24B	0.8602	0.3056	0.1912	0.070*	0.50
O1	−0.0909 (5)	0.2773 (5)	0.4110 (4)	0.0537 (13)
O2	−0.0635 (7)	0.3485 (6)	0.5334 (5)	0.0669 (15)
O3	−0.1018 (5)	0.0163 (4)	0.5695 (3)	0.0338 (9)
O4	0.1846 (10)	0.4916 (7)	0.3531 (5)	0.0344 (18)	0.50
H4	0.1170	0.5264	0.3826	0.052*	0.50
O5	0.7114 (8)	0.2386 (7)	0.2940 (5)	0.0252 (15)	0.50
H5	0.7511	0.2567	0.3367	0.038*	0.50
H2N	0.205 (8)	−0.030 (3)	0.652 (5)	0.050 (6)*
H1N	0.225 (12)	0.271 (6)	0.394 (5)	0.095 (4)*
N2	0.1736 (6)	0.0556 (5)	0.6353 (4)	0.0366 (11)
N1	0.2504 (6)	0.2002 (5)	0.4438 (4)	0.0342 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0304 (4)	0.0382 (4)	0.0374 (5)	−0.0082 (3)	0.0014 (3)	−0.0165 (3)
C1	0.031 (3)	0.042 (3)	0.036 (3)	−0.006 (2)	0.003 (2)	−0.019 (2)
C2	0.035 (3)	0.049 (3)	0.041 (3)	−0.009 (2)	0.001 (2)	−0.024 (3)
C3	0.043 (3)	0.065 (4)	0.038 (3)	−0.013 (3)	0.000 (3)	−0.022 (3)
C4	0.040 (3)	0.052 (3)	0.040 (3)	−0.015 (2)	0.003 (2)	−0.022 (2)
C5	0.029 (2)	0.044 (3)	0.047 (3)	−0.009 (2)	−0.001 (2)	−0.023 (2)
C6	0.040 (3)	0.058 (3)	0.049 (3)	−0.012 (3)	−0.002 (3)	−0.026 (3)
C7	0.038 (3)	0.063 (4)	0.061 (4)	−0.011 (3)	−0.009 (3)	−0.030 (3)
C8	0.032 (3)	0.061 (4)	0.060 (4)	−0.016 (3)	−0.005 (3)	−0.024 (3)
C9	0.036 (3)	0.054 (3)	0.053 (3)	−0.015 (3)	0.003 (3)	−0.023 (3)
C10	0.030 (2)	0.041 (3)	0.048 (3)	−0.008 (2)	0.000 (2)	−0.023 (2)
C11	0.032 (3)	0.052 (3)	0.044 (3)	−0.014 (2)	0.006 (2)	−0.024 (2)
C12	0.035 (3)	0.051 (3)	0.040 (3)	−0.015 (2)	0.007 (2)	−0.022 (3)
C13	0.048 (3)	0.067 (4)	0.046 (3)	−0.025 (3)	0.010 (3)	−0.021 (3)
C14	0.055 (3)	0.069 (4)	0.042 (3)	−0.021 (3)	0.009 (3)	−0.024 (3)
C15	0.071 (4)	0.095 (5)	0.050 (4)	−0.035 (4)	0.011 (3)	−0.021 (4)
C19	0.035 (4)	0.041 (4)	0.077 (5)	−0.008 (3)	0.003 (4)	−0.014 (4)
C20	0.077 (6)	0.055 (5)	0.083 (6)	0.014 (4)	−0.017 (5)	−0.027 (5)
C23	0.067 (10)	0.097 (12)	0.058 (9)	−0.011 (9)	0.004 (8)	0.000 (9)
C24	0.060 (9)	0.051 (8)	0.062 (9)	−0.008 (7)	−0.013 (7)	−0.016 (7)
O1	0.042 (3)	0.040 (3)	0.078 (4)	−0.001 (2)	−0.005 (2)	−0.021 (2)
O2	0.067 (4)	0.057 (3)	0.069 (4)	−0.002 (3)	−0.012 (3)	−0.014 (3)
O3	0.033 (2)	0.039 (2)	0.033 (2)	−0.0101 (17)	0.0037 (17)	−0.0157 (18)
O4	0.056 (5)	0.015 (3)	0.024 (4)	−0.001 (3)	0.009 (4)	0.000 (3)
O5	0.026 (4)	0.024 (4)	0.027 (4)	−0.008 (3)	−0.004 (3)	−0.008 (3)
N2	0.034 (3)	0.042 (3)	0.040 (3)	−0.010 (2)	0.000 (2)	−0.019 (2)
N1	0.032 (3)	0.037 (3)	0.037 (3)	−0.005 (2)	0.000 (2)	−0.017 (2)

Geometric parameters (Å, º) top

Zn1—O1	2.025 (5)	C16—H16A	0.9600
Zn1—O3	2.033 (4)	C16—H16B	0.9600
Zn1—O3ⁱ	2.043 (4)	C16—H16C	0.9600
Zn1—N2	2.100 (5)	C17—H17A	0.9600
Zn1—N1	2.104 (5)	C17—H17B	0.9600
Zn1—Zn1ⁱ	3.0670 (13)	C17—H17C	0.9600
C1—O3	1.341 (7)	C18—H18A	0.9600
C1—C2	1.407 (8)	C18—H18B	0.9600
C1—C12ⁱ	1.412 (9)	C18—H18C	0.9600
C2—C3	1.403 (9)	C16'—H16D	0.9600
C2—C4	1.501 (9)	C16'—H16E	0.9600
C3—C14ⁱ	1.370 (10)	C16'—H16F	0.9600
C3—H3	0.9300	C17'—H17D	0.9600
C4—N2	1.496 (8)	C17'—H17E	0.9600
C4—H4A	0.9700	C17'—H17F	0.9600
C4—H4B	0.9700	C18'—H18D	0.9600
C5—C6	1.385 (9)	C18'—H18E	0.9600
C5—C10	1.386 (9)	C18'—H18F	0.9600
C5—N2	1.470 (8)	C19—O2	1.223 (10)
C6—C7	1.363 (10)	C19—O1	1.276 (9)
C6—H6	0.9300	C19—C20	1.497 (11)
C7—C8	1.374 (11)	C20—H20A	0.9600
C7—H7	0.9300	C20—H20B	0.9600
C8—C9	1.386 (10)	C20—H20C	0.9600
C8—H8	0.9300	C21—O4	1.34 (3)
C9—C10	1.371 (9)	C21—C22	1.47 (3)
C9—H9	0.9300	C21—H21A	0.9700
C10—N1	1.456 (8)	C21—H21B	0.9700
C11—N1	1.511 (7)	C22—H22A	0.9600
C11—C12	1.517 (9)	C22—H22B	0.9600
C11—H11A	0.9700	C22—H22C	0.9600
C11—H11B	0.9700	C23—C24	1.40 (2)
C12—C13	1.398 (10)	C23—H23A	0.9600
C12—C1ⁱ	1.412 (9)	C23—H23B	0.9600
C13—C14	1.387 (10)	C23—H23C	0.9600
C13—H13	0.9300	C24—O5	1.446 (18)
C14—C3ⁱ	1.370 (10)	C24—H24A	0.9700
C14—C15	1.540 (11)	C24—H24B	0.9700
C15—C17'	1.40 (2)	O3—Zn1ⁱ	2.043 (4)
C15—C16	1.426 (11)	O4—H4	0.8200
C15—C17	1.426 (11)	O5—H5	0.8200
C15—C18'	1.475 (17)	N2—H2N	0.87 (3)
C15—C16'	1.479 (11)	N1—H1N	0.86 (3)
C15—C18	1.57 (2)

O1—Zn1—O3	96.05 (19)	H16A—C16—H16B	109.5
O1—Zn1—O3ⁱ	105.62 (19)	C15—C16—H16C	109.5
O3—Zn1—O3ⁱ	82.40 (17)	H16A—C16—H16C	109.5
O1—Zn1—N2	144.5 (2)	H16B—C16—H16C	109.5
O3—Zn1—N2	88.07 (18)	C15—C17—H17A	109.5
O3ⁱ—Zn1—N2	109.82 (19)	C15—C17—H17B	109.5
O1—Zn1—N1	95.6 (2)	H17A—C17—H17B	109.5
O3—Zn1—N1	168.18 (18)	C15—C17—H17C	109.5
O3ⁱ—Zn1—N1	92.33 (17)	H17A—C17—H17C	109.5
N2—Zn1—N1	83.8 (2)	H17B—C17—H17C	109.5
O1—Zn1—Zn1ⁱ	104.44 (14)	C15—C18—H18A	109.5
O3—Zn1—Zn1ⁱ	41.32 (11)	C15—C18—H18B	109.5
O3ⁱ—Zn1—Zn1ⁱ	41.08 (11)	H18A—C18—H18B	109.5
N2—Zn1—Zn1ⁱ	101.75 (15)	C15—C18—H18C	109.5
N1—Zn1—Zn1ⁱ	132.53 (13)	H18A—C18—H18C	109.5
O3—C1—C2	122.6 (6)	H18B—C18—H18C	109.5
O3—C1—C12ⁱ	118.4 (5)	C15—C16'—H16D	109.5
C2—C1—C12ⁱ	119.0 (6)	C15—C16'—H16E	109.5
C3—C2—C1	118.2 (6)	H16D—C16'—H16E	109.5
C3—C2—C4	118.5 (6)	C15—C16'—H16F	109.5
C1—C2—C4	123.2 (6)	H16D—C16'—H16F	109.5
C14ⁱ—C3—C2	123.6 (6)	H16E—C16'—H16F	109.5
C14ⁱ—C3—H3	118.2	C15—C17'—H17D	109.5
C2—C3—H3	118.2	C15—C17'—H17E	109.5
N2—C4—C2	112.9 (5)	H17D—C17'—H17E	109.5
N2—C4—H4A	109.0	C15—C17'—H17F	109.5
C2—C4—H4A	109.0	H17D—C17'—H17F	109.5
N2—C4—H4B	109.0	H17E—C17'—H17F	109.5
C2—C4—H4B	109.0	C15—C18'—H18D	109.5
H4A—C4—H4B	107.8	C15—C18'—H18E	109.5
C6—C5—C10	119.2 (6)	H18D—C18'—H18E	109.5
C6—C5—N2	121.9 (6)	C15—C18'—H18F	109.5
C10—C5—N2	118.9 (5)	H18D—C18'—H18F	109.5
C7—C6—C5	121.1 (7)	H18E—C18'—H18F	109.5
C7—C6—H6	119.5	O2—C19—O1	120.5 (7)
C5—C6—H6	119.5	O2—C19—C20	122.1 (7)
C6—C7—C8	119.9 (7)	O1—C19—C20	117.4 (8)
C6—C7—H7	120.0	C19—C20—H20A	109.5
C8—C7—H7	120.0	C19—C20—H20B	109.5
C7—C8—C9	119.4 (6)	H20A—C20—H20B	109.5
C7—C8—H8	120.3	C19—C20—H20C	109.5
C9—C8—H8	120.3	H20A—C20—H20C	109.5
C10—C9—C8	121.0 (7)	H20B—C20—H20C	109.5
C10—C9—H9	119.5	O4—C21—C22	116 (2)
C8—C9—H9	119.5	O4—C21—H21A	108.2
C9—C10—C5	119.4 (6)	C22—C21—H21A	108.2
C9—C10—N1	121.4 (6)	O4—C21—H21B	108.2
C5—C10—N1	119.2 (5)	C22—C21—H21B	108.2
N1—C11—C12	112.1 (5)	H21A—C21—H21B	107.4
N1—C11—H11A	109.2	C21—C22—H22A	109.5
C12—C11—H11A	109.2	C21—C22—H22B	109.5
N1—C11—H11B	109.2	H22A—C22—H22B	109.5
C12—C11—H11B	109.2	C21—C22—H22C	109.5
H11A—C11—H11B	107.9	H22A—C22—H22C	109.5
C13—C12—C1ⁱ	119.9 (6)	H22B—C22—H22C	109.5
C13—C12—C11	121.2 (6)	C24—C23—H23A	109.5
C1ⁱ—C12—C11	118.3 (6)	C24—C23—H23B	109.5
C14—C13—C12	121.6 (7)	H23A—C23—H23B	109.5
C14—C13—H13	119.2	C24—C23—H23C	109.5
C12—C13—H13	119.2	H23A—C23—H23C	109.5
C3ⁱ—C14—C13	117.6 (7)	H23B—C23—H23C	109.5
C3ⁱ—C14—C15	121.7 (7)	C23—C24—O5	111.0 (14)
C13—C14—C15	120.6 (7)	C23—C24—H24A	109.4
C17'—C15—C16	135.3 (16)	O5—C24—H24A	109.4
C17'—C15—C17	45.7 (11)	C23—C24—H24B	109.4
C16—C15—C17	113.1 (11)	O5—C24—H24B	109.4
C17'—C15—C18'	98.4 (13)	H24A—C24—H24B	108.0
C16—C15—C18'	56.2 (11)	C19—O1—Zn1	106.4 (5)
C17—C15—C18'	122.3 (14)	C1—O3—Zn1	128.5 (4)
C17'—C15—C16'	123.3 (15)	C1—O3—Zn1ⁱ	113.8 (4)
C16—C15—C16'	50.1 (11)	Zn1—O3—Zn1ⁱ	97.60 (17)
C17—C15—C16'	78.5 (13)	C21—O4—H4	109.5
C18'—C15—C16'	105.0 (10)	C24—O5—H5	109.5
C17'—C15—C14	108.8 (12)	C5—N2—C4	114.9 (5)
C16—C15—C14	115.4 (13)	C5—N2—Zn1	107.9 (4)
C17—C15—C14	118.0 (11)	C4—N2—Zn1	107.6 (4)
C18'—C15—C14	116.1 (10)	C5—N2—H2N	109 (5)
C16'—C15—C14	105.7 (12)	C4—N2—H2N	107 (5)
C17'—C15—C18	58.0 (8)	Zn1—N2—H2N	110 (5)
C16—C15—C18	102.3 (11)	C10—N1—C11	110.9 (5)
C17—C15—C18	99.6 (14)	C10—N1—Zn1	108.1 (4)
C18'—C15—C18	46.8 (10)	C11—N1—Zn1	110.1 (3)
C16'—C15—C18	145.6 (14)	C10—N1—H1N	124 (7)
C14—C15—C18	105.2 (12)	C11—N1—H1N	93 (7)
C15—C16—H16A	109.5	Zn1—N1—H1N	109 (7)
C15—C16—H16B	109.5

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.97	2.45	3.246 (10)	139
N1—H1N···O4	0.86 (7)	2.23 (7)	2.952 (9)	141 (6)
N2—H2N···O5ⁱⁱ	0.87 (4)	2.13 (4)	2.999 (9)	175 (4)
O4—H4···O2ⁱⁱⁱ	0.82	2.06	2.768 (10)	145
O5—H5···O1^iv	0.82	1.92	2.700 (9)	159

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

Experimental details

Crystal data
Chemical formula	[Zn₂(C₃₆H₄₂N₄O₂)(C₂H₃O₂)₂]·2C₂H₆O
M_r	903.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.0566 (3), 10.8410 (5), 14.2828 (5)
α, β, γ (°)	71.246 (4), 86.514 (3), 78.362 (3)
V (Å³)	1300.56 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.45 × 0.25 × 0.20

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.748, 0.824
No. of measured, independent and observed [I > 2σ(I)] reflections	11846, 6368, 4133
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.700

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.253, 1.05
No. of reflections	6368
No. of parameters	285
No. of restraints	655
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.15, −0.77

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLEASE PROVIDE PROGRAM NAME AND REFERENCE.

Selected bond lengths (Å) top

Zn1—O1	2.025 (5)	Zn1—N2	2.100 (5)
Zn1—O3	2.033 (4)	Zn1—N1	2.104 (5)
Zn1—O3ⁱ	2.043 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2	0.97	2.45	3.246 (10)	139
N1—H1N···O4	0.86 (7)	2.23 (7)	2.952 (9)	141 (6)
N2—H2N···O5ⁱⁱ	0.87 (4)	2.13 (4)	2.999 (9)	175 (4)
O4—H4···O2ⁱⁱⁱ	0.82	2.06	2.768 (10)	145
O5—H5···O1^iv	0.82	1.92	2.700 (9)	159

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (No. 20471014), the Program for New Century Excellent Talents in Chinese Universities (NCET-05–0320), the Fok Ying Tung Education Foundation and the Analysis and Testing Foundation of Northeast Normal University for support.

References

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