Bis(3-amino­pyrazine-2-carboxyl­ato-κ2N1,O)diaqua­manganese(II)

Zheng, M.-Y.; Wei, Y.-S.; Geng, W.; Fan, G.

doi:10.1107/S1600536810034835

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1228

doi:10.1107/S1600536810034835

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Bis(3-aminopyrazine-2-carboxylato-κ²N¹,O)diaquamanganese(II)

Min-Yan Zheng,^a ^* Yong-Sheng Wei,^a Wei Geng ^a and Guang Fan ^a

^aCollege of Chemistry & Chemical Engineering, Xianyang Normal University, Xianyang 712000, Shaanxi, People's Republic of China
^*Correspondence e-mail: zmy71@126.com

(Received 10 August 2010; accepted 29 August 2010; online 8 September 2010)

The Mn^II atom in the title compound, [Mn(C₅H₄N₃O₂)₂(H₂O)₂], exhibits an octahedral geometry comprising the two O atoms and two N atoms from two 3-aminopyrazine-2-carboxylate ligands, which act as chelating ligands, and two water molecules. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds link adjacent molecules into a three-dimensional network. The molecule lies on a twofold rotation axis.

Related literature

For the nickel(II) analog, see: Ptasiewicz-Bak & Leciejewicz (1999 ).

Experimental

Crystal data

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]
M_r = 367.20
Monoclinic, C 2/c
a = 7.9257 (11) Å
b = 12.6994 (18) Å
c = 13.663 (2) Å
β = 91.903 (2)°
V = 1374.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.889, T_max = 0.924
3373 measured reflections
1221 independent reflections
1114 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.096
S = 1.09
1221 reflections
112 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3C⋯O1ⁱ	0.86	2.33	3.044 (3)	141
N3—H3D⋯O2	0.86	2.07	2.703 (4)	130
O3—H3B⋯N2ⁱⁱ	0.89 (1)	1.95 (1)	2.833 (3)	170 (3)
O3—H3A⋯O2ⁱⁱⁱ	0.89 (1)	1.75 (1)	2.637 (3)	171 (3)
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034835/ng5015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034835/ng5015Isup2.hkl

checkCIF report

Related literature top

For the nickel(II) analog, see: Ptasiewicz-Bak & Leciejewicz (1999).

Experimental top

The title complex was obtained as the main phase from the hydrothermal reaction of manganese sulfate tetrahydrate (0.0189 g) and 3-aminopyrazine-2-carboxylic acid (0.0913 g) in a 1:2 molar ratio. The reactants along with water were placed in a Teflon-lined stainless steel Parr bomb; the bomb was held at 413 K for three days. After cooling to room temperature, pink crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure with the atom-labling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Three dimensional network of the title complex connected through hydrogen bonding.

Bis(3-aminopyrazine-2-carboxylato-κ²N¹,O)diaquamanganese(II) top

Crystal data top

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]	F(000) = 748
M_r = 367.20	D_x = 1.775 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9257 (11) Å	Cell parameters from 117 reflections
b = 12.6994 (18) Å	θ = 2.5–18.9°
c = 13.663 (2) Å	µ = 1.01 mm⁻¹
β = 91.903 (2)°	T = 296 K
V = 1374.4 (3) Å³	Block, pink
Z = 4	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker SMART APEX diffractometer	1221 independent reflections
Radiation source: fine-focus sealed tube	1114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.1°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
T_min = 0.889, T_max = 0.924	k = −15→15
3373 measured reflections	l = −16→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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0509P)² + 1.9431P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1221 reflections	Δρ_max = 0.36 e Å⁻³
112 parameters	Δρ_min = −0.22 e Å⁻³
2 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: 0.0048 (10)

Crystal data top

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]	V = 1374.4 (3) Å³
M_r = 367.20	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 7.9257 (11) Å	µ = 1.01 mm⁻¹
b = 12.6994 (18) Å	T = 296 K
c = 13.663 (2) Å	0.12 × 0.10 × 0.08 mm
β = 91.903 (2)°

Data collection top

Bruker SMART APEX diffractometer	1221 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1114 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.924	R_int = 0.021
3373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	2 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.36 e Å⁻³
1221 reflections	Δρ_min = −0.22 e Å⁻³
112 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn1	0.5000	0.30461 (4)	0.2500	0.0254 (2)
O1	0.6806 (3)	0.42418 (16)	0.23675 (14)	0.0466 (5)
O2	0.8132 (3)	0.52317 (18)	0.12895 (17)	0.0645 (7)
O3	0.6893 (3)	0.19335 (16)	0.26050 (16)	0.0475 (5)
N1	0.5308 (3)	0.31144 (16)	0.09621 (16)	0.0332 (5)
N2	0.5990 (3)	0.3363 (2)	−0.09977 (17)	0.0425 (6)
N3	0.7654 (4)	0.4795 (2)	−0.0636 (2)	0.0573 (8)
H3C	0.7829	0.4858	−0.1251	0.069*
H3D	0.8113	0.5231	−0.0225	0.069*
C1	0.4598 (3)	0.2483 (2)	0.0281 (2)	0.0396 (7)
H1	0.3855	0.1957	0.0463	0.048*
C2	0.4971 (4)	0.2615 (2)	−0.0691 (2)	0.0430 (7)
H2	0.4485	0.2158	−0.1151	0.052*
C3	0.6674 (4)	0.4023 (2)	−0.0320 (2)	0.0386 (6)
C4	0.6355 (3)	0.3870 (2)	0.0689 (2)	0.0342 (6)
C5	0.7160 (4)	0.4498 (2)	0.1509 (2)	0.0406 (7)
H3B	0.764 (3)	0.181 (2)	0.2150 (18)	0.049*
H3A	0.678 (4)	0.1343 (15)	0.295 (2)	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0323 (3)	0.0239 (3)	0.0203 (3)	0.000	0.0081 (2)	0.000
O1	0.0624 (13)	0.0430 (11)	0.0349 (11)	−0.0126 (10)	0.0109 (9)	−0.0046 (9)
O2	0.0916 (18)	0.0529 (14)	0.0506 (14)	−0.0358 (13)	0.0258 (13)	−0.0123 (11)
O3	0.0556 (13)	0.0492 (13)	0.0389 (12)	0.0155 (10)	0.0185 (10)	0.0073 (9)
N1	0.0350 (12)	0.0326 (12)	0.0324 (12)	−0.0001 (9)	0.0070 (9)	0.0017 (9)
N2	0.0480 (14)	0.0488 (14)	0.0314 (12)	0.0033 (11)	0.0100 (10)	0.0017 (11)
N3	0.083 (2)	0.0478 (15)	0.0422 (15)	−0.0173 (14)	0.0232 (14)	0.0036 (12)
C1	0.0380 (15)	0.0445 (16)	0.0364 (15)	−0.0049 (12)	0.0022 (11)	−0.0001 (13)
C2	0.0429 (16)	0.0516 (17)	0.0347 (15)	−0.0040 (14)	0.0034 (12)	−0.0018 (13)
C3	0.0444 (16)	0.0358 (14)	0.0363 (15)	0.0057 (12)	0.0127 (12)	0.0038 (12)
C4	0.0380 (14)	0.0307 (13)	0.0346 (14)	0.0032 (11)	0.0113 (11)	0.0014 (11)
C5	0.0501 (17)	0.0339 (14)	0.0386 (16)	−0.0052 (13)	0.0162 (13)	−0.0027 (12)

Geometric parameters (Å, º) top

Mn1—O3ⁱ	2.062 (2)	N1—C1	1.337 (3)
Mn1—O3	2.062 (2)	N2—C2	1.324 (4)
Mn1—O1	2.099 (2)	N2—C3	1.350 (4)
Mn1—O1ⁱ	2.099 (2)	N3—C3	1.332 (4)
Mn1—N1	2.125 (2)	N3—H3C	0.8600
Mn1—N1ⁱ	2.125 (2)	N3—H3D	0.8600
O1—C5	1.257 (3)	C1—C2	1.381 (4)
O2—C5	1.252 (3)	C1—H1	0.9300
O3—H3B	0.887 (10)	C2—H2	0.9300
O3—H3A	0.891 (10)	C3—C4	1.422 (4)
N1—C4	1.330 (3)	C4—C5	1.501 (4)

O3ⁱ—Mn1—O3	93.50 (13)	C1—N1—Mn1	127.13 (18)
O3ⁱ—Mn1—O1	170.52 (8)	C2—N2—C3	117.6 (2)
O3—Mn1—O1	90.29 (9)	C3—N3—H3C	120.0
O3ⁱ—Mn1—O1ⁱ	90.29 (9)	C3—N3—H3D	120.0
O3—Mn1—O1ⁱ	170.52 (8)	H3C—N3—H3D	120.0
O1—Mn1—O1ⁱ	87.32 (12)	N1—C1—C2	119.9 (3)
O3ⁱ—Mn1—N1	93.80 (8)	N1—C1—H1	120.1
O3—Mn1—N1	89.40 (8)	C2—C1—H1	120.1
O1—Mn1—N1	77.54 (8)	N2—C2—C1	123.0 (3)
O1ⁱ—Mn1—N1	99.02 (8)	N2—C2—H2	118.5
O3ⁱ—Mn1—N1ⁱ	89.40 (8)	C1—C2—H2	118.5
O3—Mn1—N1ⁱ	93.80 (8)	N3—C3—N2	117.4 (3)
O1—Mn1—N1ⁱ	99.02 (8)	N3—C3—C4	122.6 (3)
O1ⁱ—Mn1—N1ⁱ	77.54 (8)	N2—C3—C4	120.0 (3)
N1—Mn1—N1ⁱ	175.33 (11)	N1—C4—C3	120.2 (2)
C5—O1—Mn1	116.20 (18)	N1—C4—C5	115.3 (2)
Mn1—O3—H3B	125 (2)	C3—C4—C5	124.5 (2)
Mn1—O3—H3A	122 (2)	O2—C5—O1	125.1 (3)
H3B—O3—H3A	107 (3)	O2—C5—C4	117.8 (2)
C4—N1—C1	119.3 (2)	O1—C5—C4	117.2 (2)
C4—N1—Mn1	113.60 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···O1ⁱⁱ	0.86	2.33	3.044 (3)	141
N3—H3D···O2	0.86	2.07	2.703 (4)	130
O3—H3B···N2ⁱⁱⁱ	0.89 (1)	1.95 (1)	2.833 (3)	170 (3)
O3—H3A···O2^iv	0.89 (1)	1.75 (1)	2.637 (3)	171 (3)

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

Experimental details

Crystal data
Chemical formula	[Mn(C₅H₄N₃O₂)₂(H₂O)₂]
M_r	367.20
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	7.9257 (11), 12.6994 (18), 13.663 (2)
β (°)	91.903 (2)
V (Å³)	1374.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.889, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	3373, 1221, 1114
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.096, 1.09
No. of reflections	1221
No. of parameters	112
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.22

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3C···O1ⁱ	0.86	2.33	3.044 (3)	140.8
N3—H3D···O2	0.86	2.07	2.703 (4)	130.0
O3—H3B···N2ⁱⁱ	0.887 (10)	1.954 (12)	2.833 (3)	170 (3)
O3—H3A···O2ⁱⁱⁱ	0.891 (10)	1.754 (12)	2.637 (3)	171 (3)

Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+3/2, −y+1/2, −z; (iii) −x+3/2, y−1/2, −z+1/2.

Acknowledgements

We gratefully acknowledge the Natural Science Foundation of Shaanxi Province (2009JQ2015, 2010JM2009), the Special Foundation of the Education Department of Shaanxi Province (09 J K798) and the Special Research Fund of Xianyang Normal University for Talent Introduction (08XSYK305, 09XSYK208).

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ptasiewicz-Bak, H. & Leciejewicz, J. (1999). Pol. J. Chem. 73, 717–725. CAS 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