Tris(ethyl­enediamine)cobalt(II) sulfate

Abstract

The structure of the title compound, [Co^II(C₂H₈N₂)₃]SO₄, the cobalt example of [M(C₂H₈N₂)₃]SO₄, is reported. The Co and S atoms are located at the 2d and 2c Wyckoff sites (point symmetry 32), respectively. The Co atom is coordinated by six N atoms of three chelating ethyl­enediamine mol­ecules generated from half of the ethyl­enediamine mol­ecule in the asymmetric unit. The O atoms of the sulfate anion are disordered mostly over two crystallographic sites. The third disorder site of O (site symmetry 3) has a site occupancy approaching zero. The H atoms of the ethyl­enediamine mol­ecules inter­act with the sulfate anions via inter­molecular N—H⋯O hydrogen-bonding inter­actions.

Related literature

For isostructural [M(C₂H₈N₂)₃]SO₄ complexes, see: Haque et al. (1970 ▶); Cullen & Lingafelter (1970 ▶); Daniels et al. (1995 ▶); Lu (2009 ▶) for the nickel, copper, vanadium and manganese analogues, respectively.

Experimental

Crystal data

• [Co(C₂H₈N₂)₃]SO₄

• M _r = 335.30

• Trigonal,

• a = 8.9920 (2) Å

• c = 9.5927 (3) Å

• V = 671.71 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.45 mm⁻¹

• T = 298 K

• 0.48 × 0.22 × 0.20 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.543, T _max = 0.760

• 3638 measured reflections

• 688 independent reflections

• 589 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 0.069

• S = 1.06

• 688 reflections

• 47 parameters

• 16 restraints

• H-atom parameters constrained

• Δρ_max = 0.25 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and WinGX (Farrugia, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and WinGX (Farrugia, 1999 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.90	2.13	2.889 (12)	142
N1—H1A⋯O1i	0.90	2.15	3.049 (7)	176
N1—H1A⋯O2ii	0.90	2.22	3.054 (8)	155
N1—H1A⋯O2iii	0.90	2.32	3.104 (11)	145
N1—H1B⋯O2iv	0.90	1.98	2.843 (6)	161
N1—H1B⋯O1	0.90	2.48	3.353 (14)	165
N1—H1B⋯O1v	0.90	2.52	3.256 (10)	139

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

supplementary crystallographic information

Comment

The title complex, [Co^II(C₂H₈N₂)₃]SO₄ (Fig. 1), is isostructural to the earlier reported [Ni^II(C₂H₈N₂)₃]SO₄ (Haque et al.,, 1970), [V^II(C₂H₈N₂)₃]SO₄ (Daniels et al., 1995), [Mn^II(C₂H₈N₂)₃]SO₄ (Lu, 2009) and [Cu^II(C₂H₈N₂)₃]SO₄ (Cullen & Lingafelter, 1970) complexes, constituting the [M^II(C₂H₂N₂)₃]SO₄ series. The [M^II(C₂H₂N₂)₃]SO₄ structures crystallize in the same trigonal space group of P31c with quite similar cell parameters. Likewise, the metal and sulfur atoms are positioned in the same crystallographic sites; M^II on the 2d and S on the 2c Wyckoff sites (each with point symmetry 32). The disorder about the six-fold rotation axis found in the sulfate anion is intriguingly common in each structure, although the number of unique O atoms varies from two to four. In the structure of [Co^II(C₂H₈N₂)₃]SO₄, the O atoms were refined as being disordered over three crystallographic sites, although the site occupancy of O3 located on the 4f Wyckoff site approaches zero. The bond length associated with this O3 atom (S1—O3; 1.382 (16) Å) is notably shorter than the other S—O bonds (1.431 (5)–1.445 (5) Å). The disordered sulfate anions are linked to the [Co^II(C₂H₈N₂)₃]²⁺ cations by hydrogen bonding interactions of N—H···O type to form a hydrogen-bonding supramolecular network. The hydrogen bonding geometries are consistent with those of the previously reported [M^II(C₂H₂N₂)₃]SO₄ complexes.

Experimental

Orange blocks of the title complex were synthesized and grown from the sovolthermal reaction of Co(NO₃)₂.6H₂O (1.34 mmol), NH₂SO₃H (1.34 mmol), NH₂C₂H₄NH₂ (3.89 mmol) in ethylene glycol (160 mmol), conducted at 453 K for 72 h.

Refinement

The O atoms were positioned from a difference Fourier map, and refined with restraints using commands SUMP, SADI and SIMU in SHELXL (Sheldrick, 2008). Although there was an indication for further splitting of the O2 atom, after the final cycles of refinement, such action did not give a better result. All H-atoms were treated as riding groups on the bonded atoms, with C—H = 0.97 Å and N—H 0.90 Å, and with U_iso(H) = 1.2U_equiv(C, N).

Figures

Fig. 1.

View of the title complex showing atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. [Symmetry codes: (i) -y+1, x-y, z; (ii) -x+y+1, -x+1, z; (iii) -y+1, -x+1, -z+1/2; (iv) -x+y+1, y, -z+1/2; (v) x, x-y, -z+1/2; (vi) -y+1, x-y+1, z, (vii) -x+y, -x+1, z; (viii) -x+y, y, -z+1/2; (ix) x, x-y+1, -z+1/2]. Hydrogen atoms are omitted.

Fig. 2.

View of the hydrogen bonding interactions (dotted lines) between the disordered sulfate O atoms and the amino-H atoms of the [CoII(C2H8N2)]2+ cations. [Symmetry codes: (ii) -x+y+1, -x+1, z; (iii) -y+1, -x+1, -z+1/2; (viii) -x+y, y, -z+1/2; (ix) x, x-y+1, -z+1/2; (xiii) y, x, z+1/2; (xiv) -y+x, -y+1, -z+1/2; (xv) -x+1, -x+y+1, z+1/2].

Crystal data

[Co(C2H8N2)3]SO4	Dx = 1.658 Mg m−3
Mr = 335.30	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 589 reflections
Hall symbol: -P 3 2c	θ = 2.6–31.0°
a = 8.9920 (2) Å	µ = 1.45 mm−1
c = 9.5927 (3) Å	T = 298 K
V = 671.71 (3) Å3	Block, orange
Z = 2	0.48 × 0.22 × 0.20 mm
F(000) = 354

Data collection

Bruker SMART CCD area-detector diffractometer	688 independent reflections
Radiation source: fine-focus sealed tube	589 reflections with I > 2σ(I)
graphite	Rint = 0.027
? scan	θmax = 31.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→10
Tmin = 0.543, Tmax = 0.760	k = −11→11
3638 measured reflections	l = −11→13

Refinement

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0354P)2 + 0.1217P] where P = (Fo2 + 2Fc2)/3
688 reflections	(Δ/σ)max < 0.001
47 parameters	Δρmax = 0.25 e Å−3
16 restraints	Δρmin = −0.29 e Å−3

Special details

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.6667	0.3333	0.2500	0.02175 (16)
N1	0.68784 (18)	0.54599 (18)	0.12760 (13)	0.0332 (3)
H1A	0.6936	0.5265	0.0363	0.040*
H1B	0.5954	0.5579	0.1418	0.040*
S1	0.3333	0.6667	0.2500	0.0240 (2)
C1	0.8446 (2)	0.7024 (2)	0.17145 (19)	0.0388 (4)
H1C	0.8405	0.8031	0.1409	0.047*
H1D	0.9444	0.7056	0.1297	0.047*
O1	0.3029 (19)	0.5088 (9)	0.1852 (8)	0.096 (3)	0.319 (8)
O2	0.339 (2)	0.7851 (9)	0.1475 (6)	0.096 (4)	0.316 (9)
O3	0.3333	0.6667	0.1059 (16)	0.086 (8)	0.094 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0226 (2)	0.0226 (2)	0.0201 (2)	0.01129 (10)	0.000	0.000
N1	0.0410 (8)	0.0330 (7)	0.0283 (7)	0.0204 (6)	−0.0033 (5)	0.0031 (5)
S1	0.0243 (3)	0.0243 (3)	0.0233 (4)	0.01215 (14)	0.000	0.000
C1	0.0445 (10)	0.0267 (8)	0.0413 (9)	0.0147 (7)	0.0058 (7)	0.0076 (6)
O1	0.185 (9)	0.051 (4)	0.063 (4)	0.069 (5)	−0.012 (5)	−0.016 (3)
O2	0.194 (12)	0.055 (4)	0.044 (3)	0.067 (5)	−0.012 (4)	0.012 (3)
O3	0.118 (11)	0.118 (11)	0.021 (11)	0.059 (5)	0.000	0.000

Geometric parameters (Å, °)

Co1—N1i	2.1696 (13)	S1—O2vi	1.431 (5)
Co1—N1ii	2.1696 (13)	S1—O2v	1.431 (5)
Co1—N1iii	2.1696 (13)	S1—O2vii	1.431 (5)
Co1—N1iv	2.1696 (13)	S1—O2viii	1.431 (5)
Co1—N1	2.1696 (13)	S1—O2ix	1.431 (5)
Co1—N1v	2.1696 (13)	S1—O1ix	1.445 (5)
N1—C1	1.469 (2)	S1—O1viii	1.445 (5)
N1—H1A	0.9000	S1—O1vi	1.445 (5)
N1—H1B	0.9000	S1—O1vii	1.445 (5)
S1—O3	1.382 (16)	C1—C1iv	1.512 (4)
S1—O3v	1.382 (16)	C1—H1C	0.9700
S1—O2	1.431 (5)	C1—H1D	0.9700
N1i—Co1—N1ii	80.49 (7)	O2viii—S1—O1viii	110.7 (4)
N1i—Co1—N1iii	93.48 (5)	O2ix—S1—O1viii	138.0 (11)
N1ii—Co1—N1iii	93.17 (8)	O1ix—S1—O1viii	63.4 (8)
N1i—Co1—N1iv	93.17 (8)	O3—S1—O1vi	64.5 (3)
N1ii—Co1—N1iv	93.48 (5)	O3v—S1—O1vi	115.5 (3)
N1iii—Co1—N1iv	171.28 (7)	O2—S1—O1vi	57.2 (5)
N1i—Co1—N1	93.48 (5)	O2vi—S1—O1vi	110.7 (4)
N1ii—Co1—N1	171.28 (8)	O2v—S1—O1vi	138.0 (11)
N1iii—Co1—N1	93.48 (5)	O2vii—S1—O1vi	69.9 (6)
N1iv—Co1—N1	80.49 (7)	O2viii—S1—O1vi	45.7 (4)
N1i—Co1—N1v	171.28 (8)	O2ix—S1—O1vi	119.2 (10)
N1ii—Co1—N1v	93.48 (5)	O1ix—S1—O1vi	93.3 (11)
N1iii—Co1—N1v	80.49 (7)	O1viii—S1—O1vi	102.9 (4)
N1iv—Co1—N1v	93.48 (5)	O3—S1—O1vii	115.5 (3)
N1—Co1—N1v	93.17 (8)	O3v—S1—O1vii	64.5 (3)
C1—N1—Co1	107.94 (10)	O2—S1—O1vii	138.0 (11)
C1—N1—H1A	110.1	O2vi—S1—O1vii	69.9 (6)
Co1—N1—H1A	110.1	O2v—S1—O1vii	57.2 (5)
C1—N1—H1B	110.1	O2vii—S1—O1vii	110.7 (4)
Co1—N1—H1B	110.1	O2viii—S1—O1vii	119.2 (10)
H1A—N1—H1B	108.4	O2ix—S1—O1vii	45.7 (4)
O3—S1—O3v	180.000 (3)	O1ix—S1—O1vii	102.9 (4)
O3—S1—O2	46.6 (3)	O1viii—S1—O1vii	93.3 (11)
O3v—S1—O2	133.4 (3)	O1vi—S1—O1vii	161.1 (12)
O3—S1—O2vi	46.6 (3)	N1—C1—C1iv	108.84 (12)
O3v—S1—O2vi	133.4 (3)	N1—C1—H1C	109.9
O2—S1—O2vi	78.0 (5)	C1iv—C1—H1C	109.9
O3—S1—O2v	133.4 (3)	N1—C1—H1D	109.9
O3v—S1—O2v	46.6 (3)	C1iv—C1—H1D	109.9
O2—S1—O2v	104.4 (11)	H1C—C1—H1D	108.3
O2vi—S1—O2v	99.7 (7)	O2vi—O1—O2viii	91.9 (8)
O3—S1—O2vii	133.4 (3)	O2vi—O1—S1	66.5 (5)
O3v—S1—O2vii	46.6 (3)	O2viii—O1—S1	60.9 (3)
O2—S1—O2vii	99.7 (7)	O2vi—O1—O1vii	75.7 (11)
O2vi—S1—O2vii	176.3 (13)	O2viii—O1—O1vii	117.8 (4)
O2v—S1—O2vii	78.0 (5)	S1—O1—O1vii	58.3 (4)
O3—S1—O2viii	46.6 (3)	O2vi—O1—O2ix	108.3 (7)
O3v—S1—O2viii	133.4 (3)	O2viii—O1—O2ix	92.2 (8)
O2—S1—O2viii	78.0 (5)	S1—O1—O2ix	54.6 (4)
O2vi—S1—O2viii	78.0 (5)	O1viii—O2—O1vi	129.8 (7)
O2v—S1—O2viii	176.3 (13)	O1viii—O2—S1	67.8 (4)
O2vii—S1—O2viii	104.4 (11)	O1vi—O2—S1	61.9 (4)
O3—S1—O2ix	133.4 (3)	O1viii—O2—O1ix	63.3 (12)
O3v—S1—O2ix	46.6 (3)	O1vi—O2—O1ix	87.5 (9)
O2—S1—O2ix	176.3 (13)	S1—O2—O1ix	55.5 (3)
O2vi—S1—O2ix	104.4 (11)	O1viii—O2—O2vi	49.8 (6)
O2v—S1—O2ix	78.0 (5)	O1vi—O2—O2vi	95.3 (5)
O2vii—S1—O2ix	78.0 (5)	S1—O2—O2vi	51.0 (2)
O2viii—S1—O2ix	99.7 (7)	O1ix—O2—O2vi	91.9 (8)
O3—S1—O1ix	115.5 (3)	O1viii—O2—O2viii	106.1 (5)
O3v—S1—O1ix	64.5 (3)	S1—O2—O2viii	51.0 (2)
O2—S1—O1ix	69.9 (6)	O1ix—O2—O2viii	102.2 (4)
O2vi—S1—O1ix	119.2 (10)	O2vi—O2—O2viii	60.000 (1)
O2v—S1—O1ix	45.7 (4)	O2vi—O3—O2viii	107.9 (8)
O2vii—S1—O1ix	57.2 (5)	O2vi—O3—S1	69.0 (8)
O2viii—S1—O1ix	138.0 (11)	O2viii—O3—S1	69.0 (8)
O2ix—S1—O1ix	110.7 (4)	O2vi—O3—O1viii	61.1 (6)
O3—S1—O1viii	64.5 (3)	O2viii—O3—O1viii	128.2 (13)
O3v—S1—O1viii	115.5 (3)	S1—O3—O1viii	59.8 (5)
O2—S1—O1viii	45.7 (4)	O2vi—O3—O1vi	128.2 (13)
O2vi—S1—O1viii	57.2 (5)	O2viii—O3—O1vi	47.4 (6)
O2v—S1—O1viii	69.9 (6)	S1—O3—O1vi	59.8 (5)
O2vii—S1—O1viii	119.2 (10)	O1viii—O3—O1vi	96.9 (7)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3x	0.90	2.13	2.889 (12)	142
N1—H1A···O1x	0.90	2.15	3.049 (7)	176
N1—H1A···O2xi	0.90	2.22	3.054 (8)	155
N1—H1A···O2xii	0.90	2.32	3.104 (11)	145
N1—H1B···O2viii	0.90	1.98	2.843 (6)	161
N1—H1B···O1	0.90	2.48	3.353 (14)	165
N1—H1B···O1v	0.90	2.52	3.256 (10)	139

Symmetry codes: (x) −x+1, −y+1, −z; (xi) y, −x+y, −z; (xii) x−y+1, x, −z; (viii) −x+y, −x+1, z; (v) −y+1, −x+1, −z+1/2.