catena-Poly[[[diaqua­cobalt(II)]-μ-(3,5-dinitro-2-oxidobenzoato)-κ3O1,O2:O1′-[tetra­aqua­cobalt(II)]-μ-(3,5-dinitro-2-oxidobenzoato)-κ3O1:O1′,O2] dihydrate]

Smith, G.; Wermuth, U.D.

doi:10.1107/S1600536810052694

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Pages m119-m120

https://doi.org/10.1107/S1600536810052694

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catena-Poly[[[diaquacobalt(II)]-μ-(3,5-dinitro-2-oxidobenzoato)-κ³O¹,O²:O^1′-[tetraaquacobalt(II)]-μ-(3,5-dinitro-2-oxidobenzoato)-κ³O¹:O^1′,O²] dihydrate]

Graham Smith ^a ^* and Urs D. Wermuth ^b

^aFaculty of Science and Technology, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia, and ^bSchool of Biomolecular and Physical Sciences, Griffith University, Nathan, Queensland 4111, Australia
^*Correspondence e-mail: g.smith@qut.edu.au

(Received 22 November 2010; accepted 15 December 2010; online 24 December 2010)

In polymeric title compound, {[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]·2H₂O}_n, obtained from the reaction of 3,5-dinitrosalicylic acid with cobalt(II) acetate, both Co^II atoms are located on inversion centres and exhibit a distorted octahedral coordination geometry. The coordination sphere about one Co^II atom comprises four O-atom donors from two bidentate chelate (O_phenolate and O_carboxyl) and bridging dianionic ligands and two water molecules [Co—O range = 2.0249 (11)–2.1386 (14) Å], while that about the second Co^II atom has four water molecules and two bridging carboxylate O-donor atoms [Co—O range = 2.0690 (14)–2.1364 (11) Å]. The coordinated water molecules as well as the water molecules of solvation give O—H⋯O water–water and water–carboxyl hydrogen-bonding interactions in the three-dimensional framework structure.

Related literature

For the structures of similar hydrated complexes of Co^II, see: Deng et al. (2008 ); Sobolev et al. (2003 ); Tahir et al. (1996 , 1997 ). For the structure of a mixed-ligand Co^II complex with 3,5-dinitrosalicylic acid and the structures of the acid and its salts, see: Zhong et al. (2009 ); Kumar et al. (1999 ); Smith et al. (2003 , 2007 ).

Experimental

Crystal data

[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]·2H₂O
M_r = 714.20
Triclinic, $[P \overline 1]$
a = 6.8188 (3) Å
b = 7.7366 (4) Å
c = 11.3671 (5) Å
α = 92.658 (4)°
β = 96.313 (4)°
γ = 94.515 (4)°
V = 593.26 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 200 K
0.30 × 0.30 × 0.18 mm

Data collection

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.865, T_max = 0.980
7532 measured reflections
2560 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.07
2560 reflections
225 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O2Wⁱ	0.79 (3)	2.13 (3)	2.918 (2)	175 (2)
O1W—H12W⋯O4W	0.76 (3)	2.11 (3)	2.844 (2)	163 (3)
O2W—H21W⋯O2ⁱⁱ	0.75 (3)	2.08 (3)	2.7837 (18)	158 (3)
O2W—H22W⋯O51ⁱⁱⁱ	0.78 (3)	2.21 (3)	2.8962 (19)	146 (3)
O3W—H31W⋯O12^iv	0.84 (3)	1.94 (3)	2.6666 (19)	145 (2)
O3W—H32W⋯O4W^v	0.72 (3)	2.31 (3)	2.927 (2)	145 (3)
O4W—H41W⋯O11^vi	0.77 (3)	2.18 (3)	2.851 (2)	146 (2)
O4W—H42W⋯O32^vii	0.74 (3)	2.51 (3)	3.178 (2)	152 (3)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y, z+1; (iv) -x+1, -y, -z+1; (v) x-1, y, z; (vi) x+1, y, z; (vii) x, y-1, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810052694/rn2077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052694/rn2077Isup2.hkl

checkCIF report

Comment top

3,5-Dinitrosalicylic acid (DNSA) has proved to be a useful synthon in crystal engineering (Kumar et al., 1999) and the structures of a large number of its proton-transfer compounds with Lewis bases have been reported (Smith et al., 2003, 2007). However, the structures of the transition metal complexes of DNSA are not so common and in particular, with Co^II, there is only one example, a monomeric mixed-ligand complex with 2,2'-bipyridine (Zhong et al. , 2009), in which the DNSA ligand is dianionic and chelates through carboxyl and phenolate O donors. We obtained the title compound, having an empirical formula [Co(DNSA)(H₂O)₄], from the reaction of cobalt(II) acetate with 3,5-dinitrosalicylic acid in aqueous ethanol. This Co^II complex might have been expected to be typically octahedral and have a simple monomeric molecular formula involving the dianionic DNSA ligand in a bidentate chelate form, such as found in other similar hydrated cobalt(II) carboxylates, e.g. the acetate (Sobolev et al., 2003), the 4-nitrosalicylate (Tahir et al., 1997), the 4-formylbenzoate (Deng et al., 2008) or the 3,5-dinitrobenzoate (Tahir et al., 1996). However, the structure of (I) reported here showed the presence of a polymeric complex hydrate, {[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]. 2H₂O}_n (I), based on two slightly distorted octahedral but different Co^II centres.

In the structure (Fig. 1), the two separate six-coordinate CoO₆ complex centres lie on crystallographic inversion centres at (1, 1/2, 1/2) (Co1) and (1/2, 0, 1/2) (Co2). The coordination sphere about Co1 comprises four O donors (O_phenolate, O_carboxyl) from two trans-related bidentate chelate dianionic DNSA ligands [Co—O, 2.0249 (11), 2.0508 (11) Å] and two water molecules [Co—O1W, 2.1386 (14) Å]. The second carboxyl O of each DNSA ligand (O11, O11ⁱⁱ) [for symmetry code (ii), see Table 1], provide trans-related bridges to the second Co centre [Co—O, 2.1364 (11) Å], with four water molecules (O2W, O3W) completing the coordination [Co—O, 2.1122 (14), 2.0690 (14) Å]. This results in polymer chain substructures which extend along the b cell direction (Fig. 2). The coordinated water molecules as well as the water molecule of solvation (O4W) give both water–water and inter-chain O—H···O_{carboxyl, nitro} hydrogen-bonding associations (Table 1), giving an overall three-dimensional framework structure.

Related literature top

For the structures of similar hydrated complexes of Co^II, see: Deng et al. (2008); Sobolev et al. (2003); Tahir et al. (1996, 1997). For the structure of a mixed-ligand Co^II complex with 3,5-dinitrosalicylic acid and the structures of the acid and its salts, see: Zhong et al. (2009); Kumar et al. (1999); Smith et al. (2003, 2007).

Experimental top

The title compound was synthesized by heating together under reflux for 10 minutes, 1 mmol of cobalt(II) acetate and 2 mmol of 3,5-dinitrosalicylic acid in 50 ml of 50% ethanol–water. After concentration to ca 30 ml, partial room temperature evaporation of the hot-filtered solution gave large well formed red block crystals of (I).

Structure description top

For the structures of similar hydrated complexes of Co^II, see: Deng et al. (2008); Sobolev et al. (2003); Tahir et al. (1996, 1997). For the structure of a mixed-ligand Co^II complex with 3,5-dinitrosalicylic acid and the structures of the acid and its salts, see: Zhong et al. (2009); Kumar et al. (1999); Smith et al. (2003, 2007).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular configuration and atom-numbering scheme for (I), with non-H atoms drawn as 40% probability ellipsoids. Both Co1 and Co2 lie on crystallographic inversion centres. For symmetry codes: (i) and (ii), see Table 1.
	Fig. 2. The coordination polymer structure of (I) extending across the b cell direction showing intra-unit hydrogen-bonding associations as dashed lines.

catena-Poly[[[diaquacobalt(II)]-µ-(3,5-dinitro-2-oxidobenzoato)- κ³O¹,O²:O^1'-[tetraaquacobalt(II)]-µ-(3,5- dinitro-2-oxidobenzoato)-κ³O¹:O^1',O²] dihydrate] top

Crystal data top

[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]·2H₂O	Z = 1
M_r = 714.20	F(000) = 362
Triclinic, P1	D_x = 1.999 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8188 (3) Å	Cell parameters from 5528 reflections
b = 7.7366 (4) Å	θ = 3.3–28.7°
c = 11.3671 (5) Å	µ = 1.52 mm⁻¹
α = 92.658 (4)°	T = 200 K
β = 96.313 (4)°	Plate, red
γ = 94.515 (4)°	0.30 × 0.30 × 0.18 mm
V = 593.26 (5) Å³

Data collection top

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	2560 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 27.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −8→8
T_min = 0.865, T_max = 0.980	k = −9→9
7532 measured reflections	l = −14→14

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0341P)² + 0.1689P] where P = (F_o² + 2F_c²)/3
2560 reflections	(Δ/σ)_max < 0.001
225 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]·2H₂O	γ = 94.515 (4)°
M_r = 714.20	V = 593.26 (5) Å³
Triclinic, P1	Z = 1
a = 6.8188 (3) Å	Mo Kα radiation
b = 7.7366 (4) Å	µ = 1.52 mm⁻¹
c = 11.3671 (5) Å	T = 200 K
α = 92.658 (4)°	0.30 × 0.30 × 0.18 mm
β = 96.313 (4)°

Data collection top

Oxford Diffraction Gemini-S Ultra CCD-detector diffractometer	2560 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2236 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.980	R_int = 0.020
7532 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.32 e Å⁻³
2560 reflections	Δρ_min = −0.47 e Å⁻³
225 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	1.00000	0.50000	0.50000	0.0121 (1)
Co2	0.50000	0.00000	0.50000	0.0130 (1)
O1W	1.2442 (2)	0.45126 (19)	0.40373 (13)	0.0250 (4)
O2	0.85747 (18)	0.60915 (14)	0.36011 (10)	0.0176 (3)
O2W	0.4854 (2)	0.23727 (17)	0.59704 (13)	0.0210 (4)
O3W	0.2062 (2)	0.0052 (2)	0.43256 (14)	0.0276 (4)
O11	0.57060 (17)	0.13604 (14)	0.34878 (10)	0.0147 (3)
O12	0.85493 (18)	0.26657 (14)	0.43617 (10)	0.0179 (3)
O31	0.8352 (2)	0.89467 (15)	0.24132 (12)	0.0270 (4)
O32	0.9601 (2)	0.86453 (16)	0.07589 (12)	0.0299 (4)
O51	0.6887 (2)	0.35705 (18)	−0.17303 (11)	0.0335 (4)
O52	0.5849 (2)	0.12456 (17)	−0.09262 (12)	0.0325 (4)
N3	0.8741 (2)	0.80472 (17)	0.15690 (12)	0.0165 (4)
N5	0.6572 (2)	0.2756 (2)	−0.08527 (13)	0.0208 (4)
C1	0.7367 (2)	0.3493 (2)	0.24300 (14)	0.0125 (4)
C2	0.8069 (2)	0.5305 (2)	0.25828 (14)	0.0121 (4)
C3	0.8144 (2)	0.6185 (2)	0.15038 (14)	0.0133 (4)
C4	0.7721 (2)	0.5375 (2)	0.03877 (14)	0.0154 (5)
C5	0.7072 (2)	0.3626 (2)	0.03086 (14)	0.0153 (5)
C6	0.6860 (2)	0.2692 (2)	0.13166 (14)	0.0139 (4)
C11	0.7191 (2)	0.24360 (19)	0.35023 (14)	0.0122 (4)
O4W	1.2050 (3)	0.1926 (2)	0.21463 (14)	0.0317 (5)
H4	0.78670	0.59820	−0.02890	0.0180*
H6	0.63760	0.15300	0.12370	0.0170*
H11W	1.316 (4)	0.536 (4)	0.399 (2)	0.044 (8)*
H12W	1.230 (4)	0.399 (4)	0.345 (3)	0.050 (8)*
H21W	0.380 (5)	0.258 (4)	0.597 (3)	0.049 (9)*
H22W	0.516 (5)	0.231 (4)	0.665 (3)	0.077 (11)*
H31W	0.146 (4)	−0.086 (4)	0.451 (2)	0.050 (8)*
H32W	0.158 (5)	0.044 (4)	0.382 (3)	0.058 (9)*
H41W	1.310 (4)	0.161 (3)	0.224 (2)	0.045 (8)*
H42W	1.148 (5)	0.140 (4)	0.165 (3)	0.070 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0155 (2)	0.0109 (2)	0.0091 (2)	−0.0016 (1)	−0.0011 (1)	0.0015 (1)
Co2	0.0146 (2)	0.0127 (2)	0.0120 (2)	0.0006 (1)	0.0018 (1)	0.0030 (1)
O1W	0.0272 (7)	0.0233 (7)	0.0241 (7)	−0.0054 (6)	0.0098 (6)	−0.0056 (6)
O2	0.0282 (7)	0.0128 (5)	0.0106 (6)	0.0011 (5)	−0.0032 (5)	0.0007 (4)
O2W	0.0238 (7)	0.0198 (6)	0.0203 (7)	0.0034 (5)	0.0061 (6)	−0.0004 (5)
O3W	0.0180 (6)	0.0312 (8)	0.0339 (8)	−0.0007 (6)	−0.0009 (6)	0.0201 (7)
O11	0.0166 (6)	0.0136 (5)	0.0135 (6)	−0.0024 (4)	0.0011 (4)	0.0028 (4)
O12	0.0230 (6)	0.0147 (6)	0.0137 (6)	−0.0046 (5)	−0.0046 (5)	0.0042 (4)
O31	0.0455 (8)	0.0141 (6)	0.0228 (7)	0.0028 (6)	0.0109 (6)	−0.0007 (5)
O32	0.0448 (8)	0.0199 (6)	0.0272 (7)	−0.0054 (6)	0.0164 (6)	0.0084 (5)
O51	0.0532 (9)	0.0363 (8)	0.0093 (6)	−0.0044 (7)	0.0014 (6)	0.0025 (6)
O52	0.0432 (9)	0.0287 (7)	0.0214 (7)	−0.0152 (6)	0.0017 (6)	−0.0080 (6)
N3	0.0194 (7)	0.0139 (7)	0.0161 (7)	0.0002 (6)	0.0008 (6)	0.0049 (5)
N5	0.0220 (7)	0.0268 (8)	0.0123 (7)	−0.0005 (6)	−0.0002 (6)	−0.0025 (6)
C1	0.0122 (7)	0.0136 (7)	0.0118 (7)	0.0003 (6)	0.0019 (6)	0.0027 (6)
C2	0.0116 (7)	0.0132 (7)	0.0117 (7)	0.0016 (6)	0.0009 (6)	0.0023 (6)
C3	0.0149 (8)	0.0107 (7)	0.0144 (8)	0.0003 (6)	0.0017 (6)	0.0033 (6)
C4	0.0165 (8)	0.0185 (8)	0.0118 (8)	0.0021 (6)	0.0026 (6)	0.0047 (6)
C5	0.0160 (8)	0.0193 (8)	0.0098 (8)	0.0004 (6)	0.0000 (6)	−0.0019 (6)
C6	0.0135 (7)	0.0128 (7)	0.0149 (8)	−0.0008 (6)	0.0011 (6)	0.0010 (6)
C11	0.0163 (8)	0.0091 (7)	0.0116 (8)	0.0014 (6)	0.0030 (6)	0.0004 (6)
O4W	0.0266 (8)	0.0380 (9)	0.0288 (8)	0.0067 (7)	−0.0036 (6)	−0.0078 (7)

Geometric parameters (Å, º) top

Co1—O1W	2.1386 (14)	O1W—H12W	0.76 (3)
Co1—O2	2.0249 (11)	O1W—H11W	0.79 (3)
Co1—O12	2.0508 (11)	O2W—H21W	0.75 (3)
Co1—O1Wⁱ	2.1386 (14)	O2W—H22W	0.78 (3)
Co1—O2ⁱ	2.0249 (11)	O3W—H32W	0.72 (3)
Co1—O12ⁱ	2.0508 (11)	O3W—H31W	0.84 (3)
Co2—O2W	2.1122 (14)	O4W—H42W	0.74 (3)
Co2—O3W	2.0690 (14)	O4W—H41W	0.77 (3)
Co2—O11	2.1364 (11)	N3—C3	1.462 (2)
Co2—O2Wⁱⁱ	2.1122 (14)	N5—C5	1.447 (2)
Co2—O3Wⁱⁱ	2.0690 (14)	C1—C11	1.509 (2)
Co2—O11ⁱⁱ	2.1364 (11)	C1—C2	1.442 (2)
O2—C2	1.2817 (19)	C1—C6	1.379 (2)
O11—C11	1.2572 (18)	C2—C3	1.434 (2)
O12—C11	1.2660 (19)	C3—C4	1.379 (2)
O31—N3	1.2242 (19)	C4—C5	1.386 (2)
O32—N3	1.2335 (19)	C5—C6	1.397 (2)
O51—N5	1.234 (2)	C4—H4	0.9300
O52—N5	1.228 (2)	C6—H6	0.9300

O1W—Co1—O2	91.94 (5)	Co1—O1W—H12W	122 (2)
O1W—Co1—O12	90.72 (5)	H21W—O2W—H22W	101 (4)
O1W—Co1—O1Wⁱ	180.00	Co2—O2W—H21W	110 (2)
O1W—Co1—O2ⁱ	88.06 (5)	Co2—O2W—H22W	113 (2)
O1W—Co1—O12ⁱ	89.28 (5)	H31W—O3W—H32W	114 (3)
O2—Co1—O12	87.76 (4)	Co2—O3W—H31W	107.2 (19)
O1Wⁱ—Co1—O2	88.06 (5)	Co2—O3W—H32W	133 (3)
O2—Co1—O2ⁱ	180.00	H41W—O4W—H42W	108 (3)
O2—Co1—O12ⁱ	92.24 (4)	O31—N3—O32	122.86 (14)
O1Wⁱ—Co1—O12	89.28 (5)	O32—N3—C3	118.20 (13)
O2ⁱ—Co1—O12	92.24 (4)	O31—N3—C3	118.94 (13)
O12—Co1—O12ⁱ	180.00	O51—N5—C5	118.39 (14)
O1Wⁱ—Co1—O2ⁱ	91.94 (5)	O51—N5—O52	122.71 (15)
O1Wⁱ—Co1—O12ⁱ	90.72 (5)	O52—N5—C5	118.90 (14)
O2ⁱ—Co1—O12ⁱ	87.76 (4)	C2—C1—C11	119.84 (14)
O2W—Co2—O3W	89.80 (6)	C6—C1—C11	118.89 (14)
O2W—Co2—O11	90.74 (5)	C2—C1—C6	121.27 (14)
O2W—Co2—O2Wⁱⁱ	180.00	C1—C2—C3	114.96 (14)
O2W—Co2—O3Wⁱⁱ	90.20 (6)	O2—C2—C1	123.15 (14)
O2W—Co2—O11ⁱⁱ	89.26 (5)	O2—C2—C3	121.88 (14)
O3W—Co2—O11	86.59 (5)	C2—C3—C4	123.97 (14)
O2Wⁱⁱ—Co2—O3W	90.20 (6)	N3—C3—C2	119.02 (13)
O3W—Co2—O3Wⁱⁱ	180.00	N3—C3—C4	116.99 (14)
O3W—Co2—O11ⁱⁱ	93.41 (5)	C3—C4—C5	117.76 (14)
O2Wⁱⁱ—Co2—O11	89.26 (5)	N5—C5—C6	119.33 (14)
O3Wⁱⁱ—Co2—O11	93.41 (5)	C4—C5—C6	121.83 (15)
O11—Co2—O11ⁱⁱ	180.00	N5—C5—C4	118.84 (14)
O2Wⁱⁱ—Co2—O3Wⁱⁱ	89.80 (6)	C1—C6—C5	120.05 (14)
O2Wⁱⁱ—Co2—O11ⁱⁱ	90.74 (5)	O12—C11—C1	118.49 (13)
O3Wⁱⁱ—Co2—O11ⁱⁱ	86.59 (5)	O11—C11—O12	123.51 (14)
Co1—O2—C2	124.09 (10)	O11—C11—C1	118.00 (13)
Co2—O11—C11	123.33 (10)	C3—C4—H4	121.00
Co1—O12—C11	126.18 (10)	C5—C4—H4	121.00
H11W—O1W—H12W	110 (3)	C1—C6—H6	120.00
Co1—O1W—H11W	112.7 (19)	C5—C6—H6	120.00

O1W—Co1—O2—C2	59.16 (12)	O51—N5—C5—C6	−175.47 (14)
O12—Co1—O2—C2	−31.48 (12)	O52—N5—C5—C4	−174.28 (14)
O1Wⁱ—Co1—O2—C2	−120.84 (12)	O52—N5—C5—C6	4.8 (2)
O12ⁱ—Co1—O2—C2	148.52 (12)	C6—C1—C2—O2	−179.22 (14)
O1W—Co1—O12—C11	−99.19 (13)	C6—C1—C2—C3	1.4 (2)
O2—Co1—O12—C11	−7.27 (13)	C11—C1—C2—O2	0.3 (2)
O1Wⁱ—Co1—O12—C11	80.81 (13)	C11—C1—C2—C3	−179.01 (12)
O2ⁱ—Co1—O12—C11	172.73 (13)	C2—C1—C6—C5	1.7 (2)
O2W—Co2—O11—C11	58.56 (12)	C11—C1—C6—C5	−177.86 (13)
O3W—Co2—O11—C11	148.31 (12)	C2—C1—C11—O11	139.77 (14)
O2Wⁱⁱ—Co2—O11—C11	−121.44 (12)	C2—C1—C11—O12	−40.9 (2)
O3Wⁱⁱ—Co2—O11—C11	−31.69 (12)	C6—C1—C11—O11	−40.7 (2)
Co1—O2—C2—C1	37.23 (19)	C6—C1—C11—O12	138.71 (14)
Co1—O2—C2—C3	−143.47 (11)	O2—C2—C3—N3	−2.4 (2)
Co2—O11—C11—O12	9.1 (2)	O2—C2—C3—C4	176.25 (14)
Co2—O11—C11—C1	−171.53 (10)	C1—C2—C3—N3	176.94 (12)
Co1—O12—C11—O11	−141.37 (12)	C1—C2—C3—C4	−4.4 (2)
Co1—O12—C11—C1	39.30 (19)	N3—C3—C4—C5	−177.33 (13)
O31—N3—C3—C2	−31.2 (2)	C2—C3—C4—C5	4.0 (2)
O31—N3—C3—C4	150.07 (14)	C3—C4—C5—N5	178.51 (13)
O32—N3—C3—C2	149.57 (14)	C3—C4—C5—C6	−0.5 (2)
O32—N3—C3—C4	−29.2 (2)	N5—C5—C6—C1	178.72 (13)
O51—N5—C5—C4	5.5 (2)	C4—C5—C6—C1	−2.3 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2Wⁱ	0.79 (3)	2.13 (3)	2.918 (2)	175 (2)
O1W—H12W···O4W	0.76 (3)	2.11 (3)	2.844 (2)	163 (3)
O2W—H21W···O2ⁱⁱⁱ	0.75 (3)	2.08 (3)	2.7837 (18)	158 (3)
O2W—H22W···O51^iv	0.78 (3)	2.21 (3)	2.8962 (19)	146 (3)
O3W—H31W···O12ⁱⁱ	0.84 (3)	1.94 (3)	2.6666 (19)	145 (2)
O3W—H32W···O4W^v	0.72 (3)	2.31 (3)	2.927 (2)	145 (3)
O4W—H41W···O11^vi	0.77 (3)	2.18 (3)	2.851 (2)	146 (2)
O4W—H42W···O32^vii	0.74 (3)	2.51 (3)	3.178 (2)	152 (3)
C6—H6···O52^viii	0.93	2.52	3.420 (2)	164

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₇H₂N₂O₇)₂(H₂O)₆]·2H₂O
M_r	714.20
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	6.8188 (3), 7.7366 (4), 11.3671 (5)
α, β, γ (°)	92.658 (4), 96.313 (4), 94.515 (4)
V (Å³)	593.26 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.30 × 0.30 × 0.18

Data collection
Diffractometer	Oxford Diffraction Gemini-S Ultra CCD-detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.865, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	7532, 2560, 2236
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.07
No. of reflections	2560
No. of parameters	225
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.47

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2Wⁱ	0.79 (3)	2.13 (3)	2.918 (2)	175 (2)
O1W—H12W···O4W	0.76 (3)	2.11 (3)	2.844 (2)	163 (3)
O2W—H21W···O2ⁱⁱ	0.75 (3)	2.08 (3)	2.7837 (18)	158 (3)
O2W—H22W···O51ⁱⁱⁱ	0.78 (3)	2.21 (3)	2.8962 (19)	146 (3)
O3W—H31W···O12^iv	0.84 (3)	1.94 (3)	2.6666 (19)	145 (2)
O3W—H32W···O4W^v	0.72 (3)	2.31 (3)	2.927 (2)	145 (3)
O4W—H41W···O11^vi	0.77 (3)	2.18 (3)	2.851 (2)	146 (2)
O4W—H42W···O32^vii	0.74 (3)	2.51 (3)	3.178 (2)	152 (3)

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

Acknowledgements

The authors acknowledge financial support from the Australian Research Committee, the Faculty of Science and Technology and the University Library, Queensland University of Technology and Griffith University.

References

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