trans-Bis(acetato-κO)diaquabis­(2-amino­pyrazine-κN4)manganese(II) dihydrate

Gao, S.; Ng, S.W.

doi:10.1107/S1600536811028583

metal-organic compounds

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Volume 67| Part 8| August 2011| Page m1140

doi:10.1107/S1600536811028583

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trans-Bis(acetato-κO)diaquabis(2-aminopyrazine-κN⁴)manganese(II) dihydrate

Shan Gao ^a and Seik Weng Ng ^b ^*

^aKey Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and, Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 July 2011; accepted 16 July 2011; online 23 July 2011)

The Mn^II atom in the title compound, [Mn(CH₃COO)₂(C₄H₅N₃)₂(H₂O)₂]·2H₂O, is situated on a center of inversion and shows an octahedral coordination polyhedron made up by four O atoms and two N atoms. The octahedron is somewhat tetragonally distorted owing to the longer Mn—N bond [2.323 (3) Å]. The mononuclear complex molecule and uncoordinated water molecules are linked by O—H⋯N, N—H⋯O and O—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For the crystal structure of manganese acetate dihydrate, see: Cheng & Wang (1991 ).

Experimental

Crystal data

[Mn(C₂H₃O₂)₂(C₄H₅N₃)₂(H₂O)₂]·2H₂O
M_r = 435.31
Triclinic, $[P \overline 1]$
a = 7.0761 (7) Å
b = 8.5411 (8) Å
c = 9.5162 (10) Å
α = 100.866 (3)°
β = 105.036 (3)°
γ = 110.250 (3)°
V = 495.92 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.10 × 0.08 × 0.05 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.932, T_max = 0.965
4911 measured reflections
2249 independent reflections
1558 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.159
S = 1.07
2249 reflections
148 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.80 e Å⁻³
Δρ_min = −1.01 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O2	0.84 (1)	1.89 (2)	2.690 (4)	160 (5)
O1w—H12⋯N2ⁱ	0.84 (1)	2.02 (2)	2.837 (4)	165 (5)
O2w—H21⋯O1ⁱⁱ	0.84 (1)	2.02 (1)	2.851 (4)	171 (4)
O2w—H22⋯O2ⁱⁱⁱ	0.84 (1)	1.90 (2)	2.726 (5)	167 (5)
N3—H31⋯O2w	0.88 (1)	1.98 (1)	2.859 (5)	178 (6)
Symmetry codes: (i) x, y-1, z; (ii) x, y, z-1; (iii) x-1, y, z-1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811028583/im2304sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028583/im2304Isup2.hkl

checkCIF report

Comment top

There are few crystal structure studies of N-heterocyclic adducts of manganese acetate, the latter crystallizing as a dihydrate (Cheng & Wang, 1991). Other first-row transition metal acetates furnish a large number of adducts. The Mn^II atom in Mn(H₂O)₂(C₂H₃O₂)₂(C₄H₅N₃)₂ × 2 H₂O (Scheme I, Fig. 1) shows an octahedral coordination polyhedron made up by four O atoms and two N atoms. The octahedron is somewhat tetragonally distorted owing to the longer Mn–N bond. The mononuclear complex molecule and lattice water molecules are linked hydrogen bonds to generate a three-dimensional network (Table 1, Fig. 2).

Related literature top

For the crystal structure of manganese acetate dihydrate, see: Cheng & Wang (1991).

Experimental top

To an aqueous solution of 2-aminopyrazine (1 mmol) was added manganese acetate tetrahydrate (1 mmol). The mixture was stirred for 30 min and then filtered. Colorless crystals of the title complex separated from the solution after a few days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Mn(H₂O)₂(C₂H₃O₂)₂(C₄H₅N₃)₂ × 2 H₂O at the 50% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Three-dimensional hydrogen-bonded network of the title compound. Hydrogen bonds are depicted as dashed lines.

trans-Bis(acetato-κO)diaquabis(2-aminopyrazine- κN⁴)manganese(II) dihydrate top

Crystal data top

[Mn(C₂H₃O₂)₂(C₄H₅N₃)₂(H₂O)₂]·2H₂O	Z = 1
M_r = 435.31	F(000) = 227
Triclinic, P1	D_x = 1.458 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0761 (7) Å	Cell parameters from 3626 reflections
b = 8.5411 (8) Å	θ = 3.3–27.5°
c = 9.5162 (10) Å	µ = 0.72 mm⁻¹
α = 100.866 (3)°	T = 293 K
β = 105.036 (3)°	Prism, colorless
γ = 110.250 (3)°	0.10 × 0.08 × 0.05 mm
V = 495.92 (9) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2249 independent reflections
Radiation source: fine-focus sealed tube	1558 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
T_min = 0.932, T_max = 0.965	k = −11→11
4911 measured reflections	l = −12→12

Refinement top

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.159	w = 1/[σ²(F_o²) + (0.0633P)² + 0.7384P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2249 reflections	Δρ_max = 0.80 e Å⁻³
148 parameters	Δρ_min = −1.01 e Å⁻³
8 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (8)

Crystal data top

[Mn(C₂H₃O₂)₂(C₄H₅N₃)₂(H₂O)₂]·2H₂O	γ = 110.250 (3)°
M_r = 435.31	V = 495.92 (9) Å³
Triclinic, P1	Z = 1
a = 7.0761 (7) Å	Mo Kα radiation
b = 8.5411 (8) Å	µ = 0.72 mm⁻¹
c = 9.5162 (10) Å	T = 293 K
α = 100.866 (3)°	0.10 × 0.08 × 0.05 mm
β = 105.036 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2249 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1558 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.965	R_int = 0.033
4911 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	8 restraints
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.80 e Å⁻³
2249 reflections	Δρ_min = −1.01 e Å⁻³
148 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	0.5000	0.0358 (3)
O1	0.6700 (4)	0.6113 (3)	0.7465 (3)	0.0413 (6)
O2	0.9808 (5)	0.5959 (6)	0.7684 (4)	0.0826 (12)
O1W	0.7647 (4)	0.4463 (3)	0.4659 (3)	0.0414 (6)
H11	0.858 (6)	0.503 (5)	0.553 (3)	0.082 (18)*
H12	0.763 (8)	0.346 (3)	0.440 (5)	0.09 (2)*
O2W	0.4054 (5)	0.6764 (5)	−0.0904 (4)	0.0719 (10)
H21	0.470 (6)	0.649 (7)	−0.147 (4)	0.085 (18)*
H22	0.273 (2)	0.636 (6)	−0.141 (4)	0.084 (18)*
N1	0.6498 (5)	0.7758 (4)	0.4722 (3)	0.0406 (7)
N2	0.7601 (5)	1.1077 (4)	0.4338 (4)	0.0464 (8)
N3	0.6301 (9)	0.9802 (5)	0.1732 (4)	0.0738 (13)
H31	0.562 (9)	0.888 (5)	0.091 (4)	0.111*
H32	0.654 (10)	1.085 (4)	0.163 (7)	0.111*
C1	0.7478 (6)	0.9231 (5)	0.5927 (4)	0.0465 (9)
H1	0.7803	0.9147	0.6914	0.056*
C2	0.7999 (7)	1.0845 (5)	0.5717 (4)	0.0476 (9)
H2	0.8665	1.1830	0.6576	0.057*
C3	0.6692 (7)	0.9628 (5)	0.3141 (4)	0.0448 (9)
C4	0.6154 (6)	0.7964 (5)	0.3351 (4)	0.0408 (8)
H4	0.5537	0.6977	0.2497	0.049*
C5	0.8583 (6)	0.6370 (5)	0.8229 (4)	0.0428 (8)
C6	0.9380 (8)	0.7229 (7)	0.9942 (5)	0.0659 (13)
H6A	1.0903	0.7569	1.0363	0.099*
H6B	0.8658	0.6414	1.0402	0.099*
H6C	0.9085	0.8248	1.0145	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0395 (5)	0.0376 (4)	0.0301 (4)	0.0194 (3)	0.0089 (3)	0.0084 (3)
O1	0.0417 (14)	0.0507 (15)	0.0297 (12)	0.0216 (12)	0.0082 (10)	0.0099 (11)
O2	0.0530 (19)	0.146 (3)	0.0437 (17)	0.054 (2)	0.0102 (14)	0.0016 (19)
O1W	0.0385 (14)	0.0421 (15)	0.0414 (15)	0.0189 (11)	0.0122 (12)	0.0067 (12)
O2W	0.0502 (19)	0.097 (3)	0.0474 (18)	0.0277 (19)	0.0103 (15)	−0.0094 (17)
N1	0.0447 (17)	0.0347 (15)	0.0428 (17)	0.0181 (13)	0.0142 (14)	0.0116 (13)
N2	0.057 (2)	0.0371 (16)	0.0435 (17)	0.0194 (14)	0.0172 (15)	0.0115 (14)
N3	0.124 (4)	0.048 (2)	0.042 (2)	0.030 (2)	0.022 (2)	0.0184 (17)
C1	0.054 (2)	0.045 (2)	0.0352 (19)	0.0192 (17)	0.0118 (16)	0.0099 (16)
C2	0.055 (2)	0.0359 (19)	0.041 (2)	0.0151 (17)	0.0117 (17)	0.0050 (16)
C3	0.055 (2)	0.042 (2)	0.0385 (19)	0.0226 (17)	0.0156 (17)	0.0115 (16)
C4	0.047 (2)	0.0354 (18)	0.0382 (19)	0.0155 (15)	0.0159 (16)	0.0093 (15)
C5	0.045 (2)	0.044 (2)	0.0321 (18)	0.0159 (16)	0.0069 (15)	0.0099 (15)
C6	0.059 (3)	0.094 (4)	0.033 (2)	0.034 (3)	0.0049 (19)	0.005 (2)

Geometric parameters (Å, º) top

Mn1—O1Wⁱ	2.163 (3)	N2—C3	1.335 (5)
Mn1—O1W	2.163 (3)	N2—C2	1.336 (5)
Mn1—O1ⁱ	2.181 (2)	N3—C3	1.344 (5)
Mn1—O1	2.181 (2)	N3—H31	0.879 (10)
Mn1—N1ⁱ	2.323 (3)	N3—H32	0.878 (10)
Mn1—N1	2.323 (3)	C1—C2	1.366 (5)
O1—C5	1.260 (4)	C1—H1	0.9300
O2—C5	1.232 (5)	C2—H2	0.9300
O1W—H11	0.840 (10)	C3—C4	1.406 (5)
O1W—H12	0.841 (10)	C4—H4	0.9300
O2W—H21	0.838 (10)	C5—C6	1.516 (5)
O2W—H22	0.838 (10)	C6—H6A	0.9600
N1—C4	1.321 (5)	C6—H6B	0.9600
N1—C1	1.348 (5)	C6—H6C	0.9600

O1Wⁱ—Mn1—O1W	180.000 (1)	C3—N3—H31	121 (4)
O1Wⁱ—Mn1—O1ⁱ	91.79 (10)	C3—N3—H32	119 (4)
O1W—Mn1—O1ⁱ	88.21 (9)	H31—N3—H32	119 (6)
O1Wⁱ—Mn1—O1	88.21 (10)	N1—C1—C2	120.9 (4)
O1W—Mn1—O1	91.79 (10)	N1—C1—H1	119.6
O1ⁱ—Mn1—O1	180.000 (1)	C2—C1—H1	119.6
O1Wⁱ—Mn1—N1ⁱ	90.34 (10)	N2—C2—C1	123.2 (3)
O1W—Mn1—N1ⁱ	89.66 (10)	N2—C2—H2	118.4
O1ⁱ—Mn1—N1ⁱ	89.93 (10)	C1—C2—H2	118.4
O1—Mn1—N1ⁱ	90.07 (10)	N2—C3—N3	118.3 (4)
O1Wⁱ—Mn1—N1	89.66 (10)	N2—C3—C4	120.7 (3)
O1W—Mn1—N1	90.34 (10)	N3—C3—C4	121.0 (3)
O1ⁱ—Mn1—N1	90.07 (10)	N1—C4—C3	122.1 (3)
O1—Mn1—N1	89.93 (10)	N1—C4—H4	118.9
N1ⁱ—Mn1—N1	180.000 (1)	C3—C4—H4	118.9
C5—O1—Mn1	128.8 (2)	O2—C5—O1	124.7 (3)
Mn1—O1W—H11	99 (3)	O2—C5—C6	118.0 (4)
Mn1—O1W—H12	125 (4)	O1—C5—C6	117.4 (4)
H11—O1W—H12	109 (2)	C5—C6—H6A	109.5
H21—O2W—H22	110 (2)	C5—C6—H6B	109.5
C4—N1—C1	116.8 (3)	H6A—C6—H6B	109.5
C4—N1—Mn1	120.7 (2)	C5—C6—H6C	109.5
C1—N1—Mn1	121.9 (2)	H6A—C6—H6C	109.5
C3—N2—C2	116.2 (3)	H6B—C6—H6C	109.5

O1Wⁱ—Mn1—O1—C5	−175.9 (3)	C4—N1—C1—C2	2.6 (6)
O1W—Mn1—O1—C5	4.1 (3)	Mn1—N1—C1—C2	−168.1 (3)
N1ⁱ—Mn1—O1—C5	93.7 (3)	C3—N2—C2—C1	−1.6 (6)
N1—Mn1—O1—C5	−86.3 (3)	N1—C1—C2—N2	−0.5 (6)
O1Wⁱ—Mn1—N1—C4	−95.9 (3)	C2—N2—C3—N3	−178.7 (4)
O1W—Mn1—N1—C4	84.1 (3)	C2—N2—C3—C4	1.5 (6)
O1ⁱ—Mn1—N1—C4	−4.2 (3)	C1—N1—C4—C3	−2.7 (5)
O1—Mn1—N1—C4	175.8 (3)	Mn1—N1—C4—C3	168.1 (3)
O1Wⁱ—Mn1—N1—C1	74.3 (3)	N2—C3—C4—N1	0.7 (6)
O1W—Mn1—N1—C1	−105.7 (3)	N3—C3—C4—N1	−179.1 (4)
O1ⁱ—Mn1—N1—C1	166.1 (3)	Mn1—O1—C5—O2	−2.8 (6)
O1—Mn1—N1—C1	−13.9 (3)	Mn1—O1—C5—C6	178.0 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2	0.84 (1)	1.89 (2)	2.690 (4)	160 (5)
O1w—H12···N2ⁱⁱ	0.84 (1)	2.02 (2)	2.837 (4)	165 (5)
O2w—H21···O1ⁱⁱⁱ	0.84 (1)	2.02 (1)	2.851 (4)	171 (4)
O2w—H22···O2^iv	0.84 (1)	1.90 (2)	2.726 (5)	167 (5)
N3—H31···O2w	0.88 (1)	1.98 (1)	2.859 (5)	178 (6)

Symmetry codes: (ii) x, y−1, z; (iii) x, y, z−1; (iv) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	[Mn(C₂H₃O₂)₂(C₄H₅N₃)₂(H₂O)₂]·2H₂O
M_r	435.31
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0761 (7), 8.5411 (8), 9.5162 (10)
α, β, γ (°)	100.866 (3), 105.036 (3), 110.250 (3)
V (Å³)	495.92 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.10 × 0.08 × 0.05

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.932, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	4911, 2249, 1558
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.159, 1.07
No. of reflections	2249
No. of parameters	148
No. of restraints	8
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −1.01

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2	0.84 (1)	1.89 (2)	2.690 (4)	160 (5)
O1w—H12···N2ⁱ	0.84 (1)	2.02 (2)	2.837 (4)	165 (5)
O2w—H21···O1ⁱⁱ	0.84 (1)	2.02 (1)	2.851 (4)	171 (4)
O2w—H22···O2ⁱⁱⁱ	0.84 (1)	1.90 (2)	2.726 (5)	167 (5)
N3—H31···O2w	0.88 (1)	1.98 (1)	2.859 (5)	178 (6)

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

Acknowledgements

This work was supported by the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Innovation Team of the Education Bureau of Heilongjiang Province (No. 2010 t d03), the Key Project of the Education Bureau of Heilongjiang Province (No. 12511z023) and the University of Malaya.

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