Two-dimensional structure of poly[[[μ2-1,4-bis­(pyridin-4-yl)butane]­bis­(μ4-penta­nedioato)dicopper(II)] aceto­nitrile disolvate]

Lee, D.N.; Kim, Y.

doi:10.1107/S2414314617014481

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 10| October 2017| x171448

https://doi.org/10.1107/S2414314617014481

Open

access

Two-dimensional structure of poly[[[μ₂-1,4-bis(pyridin-4-yl)butane]bis(μ₄-pentanedioato)dicopper(II)] acetonitrile disolvate]

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 A. J. Lough, University of Toronto, Canada (Received 25 September 2017; accepted 7 October 2017; online 13 October 2017)

In the title compound, {[Cu₂(μ₄-C₅H₆O₄)₂(μ₂-C₁₄H₁₆N₂)]·2CH₃CN}_n, the Cu₂ dinuclear units are connected by glutartate ligands, forming one-dimensional double chains. These chains, are in turn bridged by 1,4-bis(pyridin-4-yl)butane ligands to form a two-dimensional layer structure parallel to (112). The carboxylate groups of the glutarate ligand bridge two copper(II) ions, forming a paddle-wheel-type Cu₂(CO₂)₄ dinuclear secondary building unit. A crystallographic inversion centre is located midway between two Cu^II ions, with a Cu⋯Cu distance of 2.639 (3) Å. The coordination geometry of the unique Cu^II ion is slightly disorted square pyramidal, formed by four equatorial carboxylate O atoms and an axial pyridyl N atom.

Keywords: crystal structure; Cu–MOF; glutarate; 1,4-bis(pyridin-4-yl)butane.

CCDC reference: 1578612

Structure description

Metal–organic frameworks (MOFs) have been constructed using metal ions and polytopic bridging ligands, and MOFs usually provide high surfaces and large pore volumes, and are thereby suitable for various advanced applications, such as selective gas sorption, heterogeneous catalysis, separation, sensors, drug delivery and biological imaging. Flexible dicarboxylates, as well as rigid aromatic dicarboxylates, have been used for the synthesis of MOFs, and flexible dicarboxylates, e.g. α,ω-alkanedicarboxylates, have been shown to be particularly suitable as ligands in MOFs of various topologies. Recently, various MOFs containing these α,ω-alkane(or alkene)dicarboxylate ligands have been reported (Hyun et al., 2013 ; Hwang et al., 2012 , 2013 ; Lee et al., 2014 ; Kim et al., 2017 ), athough they are less frequently employed in MOFs than aromatic dicarboxylates. We report herein the crystal structure of poly[[[μ₂-1,4-bis(pyridin-4-yl)butane]bis(μ₄-pentanedioato)dicopper(II)] acetonitrile disolvate].

A fragment of the two-dimensional title compound is shown in Fig. 1. The Cu₂ dinuclear units are connected by glutartate ligands, forming one-dimensional double chains, and these chains are bridged by 1,4-bis(pyridin-4-yl)butane ligands to form a two-dimensional layer structure parallel to (112) (Fig. 2). The carboxylate groups of the glutarate ligands bridge two Cu^II ions, forming a paddle-wheel-type Cu₂(CO₂)₄ dinuclear secondary building unit. A crystallographic inversion centre is located midway between two Cu^II ions, with a Cu⋯Cu distance of 2.639 (3) Å. The coordination geometry of the unique Cu^II ion is slightly distorted square-pyramidal, constructed by four equatorial carboxylate O atoms and an axial pyridyl N atom.

Figure 1
A fragment of the title compound, showing displacement ellipsoids at the 30% probability level. [Symmetry codes: (i) 1 − x, 1 − y, 2 − z; (ii) 1 − x, −y, 2 − z; (iii) 3 − x, 1 − y, 1 − z.]

Figure 2
Two-dimensional structure of the title compound. The acetonitrile solvent molecules have been omitted for clarity.

Synthesis and crystallization

Glutaric acid (0.1 mmol, 13.3 mg) and Cu(NO₃)₂·H₂O (0.1 mmol, 23.7 mg) were dissolved in 4 ml H₂O and carefully layered by a 4 ml acetonitrile solution of 1,4-bis(pyridin-4-yl)butane (0.2 mmol, 42.5 mg). Suitable crystals of the title compound were obtained within a few weeks.

Refinement

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

Table 1
Experimental details

Crystal data
Chemical formula	[Cu₂(C₅H₆O₄)₂(C₁₄H₁₆N₂)]·2C₂H₃N
M_r	681.67
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	170
a, b, c (Å)	7.7525 (11), 7.9962 (11), 12.8132 (18)
α, β, γ (°)	87.867 (2), 81.875 (2), 82.674 (2)
V (Å³)	779.76 (19)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.42
Crystal size (mm)	0.21 × 0.10 × 0.07

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997 )
T_min, T_max	0.804, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	4341, 2979, 1863
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.108, 0.89
No. of reflections	2979
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.38
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008 ), SHELXL2013 (Sheldrick, 2015 ), DIAMOND (Brandenburg & Berndt, 1998 ) and SHELXTL (Sheldrick, 2008).

Structural data

CCDC reference: 1578612

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617014481/lh4026sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617014481/lh4026Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg & Berndt, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Poly[[[µ₂-1,4-bis(pyridin-4-yl)butane]bis(µ₄-pentanedioato)dicopper(II)] acetonitrile disolvate] top

Crystal data top

[Cu₂(C₅H₆O₄)₂(C₁₄H₁₆N₂)]_.2C₂H₃N	Z = 1
M_r = 681.67	F(000) = 352
Triclinic, P1	D_x = 1.452 Mg m⁻³
a = 7.7525 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9962 (11) Å	Cell parameters from 2966 reflections
c = 12.8132 (18) Å	θ = 2.2–26.2°
α = 87.867 (2)°	µ = 1.42 mm⁻¹
β = 81.875 (2)°	T = 170 K
γ = 82.674 (2)°	Block, blue
V = 779.76 (19) Å³	0.21 × 0.10 × 0.07 mm

Data collection top

Bruker APEX CCD diffractometer	1863 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.062
Absorption correction: multi-scan (SADABS; Bruker, 1997)	θ_max = 26.0°, θ_min = 2.6°
T_min = 0.804, T_max = 0.910	h = −9→9
4341 measured reflections	k = −9→9
2979 independent reflections	l = −15→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0347P)²] where P = (F_o² + 2F_c²)/3
S = 0.89	(Δ/σ)_max = 0.002
2979 reflections	Δρ_max = 0.95 e Å⁻³
191 parameters	Δρ_min = −0.38 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.62490 (7)	0.51464 (6)	0.92000 (4)	0.0290 (2)
O11	0.5339 (4)	0.3241 (4)	0.8619 (2)	0.0412 (8)
O12	0.6750 (4)	0.7057 (4)	1.0021 (2)	0.0404 (8)
O21	0.7596 (4)	0.3508 (4)	1.0043 (2)	0.0404 (8)
O22	0.4478 (4)	0.6742 (4)	0.8592 (2)	0.0381 (8)
N31	0.8414 (5)	0.5371 (4)	0.7959 (3)	0.0331 (9)
C11	0.4123 (6)	0.2480 (5)	0.9120 (4)	0.0306 (10)
C12	0.3767 (6)	0.0878 (5)	0.8647 (4)	0.0380 (11)
H12A	0.4735	−0.0019	0.8752	0.046*
H12B	0.3788	0.1067	0.7877	0.046*
C13	0.2032 (5)	0.0246 (5)	0.9092 (4)	0.0347 (11)
H13A	0.1965	0.0125	0.9868	0.042*
H13B	0.1051	0.1095	0.8937	0.042*
C21	0.7012 (6)	0.2860 (5)	1.0915 (4)	0.0307 (10)
C22	0.8184 (6)	0.1436 (5)	1.1359 (3)	0.0343 (11)
H22A	0.7890	0.1389	1.2136	0.041*
H22B	0.9424	0.1650	1.1189	0.041*
C31	1.0050 (6)	0.4805 (5)	0.8086 (3)	0.0336 (11)
H31	1.0250	0.4252	0.8735	0.040*
C32	1.1470 (6)	0.4962 (6)	0.7344 (4)	0.0377 (11)
H32	1.2613	0.4501	0.7475	0.045*
C33	1.1231 (6)	0.5799 (6)	0.6399 (4)	0.0396 (12)
C34	0.9544 (6)	0.6400 (7)	0.6260 (4)	0.0554 (15)
H34	0.9313	0.6981	0.5625	0.067*
C35	0.8182 (6)	0.6158 (6)	0.7042 (4)	0.0468 (13)
H35	0.7020	0.6571	0.6923	0.056*
C36	1.2771 (7)	0.6114 (7)	0.5565 (4)	0.0684 (17)
H36A	1.2327	0.6280	0.4876	0.082*
H36B	1.3180	0.7186	0.5729	0.082*
C37	1.4299 (7)	0.4809 (7)	0.5443 (4)	0.0622 (16)
H37A	1.3902	0.3717	0.5311	0.075*
H37B	1.4812	0.4690	0.6111	0.075*
N1S	1.1372 (9)	0.0804 (8)	0.6005 (5)	0.105 (2)
C1S	1.0053 (11)	0.0854 (8)	0.6449 (6)	0.077 (2)
C2S	0.8316 (9)	0.0914 (9)	0.7021 (6)	0.106 (2)
H2S1	0.7528	0.0535	0.6569	0.160*
H2S2	0.7891	0.2073	0.7238	0.160*
H2S3	0.8342	0.0174	0.7647	0.160*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0282 (3)	0.0198 (3)	0.0365 (3)	−0.0045 (2)	0.0048 (2)	0.0014 (2)
O11	0.045 (2)	0.0324 (18)	0.044 (2)	−0.0143 (16)	0.0101 (16)	−0.0085 (15)
O12	0.043 (2)	0.0332 (19)	0.045 (2)	−0.0158 (16)	0.0044 (16)	−0.0070 (15)
O21	0.0339 (19)	0.0395 (19)	0.043 (2)	0.0011 (15)	0.0032 (15)	0.0080 (15)
O22	0.0339 (19)	0.0339 (18)	0.0423 (19)	0.0012 (15)	0.0019 (15)	0.0093 (15)
N31	0.031 (2)	0.031 (2)	0.036 (2)	−0.0069 (18)	−0.0005 (18)	0.0012 (17)
C11	0.032 (3)	0.023 (2)	0.037 (3)	0.001 (2)	−0.007 (2)	0.000 (2)
C12	0.044 (3)	0.027 (3)	0.044 (3)	−0.010 (2)	−0.004 (2)	−0.004 (2)
C13	0.031 (3)	0.020 (2)	0.053 (3)	−0.001 (2)	−0.008 (2)	−0.005 (2)
C21	0.031 (3)	0.019 (2)	0.044 (3)	−0.008 (2)	−0.006 (2)	−0.003 (2)
C22	0.028 (3)	0.023 (2)	0.053 (3)	−0.006 (2)	−0.009 (2)	0.003 (2)
C31	0.031 (3)	0.031 (3)	0.037 (3)	−0.004 (2)	0.001 (2)	0.004 (2)
C32	0.027 (3)	0.039 (3)	0.046 (3)	−0.001 (2)	−0.002 (2)	−0.001 (2)
C33	0.036 (3)	0.036 (3)	0.043 (3)	−0.006 (2)	0.011 (2)	−0.001 (2)
C34	0.043 (3)	0.071 (4)	0.046 (3)	0.001 (3)	0.002 (3)	0.020 (3)
C35	0.025 (3)	0.062 (4)	0.050 (3)	0.002 (2)	−0.002 (2)	0.014 (3)
C36	0.051 (4)	0.074 (4)	0.071 (4)	−0.010 (3)	0.019 (3)	0.015 (3)
C37	0.044 (3)	0.076 (4)	0.058 (4)	−0.008 (3)	0.020 (3)	0.001 (3)
N1S	0.108 (5)	0.103 (5)	0.098 (5)	−0.003 (5)	−0.001 (4)	0.017 (4)
C1S	0.090 (6)	0.062 (4)	0.072 (5)	0.008 (4)	−0.004 (4)	0.004 (4)
C2S	0.102 (6)	0.084 (5)	0.125 (6)	0.007 (5)	−0.002 (5)	−0.003 (4)

Geometric parameters (Å, º) top

Cu1—O21	1.959 (3)	C22—H22A	0.9900
Cu1—O11	1.970 (3)	C22—H22B	0.9900
Cu1—O22	1.976 (3)	C31—C32	1.364 (6)
Cu1—O12	1.994 (3)	C31—H31	0.9500
Cu1—N31	2.163 (3)	C32—C33	1.386 (6)
Cu1—Cu1ⁱ	2.6392 (11)	C32—H32	0.9500
O11—C11	1.271 (5)	C33—C34	1.368 (6)
O12—C11ⁱ	1.251 (5)	C33—C36	1.526 (6)
O21—C21	1.263 (5)	C34—C35	1.376 (6)
O22—C21ⁱ	1.245 (5)	C34—H34	0.9500
N31—C31	1.321 (5)	C35—H35	0.9500
N31—C35	1.337 (5)	C36—C37	1.470 (7)
C11—O12ⁱ	1.251 (5)	C36—H36A	0.9900
C11—C12	1.510 (5)	C36—H36B	0.9900
C12—C13	1.525 (6)	C37—C37ⁱⁱⁱ	1.508 (9)
C12—H12A	0.9900	C37—H37A	0.9900
C12—H12B	0.9900	C37—H37B	0.9900
C13—C22ⁱⁱ	1.521 (5)	N1S—C1S	1.094 (8)
C13—H13A	0.9900	C1S—C2S	1.435 (9)
C13—H13B	0.9900	C2S—H2S1	0.9800
C21—O22ⁱ	1.245 (5)	C2S—H2S2	0.9800
C21—C22	1.510 (5)	C2S—H2S3	0.9800
C22—C13ⁱⁱ	1.521 (5)

O21—Cu1—O11	88.10 (13)	C21—C22—C13ⁱⁱ	111.1 (3)
O21—Cu1—O22	167.84 (12)	C21—C22—H22A	109.4
O11—Cu1—O22	90.17 (12)	C13ⁱⁱ—C22—H22A	109.4
O21—Cu1—O12	91.43 (12)	C21—C22—H22B	109.4
O11—Cu1—O12	168.18 (12)	C13ⁱⁱ—C22—H22B	109.4
O22—Cu1—O12	87.80 (12)	H22A—C22—H22B	108.0
O21—Cu1—N31	94.73 (13)	N31—C31—C32	124.2 (4)
O11—Cu1—N31	97.41 (12)	N31—C31—H31	117.9
O22—Cu1—N31	97.42 (13)	C32—C31—H31	117.9
O12—Cu1—N31	94.39 (13)	C31—C32—C33	119.4 (4)
O21—Cu1—Cu1ⁱ	82.35 (9)	C31—C32—H32	120.3
O11—Cu1—Cu1ⁱ	84.67 (9)	C33—C32—H32	120.3
O22—Cu1—Cu1ⁱ	85.51 (9)	C34—C33—C32	117.0 (4)
O12—Cu1—Cu1ⁱ	83.57 (9)	C34—C33—C36	120.9 (4)
N31—Cu1—Cu1ⁱ	176.38 (10)	C32—C33—C36	122.1 (5)
C11—O11—Cu1	123.1 (3)	C33—C34—C35	119.8 (4)
C11ⁱ—O12—Cu1	123.7 (3)	C33—C34—H34	120.1
C21—O21—Cu1	125.6 (3)	C35—C34—H34	120.1
C21ⁱ—O22—Cu1	121.4 (3)	N31—C35—C34	123.2 (4)
C31—N31—C35	116.3 (4)	N31—C35—H35	118.4
C31—N31—Cu1	121.7 (3)	C34—C35—H35	118.4
C35—N31—Cu1	121.9 (3)	C37—C36—C33	117.4 (4)
O12ⁱ—C11—O11	124.6 (4)	C37—C36—H36A	108.0
O12ⁱ—C11—C12	118.6 (4)	C33—C36—H36A	108.0
O11—C11—C12	116.8 (4)	C37—C36—H36B	108.0
C11—C12—C13	115.4 (4)	C33—C36—H36B	108.0
C11—C12—H12A	108.4	H36A—C36—H36B	107.2
C13—C12—H12A	108.4	C36—C37—C37ⁱⁱⁱ	113.3 (6)
C11—C12—H12B	108.4	C36—C37—H37A	108.9
C13—C12—H12B	108.4	C37ⁱⁱⁱ—C37—H37A	108.9
H12A—C12—H12B	107.5	C36—C37—H37B	108.9
C22ⁱⁱ—C13—C12	112.7 (4)	C37ⁱⁱⁱ—C37—H37B	108.9
C22ⁱⁱ—C13—H13A	109.0	H37A—C37—H37B	107.7
C12—C13—H13A	109.0	N1S—C1S—C2S	179.4 (10)
C22ⁱⁱ—C13—H13B	109.0	C1S—C2S—H2S1	109.5
C12—C13—H13B	109.0	C1S—C2S—H2S2	109.5
H13A—C13—H13B	107.8	H2S1—C2S—H2S2	109.5
O22ⁱ—C21—O21	124.9 (4)	C1S—C2S—H2S3	109.5
O22ⁱ—C21—C22	117.9 (4)	H2S1—C2S—H2S3	109.5
O21—C21—C22	117.1 (4)	H2S2—C2S—H2S3	109.5

Cu1—O11—C11—O12ⁱ	7.5 (6)	N31—C31—C32—C33	1.7 (7)
Cu1—O11—C11—C12	−170.5 (3)	C31—C32—C33—C34	−1.2 (7)
O12ⁱ—C11—C12—C13	17.0 (6)	C31—C32—C33—C36	176.2 (4)
O11—C11—C12—C13	−164.8 (4)	C32—C33—C34—C35	0.0 (7)
C11—C12—C13—C22ⁱⁱ	−175.8 (3)	C36—C33—C34—C35	−177.4 (5)
Cu1—O21—C21—O22ⁱ	−5.5 (6)	C31—N31—C35—C34	−0.6 (7)
Cu1—O21—C21—C22	171.3 (2)	Cu1—N31—C35—C34	176.5 (4)
O22ⁱ—C21—C22—C13ⁱⁱ	91.8 (5)	C33—C34—C35—N31	0.9 (8)
O21—C21—C22—C13ⁱⁱ	−85.2 (5)	C34—C33—C36—C37	−147.8 (5)
C35—N31—C31—C32	−0.7 (6)	C32—C33—C36—C37	34.8 (8)
Cu1—N31—C31—C32	−177.8 (3)	C33—C36—C37—C37ⁱⁱⁱ	176.6 (5)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+3, −y+1, −z+1.

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

Brandenburg, K. & Berndt, M. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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, 12759–12763. Web of Science CSD CrossRef CAS PubMed Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
Kim, 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
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. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.