Diaqua­bis(tetra­zolo[1,5-a]pyridine-8-carboxyl­ato-κ2
               N
               1,O)manganese(II) dihydrate

doi:10.1107/S1600536809023253

Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): m812.

Published online 2009 June 24. doi: 10.1107/S1600536809023253

PMCID: PMC2969418

Diaquabis(tetrazolo[1,5-a]pyridine-8-carboxylato-κ² N ¹,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/at/163.com

Received June 7, 2009; Accepted June 17, 2009.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m812-scheme1.jpg Object name is e-65-0m812-scheme1.jpg

Experimental

Crystal data

[Mn(C₆H₃N₄O₂)₂(H₂O)₂]·2H₂O
M _r = 453.25
Orthorhombic,
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[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 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

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

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Click here to view.^{(15K, cif)}

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

Click here to view.^{(93K, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Figures

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, (more ...)

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.

Crystal data

[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

Rigaku SCXmini diffractometer	1925 independent reflections
Radiation source: fine-focus sealed tube	1755 reflections with I > 2σ(I)
graphite	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

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

Special details

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)

	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)

	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, °)

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 codes: (i) −x+1/2, −y, z.

Hydrogen-bond geometry (Å, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2463).

References

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