Diaqua­bis­(5-carb­oxy-2-propyl-1H-imidazole-4-carboxyl­ato-κ2N3,O4)cobalt(II) 3.5-hydrate

Li, S.-J.; Miao, D.-L.; Song, W.-D.; Tong, S.-W.; An, J.-B.

doi:10.1107/S1600536810052785

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Pages m106-m107

https://doi.org/10.1107/S1600536810052785

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Diaquabis(5-carboxy-2-propyl-1H-imidazole-4-carboxylato-κ²N³,O⁴)cobalt(II) 3.5-hydrate

Shi-Jie Li,^a Dong-Liang Miao,^a Wen-Dong Song,^b ^* Shao-Wei Tong ^a and Jing-Bo An ^a

^aCollege of Food Science and Technology, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China, and ^bCollege of Science, Guangdong Ocean University, Zhanjiang 524088, People's Republic of China
^*Correspondence e-mail: songwd60@163.com

(Received 13 December 2010; accepted 16 December 2010; online 24 December 2010)

In the title complex, [Co(C₈H₉N₂O₄)₂(H₂O)₂]·3.5H₂O, the Co^II cation is six-coordinated by two H₂pimda⁻ ligands (H₃pimda is 2-propyl-1H-imidazole-4,5-carboxylic acid) and two water molecules in a distorted octahedral environment. The crystal structures features a three-dimensional network stabilized by extensive O—H⋯O and N—H⋯O hydrogen bonds. The propyl groups of the ligands are disordered over two sets of sites with refined occupancies of 0.673 (8):0.327 (8) and 0.621 (17):0.379 (17). One of the water molecules is located on a site with half-occupancy.

Related literature

For our past work based on H₃pimda, see: Yan et al. (2010 ); Li, Dong et al. (2010 ); Song et al. (2010 ); He et al. (2010 ); Fan et al. (2010 ); Li, Miao et al. (2010 ); Li, Song et al. (2010 ).

Experimental

Crystal data

[Co(C₈H₉N₂O₄)₂(H₂O)₂]·3.5H₂O
M_r = 552.36
Triclinic, $[P \overline 1]$
a = 10.405 (1) Å
b = 10.6131 (11) Å
c = 11.2529 (13) Å
α = 82.371 (1)°
β = 83.743 (1)°
γ = 87.330 (2)°
V = 1223.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 298 K
0.18 × 0.09 × 0.07 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.873, T_max = 0.948
6529 measured reflections
4249 independent reflections
2522 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.101
S = 1.03
4249 reflections
376 parameters
18 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4W	0.86	1.89	2.745 (5)	171
N4—H4⋯O5Wⁱ	0.86	1.93	2.752 (5)	160
O3—H3⋯O2	0.82	1.68	2.500 (4)	179
O7—H7⋯O6	0.82	1.64	2.461 (4)	176
O1W—H1W⋯O8ⁱⁱ	0.85	1.87	2.715 (4)	178
O1W—H2W⋯O3Wⁱⁱⁱ	0.85	1.81	2.661 (4)	177
O2W—H4W⋯O7W^iv	0.85	1.94	2.791 (4)	174
O2W—H3W⋯O8^v	0.85	2.05	2.897 (4)	175
O3W—H5W⋯O2^iv	0.85	1.95	2.796 (5)	172
O3W—H6W⋯O5^vi	0.85	2.05	2.895 (4)	172
O3W—H6W⋯O6^vi	0.85	2.63	3.206 (4)	127
O4W—H8W⋯O6W	0.85	1.89	2.674 (7)	152
O5W—H9W⋯O3Wⁱⁱⁱ	0.85	2.08	2.867 (5)	153
O5W—H10W⋯O7W^iv	0.85	2.33	3.092 (5)	149
O6W—H12W⋯O6W^vii	0.85	1.68	2.162 (11)	113
O6W—H12W⋯O1^viii	0.85	2.14	2.730 (6)	126
O6W—H11W⋯O5W^iv	0.85	2.05	2.588 (7)	121
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+2, -z; (iii) x, y, z-1; (iv) -x+1, -y+1, -z+1; (v) x+1, y, z; (vi) -x+1, -y+2, -z+1; (vii) -x+1, -y+1, -z+2; (viii) x, y, z+1.

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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/S1600536810052785/bt5437sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052785/bt5437Isup2.hkl

checkCIF report

Comment top

The 2-propyl-1H-imidazole-4,5-carboxylate (H₃pimda) ligand has been used to obtain new metal-organic complexes by our research group, such as poly[diaquabis(5-carboxy-2-propyl-1H-imidazole-4-carboxylato-k³ N³, O⁴,O⁵)calcium(II)] (Song et al., 2010), [diaquabis(5-carboxy-2-propyl-1H-imidazole-4-carboxylato-k²N³,O⁴) manganese(II)]N,N-dimethylformamide (Yan et al., 2010), Diaquabis(4-carboxy-2-propyl-1H-imidazole-5-carboxylato- k²N³,O⁴)copper(II) N,N-dimethylformamide disolvate (He et al., 2010), Diaquabis(5-carboxy-2-propyl-1H-imidazole- 4-carboxylato-k²N³,O⁴)nickel(II) tetrahedrate (Fan et al., 2010), Diaquabis(5-carboxy-2-propyl-1H-imidazole-4-carboxylato- k²N³,O⁴)-manganese(II) 3.5-hydrate (Li, Miao et al., 2010), Diaquabis (5-carboxy-2-propyl-1H-imidazole-4-carboxylato-K²N³,O⁴)zinc(II) 3.5-hydrate (Li, Song et al. 2010) and Diaquabis(5-carboxy-2-propyl-1H- imidazole-4-carboxylato-k²N³,O⁴)cadmium(II) 3.5-hydrate (Li, Dong et al. 2010). In this paper, we report the synthesis and structure of a new Co(II) complex based the same ligand.

As illustrated in figure 1, the title complex molecule is isomorphous with Ni(II), Mn(II), Cd(II) and Zn(II) analogues (Fan et al., 2010; Li, Dong et al., 2010; Li, Song et al., 2010; Li, Miao et al., 2010), Similar structural description applies to the present isomorphous complex. The Co^II is six-coordinated in a distorted octahedral geometry. the H₃pimda acts as a bidentate mode to chelate the center Co(II). one carboxy group of the ligand was delocalized and the other was protonated, indicated by the difference of the bond lengths. The dihedral angle between the two imidazole rings is 84.2 (2) %A. In the crystal structure, the three-dimensional supramolecular framework is stabilized by extensive O—H···O and N—H···O hydrogen bonds.The propyl groups of H₃pimda are disordered over two sets of sites with refined occupiencies of 0.673 (8):0.327 (8) and 0.621 (17): 0.379 (17). One of the water molecules is half occupied.

Related literature top

For our past work based on H₃pimda, see: Yan et al. (2010); Li, Dong et al. (2010); Song et al. (2010); He et al. (2010); Fan et al. (2010); Li, Miao et al. (2010); Li, Song et al. (2010).

Experimental top

A mixture of Co(NO₃)₂ (0.5 mmol, 0.06 g) and 2-propyl-1H-imidazole-4,5-dicarboxylic acid(0.5 mmol, 0.99 g) in 15 ml of H₂O solution was sealed in an autoclave equipped with a Teflon liner (20 ml) and then heated at 433K for 4 days. Crystals of the title compound were obtained by slow evaporation of the solvent at room temperature.

Structure description top

For our past work based on H₃pimda, see: Yan et al. (2010); Li, Dong et al. (2010); Song et al. (2010); He et al. (2010); Fan et al. (2010); Li, Miao et al. (2010); Li, Song et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. The structure of the title compound, showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids.

Diaquabis(5-carboxy-2-propyl-1H-imidazole-4-carboxylato- κ²N³,O⁴)cobalt(II) 3.5-hydrate top

Crystal data top

[Co(C₈H₉N₂O₄)₂(H₂O)₂]·3.5H₂O	Z = 2
M_r = 552.36	F(000) = 576
Triclinic, P1	D_x = 1.499 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.405 (1) Å	Cell parameters from 1702 reflections
b = 10.6131 (11) Å	θ = 2.5–25.9°
c = 11.2529 (13) Å	µ = 0.77 mm⁻¹
α = 82.371 (1)°	T = 298 K
β = 83.743 (1)°	Cube, red
γ = 87.330 (2)°	0.18 × 0.09 × 0.07 mm
V = 1223.7 (2) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	4249 independent reflections
Radiation source: fine-focus sealed tube	2522 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→11
T_min = 0.873, T_max = 0.948	k = −12→11
6529 measured reflections	l = −13→12

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0305P)²] where P = (F_o² + 2F_c²)/3
4249 reflections	(Δ/σ)_max = 0.001
376 parameters	Δρ_max = 0.33 e Å⁻³
18 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Co(C₈H₉N₂O₄)₂(H₂O)₂]·3.5H₂O	γ = 87.330 (2)°
M_r = 552.36	V = 1223.7 (2) Å³
Triclinic, P1	Z = 2
a = 10.405 (1) Å	Mo Kα radiation
b = 10.6131 (11) Å	µ = 0.77 mm⁻¹
c = 11.2529 (13) Å	T = 298 K
α = 82.371 (1)°	0.18 × 0.09 × 0.07 mm
β = 83.743 (1)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	4249 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2522 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.948	R_int = 0.034
6529 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	18 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	Δρ_max = 0.33 e Å⁻³
4249 reflections	Δρ_min = −0.31 e Å⁻³
376 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	Occ. (<1)
Co1	0.34903 (6)	0.79029 (6)	0.19293 (6)	0.0468 (2)
N1	0.3265 (3)	0.7131 (3)	0.3764 (3)	0.0447 (9)
N2	0.3046 (3)	0.6416 (4)	0.5685 (3)	0.0548 (11)
H2	0.2910	0.6408	0.6453	0.066*
N3	0.1480 (3)	0.7861 (3)	0.1738 (3)	0.0419 (9)
N4	−0.0526 (3)	0.7781 (4)	0.1332 (3)	0.0504 (10)
H4	−0.1231	0.7478	0.1171	0.060*
O1	0.3958 (3)	0.5942 (3)	0.1833 (3)	0.0525 (8)
O2	0.4033 (3)	0.4039 (3)	0.2939 (3)	0.0629 (9)
O3	0.3743 (3)	0.3174 (3)	0.5125 (3)	0.0670 (10)
H3	0.3830	0.3458	0.4408	0.100*
O7W	0.3316 (3)	0.3924 (3)	0.6857 (3)	0.0687 (11)
O5	0.2850 (3)	0.9854 (3)	0.2050 (3)	0.0533 (9)
O6	0.1184 (3)	1.1214 (3)	0.1846 (3)	0.0633 (10)
O7	−0.1073 (3)	1.1143 (3)	0.1400 (3)	0.0606 (9)
H7	−0.0327	1.1136	0.1571	0.091*
O8	−0.2424 (3)	0.9744 (3)	0.1005 (3)	0.0585 (9)
O1W	0.3850 (3)	0.8336 (3)	0.0107 (3)	0.0766 (12)
H1W	0.3418	0.8937	−0.0259	0.115*
H2W	0.4514	0.8160	−0.0359	0.115*
O2W	0.5401 (3)	0.8259 (3)	0.2132 (3)	0.0758 (12)
H4W	0.5741	0.7575	0.2459	0.114*
H3W	0.6004	0.8732	0.1786	0.114*
O3W	0.5950 (3)	0.7723 (3)	0.8703 (3)	0.0881 (12)
H5W	0.5992	0.7238	0.8155	0.132*
H6W	0.6319	0.8410	0.8414	0.132*
O4W	0.2706 (4)	0.6669 (4)	0.8096 (3)	0.1170 (16)
H7W	0.2264	0.7287	0.8359	0.176*
H8W	0.2895	0.6117	0.8675	0.176*
O5W	0.7616 (4)	0.6532 (4)	0.0420 (4)	0.1161 (15)
H9W	0.7321	0.7065	−0.0124	0.174*
H10W	0.7077	0.6476	0.1048	0.174*
O6W	0.4094 (5)	0.5155 (6)	0.9607 (5)	0.0591 (18)	0.50
H12W	0.4516	0.5578	1.0016	0.089*	0.50
H11W	0.3534	0.4759	1.0109	0.089*	0.50
C1	0.3847 (4)	0.5225 (5)	0.2824 (4)	0.0453 (12)
C2	0.3472 (4)	0.5846 (4)	0.3905 (4)	0.0388 (11)
C3	0.3330 (4)	0.5379 (4)	0.5099 (4)	0.0424 (11)
C4	0.3452 (4)	0.4105 (5)	0.5768 (5)	0.0503 (13)
C5	0.3013 (5)	0.7456 (5)	0.4860 (5)	0.0585 (14)
C6	0.2961 (17)	0.880 (3)	0.514 (2)	0.073 (6)	0.673 (8)
H6A	0.3453	0.9326	0.4496	0.088*	0.673 (8)
H6B	0.3353	0.8828	0.5880	0.088*	0.673 (8)
C7	0.1592 (11)	0.9306 (11)	0.5282 (9)	0.090 (3)	0.673 (8)
H7A	0.1126	0.8861	0.5997	0.108*	0.673 (8)
H7B	0.1159	0.9180	0.4589	0.108*	0.673 (8)
C8	0.1612 (10)	1.0747 (8)	0.5395 (9)	0.128 (5)	0.673 (8)
H8A	0.2085	1.0867	0.6055	0.192*	0.673 (8)
H8B	0.0742	1.1075	0.5537	0.192*	0.673 (8)
H8C	0.2023	1.1188	0.4662	0.192*	0.673 (8)
C9	0.1692 (5)	1.0100 (5)	0.1877 (4)	0.0476 (12)
C10	0.0912 (4)	0.9051 (4)	0.1699 (4)	0.0406 (11)
C11	−0.0345 (4)	0.9016 (4)	0.1443 (4)	0.0410 (11)
C12	−0.1370 (5)	1.0008 (5)	0.1268 (4)	0.0485 (13)
C13	0.0583 (4)	0.7107 (5)	0.1515 (4)	0.0478 (12)
C14	0.064 (3)	0.569 (3)	0.1696 (16)	0.054 (5)	0.621 (17)
H14A	0.1520	0.5390	0.1479	0.064*	0.621 (17)
H14B	0.0087	0.5375	0.1170	0.064*	0.621 (17)
C15	0.022 (2)	0.517 (2)	0.2987 (18)	0.068 (6)	0.621 (17)
H15A	−0.0693	0.5370	0.3172	0.081*	0.621 (17)
H15B	0.0697	0.5567	0.3521	0.081*	0.621 (17)
C16	0.0448 (10)	0.3732 (14)	0.3208 (11)	0.099 (5)	0.621 (17)
H16A	0.0004	0.3336	0.2659	0.148*	0.621 (17)
H16B	0.0127	0.3423	0.4021	0.148*	0.621 (17)
H16C	0.1359	0.3532	0.3083	0.148*	0.621 (17)
C6'	0.237 (3)	0.867 (5)	0.522 (4)	0.067 (11)	0.327 (8)
H6'1	0.1850	0.8512	0.5990	0.080*	0.327 (8)
H6'2	0.1827	0.9061	0.4619	0.080*	0.327 (8)
C7'	0.350 (2)	0.954 (2)	0.532 (2)	0.083 (7)	0.327 (8)
H7'1	0.4079	0.9571	0.4579	0.099*	0.327 (8)
H7'2	0.3148	1.0395	0.5379	0.099*	0.327 (8)
C8'	0.426 (2)	0.9112 (19)	0.637 (2)	0.118 (9)	0.327 (8)
H8'1	0.3673	0.8984	0.7099	0.177*	0.327 (8)
H8'2	0.4856	0.9752	0.6444	0.177*	0.327 (8)
H8'3	0.4721	0.8329	0.6252	0.177*	0.327 (8)
C14'	0.083 (5)	0.576 (5)	0.122 (3)	0.055 (8)	0.379 (17)
H14C	0.1738	0.5519	0.1256	0.066*	0.379 (17)
H14D	0.0623	0.5708	0.0407	0.066*	0.379 (17)
C15'	−0.0004 (18)	0.4828 (17)	0.212 (2)	0.068 (6)	0.379 (17)
H15C	−0.0910	0.5058	0.2064	0.082*	0.379 (17)
H15D	0.0148	0.3974	0.1907	0.082*	0.379 (17)
C16'	0.029 (4)	0.484 (4)	0.342 (3)	0.083 (12)	0.379 (17)
H16D	0.0090	0.4031	0.3881	0.125*	0.379 (17)
H16E	−0.0218	0.5500	0.3768	0.125*	0.379 (17)
H16F	0.1194	0.4990	0.3429	0.125*	0.379 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0410 (4)	0.0498 (4)	0.0465 (4)	0.0032 (3)	−0.0074 (3)	0.0067 (3)
N1	0.047 (2)	0.045 (2)	0.042 (2)	0.0015 (18)	−0.0092 (18)	−0.001 (2)
N2	0.063 (3)	0.062 (3)	0.037 (2)	0.011 (2)	−0.0069 (19)	−0.002 (2)
N3	0.039 (2)	0.038 (2)	0.047 (2)	0.0006 (18)	−0.0086 (18)	0.0025 (18)
N4	0.039 (2)	0.054 (3)	0.057 (3)	−0.002 (2)	−0.0136 (19)	0.005 (2)
O1	0.058 (2)	0.059 (2)	0.0373 (19)	0.0130 (16)	−0.0062 (15)	0.0021 (16)
O2	0.090 (3)	0.046 (2)	0.053 (2)	0.0097 (19)	−0.0150 (18)	−0.0059 (17)
O3	0.087 (3)	0.052 (2)	0.059 (2)	0.002 (2)	−0.0148 (19)	0.0103 (19)
O7W	0.066 (2)	0.086 (3)	0.045 (2)	0.0101 (19)	−0.0042 (18)	0.0201 (19)
O5	0.0476 (19)	0.049 (2)	0.064 (2)	−0.0059 (16)	−0.0147 (16)	−0.0017 (16)
O6	0.060 (2)	0.044 (2)	0.087 (3)	0.0017 (17)	−0.0118 (18)	−0.0077 (19)
O7	0.049 (2)	0.056 (2)	0.076 (3)	0.0130 (18)	−0.0102 (17)	−0.0079 (19)
O8	0.0412 (19)	0.063 (2)	0.067 (2)	0.0035 (17)	−0.0112 (17)	0.0136 (18)
O1W	0.061 (2)	0.099 (3)	0.054 (2)	0.0337 (19)	0.0069 (17)	0.026 (2)
O2W	0.044 (2)	0.081 (3)	0.092 (3)	−0.0128 (18)	−0.0180 (18)	0.040 (2)
O3W	0.080 (3)	0.082 (3)	0.104 (3)	−0.030 (2)	0.029 (2)	−0.042 (2)
O4W	0.156 (4)	0.133 (4)	0.067 (3)	0.057 (3)	−0.025 (3)	−0.041 (3)
O5W	0.105 (3)	0.131 (4)	0.129 (4)	0.012 (3)	−0.060 (3)	−0.041 (3)
O6W	0.066 (4)	0.061 (4)	0.052 (4)	−0.008 (3)	−0.009 (3)	−0.012 (3)
C1	0.041 (3)	0.047 (3)	0.048 (3)	0.003 (2)	−0.011 (2)	−0.002 (3)
C2	0.034 (2)	0.042 (3)	0.039 (3)	0.001 (2)	−0.007 (2)	0.001 (2)
C3	0.033 (2)	0.049 (3)	0.044 (3)	0.002 (2)	−0.007 (2)	0.000 (2)
C4	0.037 (3)	0.064 (4)	0.047 (3)	0.001 (2)	−0.010 (2)	0.007 (3)
C5	0.073 (4)	0.051 (4)	0.051 (3)	0.011 (3)	−0.010 (3)	−0.007 (3)
C6	0.089 (16)	0.069 (11)	0.062 (8)	0.002 (15)	−0.006 (11)	−0.008 (7)
C7	0.105 (9)	0.076 (8)	0.087 (8)	0.014 (7)	−0.009 (6)	−0.012 (6)
C8	0.176 (11)	0.061 (7)	0.140 (10)	0.024 (7)	0.016 (8)	−0.020 (6)
C9	0.049 (3)	0.046 (3)	0.046 (3)	0.000 (3)	−0.004 (2)	0.002 (2)
C10	0.038 (3)	0.042 (3)	0.041 (3)	−0.002 (2)	−0.005 (2)	0.002 (2)
C11	0.043 (3)	0.036 (3)	0.042 (3)	−0.001 (2)	−0.003 (2)	0.002 (2)
C12	0.045 (3)	0.052 (4)	0.043 (3)	0.001 (3)	−0.001 (2)	0.007 (3)
C13	0.046 (3)	0.043 (3)	0.053 (3)	0.001 (2)	−0.011 (2)	0.001 (2)
C14	0.051 (10)	0.048 (10)	0.063 (14)	−0.004 (7)	−0.016 (11)	−0.001 (13)
C15	0.066 (8)	0.050 (10)	0.082 (17)	0.004 (6)	−0.017 (11)	0.016 (11)
C16	0.091 (8)	0.055 (9)	0.143 (11)	0.000 (6)	−0.010 (7)	0.008 (8)
C6'	0.07 (3)	0.07 (2)	0.060 (16)	0.02 (3)	−0.01 (2)	−0.007 (14)
C7'	0.102 (19)	0.072 (17)	0.073 (15)	0.001 (14)	−0.011 (12)	−0.009 (13)
C8'	0.128 (19)	0.101 (17)	0.13 (2)	−0.005 (14)	0.002 (16)	−0.031 (15)
C14'	0.053 (13)	0.047 (12)	0.06 (2)	−0.003 (10)	−0.010 (18)	0.01 (2)
C15'	0.071 (11)	0.051 (12)	0.079 (17)	−0.001 (9)	−0.009 (10)	0.001 (10)
C16'	0.074 (13)	0.09 (3)	0.08 (2)	−0.009 (17)	−0.030 (14)	0.032 (15)

Geometric parameters (Å, º) top

Co1—O1W	2.038 (3)	C5—C6'	1.51 (5)
Co1—O2W	2.083 (3)	C6—C7	1.500 (19)
Co1—N1	2.110 (4)	C6—H6A	0.9700
Co1—N3	2.129 (3)	C6—H6B	0.9700
Co1—O1	2.130 (3)	C7—C8	1.552 (13)
Co1—O5	2.163 (3)	C7—H7A	0.9700
N1—C5	1.319 (5)	C7—H7B	0.9700
N1—C2	1.362 (5)	C8—H8A	0.9600
N2—C5	1.347 (5)	C8—H8B	0.9600
N2—C3	1.361 (5)	C8—H8C	0.9600
N2—H2	0.8600	C9—C10	1.455 (6)
N3—C13	1.323 (5)	C10—C11	1.373 (5)
N3—C10	1.366 (5)	C11—C12	1.473 (6)
N4—C13	1.349 (5)	C13—C14	1.49 (3)
N4—C11	1.357 (5)	C13—C14'	1.52 (6)
N4—H4	0.8600	C14—C15	1.51 (2)
O1—C1	1.261 (5)	C14—H14A	0.9700
O2—C1	1.256 (5)	C14—H14B	0.9700
O3—C4	1.306 (6)	C15—C16	1.52 (2)
O3—H3	0.8200	C15—H15A	0.9700
O7W—C4	1.209 (5)	C15—H15B	0.9700
O5—C9	1.252 (5)	C16—H16A	0.9600
O6—C9	1.271 (5)	C16—H16B	0.9600
O7—C12	1.289 (5)	C16—H16C	0.9600
O7—H7	0.8200	C6'—C7'	1.54 (5)
O8—C12	1.221 (5)	C6'—H6'1	0.9700
O1W—H1W	0.8500	C6'—H6'2	0.9700
O1W—H2W	0.8500	C7'—C8'	1.51 (3)
O2W—H4W	0.8500	C7'—H7'1	0.9700
O2W—H3W	0.8500	C7'—H7'2	0.9700
O3W—H5W	0.8500	C8'—H8'1	0.9600
O3W—H6W	0.8500	C8'—H8'2	0.9600
O4W—H7W	0.8499	C8'—H8'3	0.9600
O4W—H8W	0.8499	C14'—C15'	1.54 (4)
O5W—H9W	0.8499	C14'—H14C	0.9700
O5W—H10W	0.8503	C14'—H14D	0.9700
O6W—H12W	0.8501	C15'—C16'	1.53 (5)
O6W—H11W	0.8503	C15'—H15C	0.9700
C1—C2	1.467 (6)	C15'—H15D	0.9700
C2—C3	1.364 (5)	C16'—H16D	0.9600
C3—C4	1.465 (6)	C16'—H16E	0.9600
C5—C6	1.50 (3)	C16'—H16F	0.9600

O1W—Co1—O2W	90.34 (12)	C8—C7—H7B	110.0
O1W—Co1—N1	169.71 (14)	H7A—C7—H7B	108.4
O2W—Co1—N1	88.21 (12)	O5—C9—O6	122.9 (5)
O1W—Co1—N3	89.35 (12)	O5—C9—C10	117.7 (4)
O2W—Co1—N3	170.64 (14)	O6—C9—C10	119.5 (4)
N1—Co1—N3	93.72 (13)	N3—C10—C11	110.0 (4)
O1W—Co1—O1	91.72 (13)	N3—C10—C9	118.4 (4)
O2W—Co1—O1	91.42 (12)	C11—C10—C9	131.6 (4)
N1—Co1—O1	78.13 (13)	N4—C11—C10	105.1 (4)
N3—Co1—O1	97.94 (13)	N4—C11—C12	122.1 (4)
O1W—Co1—O5	89.43 (12)	C10—C11—C12	132.7 (4)
O2W—Co1—O5	93.14 (12)	O8—C12—O7	123.5 (5)
N1—Co1—O5	100.82 (13)	O8—C12—C11	120.6 (5)
N3—Co1—O5	77.50 (13)	O7—C12—C11	116.0 (4)
O1—Co1—O5	175.29 (11)	N3—C13—N4	110.3 (4)
C5—N1—C2	106.3 (4)	N3—C13—C14	126.2 (12)
C5—N1—Co1	142.2 (3)	N4—C13—C14	122.2 (12)
C2—N1—Co1	111.5 (3)	N3—C13—C14'	125.0 (19)
C5—N2—C3	108.6 (4)	N4—C13—C14'	123.3 (19)
C5—N2—H2	125.7	C14—C13—C14'	21.0 (15)
C3—N2—H2	125.7	C13—C14—C15	112 (2)
C13—N3—C10	106.0 (4)	C13—C14—H14A	109.3
C13—N3—Co1	142.2 (3)	C15—C14—H14A	109.3
C10—N3—Co1	111.3 (3)	C13—C14—H14B	109.3
C13—N4—C11	108.7 (4)	C15—C14—H14B	109.3
C13—N4—H4	125.7	H14A—C14—H14B	108.0
C11—N4—H4	125.7	C14—C15—C16	111 (2)
C1—O1—Co1	115.7 (3)	C14—C15—H15A	109.3
C4—O3—H3	109.5	C16—C15—H15A	109.3
C9—O5—Co1	114.9 (3)	C14—C15—H15B	109.3
C12—O7—H7	109.5	C16—C15—H15B	109.3
Co1—O1W—H1W	119.6	H15A—C15—H15B	108.0
Co1—O1W—H2W	129.5	C5—C6'—C7'	105 (2)
H1W—O1W—H2W	108.4	C5—C6'—H6'1	110.7
Co1—O2W—H4W	107.6	C7'—C6'—H6'1	110.7
Co1—O2W—H3W	138.9	C5—C6'—H6'2	110.7
H4W—O2W—H3W	108.3	C7'—C6'—H6'2	110.7
H5W—O3W—H6W	108.6	H6'1—C6'—H6'2	108.8
H7W—O4W—H8W	110.7	C8'—C7'—C6'	114 (3)
H9W—O5W—H10W	109.1	C8'—C7'—H7'1	108.8
H12W—O6W—H11W	106.1	C6'—C7'—H7'1	108.8
O2—C1—O1	124.7 (5)	C8'—C7'—H7'2	108.8
O2—C1—C2	119.0 (4)	C6'—C7'—H7'2	108.8
O1—C1—C2	116.4 (4)	H7'1—C7'—H7'2	107.7
N1—C2—C3	110.0 (4)	C7'—C8'—H8'1	109.5
N1—C2—C1	118.2 (4)	C7'—C8'—H8'2	109.5
C3—C2—C1	131.7 (4)	H8'1—C8'—H8'2	109.5
N2—C3—C2	105.1 (4)	C7'—C8'—H8'3	109.5
N2—C3—C4	121.0 (4)	H8'1—C8'—H8'3	109.5
C2—C3—C4	133.9 (5)	H8'2—C8'—H8'3	109.5
O7W—C4—O3	121.6 (5)	C13—C14'—C15'	110 (2)
O7W—C4—C3	122.0 (5)	C13—C14'—H14C	109.6
O3—C4—C3	116.4 (4)	C15'—C14'—H14C	109.6
N1—C5—N2	110.1 (4)	C13—C14'—H14D	109.6
N1—C5—C6	124.1 (10)	C15'—C14'—H14D	109.6
N2—C5—C6	124.8 (10)	H14C—C14'—H14D	108.1
N1—C5—C6'	127.9 (19)	C16'—C15'—C14'	112 (2)
N2—C5—C6'	119.5 (18)	C16'—C15'—H15C	109.1
C6—C5—C6'	24.0 (15)	C14'—C15'—H15C	109.1
C5—C6—C7	111.0 (14)	C16'—C15'—H15D	109.1
C5—C6—H6A	109.4	C14'—C15'—H15D	109.1
C7—C6—H6A	109.4	H15C—C15'—H15D	107.9
C5—C6—H6B	109.4	C15'—C16'—H16D	109.5
C7—C6—H6B	109.4	C15'—C16'—H16E	109.5
H6A—C6—H6B	108.0	H16D—C16'—H16E	109.5
C6—C7—C8	108.5 (12)	C15'—C16'—H16F	109.5
C6—C7—H7A	110.0	H16D—C16'—H16F	109.5
C8—C7—H7A	110.0	H16E—C16'—H16F	109.5
C6—C7—H7B	110.0

O1W—Co1—N1—C5	165.8 (7)	C2—N1—C5—C6	168.5 (10)
O2W—Co1—N1—C5	83.8 (5)	Co1—N1—C5—C6	−9.7 (12)
N3—Co1—N1—C5	−87.1 (5)	C2—N1—C5—C6'	−162.0 (19)
O1—Co1—N1—C5	175.6 (5)	Co1—N1—C5—C6'	20 (2)
O5—Co1—N1—C5	−9.1 (5)	C3—N2—C5—N1	0.0 (5)
O1W—Co1—N1—C2	−12.3 (9)	C3—N2—C5—C6	−168.8 (9)
O2W—Co1—N1—C2	−94.4 (3)	C3—N2—C5—C6'	163.4 (19)
N3—Co1—N1—C2	94.8 (3)	N1—C5—C6—C7	98.6 (14)
O1—Co1—N1—C2	−2.6 (3)	N2—C5—C6—C7	−94.1 (16)
O5—Co1—N1—C2	172.7 (3)	C6'—C5—C6—C7	−9 (5)
O1W—Co1—N3—C13	85.1 (5)	C5—C6—C7—C8	−172.3 (11)
O2W—Co1—N3—C13	173.2 (7)	Co1—O5—C9—O6	−175.8 (3)
N1—Co1—N3—C13	−85.1 (5)	Co1—O5—C9—C10	3.9 (5)
O1—Co1—N3—C13	−6.6 (5)	C13—N3—C10—C11	−0.3 (5)
O5—Co1—N3—C13	174.6 (5)	Co1—N3—C10—C11	173.4 (3)
O1W—Co1—N3—C10	−84.9 (3)	C13—N3—C10—C9	−178.1 (4)
O2W—Co1—N3—C10	3.3 (10)	Co1—N3—C10—C9	−4.5 (5)
N1—Co1—N3—C10	104.9 (3)	O5—C9—C10—N3	0.4 (6)
O1—Co1—N3—C10	−176.5 (3)	O6—C9—C10—N3	−179.9 (4)
O5—Co1—N3—C10	4.7 (3)	O5—C9—C10—C11	−176.8 (4)
O1W—Co1—O1—C1	−178.8 (3)	O6—C9—C10—C11	2.8 (7)
O2W—Co1—O1—C1	90.8 (3)	C13—N4—C11—C10	0.0 (5)
N1—Co1—O1—C1	3.0 (3)	C13—N4—C11—C12	178.7 (4)
N3—Co1—O1—C1	−89.2 (3)	N3—C10—C11—N4	0.2 (5)
O5—Co1—O1—C1	−74.6 (15)	C9—C10—C11—N4	177.6 (4)
O1W—Co1—O5—C9	84.7 (3)	N3—C10—C11—C12	−178.3 (4)
O2W—Co1—O5—C9	175.0 (3)	C9—C10—C11—C12	−0.9 (8)
N1—Co1—O5—C9	−96.2 (3)	N4—C11—C12—O8	−0.6 (6)
N3—Co1—O5—C9	−4.8 (3)	C10—C11—C12—O8	177.6 (4)
O1—Co1—O5—C9	−19.6 (16)	N4—C11—C12—O7	180.0 (4)
Co1—O1—C1—O2	177.2 (3)	C10—C11—C12—O7	−1.8 (7)
Co1—O1—C1—C2	−2.7 (4)	C10—N3—C13—N4	0.2 (5)
C5—N1—C2—C3	0.7 (5)	Co1—N3—C13—N4	−170.0 (3)
Co1—N1—C2—C3	179.5 (3)	C10—N3—C13—C14	−167.0 (10)
C5—N1—C2—C1	−176.7 (4)	Co1—N3—C13—C14	22.7 (12)
Co1—N1—C2—C1	2.1 (4)	C10—N3—C13—C14'	167.2 (15)
O2—C1—C2—N1	−179.6 (4)	Co1—N3—C13—C14'	−3.1 (16)
O1—C1—C2—N1	0.4 (5)	C11—N4—C13—N3	−0.1 (5)
O2—C1—C2—C3	3.8 (7)	C11—N4—C13—C14	167.7 (9)
O1—C1—C2—C3	−176.3 (4)	C11—N4—C13—C14'	−167.3 (15)
C5—N2—C3—C2	0.4 (5)	N3—C13—C14—C15	83 (2)
C5—N2—C3—C4	179.0 (4)	N4—C13—C14—C15	−83 (2)
N1—C2—C3—N2	−0.7 (4)	C14'—C13—C14—C15	178 (10)
C1—C2—C3—N2	176.2 (4)	C13—C14—C15—C16	−172.5 (16)
N1—C2—C3—C4	−179.0 (4)	N1—C5—C6'—C7'	−95 (3)
C1—C2—C3—C4	−2.1 (8)	N2—C5—C6'—C7'	105 (3)
N2—C3—C4—O7W	−0.6 (6)	C6—C5—C6'—C7'	−5 (4)
C2—C3—C4—O7W	177.6 (4)	C5—C6'—C7'—C8'	−70 (3)
N2—C3—C4—O3	−179.1 (4)	N3—C13—C14'—C15'	123 (2)
C2—C3—C4—O3	−1.0 (7)	N4—C13—C14'—C15'	−71 (3)
C2—N1—C5—N2	−0.4 (5)	C14—C13—C14'—C15'	23 (6)
Co1—N1—C5—N2	−178.6 (3)	C13—C14'—C15'—C16'	−60 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4W	0.86	1.89	2.745 (5)	171
N4—H4···O5Wⁱ	0.86	1.93	2.752 (5)	160
O3—H3···O2	0.82	1.68	2.500 (4)	179
O7—H7···O6	0.82	1.64	2.461 (4)	176
O1W—H1W···O8ⁱⁱ	0.85	1.87	2.715 (4)	178
O1W—H2W···O3Wⁱⁱⁱ	0.85	1.81	2.661 (4)	177
O2W—H4W···O7W^iv	0.85	1.94	2.791 (4)	174
O2W—H3W···O8^v	0.85	2.05	2.897 (4)	175
O3W—H5W···O2^iv	0.85	1.95	2.796 (5)	172
O3W—H6W···O5^vi	0.85	2.05	2.895 (4)	172
O3W—H6W···O6^vi	0.85	2.63	3.206 (4)	127
O4W—H8W···O6W	0.85	1.89	2.674 (7)	152
O5W—H9W···O3Wⁱⁱⁱ	0.85	2.08	2.867 (5)	153
O5W—H10W···O7W^iv	0.85	2.33	3.092 (5)	149
O6W—H12W···O6W^vii	0.85	1.68	2.162 (11)	113
O6W—H12W···O1^viii	0.85	2.14	2.730 (6)	126
O6W—H11W···O5W^iv	0.85	2.05	2.588 (7)	121

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₉N₂O₄)₂(H₂O)₂]·3.5H₂O
M_r	552.36
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.405 (1), 10.6131 (11), 11.2529 (13)
α, β, γ (°)	82.371 (1), 83.743 (1), 87.330 (2)
V (Å³)	1223.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.18 × 0.09 × 0.07

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.873, 0.948
No. of measured, independent and observed [I > 2σ(I)] reflections	6529, 4249, 2522
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.101, 1.03
No. of reflections	4249
No. of parameters	376
No. of restraints	18
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.31

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4W	0.86	1.89	2.745 (5)	170.5
N4—H4···O5Wⁱ	0.86	1.93	2.752 (5)	160.0
O3—H3···O2	0.82	1.68	2.500 (4)	179.1
O7—H7···O6	0.82	1.64	2.461 (4)	175.9
O1W—H1W···O8ⁱⁱ	0.85	1.87	2.715 (4)	177.7
O1W—H2W···O3Wⁱⁱⁱ	0.85	1.81	2.661 (4)	177.2
O2W—H4W···O7W^iv	0.85	1.94	2.791 (4)	174.3
O2W—H3W···O8^v	0.85	2.05	2.897 (4)	174.8
O3W—H5W···O2^iv	0.85	1.95	2.796 (5)	172.2
O3W—H6W···O5^vi	0.85	2.05	2.895 (4)	172.0
O3W—H6W···O6^vi	0.85	2.63	3.206 (4)	126.6
O4W—H8W···O6W	0.85	1.89	2.674 (7)	152.4
O5W—H9W···O3Wⁱⁱⁱ	0.85	2.08	2.867 (5)	153.0
O5W—H10W···O7W^iv	0.85	2.33	3.092 (5)	148.9
O6W—H12W···O6W^vii	0.85	1.68	2.162 (11)	113.4
O6W—H12W···O1^viii	0.85	2.14	2.730 (6)	125.9
O6W—H11W···O5W^iv	0.85	2.05	2.588 (7)	120.9

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

Acknowledgements

The work was supported by the Nonprofit Industry Foundation of the National Ocean Administration of China (grant No. 2000905021), the Guangdong Oceanic Fisheries Technology Promotion Project [grant No. A2009003–018(c)], the Guangdong Chinese Academy of Science comprehensive strategic cooperation project (grant No. 2009B091300121), the Guangdong Province key project in the field of social development [grant No. A2009011–007(c)], the Science and Technology Department of Guangdong Province Project (grant No. 00087061110314018) and the Guangdong Natural Science Fundation (No. 9252408801000002).

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