Crystal structure of [NaZn(BTC)(H2O)4]·1.5H2O (BTC = benzene-1,3,5-tri­carb­oxy­l­ate): a heterometallic coordination compound

Min Ni; Quanle Li; Hao Chen; Shengqing Li

doi:10.1107/S2056989015012001

. 2015 Jun 27;71(Pt 7):m143–m144. doi: 10.1107/S2056989015012001

Crystal structure of [NaZn(BTC)(H₂O)₄]·1.5H₂O (BTC = benzene-1,3,5-tricarboxylate): a heterometallic coordination compound

Min Ni ^a, Quanle Li ^a, Hao Chen ^a, Shengqing Li ^a,^*

PMCID: PMC4518996 PMID: 26279893

Abstract

The title coordination polymer, poly[[μ-aqua-triaqua(μ₃-benzene-1,3,5-tricarboxylato)sodiumzinc] sesquihydrate], {[NaZn(C₉H₃O₆)(H₂O)₄]·1.5H₂O}_n, was obtained in ionic liquid microemulsion at room temperture by the reaction of benzene-1,3,5-tricarboxylic acid (H₃BTC) with Zn(NO₃)₂·6H₂O in the presence of NaOH. The asymmetric unit comprises two Na⁺ ions (each located on an inversion centre), one Zn²⁺ ion, one BTC ligand, four coordinating water molecules and two solvent water molecules, one of which is disordered about an inversion centre and shows half-occupation. The Zn²⁺ cation is five-coordinated by two carboxylate O atoms from two different BTC ligands and three coordinating H₂O molecules; the Zn—O bond lengths are in the range 1.975 (2)–2.058 (3) Å. The Na⁺ cations are six-coordinated but have different arrangements of the ligands: one is bound to two carboxylate O atoms of two BTC ligands and four O atoms from four coordinating H₂O molecules while the other is bound by four carboxylate O atoms from four BTC linkers and two O atoms of coordinating H₂O molecules. The completely deprotonated BTC ligand acts as a bridging ligand binding the Zn²⁺ atom and Na⁺ ions, forming a layered structure extending parallel to (100). An intricate network of O—H⋯O hydrogen bonds is present within and between the layers.

Keywords: crystal structure; heterometallic coordination compound; benzene-1,3,5-tricarboxylic acid; hydrogen bonding

Related literature

For general background to heterometallic coordination compounds, see: Stock & Biswas (2012 ▸); Gao et al. (2005 ▸); Zhou et al. (2012 ▸). For details of the synthesis, see: Shang et al. (2013 ▸); Fu et al. (2011 ▸). For the potential application of this compound, see: Huang et al. (2014 ▸). graphic file with name e-71-0m143-scheme1.jpg

Experimental

Crystal data

[NaZn(C₉H₃O₆)(H₂O)₄]·1.5H₂O
M _r = 394.56
Triclinic,
a = 7.0980 (11) Å
b = 9.8000 (16) Å
c = 11.2043 (17) Å
α = 66.923 (2)°
β = 73.598 (2)°
γ = 84.720 (3)°
V = 687.68 (19) Å³
Z = 2
Mo Kα radiation
μ = 1.88 mm⁻¹
T = 296 K
0.05 × 0.03 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.912, T _max = 0.963
7585 measured reflections
4331 independent reflections
2567 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.113
S = 0.97
4331 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS7 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015012001/zp2017sup1.cif

e-71-0m143-sup1.cif^{(265.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015012001/zp2017Isup2.hkl

e-71-0m143-Isup2.hkl^{(237.5KB, hkl)}

Click here for additional data file.^{(13.2KB, docx)}

Supporting information file. DOI: 10.1107/S2056989015012001/zp2017Isup3.docx

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015012001/zp2017fig1.tif

The molecular structure of the title compound with the atom-numbering scheme and 30% probability ellipsoids.

Click here for additional data file.^{(1.4MB, tif)}

b . DOI: 10.1107/S2056989015012001/zp2017fig2.tif

The packing diagram viewed along the b axis.

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015012001/zp2017fig3.tif

The FT–IR spectrum of the title compound.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015012001/zp2017fig4.tif

The XRD pattern of the title compound.

CCDC reference: 1055450

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O7H7AO5ⁱ	0.82	1.79	2.587(4)	162
O7H7BO12ⁱⁱ	0.82	1.93	2.740(4)	172
O8H8AO10	0.82	2.40	3.114(5)	146
O8H8AO11	0.82	1.98	2.672(8)	142
O8H8BO6ⁱⁱ	0.82	2.05	2.641(5)	128
O9H9AO12ⁱⁱⁱ	0.82	1.95	2.734(4)	159
O9H9BO2^iv	0.82	2.01	2.823(4)	170
O10H10AO5^v	0.82	2.06	2.719(6)	137
O10H10BO9^vi	0.82	2.31	3.079(5)	155
O11H11AO3^vii	0.85	2.03	2.835(8)	157
O11H11BO3^v	0.85	2.27	2.866(7)	127
O11H11BO11^viii	0.85	1.33	1.973(9)	128
O12H12AO6	0.82	1.86	2.652(4)	161
O12H12BO4^ix	0.82	1.97	2.787(3)	172

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .

Acknowledgments

Financial support by the Fundamental Research Funds for the Central Universities (grant Nos. 2011PY128 and 2014PY053) and the National Undergraduate Training Programs for Innovation and Entrepreneurship (grant No. 2015028) of Huazhong Agricultural University are gratefully acknowledged. We thank Dr Y. Qu of HZAU and Dr X. G. Meng of CCNU for their kind assistance with this work.

supplementary crystallographic information

S1. Synthesis and crystallization

In the experiment, the microemulsion of desired composition containing water, [Bmim]PF₆, and Triton X-100 was prepared using the method reported previously (Gao et al. 2005). H₃BTC (0.210 g, 1.0 mmol), NaOH (0.040 g, 1.0 mmol) and Zn(NO₃)₂.6H₂O (0.298 g, 1.0 mmol) were added one by one into the microemulsion (20 g) which was clear and transparent system including 1.444 g [Bmim]PF₆, 10.428 g Triton X-100 and 8.310 g water. The whole system was stirred continuously for 24 h at 25^oC. Then, the product crystals were collected by centrifugation at 4500 r/min and washed with alcohol three times (3x20 mL) to remove the surfactant and [Bmim]PF₆. Then, the crystals were dried in a vacuum oven at 60^oC for 24 h. The resulting colorless crystals of the title compound were obtained.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.