catena-Poly[[di­aqua­cadmium(II)]-μ2-3-(4-carboxyl­atophen­yl)propionato]

Ezenyilimba, F.C.; Staples, R.J.; LaDuca, R.L.

doi:10.1107/S2414314619009945

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 7| July 2019| x190994

https://doi.org/10.1107/S2414314619009945

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catena-Poly[[diaquacadmium(II)]-μ₂-3-(4-carboxylatophenyl)propionato]

Frederick C. Ezenyilimba,^a Richard J. Staples ^b and Robert L. LaDuca ^a ^*

^aE-35 Holmes Hall, Michigan State University, Lyman Briggs College, 919 E. Shaw Lane, East Lansing, MI 48825, USA, and ^bMichigan State University, Department of Chemistry, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 5 July 2019; accepted 11 July 2019; online 19 July 2019)

In the title compound, [Cd(C₁₀H₈O₄)(H₂O)₂)]_n, the Cd^II cation is coordinated in a distorted trigonal–prismatic fashion. 3-(4-Carboxyphenyl)propionate (cpp) ligands connect the Cd^II cations into zigzag [Cd(cpp)(H₂O)₂)]_n coordination polymer chains, which are oriented parallel to [101]. The chains aggregate into supramolecular layers oriented parallel to (10 $[\overline{1}]$ ) by means of O—H⋯O hydrogen bonding between bound water molecules and ligating cpp carboxylate O atoms. The layers stack in an ABAB pattern along [100] via other O—H⋯O hydrogen-bonding mechanisms also involving the bound water molecules. The crystal studied was an inversion twin.

Keywords: crystal structure; cadmium; 3-(4-carboxyphenyl)propionate.

CCDC reference: 1940078

Structure description

The title compound was isolated during an exploratory synthetic effort aiming to produce a cadmium coordination polymer containing both 3-(4-carboxyphenyl)propionate (cpp) and butane-(1,4-diyl)dinicotinamide (bbn) ligands. Cadmium camphorate coordination polymers containing the bbn ligand or other related dipyridylamides have shown intriguing and diverse topologies (Przybyla & LaDuca, 2018 ).

The asymmetric unit of the title compound contains a Cd^II cation, a cpp ligand, and two bound water molecules (O5, O6). The Cd^II cation is coordinated in a {CdO₆} trigonal prismatic fashion, with two bound water molecules and chelating carboxylate groups belonging to two different cpp ligands. An ellipsoid plot of the coordination environment and complete ligand set is shown in Fig. 1. The bis(bidentate) cpp ligands form [Cd(cpp)(H₂O)₂]_n zigzag coordination polymer chains oriented parallel [101] (Fig. 2). Within a chain, the Cd⋯Cd distance through a ligand measures 13.480 (2) Å.

Figure 1
The coordination environment of the Cd^II atom, showing trigonal–prismatic coordination. Displacement ellipsoids are drawn at the 50% probability level. H atom positions are shown as sticks. [Symmetry code: (i) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ].

Figure 2
[Cd(cpp)(H₂O)₂]_n coordination polymer chain in the title compound, oriented parallel [101].

The [Cd(cpp)(H₂O)₂]_n zigzag chains construct supramolecular layers oriented parallel (10 $[\overline{1}]$ ) by means of O—H⋯O hydrogen bonding (Table 1) between bound water molecules and ligating cpp carboxylate oxygen atoms (Fig. 3) The O⋯O distance across these hydrogen bonds measure 2.67 (2) and 2.735 (18) Å. The supramolecular layers in turn stack in an ABAB pattern along the a-axis direction (Fig. 4), mediated by O—H⋯O hydrogen bonding between bound water molecules and other ligated cpp carboxylate oxygen atoms with a O⋯O distance of 2.692 (16) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O4ⁱ	0.97	2.28	2.653 (15)	102
O6—H6B⋯O3ⁱⁱ	0.98	1.76	2.735 (18)	176
O5—H5A⋯O1ⁱⁱⁱ	0.90	1.87	2.692 (16)	151
O5—H5B⋯O2^iv	0.90	2.46	2.67 (2)	94
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) x, y+1, z.

Figure 3
Supramolecular layer in the title compound, oriented parallel (10 $[\overline{1}]$ ). The O—H⋯O hydrogen-bonding interactions between adjacent chain submotifs are shown as dashed lines

Figure 4
ABA parallel stacking of supramolecular layer motifs in the title compound along [100], mediated by interlayer O—H⋯O interactions, which are shown as dashed lines.

Synthesis and crystallization

Cd(NO₃)₂^.4H₂O (114 mg, 0.37 mmol), 3-(4-carboxyphenyl)propionic acid (72 mg, 0.37 mmol), butane-(1,4-diyl)dinicotinamide (110 mg, 0.37 mmol) and 0.75 ml of a 1.0 M NaOH solution were placed into 10 ml distilled water in a Teflon-lined acid digestion bomb. The bomb was sealed and heated in an oven at 393 K for 2 d, and then cooled slowly to 273 K. Colourless crystals of the title complex (51 mg, 41% yield based on Cd) were isolated after washing with distilled water and acetone, and drying in air.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal studied was an inversion twin with a refined Flack parameter (Flack, 1983 ) of 0.45 (3); the structure was best solved and refined in the non-centrosymmetric space group Cc. Attempts at refinement of the structure in the centrosymmetric space group C2/c resulted in disorder and an inability to refine the anisotropic displacement parameters properly.

Table 2
Experimental details

Crystal data
Chemical formula	[Cd(C₁₀H₈O₄)(H₂O)₂)]
M_r	340.60
Crystal system, space group	Monoclinic, Cc
Temperature (K)	173
a, b, c (Å)	11.91424 (16), 5.27697 (7), 18.0006 (3)
β (°)	100.2906 (7)
V (Å³)	1113.51 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	15.89
Crystal size (mm)	0.17 × 0.15 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.497, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	7603, 2127, 2032
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 1.09
No. of reflections	2127
No. of parameters	139
No. of restraints	63
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.49
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.45 (3)
Computer programs: COSMO (Bruker, 2009 ), SAINT (Bruker, 2016 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1940078

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619009945/wm4109sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619009945/wm4109Isup2.hkl

checkCIF report

Computing details top

Data collection: COSMO (Bruker, 2009); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[diaquacadmium(II)]-µ₂-3-(4-carboxylatophenyl)propionato] top

Crystal data top

[Cd(C₁₀H₈O₄)(H₂O)₂)]	F(000) = 672
M_r = 340.60	D_x = 2.032 Mg m⁻³
Monoclinic, Cc	Cu Kα radiation, λ = 1.54178 Å
a = 11.91424 (16) Å	Cell parameters from 6487 reflections
b = 5.27697 (7) Å	θ = 5.0–72.1°
c = 18.0006 (3) Å	µ = 15.89 mm⁻¹
β = 100.2906 (7)°	T = 173 K
V = 1113.51 (3) Å³	Plate, colourless
Z = 4	0.17 × 0.15 × 0.04 mm

Data collection top

Bruker APEXII CCD diffractometer	2127 independent reflections
Radiation source: sealed tube	2032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8.36 pixels mm^-1	θ_max = 72.2°, θ_min = 5.0°
ω and φ scans	h = −14→14
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −6→6
T_min = 0.497, T_max = 0.754	l = −22→21
7603 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0313P)² + 4.2565P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.63 e Å⁻³
2127 reflections	Δρ_min = −0.48 e Å⁻³
139 parameters	Absolute structure: Refined as an inversion twin
63 restraints	Absolute structure parameter: 0.45 (3)
Primary atom site location: dual

Special details top

Experimental. Data was collected using a BRUKER CCD (charge coupled device) based diffractometer equipped with an Oxford low-temperature apparatus operating at 173 K. A suitable crystal was chosen and mounted on a nylon loop using Paratone oil. Data were measured using omega and phi scans of 1.0° per frame for 30 s. The total number of images were based on results from the program COSMO where redundancy was expected to be 4 and completeness to 0.83Å to 100%. Cell parameters were retrieved using APEX II software and refined using SAINT on all observed reflections.Data reduction was performed using the SAINT software which corrects for Lp. Scaling and absorption corrections were applied using SADABS6 multi-scan technique, supplied by George Sheldrick. The structure was solved by the direct method using the SHELXT program and refined by least squares method on F2, SHELXL, incorporated in OLEX2.

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. The structure was refined by Least Squares using version 2014/6 of XL (Sheldrick, 2008) incorporated in Olex2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically. Hydrogen atom positions were calculated geometrically and refined using the riding model.

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

	x	y	z	U_iso*/U_eq
Cd1	0.5908 (3)	1.12031 (6)	0.6165 (2)	0.01947 (14)
O1	0.7708 (10)	0.943 (3)	0.6755 (7)	0.036 (3)
O2	0.6147 (12)	0.830 (3)	0.7140 (9)	0.029 (3)
O4	0.9084 (8)	−0.445 (3)	1.0590 (7)	0.030 (2)
O6	0.6909 (9)	1.4162 (19)	0.5733 (6)	0.0289 (8)
H6A	0.748862	1.495109	0.610632	0.043*
H6B	0.649566	1.569403	0.554435	0.043*
O3	1.0656 (11)	−0.334 (2)	1.0209 (8)	0.022 (3)
O5	0.4894 (8)	1.433 (2)	0.6558 (6)	0.0289 (8)
H5A	0.416242	1.387459	0.652929	0.043*
H5B	0.484777	1.566549	0.624244	0.043*
C9	0.8830 (8)	−0.1225 (14)	0.9731 (5)	0.0245 (13)
H9A	0.847794	−0.010297	1.006576	0.029*
H9B	0.820939	−0.212517	0.939340	0.029*
C1	0.7208 (13)	0.799 (3)	0.7186 (8)	0.0320 (17)
C2	0.7729 (5)	0.5954 (12)	0.7742 (4)	0.0319 (13)
C7	0.7093 (4)	0.4494 (14)	0.8159 (4)	0.0339 (13)
H7	0.629328	0.475108	0.810536	0.041*
C6	0.7627 (5)	0.2659 (14)	0.8653 (4)	0.0316 (12)
H6	0.719234	0.166173	0.893751	0.038*
C5	0.8797 (5)	0.2284 (12)	0.8731 (4)	0.0285 (11)
C4	0.9433 (4)	0.3743 (10)	0.8314 (4)	0.0290 (11)
H4	1.023238	0.348644	0.836746	0.035*
C3	0.8899 (5)	0.5578 (10)	0.7820 (3)	0.0305 (11)
H3	0.933335	0.657580	0.753531	0.037*
C8	0.9502 (7)	0.0358 (18)	0.9261 (5)	0.0270 (12)
H8A	0.988763	−0.079726	0.895392	0.032*
H8B	1.010205	0.128652	0.960705	0.032*
C10	0.9590 (12)	−0.313 (2)	1.0202 (7)	0.0218 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01434 (19)	0.01525 (19)	0.0281 (2)	0.0000 (4)	0.00181 (13)	0.0005 (4)
O1	0.026 (5)	0.037 (6)	0.041 (7)	0.013 (6)	−0.008 (4)	−0.010 (7)
O2	0.029 (7)	0.020 (5)	0.038 (7)	0.011 (5)	0.008 (5)	0.002 (6)
O4	0.007 (4)	0.032 (6)	0.052 (7)	−0.007 (5)	0.005 (4)	−0.006 (7)
O6	0.0179 (13)	0.0186 (17)	0.052 (2)	0.003 (3)	0.0123 (13)	0.016 (4)
O3	0.019 (6)	0.021 (5)	0.021 (6)	−0.003 (4)	−0.009 (4)	0.007 (5)
O5	0.0179 (13)	0.0186 (17)	0.052 (2)	0.003 (3)	0.0123 (13)	0.016 (4)
C9	0.025 (3)	0.017 (2)	0.026 (3)	0.009 (2)	−0.010 (2)	−0.002 (2)
C1	0.033 (3)	0.029 (3)	0.030 (3)	0.005 (3)	−0.006 (3)	−0.006 (3)
C2	0.033 (2)	0.029 (2)	0.030 (2)	0.007 (2)	−0.004 (2)	−0.002 (2)
C7	0.036 (3)	0.030 (2)	0.032 (2)	0.005 (2)	−0.005 (2)	0.001 (2)
C6	0.035 (3)	0.026 (2)	0.029 (2)	0.006 (2)	−0.007 (2)	0.0025 (19)
C5	0.032 (2)	0.0232 (19)	0.0263 (19)	0.007 (2)	−0.006 (2)	0.0050 (17)
C4	0.029 (2)	0.028 (2)	0.028 (2)	0.006 (2)	0.000 (2)	0.0090 (19)
C3	0.030 (2)	0.031 (2)	0.029 (2)	0.006 (2)	0.002 (2)	0.008 (2)
C8	0.028 (2)	0.021 (2)	0.027 (2)	0.008 (2)	−0.008 (2)	0.004 (2)
C10	0.021 (3)	0.014 (3)	0.026 (3)	0.008 (3)	−0.010 (3)	−0.009 (3)

Geometric parameters (Å, º) top

Cd1—O1	2.405 (13)	C9—C8	1.515 (12)
Cd1—O2	2.309 (16)	C9—C10	1.509 (12)
Cd1—O4ⁱ	2.418 (12)	C1—C2	1.525 (11)
Cd1—O6	2.190 (11)	C2—C7	1.3900
Cd1—O3ⁱ	2.269 (13)	C2—C3	1.3900
Cd1—O5	2.235 (12)	C7—H7	0.9500
Cd1—C10ⁱ	2.670 (11)	C7—C6	1.3900
O1—C1	1.30 (2)	C6—H6	0.9500
O2—C1	1.26 (2)	C6—C5	1.3900
O4—C10	1.22 (2)	C5—C4	1.3900
O6—H6A	0.9673	C5—C8	1.537 (7)
O6—H6B	0.9755	C4—H4	0.9500
O3—C10	1.27 (2)	C4—C3	1.3900
O5—H5A	0.8979	C3—H3	0.9500
O5—H5B	0.8986	C8—H8A	0.9900
C9—H9A	0.9900	C8—H8B	0.9900
C9—H9B	0.9900

O1—Cd1—O4ⁱ	134.65 (17)	C10—C9—H9B	109.5
O1—Cd1—C10ⁱ	115.2 (5)	C10—C9—C8	110.9 (8)
O2—Cd1—O1	55.1 (6)	O1—C1—C2	128.8 (13)
O2—Cd1—O4ⁱ	92.9 (5)	O2—C1—O1	116.4 (13)
O2—Cd1—C10ⁱ	94.0 (5)	O2—C1—C2	114.8 (14)
O4ⁱ—Cd1—C10ⁱ	27.2 (5)	C7—C2—C1	123.2 (8)
O6—Cd1—O1	86.2 (5)	C7—C2—C3	120.0
O6—Cd1—O2	137.9 (5)	C3—C2—C1	116.8 (8)
O6—Cd1—O4ⁱ	128.7 (5)	C2—C7—H7	120.0
O6—Cd1—O3ⁱ	102.2 (5)	C6—C7—C2	120.0
O6—Cd1—O5	86.83 (15)	C6—C7—H7	120.0
O6—Cd1—C10ⁱ	119.8 (4)	C7—C6—H6	120.0
O3ⁱ—Cd1—O1	93.6 (5)	C7—C6—C5	120.0
O3ⁱ—Cd1—O2	96.73 (15)	C5—C6—H6	120.0
O3ⁱ—Cd1—O4ⁱ	55.5 (5)	C6—C5—C8	125.7 (4)
O3ⁱ—Cd1—C10ⁱ	28.4 (5)	C4—C5—C6	120.0
O5—Cd1—O1	129.6 (5)	C4—C5—C8	114.3 (4)
O5—Cd1—O2	104.5 (4)	C5—C4—H4	120.0
O5—Cd1—O4ⁱ	85.6 (4)	C5—C4—C3	120.0
O5—Cd1—O3ⁱ	136.6 (4)	C3—C4—H4	120.0
O5—Cd1—C10ⁱ	111.5 (5)	C2—C3—H3	120.0
C1—O1—Cd1	91.3 (9)	C4—C3—C2	120.0
C1—O2—Cd1	96.9 (11)	C4—C3—H3	120.0
C10—O4—Cd1ⁱⁱ	88.0 (7)	C9—C8—C5	115.3 (6)
Cd1—O6—H6A	115.2	C9—C8—H8A	108.5
Cd1—O6—H6B	116.2	C9—C8—H8B	108.5
H6A—O6—H6B	98.0	C5—C8—H8A	108.5
C10—O3—Cd1ⁱⁱ	93.6 (10)	C5—C8—H8B	108.5
Cd1—O5—H5A	110.9	H8A—C8—H8B	107.5
Cd1—O5—H5B	110.7	O4—C10—Cd1ⁱⁱ	64.8 (7)
H5A—O5—H5B	103.0	O4—C10—O3	122.6 (12)
H9A—C9—H9B	108.0	O4—C10—C9	113.2 (12)
C8—C9—H9A	109.5	O3—C10—Cd1ⁱⁱ	58.0 (8)
C8—C9—H9B	109.5	O3—C10—C9	124.2 (13)
C10—C9—H9A	109.5	C9—C10—Cd1ⁱⁱ	173.8 (9)

Cd1—O1—C1—O2	−4.7 (16)	C2—C7—C6—C5	0.0
Cd1—O1—C1—C2	174.9 (14)	C7—C2—C3—C4	0.0
Cd1—O2—C1—O1	4.9 (17)	C7—C6—C5—C4	0.0
Cd1—O2—C1—C2	−174.7 (10)	C7—C6—C5—C8	179.1 (7)
Cd1ⁱⁱ—O4—C10—O3	5.6 (15)	C6—C5—C4—C3	0.0
Cd1ⁱⁱ—O4—C10—C9	−173.6 (9)	C6—C5—C8—C9	−0.1 (10)
Cd1ⁱⁱ—O3—C10—O4	−5.9 (16)	C5—C4—C3—C2	0.0
Cd1ⁱⁱ—O3—C10—C9	173.1 (11)	C4—C5—C8—C9	179.0 (6)
O1—C1—C2—C7	−178.3 (13)	C3—C2—C7—C6	0.0
O1—C1—C2—C3	1 (2)	C8—C9—C10—O4	−180.0 (11)
O2—C1—C2—C7	1.3 (18)	C8—C9—C10—O3	0.9 (17)
O2—C1—C2—C3	−179.0 (12)	C8—C5—C4—C3	−179.2 (7)
C1—C2—C7—C6	179.7 (9)	C10—C9—C8—C5	177.3 (8)
C1—C2—C3—C4	−179.7 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O4ⁱⁱⁱ	0.97	2.28	2.653 (15)	102
O6—H6B···O3^iv	0.98	1.76	2.735 (18)	176
O5—H5A···O1^v	0.90	1.87	2.692 (16)	151
O5—H5B···O2^vi	0.90	2.46	2.67 (2)	94
C3—H3···O1

Symmetry codes: (iii) x, −y+1, z−1/2; (iv) x−1/2, −y+3/2, z−1/2; (v) x−1/2, y+1/2, z; (vi) x, y+1, z.

Acknowledgements

We thank Dr G. Looks for helpful discussion.

Funding information

Funding for this research was provided by: Honors College of Michigan State University.

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