[μ-6,9-Bis(carboxylatomethyl)-3,12-bis(car­boxymethyl)-3,6,9,12-tetraaza­tetradecanedioato]bis­[aqua­cobalt(II)] tetra­hydrate

Qian, Q.; Wu, J.; Qian, J.

doi:10.1107/S1600536813000196

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page m97

doi:10.1107/S1600536813000196

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[μ-6,9-Bis(carboxylatomethyl)-3,12-bis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioato]bis[aquacobalt(II)] tetrahydrate

Qi-feng Qian,^a Jin-hui Wu ^a and Jin-liang Qian ^b ^*

^aXuchang Senior School, Xuchang 461000, People's Republic of China, and ^bZhile Second Middle School, Xuchang 461232, People's Republic of China
^*Correspondence e-mail: jinliang_qian@126.com

(Received 2 January 2013; accepted 3 January 2013; online 12 January 2013)

The binuclear title complex, [Co₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O, lies about a centre of inversion, the Co^II atom being coordinated in a distorted octahedral arrangement defined by one water molecule and N₂O₃ donors derived from one end of a 6,9-bis(carboxylatomethyl)-3,12-bis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioate (H₂TTHA⁴⁻) tetraanion. In the crystal, numerous O—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For related coordination complexes of species derived from triethylenetetraminehexaacetic acid, see: Ouyang et al. (2007 ); Xu et al. (2008 ). For a related structure, see: Song et al. (2003 ).

Experimental

Crystal data

[Co₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O
M_r = 716.38
Triclinic, $[P \overline 1]$
a = 7.0972 (15) Å
b = 8.7025 (19) Å
c = 11.968 (3) Å
α = 104.238 (4)°
β = 100.986 (3)°
γ = 100.425 (4)°
V = 682.9 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 292 K
0.10 × 0.08 × 0.05 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.881, T_max = 0.938
8012 measured reflections
3099 independent reflections
2182 reflections with I > 2σ(I)
R_int = 0.097

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.117
S = 0.94
3099 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O1ⁱ	0.82	1.68	2.483 (5)	168
O5—H5⋯O5ⁱⁱ	0.82	1.67	2.481 (5)	170
O7—H7A⋯O8	0.82	1.84	2.616 (4)	157
O7—H7B⋯O4ⁱⁱⁱ	0.82	1.95	2.732 (4)	159
O8—H8D⋯O3ⁱⁱⁱ	0.82	2.37	2.745 (5)	109
O8—H8C⋯O9	0.82	2.15	2.719 (5)	127
O9—H9A⋯O2^iv	0.82	2.48	3.067 (4)	130
O9—H9A⋯O6^iv	0.82	2.45	3.217 (5)	157
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) -x+1, -y+2, -z+2; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000196/tk5188sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000196/tk5188Isup2.hkl

checkCIF report

Comment top

H₆TTHA (triethylenetetraminehexaacetic acid) is a multicarboxyl ligand with ten potential coordinating sites and plays an important role in the self-assembly of various functional materials (Xu et al., 2008; Ouyang et al., 2007). In an effort to explore new enzyme-mimics involved with cobalt(II) and poly-carboxyl-group ligands, we have synthesized and crystallized the title complex, [Co₂(H₂TTHA)(H₂O)₂].4H₂O, (I), in water under ambient conditions via the reaction of Co(OH)₂ and H₆TTHA. Herein, we report its crystal structure.

The asymmetric unit of (I) comprises half a neutral [Co₂(H₂TTHA)(H₂O)₂] binuclear unit and two solvent water molecules (Fig. 1). The binuclear [Co₂(H₂TTHA)(H₂O)₂] is centrosymmetric with the midpoint of the ethylene C—C bond on an inversion centre. Each Co^II ion has a distorted octahedral geometry and is bonded to two N atoms and three carboxylate-O atoms from half of the H₂TTHA^4- ligand, as well as a water molecule. The Co1—N1 and Co1—N2 bond lengths are 2.216 (3) and 2.134 (3) Å, respectively, and the Co—O bond lengths range from 2.031 (3) to 2.120 (3) Å which are similar to those in its analogous structure (Song et al., 2003)

Analysis indicates (Spek, 2009) that in the crystal packing there are extensive O—H···O hydrogen-bond interactions (Table 1) between the O atoms of the six carboxylate/carboxylic acid groups of the H₂TTHA^4- ligand and/or the water molecules, leading to a three-dimensional array (Fig. 2).

Related literature top

For related coordination complexes of species derived from triethylenetetraminehexaacetic acid, see: Ouyang et al. (2007); Xu et al. (2008). For a related structure, see: Song et al. (2003).

Experimental top

A mixture of Co(OH)₂ (0.18 g, 2 mmol) and H₆TTHA (0.20 g, 0.5 mmol) was stirred in H₂O (30 ml) solution for 30 min at room temperature. The resulting solution was filtered and the clear solution was left standing for two weeks. Purple crystals of (I) suitable for X-ray diffraction were obtained at the bottom of the vessel.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structures of the components of (I) with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related by the symmetry operation: 2-x, 1-y, 1-z.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a three-dimensional network by hydrogen bonds (dashed lines). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

[µ-6,9-Bis(carboxylatomethyl)-3,12-bis(carboxymethyl)-3,6,9,12- tetraazatetradecanedioato]bis[aquacobalt(II)] tetrahydrate top

Crystal data top

[Co₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O	Z = 1
M_r = 716.38	F(000) = 372
Triclinic, P1	D_x = 1.742 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0972 (15) Å	Cell parameters from 1506 reflections
b = 8.7025 (19) Å	θ = 2.6–23.8°
c = 11.968 (3) Å	µ = 1.31 mm⁻¹
α = 104.238 (4)°	T = 292 K
β = 100.986 (3)°	Plate, violet
γ = 100.425 (4)°	0.10 × 0.08 × 0.05 mm
V = 682.9 (3) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3099 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2182 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.097
0.3° wide ω exposures scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −9→9
T_min = 0.881, T_max = 0.938	k = −11→11
8012 measured reflections	l = −15→15

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.047P)²] where P = (F_o² + 2F_c²)/3
3099 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Co₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O	γ = 100.425 (4)°
M_r = 716.38	V = 682.9 (3) Å³
Triclinic, P1	Z = 1
a = 7.0972 (15) Å	Mo Kα radiation
b = 8.7025 (19) Å	µ = 1.31 mm⁻¹
c = 11.968 (3) Å	T = 292 K
α = 104.238 (4)°	0.10 × 0.08 × 0.05 mm
β = 100.986 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	3099 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	2182 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.938	R_int = 0.097
8012 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 0.94	Δρ_max = 0.61 e Å⁻³
3099 reflections	Δρ_min = −0.53 e Å⁻³
190 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.72982 (7)	0.71114 (6)	0.70687 (4)	0.02486 (17)
N1	0.9888 (4)	0.6394 (4)	0.6502 (2)	0.0260 (7)
N2	0.9015 (4)	0.9540 (4)	0.7434 (2)	0.0255 (7)
O1	1.0763 (4)	0.5057 (4)	0.9155 (2)	0.0457 (8)
H1	1.0240	0.5153	0.9715	0.069*	0.50
O2	0.8739 (4)	0.6544 (3)	0.8584 (2)	0.0306 (6)
O3	0.6757 (5)	0.9168 (4)	0.4387 (2)	0.0548 (9)
O4	0.6154 (4)	0.7492 (3)	0.5486 (2)	0.0308 (6)
O5	0.6500 (4)	1.0653 (3)	0.9745 (2)	0.0401 (7)
H5	0.5449	1.0184	0.9830	0.060*	0.50
O6	0.5890 (4)	0.8431 (3)	0.8222 (2)	0.0335 (6)
O7	0.5376 (4)	0.4898 (3)	0.6630 (2)	0.0416 (7)
H7A	0.5779	0.4274	0.6978	0.062*
H7B	0.5143	0.4317	0.5943	0.062*
C1	0.9172 (5)	0.5213 (5)	0.5288 (3)	0.0322 (9)
H1A	0.8342	0.5670	0.4781	0.039*
H1B	0.8362	0.4217	0.5334	0.039*
C2	1.0911 (6)	0.5704 (5)	0.7386 (3)	0.0395 (10)
H2A	1.2292	0.6286	0.7657	0.047*
H2B	1.0851	0.4570	0.7004	0.047*
C3	1.0033 (6)	0.5803 (5)	0.8454 (3)	0.0302 (9)
C4	1.1120 (6)	0.7947 (5)	0.6468 (3)	0.0313 (9)
H4A	1.0630	0.8154	0.5719	0.038*
H4B	1.2472	0.7852	0.6518	0.038*
C5	1.1076 (6)	0.9363 (5)	0.7487 (3)	0.0351 (10)
H5A	1.1622	0.9181	0.8237	0.042*
H5B	1.1887	1.0362	0.7446	0.042*
C6	0.8262 (6)	1.0170 (5)	0.6438 (3)	0.0362 (10)
H6A	0.9377	1.0745	0.6224	0.043*
H6B	0.7507	1.0950	0.6706	0.043*
C7	0.6972 (6)	0.8852 (5)	0.5344 (3)	0.0330 (9)
C8	0.8807 (6)	1.0525 (5)	0.8581 (3)	0.0310 (9)
H8A	0.8829	1.1632	0.8554	0.037*
H8B	0.9912	1.0565	0.9215	0.037*
C9	0.6896 (6)	0.9799 (5)	0.8838 (3)	0.0284 (8)
O8	0.5622 (5)	0.2722 (4)	0.7785 (3)	0.0729 (11)
H8C	0.5855	0.3176	0.8501	0.109*
H8D	0.4441	0.2302	0.7658	0.109*
O9	0.3797 (6)	0.3141 (5)	0.9602 (4)	0.1021 (15)
H9A	0.3722	0.2969	1.0237	0.153*
H9B	0.2845	0.3520	0.9418	0.153*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0255 (3)	0.0292 (3)	0.0196 (3)	0.0075 (2)	0.0068 (2)	0.0049 (2)
N1	0.0287 (17)	0.0341 (18)	0.0182 (15)	0.0108 (14)	0.0098 (13)	0.0076 (13)
N2	0.0281 (17)	0.0298 (17)	0.0190 (15)	0.0065 (14)	0.0094 (13)	0.0057 (13)
O1	0.055 (2)	0.068 (2)	0.0344 (16)	0.0356 (17)	0.0201 (15)	0.0306 (16)
O2	0.0338 (15)	0.0446 (17)	0.0198 (13)	0.0194 (13)	0.0112 (12)	0.0102 (12)
O3	0.077 (2)	0.055 (2)	0.0289 (16)	0.0015 (17)	0.0066 (16)	0.0207 (15)
O4	0.0358 (16)	0.0321 (15)	0.0222 (13)	0.0067 (12)	0.0031 (12)	0.0077 (12)
O5	0.0412 (17)	0.0452 (18)	0.0286 (15)	0.0088 (14)	0.0185 (13)	−0.0050 (13)
O6	0.0301 (15)	0.0372 (16)	0.0306 (15)	0.0082 (13)	0.0126 (12)	0.0010 (13)
O7	0.0489 (18)	0.0369 (17)	0.0311 (16)	0.0011 (14)	0.0062 (14)	0.0051 (13)
C1	0.033 (2)	0.034 (2)	0.030 (2)	0.0091 (18)	0.0158 (18)	0.0037 (18)
C2	0.045 (3)	0.057 (3)	0.031 (2)	0.029 (2)	0.018 (2)	0.021 (2)
C3	0.031 (2)	0.037 (2)	0.0220 (19)	0.0077 (18)	0.0068 (17)	0.0078 (17)
C4	0.027 (2)	0.035 (2)	0.031 (2)	0.0057 (17)	0.0105 (17)	0.0063 (18)
C5	0.027 (2)	0.039 (2)	0.033 (2)	−0.0019 (18)	0.0085 (18)	0.0038 (19)
C6	0.051 (3)	0.032 (2)	0.026 (2)	0.0106 (19)	0.0110 (19)	0.0079 (18)
C7	0.036 (2)	0.041 (2)	0.025 (2)	0.0128 (19)	0.0092 (18)	0.0110 (18)
C8	0.036 (2)	0.032 (2)	0.0201 (19)	0.0051 (18)	0.0072 (17)	0.0009 (16)
C9	0.030 (2)	0.033 (2)	0.0223 (19)	0.0117 (18)	0.0046 (17)	0.0078 (17)
O8	0.073 (3)	0.077 (3)	0.064 (2)	0.005 (2)	0.010 (2)	0.027 (2)
O9	0.121 (4)	0.106 (4)	0.115 (4)	0.058 (3)	0.069 (3)	0.043 (3)

Geometric parameters (Å, º) top

Co1—O7	2.031 (3)	C1—C1ⁱ	1.527 (7)
Co1—O4	2.043 (2)	C1—H1A	0.9700
Co1—O6	2.094 (2)	C1—H1B	0.9700
Co1—O2	2.120 (2)	C2—C3	1.516 (5)
Co1—N2	2.134 (3)	C2—H2A	0.9700
Co1—N1	2.216 (3)	C2—H2B	0.9700
N1—C2	1.477 (4)	C4—C5	1.515 (5)
N1—C4	1.486 (4)	C4—H4A	0.9700
N1—C1	1.490 (4)	C4—H4B	0.9700
N2—C8	1.478 (4)	C5—H5A	0.9700
N2—C6	1.480 (4)	C5—H5B	0.9700
N2—C5	1.490 (5)	C6—C7	1.514 (5)
O1—C3	1.272 (4)	C6—H6A	0.9700
O1—H1	0.8200	C6—H6B	0.9700
O2—C3	1.226 (4)	C8—C9	1.509 (5)
O3—C7	1.230 (4)	C8—H8A	0.9700
O4—C7	1.286 (4)	C8—H8B	0.9700
O5—C9	1.267 (4)	O8—H8D	0.8200
O5—H5	0.8200	O8—H8C	0.8200
O6—C9	1.237 (4)	O8—H8D	0.8200
O7—H7A	0.8201	O9—H9A	0.8200
O7—H7B	0.8200	O9—H9B	0.8200

O7—Co1—O4	92.28 (11)	N1—C2—H2A	108.9
O7—Co1—O6	97.80 (11)	C3—C2—H2A	108.9
O4—Co1—O6	102.38 (10)	N1—C2—H2B	108.9
O7—Co1—O2	87.25 (11)	C3—C2—H2B	108.9
O4—Co1—O2	172.02 (10)	H2A—C2—H2B	107.7
O6—Co1—O2	85.56 (10)	O2—C3—O1	125.6 (3)
O7—Co1—N2	172.89 (11)	O2—C3—C2	120.8 (3)
O4—Co1—N2	82.40 (11)	O1—C3—C2	113.6 (3)
O6—Co1—N2	78.85 (11)	N1—C4—C5	111.0 (3)
O2—Co1—N2	98.68 (11)	N1—C4—H4A	109.4
O7—Co1—N1	100.97 (11)	C5—C4—H4A	109.4
O4—Co1—N1	93.72 (10)	N1—C4—H4B	109.4
O6—Co1—N1	154.68 (11)	C5—C4—H4B	109.4
O2—Co1—N1	78.57 (10)	H4A—C4—H4B	108.0
N2—Co1—N1	84.15 (11)	N2—C5—C4	110.7 (3)
C2—N1—C4	112.2 (3)	N2—C5—H5A	109.5
C2—N1—C1	112.8 (3)	C4—C5—H5A	109.5
C4—N1—C1	110.5 (3)	N2—C5—H5B	109.5
C2—N1—Co1	108.9 (2)	C4—C5—H5B	109.5
C4—N1—Co1	103.8 (2)	H5A—C5—H5B	108.1
C1—N1—Co1	108.1 (2)	N2—C6—C7	113.7 (3)
C8—N2—C6	111.9 (3)	N2—C6—H6A	108.8
C8—N2—C5	112.3 (3)	C7—C6—H6A	108.8
C6—N2—C5	111.7 (3)	N2—C6—H6B	108.8
C8—N2—Co1	108.2 (2)	C7—C6—H6B	108.8
C6—N2—Co1	107.5 (2)	H6A—C6—H6B	107.7
C5—N2—Co1	104.7 (2)	O3—C7—O4	124.8 (4)
C3—O1—H1	109.5	O3—C7—C6	117.7 (4)
C3—O2—Co1	116.4 (2)	O4—C7—C6	117.5 (3)
C7—O4—Co1	115.5 (2)	N2—C8—C9	110.6 (3)
C9—O5—H5	109.5	N2—C8—H8A	109.5
C9—O6—Co1	114.6 (2)	C9—C8—H8A	109.5
Co1—O7—H7A	113.6	N2—C8—H8B	109.5
Co1—O7—H7B	117.3	C9—C8—H8B	109.5
H7A—O7—H7B	99.1	H8A—C8—H8B	108.1
N1—C1—C1ⁱ	113.9 (4)	O6—C9—O5	124.5 (4)
N1—C1—H1A	108.8	O6—C9—C8	120.5 (3)
C1ⁱ—C1—H1A	108.8	O5—C9—C8	114.9 (3)
N1—C1—H1B	108.8	H8D—O8—H8C	99.3
C1ⁱ—C1—H1B	108.8	H8C—O8—H8D	99.3
H1A—C1—H1B	107.7	H9A—O9—H9B	104.7
N1—C2—C3	113.2 (3)

O7—Co1—N1—C2	−76.1 (3)	O4—Co1—O6—C9	−99.2 (3)
O4—Co1—N1—C2	−169.1 (2)	O2—Co1—O6—C9	80.1 (3)
O6—Co1—N1—C2	61.1 (4)	N2—Co1—O6—C9	−19.6 (3)
O2—Co1—N1—C2	8.8 (2)	N1—Co1—O6—C9	29.1 (4)
N2—Co1—N1—C2	108.9 (3)	C2—N1—C1—C1ⁱ	−67.4 (5)
O7—Co1—N1—C4	164.2 (2)	C4—N1—C1—C1ⁱ	59.1 (5)
O4—Co1—N1—C4	71.1 (2)	Co1—N1—C1—C1ⁱ	172.2 (4)
O6—Co1—N1—C4	−58.6 (3)	C4—N1—C2—C3	109.8 (4)
O2—Co1—N1—C4	−110.9 (2)	C1—N1—C2—C3	−124.6 (3)
N2—Co1—N1—C4	−10.8 (2)	Co1—N1—C2—C3	−4.6 (4)
O7—Co1—N1—C1	46.8 (2)	Co1—O2—C3—O1	−164.1 (3)
O4—Co1—N1—C1	−46.3 (2)	Co1—O2—C3—C2	15.6 (5)
O6—Co1—N1—C1	−176.0 (2)	N1—C2—C3—O2	−6.9 (5)
O2—Co1—N1—C1	131.7 (2)	N1—C2—C3—O1	172.8 (3)
N2—Co1—N1—C1	−128.2 (2)	C2—N1—C4—C5	−79.2 (4)
O4—Co1—N2—C8	127.7 (2)	C1—N1—C4—C5	154.0 (3)
O6—Co1—N2—C8	23.4 (2)	Co1—N1—C4—C5	38.2 (3)
O2—Co1—N2—C8	−60.3 (2)	C8—N2—C5—C4	161.8 (3)
N1—Co1—N2—C8	−137.7 (2)	C6—N2—C5—C4	−71.5 (4)
O4—Co1—N2—C6	6.6 (2)	Co1—N2—C5—C4	44.6 (3)
O6—Co1—N2—C6	−97.7 (2)	N1—C4—C5—N2	−59.1 (4)
O2—Co1—N2—C6	178.6 (2)	C8—N2—C6—C7	−134.5 (3)
N1—Co1—N2—C6	101.2 (2)	C5—N2—C6—C7	98.6 (4)
O4—Co1—N2—C5	−112.3 (2)	Co1—N2—C6—C7	−15.7 (4)
O6—Co1—N2—C5	143.4 (2)	Co1—O4—C7—O3	165.6 (3)
O2—Co1—N2—C5	59.7 (2)	Co1—O4—C7—C6	−15.6 (4)
N1—Co1—N2—C5	−17.8 (2)	N2—C6—C7—O3	−159.4 (4)
O7—Co1—O2—C3	88.1 (3)	N2—C6—C7—O4	21.6 (5)
O6—Co1—O2—C3	−173.8 (3)	C6—N2—C8—C9	93.7 (4)
N2—Co1—O2—C3	−95.8 (3)	C5—N2—C8—C9	−139.8 (3)
N1—Co1—O2—C3	−13.7 (3)	Co1—N2—C8—C9	−24.7 (3)
O7—Co1—O4—C7	−179.9 (3)	Co1—O6—C9—O5	−165.2 (3)
O6—Co1—O4—C7	81.6 (3)	Co1—O6—C9—C8	10.9 (4)
N2—Co1—O4—C7	4.8 (3)	N2—C8—C9—O6	10.2 (5)
N1—Co1—O4—C7	−78.8 (3)	N2—C8—C9—O5	−173.3 (3)
O7—Co1—O6—C9	166.7 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱⁱ	0.82	1.68	2.483 (5)	168
O5—H5···O5ⁱⁱⁱ	0.82	1.67	2.481 (5)	170
O7—H7A···O8	0.82	1.84	2.616 (4)	157
O7—H7B···O4^iv	0.82	1.95	2.732 (4)	159
O8—H8D···O3^iv	0.82	2.37	2.745 (5)	109
O8—H8C···O9	0.82	2.15	2.719 (5)	127
O9—H9A···O2^v	0.82	2.48	3.067 (4)	130
O9—H9A···O6^v	0.82	2.45	3.217 (5)	157

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₁₈H₂₆N₄O₁₂)(H₂O)₂]·4H₂O
M_r	716.38
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	7.0972 (15), 8.7025 (19), 11.968 (3)
α, β, γ (°)	104.238 (4), 100.986 (3), 100.425 (4)
V (Å³)	682.9 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.31
Crystal size (mm)	0.10 × 0.08 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.881, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	8012, 3099, 2182
R_int	0.097
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.117, 0.94
No. of reflections	3099
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.53

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1ⁱ	0.82	1.68	2.483 (5)	168
O5—H5···O5ⁱⁱ	0.82	1.67	2.481 (5)	170
O7—H7A···O8	0.82	1.84	2.616 (4)	157
O7—H7B···O4ⁱⁱⁱ	0.82	1.95	2.732 (4)	159
O8—H8D···O3ⁱⁱⁱ	0.82	2.37	2.745 (5)	109
O8—H8C···O9	0.82	2.15	2.719 (5)	127
O9—H9A···O2^iv	0.82	2.48	3.067 (4)	130
O9—H9A···O6^iv	0.82	2.45	3.217 (5)	157

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

Acknowledgements

We thank Henan University for providing the structural data for the title complex.

References

Bruker (2001). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ouyang, Y., Zhang, W., Xu, N., Xu, G. F., Liao, D. Z., Yoshimura, K., Yan, S. P. & Cheng, P. (2007). Inorg. Chem. 46, 8454–8456. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, L.-J., Zhang, J., Tang, Z.-R., Wang, W.-G. & Ju, Z.-F. (2003). Acta Cryst. E59, m867–m869. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, G. F., Liu, B., Song, H. B., Wang, Q. L., Yan, S. P. & Liao, D. Z. (2008). Inorg. Chem. Commun. 11, 714–716. Web of Science CSD CrossRef CAS Google Scholar

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Volume 69| Part 2| February 2013| Page m97

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

[μ-6,9-Bis(carboxylato­methyl)-3,12-bis­(car­boxymethyl)-3,6,9,12-tetra­aza­tetra­decanedioato]bis­­[aqua­cobalt(II)] tetra­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

[μ-6,9-Bis(carboxylatomethyl)-3,12-bis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioato]bis[aquacobalt(II)] tetrahydrate