Diaqua­bis(tetra­zolo[1,5-a]pyridine-8-carboxyl­ato-κ2N1,O)manganese(II) dihydrate

Zhao, J.-D.

doi:10.1107/S1600536809023253

metal-organic compounds

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Volume 65| Part 7| July 2009| Page m812

doi:10.1107/S1600536809023253

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Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato-κ²N¹,O)manganese(II) dihydrate

Jian-De Zhao ^a ^*

^aSchool of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300191, People's Republic of China
^*Correspondence e-mail: jiande-zhao@163.com

(Received 7 June 2009; accepted 17 June 2009; online 24 June 2009)

In the title compound, [Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O, the Mn^II atom is located on a twofold rotation axis and is octahedrally coordinated by the N and O atoms of the chelating tetrazolo[1,5-a]pyridine-8-carboxylate anions and the O atoms of two water molecules. Hydrogen bonds of the O—H⋯O and O—H⋯N types lead to the formation of layers parallel to (100).

Related literature

For background to coordination compounds, see: Kulynych & Shimizu (2002 ); Liu et al. (2001 ); Xue & Liu (2009 ).

Experimental

Crystal data

[Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O
M_r = 453.25
Orthorhombic, P n n a
a = 19.041 (4) Å
b = 11.694 (2) Å
c = 7.5371 (15) Å
V = 1678.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 293 K
0.5 × 0.5 × 0.5 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.60, T_max = 0.662
16422 measured reflections
1925 independent reflections
1755 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 1.20
1925 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11⋯O2ⁱ	0.85	1.93	2.7644 (17)	166
O1W—H12⋯O2Wⁱⁱ	0.85	1.91	2.7538 (19)	171
O2W—H21⋯O1	0.89	1.95	2.8287 (18)	172
O2W—H22⋯N2ⁱⁱⁱ	0.76	2.25	3.003 (2)	169
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y, z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SCXmini (Rigaku, 2006 ); cell refinement: PROCESS-AUTO (Rigaku, 1998 ); data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023253/dn2463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023253/dn2463Isup2.hkl

checkCIF report

Comment top

Coordination complexes have attracted great attention in recent years. (Kulynych & Shimizu, 2002). Polydentate ligand have some heteroatom can coordinated to metal in different ways, and can form Hydrogen bonds between to give supermolecule net(Liu et al., 2001). The tetrazolo(1,5-a)pyridine-8-carboxylate have multi-coordinated position and may behavs as a polydentate ligand. The related maganese structure with two water molecules as solvent has been recently reported (Xue & Liu, 2009).

In the title compound, the manganese atom is located on a two fold axis and octahedrally coordinated by two water molecules and two bidentate N,O tetrazolo(1,5-a)pyridine-8-carboxylate,(Fig. 1).

Each tetrazolo(1,5-a) pyridine-8-carboxylate chelates to one manganese atom. One type of water coordinates to the manganese atom whereas the other acts as lattice water. A two dimensional supramolecular network parallel to the (1 0 0) plane, is formed by the hydrogen bond interactions between the water molecules and the nitrogen of the tetrazolo(1,5-a)pyridine-8-carboxylate ligands (Table 1, Fig. 2).

The structure is closely related to the dihydrate complex (Xue & Liu, 2009), the only difference being the occurence of two solvate water molecules in the previous structure.

Related literature top

For background to coordination compounds, see: Kulynych & Shimizu (2002); Liu et al. (2001); Xue & Liu (2009).

Experimental top

A mixture of manganeset(II)nitrate and sodium azide (1 mmol), 2-chloronicotinic acid(0.5 mmol), in 10 ml of water was sealed in a Teflon-lined stainless-steel Parr bomb that was heated at 363 K for 48 h. Red crystals of the title complex were collected after the bomb was allowed to cool to room temperature.Yield 20% based on manganese(II). Caution: Azides may be explosive. Although we have met no problems in this work, only a small amount of them should be prepared and handled with great caution.

Computing details top

Data collection: SCXmini (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound showing the coordination of Mn atom with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms and the solvate water molecule have been omitted for clarity. [ Symmetry codes: (i) -x+1/2, -y, z]
	Fig. 2. Partial packing view showing the formation of layers parallel to the (1 0 0) plane. H atoms not involved in hydrogen bondings have been omitted for clarity. H bonds are shown as dashed lines.

Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato- κ²N¹,O)manganese(II) dihydrate top

Crystal data top

[Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O	F(000) = 924
M_r = 453.25	D_x = 1.794 Mg m⁻³
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 15650 reflections
a = 19.041 (4) Å	θ = 3.2–27.9°
b = 11.694 (2) Å	µ = 0.85 mm⁻¹
c = 7.5371 (15) Å	T = 293 K
V = 1678.3 (6) Å³	Block, yellow
Z = 4	0.5 × 0.5 × 0.5 mm

Data collection top

Rigaku SCXmini diffractometer	1925 independent reflections
Radiation source: fine-focus sealed tube	1755 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −24→24
T_min = 0.60, T_max = 0.662	k = −15→15
16422 measured reflections	l = −9→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 = 1.20	w = 1/[σ²(F_o²) + (0.0386P)² + 0.6168P] where P = (F_o² + 2F_c²)/3
1925 reflections	(Δ/σ)_max = 0.001
132 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O	V = 1678.3 (6) Å³
M_r = 453.25	Z = 4
Orthorhombic, Pnna	Mo Kα radiation
a = 19.041 (4) Å	µ = 0.85 mm⁻¹
b = 11.694 (2) Å	T = 293 K
c = 7.5371 (15) Å	0.5 × 0.5 × 0.5 mm

Data collection top

Rigaku SCXmini diffractometer	1925 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1755 reflections with I > 2σ(I)
T_min = 0.60, T_max = 0.662	R_int = 0.029
16422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.081	H-atom parameters constrained
S = 1.20	Δρ_max = 0.26 e Å⁻³
1925 reflections	Δρ_min = −0.34 e Å⁻³
132 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.2500	0.0000	0.86700 (4)	0.01925 (12)
O1	0.19724 (6)	0.09901 (10)	0.66846 (16)	0.0263 (3)
O1W	0.21023 (6)	0.11467 (10)	1.06874 (17)	0.0294 (3)
H11	0.1888	0.1746	1.0359	0.044*
H12	0.2351	0.1270	1.1599	0.044*
O2	0.12016 (6)	0.21215 (10)	0.53402 (17)	0.0306 (3)
N1	0.14757 (7)	−0.09265 (11)	0.85974 (18)	0.0233 (3)
N2	0.12692 (8)	−0.18779 (12)	0.9450 (2)	0.0279 (3)
N3	0.05962 (8)	−0.20081 (12)	0.9411 (2)	0.0285 (3)
N4	0.03454 (7)	−0.10924 (11)	0.84998 (17)	0.0212 (3)
C1	0.13563 (9)	0.13028 (13)	0.6301 (2)	0.0201 (3)
C2	0.07619 (8)	0.05909 (13)	0.7039 (2)	0.0194 (3)
C3	0.00732 (9)	0.08539 (14)	0.6756 (2)	0.0244 (3)
H3	−0.0036	0.1528	0.6161	0.029*
C4	−0.04836 (9)	0.01396 (14)	0.7335 (2)	0.0276 (4)
H4	−0.0946	0.0355	0.7122	0.033*
C5	−0.03481 (9)	−0.08466 (15)	0.8190 (2)	0.0261 (4)
H5	−0.0706	−0.1336	0.8551	0.031*
C6	0.08933 (8)	−0.04294 (13)	0.7994 (2)	0.0185 (3)
O2W	0.28824 (7)	0.12927 (11)	0.37555 (17)	0.0354 (3)
H21	0.2590	0.1132	0.4635	0.053*
H22	0.3103	0.1791	0.4079	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.01548 (18)	0.02138 (19)	0.02089 (19)	0.00086 (12)	0.000	0.000
O1	0.0199 (6)	0.0302 (6)	0.0287 (6)	−0.0007 (5)	−0.0003 (5)	0.0108 (5)
O1W	0.0325 (7)	0.0280 (6)	0.0277 (6)	0.0091 (5)	−0.0033 (5)	−0.0048 (5)
O2	0.0297 (6)	0.0260 (6)	0.0362 (7)	−0.0035 (5)	−0.0053 (6)	0.0141 (5)
N1	0.0222 (7)	0.0181 (6)	0.0295 (7)	−0.0005 (5)	−0.0016 (5)	0.0066 (5)
N2	0.0295 (7)	0.0215 (7)	0.0326 (8)	−0.0017 (6)	0.0003 (6)	0.0083 (6)
N3	0.0312 (8)	0.0219 (7)	0.0324 (8)	−0.0038 (6)	0.0002 (6)	0.0079 (6)
N4	0.0215 (7)	0.0194 (6)	0.0226 (7)	−0.0044 (5)	0.0011 (5)	0.0018 (5)
C1	0.0230 (8)	0.0190 (7)	0.0185 (7)	−0.0021 (6)	−0.0002 (6)	0.0016 (6)
C2	0.0224 (8)	0.0175 (7)	0.0183 (7)	−0.0011 (6)	0.0004 (6)	0.0007 (6)
C3	0.0248 (8)	0.0245 (8)	0.0239 (8)	0.0018 (6)	−0.0025 (6)	0.0016 (6)
C4	0.0171 (7)	0.0369 (9)	0.0289 (9)	0.0015 (7)	−0.0009 (7)	−0.0018 (7)
C5	0.0178 (8)	0.0326 (9)	0.0279 (8)	−0.0068 (7)	0.0027 (7)	−0.0021 (7)
C6	0.0177 (7)	0.0187 (7)	0.0190 (7)	−0.0023 (6)	0.0001 (6)	−0.0003 (6)
O2W	0.0383 (8)	0.0386 (7)	0.0293 (7)	−0.0081 (6)	0.0032 (5)	−0.0043 (5)

Geometric parameters (Å, º) top

Mn1—O1	2.1422 (12)	N3—N4	1.3588 (19)
Mn1—O1ⁱ	2.1422 (12)	N4—C6	1.3546 (19)
Mn1—O1W	2.1642 (12)	N4—C5	1.372 (2)
Mn1—O1Wⁱ	2.1642 (12)	C1—C2	1.511 (2)
Mn1—N1	2.2317 (14)	C2—C3	1.364 (2)
Mn1—N1ⁱ	2.2317 (14)	C2—C6	1.416 (2)
O1—C1	1.262 (2)	C3—C4	1.418 (2)
O1W—H11	0.8477	C3—H3	0.9300
O1W—H12	0.8471	C4—C5	1.346 (2)
O2—C1	1.2362 (19)	C4—H4	0.9300
N1—C6	1.332 (2)	C5—H5	0.9300
N1—N2	1.3438 (19)	O2W—H21	0.8853
N2—N3	1.291 (2)	O2W—H22	0.7585

O1—Mn1—O1ⁱ	91.38 (7)	N2—N3—N4	105.51 (12)
O1—Mn1—O1W	89.53 (5)	C6—N4—N3	108.82 (13)
O1ⁱ—Mn1—O1W	171.80 (5)	C6—N4—C5	125.01 (14)
O1—Mn1—O1Wⁱ	171.80 (5)	N3—N4—C5	126.13 (14)
O1ⁱ—Mn1—O1Wⁱ	89.53 (5)	O2—C1—O1	125.44 (15)
O1W—Mn1—O1Wⁱ	90.73 (7)	O2—C1—C2	117.64 (14)
O1—Mn1—N1	80.53 (5)	O1—C1—C2	116.89 (13)
O1ⁱ—Mn1—N1	97.49 (5)	C3—C2—C6	116.08 (14)
O1W—Mn1—N1	90.70 (5)	C3—C2—C1	122.57 (14)
O1Wⁱ—Mn1—N1	91.27 (5)	C6—C2—C1	121.27 (14)
O1—Mn1—N1ⁱ	97.49 (5)	C2—C3—C4	122.53 (15)
O1ⁱ—Mn1—N1ⁱ	80.53 (5)	C2—C3—H3	118.7
O1W—Mn1—N1ⁱ	91.27 (5)	C4—C3—H3	118.7
O1Wⁱ—Mn1—N1ⁱ	90.70 (5)	C5—C4—C3	120.56 (16)
N1—Mn1—N1ⁱ	177.19 (7)	C5—C4—H4	119.7
C1—O1—Mn1	138.78 (10)	C3—C4—H4	119.7
Mn1—O1W—H11	118.4	C4—C5—N4	116.47 (15)
Mn1—O1W—H12	118.7	C4—C5—H5	121.8
H11—O1W—H12	111.4	N4—C5—H5	121.8
C6—N1—N2	106.31 (13)	N1—C6—N4	107.18 (13)
C6—N1—Mn1	121.61 (10)	N1—C6—C2	133.50 (14)
N2—N1—Mn1	130.24 (11)	N4—C6—C2	119.29 (14)
N3—N2—N1	112.16 (13)	H21—O2W—H22	105.7

Symmetry code: (i) −x+1/2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O2ⁱⁱ	0.85	1.93	2.7644 (17)	166
O1W—H12···O2Wⁱⁱⁱ	0.85	1.91	2.7538 (19)	171
O2W—H21···O1	0.89	1.95	2.8287 (18)	172
O2W—H22···N2^iv	0.76	2.25	3.003 (2)	169

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

Experimental details

Crystal data
Chemical formula	[Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O
M_r	453.25
Crystal system, space group	Orthorhombic, Pnna
Temperature (K)	293
a, b, c (Å)	19.041 (4), 11.694 (2), 7.5371 (15)
V (Å³)	1678.3 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.5 × 0.5 × 0.5

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.60, 0.662
No. of measured, independent and observed [I > 2σ(I)] reflections	16422, 1925, 1755
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.20
No. of reflections	1925
No. of parameters	132
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.34

Computer programs: SCXmini (Rigaku, 2006), PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O2ⁱ	0.85	1.93	2.7644 (17)	166.2
O1W—H12···O2Wⁱⁱ	0.85	1.91	2.7538 (19)	170.6
O2W—H21···O1	0.89	1.95	2.8287 (18)	172.2
O2W—H22···N2ⁱⁱⁱ	0.76	2.25	3.003 (2)	169.2

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

References

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