Diaqua­bis[5-(2-pyridylmeth­yl)tetra­zolato-κ2N1,N5]manganese(II)

Wang, W.

doi:10.1107/S1600536808019272

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m999

doi:10.1107/S1600536808019272

Open

access

Diaquabis[5-(2-pyridylmethyl)tetrazolato-κ²N¹,N⁵]manganese(II)

Wei Wang ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: seuwangwei@gmail.com

(Received 20 June 2008; accepted 25 June 2008; online 5 July 2008)

The title complex, [Mn(C₇H₆N₅)₂(H₂O)₂], was obtained by the in situ hydrothermal reaction of MnCl₂ with 2-(2-pyridyl)acetonitrile in the presence of NaN₃. The Mn^II atom, which is located on an inversion centre, has a distorted octahedral coordination geometry formed by two water molecules and two chelating ligands. Intermolecular hydrogen bonds and π–π interactions (3.452 Å) stabilize the crystal structure and lead to the formation of a three-dimensional network.

Related literature

For related literature, see: Demko & Sharpless (2001 ); Zhao et al. (2008 ). For the synthesis of similar complexes, see: Hu et al. (2007 ); Liu & Fan (2007 ).

Experimental

Crystal data

[Mn(C₇H₆N₅)₂(H₂O)₂]
M_r = 411.31
Monoclinic, P 2₁ /n
a = 6.638 (2) Å
b = 13.788 (5) Å
c = 8.771 (3) Å
β = 90.01 (5)°
V = 802.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 293 (2) K
0.20 × 0.12 × 0.12 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.802, T_max = 1.000 (expected range = 0.723–0.902)
8070 measured reflections
1836 independent reflections
1550 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.172
S = 1.13
1836 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N2ⁱ	0.96	2.04	2.889 (8)	146
O1—H1B⋯N5ⁱ	0.96	2.45	3.371 (8)	162
O1—H1C⋯N4ⁱⁱ	0.96	1.96	2.786 (8)	142
C6—H6A⋯N5ⁱⁱⁱ	0.97	2.60	3.343 (5)	133
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x-1, y, z.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019272/hg2418sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019272/hg2418Isup2.hkl

checkCIF report

Comment top

Since Sharpless et al. reported the environmentally friendly process for the preparation of tetrazole (Demko & Sharpless, 2001), many novel tetrazole compounds have been reported through 2 + 3 cycloaddition reactions. Work in our group have found that single crystals of coordination polymers can often be generated under hydrothermal conditions through in situ synthesis. (Zhao et al., 2008) The title complex was obtained by the in situ hydrothermal reaction of MnCl₂ with pyridin-2-yl-acetonitrile in the presence of NaN₃.

In the title compound, the central Mn(II) ion is located on an inversion center and coordinated by two water molecules and two 5-(pyridin-2-ylmethyl)tetrazolate ligands through the pyridine N and tetrazole N atoms with a distorted octahedral geometry (Fig. 1). Extensive intermolecular O—H···N and C—H···N hydrogen bonds and π-π interactions stabilize the crystal structure which leads to the formation of a three-dimensional network.

Related literature top

For related literature, see: Demko & Sharpless (2001); Zhao et al. (2008). For the synthesis of similar complexes, see: Hu et al. (2007); Liu & Fan (2007).

Experimental top

A mixture of pyridin-2-yl-acetonitrile (26 mg, 0.2 mmol), NaN₃ (26 mg, 0.4 mmol), MnCl₂.4H₂O(59.3 mg, 0.3 mmol), ethanol (1 ml) and a few drops of water sealed in a glass tube was maintained at 105°C. Colorless crystals suitable for X-ray analysis were obtained after a week.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. [symmetry code: -x, -y+2, -z+2]
	Fig. 2. The packing view of title compound with π···π stacking along the b axis.

Diaquabis[5-(2-pyridylmethyl)tetrazolato-κ²N¹,N⁵]manganese(II) top

Crystal data top

[Mn(C₇H₆N₅)₂(H₂O)₂]	F(000) = 422
M_r = 411.31	D_x = 1.701 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2050 reflections
a = 6.639 (2) Å	θ = 2.8–27.5°
b = 13.788 (5) Å	µ = 0.86 mm⁻¹
c = 8.771 (3) Å	T = 293 K
β = 90.01 (5)°	Prism, colorless
V = 802.9 (4) Å³	0.20 × 0.12 × 0.12 mm
Z = 2

Data collection top

Rigaku Mercury2) diffractometer	1836 independent reflections
Radiation source: fine-focus sealed tube	1550 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.802, T_max = 1.000	l = −11→11
8070 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0834P)² + 0.8368P] where P = (F_o² + 2F_c²)/3
1836 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

[Mn(C₇H₆N₅)₂(H₂O)₂]	V = 802.9 (4) Å³
M_r = 411.31	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.639 (2) Å	µ = 0.86 mm⁻¹
b = 13.788 (5) Å	T = 293 K
c = 8.771 (3) Å	0.20 × 0.12 × 0.12 mm
β = 90.01 (5)°

Data collection top

Rigaku Mercury2) diffractometer	1836 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1550 reflections with I > 2σ(I)
T_min = 0.802, T_max = 1.000	R_int = 0.057
8070 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.13	Δρ_max = 0.39 e Å⁻³
1836 reflections	Δρ_min = −0.73 e Å⁻³
124 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
Mn1	0.0000	1.0000	1.0000	0.0261 (3)
N5	0.4367 (4)	0.7962 (2)	0.8387 (3)	0.0354 (7)
O1	0.2353 (4)	1.10029 (18)	0.9172 (3)	0.0382 (6)
H1B	0.3241	1.1164	0.9997	0.057*
H1C	0.1730	1.1583	0.8792	0.057*
N3	0.1879 (4)	0.88112 (19)	0.9162 (3)	0.0299 (6)
C7	0.1284 (5)	0.8238 (2)	0.8048 (4)	0.0275 (7)
N2	0.3843 (4)	0.8625 (2)	0.9339 (3)	0.0346 (7)
N4	0.2778 (4)	0.7701 (2)	0.7545 (3)	0.0332 (6)
C6	−0.0793 (5)	0.8223 (2)	0.7415 (4)	0.0317 (7)
H6A	−0.1720	0.8028	0.8214	0.038*
H6B	−0.0860	0.7738	0.6614	0.038*
C5	−0.1465 (5)	0.9175 (2)	0.6782 (4)	0.0289 (7)
C4	−0.2173 (5)	0.9233 (3)	0.5316 (4)	0.0359 (8)
H4A	−0.2262	0.8677	0.4720	0.043*
C3	−0.2743 (6)	1.0105 (3)	0.4737 (4)	0.0371 (8)
H3A	−0.3202	1.0155	0.3738	0.045*
C2	−0.2628 (6)	1.0907 (3)	0.5649 (4)	0.0377 (8)
H2A	−0.3022	1.1513	0.5290	0.045*
C1	−0.1925 (5)	1.0797 (2)	0.7089 (4)	0.0340 (8)
H1A	−0.1832	1.1345	0.7704	0.041*
N1	−0.1363 (4)	0.99533 (17)	0.7671 (3)	0.0273 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0329 (4)	0.0185 (4)	0.0270 (4)	0.0025 (2)	−0.0001 (3)	−0.0016 (2)
N5	0.0353 (15)	0.0297 (15)	0.0413 (16)	0.0058 (12)	−0.0018 (12)	−0.0047 (12)
O1	0.0381 (13)	0.0326 (13)	0.0439 (14)	−0.0103 (10)	−0.0061 (11)	0.0116 (11)
N3	0.0341 (15)	0.0230 (13)	0.0326 (14)	0.0049 (11)	−0.0004 (11)	−0.0030 (11)
C7	0.0324 (16)	0.0155 (13)	0.0345 (16)	0.0003 (11)	0.0025 (13)	−0.0007 (12)
N2	0.0328 (15)	0.0265 (14)	0.0446 (16)	0.0041 (11)	−0.0027 (12)	−0.0019 (12)
N4	0.0371 (15)	0.0253 (13)	0.0371 (16)	0.0054 (11)	−0.0003 (12)	−0.0037 (12)
C6	0.0339 (17)	0.0217 (15)	0.0395 (17)	−0.0018 (12)	−0.0022 (14)	−0.0058 (13)
C5	0.0271 (15)	0.0245 (15)	0.0349 (17)	−0.0007 (12)	−0.0006 (13)	−0.0032 (13)
C4	0.0334 (17)	0.0372 (19)	0.0373 (18)	0.0010 (14)	−0.0045 (14)	−0.0081 (15)
C3	0.0299 (18)	0.051 (2)	0.0303 (17)	−0.0013 (14)	−0.0013 (14)	0.0029 (15)
C2	0.0399 (19)	0.0357 (18)	0.0376 (18)	0.0039 (15)	−0.0015 (15)	0.0079 (15)
C1	0.0417 (19)	0.0246 (16)	0.0357 (17)	0.0038 (13)	0.0001 (14)	0.0003 (13)
N1	0.0289 (14)	0.0239 (14)	0.0291 (14)	0.0009 (9)	0.0012 (11)	0.0003 (10)

Geometric parameters (Å, º) top

Mn1—N3	2.187 (5)	C6—H6A	0.9700
Mn1—O1	2.209 (5)	C6—H6B	0.9700
Mn1—N1	2.235 (3)	C5—N1	1.328 (5)
N5—N2	1.286 (5)	C5—C4	1.371 (6)
N5—N4	1.337 (5)	C4—C3	1.359 (6)
O1—H1B	0.9600	C4—H4A	0.9300
O1—H1C	0.9600	C3—C2	1.367 (6)
N3—C7	1.317 (5)	C3—H3A	0.9300
N3—N2	1.338 (6)	C2—C1	1.355 (6)
C7—N4	1.314 (5)	C2—H2A	0.9300
C7—C6	1.487 (6)	C1—N1	1.324 (5)
C6—C5	1.494 (6)	C1—H1A	0.9300

N3—Mn1—O1	87.43 (11)	C7—C6—H6B	108.8
N3ⁱ—Mn1—O1	92.57 (5)	C5—C6—H6B	108.8
N3—Mn1—N1	84.39 (17)	H6A—C6—H6B	107.7
N3ⁱ—Mn1—N1	95.61 (17)	N1—C5—C4	121.4 (3)
O1ⁱ—Mn1—N1	89.79 (18)	N1—C5—C6	118.5 (4)
O1—Mn1—N1	90.21 (18)	C4—C5—C6	120.1 (3)
N2—N5—N4	109.6 (3)	C3—C4—C5	119.9 (3)
Mn1—O1—H1B	109.3	C3—C4—H4A	120.1
Mn1—O1—H1C	109.3	C5—C4—H4A	120.1
H1B—O1—H1C	109.5	C4—C3—C2	118.8 (4)
C7—N3—N2	105.3 (3)	C4—C3—H3A	120.6
C7—N3—Mn1	121.9 (3)	C2—C3—H3A	120.6
N2—N3—Mn1	131.4 (2)	C1—C2—C3	118.3 (4)
N3—C7—N4	111.1 (3)	C1—C2—H2A	120.9
N3—C7—C6	124.3 (3)	C3—C2—H2A	120.9
N4—C7—C6	124.5 (3)	N1—C1—C2	123.7 (3)
N5—N2—N3	109.0 (3)	N1—C1—H1A	118.2
C7—N4—N5	105.0 (3)	C2—C1—H1A	118.2
C7—C6—C5	113.8 (3)	C1—N1—C5	118.0 (4)
C7—C6—H6A	108.8	C1—N1—Mn1	116.2 (2)
C5—C6—H6A	108.8	C5—N1—Mn1	125.5 (2)

O1ⁱ—Mn1—N3—C7	64.4 (3)	C7—C6—C5—C4	125.9 (3)
O1—Mn1—N3—C7	−115.6 (3)	N1—C5—C4—C3	1.5 (5)
N1—Mn1—N3—C7	−25.2 (3)	C6—C5—C4—C3	−178.6 (3)
O1ⁱ—Mn1—N3—N2	−131.9 (3)	C5—C4—C3—C2	−1.1 (6)
O1—Mn1—N3—N2	48.1 (3)	C4—C3—C2—C1	0.8 (6)
N1—Mn1—N3—N2	138.5 (3)	C3—C2—C1—N1	−0.8 (6)
N1ⁱ—Mn1—N3—N2	−41.5 (3)	C2—C1—N1—C5	1.1 (5)
N2—N3—C7—N4	0.8 (4)	C2—C1—N1—Mn1	174.6 (3)
Mn1—N3—C7—N4	168.2 (2)	C4—C5—N1—C1	−1.5 (5)
N2—N3—C7—C6	−177.6 (3)	C6—C5—N1—C1	178.7 (3)
Mn1—N3—C7—C6	−10.2 (4)	C4—C5—N1—Mn1	−174.3 (2)
N4—N5—N2—N3	0.7 (4)	C6—C5—N1—Mn1	5.9 (4)
C7—N3—N2—N5	−0.9 (4)	N3—Mn1—N1—C1	−145.1 (3)
Mn1—N3—N2—N5	−166.6 (2)	N3ⁱ—Mn1—N1—C1	34.9 (3)
N3—C7—N4—N5	−0.3 (4)	O1ⁱ—Mn1—N1—C1	122.3 (3)
C6—C7—N4—N5	178.0 (3)	O1—Mn1—N1—C1	−57.7 (3)
N2—N5—N4—C7	−0.3 (4)	N3—Mn1—N1—C5	27.8 (3)
N3—C7—C6—C5	59.0 (5)	N3ⁱ—Mn1—N1—C5	−152.2 (3)
N4—C7—C6—C5	−119.2 (4)	O1ⁱ—Mn1—N1—C5	−64.8 (3)
C7—C6—C5—N1	−54.2 (4)	O1—Mn1—N1—C5	115.2 (3)

Symmetry code: (i) −x, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N2ⁱⁱ	0.96	2.04	2.889 (8)	146
O1—H1B···N5ⁱⁱ	0.96	2.45	3.371 (8)	162
O1—H1C···N4ⁱⁱⁱ	0.96	1.96	2.786 (8)	142
C6—H6A···N5^iv	0.97	2.60	3.343 (5)	133

Symmetry codes: (ii) −x+1, −y+2, −z+2; (iii) −x+1/2, y+1/2, −z+3/2; (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Mn(C₇H₆N₅)₂(H₂O)₂]
M_r	411.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.639 (2), 13.788 (5), 8.771 (3)
β (°)	90.01 (5)
V (Å³)	802.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.20 × 0.12 × 0.12

Data collection
Diffractometer	Rigaku Mercury2) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.802, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8070, 1836, 1550
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.173, 1.13
No. of reflections	1836
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.73

Computer programs: CrystalClear (Rigaku, 2005), 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···N2ⁱ	0.96	2.04	2.889 (8)	146.1
O1—H1B···N5ⁱ	0.96	2.45	3.371 (8)	161.8
O1—H1C···N4ⁱⁱ	0.96	1.96	2.786 (8)	142.1
C6—H6A···N5ⁱⁱⁱ	0.97	2.60	3.343 (5)	133.2

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x−1, y, z.

Acknowledgements

The authors are grateful to the Starter Fund of Southeast University for financial support to buy the CCD X-ray diffractometer.

References

Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem. 66, 7945–7950. Web of Science CrossRef PubMed CAS Google Scholar
Hu, B., Xu, X.-B., Li, Y.-X. & Ye, H.-Y. (2007). Acta Cryst. E63, m2698. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, J.-T. & Fan, S.-D. (2007). Acta Cryst. E63, m1628. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev. 37, 84–100. Web of Science CrossRef PubMed Google Scholar