Tris(ethyl-enediamine)manganese(II) sulfate.

In the title compound, [Mn(C(2)H(8)N(2))(3)]SO(4), the metal atom (site symmetry 3.2) is coordinated by six N atoms from three ethyl-enediamine (en) ligands in a slightly distorted octa-hedral geometry. The en ligands are generated from one half-mol-ecule 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.

Related literature

For a structure containing MnII 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 ▶).

Experimental

Crystal data

[Mn(C2H8N2)3]SO4

M = 331.31

Trigonal,

a = 8.9460 (13) Å

c = 9.6230 (19) Å

V = 666.96 (19) Å3

Z = 2

Mo Kα radiation

μ = 1.17 mm−1

T = 293 K

0.35 × 0.30 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.686, T max = 0.736

2640 measured reflections

402 independent reflections

386 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.159

S = 1.55

402 reflections

44 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.72 e Å−3

Δρmin = −0.63 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 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034874/hb5060sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034874/hb5060Isup2.hkl

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

[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) Å3	T = 293 K
Z = 2	Block, violet
F(000) = 350	0.35 × 0.30 × 0.28 mm

Bruker SMART CCD diffractometer	402 independent reflections
Radiation source: fine-focus sealed tube	386 reflections with I > 2σ(I)
graphite	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 on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058	H-atom parameters constrained
wR(F2) = 0.159	w = 1/[σ2(Fo2) + (0.0637P)2 + 1.2291P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.051 (15)

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.

	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*

	U11	U22	U33	U12	U13	U23
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)

Mn1—N1i	2.125 (6)	S1—O2iii	1.48 (3)
Mn1—N1ii	2.125 (6)	S1—O2vii	1.48 (3)
Mn1—N1iii	2.125 (6)	S1—O2viii	1.48 (3)
Mn1—N1iv	2.125 (6)	S1—O2ii	1.48 (3)
Mn1—N1v	2.125 (6)	O1—O1viii	1.74 (5)
Mn1—N1	2.125 (6)	O2—O2viii	1.72 (6)
S1—O4	1.30 (9)	O3—O3iii	1.82 (4)
S1—O4vi	1.30 (9)	O3—O3ii	1.82 (4)
S1—O3vii	1.45 (3)	N1—C1	1.471 (9)
S1—O3iii	1.45 (3)	N1—H1A	0.9000
S1—O3	1.45 (3)	N1—H1B	0.9000
S1—O3vi	1.45 (3)	C1—C1iv	1.496 (15)
S1—O3ii	1.45 (3)	C1—H1C	0.9700
S1—O3viii	1.45 (3)	C1—H1D	0.9700
N1i—Mn1—N1ii	81.6 (3)	O3ii—S1—O2iii	99.3 (13)
N1i—Mn1—N1iii	93.5 (3)	O3viii—S1—O2iii	170.3 (17)
N1ii—Mn1—N1iii	92.7 (2)	O4—S1—O2vii	124.3 (10)
N1i—Mn1—N1iv	92.7 (2)	O4vi—S1—O2vii	55.7 (10)
N1ii—Mn1—N1iv	93.5 (3)	O3vii—S1—O2vii	62.4 (15)
N1iii—Mn1—N1iv	171.8 (3)	O3iii—S1—O2vii	97 (2)
N1i—Mn1—N1v	92.7 (2)	O3—S1—O2vii	94 (3)
N1ii—Mn1—N1v	171.8 (3)	O3vi—S1—O2vii	30.1 (12)
N1iii—Mn1—N1v	81.6 (3)	O3ii—S1—O2vii	170.3 (17)
N1iv—Mn1—N1v	92.7 (2)	O3viii—S1—O2vii	99.3 (13)
N1i—Mn1—N1	171.8 (3)	O2iii—S1—O2vii	71 (2)
N1ii—Mn1—N1	92.7 (2)	O4—S1—O2viii	124.3 (11)
N1iii—Mn1—N1	92.7 (2)	O4vi—S1—O2viii	55.7 (10)
N1iv—Mn1—N1	81.6 (3)	O3vii—S1—O2viii	30.1 (12)
N1v—Mn1—N1	93.5 (3)	O3iii—S1—O2viii	170.3 (18)
O4—S1—O4vi	180.000 (19)	O3—S1—O2viii	97 (2)
O4—S1—O3vii	133.7 (10)	O3vi—S1—O2viii	99.3 (13)
O4vi—S1—O3vii	46.3 (10)	O3ii—S1—O2viii	94 (3)
O4—S1—O3iii	46.3 (10)	O3viii—S1—O2viii	62.4 (15)
O4vi—S1—O3iii	133.7 (10)	O2iii—S1—O2viii	116 (3)
O3vii—S1—O3iii	156 (4)	O2vii—S1—O2viii	91.3 (15)
O4—S1—O3	46.3 (10)	O4—S1—O2ii	55.7 (10)
O4vi—S1—O3	133.7 (10)	O4vi—S1—O2ii	124.3 (10)
O3vii—S1—O3	90 (2)	O3vii—S1—O2ii	170.3 (17)
O3iii—S1—O3	77.5 (15)	O3iii—S1—O2ii	30.1 (12)
O4—S1—O3vi	133.7 (10)	O3—S1—O2ii	99.3 (13)
O4vi—S1—O3vi	46.3 (10)	O3vi—S1—O2ii	97 (2)
O3vii—S1—O3vi	77.5 (15)	O3ii—S1—O2ii	62.4 (15)
O3iii—S1—O3vi	90 (2)	O3viii—S1—O2ii	94 (3)
O3—S1—O3vi	121 (3)	O2iii—S1—O2ii	91.3 (15)
O4—S1—O3ii	46.3 (10)	O2vii—S1—O2ii	116 (3)
O4vi—S1—O3ii	133.7 (10)	O2viii—S1—O2ii	147 (4)
O3vii—S1—O3ii	121 (3)	S1—O1—O1viii	54.1 (11)
O3iii—S1—O3ii	77.5 (15)	S1—O2—O2viii	54.5 (12)
O3—S1—O3ii	77.5 (15)	S1—O3—O3iii	51.2 (7)
O3vi—S1—O3ii	156 (4)	S1—O3—O3ii	51.2 (7)
O4—S1—O3viii	133.7 (10)	O3iii—O3—O3ii	60.000 (1)
O4vi—S1—O3viii	46.3 (10)	C1—N1—Mn1	107.9 (4)
O3vii—S1—O3viii	77.5 (15)	C1—N1—H1A	110.1
O3iii—S1—O3viii	121 (3)	Mn1—N1—H1A	110.1
O3—S1—O3viii	156 (4)	C1—N1—H1B	110.1
O3vi—S1—O3viii	77.5 (15)	Mn1—N1—H1B	110.1
O3ii—S1—O3viii	90 (2)	H1A—N1—H1B	108.4
O4—S1—O2iii	55.7 (10)	N1—C1—C1iv	108.9 (5)
O4vi—S1—O2iii	124.3 (10)	N1—C1—H1C	109.9
O3vii—S1—O2iii	97 (2)	C1iv—C1—H1C	109.9
O3iii—S1—O2iii	62.4 (15)	N1—C1—H1D	109.9
O3—S1—O2iii	30.1 (12)	C1iv—C1—H1D	109.9
O3vi—S1—O2iii	94 (3)	H1C—C1—H1D	108.3
O4—S1—O1—O1viii	−129 (2)	O3vii—S1—O3—O3iii	−159 (3)
O4vi—S1—O1—O1viii	51 (2)	O3vi—S1—O3—O3iii	−83 (2)
O3vii—S1—O1—O1viii	65.8 (19)	O3ii—S1—O3—O3iii	79.8 (10)
O3iii—S1—O1—O1viii	−140 (3)	O3viii—S1—O3—O3iii	141.8 (18)
O3—S1—O1—O1viii	179 (3)	O2iii—S1—O3—O3iii	−55 (3)
O3vi—S1—O1—O1viii	100 (3)	O2vii—S1—O3—O3iii	−96 (3)
O3ii—S1—O1—O1viii	−77 (2)	O2viii—S1—O3—O3iii	172 (3)
O3viii—S1—O1—O1viii	0(2)	O2ii—S1—O3—O3iii	20.9 (16)
O2iii—S1—O1—O1viii	171 (2)	O4—S1—O3—O3ii	−39.9 (5)
O2vii—S1—O1—O1viii	112.2 (18)	O4vi—S1—O3—O3ii	140.1 (5)
O2viii—S1—O1—O1viii	34.5 (19)	O3vii—S1—O3—O3ii	122 (4)
O2ii—S1—O1—O1viii	−108 (3)	O3iii—S1—O3—O3ii	−79.8 (10)
O4—S1—O2—O2viii	163 (4)	O3vi—S1—O3—O3ii	−163 (2)
O4vi—S1—O2—O2viii	−17 (4)	O3viii—S1—O3—O3ii	62 (2)
O3vii—S1—O2—O2viii	20 (2)	O2iii—S1—O3—O3ii	−135 (3)
O3iii—S1—O2—O2viii	179 (4)	O2vii—S1—O3—O3ii	−176 (3)
O3—S1—O2—O2viii	109 (4)	O2viii—S1—O3—O3ii	92 (3)
O3vi—S1—O2—O2viii	−3(22)	O2ii—S1—O3—O3ii	−58.9 (16)
O3ii—S1—O2—O2viii	−136 (5)	N1i—Mn1—N1—C1	32.2 (4)
O3viii—S1—O2—O2viii	−58 (2)	N1ii—Mn1—N1—C1	78.5 (5)
O2iii—S1—O2—O2viii	117 (4)	N1iii—Mn1—N1—C1	171.4 (4)
O2vii—S1—O2—O2viii	61 (2)	N1iv—Mn1—N1—C1	−14.7 (3)
O2ii—S1—O2—O2viii	−151 (4)	N1v—Mn1—N1—C1	−106.9 (4)
O4—S1—O3—O3iii	39.9 (5)	Mn1—N1—C1—C1iv	41.5 (7)
O4vi—S1—O3—O3iii	−140.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ix	0.90	2.28	3.16 (3)	166
N1—H1A···O1x	0.90	2.43	3.15 (3)	138
N1—H1B···O1xi	0.90	2.17	3.06 (2)	170
N1—H1B···O2xi	0.90	2.11	3.00 (2)	167
N1—H1A···O2xii	0.90	2.14	2.95 (5)	148
N1—H1A···O3ix	0.90	1.92	2.80 (3)	166
N1—H1B···O3xi	0.90	2.15	2.96 (3)	150
N1—H1B···O3xiii	0.90	2.36	3.18 (3)	152
N1—H1B···O4xiv	0.90	2.15	2.94 (7)	146

Mn1—N1

2.125 (6)

N1i—Mn1—N1

81.6 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ii	0.90	2.28	3.16 (3)	166
N1—H1A⋯O1iii	0.90	2.43	3.15 (3)	138
N1—H1B⋯O1iv	0.90	2.17	3.06 (2)	170
N1—H1B⋯O2iv	0.90	2.11	3.00 (2)	167
N1—H1A⋯O2v	0.90	2.14	2.95 (5)	148
N1—H1A⋯O3ii	0.90	1.92	2.80 (3)	166
N1—H1B⋯O3iv	0.90	2.15	2.96 (3)	150
N1—H1B⋯O3vi	0.90	2.36	3.18 (3)	152
N1—H1B⋯O4vii	0.90	2.15	2.94 (7)	146

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .