Diaqua­bis(pyrazine-2-carboxyl­ato-κ2N1,O)manganese(II) dihydrate

Xie, H.-D.; Xie, C.-Z.; Dang, F.-F.

doi:10.1107/S1600536808006417

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page m558

doi:10.1107/S1600536808006417

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Diaquabis(pyrazine-2-carboxylato-κ²N¹,O)manganese(II) dihydrate

Hui-Dong Xie,^a ^* Cheng-Zhi Xie ^b and Fang-Fang Dang ^a

^aSchool of Science, Xi'an University of Architecture and Technology, Xi'an 710055, People's Republic of China, and ^bDepartment of Chemistry, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: xhd02@mails.thu.edu.cn

(Received 6 January 2008; accepted 7 March 2008; online 14 March 2008)

In the title compound, [Mn(C₅H₃N₂O₂)₂(H₂O)₂]·2H₂O, the Mn^II atom, lying on an inversion centre, has a distorted octahedral environment and the molecules are linked by O—H⋯O and N—H⋯O hydrogen bonds to form a three-dimensional supramolecular structure.

Related literature

For related literature, see: Ciurtin et al. (2002 ); Dong et al. (2000 ); Klein et al. (1982 ); O'Connor & Sinn (1981 ); Ptasiewicz-Bak et al. (1995 ).

Experimental

Crystal data

[Mn(C₅H₃N₂O₂)₂(H₂O)₂]·2H₂O
M_r = 373.19
Monoclinic, P 2₁ /n
a = 7.233 (2) Å
b = 13.003 (4) Å
c = 8.257 (3) Å
β = 102.207 (5)°
V = 759.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.91 mm⁻¹
T = 293 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.838, T_max = 0.914
4297 measured reflections
1552 independent reflections
1252 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 1.08
1552 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Mn1—O3	2.0670 (18)
Mn1—O1	2.0738 (16)
Mn1—N1	2.1246 (19)

O3—Mn1—O1ⁱ	90.24 (7)
O3—Mn1—O1	89.76 (7)
O3—Mn1—N1ⁱ	91.51 (8)
O1—Mn1—N1ⁱ	101.65 (7)
O3—Mn1—N1	88.49 (8)
O1—Mn1—N1	78.35 (7)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O4ⁱⁱ	0.85	1.79	2.639 (3)	176
O3—H3A⋯O2ⁱⁱⁱ	0.85	1.87	2.715 (2)	171
O4—H4A⋯O2^iv	0.85	1.98	2.806 (3)	164
O4—H4B⋯N2	0.85	2.03	2.865 (3)	170
Symmetry codes: (ii) x-1, y, z-1; (iii) -x+1, -y+1, -z; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); 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/S1600536808006417/cs2069sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006417/cs2069Isup2.hkl

checkCIF report

Comment top

In the past decades, self-assembly processes involving metal ions and organic ligands directed by either metal coordination or hydrogen bonds have received a great deal of attention in the field of supramolecular chemistry and crystal engineering. Pyrazine carboxylic acids, containing O– or N– donors, are excellent bridging ligands when coordinated to transition metals and have been extensively studied as active ligands in the course of electron-transfer and magnetochemistry research (Klein et al., 1982; O'Connor et al., 1981). The cobalt(II), nickel(II), copper(II), zinc(II) and manganese(II) complexes of the 2-pyrazinecarboxylic acid ligand have been reported (Ciurtin et al., 2002; Dong et al., 2000; Ptasiewicz-Bak et al., 1995). Ptasiewicz-Bak et al. reported an orthorhombic manganese(II) dipyrazinate dihydrate complex (space group Fdd2), in which the coordination polyhedron around the Mn^II atom is a distorted octahedron with cis positioned water molecules. The title complex is another monomeric complex of Mn^II with the 2-pyrazinecarboxylic acid ligand, which is isostructrual to the cobalt(II) complex (Ptasiewicz-Bak et al., 1995).

The Mn^II atom sits on an inversion center and the coordination geometry for the Mn^II atom (Fig. 1) is distorted octahedral (Table 1). Each Mn^II atom is axially coordinated by water molecules and consists of an equatorial plane of two oxygen donors and two nitrogen donors from two chelating 2-pyrazinecarboxylato group. As a consequence of the reaction the carboxylic groups of the starting diacid in position 3 are decarboxylated while the coordinated carboxylic groups in 2-position are kept and are deprotonated. The title molecules are connected by the O—H···N and O—H···O hydrogen-bonding interactions (Fig. 2); see Table 2 for the geometric parameters describing these interactions.

Related literature top

For related literature, see: Ciurtin et al. (2002); Dong et al. (2000); Klein et al. (1982); O'Connor & Sinn (1981); Ptasiewicz-Bak et al. (1995).

Experimental top

A mixture of manganese(II) chloride tetrahydrate, (0.4 mmol, 79.2 mg), pyrazine-2,3-dicarboxylic acid (0.8 mmol, 134.5 mg), and H₂O (1.0 mol, 18.0 ml) in the molar ratio of 1: 2: 2500 was sealed in a 40 ml stainless steel reactor with Teflon liner and directly heated to 160 °C, kept at 160 °C for 72 h, and then directly cooled to the room temperature. Light-yellow block-shaped crystals of the title complex were collected by filtration and washed with ethanol (2×5 ml) for the structural analysis.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 structure of the title compound and the atomic numbering scheme, with atom labels and 35% probability displacement ellipsoids for non-H atoms (small spheres for the H atoms).
	Fig. 2. The packing of the title compound viewed down the b axis, showing the hydrogen bond donor-acceptor atoms. H atoms have been omitted for clarity.

Diaquabis(pyrazine-2-carboxylato-κ²N¹,O)manganese(II) dihydrate top

Crystal data top

[Mn(C₅H₃N₂O₂)₂(H₂O)₂]·2H₂O	F(000) = 382
M_r = 373.19	D_x = 1.633 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 931 reflections
a = 7.233 (2) Å	θ = 3.0–26.4°
b = 13.003 (4) Å	µ = 0.91 mm⁻¹
c = 8.257 (3) Å	T = 293 K
β = 102.207 (5)°	Block, light-yellow
V = 759.1 (4) Å³	0.20 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1552 independent reflections
Radiation source: fine-focus sealed tube	1252 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 26.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→9
T_min = 0.838, T_max = 0.914	k = −16→15
4297 measured reflections	l = −10→9

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0336P)² + 0.3749P] where P = (F_o² + 2F_c²)/3
1552 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Mn(C₅H₃N₂O₂)₂(H₂O)₂]·2H₂O	V = 759.1 (4) Å³
M_r = 373.19	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.233 (2) Å	µ = 0.91 mm⁻¹
b = 13.003 (4) Å	T = 293 K
c = 8.257 (3) Å	0.20 × 0.10 × 0.10 mm
β = 102.207 (5)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1552 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1252 reflections with I > 2σ(I)
T_min = 0.838, T_max = 0.914	R_int = 0.025
4297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.08	Δρ_max = 0.33 e Å⁻³
1552 reflections	Δρ_min = −0.23 e Å⁻³
106 parameters

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

	x	y	z	U_iso*/U_eq
Mn1	0.0000	0.5000	0.0000	0.02497 (15)
C2	0.3799 (3)	0.50843 (18)	0.2061 (3)	0.0321 (5)
O1	0.2234 (2)	0.40214 (13)	−0.0110 (2)	0.0374 (4)
N1	0.2126 (3)	0.55522 (15)	0.1991 (2)	0.0344 (5)
C1	0.3768 (3)	0.41836 (17)	0.0906 (3)	0.0316 (5)
C5	0.2082 (4)	0.6331 (2)	0.3022 (3)	0.0449 (6)
H5	0.0940	0.6661	0.3015	0.054*
O2	0.5231 (2)	0.36634 (14)	0.1034 (2)	0.0461 (5)
N2	0.5373 (3)	0.62300 (17)	0.4146 (3)	0.0457 (5)
C3	0.5411 (3)	0.5443 (2)	0.3121 (3)	0.0388 (6)
H3	0.6561	0.5123	0.3119	0.047*
C4	0.3699 (4)	0.6661 (2)	0.4106 (3)	0.0495 (7)
H4	0.3612	0.7200	0.4827	0.059*
O3	0.0978 (2)	0.60221 (15)	−0.1543 (2)	0.0554 (5)
H3A	0.2145	0.6136	−0.1497	0.083*
H3B	0.0328	0.6326	−0.2386	0.083*
O4	0.9068 (3)	0.69223 (17)	0.5751 (3)	0.0703 (7)
H4B	0.7931	0.6798	0.5266	0.105*
H4A	0.9341	0.7505	0.5398	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0141 (2)	0.0262 (2)	0.0330 (3)	0.00080 (19)	0.00120 (16)	0.0019 (2)
C2	0.0266 (10)	0.0339 (12)	0.0354 (12)	−0.0008 (10)	0.0058 (9)	0.0064 (10)
O1	0.0273 (8)	0.0382 (10)	0.0439 (10)	−0.0004 (7)	0.0009 (7)	−0.0047 (8)
N1	0.0285 (10)	0.0322 (11)	0.0419 (11)	0.0015 (8)	0.0061 (8)	0.0012 (9)
C1	0.0253 (11)	0.0315 (12)	0.0388 (13)	−0.0017 (9)	0.0081 (9)	0.0025 (10)
C5	0.0421 (15)	0.0396 (15)	0.0527 (16)	0.0052 (11)	0.0098 (12)	−0.0058 (12)
O2	0.0262 (9)	0.0475 (11)	0.0635 (12)	0.0075 (8)	0.0071 (8)	−0.0069 (9)
N2	0.0465 (13)	0.0424 (13)	0.0438 (13)	−0.0070 (10)	−0.0005 (10)	−0.0009 (10)
C3	0.0305 (12)	0.0406 (13)	0.0429 (14)	−0.0025 (10)	0.0022 (10)	0.0032 (12)
C4	0.0584 (17)	0.0384 (15)	0.0495 (16)	−0.0011 (13)	0.0066 (13)	−0.0080 (12)
O3	0.0276 (9)	0.0690 (14)	0.0664 (13)	−0.0023 (8)	0.0024 (9)	0.0293 (11)
O4	0.0569 (13)	0.0736 (16)	0.0679 (14)	−0.0166 (11)	−0.0148 (11)	0.0273 (12)

Geometric parameters (Å, º) top

Mn1—O3	2.0670 (18)	C1—O2	1.242 (3)
Mn1—O3ⁱ	2.0670 (18)	C5—C4	1.382 (4)
Mn1—O1ⁱ	2.0738 (16)	C5—H5	0.9300
Mn1—O1	2.0738 (16)	N2—C4	1.328 (4)
Mn1—N1ⁱ	2.1246 (19)	N2—C3	1.332 (3)
Mn1—N1	2.1246 (19)	C3—H3	0.9300
C2—N1	1.345 (3)	C4—H4	0.9300
C2—C3	1.383 (3)	O3—H3A	0.8500
C2—C1	1.507 (3)	O3—H3B	0.8500
O1—C1	1.259 (3)	O4—H4B	0.8500
N1—C5	1.328 (3)	O4—H4A	0.8501

O3—Mn1—O3ⁱ	180.0	C5—N1—Mn1	129.97 (17)
O3—Mn1—O1ⁱ	90.24 (7)	C2—N1—Mn1	112.20 (15)
O3ⁱ—Mn1—O1ⁱ	89.76 (7)	O2—C1—O1	125.5 (2)
O3—Mn1—O1	89.76 (7)	O2—C1—C2	118.1 (2)
O3ⁱ—Mn1—O1	90.24 (7)	O1—C1—C2	116.42 (19)
O1ⁱ—Mn1—O1	180.0	N1—C5—C4	121.3 (2)
O3—Mn1—N1ⁱ	91.51 (8)	N1—C5—H5	119.3
O3ⁱ—Mn1—N1ⁱ	88.49 (8)	C4—C5—H5	119.3
O1ⁱ—Mn1—N1ⁱ	78.35 (7)	C4—N2—C3	116.7 (2)
O1—Mn1—N1ⁱ	101.65 (7)	N2—C3—C2	122.2 (2)
O3—Mn1—N1	88.49 (8)	N2—C3—H3	118.9
O3ⁱ—Mn1—N1	91.51 (8)	C2—C3—H3	118.9
O1ⁱ—Mn1—N1	101.65 (7)	N2—C4—C5	121.9 (3)
O1—Mn1—N1	78.35 (7)	N2—C4—H4	119.1
N1ⁱ—Mn1—N1	180.00 (8)	C5—C4—H4	119.1
N1—C2—C3	120.4 (2)	Mn1—O3—H3A	123.4
N1—C2—C1	115.55 (19)	Mn1—O3—H3B	126.9
C3—C2—C1	124.1 (2)	H3A—O3—H3B	109.2
C1—O1—Mn1	116.93 (15)	H4B—O4—H4A	106.2
C5—N1—C2	117.5 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O4ⁱⁱ	0.85	1.79	2.639 (3)	176
O3—H3A···O2ⁱⁱⁱ	0.85	1.87	2.715 (2)	171
O4—H4A···O2^iv	0.85	1.98	2.806 (3)	164
O4—H4B···N2	0.85	2.03	2.865 (3)	170

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

Experimental details

Crystal data
Chemical formula	[Mn(C₅H₃N₂O₂)₂(H₂O)₂]·2H₂O
M_r	373.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.233 (2), 13.003 (4), 8.257 (3)
β (°)	102.207 (5)
V (Å³)	759.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.91
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.838, 0.914
No. of measured, independent and observed [I > 2σ(I)] reflections	4297, 1552, 1252
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.08
No. of reflections	1552
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Mn1—O3	2.0670 (18)	O1—C1	1.259 (3)
Mn1—O1	2.0738 (16)	C1—O2	1.242 (3)
Mn1—N1	2.1246 (19)

O3—Mn1—O1ⁱ	90.24 (7)	O1—Mn1—N1ⁱ	101.65 (7)
O3—Mn1—O1	89.76 (7)	O3—Mn1—N1	88.49 (8)
O3—Mn1—N1ⁱ	91.51 (8)	O1—Mn1—N1	78.35 (7)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O4ⁱⁱ	0.85	1.79	2.639 (3)	175.8
O3—H3A···O2ⁱⁱⁱ	0.85	1.87	2.715 (2)	170.9
O4—H4A···O2^iv	0.85	1.98	2.806 (3)	163.8
O4—H4B···N2	0.85	2.03	2.865 (3)	169.5

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

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 50590402).

References

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