Bis[tetra­aqua­(1,10-phenanthroline-κ2N,N′)cobalt(II)] hexa­aqua­cobalt(II) bis­[3,5-bis­(carboxyl­atometh­oxy)benzoate] tetra­hydrate

Song, H.-Y.; Wang, X.-J.; Qiu, S.-Z.; Feng, Y.-L.

doi:10.1107/S1600536810046386

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1577-m1578

https://doi.org/10.1107/S1600536810046386

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Bis[tetraaqua(1,10-phenanthroline-κ²N,N′)cobalt(II)] hexaaquacobalt(II) bis[3,5-bis(carboxylatomethoxy)benzoate] tetrahydrate

Hui-Ying Song,^a Xiao-Juan Wang,^b Shi-Zhen Qiu ^a and Yun-Long Feng ^b ^*

^aCollege of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, and ^bZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: sky37@zjnu.edu.cn

(Received 6 November 2010; accepted 10 November 2010; online 17 November 2010)

The title compound, [Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂·4H₂O, was obtanied by the reaction of cobalt acetate with 3,5-bis(carboxymethoxy)benzoic acid and 1,10-phenanthroline. The asymmetric unit contains one tetraaqua(1,10-phenanthroline)cobalt(II) cation, one half of a hexaaquacobalt(II) cation that is completed by inversion symmetry, one 3,5-bis(carboxylatomethoxy)benzoate trianion and two lattice water molecules. The two Co^II atoms each show a slightly distorted octahedral coordination (CoO₆ and CoO₄N₂). The cations, anions and lattice water molecules are linked by an intricate network of O—H⋯O hydrogen bonds into a three-dimensional structure.

Related literature

For background to multicarboxylate ligands, see: Cao et al. (2002 ); Dai et al. (2002 ); He et al. (2008 ); Rowsell et al. (2005 ); Wang et al. (2005 ).

Experimental

Crystal data

[Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂·4H₂O
M_r = 1395.82
Monoclinic, P 2₁ /n
a = 7.0924 (1) Å
b = 20.3779 (4) Å
c = 20.1810 (3) Å
β = 99.063 (1)°
V = 2880.31 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 296 K
0.22 × 0.15 × 0.07 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.839, T_max = 0.933
21923 measured reflections
5080 independent reflections
3751 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.100
S = 1.09
5080 reflections
450 parameters
27 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O5W	2.0144 (19)
Co1—O6W	2.112 (2)
Co1—O7W	2.115 (3)
Co2—O2W	2.072 (2)
Co2—O1W	2.093 (2)
Co2—O4W	2.102 (2)
Co2—N1	2.109 (2)
Co2—O3W	2.118 (2)
Co2—N2	2.157 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4W—H4WA⋯O7ⁱ	0.84 (2)	1.88 (2)	2.713 (3)	173 (3)
O2W—H2WA⋯O8ⁱ	0.86 (2)	1.86 (2)	2.690 (3)	163 (3)
O8W—H8WA⋯O1ⁱ	0.84 (2)	1.91 (2)	2.732 (3)	163 (4)
O4W—H4WB⋯O2ⁱⁱ	0.84 (2)	1.91 (2)	2.731 (3)	169 (3)
O7W—H7WA⋯O9Wⁱⁱ	0.84 (2)	2.01 (2)	2.818 (3)	164 (3)
O8W—H8WB⋯O4ⁱⁱ	0.85 (2)	2.29 (3)	2.945 (3)	134 (4)
O3W—H3WA⋯O7ⁱⁱⁱ	0.83 (2)	2.12 (2)	2.881 (3)	152 (3)
O5W—H5WA⋯O1ⁱⁱⁱ	0.84 (2)	1.77 (2)	2.609 (3)	175 (4)
O1W—H1WB⋯O7ⁱⁱⁱ	0.84 (2)	1.88 (2)	2.711 (3)	170 (3)
O6W—H6WB⋯O5^iv	0.81 (2)	2.00 (2)	2.812 (3)	177 (3)
O5W—H5WB⋯O4^iv	0.83 (2)	1.89 (2)	2.715 (3)	174 (4)
O3W—H3WB⋯O4^iv	0.79 (2)	2.25 (2)	3.029 (3)	168 (4)
O3W—H3WB⋯O3^iv	0.79 (2)	2.54 (3)	3.080 (3)	127 (3)
O9W—H9WB⋯O2^v	0.82 (2)	2.00 (2)	2.818 (3)	172 (4)
O7W—H7WB⋯O9W^vi	0.83 (2)	1.97 (2)	2.805 (4)	174 (4)
O1W—H1WA⋯O5^vii	0.82 (2)	1.97 (2)	2.785 (3)	172 (4)
O6W—H6WA⋯O2	0.79 (2)	2.00 (2)	2.775 (3)	169 (3)
O2W—H2WB⋯O8W	0.85 (2)	1.88 (2)	2.723 (3)	177 (3)
O9W—H9WA⋯O5	0.83 (2)	2.00 (2)	2.831 (3)	173 (3)
Symmetry codes: (i) -x+2, -y, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) x, y, z+1.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046386/wm2426sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046386/wm2426Isup2.hkl

checkCIF report

Comment top

Multibenzenecarboxylate ligands, such as terephthalic acid, 1,3,5-benzenetricarboxylic acid, or 1,2,4,5-benzenetetracarboxylic acid, have been employed in the construction of numerous framework compounds (Dai et al., 2002; Rowsell et al., 2005; Wang et al., 2005; Cao et al., 2002). Herein, on the basis of the rigidity of 3,5-dihydroxybenzoic acid, we successfully designed a new multicarboxylate ligand, viz. 3,5-bis-carboxymethoxy-benzoic acid (C₁₁H₁₀O₈) (He et al., 2008). In this work, we report the synthesis and structure of a new compound, [Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂^.4H₂O, (I).

A perspective view of the molecular entities of compound (I) is presented in Fig.1. The asymmetric unit consists of one [Co(C₁₂H₈N₂)(H₂O)₄]²⁺, half a [Co(H₂O)₆]²⁺ cation (1 symmetry), one (C₁₁H₇O₈)₂^3- anion, and two lattice water molecules. In the cations, the Co^II atoms show a slightly distorted octahedral coordination (CoO₆ and CoO₄N₂, respectively). In the anion, one of the carboxymethyl groups is almost co-planar to the benzene ring with the dihedral angle of 3.5 (1)°, while the formate group makes a dihedral angle of 17.2 (1)° with the benzene ring. The other carboxymethyl group is almost perpendicular to the benzene ring with the torsion angle C17—O6—C22—C23 of 81.3 (3)°. Together with lattice water molecules, the carboxylic O atoms act as acceptors of O—H···O hydrogen bonds forming a three-dimensional structure (Fig. 2).

Related literature top

For background to multicarboxylate ligands, see: Cao et al. (2002); Dai et al. (2002); He et al. (2008); Rowsell et al. (2005); Wang et al. (2005).

Experimental top

A mixture of 3,5-bis-carboxymethoxy-benzoic acid (0.373 g, 1.50 mmol), Co(CH₃COO)₂^.4H₂O (0.282 g, 1.00 mmol), 1,10-phenanthroline (0.049 g, 0.25 mmol), and Na₂CO₃ (0.079 g, 0.75 mmol) in C₂H₅OH (2 ml)/H₂O (16 ml) was placed in a Teflon-lined stainless steel vessel and heated at 433 K for 72 h, and then cooled to room temperature over 3 days. Then the reaction mixture was filtered and well-shaped pink crystals of compound (I) were obtained from the mother liquor by slow evaporation at room temperature for several days.

Structure description top

For background to multicarboxylate ligands, see: Cao et al. (2002); Dai et al. (2002); He et al. (2008); Rowsell et al. (2005); Wang et al. (2005).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of the molecular entities of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The three-dimensional set up of structure of (I), viewed down [100]. Dashed lines indicate hydrogen bonds.

Bis[tetraaqua(1,10-phenanthroline-κ²N,N')cobalt(II)] hexaaquacobalt(II) bis[3,5-bis(carboxylatomethoxy)benzoate] tetrahydrate top

Crystal data top

[Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂·4H₂O	F(000) = 1446
M_r = 1395.82	D_x = 1.609 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3158 reflections
a = 7.0924 (1) Å	θ = 1.4–25.0°
b = 20.3779 (4) Å	µ = 0.96 mm⁻¹
c = 20.1810 (3) Å	T = 296 K
β = 99.063 (1)°	Block, pink
V = 2880.31 (8) Å³	0.22 × 0.15 × 0.07 mm
Z = 2

Data collection top

Bruker APEXII area-detector diffractometer	5080 independent reflections
Radiation source: fine-focus sealed tube	3751 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.839, T_max = 0.933	k = −24→24
21923 measured reflections	l = −23→23

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0472P)²] where P = (F_o² + 2F_c²)/3
5080 reflections	(Δ/σ)_max = 0.001
450 parameters	Δρ_max = 0.31 e Å⁻³
27 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂·4H₂O	V = 2880.31 (8) Å³
M_r = 1395.82	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0924 (1) Å	µ = 0.96 mm⁻¹
b = 20.3779 (4) Å	T = 296 K
c = 20.1810 (3) Å	0.22 × 0.15 × 0.07 mm
β = 99.063 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	5080 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3751 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.933	R_int = 0.054
21923 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	27 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.31 e Å⁻³
5080 reflections	Δρ_min = −0.30 e Å⁻³
450 parameters

Special details top

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.

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 > σ(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.

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

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.0000	0.5000	0.03353 (17)
Co2	0.74606 (6)	0.243825 (19)	0.763479 (18)	0.03271 (14)
N1	0.7089 (3)	0.34589 (12)	0.74971 (11)	0.0339 (6)
N2	0.7521 (3)	0.25550 (12)	0.65761 (11)	0.0344 (6)
O1W	0.6596 (4)	0.23471 (14)	0.85757 (11)	0.0551 (7)
H1WA	0.696 (4)	0.2535 (16)	0.8930 (12)	0.066*
H1WB	0.548 (3)	0.2210 (18)	0.8584 (16)	0.066*
O1	0.7285 (4)	0.00598 (10)	0.32671 (11)	0.0589 (7)
O2W	0.8488 (3)	0.14848 (11)	0.76823 (11)	0.0441 (6)
H2WA	0.921 (4)	0.1411 (17)	0.8057 (9)	0.053*
H2WB	0.926 (4)	0.1379 (16)	0.7422 (11)	0.053*
O2	0.6887 (3)	0.11208 (10)	0.34103 (9)	0.0383 (5)
O3W	0.4615 (3)	0.21473 (13)	0.72790 (10)	0.0486 (6)
H3WA	0.395 (4)	0.1961 (15)	0.7526 (12)	0.058*
H3WB	0.413 (4)	0.2101 (17)	0.6903 (8)	0.058*
O3	0.7342 (3)	0.20327 (10)	0.11420 (9)	0.0472 (6)
O4	0.7996 (3)	0.32426 (10)	0.08547 (9)	0.0479 (6)
O4W	1.0173 (3)	0.26858 (11)	0.81544 (12)	0.0474 (6)
H4WA	1.106 (4)	0.2421 (12)	0.8289 (16)	0.057*
H4WB	1.072 (4)	0.3051 (9)	0.8180 (16)	0.057*
O5W	0.4188 (4)	0.04985 (11)	0.57696 (12)	0.0663 (8)
H5WA	0.367 (5)	0.0307 (15)	0.6061 (15)	0.080*
H5WB	0.389 (6)	0.0890 (9)	0.5780 (18)	0.080*
O5	0.7541 (3)	0.30672 (10)	−0.02457 (9)	0.0382 (5)
O6W	0.4901 (3)	0.08954 (10)	0.44683 (10)	0.0457 (6)
H6WA	0.533 (4)	0.0971 (15)	0.4139 (12)	0.055*
H6WB	0.420 (4)	0.1186 (13)	0.4560 (15)	0.055*
O6	0.6088 (4)	−0.02370 (11)	0.07416 (10)	0.0524 (6)
O7W	0.7879 (4)	0.02001 (14)	0.54018 (13)	0.0592 (7)
H7WA	0.849 (4)	0.0467 (13)	0.5203 (16)	0.071*
H7WB	0.860 (5)	−0.0126 (12)	0.5454 (18)	0.071*
O7	0.6937 (3)	−0.18124 (10)	0.15287 (10)	0.0434 (5)
O8	0.8981 (3)	−0.10571 (11)	0.12730 (10)	0.0465 (6)
O8W	1.1066 (5)	0.11321 (14)	0.68801 (14)	0.0824 (10)
H8WB	1.097 (6)	0.1260 (18)	0.6478 (12)	0.099*
H8WA	1.137 (6)	0.0734 (10)	0.6857 (19)	0.099*
O9W	0.4790 (4)	0.40818 (12)	−0.04843 (13)	0.0514 (6)
H9WA	0.552 (4)	0.3760 (13)	−0.0411 (14)	0.048 (11)*
H9WB	0.401 (5)	0.3993 (19)	−0.0817 (15)	0.104 (19)*
C1	0.6998 (4)	0.39104 (16)	0.79609 (15)	0.0417 (8)
H1A	0.7074	0.3775	0.8404	0.050*
C2	0.6795 (5)	0.45779 (17)	0.78211 (17)	0.0518 (9)
H2A	0.6779	0.4881	0.8165	0.062*
C3	0.6622 (5)	0.47783 (17)	0.71727 (19)	0.0530 (9)
H3A	0.6446	0.5221	0.7068	0.064*
C4	0.6708 (4)	0.43239 (16)	0.66644 (15)	0.0420 (8)
C5	0.6501 (5)	0.44923 (19)	0.59653 (17)	0.0543 (10)
H5A	0.6294	0.4927	0.5835	0.065*
C6	0.6604 (5)	0.40298 (19)	0.54975 (16)	0.0521 (9)
H6A	0.6444	0.4151	0.5048	0.062*
C7	0.6953 (4)	0.33579 (17)	0.56737 (14)	0.0406 (8)
C8	0.6990 (4)	0.36689 (15)	0.68516 (14)	0.0335 (7)
C9	0.7180 (4)	0.31756 (15)	0.63583 (13)	0.0325 (7)
C10	0.7060 (5)	0.28512 (19)	0.52134 (16)	0.0498 (9)
H10A	0.6904	0.2943	0.4757	0.060*
C11	0.7391 (5)	0.2229 (2)	0.54308 (15)	0.0512 (9)
H11A	0.7459	0.1892	0.5125	0.061*
C12	0.7631 (5)	0.20916 (17)	0.61220 (15)	0.0446 (8)
H12A	0.7876	0.1662	0.6266	0.054*
C13	0.6916 (4)	0.07233 (14)	0.22994 (13)	0.0324 (7)
C14	0.7154 (4)	0.13290 (14)	0.20404 (13)	0.0326 (7)
H14A	0.7379	0.1691	0.2323	0.039*
C15	0.7059 (4)	0.14038 (14)	0.13487 (13)	0.0335 (7)
C16	0.6709 (4)	0.08749 (14)	0.09286 (14)	0.0352 (7)
H16A	0.6637	0.0925	0.0467	0.042*
C17	0.6463 (4)	0.02584 (15)	0.12065 (14)	0.0375 (7)
C18	0.6587 (4)	0.01780 (15)	0.18883 (14)	0.0373 (7)
H18A	0.6453	−0.0235	0.2070	0.045*
C19	0.7032 (4)	0.06265 (15)	0.30421 (13)	0.0364 (7)
C20	0.7191 (4)	0.21662 (14)	0.04494 (12)	0.0303 (7)
H20A	0.5913	0.2064	0.0225	0.036*
H20B	0.8088	0.1896	0.0254	0.036*
C21	0.7619 (4)	0.28832 (14)	0.03547 (13)	0.0301 (7)
C22	0.5633 (5)	−0.08635 (15)	0.09867 (16)	0.0491 (9)
H22A	0.4917	−0.1110	0.0620	0.059*
H22B	0.4811	−0.0801	0.1323	0.059*
C23	0.7349 (5)	−0.12653 (16)	0.12912 (13)	0.0366 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0424 (4)	0.0287 (3)	0.0329 (3)	0.0087 (3)	0.0163 (3)	0.0036 (2)
Co2	0.0366 (3)	0.0297 (3)	0.0316 (2)	0.00050 (19)	0.00464 (18)	−0.00106 (17)
N1	0.0316 (15)	0.0339 (15)	0.0350 (13)	0.0041 (12)	0.0014 (11)	−0.0024 (11)
N2	0.0332 (16)	0.0364 (16)	0.0336 (13)	−0.0016 (12)	0.0057 (11)	−0.0043 (11)
O1W	0.0514 (16)	0.0808 (19)	0.0353 (12)	−0.0249 (14)	0.0131 (12)	−0.0124 (12)
O1	0.106 (2)	0.0308 (14)	0.0483 (12)	0.0189 (13)	0.0372 (14)	0.0146 (10)
O2W	0.0503 (16)	0.0350 (13)	0.0458 (12)	0.0040 (12)	0.0035 (11)	−0.0021 (11)
O2	0.0557 (15)	0.0302 (12)	0.0309 (10)	0.0071 (10)	0.0126 (10)	0.0033 (9)
O3W	0.0424 (15)	0.0666 (17)	0.0352 (11)	−0.0129 (13)	0.0014 (11)	0.0045 (12)
O3	0.0793 (18)	0.0323 (13)	0.0291 (10)	−0.0105 (12)	0.0054 (11)	0.0057 (9)
O4	0.0784 (17)	0.0317 (13)	0.0357 (11)	−0.0141 (12)	0.0151 (11)	−0.0048 (10)
O4W	0.0341 (14)	0.0287 (13)	0.0752 (16)	−0.0024 (11)	−0.0048 (12)	0.0041 (12)
O5W	0.120 (2)	0.0343 (14)	0.0587 (14)	0.0220 (15)	0.0592 (15)	0.0090 (12)
O5	0.0533 (14)	0.0325 (12)	0.0288 (10)	−0.0056 (10)	0.0066 (10)	0.0048 (9)
O6W	0.0620 (17)	0.0366 (14)	0.0452 (12)	0.0151 (12)	0.0291 (12)	0.0126 (10)
O6	0.0850 (19)	0.0275 (13)	0.0391 (11)	0.0028 (12)	−0.0075 (12)	−0.0026 (10)
O7W	0.0489 (17)	0.0568 (18)	0.0733 (16)	0.0085 (13)	0.0140 (13)	0.0192 (14)
O7	0.0420 (14)	0.0323 (13)	0.0552 (13)	0.0002 (11)	0.0058 (11)	0.0082 (10)
O8	0.0469 (16)	0.0452 (15)	0.0470 (13)	−0.0055 (12)	0.0065 (11)	0.0075 (10)
O8W	0.115 (3)	0.0616 (19)	0.0827 (19)	0.0341 (19)	0.0517 (19)	0.0138 (16)
O9W	0.0445 (16)	0.0475 (17)	0.0584 (16)	0.0085 (14)	−0.0037 (13)	−0.0078 (13)
C1	0.040 (2)	0.041 (2)	0.0430 (17)	0.0031 (16)	0.0013 (15)	−0.0073 (15)
C2	0.051 (2)	0.042 (2)	0.061 (2)	0.0047 (18)	0.0050 (18)	−0.0142 (17)
C3	0.047 (2)	0.032 (2)	0.080 (3)	0.0069 (17)	0.0096 (19)	0.0036 (18)
C4	0.034 (2)	0.037 (2)	0.0546 (19)	0.0015 (16)	0.0040 (15)	0.0088 (16)
C5	0.046 (2)	0.049 (2)	0.067 (2)	0.0035 (19)	0.0087 (18)	0.0227 (19)
C6	0.046 (2)	0.062 (3)	0.048 (2)	0.0006 (19)	0.0068 (17)	0.0248 (18)
C7	0.0276 (18)	0.057 (2)	0.0373 (16)	−0.0055 (16)	0.0056 (14)	0.0055 (15)
C8	0.0247 (17)	0.0343 (18)	0.0404 (16)	−0.0015 (14)	0.0018 (13)	0.0021 (14)
C9	0.0231 (17)	0.0380 (19)	0.0360 (15)	−0.0038 (14)	0.0036 (13)	0.0057 (13)
C10	0.043 (2)	0.072 (3)	0.0354 (17)	−0.008 (2)	0.0093 (16)	0.0033 (18)
C11	0.046 (2)	0.070 (3)	0.0389 (18)	−0.006 (2)	0.0102 (16)	−0.0157 (17)
C12	0.045 (2)	0.044 (2)	0.0459 (18)	0.0017 (17)	0.0081 (16)	−0.0065 (16)
C13	0.0323 (18)	0.0343 (18)	0.0321 (15)	0.0024 (14)	0.0101 (13)	0.0015 (13)
C14	0.0398 (19)	0.0258 (17)	0.0329 (15)	0.0004 (14)	0.0081 (14)	0.0028 (12)
C15	0.0407 (19)	0.0265 (17)	0.0334 (15)	−0.0006 (14)	0.0059 (14)	0.0087 (13)
C16	0.040 (2)	0.0321 (18)	0.0327 (15)	0.0024 (15)	0.0025 (14)	0.0057 (13)
C17	0.042 (2)	0.0303 (18)	0.0378 (16)	0.0029 (15)	−0.0010 (14)	−0.0046 (13)
C18	0.044 (2)	0.0290 (17)	0.0388 (16)	0.0024 (15)	0.0048 (14)	0.0067 (13)
C19	0.041 (2)	0.0363 (19)	0.0353 (15)	0.0046 (16)	0.0155 (14)	0.0081 (14)
C20	0.0342 (18)	0.0302 (17)	0.0258 (14)	−0.0016 (14)	0.0025 (13)	0.0018 (12)
C21	0.0338 (18)	0.0262 (17)	0.0314 (15)	−0.0027 (14)	0.0086 (13)	0.0016 (13)
C22	0.061 (3)	0.0277 (19)	0.0520 (19)	−0.0018 (17)	−0.0109 (17)	−0.0066 (15)
C23	0.047 (2)	0.035 (2)	0.0256 (14)	0.0019 (17)	0.0007 (14)	−0.0030 (13)

Geometric parameters (Å, º) top

Co1—O5Wⁱ	2.0144 (19)	O8W—H8WB	0.845 (18)
Co1—O5W	2.0144 (19)	O8W—H8WA	0.842 (18)
Co1—O6Wⁱ	2.112 (2)	O9W—H9WA	0.833 (17)
Co1—O6W	2.112 (2)	O9W—H9WB	0.819 (18)
Co1—O7W	2.115 (3)	C1—C2	1.392 (5)
Co1—O7Wⁱ	2.115 (3)	C1—H1A	0.9300
Co2—O2W	2.072 (2)	C2—C3	1.358 (5)
Co2—O1W	2.093 (2)	C2—H2A	0.9300
Co2—O4W	2.102 (2)	C3—C4	1.390 (4)
Co2—N1	2.109 (2)	C3—H3A	0.9300
Co2—O3W	2.118 (2)	C4—C8	1.393 (4)
Co2—N2	2.157 (2)	C4—C5	1.437 (4)
N1—C1	1.321 (4)	C5—C6	1.344 (5)
N1—C8	1.362 (3)	C5—H5A	0.9300
N2—C12	1.327 (4)	C6—C7	1.426 (5)
N2—C9	1.348 (4)	C6—H6A	0.9300
O1W—H1WA	0.816 (17)	C7—C10	1.399 (5)
O1W—H1WB	0.839 (17)	C7—C9	1.415 (4)
O1—C19	1.244 (3)	C8—C9	1.436 (4)
O2W—H2WA	0.856 (17)	C10—C11	1.350 (5)
O2W—H2WB	0.846 (17)	C10—H10A	0.9300
O2—C19	1.266 (3)	C11—C12	1.406 (4)
O3W—H3WA	0.831 (17)	C11—H11A	0.9300
O3W—H3WB	0.788 (17)	C12—H12A	0.9300
O3—C15	1.372 (3)	C13—C14	1.361 (4)
O3—C20	1.412 (3)	C13—C18	1.384 (4)
O4—C21	1.241 (3)	C13—C19	1.501 (3)
O4W—H4WA	0.841 (17)	C14—C15	1.395 (3)
O4W—H4WB	0.837 (17)	C14—H14A	0.9300
O5W—H5WA	0.837 (17)	C15—C16	1.370 (4)
O5W—H5WB	0.826 (18)	C16—C17	1.398 (4)
O5—C21	1.261 (3)	C16—H16A	0.9300
O6W—H6WA	0.788 (17)	C17—C18	1.375 (4)
O6W—H6WB	0.810 (17)	C18—H18A	0.9300
O6—C17	1.375 (3)	C20—C21	1.511 (4)
O6—C22	1.424 (4)	C20—H20A	0.9700
O7W—H7WA	0.836 (18)	C20—H20B	0.9700
O7W—H7WB	0.834 (18)	C22—C23	1.515 (4)
O7—C23	1.266 (4)	C22—H22A	0.9700
O8—C23	1.239 (4)	C22—H22B	0.9700

O5Wⁱ—Co1—O5W	180.00 (8)	C2—C3—H3A	119.9
O5Wⁱ—Co1—O6Wⁱ	88.01 (8)	C4—C3—H3A	119.9
O5W—Co1—O6Wⁱ	91.99 (8)	C3—C4—C8	117.3 (3)
O5Wⁱ—Co1—O6W	91.99 (8)	C3—C4—C5	123.8 (3)
O5W—Co1—O6W	88.01 (8)	C8—C4—C5	118.9 (3)
O6Wⁱ—Co1—O6W	180.000 (1)	C6—C5—C4	120.9 (3)
O5Wⁱ—Co1—O7W	90.96 (12)	C6—C5—H5A	119.5
O5W—Co1—O7W	89.04 (12)	C4—C5—H5A	119.5
O6Wⁱ—Co1—O7W	91.08 (10)	C5—C6—C7	121.6 (3)
O6W—Co1—O7W	88.92 (10)	C5—C6—H6A	119.2
O5Wⁱ—Co1—O7Wⁱ	89.04 (12)	C7—C6—H6A	119.2
O5W—Co1—O7Wⁱ	90.96 (12)	C10—C7—C9	116.4 (3)
O6Wⁱ—Co1—O7Wⁱ	88.92 (10)	C10—C7—C6	124.6 (3)
O6W—Co1—O7Wⁱ	91.08 (10)	C9—C7—C6	118.9 (3)
O7W—Co1—O7Wⁱ	180.0	N1—C8—C4	123.0 (3)
O2W—Co2—O1W	91.48 (10)	N1—C8—C9	116.5 (3)
O2W—Co2—O4W	85.09 (9)	C4—C8—C9	120.5 (3)
O1W—Co2—O4W	86.82 (10)	N2—C9—C7	123.5 (3)
O2W—Co2—N1	165.12 (9)	N2—C9—C8	117.5 (2)
O1W—Co2—N1	99.13 (10)	C7—C9—C8	119.0 (3)
O4W—Co2—N1	85.11 (9)	C11—C10—C7	120.1 (3)
O2W—Co2—O3W	93.59 (10)	C11—C10—H10A	119.9
O1W—Co2—O3W	83.29 (9)	C7—C10—H10A	119.9
O4W—Co2—O3W	169.99 (9)	C10—C11—C12	119.8 (3)
N1—Co2—O3W	97.97 (10)	C10—C11—H11A	120.1
O2W—Co2—N2	95.03 (9)	C12—C11—H11A	120.1
O1W—Co2—N2	164.28 (10)	N2—C12—C11	122.2 (3)
O4W—Co2—N2	107.96 (10)	N2—C12—H12A	118.9
N1—Co2—N2	77.42 (9)	C11—C12—H12A	118.9
O3W—Co2—N2	82.04 (8)	C14—C13—C18	121.1 (2)
C1—N1—C8	117.2 (3)	C14—C13—C19	120.8 (3)
C1—N1—Co2	127.8 (2)	C18—C13—C19	118.1 (3)
C8—N1—Co2	114.98 (19)	C13—C14—C15	119.6 (3)
C12—N2—C9	118.0 (3)	C13—C14—H14A	120.2
C12—N2—Co2	128.2 (2)	C15—C14—H14A	120.2
C9—N2—Co2	113.33 (17)	C16—C15—O3	124.6 (2)
Co2—O1W—H1WA	131 (2)	C16—C15—C14	120.6 (3)
Co2—O1W—H1WB	117 (2)	O3—C15—C14	114.8 (3)
H1WA—O1W—H1WB	108 (2)	C15—C16—C17	118.7 (3)
Co2—O2W—H2WA	111 (2)	C15—C16—H16A	120.6
Co2—O2W—H2WB	118 (2)	C17—C16—H16A	120.6
H2WA—O2W—H2WB	99 (2)	C18—C17—O6	124.8 (3)
Co2—O3W—H3WA	122 (2)	C18—C17—C16	121.1 (3)
Co2—O3W—H3WB	127 (2)	O6—C17—C16	114.1 (2)
H3WA—O3W—H3WB	109 (3)	C17—C18—C13	118.9 (3)
C15—O3—C20	119.3 (2)	C17—C18—H18A	120.6
Co2—O4W—H4WA	126 (2)	C13—C18—H18A	120.6
Co2—O4W—H4WB	129 (2)	O1—C19—O2	123.0 (2)
H4WA—O4W—H4WB	103 (2)	O1—C19—C13	117.9 (3)
Co1—O5W—H5WA	121 (2)	O2—C19—C13	119.0 (3)
Co1—O5W—H5WB	128 (2)	O3—C20—C21	109.0 (2)
H5WA—O5W—H5WB	107 (2)	O3—C20—H20A	109.9
Co1—O6W—H6WA	128 (2)	C21—C20—H20A	109.9
Co1—O6W—H6WB	119 (2)	O3—C20—H20B	109.9
H6WA—O6W—H6WB	112 (3)	C21—C20—H20B	109.9
C17—O6—C22	116.8 (2)	H20A—C20—H20B	108.3
Co1—O7W—H7WA	119 (2)	O4—C21—O5	125.2 (3)
Co1—O7W—H7WB	115 (3)	O4—C21—C20	119.3 (2)
H7WA—O7W—H7WB	103 (2)	O5—C21—C20	115.5 (2)
H8WB—O8W—H8WA	103 (2)	O6—C22—C23	114.4 (3)
H9WA—O9W—H9WB	107 (3)	O6—C22—H22A	108.6
N1—C1—C2	123.5 (3)	C23—C22—H22A	108.6
N1—C1—H1A	118.3	O6—C22—H22B	108.6
C2—C1—H1A	118.3	C23—C22—H22B	108.6
C3—C2—C1	118.7 (3)	H22A—C22—H22B	107.6
C3—C2—H2A	120.7	O8—C23—O7	125.8 (3)
C1—C2—H2A	120.7	O8—C23—C22	119.9 (3)
C2—C3—C4	120.2 (3)	O7—C23—C22	114.3 (3)

O2W—Co2—N1—C1	−114.6 (4)	Co2—N2—C9—C8	5.0 (3)
O1W—Co2—N1—C1	20.4 (3)	C10—C7—C9—N2	1.2 (4)
O4W—Co2—N1—C1	−65.6 (3)	C6—C7—C9—N2	−179.7 (3)
O3W—Co2—N1—C1	104.8 (3)	C10—C7—C9—C8	−177.0 (3)
N2—Co2—N1—C1	−175.2 (3)	C6—C7—C9—C8	2.1 (4)
O2W—Co2—N1—C8	63.3 (4)	N1—C8—C9—N2	−2.8 (4)
O1W—Co2—N1—C8	−161.7 (2)	C4—C8—C9—N2	177.6 (3)
O4W—Co2—N1—C8	112.3 (2)	N1—C8—C9—C7	175.5 (3)
O3W—Co2—N1—C8	−77.3 (2)	C4—C8—C9—C7	−4.1 (4)
N2—Co2—N1—C8	2.66 (19)	C9—C7—C10—C11	−0.8 (5)
O2W—Co2—N2—C12	17.1 (3)	C6—C7—C10—C11	−179.8 (3)
O1W—Co2—N2—C12	−97.0 (4)	C7—C10—C11—C12	−0.2 (5)
O4W—Co2—N2—C12	103.6 (3)	C9—N2—C12—C11	−0.5 (5)
N1—Co2—N2—C12	−175.9 (3)	Co2—N2—C12—C11	170.9 (2)
O3W—Co2—N2—C12	−75.8 (3)	C10—C11—C12—N2	0.9 (5)
O2W—Co2—N2—C9	−171.1 (2)	C18—C13—C14—C15	0.2 (4)
O1W—Co2—N2—C9	74.8 (4)	C19—C13—C14—C15	179.3 (3)
O4W—Co2—N2—C9	−84.6 (2)	C20—O3—C15—C16	2.9 (4)
N1—Co2—N2—C9	−4.08 (19)	C20—O3—C15—C14	−177.2 (3)
O3W—Co2—N2—C9	96.0 (2)	C13—C14—C15—C16	0.7 (5)
C8—N1—C1—C2	0.5 (5)	C13—C14—C15—O3	−179.2 (3)
Co2—N1—C1—C2	178.4 (2)	O3—C15—C16—C17	179.5 (3)
N1—C1—C2—C3	2.1 (5)	C14—C15—C16—C17	−0.5 (5)
C1—C2—C3—C4	−2.0 (5)	C22—O6—C17—C18	5.8 (5)
C2—C3—C4—C8	−0.5 (5)	C22—O6—C17—C16	−173.9 (3)
C2—C3—C4—C5	178.8 (3)	C15—C16—C17—C18	−0.7 (5)
C3—C4—C5—C6	179.8 (3)	C15—C16—C17—O6	179.0 (3)
C8—C4—C5—C6	−0.9 (5)	O6—C17—C18—C13	−178.0 (3)
C4—C5—C6—C7	−1.1 (5)	C16—C17—C18—C13	1.6 (5)
C5—C6—C7—C10	179.4 (3)	C14—C13—C18—C17	−1.4 (5)
C5—C6—C7—C9	0.5 (5)	C19—C13—C18—C17	179.5 (3)
C1—N1—C8—C4	−3.2 (4)	C14—C13—C19—O1	−162.3 (3)
Co2—N1—C8—C4	178.6 (2)	C18—C13—C19—O1	16.8 (4)
C1—N1—C8—C9	177.2 (3)	C14—C13—C19—O2	17.1 (4)
Co2—N1—C8—C9	−1.0 (3)	C18—C13—C19—O2	−163.8 (3)
C3—C4—C8—N1	3.3 (5)	C15—O3—C20—C21	−178.3 (2)
C5—C4—C8—N1	−176.1 (3)	O3—C20—C21—O4	−0.9 (4)
C3—C4—C8—C9	−177.2 (3)	O3—C20—C21—O5	179.7 (2)
C5—C4—C8—C9	3.5 (4)	C17—O6—C22—C23	−81.3 (3)
C12—N2—C9—C7	−0.6 (4)	O6—C22—C23—O8	−4.5 (4)
Co2—N2—C9—C7	−173.3 (2)	O6—C22—C23—O7	177.7 (2)
C12—N2—C9—C8	177.7 (3)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H4WA···O7ⁱⁱ	0.84 (2)	1.88 (2)	2.713 (3)	173 (3)
O2W—H2WA···O8ⁱⁱ	0.86 (2)	1.86 (2)	2.690 (3)	163 (3)
O8W—H8WA···O1ⁱⁱ	0.84 (2)	1.91 (2)	2.732 (3)	163 (4)
O4W—H4WB···O2ⁱⁱⁱ	0.84 (2)	1.91 (2)	2.731 (3)	169 (3)
O7W—H7WA···O9Wⁱⁱⁱ	0.84 (2)	2.01 (2)	2.818 (3)	164 (3)
O8W—H8WB···O4ⁱⁱⁱ	0.85 (2)	2.29 (3)	2.945 (3)	134 (4)
O3W—H3WA···O7ⁱ	0.83 (2)	2.12 (2)	2.881 (3)	152 (3)
O5W—H5WA···O1ⁱ	0.84 (2)	1.77 (2)	2.609 (3)	175 (4)
O1W—H1WB···O7ⁱ	0.84 (2)	1.88 (2)	2.711 (3)	170 (3)
O6W—H6WB···O5^iv	0.81 (2)	2.00 (2)	2.812 (3)	177 (3)
O5W—H5WB···O4^iv	0.83 (2)	1.89 (2)	2.715 (3)	174 (4)
O3W—H3WB···O4^iv	0.79 (2)	2.25 (2)	3.029 (3)	168 (4)
O3W—H3WB···O3^iv	0.79 (2)	2.54 (3)	3.080 (3)	127 (3)
O9W—H9WB···O2^v	0.82 (2)	2.00 (2)	2.818 (3)	172 (4)
O7W—H7WB···O9W^vi	0.83 (2)	1.97 (2)	2.805 (4)	174 (4)
O1W—H1WA···O5^vii	0.82 (2)	1.97 (2)	2.785 (3)	172 (4)
O6W—H6WA···O2	0.79 (2)	2.00 (2)	2.775 (3)	169 (3)
O2W—H2WB···O8W	0.85 (2)	1.88 (2)	2.723 (3)	177 (3)
O9W—H9WA···O5	0.83 (2)	2.00 (2)	2.831 (3)	173 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₈N₂)(H₂O)₄]₂[Co(H₂O)₆](C₁₁H₇O₈)₂·4H₂O
M_r	1395.82
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.0924 (1), 20.3779 (4), 20.1810 (3)
β (°)	99.063 (1)
V (Å³)	2880.31 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.96
Crystal size (mm)	0.22 × 0.15 × 0.07

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.839, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	21923, 5080, 3751
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.100, 1.09
No. of reflections	5080
No. of parameters	450
No. of restraints	27
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.30

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O5W	2.0144 (19)	Co2—O4W	2.102 (2)
Co1—O6W	2.112 (2)	Co2—N1	2.109 (2)
Co1—O7W	2.115 (3)	Co2—O3W	2.118 (2)
Co2—O2W	2.072 (2)	Co2—N2	2.157 (2)
Co2—O1W	2.093 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4W—H4WA···O7ⁱ	0.841 (17)	1.878 (18)	2.713 (3)	173 (3)
O2W—H2WA···O8ⁱ	0.856 (17)	1.86 (2)	2.690 (3)	163 (3)
O8W—H8WA···O1ⁱ	0.842 (18)	1.91 (2)	2.732 (3)	163 (4)
O4W—H4WB···O2ⁱⁱ	0.837 (17)	1.905 (18)	2.731 (3)	169 (3)
O7W—H7WA···O9Wⁱⁱ	0.836 (18)	2.01 (2)	2.818 (3)	164 (3)
O8W—H8WB···O4ⁱⁱ	0.845 (18)	2.29 (3)	2.945 (3)	134 (4)
O3W—H3WA···O7ⁱⁱⁱ	0.831 (17)	2.122 (18)	2.881 (3)	152 (3)
O5W—H5WA···O1ⁱⁱⁱ	0.837 (17)	1.774 (18)	2.609 (3)	175 (4)
O1W—H1WB···O7ⁱⁱⁱ	0.839 (17)	1.880 (17)	2.711 (3)	170 (3)
O6W—H6WB···O5^iv	0.810 (17)	2.002 (18)	2.812 (3)	177 (3)
O5W—H5WB···O4^iv	0.826 (18)	1.891 (19)	2.715 (3)	174 (4)
O3W—H3WB···O4^iv	0.788 (17)	2.253 (18)	3.029 (3)	168 (4)
O3W—H3WB···O3^iv	0.788 (17)	2.54 (3)	3.080 (3)	127 (3)
O9W—H9WB···O2^v	0.819 (18)	2.004 (18)	2.818 (3)	172 (4)
O7W—H7WB···O9W^vi	0.834 (18)	1.974 (18)	2.805 (4)	174 (4)
O1W—H1WA···O5^vii	0.816 (17)	1.974 (18)	2.785 (3)	172 (4)
O6W—H6WA···O2	0.788 (17)	1.997 (17)	2.775 (3)	169 (3)
O2W—H2WB···O8W	0.846 (17)	1.877 (18)	2.723 (3)	177 (3)
O9W—H9WA···O5	0.833 (17)	2.004 (18)	2.831 (3)	173 (3)

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

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