Retracted: Tris(ethyl­enediamine)manganese(II) sulfate

In the title compound, [Mn(C₂H₈N₂)₃]SO₄, the metal atom (site symmetry 3.2) is coordinated by six N atoms from three ethyl­enediamine (en) ligands in a slightly distorted octa­hedral geometry. The en ligands are generated from one half-mol­ecule in the asymmetric unit. The O atoms of the sulfate anion (S site symmetry 3.2) are disordered over four orientations in a 0.220 (12):0.210 (13):0.203 (14):0.10 (2) ratio, with one of the O atoms having site symmetry 3. In the crystal, the ions are connected by N—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.011 Å
• Disorder in main residue
• R factor = 0.058
• wR factor = 0.159
• Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.14
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  N1      ..       9.10 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         11
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

Alert level G
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................      12.00 Perc.
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            O3  -S1  -O2  -O2     -3.00 22.00   4.665   1.555   1.555   6.565
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         44
            N1  -MN1 -N1  -C1     32.20  0.40   6.566   1.555   1.555   1.555
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      30.10 Deg.
              O3   -S1   -O2      1.555   1.555   2.665
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      30.10 Deg.
              O3   -S1   -O2      4.665   1.555   5.555
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      30.10 Deg.
              O3   -S1   -O2      5.555   1.555   6.565
PLAT779_ALERT_4_G Suspect or Irrelevant (Bond) Angle in CIF ......      30.10 Deg.
              O3   -S1   -O2      2.665   1.555   3.565
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          !

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

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

---

S1. Comment

Ethylenediamine (en) ligand has been seen in a number of coordination compound (Cullen et al., 1970; Daniels et al., 1995 and Jameson et al., 1982), because it can not only chelate metal center by two nitrogen atoms, but also offer hydrogen atoms to form N—H···X hydrogen bonds. In this paper, we report the structure of the title compound, (I).

In the title compound (Fig. 1), [Mn(C₂H₈N₂)₃]SO₄, the cation and anion are situated on a sixfold rotation axis. The Mn(II) is coordinated by six N atoms from three en ligands in a distorted octahedral geometry. The Mn—N bond length is 2.129 Å, which is shorter than the distance between Mn(II) and aromatic nitrogen atom (Shang et al., 2009). The O atoms of the sulfate anions are disordered. The disordered anions hydrogen bond with the coordination cations by N—H···O hydrogen bonds, forming three-dimensional supramolecular network. The hydrogen bond is listed in table 1.

Related literature

For a structure contaiing Mn(II) and aromatic amine ligands, see: Shang et al. (2009). For other compounds containing transition metals coordinated by ethylenediamine, see: Cullen & Lingafelter (1970); Daniels et al. (1995); Jameson et al. (1982).

S2. Experimental

Manganese sulfate (0.2 mmol) and malic acid (0.4 mmol) were added to water (15 ml). The pH value was adjusted to 9 by en. Violet blocks of (I) were obtained after several days in 30% yield. Elemental analysis, Found:C, 21.73; H, 7.24; N, 25.35%. Calc. for C₆H₂₄N₆MnSO₄: C, 21.20; H, 7.00; N, 24.93%.

S3. Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H 0.970 and N—H 0.900 Å, and with U_iso(H) = 1.2U_eq(C,N). The O atoms are resolved into four positions by PART instructions. The geometries and anisotropic displacement parameters of disordered atoms were refined with soft restraints using the SHELXL commands SUMP, SIMU and EADP.

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); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of (I) with 50% probability displacement ellipsoids. The symmetry codes for N and C atoms: A -y+1, x-y+1, z; B -x+y, -x+1, z; C -y+1, -x+1, -z+3/2; D -x+y, y, -z+3/2; E x, x-y+1, -z+3/2.

Tris(ethylenediamine)manganese(II) sulfate

Crystal data

[Mn(C2H8N2)3]SO4	Dx = 1.650 Mg m^−3
Mr = 331.31	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 2640 reflections
a = 8.9460 (13) Å	θ = 2.6–25.0°
c = 9.6230 (19) Å	µ = 1.17 mm^−1
V = 666.96 (19) Å^3	T = 293 K
Z = 2	Block, violet
F(000) = 350	0.35 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer	402 independent reflections
Radiation source: fine-focus sealed tube	386 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→10
Tmin = 0.686, Tmax = 0.736	k = −10→4
2640 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.0637P)^2 + 1.2291P] where P = (Fo^2 + 2Fc^2)/3
S = 1.55	(Δ/σ)max = 0.001
402 reflections	Δρmax = 0.72 e Å^−3
44 parameters	Δρmin = −0.63 e Å^−3
2 restraints	Extinction correction: SHELXS97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.051 (15)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.3333	0.6667	0.7500	0.0200 (8)
S1	0.3333	0.6667	0.2500	0.0332 (10)
O1	0.489 (3)	0.813 (4)	0.186 (2)	0.051 (4)	0.220 (12)
O2	0.489 (3)	0.721 (6)	0.163 (3)	0.051 (4)	0.210 (13)
O3	0.373 (6)	0.799 (3)	0.146 (3)	0.051 (4)	0.203 (14)
O4	0.3333	0.6667	0.114 (9)	0.051 (4)	0.10 (2)
N1	0.3136 (7)	0.4590 (8)	0.8712 (6)	0.0427 (14)
H1A	0.4072	0.4479	0.8581	0.051*
H1B	0.3070	0.4791	0.9621	0.051*
C1	0.1570 (9)	0.3007 (9)	0.8275 (8)	0.0491 (18)
H1C	0.0561	0.2960	0.8692	0.059*
H1D	0.1626	0.2002	0.8578	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0208 (9)	0.0208 (9)	0.0184 (12)	0.0104 (5)	0.000	0.000
S1	0.0327 (13)	0.0327 (13)	0.034 (2)	0.0163 (7)	0.000	0.000
O1	0.045 (8)	0.042 (12)	0.047 (7)	0.008 (10)	0.007 (6)	0.000 (8)
O2	0.045 (8)	0.042 (12)	0.047 (7)	0.008 (10)	0.007 (6)	0.000 (8)
O3	0.045 (8)	0.042 (12)	0.047 (7)	0.008 (10)	0.007 (6)	0.000 (8)
O4	0.045 (8)	0.042 (12)	0.047 (7)	0.008 (10)	0.007 (6)	0.000 (8)
N1	0.041 (3)	0.051 (3)	0.040 (3)	0.026 (3)	0.008 (2)	0.000 (2)
C1	0.051 (4)	0.053 (4)	0.054 (4)	0.035 (3)	0.002 (3)	−0.006 (3)

Geometric parameters (Å, º)

Mn1—N1^i	2.125 (6)	S1—O2^iii	1.48 (3)
Mn1—N1^ii	2.125 (6)	S1—O2^vii	1.48 (3)
Mn1—N1^iii	2.125 (6)	S1—O2^viii	1.48 (3)
Mn1—N1^iv	2.125 (6)	S1—O2^ii	1.48 (3)
Mn1—N1^v	2.125 (6)	O1—O1^viii	1.74 (5)
Mn1—N1	2.125 (6)	O2—O2^viii	1.72 (6)
S1—O4	1.30 (9)	O3—O3^iii	1.82 (4)
S1—O4^vi	1.30 (9)	O3—O3^ii	1.82 (4)
S1—O3^vii	1.45 (3)	N1—C1	1.471 (9)
S1—O3^iii	1.45 (3)	N1—H1A	0.9000
S1—O3	1.45 (3)	N1—H1B	0.9000
S1—O3^vi	1.45 (3)	C1—C1^iv	1.496 (15)
S1—O3^ii	1.45 (3)	C1—H1C	0.9700
S1—O3^viii	1.45 (3)	C1—H1D	0.9700
N1^i—Mn1—N1^ii	81.6 (3)	O3^ii—S1—O2^iii	99.3 (13)
N1^i—Mn1—N1^iii	93.5 (3)	O3^viii—S1—O2^iii	170.3 (17)
N1^ii—Mn1—N1^iii	92.7 (2)	O4—S1—O2^vii	124.3 (10)
N1^i—Mn1—N1^iv	92.7 (2)	O4^vi—S1—O2^vii	55.7 (10)
N1^ii—Mn1—N1^iv	93.5 (3)	O3^vii—S1—O2^vii	62.4 (15)
N1^iii—Mn1—N1^iv	171.8 (3)	O3^iii—S1—O2^vii	97 (2)
N1^i—Mn1—N1^v	92.7 (2)	O3—S1—O2^vii	94 (3)
N1^ii—Mn1—N1^v	171.8 (3)	O3^vi—S1—O2^vii	30.1 (12)
N1^iii—Mn1—N1^v	81.6 (3)	O3^ii—S1—O2^vii	170.3 (17)
N1^iv—Mn1—N1^v	92.7 (2)	O3^viii—S1—O2^vii	99.3 (13)
N1^i—Mn1—N1	171.8 (3)	O2^iii—S1—O2^vii	71 (2)
N1^ii—Mn1—N1	92.7 (2)	O4—S1—O2^viii	124.3 (11)
N1^iii—Mn1—N1	92.7 (2)	O4^vi—S1—O2^viii	55.7 (10)
N1^iv—Mn1—N1	81.6 (3)	O3^vii—S1—O2^viii	30.1 (12)
N1^v—Mn1—N1	93.5 (3)	O3^iii—S1—O2^viii	170.3 (18)
O4—S1—O4^vi	180.000 (19)	O3—S1—O2^viii	97 (2)
O4—S1—O3^vii	133.7 (10)	O3^vi—S1—O2^viii	99.3 (13)
O4^vi—S1—O3^vii	46.3 (10)	O3^ii—S1—O2^viii	94 (3)
O4—S1—O3^iii	46.3 (10)	O3^viii—S1—O2^viii	62.4 (15)
O4^vi—S1—O3^iii	133.7 (10)	O2^iii—S1—O2^viii	116 (3)
O3^vii—S1—O3^iii	156 (4)	O2^vii—S1—O2^viii	91.3 (15)
O4—S1—O3	46.3 (10)	O4—S1—O2^ii	55.7 (10)
O4^vi—S1—O3	133.7 (10)	O4^vi—S1—O2^ii	124.3 (10)
O3^vii—S1—O3	90 (2)	O3^vii—S1—O2^ii	170.3 (17)
O3^iii—S1—O3	77.5 (15)	O3^iii—S1—O2^ii	30.1 (12)
O4—S1—O3^vi	133.7 (10)	O3—S1—O2^ii	99.3 (13)
O4^vi—S1—O3^vi	46.3 (10)	O3^vi—S1—O2^ii	97 (2)
O3^vii—S1—O3^vi	77.5 (15)	O3^ii—S1—O2^ii	62.4 (15)
O3^iii—S1—O3^vi	90 (2)	O3^viii—S1—O2^ii	94 (3)
O3—S1—O3^vi	121 (3)	O2^iii—S1—O2^ii	91.3 (15)
O4—S1—O3^ii	46.3 (10)	O2^vii—S1—O2^ii	116 (3)
O4^vi—S1—O3^ii	133.7 (10)	O2^viii—S1—O2^ii	147 (4)
O3^vii—S1—O3^ii	121 (3)	S1—O1—O1^viii	54.1 (11)
O3^iii—S1—O3^ii	77.5 (15)	S1—O2—O2^viii	54.5 (12)
O3—S1—O3^ii	77.5 (15)	S1—O3—O3^iii	51.2 (7)
O3^vi—S1—O3^ii	156 (4)	S1—O3—O3^ii	51.2 (7)
O4—S1—O3^viii	133.7 (10)	O3^iii—O3—O3^ii	60.000 (1)
O4^vi—S1—O3^viii	46.3 (10)	C1—N1—Mn1	107.9 (4)
O3^vii—S1—O3^viii	77.5 (15)	C1—N1—H1A	110.1
O3^iii—S1—O3^viii	121 (3)	Mn1—N1—H1A	110.1
O3—S1—O3^viii	156 (4)	C1—N1—H1B	110.1
O3^vi—S1—O3^viii	77.5 (15)	Mn1—N1—H1B	110.1
O3^ii—S1—O3^viii	90 (2)	H1A—N1—H1B	108.4
O4—S1—O2^iii	55.7 (10)	N1—C1—C1^iv	108.9 (5)
O4^vi—S1—O2^iii	124.3 (10)	N1—C1—H1C	109.9
O3^vii—S1—O2^iii	97 (2)	C1^iv—C1—H1C	109.9
O3^iii—S1—O2^iii	62.4 (15)	N1—C1—H1D	109.9
O3—S1—O2^iii	30.1 (12)	C1^iv—C1—H1D	109.9
O3^vi—S1—O2^iii	94 (3)	H1C—C1—H1D	108.3
O4—S1—O1—O1^viii	−129 (2)	O3^vii—S1—O3—O3^iii	−159 (3)
O4^vi—S1—O1—O1^viii	51 (2)	O3^vi—S1—O3—O3^iii	−83 (2)
O3^vii—S1—O1—O1^viii	65.8 (19)	O3^ii—S1—O3—O3^iii	79.8 (10)
O3^iii—S1—O1—O1^viii	−140 (3)	O3^viii—S1—O3—O3^iii	141.8 (18)
O3—S1—O1—O1^viii	179 (3)	O2^iii—S1—O3—O3^iii	−55 (3)
O3^vi—S1—O1—O1^viii	100 (3)	O2^vii—S1—O3—O3^iii	−96 (3)
O3^ii—S1—O1—O1^viii	−77 (2)	O2^viii—S1—O3—O3^iii	172 (3)
O3^viii—S1—O1—O1^viii	0 (2)	O2^ii—S1—O3—O3^iii	20.9 (16)
O2^iii—S1—O1—O1^viii	171 (2)	O4—S1—O3—O3^ii	−39.9 (5)
O2^vii—S1—O1—O1^viii	112.2 (18)	O4^vi—S1—O3—O3^ii	140.1 (5)
O2^viii—S1—O1—O1^viii	34.5 (19)	O3^vii—S1—O3—O3^ii	122 (4)
O2^ii—S1—O1—O1^viii	−108 (3)	O3^iii—S1—O3—O3^ii	−79.8 (10)
O4—S1—O2—O2^viii	163 (4)	O3^vi—S1—O3—O3^ii	−163 (2)
O4^vi—S1—O2—O2^viii	−17 (4)	O3^viii—S1—O3—O3^ii	62 (2)
O3^vii—S1—O2—O2^viii	20 (2)	O2^iii—S1—O3—O3^ii	−135 (3)
O3^iii—S1—O2—O2^viii	179 (4)	O2^vii—S1—O3—O3^ii	−176 (3)
O3—S1—O2—O2^viii	109 (4)	O2^viii—S1—O3—O3^ii	92 (3)
O3^vi—S1—O2—O2^viii	−3 (22)	O2^ii—S1—O3—O3^ii	−58.9 (16)
O3^ii—S1—O2—O2^viii	−136 (5)	N1^i—Mn1—N1—C1	32.2 (4)
O3^viii—S1—O2—O2^viii	−58 (2)	N1^ii—Mn1—N1—C1	78.5 (5)
O2^iii—S1—O2—O2^viii	117 (4)	N1^iii—Mn1—N1—C1	171.4 (4)
O2^vii—S1—O2—O2^viii	61 (2)	N1^iv—Mn1—N1—C1	−14.7 (3)
O2^ii—S1—O2—O2^viii	−151 (4)	N1^v—Mn1—N1—C1	−106.9 (4)
O4—S1—O3—O3^iii	39.9 (5)	Mn1—N1—C1—C1^iv	41.5 (7)
O4^vi—S1—O3—O3^iii	−140.1 (5)

Symmetry codes: (i) x, x−y+1, −z+3/2; (ii) −x+y, −x+1, z; (iii) −y+1, x−y+1, z; (iv) −x+y, y, −z+3/2; (v) −y+1, −x+1, −z+3/2; (vi) −y+1, −x+1, −z+1/2; (vii) −x+y, y, −z+1/2; (viii) 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···O1^ix	0.90	2.28	3.16 (3)	166
N1—H1A···O1^x	0.90	2.43	3.15 (3)	138
N1—H1B···O1^xi	0.90	2.17	3.06 (2)	170
N1—H1B···O2^xi	0.90	2.11	3.00 (2)	167
N1—H1A···O2^xii	0.90	2.14	2.95 (5)	148
N1—H1A···O3^ix	0.90	1.92	2.80 (3)	166
N1—H1B···O3^xi	0.90	2.15	2.96 (3)	150
N1—H1B···O3^xiii	0.90	2.36	3.18 (3)	152
N1—H1B···O4^xiv	0.90	2.15	2.94 (7)	146

Symmetry codes: (ix) x−y+1, x, −z+1; (x) −x+1, −x+y, z+1/2; (xi) −x+y, −x+1, z+1; (xii) −x+1, −y+1, −z+1; (xiii) −y+1, x−y+1, z+1; (xiv) x, y, z+1.