2,2′-Biimidazolium hexa­aqua­manganese(II) bis­(sulfate)

Kurawa, M.A.; Adams, C.J.; Orpen, A.G.

doi:10.1107/S1600536808020291

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1005

doi:10.1107/S1600536808020291

Open

access

2,2′-Biimidazolium hexaaquamanganese(II) bis(sulfate)

Mukhtar A. Kurawa,^a Christopher J. Adams ^a and A. Guy Orpen ^a ^*

^aSchool of Chemistry, University of Bristol, Bristol BS8 1TS, England
^*Correspondence e-mail: guy.orpen@bris.ac.uk

(Received 25 June 2008; accepted 2 July 2008; online 9 July 2008)

The title compound, (C₆H₈N₄)[Mn(H₂O)₆](SO₄)₂, was obtained by cocrystallization of 2,2′-biimidazolium sulfate and bis(tetrabutylammonium) tetrachloridomanganate(II). The asymmetric unit contains one isolated (SO₄)²⁻ anion, one half of an octahedral [Mn(H₂O)₆]²⁺ dication and one half of a 2,2′-biimidazolium dication, each of which lies on an inversion centre. Molecules are connected by a three-dimensional N—H⋯O and O—H⋯O hydrogen-bond network.

Related literature

For the syntheses, structural studies and thermal behaviour of related compounds, see: Rekik et al. (2006 , 2007 ).

Experimental

Crystal data

(C₆H₈N₄)[Mn(H₂O)₆](SO₄)₂
M_r = 491.34
Monoclinic, P 2₁ /c
a = 6.0625 (7) Å
b = 11.606 (2) Å
c = 12.218 (2) Å
β = 91.65 (1)°
V = 859.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 100 (2) K
0.4 × 0.3 × 0.2 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick,1996 ) T_min = 0.686, T_max = 0.800
9389 measured reflections
1954 independent reflections
1897 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.066
S = 1.06
1954 reflections
142 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—O6	2.1335 (10)
Mn1—O7	2.1856 (10)
Mn1—O5	2.2218 (10)
Symmetry code: (i) -x, -y+2, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱⁱ	0.88	1.93	2.7699 (15)	159
N1—H1A⋯O2ⁱⁱ	0.88	2.45	3.0994 (15)	131
N2—H2A⋯O3ⁱⁱⁱ	0.88	1.92	2.7562 (16)	159
O5—H5A⋯O2	0.843 (14)	1.917 (15)	2.7600 (15)	176.8 (18)
O5—H5B⋯O3^iv	0.813 (14)	2.088 (15)	2.8638 (15)	159.7 (17)
O6—H6A⋯O4^v	0.839 (14)	1.908 (15)	2.7402 (15)	171.2 (18)
O6—H6B⋯O1^vi	0.846 (14)	1.847 (15)	2.6904 (14)	174.2 (18)
O7—H7A⋯O4^vii	0.851 (14)	1.888 (15)	2.7298 (15)	169.5 (18)
O7—H7B⋯O2^v	0.846 (14)	1.892 (14)	2.7266 (14)	169.0 (17)
Symmetry codes: (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x-1, y, z; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) -x+1, -y+1, -z; (vii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020291/hy2142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020291/hy2142Isup2.hkl

checkCIF report

Comment top

The syntheses, structural studies and thermal behaviour of similar complexes with piperazinium, (C₄H₁₂N₂)²⁺, and 1,4-diaza-bicyclo[2.2.2]octandiium, (C₆H₁₄N₂)²⁺, cations have been reported (Rekik et al., 2006, 2007).

In the crystal structure of the title compound (Fig. 1; Table 1), the (C₆H₈N₄)²⁺, [Mn(H₂O)₆]²⁺ and (SO₄)^2- ions are connected by N—H···O and O—H···O hydrogen bonds (Table 2), with the 2,2'-biimidazolium dications in the supramolecular cavities formed by the metal–sulfate framework (Fig. 2). The corresponding structures of some first row transition metal M^II sulfates (M = Mn, Ni, Fe and Cu) templated with piperazinium display similar three-dimensional hydrogen-bonded networks (Rekik, Naili, Bataille et al., 2006). In particular, the structures of the (C₄H₁₂N₂)²⁺[M(H₂O)₆]²⁺(SO₄)₂^2- (M = Mn or Ni) compounds contain channels (running parallel to the c-axis in those cases), which are defined by a square arrangement of [M(H₂O)₆]²⁺ cations and which contain the organic dications, mirroring the channels seen in the title compound (Fig. 2).

Related literature top

For the syntheses, structural studies and thermal behaviour of related compounds, see: Rekik et al. (2006, 2007).

Experimental top

The title compound was obtained unintentionally as the product of an attempted synthesis of a hydrogen-bonded salt of the tetrachloromanganate(II) anion and the biimidazolium cation, using slow evaporation of a water–acetonitrile solution (1:1 v/v) of equimolar amounts of bis(tetrabutylammonium) tetrachloromanganate(II) and 2,2'-biimidazolium sulfate at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, 2-y, -z; (vi) 1-x, 1-y, -z.]
	Fig. 2. Packing diagram for the title compound viewed along the a-axis.

2,2'-Biimidazolium hexaaquamanganese(II) bis(sulfate) top

Crystal data top

(C₆H₈N₄)[Mn(H₂O)₆](SO₄)₂	F(000) = 506
M_r = 491.34	D_x = 1.899 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7442 reflections
a = 6.0625 (7) Å	θ = 2.4–27.5°
b = 11.606 (2) Å	µ = 1.09 mm⁻¹
c = 12.218 (2) Å	T = 100 K
β = 91.65 (1)°	Block, colourless
V = 859.3 (2) Å³	0.4 × 0.3 × 0.2 mm
Z = 2

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1954 independent reflections
Radiation source: fine-focus sealed tube	1897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	h = −7→7
T_min = 0.686, T_max = 0.800	k = −15→15
9389 measured reflections	l = −15→15

Refinement top

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.042P)² + 0.4497P] where P = (F_o² + 2F_c²)/3
1954 reflections	(Δ/σ)_max < 0.001
142 parameters	Δρ_max = 0.29 e Å⁻³
6 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

(C₆H₈N₄)[Mn(H₂O)₆](SO₄)₂	V = 859.3 (2) Å³
M_r = 491.34	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0625 (7) Å	µ = 1.09 mm⁻¹
b = 11.606 (2) Å	T = 100 K
c = 12.218 (2) Å	0.4 × 0.3 × 0.2 mm
β = 91.65 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1954 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick,1996)	1897 reflections with I > 2σ(I)
T_min = 0.686, T_max = 0.800	R_int = 0.018
9389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	6 restraints
wR(F²) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.29 e Å⁻³
1954 reflections	Δρ_min = −0.65 e Å⁻³
142 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.5000	0.5000	0.0000	0.00892 (9)
S1	0.87954 (5)	0.76694 (3)	0.24181 (2)	0.00829 (10)
N1	0.20621 (19)	1.00486 (9)	0.11407 (9)	0.0107 (2)
H1A	0.1629	1.0584	0.1597	0.013*
N2	0.21706 (17)	0.89187 (9)	−0.02676 (9)	0.0105 (2)
H2A	0.1825	0.8585	−0.0896	0.013*
C1	0.3926 (2)	0.93818 (11)	0.12742 (11)	0.0125 (2)
H1B	0.4969	0.9413	0.1869	0.015*
C2	0.3988 (2)	0.86702 (11)	0.03924 (11)	0.0124 (2)
H2B	0.5082	0.8106	0.0257	0.015*
C3	0.1021 (2)	0.97533 (11)	0.02099 (10)	0.0098 (2)
O1	0.87996 (15)	0.78300 (8)	0.12285 (7)	0.0128 (2)
O2	0.65505 (15)	0.73605 (8)	0.27723 (8)	0.0126 (2)
O3	1.02939 (15)	0.66897 (8)	0.27336 (7)	0.01179 (19)
O4	0.95582 (15)	0.87250 (8)	0.29863 (8)	0.01210 (19)
O5	0.39485 (16)	0.59047 (8)	0.15004 (8)	0.0137 (2)
O6	0.19308 (16)	0.40995 (8)	−0.00527 (8)	0.0135 (2)
O7	0.63321 (15)	0.36233 (8)	0.10452 (8)	0.01286 (19)
H5A	0.474 (3)	0.6368 (14)	0.1868 (14)	0.015*
H6A	0.134 (3)	0.4002 (15)	0.0553 (13)	0.015*
H7A	0.753 (3)	0.3688 (15)	0.1418 (14)	0.015*
H5B	0.273 (2)	0.6050 (15)	0.1724 (14)	0.015*
H6B	0.162 (3)	0.3514 (14)	−0.0441 (14)	0.015*
H7B	0.548 (3)	0.3290 (15)	0.1482 (13)	0.015*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.00931 (15)	0.00906 (15)	0.00839 (15)	−0.00039 (9)	0.00042 (10)	0.00021 (9)
S1	0.00802 (16)	0.00845 (16)	0.00839 (17)	0.00010 (10)	0.00033 (11)	−0.00019 (10)
N1	0.0120 (5)	0.0100 (5)	0.0103 (5)	0.0002 (4)	0.0001 (4)	−0.0003 (4)
N2	0.0109 (5)	0.0105 (5)	0.0102 (5)	−0.0002 (4)	0.0007 (4)	−0.0012 (4)
C1	0.0128 (6)	0.0120 (6)	0.0127 (6)	0.0003 (4)	−0.0010 (4)	0.0025 (5)
C2	0.0112 (6)	0.0119 (6)	0.0141 (6)	0.0008 (4)	−0.0006 (4)	0.0019 (5)
C3	0.0103 (6)	0.0089 (5)	0.0104 (6)	−0.0016 (5)	0.0015 (4)	0.0009 (4)
O1	0.0167 (5)	0.0125 (4)	0.0090 (4)	−0.0011 (3)	−0.0005 (3)	0.0010 (3)
O2	0.0088 (4)	0.0139 (4)	0.0150 (5)	−0.0014 (3)	0.0021 (3)	−0.0016 (3)
O3	0.0116 (4)	0.0115 (4)	0.0123 (4)	0.0028 (3)	0.0006 (3)	0.0016 (3)
O4	0.0124 (4)	0.0110 (4)	0.0129 (4)	−0.0018 (3)	0.0009 (3)	−0.0027 (3)
O5	0.0106 (4)	0.0166 (5)	0.0141 (5)	−0.0010 (4)	0.0026 (3)	−0.0052 (4)
O6	0.0139 (4)	0.0152 (5)	0.0116 (5)	−0.0036 (4)	0.0027 (3)	−0.0025 (4)
O7	0.0106 (4)	0.0145 (5)	0.0134 (5)	−0.0004 (3)	0.0002 (3)	0.0035 (3)

Geometric parameters (Å, º) top

Mn1—O6	2.1335 (10)	N2—C3	1.3371 (16)
Mn1—O6ⁱ	2.1335 (10)	N2—C2	1.3771 (17)
Mn1—O7ⁱ	2.1856 (10)	N2—H2A	0.8800
Mn1—O7	2.1856 (10)	C1—C2	1.3589 (19)
Mn1—O5	2.2218 (10)	C1—H1B	0.9500
Mn1—O5ⁱ	2.2218 (10)	C2—H2B	0.9500
S1—O1	1.4653 (10)	C3—C3ⁱⁱ	1.445 (2)
S1—O4	1.4759 (10)	O5—H5A	0.843 (14)
S1—O2	1.4839 (10)	O5—H5B	0.813 (14)
S1—O2	1.4839 (10)	O6—H6A	0.839 (14)
S1—O3	1.4989 (9)	O6—H6B	0.846 (14)
N1—C3	1.3296 (17)	O7—H7A	0.851 (14)
N1—C1	1.3754 (17)	O7—H7B	0.846 (14)
N1—H1A	0.8800

O6—Mn1—O6ⁱ	180.0	C3—N1—C1	108.94 (11)
O6—Mn1—O7ⁱ	91.90 (4)	C3—N1—H1A	125.5
O6ⁱ—Mn1—O7ⁱ	88.10 (4)	C1—N1—H1A	125.5
O6—Mn1—O7	88.10 (4)	C3—N2—C2	108.33 (11)
O6ⁱ—Mn1—O7	91.90 (4)	C3—N2—H2A	125.8
O7ⁱ—Mn1—O7	180.0	C2—N2—H2A	125.8
O6—Mn1—O5	89.18 (4)	C2—C1—N1	106.82 (11)
O6ⁱ—Mn1—O5	90.82 (4)	C2—C1—H1B	126.6
O7ⁱ—Mn1—O5	91.53 (4)	N1—C1—H1B	126.6
O7—Mn1—O5	88.47 (4)	C1—C2—N2	107.28 (11)
O6—Mn1—O5ⁱ	90.82 (4)	C1—C2—H2B	126.4
O6ⁱ—Mn1—O5ⁱ	89.18 (4)	N2—C2—H2B	126.4
O7ⁱ—Mn1—O5ⁱ	88.47 (4)	N1—C3—N2	108.63 (11)
O7—Mn1—O5ⁱ	91.53 (4)	N1—C3—C3ⁱⁱ	125.62 (15)
O5—Mn1—O5ⁱ	180.0	N2—C3—C3ⁱⁱ	125.75 (15)
O1—S1—O4	110.58 (6)	Mn1—O5—H5A	124.6 (12)
O1—S1—O2	110.35 (6)	Mn1—O5—H5B	131.4 (13)
O4—S1—O2	109.94 (6)	H5A—O5—H5B	101.5 (17)
O1—S1—O2	110.35 (6)	Mn1—O6—H6A	115.7 (12)
O4—S1—O2	109.94 (6)	Mn1—O6—H6B	126.2 (12)
O1—S1—O3	109.47 (6)	H6A—O6—H6B	107.0 (17)
O4—S1—O3	109.23 (6)	Mn1—O7—H7A	123.0 (12)
O2—S1—O3	107.21 (6)	Mn1—O7—H7B	118.8 (12)
O2—S1—O3	107.21 (6)	H7A—O7—H7B	103.3 (17)

C3—N1—C1—C2	0.07 (15)	C1—N1—C3—C3ⁱⁱ	179.08 (15)
N1—C1—C2—N2	0.36 (14)	C2—N2—C3—N1	0.71 (14)
C3—N2—C2—C1	−0.66 (14)	C2—N2—C3—C3ⁱⁱ	−178.85 (15)
C1—N1—C3—N2	−0.48 (14)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱⁱ	0.88	1.93	2.7699 (15)	159
N1—H1A···O2ⁱⁱⁱ	0.88	2.45	3.0994 (15)	131
N2—H2A···O3^iv	0.88	1.92	2.7562 (16)	159
O5—H5A···O2	0.84 (1)	1.92 (2)	2.7600 (15)	177 (2)
O5—H5B···O3^v	0.81 (1)	2.09 (2)	2.8638 (15)	160 (2)
O6—H6A···O4^vi	0.84 (1)	1.91 (2)	2.7402 (15)	171 (2)
O6—H6B···O1ⁱ	0.85 (1)	1.85 (2)	2.6904 (14)	174 (2)
O7—H7A···O4^vii	0.85 (1)	1.89 (2)	2.7298 (15)	170 (2)
O7—H7B···O2^vi	0.85 (1)	1.89 (1)	2.7266 (14)	169 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1, −y+3/2, z−1/2; (v) x−1, y, z; (vi) −x+1, y−1/2, −z+1/2; (vii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	(C₆H₈N₄)[Mn(H₂O)₆](SO₄)₂
M_r	491.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.0625 (7), 11.606 (2), 12.218 (2)
β (°)	91.65 (1)
V (Å³)	859.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.4 × 0.3 × 0.2

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick,1996)
T_min, T_max	0.686, 0.800
No. of measured, independent and observed [I > 2σ(I)] reflections	9389, 1954, 1897
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.066, 1.06
No. of reflections	1954
No. of parameters	142
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.65

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mn1—O6	2.1335 (10)	Mn1—O5	2.2218 (10)
Mn1—O7	2.1856 (10)	C3—C3ⁱ	1.445 (2)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱ	0.88	1.93	2.7699 (15)	159
N1—H1A···O2ⁱⁱ	0.88	2.45	3.0994 (15)	131
N2—H2A···O3ⁱⁱⁱ	0.88	1.92	2.7562 (16)	159
O5—H5A···O2	0.843 (14)	1.917 (15)	2.7600 (15)	176.8 (18)
O5—H5B···O3^iv	0.813 (14)	2.088 (15)	2.8638 (15)	159.7 (17)
O6—H6A···O4^v	0.839 (14)	1.908 (15)	2.7402 (15)	171.2 (18)
O6—H6B···O1^vi	0.846 (14)	1.847 (15)	2.6904 (14)	174.2 (18)
O7—H7A···O4^vii	0.851 (14)	1.888 (15)	2.7298 (15)	169.5 (18)
O7—H7B···O2^v	0.846 (14)	1.892 (14)	2.7266 (14)	169.0 (17)

Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, −y+3/2, z−1/2; (iv) x−1, y, z; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z; (vii) −x+2, y−1/2, −z+1/2.

Acknowledgements

MAK thanks Bayero University, Kano, Nigeria, for funding.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rekik, W., Naili, H., Bataille, T., Roisnel, T. & Mhiri, T. (2006). Inorg. Chim. Acta, 359, 3954–3962. Web of Science CSD CrossRef CAS Google Scholar
Rekik, W., Naili, H., Mhiri, T. & Bataille, T. (2007). J. Chem. Crystallogr. 37, 149–155. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar