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

Gao, S.; Ng, S.W.

doi:10.1107/S1600536810035233

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1223

doi:10.1107/S1600536810035233

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

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

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 30 August 2010; accepted 1 September 2010; online 8 September 2010)

In the title compound, [Mn(C₅H₄N₃O₂)₂(H₂O)₂]·H₂O, the Mn^II cation, located on a twofold rotation axis, is N,O-chelated by two 3-aminopyrazine-2-carboxylate anions and coordinated by two water molecules in a distorted octahedral geometry. The uncoordinated water molecules lies on a twofold rotation axis. Adjacent molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network motif.

Related literature

For the isostructural magnesium analog, see: Ptasiewicz-Bak & Leciejewicz (1997 ); Marsh (2004 ).

Experimental

Crystal data

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]·H₂O
M_r = 385.21
Orthorhombic, F d d 2
a = 8.3107 (6) Å
b = 29.5862 (17) Å
c = 12.3791 (7) Å
V = 3043.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.875, T_max = 0.930
7239 measured reflections
1684 independent reflections
1086 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.165
S = 1.14
1684 reflections
126 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 775 Friedel pairs
Flack parameter: −0.02 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O2ⁱ	0.84 (7)	1.89 (3)	2.704 (7)	162 (9)
O1w—H12⋯N2ⁱⁱ	0.84 (7)	2.02 (4)	2.792 (7)	152 (9)
O2w—H2⋯O1	0.84 (7)	2.10 (4)	2.902 (7)	159 (10)
N3—H31⋯O2	0.88 (7)	2.17 (9)	2.690 (8)	118 (8)
N3—H32⋯O2wⁱⁱⁱ	0.88 (3)	2.15 (3)	3.001 (7)	161 (9)
Symmetry codes: (i) $[-x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 4}}, -y+{\script{3\over 4}}, z+{\script{1\over 4}}]$ ; (iii) $[-x-{\script{1\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (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/S1600536810035233/xu5022sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035233/xu5022Isup2.hkl

checkCIF report

Comment top

The crystal structure of Mg(H₂O)₂(C₅H₄N₃O₂)₂^.H₂O was described in the Cc space group (Ptasiewicz-Bak & Leciejewicz, 1997); the space group was revised to the Fdd2 space group (Marsh, 2004). The manganese analog (Scheme I) is isostructural; The water-coordinated manganese atom is N,O-chelated by the carboxylate ion (Fig. 2) in an octahedral environment. The mononuclear and lattice water both lie on a twofold rotation axis. Adjacent molecules are linked by O–H···O and N–H···O hydrogen bonds into a three-dimensional network motif.

Related literature top

For the isostructural magnesium analog, see: Ptasiewicz-Bak & Leciejewicz (1997); Marsh (2004).

Experimental top

Manganese acetate (1 mmol) and 2-aminopyrazine-3-carboxylic acid (2 mmol) and sodium hydroxide (2 mmol) were dissolved in a small volume of water to give a light yellow solution. Prismatic crystals 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: CrystalStructure (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(C₅H₄N₃O₂)₂^.H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The Mn and lattice water molecule lie on a twofold rotation axis. Symmetry-related atoms are not labeled.

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

Crystal data top

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]·H₂O	F(000) = 1576
M_r = 385.21	D_x = 1.681 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 4731 reflections
a = 8.3107 (6) Å	θ = 3.0–27.4°
b = 29.5862 (17) Å	µ = 0.92 mm⁻¹
c = 12.3791 (7) Å	T = 293 K
V = 3043.8 (3) Å³	Prism, yellow
Z = 8	0.15 × 0.10 × 0.08 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1684 independent reflections
Radiation source: fine-focus sealed tube	1086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.4°, θ_min = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −38→38
T_min = 0.875, T_max = 0.930	l = −16→15
7239 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0722P)² + 15.3101P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.165	(Δ/σ)_max = 0.001
S = 1.14	Δρ_max = 0.50 e Å⁻³
1684 reflections	Δρ_min = −0.90 e Å⁻³
126 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0014 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 775 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (5)

Crystal data top

[Mn(C₅H₄N₃O₂)₂(H₂O)₂]·H₂O	V = 3043.8 (3) Å³
M_r = 385.21	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 8.3107 (6) Å	µ = 0.92 mm⁻¹
b = 29.5862 (17) Å	T = 293 K
c = 12.3791 (7) Å	0.15 × 0.10 × 0.08 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1684 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1086 reflections with I > 2σ(I)
T_min = 0.875, T_max = 0.930	R_int = 0.056
7239 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.0722P)² + 15.3101P] where P = (F_o² + 2F_c²)/3
S = 1.14	Δρ_max = 0.50 e Å⁻³
1684 reflections	Δρ_min = −0.90 e Å⁻³
126 parameters	Absolute structure: Flack (1983), 775 Friedel pairs
6 restraints	Absolute structure parameter: −0.02 (5)

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

	x	y	z	U_iso*/U_eq
Mn1	0.2500	0.2500	0.53687 (11)	0.0378 (4)
O1	0.0649 (6)	0.26569 (16)	0.4190 (4)	0.0457 (11)
O2	−0.0500 (7)	0.31796 (16)	0.3169 (4)	0.0606 (16)
O1W	0.0675 (8)	0.24512 (17)	0.6593 (4)	0.0561 (16)
H11	0.084 (11)	0.225 (2)	0.706 (5)	0.084*
H12	0.006 (9)	0.267 (2)	0.675 (8)	0.084*
O2W	−0.2500	0.2500	0.5133 (9)	0.069 (3)
H2	−0.164 (7)	0.248 (4)	0.478 (7)	0.104*
N1	0.2472 (6)	0.32757 (14)	0.5175 (4)	0.0348 (13)
N2	0.2176 (7)	0.41941 (18)	0.4774 (5)	0.0515 (16)
N3	0.0251 (9)	0.4054 (2)	0.3489 (6)	0.0634 (19)
H31	−0.048 (9)	0.391 (3)	0.311 (7)	0.095*
H32	0.035 (11)	0.4344 (8)	0.335 (8)	0.095*
C1	0.0468 (8)	0.30645 (19)	0.3886 (5)	0.0409 (14)
C2	0.1439 (7)	0.34192 (19)	0.4439 (5)	0.0349 (12)
C3	0.1271 (8)	0.3890 (2)	0.4229 (5)	0.0427 (14)
C4	0.3184 (10)	0.4035 (2)	0.5501 (7)	0.0587 (19)
H4	0.3808	0.4241	0.5886	0.070*
C5	0.3368 (9)	0.3572 (2)	0.5727 (6)	0.0503 (17)
H5	0.4095	0.3474	0.6248	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0457 (7)	0.0301 (6)	0.0376 (7)	0.0012 (7)	0.000	0.000
O1	0.051 (3)	0.035 (2)	0.051 (3)	−0.001 (2)	−0.009 (2)	0.000 (2)
O2	0.076 (4)	0.050 (2)	0.055 (4)	0.010 (2)	−0.035 (3)	0.000 (2)
O1W	0.070 (4)	0.048 (3)	0.050 (3)	0.010 (3)	0.019 (3)	0.008 (2)
O2W	0.044 (4)	0.055 (4)	0.109 (10)	−0.009 (4)	0.000	0.000
N1	0.041 (2)	0.030 (2)	0.033 (4)	−0.001 (2)	−0.009 (3)	0.003 (2)
N2	0.056 (4)	0.039 (3)	0.059 (4)	−0.015 (3)	−0.008 (3)	0.004 (3)
N3	0.075 (5)	0.042 (3)	0.073 (5)	−0.001 (3)	−0.029 (4)	0.019 (3)
C1	0.050 (4)	0.033 (3)	0.040 (3)	0.001 (3)	−0.001 (3)	−0.003 (3)
C2	0.041 (3)	0.034 (3)	0.030 (3)	0.002 (2)	−0.008 (3)	−0.003 (2)
C3	0.046 (4)	0.037 (3)	0.044 (4)	−0.001 (3)	−0.001 (3)	0.006 (3)
C4	0.063 (4)	0.045 (4)	0.068 (5)	−0.019 (3)	−0.014 (4)	0.013 (4)
C5	0.055 (4)	0.043 (3)	0.053 (4)	−0.007 (3)	−0.021 (3)	0.006 (3)

Geometric parameters (Å, º) top

Mn1—O1Wⁱ	2.149 (6)	N1—C5	1.338 (8)
Mn1—O1W	2.149 (6)	N2—C4	1.316 (10)
Mn1—O1	2.170 (5)	N2—C3	1.352 (8)
Mn1—O1ⁱ	2.170 (5)	N3—C3	1.339 (8)
Mn1—N1ⁱ	2.308 (4)	N3—H31	0.88 (7)
Mn1—N1	2.308 (4)	N3—H32	0.88 (3)
O1—C1	1.273 (7)	C1—C2	1.490 (8)
O2—C1	1.245 (8)	C2—C3	1.424 (8)
O1W—H11	0.84 (7)	C4—C5	1.409 (9)
O1W—H12	0.84 (7)	C4—H4	0.9300
O2W—H2	0.84 (7)	C5—H5	0.9300
N1—C2	1.322 (7)

O1Wⁱ—Mn1—O1W	90.3 (4)	C5—N1—Mn1	126.3 (4)
O1Wⁱ—Mn1—O1	163.73 (16)	C4—N2—C3	117.2 (6)
O1W—Mn1—O1	89.33 (18)	C3—N3—H31	129 (7)
O1Wⁱ—Mn1—O1ⁱ	89.33 (18)	C3—N3—H32	115 (6)
O1W—Mn1—O1ⁱ	163.73 (16)	H31—N3—H32	115 (9)
O1—Mn1—O1ⁱ	95.5 (3)	O2—C1—O1	123.1 (6)
O1Wⁱ—Mn1—N1ⁱ	97.65 (18)	O2—C1—C2	119.0 (5)
O1W—Mn1—N1ⁱ	90.79 (18)	O1—C1—C2	117.9 (6)
O1—Mn1—N1ⁱ	98.61 (18)	N1—C2—C3	120.2 (5)
O1ⁱ—Mn1—N1ⁱ	73.16 (17)	N1—C2—C1	116.2 (5)
O1Wⁱ—Mn1—N1	90.79 (18)	C3—C2—C1	123.5 (5)
O1W—Mn1—N1	97.65 (18)	N3—C3—N2	116.9 (6)
O1—Mn1—N1	73.16 (17)	N3—C3—C2	122.7 (6)
O1ⁱ—Mn1—N1	98.61 (18)	N2—C3—C2	120.3 (6)
N1ⁱ—Mn1—N1	168.0 (3)	N2—C4—C5	123.5 (7)
C1—O1—Mn1	119.0 (4)	N2—C4—H4	118.2
Mn1—O1W—H11	115 (6)	C5—C4—H4	118.2
Mn1—O1W—H12	122 (7)	N1—C5—C4	118.4 (6)
H11—O1W—H12	119 (10)	N1—C5—H5	120.8
C2—N1—C5	120.2 (5)	C4—C5—H5	120.8
C2—N1—Mn1	113.4 (4)

O1Wⁱ—Mn1—O1—C1	14.2 (12)	Mn1—N1—C2—C3	179.6 (5)
O1W—Mn1—O1—C1	102.9 (5)	C5—N1—C2—C1	−178.6 (6)
O1ⁱ—Mn1—O1—C1	−92.7 (5)	Mn1—N1—C2—C1	1.0 (7)
N1ⁱ—Mn1—O1—C1	−166.4 (5)	O2—C1—C2—N1	−178.5 (6)
N1—Mn1—O1—C1	4.7 (5)	O1—C1—C2—N1	3.0 (9)
O1Wⁱ—Mn1—N1—C2	179.9 (4)	O2—C1—C2—C3	3.0 (9)
O1W—Mn1—N1—C2	−89.8 (4)	O1—C1—C2—C3	−175.5 (6)
O1—Mn1—N1—C2	−2.8 (4)	C4—N2—C3—N3	−179.9 (8)
O1ⁱ—Mn1—N1—C2	90.4 (4)	C4—N2—C3—C2	−0.7 (10)
N1ⁱ—Mn1—N1—C2	44.8 (4)	N1—C2—C3—N3	179.6 (7)
O1Wⁱ—Mn1—N1—C5	−0.6 (6)	C1—C2—C3—N3	−1.9 (10)
O1W—Mn1—N1—C5	89.8 (6)	N1—C2—C3—N2	0.5 (10)
O1—Mn1—N1—C5	176.8 (6)	C1—C2—C3—N2	178.9 (6)
O1ⁱ—Mn1—N1—C5	−90.0 (6)	C3—N2—C4—C5	0.5 (13)
N1ⁱ—Mn1—N1—C5	−135.6 (5)	C2—N1—C5—C4	−0.2 (10)
Mn1—O1—C1—O2	175.7 (5)	Mn1—N1—C5—C4	−179.8 (5)
Mn1—O1—C1—C2	−5.8 (8)	N2—C4—C5—N1	0.0 (13)
C5—N1—C2—C3	0.0 (9)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O2ⁱⁱ	0.84 (7)	1.89 (3)	2.704 (7)	162 (9)
O1w—H12···N2ⁱⁱⁱ	0.84 (7)	2.02 (4)	2.792 (7)	152 (9)
O2w—H2···O1	0.84 (7)	2.10 (4)	2.902 (7)	159 (10)
N3—H31···O2	0.88 (7)	2.17 (9)	2.690 (8)	118 (8)
N3—H32···O2w^iv	0.88 (3)	2.15 (3)	3.001 (7)	161 (9)

Symmetry codes: (ii) −x, −y+1/2, z+1/2; (iii) x−1/4, −y+3/4, z+1/4; (iv) −x−1/4, y+1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	[Mn(C₅H₄N₃O₂)₂(H₂O)₂]·H₂O
M_r	385.21
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	293
a, b, c (Å)	8.3107 (6), 29.5862 (17), 12.3791 (7)
V (Å³)	3043.8 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.15 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.875, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	7239, 1684, 1086
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.165, 1.14
No. of reflections	1684
No. of parameters	126
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.0722P)² + 15.3101P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.90
Absolute structure	Flack (1983), 775 Friedel pairs
Absolute structure parameter	−0.02 (5)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (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···O2ⁱ	0.84 (7)	1.89 (3)	2.704 (7)	162 (9)
O1w—H12···N2ⁱⁱ	0.84 (7)	2.02 (4)	2.792 (7)	152 (9)
O2w—H2···O1	0.84 (7)	2.10 (4)	2.902 (7)	159 (10)
N3—H31···O2	0.88 (7)	2.17 (9)	2.690 (8)	118 (8)
N3—H32···O2wⁱⁱⁱ	0.88 (3)	2.15 (3)	3.001 (7)	161 (9)

Symmetry codes: (i) −x, −y+1/2, z+1/2; (ii) x−1/4, −y+3/4, z+1/4; (iii) −x−1/4, y+1/4, z−1/4.

Acknowledgements

We thank 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), Heilongjiang University and the University of Malaya for supporting this study.

References

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