metal-organic compounds
catena-Poly[{μ3-3,3′-[(1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene)]dibenzoato}cobalt(II)]
aCenter for Functional Nanoscale Materials, Department of Chemistry, Clark Atlanta University, 223 James P. Brawley Drive, Atlanta, GA 30314, USA, and bX-ray Crystallography Center, Emory University, Atlanta, GA 30322, USA
*Correspondence e-mail: cingram@cau.edu
The title compound, [Co(C24H28N2O6)]n, crystallizes as infinite chains related to one another by inversion centers, giving a centrosymmetric coordination polymer. The CoII ion, situated on a twofold rotation axis, forms a complex with the crown-4 moiety of the 3,3′-[(1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene)]dibenzoate anion. The distorted octahedral coordination sphere of the CoII ion is completed by two carboxylate O atoms from two bridging intra-chain ligands. Metallomacrocyclic rings of 16 atoms are present, with each ring containing two CoII ions and 14 atoms from the bridging ligands. These units repeat as infinite zigzag chains along [101].
CCDC reference: 975042
Related literature
For the structures of coordination polymers (CPs) or compounds with metal-organic frameworks including one-dimensional CPs or MOFs, see: Du et al. (2013); Ingram et al. (2012, 2013); Janiak (2013); Leong & Vittal (2011).
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2.
Supporting information
CCDC reference: 975042
https://doi.org/10.1107/S1600536813032832/gg2131sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032832/gg2131Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032832/gg2131Isup3.cdx
The title compound was synthesized in an autoclave by mixing the ligand, 3,3'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene))dibenzoic acid, LH2 (4x10-5 mol), (Ingram et al. (2012), (2013)) Co(NO3)2·6H2O (1.2x10-4 mol, 35.8 mg), H2O (12 ml) and pyridine (4x10-2 ml). The mixture was heated at 130 °C in an autoclave for 7 days and then cooled to ambient temperature. Red crystals were collected and washed with H2O by filtration. Elem. anal. calcd. C24H28N2O6Co %: C, 57.72; H, 5.65; N, 5.61; Found: C, 57.79; H, 5.74; N, 5.46.
Refinement
of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt), etc and is not relevant to the choice of reflections for R-factors based on F2 are statistically about twice as large as those based on F and R– factors based on ALL data will be even larger. Computing details Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009);program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).The title compound is the one of a series of coordination polymers prepared from the anionic ligand LH2, 3,3'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene))dibenzoate. This ligand shows unusual adaptability in that it displays two complexation modes on binding to metals. The ligand attaches to the metal via two oxygen and two nitrogen atoms (forming a crown complex). The crown forms four bonds to the metal, while an ideal
for a CoII ion is 6. Thus vacant coordination sites suitable for coordination by the carboxylate groups exist. The carboxylate ions behave as monodentate bridging ligands and the entire ligand is hexadentate. The CoII atom is moved out of the best plane of the crown since this arrangement is better for forming optimal bonds to the ligand. This new compound is novel in that, although the ligands bridge the metal atoms forming one-dimensional chains, the metal atoms are positioned in the center of the organic linker. Topologically, the CoII atoms and the ligands forms nodes in the network rather than the metal atoms only.The title compound is synthesized from the ligand LH2, 3,3'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene)) dibenzoic acid. The metal atoms are positioned in the center of the organic linker. The
of the compound contains a CoII ion and a deprotonated ligand L with formula C24H28N2O6Co. The CoII ion is 6-coordinate in a distorted octahedral geometry being bound to two N atoms and two O atoms of the crown (1,7-diaza-12-crown-4) and two carboxylic O atoms, one from each of two additional intra-chain ligands (Figure 1s). The Co1—O1, Co1—O3 and Co1—N1 bond lengths are 1.9886 (16), 2.2399 (16) and 2.2213 (17) Å, respectively. The O1—Co1—O1 angle is 104.15 (9)°. The shortest distance between two neighboring CoII ions along a chain is 9.046 (1) Å. The CoII ion of the Co(crown-4)2+ unit is located on a 2-fold rotation axis. The symmetry independent atoms consist of one half of the ligand with the rotation axis generating the second half of the ligand at the Co atom. Bond circuits consisting of sixteen-membered metallomacrocycle rings can be identified in the structure. Each ring contains two CoII ions and fourteen non-H atoms of the ligand. Each CoII ion is a node for three ligands and two connected macrocycle rings. The pair of benzene moieties within a metallomacrocycle ring are remarkably co-planar (the two rings are in the same plane within experimental error). The dihedral angle between this plane and the plane of the next two nearest phenyl rings along the 1-D chain is 68.79 (5)°. Repetition of these units creates a 1-D with an infinite number of these rings.For the structures of coordination polymers (CPs) or compounds with metal-organic frameworks including one-dimensional CPs or MOFs, see: Du et al. (2013); Ingram et al. (2012, 2013); Janiak (2013); Leong & Vittal (2011).
Data collection: APEX2 (Bruker, 2011); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Co(C24H28N2O6)] | F(000) = 1044 |
Mr = 499.41 | Dx = 1.612 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.626 (2) Å | Cell parameters from 4901 reflections |
b = 8.9778 (10) Å | θ = 2.5–31.0° |
c = 13.9263 (16) Å | µ = 0.88 mm−1 |
β = 127.051 (1)° | T = 173 K |
V = 2058.2 (4) Å3 | Needle, red |
Z = 4 | 0.40 × 0.14 × 0.14 mm |
Bruker D8 diffractometer with a APEXII detector | 2930 independent reflections |
Radiation source: fine-focus sealed tube | 2290 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 512 pixels mm-1 | θmax = 31.2°, θmin = 2.6° |
φ and ω scans with a narrow frame width | h = −28→18 |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | k = −12→4 |
Tmin = 0.606, Tmax = 0.746 | l = −20→19 |
3614 measured reflections |
Refinement on F2 | Primary atom site location: iterative |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.073P)2] where P = (Fo2 + 2Fc2)/3 |
2930 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[Co(C24H28N2O6)] | V = 2058.2 (4) Å3 |
Mr = 499.41 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.626 (2) Å | µ = 0.88 mm−1 |
b = 8.9778 (10) Å | T = 173 K |
c = 13.9263 (16) Å | 0.40 × 0.14 × 0.14 mm |
β = 127.051 (1)° |
Bruker D8 diffractometer with a APEXII detector | 2930 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 2290 reflections with I > 2σ(I) |
Tmin = 0.606, Tmax = 0.746 | Rint = 0.018 |
3614 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.80 e Å−3 |
2930 reflections | Δρmin = −0.47 e Å−3 |
150 parameters |
Experimental. Absorption correction: SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0566 before and 0.0407 after correction. The Ratio of minimum to maximum transmission is 0.8118. The λ/2 correction factor is 0.0015. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
H3 | 0.2131 | −0.1861 | 0.3961 | 0.018* | |
H5 | 0.3214 | 0.0551 | 0.2858 | 0.021* | |
H6 | 0.1962 | 0.0922 | 0.1030 | 0.020* | |
H7 | 0.0799 | −0.0063 | 0.0656 | 0.017* | |
H8a | 0.3537 | −0.1744 | 0.5242 | 0.018* | |
H8b | 0.3996 | −0.1315 | 0.4708 | 0.018* | |
H9a | 0.3126 | 0.0166 | 0.5936 | 0.022* | |
H9b | 0.2955 | 0.1475 | 0.5068 | 0.022* | |
H10a | 0.3343 | 0.2306 | 0.6986 | 0.025* | |
H10b | 0.3890 | 0.2984 | 0.6656 | 0.025* | |
H11a | 0.4755 | 0.2883 | 0.9128 | 0.023* | |
H11b | 0.5171 | 0.3117 | 0.8492 | 0.023* | |
H12a | 0.3833 | 0.2132 | 0.4673 | 0.022* | |
H12b | 0.4423 | 0.0940 | 0.4768 | 0.022* | |
C1 | 0.06017 (14) | −0.1928 (2) | 0.19467 (19) | 0.0158 (4) | |
C2 | 0.13474 (13) | −0.1115 (2) | 0.22645 (18) | 0.0134 (4) | |
C3 | 0.20986 (14) | −0.1300 (2) | 0.33718 (19) | 0.0148 (4) | |
C4 | 0.28076 (14) | −0.0671 (2) | 0.36296 (18) | 0.0139 (4) | |
C5 | 0.27494 (14) | 0.0150 (3) | 0.27221 (19) | 0.0174 (5) | |
C6 | 0.19972 (15) | 0.0363 (2) | 0.16222 (19) | 0.0171 (4) | |
C7 | 0.12995 (14) | −0.0239 (2) | 0.13905 (19) | 0.0143 (4) | |
C8 | 0.36136 (14) | −0.0955 (2) | 0.48429 (19) | 0.0153 (4) | |
C9 | 0.33771 (14) | 0.0978 (3) | 0.5810 (2) | 0.0185 (5) | |
C10 | 0.37353 (14) | 0.2069 (3) | 0.6840 (2) | 0.0205 (5) | |
C11 | 0.50015 (14) | 0.2376 (2) | 0.8806 (2) | 0.0194 (5) | |
C12 | 0.42768 (14) | 0.1462 (2) | 0.52219 (19) | 0.0184 (5) | |
N1 | 0.39880 (11) | 0.03569 (18) | 0.56797 (16) | 0.0130 (4) | |
O1 | 0.07535 (10) | −0.31870 (17) | 0.24829 (14) | 0.0177 (3) | |
O2 | −0.00750 (10) | −0.1403 (2) | 0.11880 (15) | 0.0266 (4) | |
O3 | 0.44337 (10) | 0.13620 (18) | 0.78732 (13) | 0.0184 (3) | |
Co1 | 0.0000 | −0.45483 (4) | 0.2500 | 0.01262 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0172 (12) | 0.0174 (10) | 0.0141 (9) | −0.0039 (8) | 0.0102 (9) | −0.0025 (8) |
C2 | 0.0121 (11) | 0.0108 (9) | 0.0152 (9) | −0.0006 (7) | 0.0070 (8) | −0.0018 (7) |
C3 | 0.0175 (11) | 0.0117 (9) | 0.0141 (9) | 0.0000 (8) | 0.0090 (9) | 0.0014 (7) |
C4 | 0.0128 (11) | 0.0142 (10) | 0.0121 (9) | 0.0002 (7) | 0.0062 (8) | −0.0003 (7) |
C5 | 0.0153 (12) | 0.0193 (11) | 0.0161 (10) | −0.0031 (8) | 0.0086 (9) | −0.0003 (8) |
C6 | 0.0205 (12) | 0.0151 (10) | 0.0148 (9) | −0.0033 (8) | 0.0103 (9) | 0.0013 (8) |
C7 | 0.0138 (11) | 0.0138 (10) | 0.0120 (9) | 0.0012 (8) | 0.0060 (8) | 0.0005 (7) |
C8 | 0.0132 (11) | 0.0135 (9) | 0.0154 (9) | 0.0002 (8) | 0.0066 (9) | −0.0007 (7) |
C9 | 0.0120 (11) | 0.0204 (11) | 0.0165 (10) | 0.0034 (8) | 0.0052 (9) | 0.0006 (8) |
C10 | 0.0167 (12) | 0.0202 (11) | 0.0181 (10) | 0.0061 (9) | 0.0071 (9) | 0.0003 (8) |
C11 | 0.0162 (12) | 0.0169 (11) | 0.0178 (10) | 0.0027 (8) | 0.0064 (9) | −0.0049 (8) |
C12 | 0.0178 (12) | 0.0175 (10) | 0.0153 (9) | −0.0032 (8) | 0.0075 (9) | 0.0035 (8) |
N1 | 0.0104 (9) | 0.0122 (8) | 0.0139 (8) | −0.0011 (6) | 0.0059 (7) | −0.0004 (6) |
O1 | 0.0156 (8) | 0.0148 (7) | 0.0219 (8) | 0.0001 (6) | 0.0110 (7) | 0.0024 (6) |
O2 | 0.0132 (9) | 0.0302 (10) | 0.0244 (8) | −0.0007 (7) | 0.0049 (7) | 0.0103 (7) |
O3 | 0.0140 (8) | 0.0165 (7) | 0.0152 (7) | 0.0027 (6) | 0.0037 (6) | −0.0016 (6) |
Co1 | 0.0105 (2) | 0.0114 (2) | 0.0141 (2) | 0.000 | 0.00639 (17) | 0.000 |
C1—C2 | 1.508 (3) | C11—H11b | 0.9700 |
C2—C3 | 1.388 (3) | C11—C12i | 1.515 (3) |
C2—C7 | 1.402 (3) | C12—H12a | 0.9700 |
C3—H3 | 0.9300 | C12—H12b | 0.9700 |
C4—C3 | 1.398 (3) | C12—C11i | 1.515 (3) |
C4—C8 | 1.516 (3) | N1—C8 | 1.502 (3) |
C5—H5 | 0.9300 | N1—C9 | 1.486 (3) |
C5—C4 | 1.404 (3) | N1—C12 | 1.484 (3) |
C6—H6 | 0.9300 | N1—Co1ii | 2.2212 (17) |
C6—C5 | 1.388 (3) | O1—C1 | 1.285 (3) |
C7—H7 | 0.9300 | O2—C1 | 1.229 (3) |
C7—C6 | 1.381 (3) | O3—C10 | 1.432 (3) |
C8—H8a | 0.9700 | O3—C11 | 1.433 (3) |
C8—H8b | 0.9700 | O3—Co1ii | 2.2400 (16) |
C9—H9a | 0.9700 | Co1—N1iii | 2.2213 (17) |
C9—H9b | 0.9700 | Co1—N1ii | 2.2213 (17) |
C9—C10 | 1.511 (3) | Co1—O1 | 1.9886 (16) |
C10—H10a | 0.9700 | Co1—O1iv | 1.9886 (16) |
C10—H10b | 0.9700 | Co1—O3iii | 2.2399 (16) |
C11—H11a | 0.9700 | Co1—O3ii | 2.2399 (16) |
O1—C1—C2 | 114.0 (2) | O3—C10—C9 | 106.67 (18) |
O2—C1—C2 | 119.75 (19) | H11a—C11—H11b | 108.6 |
O2—C1—O1 | 126.2 (2) | C12i—C11—H11a | 110.3 |
C3—C2—C1 | 121.76 (19) | C12i—C11—H11b | 110.3 |
C3—C2—C7 | 118.7 (2) | O3—C11—H11a | 110.3 |
C7—C2—C1 | 119.40 (19) | O3—C11—H11b | 110.3 |
C2—C3—H3 | 118.9 | O3—C11—C12i | 107.00 (17) |
C2—C3—C4 | 122.10 (19) | H12a—C12—H12b | 107.6 |
C4—C3—H3 | 118.9 | C11i—C12—H12a | 108.7 |
C3—C4—C5 | 118.2 (2) | C11i—C12—H12b | 108.7 |
C3—C4—C8 | 119.56 (19) | N1—C12—H12a | 108.7 |
C5—C4—C8 | 122.2 (2) | N1—C12—H12b | 108.7 |
C4—C5—H5 | 120.1 | N1—C12—C11i | 114.25 (17) |
C6—C5—H5 | 120.1 | C8—N1—Co1ii | 108.63 (12) |
C6—C5—C4 | 119.9 (2) | C9—N1—C8 | 108.17 (17) |
C5—C6—H6 | 119.4 | C9—N1—Co1ii | 105.43 (12) |
C7—C6—H6 | 119.4 | C12—N1—C8 | 110.02 (17) |
C7—C6—C5 | 121.2 (2) | C12—N1—C9 | 113.03 (17) |
C2—C7—H7 | 120.1 | C12—N1—Co1ii | 111.36 (13) |
C6—C7—H7 | 120.1 | C1—O1—Co1 | 128.97 (15) |
C6—C7—C2 | 119.9 (2) | C10—O3—C11 | 114.03 (17) |
H8a—C8—H8b | 107.4 | C10—O3—Co1ii | 116.01 (13) |
C4—C8—H8a | 108.3 | C11—O3—Co1ii | 114.60 (13) |
C4—C8—H8b | 108.3 | N1iii—Co1—N1ii | 141.85 (9) |
N1—C8—H8a | 108.3 | N1iii—Co1—O3iii | 76.37 (6) |
N1—C8—H8b | 108.3 | N1ii—Co1—O3iii | 76.14 (6) |
N1—C8—C4 | 116.03 (17) | N1ii—Co1—O3ii | 76.37 (6) |
H9a—C9—H9b | 107.8 | N1iii—Co1—O3ii | 76.14 (6) |
C10—C9—H9a | 108.9 | O1—Co1—N1ii | 90.61 (7) |
C10—C9—H9b | 108.9 | O1iv—Co1—N1ii | 113.02 (7) |
N1—C9—H9a | 108.9 | O1iv—Co1—N1iii | 90.61 (7) |
N1—C9—H9b | 108.9 | O1—Co1—N1iii | 113.02 (7) |
N1—C9—C10 | 113.18 (19) | O1iv—Co1—O1 | 104.15 (9) |
H10b—C10—H10a | 108.6 | O1—Co1—O3ii | 85.61 (6) |
C9—C10—H10a | 110.4 | O1iv—Co1—O3iii | 85.61 (6) |
C9—C10—H10b | 110.4 | O1—Co1—O3iii | 165.96 (6) |
O3—C10—H10a | 110.4 | O1iv—Co1—O3ii | 165.96 (6) |
O3—C10—H10b | 110.4 | O3iii—Co1—O3ii | 86.74 (9) |
C1—C2—C3—C4 | 173.4 (2) | C10—O3—C11—C12i | −175.92 (19) |
C1—C2—C7—C6 | −172.2 (2) | C11—O3—C10—C9 | 159.56 (19) |
C2—C7—C6—C5 | −1.7 (3) | C12—N1—C8—C4 | −70.1 (2) |
C3—C2—C7—C6 | 2.9 (3) | C12—N1—C9—C10 | −71.2 (2) |
C3—C4—C8—N1 | −110.1 (2) | N1—C9—C10—O3 | −49.7 (3) |
C5—C4—C3—C2 | −1.1 (3) | O1—C1—C2—C3 | −28.4 (3) |
C5—C4—C8—N1 | 73.0 (3) | O1—C1—C2—C7 | 146.5 (2) |
C6—C5—C4—C3 | 2.4 (3) | O2—C1—C2—C3 | 155.1 (2) |
C6—C5—C4—C8 | 179.3 (2) | O2—C1—C2—C7 | −30.0 (3) |
C7—C2—C3—C4 | −1.5 (3) | Co1ii—N1—C8—C4 | 167.72 (15) |
C7—C6—C5—C4 | −1.0 (3) | Co1ii—N1—C9—C10 | 50.7 (2) |
C8—C4—C3—C2 | −178.10 (19) | Co1ii—N1—C12—C11i | −30.1 (2) |
C8—N1—C9—C10 | 166.73 (18) | Co1—O1—C1—C2 | 172.68 (13) |
C8—N1—C12—C11i | −150.6 (2) | Co1—O1—C1—O2 | −11.1 (3) |
C9—N1—C8—C4 | 53.8 (2) | Co1ii—O3—C10—C9 | 23.1 (2) |
C9—N1—C12—C11i | 88.3 (2) | Co1ii—O3—C11—C12i | −38.8 (2) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, −y−1/2, −z+1; (iii) x−1/2, −y−1/2, z−1/2; (iv) −x, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C24H28N2O6)] |
Mr | 499.41 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 20.626 (2), 8.9778 (10), 13.9263 (16) |
β (°) | 127.051 (1) |
V (Å3) | 2058.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.40 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Bruker D8 diffractometer with a APEXII detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2012) |
Tmin, Tmax | 0.606, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3614, 2930, 2290 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.729 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.125, 1.02 |
No. of reflections | 2930 |
No. of parameters | 150 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.47 |
Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).
Acknowledgements
Financial support of NSF/CREST/ CFNM (award No. HRD-1137751) is acknowledged.
References
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The title compound is the one of a series of coordination polymers prepared from the anionic ligand LH2, 3,3'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene))dibenzoate. This ligand shows unusual adaptability in that it displays two complexation modes on binding to metals. The ligand attaches to the metal via two oxygen and two nitrogen atoms (forming a crown complex). The crown forms four bonds to the metal, while an ideal coordination number for a CoII ion is 6. Thus vacant coordination sites suitable for coordination by the carboxylate groups exist. The carboxylate ions behave as monodentate bridging ligands and the entire ligand is hexadentate. The CoII atom is moved out of the best plane of the crown since this arrangement is better for forming optimal bonds to the ligand. This new compound is novel in that, although the ligands bridge the metal atoms forming one-dimensional chains, the metal atoms are positioned in the center of the organic linker. Topologically, the CoII atoms and the ligands forms nodes in the network rather than the metal atoms only.
The title compound is synthesized from the ligand LH2, 3,3'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(methylene)) dibenzoic acid. The metal atoms are positioned in the center of the organic linker. The asymmetric unit of the compound contains a CoII ion and a deprotonated ligand L with formula C24H28N2O6Co. The CoII ion is 6-coordinate in a distorted octahedral geometry being bound to two N atoms and two O atoms of the crown (1,7-diaza-12-crown-4) and two carboxylic O atoms, one from each of two additional intra-chain ligands (Figure 1s). The Co1—O1, Co1—O3 and Co1—N1 bond lengths are 1.9886 (16), 2.2399 (16) and 2.2213 (17) Å, respectively. The O1—Co1—O1 angle is 104.15 (9)°. The shortest distance between two neighboring CoII ions along a chain is 9.046 (1) Å. The CoII ion of the Co(crown-4)2+ unit is located on a 2-fold rotation axis. The symmetry independent atoms consist of one half of the ligand with the rotation axis generating the second half of the ligand at the Co atom. Bond circuits consisting of sixteen-membered metallomacrocycle rings can be identified in the structure. Each ring contains two CoII ions and fourteen non-H atoms of the ligand. Each CoII ion is a node for three ligands and two connected macrocycle rings. The pair of benzene moieties within a metallomacrocycle ring are remarkably co-planar (the two rings are in the same plane within experimental error). The dihedral angle between this plane and the plane of the next two nearest phenyl rings along the 1-D chain is 68.79 (5)°. Repetition of these units creates a 1-D polymer network with an infinite number of these rings.