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

Lee, D.N.; Kim, Y.

doi:10.1107/S241431461701642X

metal-organic compounds

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ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171642

https://doi.org/10.1107/S241431461701642X

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

Do Nam Lee ^a and Youngmee Kim ^b ^*

^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 Zn^II 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 Zn^II ions as the nodes. Twofold rotation axes are located at the Zn^II 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 Zn^II 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.

Keywords: crystal structure; Zn-MOF; 2-butyndioate; 1,2-(pyridin-4-yl)ethylene.

CCDC reference: 1585720

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 Zn^II 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 ). 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 ; Kim et al., 2017 ). 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 ). Cd^II-MOFs containing succinate and bipyridyl ligands have been prepared and their structures determined (Lee et al., 2014 ). 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. 2-Butyndioate and 1,2-bis(pyridin-4-yl)ethylene ligands bridge Zn^II ions to form a three-dimensional network (Fig. 2). The networks are fivefold interpenetrated (Fig. 3), and each features a 4-connected unimodal net with a Schläfli symbol of 6⁶ (dia) with the Zn^II ions as nodes, based on a ToposPro analysis (Blatov et al., 2014 ). Twofold rotation axes are located at the Zn^II 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 Zn^II 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). 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 and Table 1). The solvent-free Zn^II three-dimensional framework has a 19.1% void volume based on a PLATON analysis (Spek, 2009 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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
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
Three-dimensional network viewed along the b axis. Water solvate molecules are omitted for clarity.

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
Hydrogen-bonding interactions (green dotted lines) between water solvate molecules forming chains and between these chains and non-coordinating carboxylate O atoms (Table 1

). 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. 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
M_r	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)
V (Å³)	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 )
T_min, T_max	0.830, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	5404, 2071, 1980
R_int	0.015
(sin θ/λ)_max (Å⁻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
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.34
Computer programs: SMART and SAINT (Bruker, 2003), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2015 (Sheldrick, 2015 ) and DIAMOND (Brandenburg & Berndt, 1998 ).

Structural data

CCDC reference: 1585720

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431461701642X/zl4021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461701642X/zl4021Isup3.hkl

checkCIF report

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)]·2H₂O	F(000) = 808
M_r = 395.66	D_x = 1.525 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.771 (5) Å	Cell parameters from 3432 reflections
b = 5.5777 (11) Å	θ = 2.5–27.9°
c = 16.306 (3) Å	µ = 1.46 mm⁻¹
β = 123.679 (3)°	T = 170 K
V = 1723.4 (6) Å³	Block, pale yellow
Z = 4	0.15 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD diffractometer	1980 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.015
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 28.4°, θ_min = 3.0°
T_min = 0.830, T_max = 0.891	h = −30→29
5404 measured reflections	k = −7→5
2071 independent reflections	l = −18→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0416P)² + 0.9936P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max < 0.001
2071 reflections	Δρ_max = 0.36 e Å⁻³
134 parameters	Δρ_min = −0.34 e Å⁻³
25 restraints	Extinction correction: SHELXL2015 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction 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 U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.5U_eq(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.0000	0.42032 (4)	0.7500	0.02426 (12)
O1	−0.00608 (7)	0.2056 (2)	0.65262 (10)	0.0404 (3)
O2	0.07226 (10)	0.3913 (3)	0.63460 (15)	0.0639 (5)
N1	0.08162 (7)	0.6435 (3)	0.83668 (10)	0.0275 (3)
C1	0.02781 (9)	0.2373 (3)	0.61313 (13)	0.0349 (4)
C2	0.00843 (10)	0.0689 (3)	0.53244 (15)	0.0354 (4)
C3	0.10795 (10)	0.7876 (3)	0.79870 (12)	0.0345 (4)
H3	0.0911	0.7699	0.7311	0.041*
C4	0.15811 (11)	0.9591 (4)	0.85292 (14)	0.0384 (4)
H4	0.1754	1.0568	0.8230	0.046*
C5	0.18358 (9)	0.9893 (3)	0.95234 (12)	0.0315 (3)
C6	0.15629 (10)	0.8391 (4)	0.99139 (13)	0.0386 (4)
H6	0.1723	0.8526	1.0588	0.046*
C7	0.10609 (10)	0.6709 (4)	0.93236 (13)	0.0369 (4)
H7	0.0880	0.5702	0.9604	0.044*
C8	0.23647 (9)	1.1699 (3)	1.01505 (13)	0.0360 (4)
H8	0.2527	1.1723	1.0827	0.043*
O1W	0.2227 (3)	0.450 (3)	0.7360 (5)	0.093 (2)	0.76 (3)
H1A	0.1820 (7)	0.395 (7)	0.708 (3)	0.139*	0.76 (3)
H1B	0.219 (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

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02654 (16)	0.02265 (16)	0.02250 (15)	0.000	0.01291 (12)	0.000
O1	0.0499 (7)	0.0386 (7)	0.0373 (7)	−0.0020 (6)	0.0271 (6)	−0.0106 (5)
O2	0.0668 (11)	0.0659 (11)	0.0721 (12)	−0.0311 (9)	0.0466 (10)	−0.0396 (9)
N1	0.0272 (6)	0.0269 (6)	0.0237 (6)	−0.0003 (5)	0.0112 (5)	−0.0017 (5)
C1	0.0362 (8)	0.0322 (8)	0.0322 (8)	0.0043 (7)	0.0164 (7)	−0.0065 (7)
C2	0.0368 (9)	0.0343 (9)	0.0376 (9)	−0.0001 (7)	0.0223 (8)	−0.0068 (6)
C3	0.0404 (9)	0.0361 (9)	0.0260 (8)	−0.0088 (7)	0.0178 (7)	−0.0063 (6)
C4	0.0443 (10)	0.0419 (10)	0.0320 (9)	−0.0153 (8)	0.0231 (8)	−0.0088 (7)
C5	0.0281 (8)	0.0337 (8)	0.0281 (8)	−0.0041 (7)	0.0127 (7)	−0.0068 (7)
C6	0.0427 (9)	0.0455 (10)	0.0237 (8)	−0.0104 (8)	0.0159 (7)	−0.0056 (7)
C7	0.0407 (9)	0.0398 (9)	0.0279 (8)	−0.0089 (8)	0.0177 (7)	−0.0019 (7)
C8	0.0334 (8)	0.0406 (9)	0.0286 (8)	−0.0077 (7)	0.0138 (7)	−0.0100 (7)
O1W	0.0539 (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—O1	1.9315 (13)	C4—H4	0.9500
Zn1—O1ⁱ	1.9315 (13)	C5—C6	1.390 (3)
Zn1—N1ⁱ	2.0219 (14)	C5—C8	1.464 (2)
Zn1—N1	2.0219 (14)	C6—C7	1.376 (3)
O1—C1	1.262 (2)	C6—H6	0.9500
O2—C1	1.221 (2)	C7—H7	0.9500
N1—C3	1.342 (2)	C8—C8ⁱⁱⁱ	1.324 (4)
N1—C7	1.343 (2)	C8—H8	0.9500
C1—C2	1.471 (2)	O1W—H1A	0.831 (16)
C2—C2ⁱⁱ	1.186 (4)	O1W—H1B	0.866 (19)
C3—C4	1.372 (2)	O1W—H1A	0.805 (18)
C3—H3	0.9500	O1W—H1B	0.83 (2)
C4—C5	1.397 (2)

O1—Zn1—O1ⁱ	103.37 (9)	C3—C4—C5	119.58 (17)
O1—Zn1—N1ⁱ	100.84 (6)	C3—C4—H4	120.2
O1ⁱ—Zn1—N1ⁱ	125.13 (6)	C5—C4—H4	120.2
O1—Zn1—N1	125.13 (6)	C6—C5—C4	117.11 (16)
O1ⁱ—Zn1—N1	100.84 (6)	C6—C5—C8	119.89 (16)
N1ⁱ—Zn1—N1	104.00 (8)	C4—C5—C8	123.01 (17)
C1—O1—Zn1	123.18 (12)	C7—C6—C5	119.97 (16)
C3—N1—C7	117.66 (15)	C7—C6—H6	120.0
C3—N1—Zn1	121.26 (11)	C5—C6—H6	120.0
C7—N1—Zn1	120.69 (12)	N1—C7—C6	122.60 (17)
O2—C1—O1	126.62 (17)	N1—C7—H7	118.7
O2—C1—C2	119.67 (18)	C6—C7—H7	118.7
O1—C1—C2	113.70 (16)	C8ⁱⁱⁱ—C8—C5	125.2 (2)
C2ⁱⁱ—C2—C1	178.5 (3)	C8ⁱⁱⁱ—C8—H8	117.4
N1—C3—C4	123.07 (16)	C5—C8—H8	117.4
N1—C3—H3	118.5	H1A—O1W—H1B	107 (3)
C4—C3—H3	118.5	H1A—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···A	D—H	H···A	D···A	D—H···A
C3—H3···O2	0.95	2.52	3.208 (2)	129
O1W—H1B···O1W^iv	0.87 (2)	2.28 (4)	2.984 (4)	138 (6)
O1W—H1B···O1W*^v	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: (iv) −x+1/2, y+1/2, −z+3/2; (v) −x+1/2, y−1/2, −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.

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