catena-Poly[{μ₃-3,3′-[(1,7-dioxa-4,10-di­aza­cyclo­dodecane-4,10-di­yl)bis­(methyl­ene)]dibenzoato}cobalt(II)]

Abstract

The title compound, [Co(C₂₄H₂₈N₂O₆)]_n, crystallizes as infinite chains related to one another by inversion centers, giving a centrosymmetric coordination polymer. The Co^II 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 Co^II 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 Co^II ions and 14 atoms from the bridging ligands. These units repeat as infinite zigzag chains along [101].

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  

• [Co(C₂₄H₂₈N₂O₆)]

• M _r = 499.41

• Monoclinic,

• a = 20.626 (2) Å

• b = 8.9778 (10) Å

• c = 13.9263 (16) Å

• β = 127.051 (1)°

• V = 2058.2 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.88 mm⁻¹

• T = 173 K

• 0.40 × 0.14 × 0.14 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2012) ▶ T _min = 0.606, T _max = 0.746

• 3614 measured reflections

• 2930 independent reflections

• 2290 reflections with I > 2σ(I)

• R _int = 0.018

Refinement  

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.125

• S = 1.02

• 2930 reflections

• 150 parameters

• H-atom parameters constrained

• Δρ_max = 0.80 e Å⁻³

• Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: 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.

Supplementary Material

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

1. Comment

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 Co^II 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 Co^II 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 Co^II 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 Co^II ion and a deprotonated ligand L with formula C₂₄H₂₈N₂O₆Co. The Co^II 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 Co^II ions along a chain is 9.046 (1) Å. The Co^II 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 Co^II ions and fourteen non-H atoms of the ligand. Each Co^II 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.

2. Experimental

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.

3. Refinement

Refinement 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 refinement. 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 refinement: 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).

Figures

Fig. 1.

A view of a portion of one of the chains of (I). Non-H atoms are represented by ellipsoids at the 50% probability level. Sixteen membered metallomacrocycle rings can be identified from this figure.

Crystal data

[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

Data collection

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

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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	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

Geometric parameters (Å, º)

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.