Diaqua­[5-(2-pyrid­yl)tetra­zolato-κ2N1,N5]manganese(II)

Wen, X.-C.

doi:10.1107/S1600536808010106

metal-organic compounds

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Volume 64| Part 6| June 2008| Page m768

doi:10.1107/S1600536808010106

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Diaqua[5-(2-pyridyl)tetrazolato-κ²N¹,N⁵]manganese(II)

Xiao-Chun Wen ^a ^*

^aOrdered Matter Science Research Centre, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 12 April 2008; accepted 13 April 2008; online 3 May 2008)

The title compound, [Mn(C₆H₄N₅)₂(H₂O)₂], was synthesized by the hydrothermal reaction of Mn(NO₃)₂ with picolinonitrile in the presence of NaN₃. The Mn atom lies on an inversion centre. The distorted octahedral Mn environment contains two planar trans-related N,N′-chelating 5-(2-pyridyl)tetrazolate ligands in the equatorial plane and two axial water molecules. O—H⋯N hydrogen bonds generate an infinite three-dimensional network.

Related literature

For the chemisty of tetrazole, see: Arp et al. (2000 ); Dunica et al. (1991 ); Wang et al. (2005 ); Wittenberger & Donner (1993 ).

Experimental

Crystal data

[Mn(C₆H₄N₅)₂(H₂O)₂]
M_r = 383.26
Monoclinic, P 2₁ /n
a = 6.185 (3) Å
b = 12.110 (7) Å
c = 10.615 (5) Å
β = 106.597 (12)°
V = 761.9 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 293 (2) K
0.5 × 0.5 × 0.4 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.638, T_max = 0.695
7656 measured reflections
1803 independent reflections
1660 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 1.10
1803 reflections
115 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯N3ⁱ	0.85	2.03	2.864 (2)	169
O1W—H1W⋯N5ⁱⁱ	0.86	1.93	2.788 (2)	175
Symmetry codes: (i) x+1, y, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP3 (Farrugia, 1997 ) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010106/dn2338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010106/dn2338Isup2.hkl

checkCIF report

Comment top

The tetrazole functional group has found a wide range of applications in coordination chemistry as ligands, in medicinal chemistry as a metabolically stable surrogate for a carboxylic acid group, and in materials science as high density energy materials(Wang et al., 2005; Dunica et al., 1991; Wittenberger & Donner, 1993). We report here the crystal structure of the title compound, 5-(2-pyridyl)tetrazolate-Manganese(II) dihydrate.

The Mn atom lies on an inversion centre. The distorted octahedral Mn environment contains two planar trans-related N,N-chelating 5-(2-pyridyl)tetrazolate ligands in the equatorial plane and two water molecules ligands. The pyridine and tetrazole rings are nearly coplanar and are twisted from each other by a dihedral angle of only 4.02 (0.09) °(Fig.1). The bond distances and bond angles of the tetrazole rings are in the usual ranges (Wang et al., 2005; Arp et al., 2000).

The O atoms from water molecules are involved in intermolecular hydrogen bonds building up an infinite three-dimensional network(Table 1, Fig. 2).

Related literature top

For the chemisty of tetrazole, see: Arp et al. (2000); Dunica et al. (1991); Wang et al. (2005); Wittenberger & Donner (1993).

Experimental top

A mixture of picolinonitrile (0.2 mmol), NaN₃ (0.4 mmol), Mn(NO₃)₂(0.15 mmol) ethanol (1 ml) and a few drops of water sealed in a glass tube was maintained at 120 °C. Yellow block crystals suitable for X-ray analysis were obtained after 3 days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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-32 (Farrugia, 1998) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry code : (i) 1-x, 1-y, 1-z]
	Fig. 2. The crystal packing of the title compound viewed along the a axis showing the three dimensionnal hydrogen bondings network (dashed line). Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Diaqua[5-(2-pyridyl)tetrazolato-κ²N¹,N⁵]manganese(II) top

Crystal data top

[Mn(C₆H₄N₅)₂(H₂O)₂]	F(000) = 390
M_r = 383.26	D_x = 1.671 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2090 reflections
a = 6.185 (3) Å	θ = 3.8–27.5°
b = 12.110 (7) Å	µ = 0.90 mm⁻¹
c = 10.615 (5) Å	T = 293 K
β = 106.597 (12)°	Block, yellow
V = 761.9 (7) Å³	0.5 × 0.5 × 0.4 mm
Z = 2

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	1803 independent reflections
Radiation source: fine-focus sealed tube	1660 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.638, T_max = 0.695	l = −13→13
7656 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0346P)² + 0.2477P] where P = (F_o² + 2F_c²)/3
1803 reflections	(Δ/σ)_max = 0.001
115 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Mn(C₆H₄N₅)₂(H₂O)₂]	V = 761.9 (7) Å³
M_r = 383.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.185 (3) Å	µ = 0.90 mm⁻¹
b = 12.110 (7) Å	T = 293 K
c = 10.615 (5) Å	0.5 × 0.5 × 0.4 mm
β = 106.597 (12)°

Data collection top

Rigaku Mercury2 (2x2 bin mode) diffractometer	1803 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1660 reflections with I > 2σ(I)
T_min = 0.638, T_max = 0.695	R_int = 0.021
7656 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.11	Δρ_max = 0.26 e Å⁻³
1803 reflections	Δρ_min = −0.30 e Å⁻³
115 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
C1	0.2334 (2)	0.69220 (11)	0.35475 (13)	0.0241 (3)
C2	0.4533 (2)	0.74376 (11)	0.41494 (13)	0.0244 (3)
C3	0.4930 (3)	0.85522 (12)	0.40133 (15)	0.0344 (3)
H3	0.3799	0.9008	0.3511	0.041*
C4	0.7043 (3)	0.89713 (13)	0.46408 (17)	0.0412 (4)
H4	0.7349	0.9717	0.4569	0.049*
C5	0.8696 (3)	0.82755 (14)	0.53750 (16)	0.0393 (4)
H5	1.0121	0.8544	0.5814	0.047*
C6	0.8179 (2)	0.71703 (13)	0.54410 (15)	0.0325 (3)
H6	0.9299	0.6698	0.5921	0.039*
Mn1	0.5000	0.5000	0.5000	0.02576 (11)
N1	0.61452 (19)	0.67490 (9)	0.48475 (11)	0.0255 (2)
N2	0.19348 (18)	0.58625 (9)	0.37478 (12)	0.0275 (2)
N3	−0.0219 (2)	0.56898 (11)	0.30475 (13)	0.0338 (3)
N4	−0.1061 (2)	0.66105 (11)	0.24559 (13)	0.0368 (3)
N5	0.0515 (2)	0.74084 (10)	0.27584 (12)	0.0318 (3)
O1W	0.58488 (19)	0.45145 (9)	0.32058 (11)	0.0393 (3)
H1W	0.5510	0.3858	0.2905	0.059*
H2W	0.7096	0.4775	0.3151	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0229 (6)	0.0215 (6)	0.0268 (6)	0.0016 (5)	0.0055 (5)	0.0021 (5)
C2	0.0237 (6)	0.0221 (6)	0.0267 (6)	−0.0007 (5)	0.0059 (5)	0.0014 (5)
C3	0.0350 (7)	0.0238 (7)	0.0409 (8)	−0.0016 (6)	0.0050 (6)	0.0051 (6)
C4	0.0445 (9)	0.0267 (7)	0.0491 (9)	−0.0124 (6)	0.0082 (7)	0.0013 (6)
C5	0.0299 (7)	0.0422 (9)	0.0407 (8)	−0.0135 (6)	0.0019 (6)	−0.0014 (7)
C6	0.0243 (6)	0.0366 (8)	0.0327 (7)	−0.0011 (6)	0.0020 (5)	0.0024 (6)
Mn1	0.02613 (16)	0.01760 (16)	0.03133 (17)	0.00182 (10)	0.00463 (12)	0.00246 (10)
N1	0.0235 (5)	0.0237 (5)	0.0277 (5)	0.0000 (4)	0.0047 (4)	0.0021 (4)
N2	0.0222 (5)	0.0227 (6)	0.0342 (6)	−0.0018 (4)	0.0026 (5)	0.0001 (4)
N3	0.0239 (6)	0.0332 (7)	0.0400 (7)	−0.0042 (5)	0.0023 (5)	−0.0009 (5)
N4	0.0246 (6)	0.0402 (7)	0.0407 (7)	−0.0016 (5)	0.0012 (5)	0.0044 (6)
N5	0.0240 (6)	0.0316 (6)	0.0363 (6)	0.0023 (5)	0.0029 (5)	0.0075 (5)
O1W	0.0422 (6)	0.0340 (6)	0.0472 (6)	−0.0123 (5)	0.0213 (5)	−0.0121 (5)

Geometric parameters (Å, º) top

C1—N5	1.3325 (17)	C6—H6	0.9300
C1—N2	1.3350 (18)	Mn1—O1Wⁱ	2.1954 (14)
C1—C2	1.4670 (19)	Mn1—O1W	2.1954 (14)
C2—N1	1.3478 (17)	Mn1—N2ⁱ	2.2388 (14)
C2—C3	1.387 (2)	Mn1—N2	2.2388 (14)
C3—C4	1.383 (2)	Mn1—N1ⁱ	2.2538 (16)
C3—H3	0.9300	Mn1—N1	2.2538 (16)
C4—C5	1.381 (2)	N2—N3	1.3438 (17)
C4—H4	0.9300	N3—N4	1.3122 (19)
C5—C6	1.382 (2)	N4—N5	1.3449 (18)
C5—H5	0.9300	O1W—H1W	0.8597
C6—N1	1.3367 (18)	O1W—H2W	0.8507

N5—C1—N2	111.33 (12)	N2ⁱ—Mn1—N2	180.0
N5—C1—C2	126.65 (12)	O1Wⁱ—Mn1—N1ⁱ	91.80 (5)
N2—C1—C2	122.03 (11)	O1W—Mn1—N1ⁱ	88.20 (5)
N1—C2—C3	122.30 (13)	N2ⁱ—Mn1—N1ⁱ	75.47 (5)
N1—C2—C1	115.11 (12)	N2—Mn1—N1ⁱ	104.53 (5)
C3—C2—C1	122.59 (12)	O1Wⁱ—Mn1—N1	88.20 (5)
C4—C3—C2	118.56 (14)	O1W—Mn1—N1	91.80 (5)
C4—C3—H3	120.7	N2ⁱ—Mn1—N1	104.53 (5)
C2—C3—H3	120.7	N2—Mn1—N1	75.47 (5)
C5—C4—C3	119.57 (14)	N1ⁱ—Mn1—N1	180.0
C5—C4—H4	120.2	C6—N1—C2	118.14 (12)
C3—C4—H4	120.2	C6—N1—Mn1	126.70 (10)
C4—C5—C6	118.32 (14)	C2—N1—Mn1	115.00 (9)
C4—C5—H5	120.8	C1—N2—N3	105.11 (11)
C6—C5—H5	120.8	C1—N2—Mn1	112.29 (9)
N1—C6—C5	123.09 (14)	N3—N2—Mn1	142.51 (9)
N1—C6—H6	118.5	N4—N3—N2	109.13 (12)
C5—C6—H6	118.5	N3—N4—N5	109.55 (12)
O1Wⁱ—Mn1—O1W	180.0	C1—N5—N4	104.88 (12)
O1Wⁱ—Mn1—N2ⁱ	88.95 (5)	Mn1—O1W—H1W	118.4
O1W—Mn1—N2ⁱ	91.05 (5)	Mn1—O1W—H2W	114.0
O1Wⁱ—Mn1—N2	91.05 (5)	H1W—O1W—H2W	116.5
O1W—Mn1—N2	88.95 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···N3ⁱⁱ	0.85	2.03	2.864 (2)	169
O1W—H1W···N5ⁱⁱⁱ	0.86	1.93	2.788 (2)	175

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

Experimental details

Crystal data
Chemical formula	[Mn(C₆H₄N₅)₂(H₂O)₂]
M_r	383.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.185 (3), 12.110 (7), 10.615 (5)
β (°)	106.597 (12)
V (Å³)	761.9 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.5 × 0.5 × 0.4

Data collection
Diffractometer	Rigaku Mercury2 (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.638, 0.695
No. of measured, independent and observed [I > 2σ(I)] reflections	7656, 1803, 1660
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.11
No. of reflections	1803
No. of parameters	115
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.30

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-32 (Farrugia, 1998) and SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···N3ⁱ	0.85	2.03	2.864 (2)	168.5
O1W—H1W···N5ⁱⁱ	0.86	1.93	2.788 (2)	175.0

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

Acknowledgements

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

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