metal-organic compounds
Tetraaquabis(2,3-dihydro-1,4-benzodioxine-2-carboxylato)calcium(II)
aCentro Especializado en Investigaciones en Química Inorgánica (CEIQUI), Escuela de Química, Universidad Autónoma de Chiriquí, David, Panama, bCentro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica, 11501-2060. San José, Costa Rica, and cEscuela de Química, Universidad de Costa Rica, 11501-2060, San José, Costa Rica
*Correspondence e-mail: esmit.camargo@unachi.ac.pa
The acid–base reaction of 1,4-benzodioxane 2-carboxylic acid with calcium carbonate furnished the centrosymmetric title compound, [Ca(C9H7O4)2(H2O)4], in which the metal ion is octahedrally coordinated by two monodentate 1,4-benzodioxane 2-carboxylate ligands and four water molecules. In the crystal, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.
CCDC reference: 1970573
Structure description
1,4-Benzodioxanes are components of some therapeutic agents used in cardiovascular treatments, acting as α- and β-adrenergic antagonists (Nelson et al., 1977, 1979; Pigini et al., 1988). For the latter application, the enantiopure derivatives of chiral 2-substituted 1,4-benzodioxanes lend affinity and selectivity, mainly those derived from 1,4-benzodioxane 2-carboxylic acid (Ennis & Old, 1992; Antus et al., 1993; Khouili et al., 1999; Jasinski et al., 2009). Naturally ocurring compounds with a similar structure to these heterocyclic scaffolds are known as 1,4-benzodioxane which also exhibit a wide array of biological activities (e.g., anticancer, antioxidant; Pilkington & Barker, 2015).
In this work, we report the synthesis and the structure of the coordination properties of 1,4-benzodioxane 2-carboxylic acid toward calcium carbonate to afford the title compound Ca(C9H7O4)2(H2O)4.
The ). The Ca1—O1, Ca1—O5, and Ca1—O6 bond lengths are 2.304 (2), 2.358 (2) and 2.317 (2) Å, respectively. The dioxane ring adopts a half-chair conformation with the pendant carboxylate group in an axial orientation. In the arbitrarily chosen C2 has an R configuration but crystal symmetry generates a racemic mixture.
of the title compound has monoclinic symmetry with half a molecule in the the other half being generated by a crystallographic inversion center. The calcium ion is bonded to four aqua ligands and two 1,4-benzodioxane 2-carboxylate ligands, whose carboxylate groups link to the central atom in monodentate mode (Fig. 1In the crystal, O—H⋯O hydrogen bonds link the molecules into (010) sheets with the acceptor O atoms being parts of carboxylate groups (O1 and O2) and the dioxane ring (O4) and the packing is consolidated by weak C—H⋯O interactions (Fig. 2, Table 1).
Synthesis and crystallization
In a 100 mL two-necked flask, anhydrous CaCO3 (0.0100 g, 0.100 mmol) was dissolved in deionized water (20 mL) by heating to 338 K, and a solution of 1,4-benzodioxane-2-carboxylic acid (0.0560 g, 0.200 mmol) dissolved in distilled water (10 mL) was added dropwise at 353 K. The reaction mixture was refluxed for 2 h and then concentrated under vacuum to 10 mL. The precipitate obtained upon cooling overnight was filtered off and washed with cold distilled water. Colorless crystals suitable for X-ray analysis were grown from a warm water–methanol mixed solvent mixture (1:1) at room temperature. Yield: 0.0362 g (55%), m.p. 501–505 K. FTIR data (KBr, cm−1): 3600 and 3000 (br, m); 3568 (m); 1330 (m); 879 (m); 833 (s); 767 (s); 752 (s); 654 (m); 569 (m); 545 (w); 476 (m). 1H NMR (400 MHz, mix 1:1 D2O: CD4O, 298 K): δ 6.87–6.99 (s, 4H), 4.82 (dd, 1H), 4.35 p.p.m. (qd, 2H). 13C NMR (400 MHz, 1:1 mix D2O: CD4O, 298 K): δ 176, 143, 142, 123, 122, 117, 115, 73.5, 66 p.p.m. The 1H NMR and 13C NMR spectra for the title compound are included in the supporting information.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1970573
https://doi.org/10.1107/S2414314620010925/hb4355sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620010925/hb4355Isup2.hkl
1H and 13C NMR spectra of the title compound. DOI: https://doi.org/10.1107/S2414314620010925/hb4355sup3.pdf
Data collection: APEX3 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).[Ca(C9H7O4)2(H2O)4] | F(000) = 492 |
Mr = 470.44 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.3477 (4) Å | Cell parameters from 9843 reflections |
b = 26.6084 (18) Å | θ = 2.9–27.4° |
c = 7.7367 (5) Å | µ = 0.36 mm−1 |
β = 106.715 (2)° | T = 100 K |
V = 1054.37 (13) Å3 | Block, clear light white |
Z = 2 | 0.35 × 0.25 × 0.15 mm |
Bruker D8 Venture diffractometer | 2384 independent reflections |
Mirrors monochromator | 2242 reflections with I > 2σ(I) |
Detector resolution: 10.4167 pixels mm-1 | Rint = 0.036 |
ω scans | θmax = 27.4°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −6→6 |
Tmin = 0.661, Tmax = 0.746 | k = −34→34 |
32373 measured reflections | l = −10→8 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: mixed |
wR(F2) = 0.133 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.39 | w = 1/[σ2(Fo2) + 3.3804P] where P = (Fo2 + 2Fc2)/3 |
2384 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.42 e Å−3 |
6 restraints | Δρmin = −0.43 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Ca1 | 0.5 | 0.5 | 1.0 | 0.0115 (2) | |
O1 | 0.6722 (4) | 0.55435 (8) | 0.8323 (3) | 0.0144 (4) | |
O2 | 0.8347 (4) | 0.54948 (9) | 0.5982 (3) | 0.0164 (5) | |
O3 | 0.5527 (5) | 0.66992 (9) | 0.6702 (3) | 0.0199 (5) | |
O4 | 0.4402 (4) | 0.60021 (8) | 0.3776 (3) | 0.0144 (4) | |
O5 | 0.2000 (4) | 0.56223 (9) | 1.0277 (3) | 0.0167 (5) | |
H5A | 0.041 (3) | 0.5599 (16) | 0.972 (4) | 0.030 (12)* | |
H5B | 0.210 (7) | 0.5750 (15) | 1.129 (3) | 0.033 (12)* | |
O6 | 0.1782 (4) | 0.47510 (9) | 0.7438 (3) | 0.0158 (5) | |
H6A | 0.208 (8) | 0.4613 (13) | 0.655 (3) | 0.028 (12)* | |
H6B | 0.070 (7) | 0.4981 (12) | 0.703 (5) | 0.043 (14)* | |
C1 | 0.6624 (6) | 0.56196 (11) | 0.6687 (4) | 0.0116 (6) | |
C2 | 0.4144 (6) | 0.58769 (12) | 0.5516 (4) | 0.0121 (6) | |
H2 | 0.2671 | 0.5632 | 0.5335 | 0.015* | |
C3 | 0.3443 (6) | 0.63398 (12) | 0.6413 (5) | 0.0171 (6) | |
H3A | 0.1807 | 0.6488 | 0.5636 | 0.021* | |
H3B | 0.316 | 0.6247 | 0.7582 | 0.021* | |
C4 | 0.6346 (6) | 0.67786 (12) | 0.5198 (4) | 0.0160 (6) | |
C5 | 0.7822 (7) | 0.72053 (13) | 0.5151 (5) | 0.0226 (7) | |
H5 | 0.8188 | 0.7437 | 0.6124 | 0.027* | |
C6 | 0.8762 (7) | 0.72926 (13) | 0.3682 (5) | 0.0261 (8) | |
H6 | 0.9784 | 0.7583 | 0.3656 | 0.031* | |
C7 | 0.8210 (7) | 0.69567 (14) | 0.2255 (5) | 0.0251 (8) | |
H7 | 0.8838 | 0.702 | 0.1246 | 0.03* | |
C8 | 0.6745 (6) | 0.65272 (13) | 0.2289 (4) | 0.0191 (7) | |
H8 | 0.6373 | 0.6297 | 0.1311 | 0.023* | |
C9 | 0.5828 (6) | 0.64388 (11) | 0.3781 (4) | 0.0129 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0075 (4) | 0.0198 (4) | 0.0070 (4) | 0.0002 (3) | 0.0018 (3) | 0.0016 (3) |
O1 | 0.0118 (10) | 0.0243 (12) | 0.0078 (10) | 0.0001 (8) | 0.0037 (8) | 0.0026 (8) |
O2 | 0.0128 (10) | 0.0270 (12) | 0.0100 (10) | 0.0058 (9) | 0.0041 (8) | 0.0011 (9) |
O3 | 0.0215 (12) | 0.0206 (12) | 0.0194 (12) | −0.0010 (9) | 0.0089 (9) | −0.0046 (9) |
O4 | 0.0146 (10) | 0.0181 (11) | 0.0091 (10) | −0.0028 (8) | 0.0013 (8) | 0.0012 (8) |
O5 | 0.0087 (10) | 0.0279 (12) | 0.0125 (11) | 0.0006 (9) | 0.0015 (8) | −0.0042 (9) |
O6 | 0.0144 (11) | 0.0227 (12) | 0.0095 (10) | 0.0042 (9) | 0.0022 (8) | −0.0015 (9) |
C1 | 0.0105 (13) | 0.0133 (13) | 0.0107 (13) | −0.0024 (10) | 0.0025 (11) | −0.0008 (10) |
C2 | 0.0080 (13) | 0.0196 (15) | 0.0090 (13) | −0.0004 (11) | 0.0027 (10) | 0.0020 (11) |
C3 | 0.0113 (14) | 0.0227 (16) | 0.0209 (16) | 0.0027 (12) | 0.0103 (12) | 0.0029 (13) |
C4 | 0.0125 (14) | 0.0164 (15) | 0.0179 (15) | 0.0035 (11) | 0.0023 (12) | 0.0026 (12) |
C5 | 0.0173 (16) | 0.0154 (15) | 0.0330 (19) | 0.0005 (12) | 0.0039 (14) | 0.0005 (14) |
C6 | 0.0172 (17) | 0.0210 (17) | 0.038 (2) | −0.0025 (13) | 0.0051 (15) | 0.0121 (15) |
C7 | 0.0187 (16) | 0.0316 (19) | 0.0244 (18) | 0.0005 (14) | 0.0053 (14) | 0.0144 (15) |
C8 | 0.0182 (16) | 0.0249 (17) | 0.0124 (15) | 0.0016 (13) | 0.0016 (12) | 0.0059 (12) |
C9 | 0.0077 (13) | 0.0177 (15) | 0.0141 (14) | 0.0025 (11) | 0.0041 (11) | 0.0042 (11) |
Ca1—O1i | 2.304 (2) | O6—H6B | 0.839 (10) |
Ca1—O1 | 2.304 (2) | C1—C2 | 1.535 (4) |
Ca1—O6i | 2.317 (2) | C2—C3 | 1.513 (4) |
Ca1—O6 | 2.317 (2) | C2—H2 | 1.0 |
Ca1—O5i | 2.358 (2) | C3—H3A | 0.99 |
Ca1—O5 | 2.358 (2) | C3—H3B | 0.99 |
Ca1—H6B | 2.74 (4) | C4—C9 | 1.386 (4) |
O1—C1 | 1.268 (4) | C4—C5 | 1.389 (5) |
O2—C1 | 1.243 (4) | C5—C6 | 1.388 (5) |
O3—C4 | 1.372 (4) | C5—H5 | 0.95 |
O3—C3 | 1.437 (4) | C6—C7 | 1.385 (6) |
O4—C9 | 1.389 (4) | C6—H6 | 0.95 |
O4—C2 | 1.432 (3) | C7—C8 | 1.390 (5) |
O5—H5A | 0.838 (10) | C7—H7 | 0.95 |
O5—H5B | 0.838 (10) | C8—C9 | 1.397 (4) |
O6—H6A | 0.837 (10) | C8—H8 | 0.95 |
O1i—Ca1—O1 | 180.0 | O1—C1—C2 | 116.1 (3) |
O1i—Ca1—O6i | 90.95 (8) | O4—C2—C3 | 110.2 (2) |
O1—Ca1—O6i | 89.05 (8) | O4—C2—C1 | 111.0 (2) |
O1i—Ca1—O6 | 89.05 (8) | C3—C2—C1 | 112.3 (2) |
O1—Ca1—O6 | 90.95 (8) | O4—C2—H2 | 107.7 |
O6i—Ca1—O6 | 180.00 (10) | C3—C2—H2 | 107.7 |
O1i—Ca1—O5i | 90.17 (8) | C1—C2—H2 | 107.7 |
O1—Ca1—O5i | 89.83 (8) | O3—C3—C2 | 109.3 (2) |
O6i—Ca1—O5i | 85.49 (8) | O3—C3—H3A | 109.8 |
O6—Ca1—O5i | 94.51 (8) | C2—C3—H3A | 109.8 |
O1i—Ca1—O5 | 89.83 (8) | O3—C3—H3B | 109.8 |
O1—Ca1—O5 | 90.17 (8) | C2—C3—H3B | 109.8 |
O6i—Ca1—O5 | 94.51 (8) | H3A—C3—H3B | 108.3 |
O6—Ca1—O5 | 85.49 (8) | O3—C4—C9 | 122.0 (3) |
O5i—Ca1—O5 | 180.0 | O3—C4—C5 | 118.1 (3) |
O1i—Ca1—H6B | 94.9 (10) | C9—C4—C5 | 119.9 (3) |
O1—Ca1—H6B | 85.1 (9) | C6—C5—C4 | 120.0 (3) |
O6i—Ca1—H6B | 163.5 (6) | C6—C5—H5 | 120.0 |
O6—Ca1—H6B | 16.5 (6) | C4—C5—H5 | 120.0 |
O5i—Ca1—H6B | 109.8 (6) | C7—C6—C5 | 120.0 (3) |
O5—Ca1—H6B | 70.2 (6) | C7—C6—H6 | 120.0 |
C1—O1—Ca1 | 138.9 (2) | C5—C6—H6 | 120.0 |
C4—O3—C3 | 113.1 (2) | C6—C7—C8 | 120.5 (3) |
C9—O4—C2 | 113.2 (2) | C6—C7—H7 | 119.7 |
Ca1—O5—H5A | 121 (3) | C8—C7—H7 | 119.7 |
Ca1—O5—H5B | 120 (3) | C7—C8—C9 | 119.2 (3) |
H5A—O5—H5B | 107 (2) | C7—C8—H8 | 120.4 |
Ca1—O6—H6A | 124 (3) | C9—C8—H8 | 120.4 |
Ca1—O6—H6B | 112 (3) | C4—C9—O4 | 122.1 (3) |
H6A—O6—H6B | 106 (2) | C4—C9—C8 | 120.4 (3) |
O2—C1—O1 | 124.9 (3) | O4—C9—C8 | 117.5 (3) |
O2—C1—C2 | 118.9 (3) | ||
Ca1—O1—C1—O2 | −102.2 (4) | O3—C4—C5—C6 | 178.0 (3) |
Ca1—O1—C1—C2 | 76.5 (4) | C9—C4—C5—C6 | 0.4 (5) |
C9—O4—C2—C3 | 45.0 (3) | C4—C5—C6—C7 | 0.6 (5) |
C9—O4—C2—C1 | −79.9 (3) | C5—C6—C7—C8 | −0.8 (5) |
O2—C1—C2—O4 | −8.8 (4) | C6—C7—C8—C9 | 0.2 (5) |
O1—C1—C2—O4 | 172.4 (2) | O3—C4—C9—O4 | 1.4 (5) |
O2—C1—C2—C3 | −132.6 (3) | C5—C4—C9—O4 | 178.9 (3) |
O1—C1—C2—C3 | 48.5 (4) | O3—C4—C9—C8 | −178.6 (3) |
C4—O3—C3—C2 | 48.5 (3) | C5—C4—C9—C8 | −1.1 (5) |
O4—C2—C3—O3 | −63.0 (3) | C2—O4—C9—C4 | −15.5 (4) |
C1—C2—C3—O3 | 61.3 (3) | C2—O4—C9—C8 | 164.4 (3) |
C3—O3—C4—C9 | −19.4 (4) | C7—C8—C9—C4 | 0.8 (5) |
C3—O3—C4—C5 | 163.1 (3) | C7—C8—C9—O4 | −179.1 (3) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O1ii | 0.84 (2) | 1.96 (2) | 2.800 (3) | 178 (4) |
O5—H5B···O4iii | 0.84 (3) | 2.07 (3) | 2.828 (3) | 149 (4) |
O6—H6A···O2iv | 0.83 (3) | 1.93 (2) | 2.707 (3) | 155 (3) |
O6—H6B···O2ii | 0.84 (3) | 1.88 (4) | 2.715 (3) | 176 (3) |
C2—H2···O2ii | 1.00 | 2.53 | 3.379 (4) | 143 |
C6—H6···O3v | 0.95 | 2.54 | 3.357 (4) | 145 |
Symmetry codes: (ii) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+1; (v) x+1/2, −y+3/2, z−1/2. |
Acknowledgements
Rectoría and Vicerrectoría de Investigación, Universidad de Costa Rica are acknowledged for funding the purchase of a D8 Venture SC XRD. CELEQ is thanked for supporting liquid nitrogen for the X-ray measurements.
Funding information
Funding for this research was provided by: Centro de Electroquímica y Energía Química (CELEQ), Universidad de Costa Rica; Escuela de Química, Universidad de Costa Rica; Vicerrectoría de Investigación y Posgrado, Universidad Autónoma de Chiriquí, Panamá (grant No. 1.87-205-100-2016-23-i01).
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