Tetra­aqua­bis­[5-(pyridin-3-yl)tetra­zolido-κN5]manganese(II) tetra­hydrate

Qi, C.; He, X.; Shao, M.; Li, M.-X.

doi:10.1107/S160053681202510X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m890

https://doi.org/10.1107/S160053681202510X

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Tetraaquabis[5-(pyridin-3-yl)tetrazolido-κN⁵]manganese(II) tetrahydrate

Chen Qi,^a Xiang He,^a Min Shao ^b and Ming-Xing Li ^a ^*

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai, 200444, People's Republic of China, and ^bLaboratory for Microstructures, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: mx_li@mail.shu.edu.cn

(Received 27 May 2012; accepted 1 June 2012; online 13 June 2012)

The title compound, [Mn(C₆H₄N₅)₂(H₂O)₄]·4H₂O, was obtained by the solution reaction of MnCl₂ and 3-(2H-tetrazol-5-yl)pyridine. The Mn^II atom, located on an inversion center, shows a slightly distorted octahedral geometry and is coordinated by two pyridine N atoms from two 5-(pyridin-3-yl)tetrazolide ligands occupying trans positions and four water molecules. In the crystal, the mononuclear complex molecules and solvent water molecules are connected into a three-dimensional framework by O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For the synthesis and crystal structure of the isotypic zinc(II) complex [Zn(C₆H₄N₅)₂(H₂O)₄]·4H₂O, see: Mu et al. (2010 ).

Experimental

Crystal data

[Mn(C₆H₄N₅)₂(H₂O)₄]·4H₂O
M_r = 491.35
Triclinic, $[P \overline 1]$
a = 8.137 (8) Å
b = 8.629 (8) Å
c = 8.761 (8) Å
α = 84.878 (10)°
β = 65.347 (8)°
γ = 72.571 (10)°
V = 533.0 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.922, T_max = 0.934
2785 measured reflections
1850 independent reflections
1712 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.080
S = 1.05
1850 reflections
143 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O4ⁱ	0.85	1.94	2.783 (3)	172
O1—H1A⋯N5ⁱⁱ	0.85	1.91	2.731 (3)	163
O2—H2A⋯O3ⁱⁱⁱ	0.85	1.99	2.836 (3)	171
O2—H2B⋯O3^iv	0.85	1.96	2.800 (3)	169
O3—H3B⋯O4	0.85	1.96	2.803 (3)	171
O3—H3A⋯N2	0.85	1.96	2.797 (3)	170
O4—H4B⋯N3^v	0.85	2.03	2.878 (3)	177
O4—H4A⋯N4^vi	0.85	2.00	2.849 (3)	176
Symmetry codes: (i) x, y+1, z; (ii) -x+1, -y+2, -z; (iii) x+1, y, z; (iv) -x+1, -y+2, -z+1; (v) -x, -y+1, -z+1; (vi) x, y, z+1.

Data collection: APEX2 (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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681202510X/gk2497sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681202510X/gk2497Isup2.hkl

checkCIF report

Comment top

3-(2H-Tetrazol-5-yl)pyridine (3-Ptz) is a multifunctional ligand which possesses five potential coordinate nitrogen atoms. Recently Mu et al. (2010) reported that hydrothermal reaction of Zn(OAc)₂ with 3-Ptz results in a mononuclear zinc complex [Zn(C₆H₄N₅)₂(H₂O)₄].4H₂O. We were able to prepare an analogues manganese(II) compound, [Mn(C₆H₄N₅)₂(H₂O)₄].4H₂O, by the solution reaction of MnCl₂ with 3-Ptz in a basic H₂O/ethanol solution. This compound is closely isostructural with the Zn complex reported by Mu et al. (2010)

Related literature top

For the synthesis and crystal structure of the isotypic zinc(II) complex [Zn(C₆H₄N₅)₂(H₂O)₄].4H₂O, see: Mu et al. (2010).

Experimental top

A mixture of MnCl₂ (0.1 mmol), 3-Ptz (0.1 mmol), 1 ml NaOH solution (0.1 mol L^-1) was added into 10 ml H₂O/ethanol mixed solvent (1:1). After being stirred for twenty minutes, the mixture was filtered. The filtrate was left undisturbed for two days to give yellow block crystals with 35% yield based on 3-Ptz. Anal. calcd for C₁₂H₂₄MnN₁₀O₈ (%): C, 29.33; H, 4.92; N, 28.51. Found: C, 29.24; H, 4.83; N, 28.66. IR (KBr pellet, cm^-1): 3400m, 1613m, 1588m, 1464m, 1426s, 1372m, 1153s, 1019m, 787s, 750s, 696s, 642m, 463m.

Structure description top

The asymmetric unit of the title complex consists of a mononuclear [Mn(C6H4N5)2(H2O)4] unit and four lattice water molecules (Figure 1). The Mn(II) atom is located on an inversion center and is six-coordinated by two pyridine groups and four H2O molecules in a trans-octahedral geometry. Two 3-Ptz ligands coordinate to the Mn(II) in the axial positions with the Mn–N bond length of 2.290 Å. Four coordinate water molecules occupy the equatorial plane with the average Mn–O bond length of 2.178 Å. The bond angle of O(1)#1-Mn(1)-N(1), O(2)#1-Mn(1)-N(1), O(1)-Mn(1)-O(2) are 84.98 (7) °, 92.50 (6) °, 91.41 (7) °, respectively. 3-(2H-tetrazol-5-yl)pyridine is deprotonated. The pyridine ring and tetrazole group are essentially coplanar, with a dihedral angle of 9.72 (7)°. The mononuclear complex is further extended to three-dimensional supramolecular network by hydrogen-bond interactions linking tetrazole group, coordinate and lattice water molecules as shown in Figure 2

Figure 1

Figure 2

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 asymmetric unit of the title complex. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) -x, -y, -z].
	Fig. 2. A crystal packing diagram of the title compound with hydrogen bonds shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

Tetraaquabis[5-(pyridin-3-yl)tetrazolido-κN⁵]manganese(II) tetrahydrate top

Crystal data top

[Mn(C₆H₄N₅)₂(H₂O)₄]·4H₂O	Z = 1
M_r = 491.35	F(000) = 255
Triclinic, P1	D_x = 1.531 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.137 (8) Å	Cell parameters from 1565 reflections
b = 8.629 (8) Å	θ = 2.5–27.3°
c = 8.761 (8) Å	µ = 0.68 mm⁻¹
α = 84.878 (10)°	T = 293 K
β = 65.347 (8)°	Block, yellow
γ = 72.571 (10)°	0.15 × 0.10 × 0.10 mm
V = 533.0 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	1850 independent reflections
Radiation source: fine-focus sealed tube	1712 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −7→9
T_min = 0.922, T_max = 0.934	k = −6→10
2785 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0343P)² + 0.2064P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1850 reflections	Δρ_max = 0.23 e Å⁻³
143 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.063 (6)

Crystal data top

[Mn(C₆H₄N₅)₂(H₂O)₄]·4H₂O	γ = 72.571 (10)°
M_r = 491.35	V = 533.0 (9) Å³
Triclinic, P1	Z = 1
a = 8.137 (8) Å	Mo Kα radiation
b = 8.629 (8) Å	µ = 0.68 mm⁻¹
c = 8.761 (8) Å	T = 293 K
α = 84.878 (10)°	0.15 × 0.10 × 0.10 mm
β = 65.347 (8)°

Data collection top

Bruker APEXII CCD diffractometer	1850 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	1712 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.934	R_int = 0.026
2785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
1850 reflections	Δρ_min = −0.32 e Å⁻³
143 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4972 (3)	0.8406 (3)	0.1955 (2)	0.0309 (5)
H1	0.3863	0.8330	0.2844	0.037*
C2	0.5378 (3)	0.7784 (2)	0.0396 (2)	0.0250 (4)
C3	0.7038 (3)	0.7881 (3)	−0.0919 (2)	0.0312 (4)
H3	0.7369	0.7485	−0.1993	0.037*
C4	0.8196 (3)	0.8579 (3)	−0.0606 (3)	0.0367 (5)
H4	0.9326	0.8647	−0.1468	0.044*
C5	0.7665 (3)	0.9175 (2)	0.0990 (3)	0.0313 (4)
H5	0.8457	0.9643	0.1180	0.038*
C6	0.4027 (3)	0.7086 (2)	0.0214 (2)	0.0253 (4)
Mn1	0.5000	1.0000	0.5000	0.02565 (17)
N1	0.6059 (2)	0.9108 (2)	0.22757 (19)	0.0291 (4)
N2	0.2536 (2)	0.6822 (2)	0.1516 (2)	0.0316 (4)
N3	0.1654 (2)	0.6214 (2)	0.0825 (2)	0.0345 (4)
N4	0.2572 (2)	0.6120 (2)	−0.0813 (2)	0.0335 (4)
N5	0.4088 (2)	0.6669 (2)	−0.12397 (19)	0.0293 (4)
O1	0.4248 (2)	1.25174 (18)	0.44974 (18)	0.0465 (4)
H1B	0.3486	1.3288	0.5213	0.056*
H1A	0.4587	1.2950	0.3548	0.056*
O2	0.79389 (19)	0.99831 (18)	0.44105 (18)	0.0364 (4)
H2A	0.8730	0.9173	0.4589	0.044*
H2B	0.8229	1.0820	0.4526	0.044*
O3	0.0823 (2)	0.75323 (18)	0.49811 (18)	0.0372 (4)
H3B	0.0942	0.6696	0.5562	0.045*
H3A	0.1346	0.7196	0.3958	0.045*
O4	0.1519 (2)	0.48719 (18)	0.69383 (17)	0.0359 (4)
H4B	0.0608	0.4519	0.7598	0.043*
H4A	0.1855	0.5271	0.7575	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0302 (10)	0.0403 (11)	0.0217 (10)	−0.0155 (9)	−0.0058 (8)	−0.0023 (8)
C2	0.0279 (10)	0.0230 (9)	0.0239 (10)	−0.0064 (8)	−0.0108 (8)	−0.0002 (7)
C3	0.0317 (10)	0.0378 (11)	0.0216 (10)	−0.0100 (9)	−0.0071 (8)	−0.0061 (8)
C4	0.0286 (10)	0.0506 (13)	0.0277 (11)	−0.0162 (10)	−0.0043 (8)	−0.0034 (9)
C5	0.0277 (10)	0.0374 (11)	0.0320 (11)	−0.0116 (8)	−0.0134 (8)	−0.0010 (9)
C6	0.0292 (10)	0.0226 (9)	0.0234 (10)	−0.0065 (8)	−0.0104 (8)	−0.0011 (7)
Mn1	0.0264 (2)	0.0299 (3)	0.0210 (2)	−0.00911 (17)	−0.00862 (17)	−0.00332 (16)
N1	0.0311 (9)	0.0351 (9)	0.0230 (8)	−0.0125 (7)	−0.0105 (7)	−0.0017 (7)
N2	0.0307 (9)	0.0386 (10)	0.0264 (9)	−0.0142 (7)	−0.0091 (7)	−0.0018 (7)
N3	0.0341 (9)	0.0405 (10)	0.0320 (9)	−0.0165 (8)	−0.0122 (7)	−0.0018 (8)
N4	0.0370 (9)	0.0370 (10)	0.0314 (9)	−0.0153 (8)	−0.0152 (8)	−0.0008 (7)
N5	0.0348 (9)	0.0320 (9)	0.0237 (9)	−0.0141 (7)	−0.0109 (7)	−0.0014 (7)
O1	0.0623 (10)	0.0321 (8)	0.0252 (8)	−0.0059 (7)	−0.0044 (7)	0.0003 (6)
O2	0.0302 (7)	0.0385 (8)	0.0429 (9)	−0.0084 (6)	−0.0166 (6)	−0.0071 (6)
O3	0.0407 (8)	0.0377 (8)	0.0292 (8)	−0.0113 (7)	−0.0100 (6)	−0.0011 (6)
O4	0.0401 (8)	0.0413 (8)	0.0273 (8)	−0.0177 (7)	−0.0094 (6)	−0.0044 (6)

Geometric parameters (Å, º) top

C1—N1	1.337 (3)	Mn1—O2ⁱ	2.222 (3)
C1—C2	1.382 (3)	Mn1—O2	2.222 (3)
C1—H1	0.9300	Mn1—N1	2.290 (3)
C2—C3	1.383 (3)	Mn1—N1ⁱ	2.290 (3)
C2—C6	1.468 (3)	N2—N3	1.342 (2)
C3—C4	1.382 (3)	N3—N4	1.309 (3)
C3—H3	0.9300	N4—N5	1.349 (3)
C4—C5	1.377 (3)	O1—H1B	0.8500
C4—H4	0.9300	O1—H1A	0.8500
C5—N1	1.336 (3)	O2—H2A	0.8500
C5—H5	0.9300	O2—H2B	0.8501
C6—N5	1.331 (3)	O3—H3B	0.8500
C6—N2	1.338 (3)	O3—H3A	0.8501
Mn1—O1	2.132 (2)	O4—H4B	0.8500
Mn1—O1ⁱ	2.132 (2)	O4—H4A	0.8501

N1—C1—C2	124.70 (17)	O1—Mn1—N1	95.02 (7)
N1—C1—H1	117.6	O1ⁱ—Mn1—N1	84.98 (7)
C2—C1—H1	117.6	O2ⁱ—Mn1—N1	92.50 (6)
C1—C2—C3	117.48 (18)	O2—Mn1—N1	87.50 (6)
C1—C2—C6	118.90 (17)	O1—Mn1—N1ⁱ	84.98 (7)
C3—C2—C6	123.61 (18)	O1ⁱ—Mn1—N1ⁱ	95.02 (7)
C4—C3—C2	118.66 (19)	O2ⁱ—Mn1—N1ⁱ	87.50 (5)
C4—C3—H3	120.7	O2—Mn1—N1ⁱ	92.50 (6)
C2—C3—H3	120.7	N1—Mn1—N1ⁱ	179.999 (1)
C5—C4—C3	119.62 (19)	C5—N1—C1	116.74 (18)
C5—C4—H4	120.2	C5—N1—Mn1	127.06 (13)
C3—C4—H4	120.2	C1—N1—Mn1	116.17 (13)
N1—C5—C4	122.78 (19)	C6—N2—N3	104.94 (17)
N1—C5—H5	118.6	N4—N3—N2	109.54 (17)
C4—C5—H5	118.6	N3—N4—N5	109.28 (15)
N5—C6—N2	111.27 (17)	C6—N5—N4	104.97 (15)
N5—C6—C2	125.30 (17)	Mn1—O1—H1B	126.3
N2—C6—C2	123.42 (17)	Mn1—O1—H1A	127.6
O1—Mn1—O1ⁱ	180.0	H1B—O1—H1A	106.1
O1—Mn1—O2ⁱ	88.59 (7)	Mn1—O2—H2A	122.5
O1ⁱ—Mn1—O2ⁱ	91.41 (7)	Mn1—O2—H2B	123.2
O1—Mn1—O2	91.41 (7)	H2A—O2—H2B	106.1
O1ⁱ—Mn1—O2	88.59 (7)	H3B—O3—H3A	106.7
O2ⁱ—Mn1—O2	180.000 (1)	H4B—O4—H4A	105.2

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O4ⁱⁱ	0.85	1.94	2.783 (3)	172
O1—H1A···N5ⁱⁱⁱ	0.85	1.91	2.731 (3)	163
O2—H2A···O3^iv	0.85	1.99	2.836 (3)	171
O2—H2B···O3ⁱ	0.85	1.96	2.800 (3)	169
O3—H3B···O4	0.85	1.96	2.803 (3)	171
O3—H3A···N2	0.85	1.96	2.797 (3)	170
O4—H4B···N3^v	0.85	2.03	2.878 (3)	177
O4—H4A···N4^vi	0.85	2.00	2.849 (3)	176

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+2, −z; (iv) x+1, y, z; (v) −x, −y+1, −z+1; (vi) x, y, z+1.

Experimental details

Crystal data
Chemical formula	[Mn(C₆H₄N₅)₂(H₂O)₄]·4H₂O
M_r	491.35
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.137 (8), 8.629 (8), 8.761 (8)
α, β, γ (°)	84.878 (10), 65.347 (8), 72.571 (10)
V (Å³)	533.0 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.922, 0.934
No. of measured, independent and observed [I > 2σ(I)] reflections	2785, 1850, 1712
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.080, 1.05
No. of reflections	1850
No. of parameters	143
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.32

Computer programs: APEX2 (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O4ⁱ	0.85	1.94	2.783 (3)	172
O1—H1A···N5ⁱⁱ	0.85	1.91	2.731 (3)	163
O2—H2A···O3ⁱⁱⁱ	0.85	1.99	2.836 (3)	171
O2—H2B···O3^iv	0.85	1.96	2.800 (3)	169
O3—H3B···O4	0.85	1.96	2.803 (3)	171
O3—H3A···N2	0.85	1.96	2.797 (3)	170
O4—H4B···N3^v	0.85	2.03	2.878 (3)	177
O4—H4A···N4^vi	0.85	2.00	2.849 (3)	176

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z; (iii) x+1, y, z; (iv) −x+1, −y+2, −z+1; (v) −x, −y+1, −z+1; (vi) x, y, z+1.

Acknowledgements

The project was supported by the National Natural Science Foundation of China (21171115), the Leading Academic Discipline Project (J50102) and the Innovation Program (12ZZ089) of Shanghai Municipal Education Commission, China.

References

Bruker (2000). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mu, Y.-Q., Zhao, J. & Li, C. (2010). Acta Cryst. E66, m1667. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2007). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar