Tris(ethyl­enediamine)cobalt(II) sulfate

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.028
• wR factor = 0.069
• Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for         S1

Author Response: The sulfate unit is highly disordered about the 2<i>c</i> site, and this should be responsible for the significantly higher Ueq for surrounding O atoms compared to the centered S1 atom.

Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         32
PLAT950_ALERT_1_C Reported and Calculated Hmax Values Differ by ..          3
PLAT951_ALERT_1_C Reported and Calculated Kmax Values Differ by ..          2

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           31.01
           From the CIF: _reflns_number_total                688
           From the CIF: _diffrn_reflns_limit_ max hkl   10.   11.   13.
           From the CIF: _diffrn_reflns_limit_ min hkl   -8.  -11.  -11.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   13.   13.   13.
           Calculated minimum hkl  -13.  -13.  -13.
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      14.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         16
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. 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.

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.

S2. 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.

S3. 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).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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).

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 [Co^II(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].

Tris(ethylenediamine)cobalt(II) sulfate

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) Å^3	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 monochromator	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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 0.1217P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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, º)

Co1—N1^i	2.1696 (13)	S1—O2^vi	1.431 (5)
Co1—N1^ii	2.1696 (13)	S1—O2^v	1.431 (5)
Co1—N1^iii	2.1696 (13)	S1—O2^vii	1.431 (5)
Co1—N1^iv	2.1696 (13)	S1—O2^viii	1.431 (5)
Co1—N1	2.1696 (13)	S1—O2^ix	1.431 (5)
Co1—N1^v	2.1696 (13)	S1—O1^ix	1.445 (5)
N1—C1	1.469 (2)	S1—O1^viii	1.445 (5)
N1—H1A	0.9000	S1—O1^vi	1.445 (5)
N1—H1B	0.9000	S1—O1^vii	1.445 (5)
S1—O3	1.382 (16)	C1—C1^iv	1.512 (4)
S1—O3^v	1.382 (16)	C1—H1C	0.9700
S1—O2	1.431 (5)	C1—H1D	0.9700
N1^i—Co1—N1^ii	80.49 (7)	O2^viii—S1—O1^viii	110.7 (4)
N1^i—Co1—N1^iii	93.48 (5)	O2^ix—S1—O1^viii	138.0 (11)
N1^ii—Co1—N1^iii	93.17 (8)	O1^ix—S1—O1^viii	63.4 (8)
N1^i—Co1—N1^iv	93.17 (8)	O3—S1—O1^vi	64.5 (3)
N1^ii—Co1—N1^iv	93.48 (5)	O3^v—S1—O1^vi	115.5 (3)
N1^iii—Co1—N1^iv	171.28 (7)	O2—S1—O1^vi	57.2 (5)
N1^i—Co1—N1	93.48 (5)	O2^vi—S1—O1^vi	110.7 (4)
N1^ii—Co1—N1	171.28 (8)	O2^v—S1—O1^vi	138.0 (11)
N1^iii—Co1—N1	93.48 (5)	O2^vii—S1—O1^vi	69.9 (6)
N1^iv—Co1—N1	80.49 (7)	O2^viii—S1—O1^vi	45.7 (4)
N1^i—Co1—N1^v	171.28 (8)	O2^ix—S1—O1^vi	119.2 (10)
N1^ii—Co1—N1^v	93.48 (5)	O1^ix—S1—O1^vi	93.3 (11)
N1^iii—Co1—N1^v	80.49 (7)	O1^viii—S1—O1^vi	102.9 (4)
N1^iv—Co1—N1^v	93.48 (5)	O3—S1—O1^vii	115.5 (3)
N1—Co1—N1^v	93.17 (8)	O3^v—S1—O1^vii	64.5 (3)
C1—N1—Co1	107.94 (10)	O2—S1—O1^vii	138.0 (11)
C1—N1—H1A	110.1	O2^vi—S1—O1^vii	69.9 (6)
Co1—N1—H1A	110.1	O2^v—S1—O1^vii	57.2 (5)
C1—N1—H1B	110.1	O2^vii—S1—O1^vii	110.7 (4)
Co1—N1—H1B	110.1	O2^viii—S1—O1^vii	119.2 (10)
H1A—N1—H1B	108.4	O2^ix—S1—O1^vii	45.7 (4)
O3—S1—O3^v	180.000 (3)	O1^ix—S1—O1^vii	102.9 (4)
O3—S1—O2	46.6 (3)	O1^viii—S1—O1^vii	93.3 (11)
O3^v—S1—O2	133.4 (3)	O1^vi—S1—O1^vii	161.1 (12)
O3—S1—O2^vi	46.6 (3)	N1—C1—C1^iv	108.84 (12)
O3^v—S1—O2^vi	133.4 (3)	N1—C1—H1C	109.9
O2—S1—O2^vi	78.0 (5)	C1^iv—C1—H1C	109.9
O3—S1—O2^v	133.4 (3)	N1—C1—H1D	109.9
O3^v—S1—O2^v	46.6 (3)	C1^iv—C1—H1D	109.9
O2—S1—O2^v	104.4 (11)	H1C—C1—H1D	108.3
O2^vi—S1—O2^v	99.7 (7)	O2^vi—O1—O2^viii	91.9 (8)
O3—S1—O2^vii	133.4 (3)	O2^vi—O1—S1	66.5 (5)
O3^v—S1—O2^vii	46.6 (3)	O2^viii—O1—S1	60.9 (3)
O2—S1—O2^vii	99.7 (7)	O2^vi—O1—O1^vii	75.7 (11)
O2^vi—S1—O2^vii	176.3 (13)	O2^viii—O1—O1^vii	117.8 (4)
O2^v—S1—O2^vii	78.0 (5)	S1—O1—O1^vii	58.3 (4)
O3—S1—O2^viii	46.6 (3)	O2^vi—O1—O2^ix	108.3 (7)
O3^v—S1—O2^viii	133.4 (3)	O2^viii—O1—O2^ix	92.2 (8)
O2—S1—O2^viii	78.0 (5)	S1—O1—O2^ix	54.6 (4)
O2^vi—S1—O2^viii	78.0 (5)	O1^viii—O2—O1^vi	129.8 (7)
O2^v—S1—O2^viii	176.3 (13)	O1^viii—O2—S1	67.8 (4)
O2^vii—S1—O2^viii	104.4 (11)	O1^vi—O2—S1	61.9 (4)
O3—S1—O2^ix	133.4 (3)	O1^viii—O2—O1^ix	63.3 (12)
O3^v—S1—O2^ix	46.6 (3)	O1^vi—O2—O1^ix	87.5 (9)
O2—S1—O2^ix	176.3 (13)	S1—O2—O1^ix	55.5 (3)
O2^vi—S1—O2^ix	104.4 (11)	O1^viii—O2—O2^vi	49.8 (6)
O2^v—S1—O2^ix	78.0 (5)	O1^vi—O2—O2^vi	95.3 (5)
O2^vii—S1—O2^ix	78.0 (5)	S1—O2—O2^vi	51.0 (2)
O2^viii—S1—O2^ix	99.7 (7)	O1^ix—O2—O2^vi	91.9 (8)
O3—S1—O1^ix	115.5 (3)	O1^viii—O2—O2^viii	106.1 (5)
O3^v—S1—O1^ix	64.5 (3)	S1—O2—O2^viii	51.0 (2)
O2—S1—O1^ix	69.9 (6)	O1^ix—O2—O2^viii	102.2 (4)
O2^vi—S1—O1^ix	119.2 (10)	O2^vi—O2—O2^viii	60.000 (1)
O2^v—S1—O1^ix	45.7 (4)	O2^vi—O3—O2^viii	107.9 (8)
O2^vii—S1—O1^ix	57.2 (5)	O2^vi—O3—S1	69.0 (8)
O2^viii—S1—O1^ix	138.0 (11)	O2^viii—O3—S1	69.0 (8)
O2^ix—S1—O1^ix	110.7 (4)	O2^vi—O3—O1^viii	61.1 (6)
O3—S1—O1^viii	64.5 (3)	O2^viii—O3—O1^viii	128.2 (13)
O3^v—S1—O1^viii	115.5 (3)	S1—O3—O1^viii	59.8 (5)
O2—S1—O1^viii	45.7 (4)	O2^vi—O3—O1^vi	128.2 (13)
O2^vi—S1—O1^viii	57.2 (5)	O2^viii—O3—O1^vi	47.4 (6)
O2^v—S1—O1^viii	69.9 (6)	S1—O3—O1^vi	59.8 (5)
O2^vii—S1—O1^viii	119.2 (10)	O1^viii—O3—O1^vi	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, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3^x	0.90	2.13	2.889 (12)	142
N1—H1A···O1^x	0.90	2.15	3.049 (7)	176
N1—H1A···O2^xi	0.90	2.22	3.054 (8)	155
N1—H1A···O2^xii	0.90	2.32	3.104 (11)	145
N1—H1B···O2^viii	0.90	1.98	2.843 (6)	161
N1—H1B···O1	0.90	2.48	3.353 (14)	165
N1—H1B···O1^v	0.90	2.52	3.256 (10)	139

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