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

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Poly[[(μ2-but-2-ynedioato)[μ2-1,2-(pyridin-4-yl)ethyl­ene]zinc(II)] dihydrate]

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aIngenium College of Liberal Arts (Chemistry), Kwangwoon University, Seoul 01897, Republic of Korea, and bDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Republic of Korea
*Correspondence e-mail: ymeekim@ewha.ac.kr

Edited by M. Zeller, Purdue University, USA (Received 13 October 2017; accepted 15 November 2017; online 21 November 2017)

In the title compound, poly[[(μ2-oxalato)[μ2-1,2-(pyridin-4-yl)ethyl­ene]zinc(II)] dihydrate], {[Zn(μ2-C4O4)(μ2-C12H10N2)]·2H2O}n, 2-butyndioate and 1,2-bis­(pyridin-4-yl)ethyl­ene ligands bridge ZnII ions to form a three-dimensional network. The three-dimensional networks are fivefold inter­penetrated, and each network features a 4-connected unimodal net with a Schläfli symbol of 66 (dia) with the ZnII ions as the nodes. Twofold rotation axes are located at the ZnII ions and the midpoints of the C≡C bond of 2-butyndioate and the C=C bond of 1,2-bis­(pyridin-4-yl)ethyl­ene. The coordination geometry around the ZnII ions is tetra­hedral constructed from two O atoms from 2-butyndioate and two N atoms from 1,2-bis­(pyridin-4-yl)ethyl­ene. Solvate water mol­ecules are connected with each other via hydrogen bonds to create chains running parallel to [010] that are captured in infinite channels of the three-dimensional framework through hydrogen bonds to the non-coordinating carboxyl­ate O atoms of the 2-butyndioate units. The water mol­ecules are disordered, with two alternative positions that are distinguished by the direction of the chains, but that share the H atom hydrogen bonded to the carboxyl­ate O atom.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Rigid aromatic di­carboxyl­ates have been used for the synthesis of MOFs (metal–organic frameworks), providing high surface areas and large pore volumes suitable for various advanced applications. Flexible di­carboxyl­ates as well as rigid aromatic di­carboxyl­ates have been paid attention in the design of new MOFs. Recently, various MOFs containing flexible α,ω-alkane (or alkene)-di­carboxyl­ates have been reported: three-dimensional ZnII frameworks containing malonates and various bipyridyl pillars [4,4-bi­pyridine, 1,2-bis­(pyridin-4-yl)ethane, 1,2-bis­(pyridin-4-yl)ethyl­ene, and 1,3-bis­(pyridin-4-yl)propane] have been prepared and their structures determined (Hyun et al. 2013[Hyun, M. Y., Hwang, I. H., Lee, M. M., Kim, H., Kim, K. B., Kim, C., Kim, H.-Y., Kim, Y. & Kim, S.-J. (2013). Polyhedron, 53, 166-171.]). Zn-MOFs containing five flexible α,ω-alkane- (or alkene-)di­carboxyl­ates and bipyridyl ligands have also been synthesized and their structures determined (Hwang et al., 2013[Hwang, I. H., Kim, H.-Y., Lee, M. M., Na, Y. J., Kim, J. H., Kim, H.-C., Kim, C., Huh, S., Kim, Y. & Kim, S.-J. (2013). Cryst. Growth Des. 13, 4815-4823.]; Kim et al., 2017[Kim, H.-C., Huh, S., Kim, J. Y., Moon, H. R., Lee, D. N. & Kim, Y. (2017). CrystEngComm, 19, 99-109.]). Bifunctional three-dimensional Cu-MOFs containing glutarates and bipyridyl ligands possess a very similar pore shape with different pore dimensions, and both MOFs showed good CO2 selectivity over N2 and H2 (Hwang et al., 2012[Hwang, I. H., Bae, J. M., Kim, W.-S., Jo, Y. D., Kim, C., Kim, Y., Kim, S.-J. & Huh, S. (2012). Dalton Trans. 41, 12759-12765.]). CdII-MOFs containing succinate and bipyridyl ligands have been prepared and their structures determined (Lee et al., 2014[Lee, M. M., Kim, H.-Y., Hwang, I. H., Bae, J. M., Kim, C., Yo, C.-H., Kim, Y. & Kim, S.-J. (2014). Bull. Korean Chem. Soc. 35, 1777-1783.]). We report here the structure of {[Zn(μ2-C4O4)(μ2-C12H10N2)]·2H2O}n containing a rigid non-aromatic 2-butyndioate ligand.

A fragment of the three-dimensional framework of the title compound is shown in Fig. 1[link]. 2-Butyndioate and 1,2-bis(pyridin-4-yl)ethyl­ene ligands bridge ZnII ions to form a three-dimensional network (Fig. 2[link]). The networks are fivefold inter­penetrated (Fig. 3[link]), and each features a 4-connected unimodal net with a Schläfli symbol of 66 (dia) with the ZnII ions as nodes, based on a ToposPro analysis (Blatov et al., 2014[Blatov, V. A., Shevchenko, A. P. & Proserpio, D. M. (2014). Cryst. Growth Des. 14, 3576-3586.]). Twofold rotation axes are located at the ZnII ions and the midpoints of the C≡C bond of 2-butyndioate and the C=C bond of 1,2-bis­(pyridin-4-yl)ethyl­ene. The coordination geometry around the ZnII ion is approximately tetra­hedral constructed by two O atoms from 2-butyndioate and two N atoms from 1,2-bis­(pyridin-4-yl)ethyl­ene. The solvate water mol­ecule was refined as disordered, with one of the H atoms, hydrogen-bonded to the oxygen atom of the 2-butyndioate units not coordinated to zinc, set to be shared exactly between the disordered water mol­ecules. Hydrogen bonds between neigboring water solvate mol­ecules lead to the formation of chains along [010] (Table 1[link]). Each disordered water mol­ecule forms one infinite chain, distinguished from the other by the direction of the hydrogen-bonding inter­actions. The hydrogen-bonded water solvate chains are captured in infinite channels of the three-dimensional network through hydrogen-bonding inter­actions to the non-coordinating carboxyl­ate O atoms (Fig. 4[link] and Table 1[link]). The solvent-free ZnII three-dimensional framework has a 19.1% void volume based on a PLATON analysis (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3⋯O2 0.95 2.52 3.208 (2) 129
O1W—H1B⋯O1Wi 0.87 (2) 2.28 (4) 2.984 (4) 138 (6)
O1W*—H1B*⋯O1W*ii 0.83 (2) 2.39 (9) 3.041 (16) 136 (11)
O1W—H1A⋯O2 0.84 (2) 2.08 (2) 2.880 (7) 160 (4)
O1W*—H1A*⋯O2 0.81 (2) 2.08 (2) 2.81 (2) 150 (4)
Symmetry codes: (i) [-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].
[Figure 1]
Figure 1
A fragment of the three-dimensional network of the title compound showing displacement ellipsoids at the 50% probability level. The disordered water solvate mol­ecules are shown, and one of the H atoms is set to be exactly shared between the two water mol­ecules. [Symmetry codes: (i) −x, y, [{3\over 2}] − z; (ii) −x, −y, 1 − z; (iii) [{1\over 2}] − x, [{5\over 2}] − y, 2 − z.]
[Figure 2]
Figure 2
Three-dimensional network viewed along the b axis. Water solvate mol­ecules are omitted for clarity.
[Figure 3]
Figure 3
Fivefold inter­penetrated three-dimensional networks of the title compound are shown in different colors. Water solvate mol­ecules and all hydrogen atoms are omitted for clarity.
[Figure 4]
Figure 4
Hydrogen-bonding inter­actions (green dotted lines) between water solvate mol­ecules forming chains and between these chains and non-coordinating carboxyl­ate O atoms (Table 1[link]). Only the chains formed from the major of the two disordered water mol­ecules are shown.

Synthesis and crystallization

2-Butyndioic acid (0.1 mmol, 11.4 mg) and Zn(NO3)2·6H2O (0.1 mmol, 30.4 mg) were dissolved in 4 ml water, and 1.5 ml 25% ammonia water was added. This solution was carefully layered with an 4 ml aceto­nitrile solution of 1,2-bis­(pyridin-4-yl)ethyl­ene (0.2 mmol, 36.4 mg). Suitable crystals of the title compound were obtained in a few weeks, yield 58 mg (14.6%). The pale-yellow block-shaped crystals retain crystallinity upon desolvation.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. H atoms hydrogen bonded to the 2-butyndioate O atom were constrained to be exactly shared between the two disordered units. The disorder ratio of the water mol­ecules refined to 0.76 (3) to 0.24 (3).

Table 2
Experimental details

Crystal data
Chemical formula [Zn(C4O4)(C12H10N2)]·2H2O
Mr 395.66
Crystal system, space group Monoclinic, C2/c
Temperature (K) 170
a, b, c (Å) 22.771 (5), 5.5777 (11), 16.306 (3)
β (°) 123.679 (3)
V3) 1723.4 (6)
Z 4
Radiation type Mo Kα
μ (mm−1) 1.46
Crystal size (mm) 0.15 × 0.10 × 0.08
 
Data collection
Diffractometer Bruker SMART CCD
Absorption correction Multi-scan (SADABS; Bruker, 2003[Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.830, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections 5404, 2071, 1980
Rint 0.015
(sin θ/λ)max−1) 0.669
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.076, 1.17
No. of reflections 2071
No. of parameters 134
No. of restraints 25
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.36, −0.34
Computer programs: SMART and SAINT (Bruker, 2003[Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2015 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and DIAMOND (Brandenburg & Berndt, 1998[Brandenburg, K. & Berndt, M. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.]).

Structural data


Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Berndt, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[[(µ2-but-2-ynedioato)[µ2-1,2-(pyridin-4-yl)ethylene]zinc(II)] dihydrate] top
Crystal data top
[Zn(C4O4)(C12H10N2)]·2H2OF(000) = 808
Mr = 395.66Dx = 1.525 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 22.771 (5) ÅCell parameters from 3432 reflections
b = 5.5777 (11) Åθ = 2.5–27.9°
c = 16.306 (3) ŵ = 1.46 mm1
β = 123.679 (3)°T = 170 K
V = 1723.4 (6) Å3Block, pale yellow
Z = 40.15 × 0.10 × 0.08 mm
Data collection top
Bruker SMART CCD
diffractometer
1980 reflections with I > 2σ(I)
φ and ω scansRint = 0.015
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
θmax = 28.4°, θmin = 3.0°
Tmin = 0.830, Tmax = 0.891h = 3029
5404 measured reflectionsk = 75
2071 independent reflectionsl = 1821
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0416P)2 + 0.9936P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max < 0.001
2071 reflectionsΔρmax = 0.36 e Å3
134 parametersΔρmin = 0.34 e Å3
25 restraintsExtinction correction: SHELXL2015 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0073 (8)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. H atoms bonded to C atoms of pyridylaromatic rings were placed in calculated positions with C—H distances of 0.95 Å. They were included in the refinement in riding-motion approximation with Uiso(H) = 1.2Ueq(C). H atoms bonded to O atoms of the water solvate molecule were refined with O—H distances restrained to 0.84 (2) Å and Uiso(H) = 1.5Ueq(O). The H atoms hydrogen bonded to the 2-butyndioate O atom were constrained to be exactly shared between the two disordered units. H···H distances within the water solvate molecules were restrained to 1.36 (2) Å, and the H1A···O2 distance was restrained to 2.10 (2)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.00000.42032 (4)0.75000.02426 (12)
O10.00608 (7)0.2056 (2)0.65262 (10)0.0404 (3)
O20.07226 (10)0.3913 (3)0.63460 (15)0.0639 (5)
N10.08162 (7)0.6435 (3)0.83668 (10)0.0275 (3)
C10.02781 (9)0.2373 (3)0.61313 (13)0.0349 (4)
C20.00843 (10)0.0689 (3)0.53244 (15)0.0354 (4)
C30.10795 (10)0.7876 (3)0.79870 (12)0.0345 (4)
H30.09110.76990.73110.041*
C40.15811 (11)0.9591 (4)0.85292 (14)0.0384 (4)
H40.17541.05680.82300.046*
C50.18358 (9)0.9893 (3)0.95234 (12)0.0315 (3)
C60.15629 (10)0.8391 (4)0.99139 (13)0.0386 (4)
H60.17230.85261.05880.046*
C70.10609 (10)0.6709 (4)0.93236 (13)0.0369 (4)
H70.08800.57020.96040.044*
C80.23647 (9)1.1699 (3)1.01505 (13)0.0360 (4)
H80.25271.17231.08270.043*
O1W0.2227 (3)0.450 (3)0.7360 (5)0.093 (2)0.76 (3)
H1A0.1820 (7)0.395 (7)0.708 (3)0.139*0.76 (3)
H1B0.219 (3)0.592 (7)0.713 (5)0.139*0.76 (3)
O1W*0.2192 (10)0.326 (7)0.7361 (13)0.079 (4)0.24 (3)
H1A*0.1820 (7)0.395 (7)0.708 (3)0.118*0.24 (3)
H1B*0.216 (4)0.182 (9)0.746 (13)0.118*0.24 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02654 (16)0.02265 (16)0.02250 (15)0.0000.01291 (12)0.000
O10.0499 (7)0.0386 (7)0.0373 (7)0.0020 (6)0.0271 (6)0.0106 (5)
O20.0668 (11)0.0659 (11)0.0721 (12)0.0311 (9)0.0466 (10)0.0396 (9)
N10.0272 (6)0.0269 (6)0.0237 (6)0.0003 (5)0.0112 (5)0.0017 (5)
C10.0362 (8)0.0322 (8)0.0322 (8)0.0043 (7)0.0164 (7)0.0065 (7)
C20.0368 (9)0.0343 (9)0.0376 (9)0.0001 (7)0.0223 (8)0.0068 (6)
C30.0404 (9)0.0361 (9)0.0260 (8)0.0088 (7)0.0178 (7)0.0063 (6)
C40.0443 (10)0.0419 (10)0.0320 (9)0.0153 (8)0.0231 (8)0.0088 (7)
C50.0281 (8)0.0337 (8)0.0281 (8)0.0041 (7)0.0127 (7)0.0068 (7)
C60.0427 (9)0.0455 (10)0.0237 (8)0.0104 (8)0.0159 (7)0.0056 (7)
C70.0407 (9)0.0398 (9)0.0279 (8)0.0089 (8)0.0177 (7)0.0019 (7)
C80.0334 (8)0.0406 (9)0.0286 (8)0.0077 (7)0.0138 (7)0.0100 (7)
O1W0.0539 (18)0.145 (7)0.070 (2)0.013 (3)0.0282 (15)0.016 (3)
O1W*0.062 (5)0.137 (9)0.047 (4)0.020 (7)0.037 (3)0.009 (7)
Geometric parameters (Å, º) top
Zn1—O11.9315 (13)C4—H40.9500
Zn1—O1i1.9315 (13)C5—C61.390 (3)
Zn1—N1i2.0219 (14)C5—C81.464 (2)
Zn1—N12.0219 (14)C6—C71.376 (3)
O1—C11.262 (2)C6—H60.9500
O2—C11.221 (2)C7—H70.9500
N1—C31.342 (2)C8—C8iii1.324 (4)
N1—C71.343 (2)C8—H80.9500
C1—C21.471 (2)O1W—H1A0.831 (16)
C2—C2ii1.186 (4)O1W—H1B0.866 (19)
C3—C41.372 (2)O1W*—H1A*0.805 (18)
C3—H30.9500O1W*—H1B*0.83 (2)
C4—C51.397 (2)
O1—Zn1—O1i103.37 (9)C3—C4—C5119.58 (17)
O1—Zn1—N1i100.84 (6)C3—C4—H4120.2
O1i—Zn1—N1i125.13 (6)C5—C4—H4120.2
O1—Zn1—N1125.13 (6)C6—C5—C4117.11 (16)
O1i—Zn1—N1100.84 (6)C6—C5—C8119.89 (16)
N1i—Zn1—N1104.00 (8)C4—C5—C8123.01 (17)
C1—O1—Zn1123.18 (12)C7—C6—C5119.97 (16)
C3—N1—C7117.66 (15)C7—C6—H6120.0
C3—N1—Zn1121.26 (11)C5—C6—H6120.0
C7—N1—Zn1120.69 (12)N1—C7—C6122.60 (17)
O2—C1—O1126.62 (17)N1—C7—H7118.7
O2—C1—C2119.67 (18)C6—C7—H7118.7
O1—C1—C2113.70 (16)C8iii—C8—C5125.2 (2)
C2ii—C2—C1178.5 (3)C8iii—C8—H8117.4
N1—C3—C4123.07 (16)C5—C8—H8117.4
N1—C3—H3118.5H1A—O1W—H1B107 (3)
C4—C3—H3118.5H1A*—O1W*—H1B*114 (4)
Symmetry codes: (i) x, y, z+3/2; (ii) x, y, z+1; (iii) x+1/2, y+5/2, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O20.952.523.208 (2)129
O1W—H1B···O1Wiv0.87 (2)2.28 (4)2.984 (4)138 (6)
O1W*—H1B*···O1W*v0.83 (2)2.39 (9)3.041 (16)136 (11)
O1W—H1A···O20.84 (2)2.08 (2)2.880 (7)160 (4)
O1W*—H1A*···O20.81 (2)2.08 (2)2.81 (2)150 (4)
Symmetry codes: (iv) x+1/2, y+1/2, z+3/2; (v) x+1/2, y1/2, z+3/2.
 

Funding information

This work was supported by the Basic Science Research Program of the National Research Foundation of Korea (NRF-2017R1D1A1A02017607) and by Kwangwoon University in the year 2017.

References

First citationBlatov, V. A., Shevchenko, A. P. & Proserpio, D. M. (2014). Cryst. Growth Des. 14, 3576–3586.  Web of Science CrossRef CAS Google Scholar
First citationBrandenburg, K. & Berndt, M. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHwang, I. H., Bae, J. M., Kim, W.-S., Jo, Y. D., Kim, C., Kim, Y., Kim, S.-J. & Huh, S. (2012). Dalton Trans. 41, 12759–12765.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationHwang, I. H., Kim, H.-Y., Lee, M. M., Na, Y. J., Kim, J. H., Kim, H.-C., Kim, C., Huh, S., Kim, Y. & Kim, S.-J. (2013). Cryst. Growth Des. 13, 4815–4823.  Web of Science CSD CrossRef CAS Google Scholar
First citationHyun, M. Y., Hwang, I. H., Lee, M. M., Kim, H., Kim, K. B., Kim, C., Kim, H.-Y., Kim, Y. & Kim, S.-J. (2013). Polyhedron, 53, 166–171.  Web of Science CSD CrossRef CAS Google Scholar
First citationKim, H.-C., Huh, S., Kim, J. Y., Moon, H. R., Lee, D. N. & Kim, Y. (2017). CrystEngComm, 19, 99–109.  Web of Science CSD CrossRef CAS Google Scholar
First citationLee, M. M., Kim, H.-Y., Hwang, I. H., Bae, J. M., Kim, C., Yo, C.-H., Kim, Y. & Kim, S.-J. (2014). Bull. Korean Chem. Soc. 35, 1777–1783.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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