Diaqua­bis­[5-(1-oxidopyridin-1-ium-2-yl)-1,2,3,4-tetrazolido]manganese(II) di­hydrate

Abstract

In the title compound, [Mn(C₆H₄N₅O)₂(H₂O)₂]·2H₂O, the Mn^II ion is situated on an inversion centre and is coordinated by the O and N atoms of two bis-chelating 5-(2-pyridyl-1-oxide)tetra­zolate ligands and two O atoms of two water mol­ecules in a distorted octa­hedral geometry. All the water H atoms are involved in O—H⋯N and O—H⋯O hydrogen bonds with uncoordinated water O atoms and tetra­zole N atoms, which link the mol­ecules into a three-dimensional network.

Related literature

For backgroud to tetra­zolate derivatives in coordination chemistry, see: Jiang et al. (2007 ▶); Song et al. (2009 ▶); Zhang (2009) ▶. For related structures, see: Facchetti et al. (2004 ▶); Lin et al. (2005 ▶); Vrbova et al. (2000 ▶)

Experimental

Crystal data

• [Mn(C₆H₄N₅O)₂(H₂O)₂]·2H₂O

• M _r = 451.29

• Monoclinic,

• a = 6.4808 (13) Å

• b = 12.034 (2) Å

• c = 12.787 (4) Å

• β = 116.24 (2)°

• V = 894.5 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 0.80 mm⁻¹

• T = 293 K

• 0.10 × 0.10 × 0.08 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.925, T _max = 0.939

• 7432 measured reflections

• 1579 independent reflections

• 1102 reflections with I > 2σ(I)

• R _int = 0.115

Refinement

• R[F ² > 2σ(F ²)] = 0.078

• wR(F ²) = 0.133

• S = 1.14

• 1579 reflections

• 133 parameters

• H-atom parameters constrained

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N2	0.88	2.15	3.010 (5)	164
O2—H2A⋯O3i	0.84	2.01	2.756 (5)	147
O2—H2B⋯N3ii	0.86	2.06	2.858 (5)	154
O3—H3B⋯N4ii	0.82	2.10	2.917 (6)	176

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Tetrazole as functional group plays an important role in coordination chemistry, medicinal chemistry and materials science applications (Song et al., 2009; Jiang et al., 2007; Zhang, 2009). It's interesting for the study of tetrazolate complexes to delineate the ways in which tetrazoles bind to metal centres. Here we report the structure of a novel substituted tetrazolato-metal complex, diaquabis(5-(2-pyridyl-1-oxide)tetrazolato)manganese(II) dihydrate.

The crystal structure of the title complex consists of the mononuclear manganese (II) unit [Mn(C₆H₄N₅O)₂(H₂O)₂], and two lattice water molecules (Fig. 1). In the mononuclear unit, manganese(II) ion is in a distorted octahedral environment, being six-coordinated by two N atoms and two O atoms from two bidentate 5-(2-pyridyl-1-oxide)tetrazolato-ligands, and two O atoms of two coordinated water molecules with Mn–O distances from 2.090 (4)Å to 2.209 (3) Å, Mn–N bond length of 2.255 (4)Å and O1–Mn1–N1 angle of 79.47 (14)°, which are comparable with the values observed in other metal-tetrazolate complexes (Vrbova et al., 2000; Lin et al., 2005; Facchetti et al., 2004). The pyridine and tetrazole rings are twisted against each other by 20.466 (190)°. In the crystal structure, all the water H atoms are involved in O–H···N and O–H···O hydrogen bonds with the solvate water O (O3W) and the tetrazole N (N2, N4) atoms. The interactions link the molecules into a three dimensional network (Table 1 and Fig. 2).

Experimental

A solution of 5-(2-pyridyl-1-oxide)tetrazole (32.6 mg, 0.2 mmol) and K₂CO₃ (13.8 mg, 0.1 mmol) in H₂O (10 ml) was dropped slowly into a solution of Mn(ClO₄).6H₂O (36.2 mg, 0.1 mmol) dissolved in methanol (10 ml). The resulting brown suspension solution was stirred for 24 h at room temperature and filtered. Yellow crystals were separated from filtrate after about one month and collected for X-ray analysis (m.p. >573 K).

Refinement

H atoms were placed in calculated positions, with C–H = 0.93Å and O–H = 0.82-0.88 Å, and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(parent atom).

Figures

Fig. 1.

The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) - x + 1, - y + 1, - z + 1. ]

Fig. 2.

A view of the O–H···O and O–H···N hydrogen bonds (dotted lines) in the crystal structure of the title compound.

Crystal data

[Mn(C6H4N5O)2(H2O)2]·2H2O	F(000) = 462
Mr = 451.29	Dx = 1.676 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7005 reflections
a = 6.4808 (13) Å	θ = 3.1–27.6°
b = 12.034 (2) Å	µ = 0.80 mm−1
c = 12.787 (4) Å	T = 293 K
β = 116.24 (2)°	Block, yellow
V = 894.5 (4) Å3	0.10 × 0.10 × 0.08 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1579 independent reflections
Radiation source: fine-focus sealed tube	1102 reflections with I > 2σ(I)
graphite	Rint = 0.115
Detector resolution: 10.0 pixels mm-1	θmax = 25.0°, θmin = 3.4°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −14→14
Tmin = 0.925, Tmax = 0.939	l = −15→15
7432 measured reflections

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)] = 0.078	Hydrogen site location: difference Fourier map
wR(F2) = 0.133	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0354P)2 + 1.2794P] where P = (Fo2 + 2Fc2)/3
1579 reflections	(Δ/σ)max < 0.001
133 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.5000	0.5000	0.0282 (3)
C1	0.4458 (9)	0.2469 (4)	0.4227 (4)	0.0260 (12)
C2	0.3159 (8)	0.2280 (4)	0.4903 (4)	0.0276 (12)
C3	0.2946 (10)	0.1223 (5)	0.5282 (5)	0.0406 (15)
H3	0.3648	0.0631	0.5099	0.049*
C4	0.1752 (11)	0.1017 (6)	0.5912 (5)	0.0531 (18)
H4	0.1668	0.0303	0.6168	0.064*
C5	0.0688 (10)	0.1883 (6)	0.6155 (5)	0.0508 (17)
H2	−0.0165	0.1759	0.6568	0.061*
C6	0.0860 (9)	0.2922 (5)	0.5800 (5)	0.0407 (15)
H1	0.0140	0.3510	0.5979	0.049*
N1	0.5349 (7)	0.3443 (3)	0.4111 (3)	0.0289 (10)
N2	0.6423 (7)	0.3211 (4)	0.3443 (4)	0.0338 (11)
N3	0.6179 (8)	0.2138 (4)	0.3188 (4)	0.0368 (12)
N4	0.4943 (7)	0.1654 (4)	0.3670 (4)	0.0346 (11)
N5	0.2085 (7)	0.3114 (4)	0.5179 (4)	0.0344 (11)
O1	0.2069 (6)	0.4131 (3)	0.4819 (4)	0.0491 (11)
O2	0.2698 (6)	0.5780 (3)	0.3322 (3)	0.0396 (10)
H2A	0.1657	0.5331	0.2904	0.048*
H2B	0.2775	0.6340	0.2925	0.048*
O3	0.8363 (6)	0.4852 (3)	0.2336 (3)	0.0447 (10)
H3A	0.7951	0.4450	0.2787	0.054*
H3B	0.7388	0.5334	0.2038	0.054*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Mn1	0.0324 (7)	0.0249 (6)	0.0313 (7)	−0.0007 (6)	0.0178 (5)	−0.0026 (6)
C1	0.028 (3)	0.024 (3)	0.025 (3)	0.001 (2)	0.011 (3)	0.002 (2)
C2	0.027 (3)	0.027 (3)	0.027 (3)	0.003 (2)	0.011 (3)	−0.005 (2)
C3	0.053 (4)	0.037 (4)	0.040 (4)	−0.001 (3)	0.028 (3)	−0.002 (3)
C4	0.069 (5)	0.050 (4)	0.046 (4)	−0.012 (4)	0.030 (4)	0.000 (3)
C5	0.046 (4)	0.069 (5)	0.038 (4)	−0.010 (4)	0.019 (3)	0.005 (4)
C6	0.033 (3)	0.061 (4)	0.035 (4)	0.005 (3)	0.021 (3)	−0.014 (3)
N1	0.030 (2)	0.033 (3)	0.026 (2)	0.000 (2)	0.016 (2)	−0.003 (2)
N2	0.032 (3)	0.041 (3)	0.032 (3)	−0.001 (2)	0.018 (2)	−0.003 (2)
N3	0.038 (3)	0.042 (3)	0.034 (3)	0.003 (2)	0.019 (2)	−0.007 (2)
N4	0.043 (3)	0.032 (3)	0.035 (3)	−0.002 (2)	0.024 (3)	−0.009 (2)
N5	0.035 (3)	0.029 (3)	0.034 (3)	0.004 (2)	0.011 (2)	0.002 (2)
O1	0.043 (3)	0.038 (2)	0.076 (3)	−0.0019 (19)	0.035 (2)	0.000 (2)
O2	0.049 (2)	0.038 (2)	0.030 (2)	−0.0062 (19)	0.016 (2)	0.0060 (18)
O3	0.046 (2)	0.040 (2)	0.055 (3)	0.005 (2)	0.028 (2)	0.012 (2)

Geometric parameters (Å, °)

Mn1—O1	2.090 (4)	C4—H4	0.9300
Mn1—O1i	2.090 (4)	C5—C6	1.351 (8)
Mn1—O2	2.209 (3)	C5—H2	0.9300
Mn1—O2i	2.209 (3)	C6—N5	1.369 (6)
Mn1—N1	2.255 (4)	C6—H1	0.9300
Mn1—N1i	2.255 (4)	N1—N2	1.348 (5)
C1—N4	1.329 (6)	N2—N3	1.324 (6)
C1—N1	1.344 (6)	N3—N4	1.341 (6)
C1—C2	1.467 (7)	N5—O1	1.306 (5)
C2—N5	1.353 (6)	O2—H2A	0.8446
C2—C3	1.390 (7)	O2—H2B	0.8583
C3—C4	1.363 (7)	O3—H3A	0.8803
C3—H3	0.9300	O3—H3B	0.8172
C4—C5	1.359 (8)
O1—Mn1—O1i	180.0	C5—C4—C3	118.3 (6)
O1—Mn1—O2	85.11 (15)	C5—C4—H4	120.9
O1i—Mn1—O2	94.89 (14)	C3—C4—H4	120.9
O1—Mn1—O2i	94.89 (15)	C6—C5—C4	120.4 (6)
O1i—Mn1—O2i	85.11 (14)	C6—C5—H2	119.8
O2—Mn1—O2i	180.000 (1)	C4—C5—H2	119.8
O1—Mn1—N1	79.47 (14)	C5—C6—N5	120.4 (5)
O1i—Mn1—N1	100.53 (14)	C5—C6—H1	119.8
O2—Mn1—N1	92.20 (14)	N5—C6—H1	119.8
O2i—Mn1—N1	87.80 (14)	C1—N1—N2	104.9 (4)
O1—Mn1—N1i	100.53 (14)	C1—N1—Mn1	121.7 (3)
O1i—Mn1—N1i	79.47 (14)	N2—N1—Mn1	133.4 (3)
O2—Mn1—N1i	87.80 (14)	N3—N2—N1	108.6 (4)
O2i—Mn1—N1i	92.20 (14)	N2—N3—N4	109.9 (4)
N1—Mn1—N1i	180.000 (1)	C1—N4—N3	104.9 (4)
N4—C1—N1	111.7 (4)	O1—N5—C2	121.8 (4)
N4—C1—C2	122.4 (4)	O1—N5—C6	116.5 (5)
N1—C1—C2	125.9 (4)	C2—N5—C6	121.6 (5)
N5—C2—C3	116.4 (5)	N5—O1—Mn1	124.4 (3)
N5—C2—C1	122.3 (5)	Mn1—O2—H2A	110.5
C3—C2—C1	121.2 (5)	Mn1—O2—H2B	135.8
C4—C3—C2	122.8 (6)	H2A—O2—H2B	111.6
C4—C3—H3	118.6	H3A—O3—H3B	107.3
C2—C3—H3	118.6
N4—C1—C2—N5	−160.1 (5)	O2i—Mn1—N1—N2	−109.1 (4)
N1—C1—C2—N5	21.7 (8)	C1—N1—N2—N3	−0.5 (5)
N4—C1—C2—C3	19.1 (8)	Mn1—N1—N2—N3	177.0 (3)
N1—C1—C2—C3	−159.1 (5)	N1—N2—N3—N4	0.4 (5)
N5—C2—C3—C4	−0.7 (8)	N1—C1—N4—N3	−0.1 (6)
C1—C2—C3—C4	180.0 (5)	C2—C1—N4—N3	−178.5 (4)
C2—C3—C4—C5	1.4 (9)	N2—N3—N4—C1	−0.2 (5)
C3—C4—C5—C6	−1.4 (9)	C3—C2—N5—O1	−176.5 (5)
C4—C5—C6—N5	0.8 (9)	C1—C2—N5—O1	2.8 (7)
N4—C1—N1—N2	0.3 (6)	C3—C2—N5—C6	0.1 (7)
C2—C1—N1—N2	178.7 (5)	C1—C2—N5—C6	179.3 (5)
N4—C1—N1—Mn1	−177.5 (3)	C5—C6—N5—O1	176.6 (5)
C2—C1—N1—Mn1	0.9 (7)	C5—C6—N5—C2	−0.1 (8)
O1—Mn1—N1—C1	−27.4 (4)	C2—N5—O1—Mn1	−50.6 (6)
O1i—Mn1—N1—C1	152.6 (4)	C6—N5—O1—Mn1	132.7 (4)
O2—Mn1—N1—C1	−112.1 (4)	O2—Mn1—O1—N5	146.5 (4)
O2i—Mn1—N1—C1	67.9 (4)	O2i—Mn1—O1—N5	−33.5 (4)
O1—Mn1—N1—N2	155.5 (4)	N1—Mn1—O1—N5	53.3 (4)
O1i—Mn1—N1—N2	−24.5 (4)	N1i—Mn1—O1—N5	−126.7 (4)
O2—Mn1—N1—N2	70.9 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2	0.88	2.15	3.010 (5)	164
O2—H2A···O3ii	0.84	2.01	2.756 (5)	147
O2—H2B···N3iii	0.86	2.06	2.858 (5)	154
O3—H3B···N4iii	0.82	2.10	2.917 (6)	176

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