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

Abstract

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,

• 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) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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

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.

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
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⋯O3iv	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⋯N3v	0.85	2.03	2.878 (3)	177
O4—H4A⋯N4vi	0.85	2.00	2.849 (3)	176

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

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)

Experimental

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.

Refinement

All the H atoms were positioned geometrically (C—H = 0.93 Å, O—H = 0.85 Å), and allowed to ride on their parent atoms, with U_iso(H) = 1.2 U_eq(C) or 1.5Ueq(O).

Figures

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.

Crystal data

[Mn(C6H4N5)2(H2O)4]·4H2O	Z = 1
Mr = 491.35	F(000) = 255
Triclinic, P1	Dx = 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

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

Refinement

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(Fo2) + (0.0343P)2 + 0.2064P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1850 reflections	Δρmax = 0.23 e Å−3
143 parameters	Δρmin = −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)

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
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 (Ų)

	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)

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)

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···O3iv	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···N3v	0.85	2.03	2.878 (3)	177
O4—H4A···N4vi	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.