catena-Poly[[bis­(1H-indole-5-carboxyl­ato-κ2O,O′)zinc(II)]-μ-4,4′-azobi­pyridine-κ2N1:N1′]

Sathya, U.; Nirmal Ram, J.S.; Gomathi, S.; Jegan Jennifer, S.; Abdul Razak, I.

doi:10.1107/S2414314621005228

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 5| May 2021| x210522

https://doi.org/10.1107/S2414314621005228

Open

access

catena-Poly[[bis(1H-indole-5-carboxylato-κ²O,O′)zinc(II)]-μ-4,4′-azobipyridine-κ²N¹:N^1′]

Udhayasuriyan Sathya,^a Jeyaraman Selvaraj Nirmal Ram,^a ^* Sundaramoorthy Gomathi,^b Samson Jegan Jennifer ^c and Ibrahim Abdul Razak ^c

^aCentre for Research and Development, PRIST Deemed to be University, Thanjavur, 613 403, Tamil Nadu, India, ^bDepartment of Chemistry, Periyar Maniammai Institute of Science and Technology, Thanjavur 613 403, Tamil Nadu, India, and ^cX-ray Crystallography Unit, School of Physics, University Sains Malaysia, 11800, USM, Penang, Malaysia
^*Correspondence e-mail: nirmalramjs@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 12 May 2021; accepted 15 May 2021; online 21 May 2021)

The asymmetric unit of the title coordination polymer [Zn(C₉H₆NO₂)₂(C₁₀H₈N₄)]_n, consists of one Zn^II cation, one bidentate 1H-indole-5-carboxylate (I5C) anion and half of a 4,4′-azobipyridine (Abpy) neutral ligand. In the coordination polyhedron, the Zn^II ion adopts a distorted octahedral geometry. The coordination polymer is stabilized by a combination of N—H⋯O and C—H⋯π interactions, which leads to the formation of wave-like two-dimensional coordination polymeric layers.

Keywords: crystal engineering; coordination polymer; metal-organic framework; structural chemistry; non-covalent interactions; crystal structure.

CCDC reference: 2083957

Structure description

The design of coordination polymers (CPs) and metal–organic frameworks (MOFs) is one of the most important fields in inorganic crystal engineering and material science because of their utility, functions and interesting architectures (Ying et al., 2015 ; Li et al., 2018 ). The self-assembly of metal–organic frameworks and coordination polymers is obtained by complexing metal ions with organic ligands (Li et al., 2018). In the field of storage and separation sciences, MOFs are a strong competitor for zeolites and carbon nanotubes (Naik et al., 2011 ; Cui et al., 2014 ). Several MOF structures with Zn^II ions have recently been reported (Ying et al., 2015; Huang et al., 2015 ; Liu et al., 2017 ; Chen et al., 2020 ). In the present work, we report the crystal structure of a Zn^II-containing coordination polymer constructed using 4,4′-azopyridine and indole-5-carboxylic acid.

The asymmetric unit consists of one Zn^II cation, one bidentate 1H-indole-5-carboxylate (I5C) anion and half of a 4,4′-azobipyridine (Abpy) neutral ligand. The other half of the Abpy ligand is generated by a centre of inversion (symmetry operation − $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, −z) and it bridges the adjacent Zn^II ion as shown in Fig. 1. Thus, one neutral Abpy ligand bridges two Zn^II ions. Each of the Zn^II centres has a six-coordinate N₂O₄ environment being bonded to the O atoms of two bidentate (I5C) anions and the N atoms of two (Abpy) ligands in a distorted octahedral geometry. The Zn—O1, Zn—O2 and Zn—N2 distances are 2.145 (3), 2.227 (3) and 2.098 (3) Å, respectively.

Figure 1
The title complex showing the local coordination around the Zn^II metal. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) −x, y, $[{1\over 2}]$ − z; (ii) $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z.

The six-coordinated monomeric Zn^II unit extends as a zigzag chain in the [ $[\overline{1}]$ 01] direction. Adjacent chains are linked through N—H⋯Oⁱ [symmetry code: (i) x, −y, − $[{1\over 2}]$ + z] hydrogen bonds connecting the N atom of an indole moiety and an O atom of a symmetry-related indole moiety (Table 1, Fig. 2). Adjacent layers are held together by weak C—H⋯π interactions between the C—H group of an Abpy ligand and the aromatic ring of an I5C anion (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.84 (4)	2.02 (4)	2.840 (5)	165 (4)
C12—H12⋯Cgⁱⁱ	0.93	2.79	3.454 (5)	129
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
Polyhedral representation of the one-dimensional coordination polymer linked together by N—H⋯O (blue dotted lines).

Synthesis and crystallization

Zn(CH₃COO)₂(H₂O)₂ (50 mg), indole-5-carboxylic acid (35 mg), 4,4′-azopyridine (35 mg) and deionized water (2.5 ml) were loaded into a 25 ml Teflon-lined stainless steel autoclave to produce the title complex. After being heated at 90°C for 3 d, the autoclave was then cooled to room temperature. Orange–yellow needle-shaped crystals suitable for X-ray diffraction studies were obtained in 65% yield based on the initial Zn(CH₃COO)₂(H₂O)₂ input. The reaction scheme is shown in Fig. 3

Figure 3
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Zn(C₉H₆NO₂)₂(C₁₀H₈N₄)]
M_r	569.89
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.982 (3), 11.603 (3), 14.237 (3)
β (°)	119.545 (9)
V (Å³)	2727.9 (10)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.95
Crystal size (mm)	0.45 × 0.40 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.892, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	36639, 3148, 2047
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.147, 1.07
No. of reflections	3148
No. of parameters	181
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.31
Computer programs: APEX2 and SAINT (Bruker, 2016), SHELXS97 (Sheldrick 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), PLATON (Spek, 2020 ), Mercury (Macrae et al., 2020 ), POVRay (Cason, 2004 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2083957

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621005228/bt4113sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621005228/bt4113Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020), Mercury (Macrae et al., 2020) and POVRay (Cason, 2004); software used to prepare material for publication: PLATON (Spek, 2020) and publCIF (Westrip, 2010).

catena-Poly[[bis(1H-indole-5-carboxylato-κ²O,O')zinc(II)]-µ-4,4'-azobipyridine-κ²N¹:N^1'] top

Crystal data top

[Zn(C₉H₆NO₂)₂(C₁₀H₈N₄)]	F(000) = 1168
M_r = 569.89	D_x = 1.388 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.982 (3) Å	Cell parameters from 3148 reflections
b = 11.603 (3) Å	θ = 3.0–27.6°
c = 14.237 (3) Å	µ = 0.95 mm⁻¹
β = 119.545 (9)°	T = 293 K
V = 2727.9 (10) Å³	Needle, orange yellow
Z = 4	0.45 × 0.40 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2047 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.093
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θ_max = 27.6°, θ_min = 3.0°
T_min = 0.892, T_max = 1.000	h = −24→24
36639 measured reflections	k = −14→15
3148 independent reflections	l = −18→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0694P)² + 3.0748P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
3148 reflections	Δρ_max = 0.80 e Å⁻³
181 parameters	Δρ_min = −0.31 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.

Refinement. H atoms bonded to C were positioned geometrically and refined using a riding model with C—H = 0.93 and with U_iso(H) = 1.2 U_eq(C). The H atom bonded to N was freely refined.

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

	x	y	z	U_iso*/U_eq
Zn	0.000000	0.32303 (5)	0.250000	0.0404 (2)
O1	−0.03670 (16)	0.2799 (2)	0.3661 (2)	0.0602 (7)
O2	−0.08988 (17)	0.1830 (2)	0.2149 (2)	0.0575 (7)
N2	0.08542 (17)	0.4456 (2)	0.3501 (2)	0.0434 (7)
N1	−0.1652 (2)	−0.1717 (3)	0.4864 (3)	0.0613 (10)
C11	0.1396 (2)	0.4866 (3)	0.3247 (3)	0.0526 (10)
H11	0.142954	0.452255	0.268083	0.063*
C15	0.0838 (2)	0.4929 (3)	0.4348 (3)	0.0583 (10)
H15	0.047793	0.463582	0.455364	0.070*
C10	−0.0757 (2)	0.1944 (3)	0.3109 (3)	0.0469 (9)
C5	−0.1028 (2)	0.1024 (3)	0.3604 (3)	0.0425 (8)
C4	−0.0774 (2)	0.1069 (3)	0.4716 (3)	0.0482 (9)
H4	−0.048102	0.170393	0.511737	0.058*
C3	−0.0950 (2)	0.0195 (3)	0.5220 (3)	0.0532 (10)
H3	−0.078181	0.022609	0.595334	0.064*
C2	−0.1391 (2)	−0.0739 (3)	0.4587 (3)	0.0469 (9)
C7	−0.1657 (2)	−0.0803 (3)	0.3476 (3)	0.0452 (9)
C6	−0.1464 (2)	0.0091 (3)	0.2991 (3)	0.0452 (8)
H6	−0.162844	0.006069	0.225859	0.054*
C8	−0.2084 (3)	−0.1871 (3)	0.3108 (3)	0.0610 (11)
H8	−0.232998	−0.215508	0.240609	0.073*
C9	−0.2062 (3)	−0.2386 (4)	0.3965 (4)	0.0673 (12)
H9	−0.229238	−0.309784	0.394937	0.081*
N3	0.23604 (19)	0.7221 (3)	0.5240 (2)	0.0514 (8)
C13	0.1860 (2)	0.6272 (3)	0.4617 (3)	0.0452 (8)
C12	0.1904 (2)	0.5767 (3)	0.3778 (3)	0.0513 (9)
H12	0.227142	0.602936	0.357322	0.062*
C14	0.1330 (3)	0.5827 (4)	0.4924 (3)	0.0622 (11)
H14	0.130747	0.613281	0.551185	0.075*
H1	−0.151 (3)	−0.180 (3)	0.552 (4)	0.063 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0440 (4)	0.0333 (3)	0.0460 (4)	0.000	0.0237 (3)	0.000
O1	0.0641 (18)	0.0530 (16)	0.0655 (18)	−0.0108 (14)	0.0335 (15)	0.0033 (14)
O2	0.0726 (18)	0.0563 (17)	0.0555 (17)	0.0030 (14)	0.0406 (14)	0.0111 (13)
N2	0.0444 (17)	0.0367 (16)	0.0532 (18)	−0.0036 (13)	0.0272 (15)	−0.0041 (13)
N1	0.064 (2)	0.068 (2)	0.056 (2)	−0.0037 (18)	0.0317 (19)	0.020 (2)
C11	0.059 (2)	0.047 (2)	0.059 (2)	−0.0088 (19)	0.035 (2)	−0.0158 (19)
C15	0.068 (3)	0.056 (2)	0.066 (3)	−0.019 (2)	0.045 (2)	−0.015 (2)
C10	0.0398 (19)	0.045 (2)	0.059 (2)	0.0081 (17)	0.0265 (18)	0.0116 (19)
C5	0.046 (2)	0.046 (2)	0.0423 (19)	0.0089 (16)	0.0267 (17)	0.0100 (16)
C4	0.050 (2)	0.049 (2)	0.046 (2)	−0.0010 (17)	0.0241 (18)	−0.0024 (17)
C3	0.055 (2)	0.069 (3)	0.039 (2)	0.005 (2)	0.0255 (18)	0.0095 (19)
C2	0.044 (2)	0.051 (2)	0.047 (2)	0.0038 (17)	0.0238 (17)	0.0115 (18)
C7	0.046 (2)	0.047 (2)	0.045 (2)	0.0044 (17)	0.0249 (17)	0.0049 (17)
C6	0.050 (2)	0.051 (2)	0.0383 (19)	0.0025 (17)	0.0242 (17)	0.0044 (17)
C8	0.066 (3)	0.058 (3)	0.055 (2)	−0.007 (2)	0.027 (2)	0.005 (2)
C9	0.067 (3)	0.058 (3)	0.072 (3)	−0.008 (2)	0.031 (2)	0.008 (2)
N3	0.0558 (19)	0.0453 (18)	0.0508 (19)	−0.0127 (15)	0.0245 (15)	−0.0079 (15)
C13	0.048 (2)	0.0369 (19)	0.048 (2)	−0.0060 (16)	0.0219 (18)	−0.0058 (16)
C12	0.052 (2)	0.045 (2)	0.066 (3)	−0.0098 (17)	0.036 (2)	−0.0088 (19)
C14	0.081 (3)	0.061 (3)	0.059 (2)	−0.023 (2)	0.045 (2)	−0.020 (2)

Geometric parameters (Å, º) top

Zn—N2	2.098 (3)	C5—C6	1.381 (5)
Zn—N2ⁱ	2.098 (3)	C5—C4	1.410 (5)
Zn—O1	2.145 (3)	C4—C3	1.375 (5)
Zn—O1ⁱ	2.145 (3)	C4—H4	0.9300
Zn—O2ⁱ	2.227 (3)	C3—C2	1.394 (5)
Zn—O2	2.227 (3)	C3—H3	0.9300
Zn—C10ⁱ	2.505 (4)	C2—C7	1.405 (5)
Zn—C10	2.505 (4)	C7—C6	1.392 (5)
O1—C10	1.255 (4)	C7—C8	1.431 (5)
O2—C10	1.263 (5)	C6—H6	0.9300
N2—C11	1.333 (4)	C8—C9	1.340 (6)
N2—C15	1.340 (4)	C8—H8	0.9300
N1—C9	1.365 (6)	C9—H9	0.9300
N1—C2	1.373 (5)	N3—N3ⁱⁱ	1.236 (6)
N1—H1	0.84 (4)	N3—C13	1.438 (5)
C11—C12	1.370 (5)	C13—C12	1.369 (5)
C11—H11	0.9300	C13—C14	1.379 (5)
C15—C14	1.370 (5)	C12—H12	0.9300
C15—H15	0.9300	C14—H14	0.9300
C10—C5	1.502 (5)

N2—Zn—N2ⁱ	94.68 (15)	C14—C15—H15	118.7
N2—Zn—O1	94.06 (11)	O1—C10—O2	120.3 (3)
N2ⁱ—Zn—O1	104.19 (11)	O1—C10—C5	120.1 (3)
N2—Zn—O1ⁱ	104.19 (11)	O2—C10—C5	119.6 (3)
N2ⁱ—Zn—O1ⁱ	94.06 (11)	O1—C10—Zn	58.88 (19)
O1—Zn—O1ⁱ	153.04 (16)	O2—C10—Zn	62.61 (19)
N2—Zn—O2ⁱ	95.28 (10)	C5—C10—Zn	166.6 (2)
N2ⁱ—Zn—O2ⁱ	153.72 (10)	C6—C5—C4	120.4 (3)
O1—Zn—O2ⁱ	99.28 (10)	C6—C5—C10	119.8 (3)
O1ⁱ—Zn—O2ⁱ	59.90 (10)	C4—C5—C10	119.6 (3)
N2—Zn—O2	153.72 (10)	C3—C4—C5	121.4 (3)
N2ⁱ—Zn—O2	95.28 (10)	C3—C4—H4	119.3
O1—Zn—O2	59.91 (10)	C5—C4—H4	119.3
O1ⁱ—Zn—O2	99.28 (10)	C4—C3—C2	117.3 (3)
O2ⁱ—Zn—O2	86.31 (14)	C4—C3—H3	121.3
N2—Zn—C10ⁱ	104.80 (11)	C2—C3—H3	121.3
N2ⁱ—Zn—C10ⁱ	123.50 (12)	N1—C2—C3	130.1 (4)
O1—Zn—C10ⁱ	125.99 (13)	N1—C2—C7	107.4 (3)
O1ⁱ—Zn—C10ⁱ	30.07 (11)	C3—C2—C7	122.5 (3)
O2ⁱ—Zn—C10ⁱ	30.23 (11)	C6—C7—C2	118.8 (3)
O2—Zn—C10ⁱ	89.71 (10)	C6—C7—C8	134.7 (3)
N2—Zn—C10	123.50 (12)	C2—C7—C8	106.5 (3)
N2ⁱ—Zn—C10	104.80 (11)	C5—C6—C7	119.5 (3)
O1—Zn—C10	30.07 (11)	C5—C6—H6	120.2
O1ⁱ—Zn—C10	125.99 (13)	C7—C6—H6	120.2
O2ⁱ—Zn—C10	89.71 (10)	C9—C8—C7	107.1 (4)
O2—Zn—C10	30.23 (11)	C9—C8—H8	126.4
C10ⁱ—Zn—C10	106.87 (17)	C7—C8—H8	126.4
C10—O1—Zn	91.0 (2)	C8—C9—N1	110.3 (4)
C10—O2—Zn	87.2 (2)	C8—C9—H9	124.8
C11—N2—C15	117.4 (3)	N1—C9—H9	124.8
C11—N2—Zn	119.9 (2)	N3ⁱⁱ—N3—C13	113.1 (4)
C15—N2—Zn	122.4 (2)	C12—C13—C14	118.9 (3)
C9—N1—C2	108.7 (4)	C12—C13—N3	124.1 (3)
C9—N1—H1	134 (3)	C14—C13—N3	117.0 (3)
C2—N1—H1	117 (3)	C13—C12—C11	118.6 (3)
N2—C11—C12	123.4 (3)	C13—C12—H12	120.7
N2—C11—H11	118.3	C11—C12—H12	120.7
C12—C11—H11	118.3	C15—C14—C13	119.0 (4)
N2—C15—C14	122.6 (4)	C15—C14—H14	120.5
N2—C15—H15	118.7	C13—C14—H14	120.5

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C2–C7 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱⁱ	0.84 (4)	2.02 (4)	2.840 (5)	165 (4)
C12—H12···Cg^iv	0.93	2.79	3.454 (5)	129

Symmetry codes: (iii) x, −y, z+1/2; (iv) x+1/2, y+1/2, z.

References

Bruker (2016). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cason, C. J. (2004). POV-RAY for Windows. Persistence of Vision, Raytracer Pty. Ltd, Victoria, Australia. URL: https://www.povray. org Google Scholar
Chen, N.-N., Zhang, C. & Tao, J.-Q. (2020). Acta Cryst. C76, 850–855. CSD CrossRef IUCr Journals Google Scholar
Cui, G.-G., Yang, X.-X. & Yang, J.-P. (2014). Acta Cryst. C70, 498–501. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, Q.-Y., Yang, Y. & Meng, X.-R. (2015). Acta Cryst. C71, 701–705. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, X.-Y., Peng, Y.-Q., Li, J., Fu, W.-W., Liu, Y. & Li, Y.-M. (2018). Acta Cryst. E74, 28–33. CSD CrossRef IUCr Journals Google Scholar
Liu, F., Ding, Y., Li, Q. & Zhang, L. (2017). Acta Cryst. E73, 1402–1404. CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Naik, A. D., Dîrtu, M. M., Railliet, A. P., Marchand-Brynaert, J. & Garcia, Y. (2011). Polymers, 3, 1750–1775. Web of Science 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ying, S.-M., Ru, J.-J. & Luo, W.-K. (2015). Acta Cryst. C71, 618–622. Web of Science CSD 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.