[μ-6,9-Bis(carboxylatomethyl)-3,12-bis(car-boxymethyl)-3,6,9,12-tetraaza-tetradecanedioato]bis-[aqua-cobalt(II)] tetra-hydrate.

The binuclear title complex, [Co(2)(C(18)H(26)N(4)O(12))(H(2)O)(2)]·4H(2)O, lies about a centre of inversion, the Co(II) atom being coordinated in a distorted octa-hedral arrangement defined by one water mol-ecule and N(2)O(3) donors derived from one end of a 6,9-bis(carboxylatomethyl)-3,12-bis(car-boxy-methyl)-3,6,9,12-tetraaza-tetradecanedioate (H(2)TTHA(4-)) tetra-anion. In the crystal, numerous O-H⋯O hydrogen bonds link the mol-ecules 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 = 716.38

Triclinic,

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[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.117

S = 0.94

3099 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.53 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000196/tk5188sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co2(C18H26N4O12)(H2O)2]·4H2O	Z = 1
Mr = 716.38	F(000) = 372
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.047P)2] where P = (Fo2 + 2Fc2)/3
3099 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.61 e Å−3
0 restraints	Δρmin = −0.53 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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···O4iv	0.82	1.95	2.732 (4)	159
O8—H8D···O3iv	0.82	2.37	2.745 (5)	109
O8—H8C···O9	0.82	2.15	2.719 (5)	127
O9—H9A···O2v	0.82	2.48	3.067 (4)	130
O9—H9A···O6v	0.82	2.45	3.217 (5)	157

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⋯O2iv	0.82	2.48	3.067 (4)	130
O9—H9A⋯O6iv	0.82	2.45	3.217 (5)	157

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .