Tetra­aqua­bis­(tetra­zolido-κN1)magnesium

Liu, T.-L.; Deng, J.-H.; Sun, S.-J.

doi:10.1107/S1600536810027625

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page m979

https://doi.org/10.1107/S1600536810027625

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Tetraaquabis(tetrazolido-κN¹)magnesium

Ti-Lou Liu,^a Ji-Hua Deng ^b and Shuang-Jiao Sun ^a ^*

^aShaoyang Medical College, Shaoyang, Hunan 422000, People's Republic of China, and ^bCollege of Chemistry and Bio-engineering, Yichun University, Yichun, Jiangxi 336000, People's Republic of China
^*Correspondence e-mail: sshj_2008@yahoo.cn

(Received 7 July 2010; accepted 12 July 2010; online 21 July 2010)

In the crystal structure of the title compound, [Mg(CHN₄)₂(H₂O)₄], the Mg^II atom is six-coordinated by two N atoms from two tetrazolide anions and four O atoms from four coordinated water molecules in a slightly distorted octahedral geometry. The Mg atom is located on centres of inversion whereas the tetrazolide anion and the water molecules occupy general positions. The crystal packing is stabilized by intermolecular O—H⋯N hydrogen bonding between the tetrazolide anions and the coordinated water molecules.

Related literature

For metal complexes with tetrazolide anions, see: Zhang et al. (2007 ); He et al. (2006 ).

Experimental

Crystal data

[Mg(CHN₄)₂(H₂O)₄]
M_r = 234.49
Monoclinic, P 2₁ /c
a = 5.7570 (19) Å
b = 11.638 (4) Å
c = 6.963 (2) Å
β = 99.785 (5)°
V = 459.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 173 K
0.36 × 0.28 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.929, T_max = 0.955
1806 measured reflections
792 independent reflections
709 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.097
S = 1.01
792 reflections
86 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N3ⁱ	0.83 (2)	1.96 (2)	2.7797 (19)	173 (2)
O1—H1B⋯N1ⁱⁱ	0.88 (2)	1.89 (2)	2.755 (2)	169 (2)
O1—H1A⋯N4ⁱⁱⁱ	0.81 (2)	2.15 (2)	2.956 (2)	173 (2)
O2—H2A⋯N4^iv	0.83 (2)	2.06 (2)	2.892 (2)	171 (2)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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/S1600536810027625/nc2193sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027625/nc2193Isup2.hkl

checkCIF report

Comment top

Tetrazolide anions are found in a number of metal complexes as ligands and the crystal structures and properties of several of such metal complexes have been reported in literature (Zhang et al., 2007; He et al., 2006) In the present contribution we report the synthesis and crystal structure of it's magnesium(II) complex. In the crystal structure of the title compound the Mg atoms are six-coordinated by two N atoms from two symmetry equivalent tetrazolide anions and four O atoms of two pairs of symmetry equivalent water molecules. The coordination polyhedra around the Mg atoms can be described as slightly distorted tetrahedra (Fig. 1). In the crystal structure the complexes are connected by intermolecular O—H···N hydrogen bonding into a three-dimensional network (Fig. 2 and Tab. 1).

Related literature top

For metal complexes with tetrazolide anions, see: Zhang et al. (2007); He et al. (2006).

Experimental top

A solution of MgCl₂ 2H₂O (1 mmol) in water (5 ml) was slowly added to a solution of tetrazole (1 mmol) in water (14 ml) with continuous stirring at room temperature. After 30 minutes, the mixture was sealed in a 25 ml Teflon-lined stainless steel vessel and heated under autogenous pressure at 160 °C for 4 days, then slowly cooled to room temperature. The colorless crystals were collected by filtration, washed with distilled water and dried in air. Yield: 60% (based on Mg).

Structure description top

For metal complexes with tetrazolide anions, see: Zhang et al. (2007); He et al. (2006).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 structure of (I), showing 30% probability displacement ellipsoids and the atom-labeling scheme. Symmetry code: i = x, y, z.
	Fig. 2. Crystal structure of title compound with view along the a axis. Hydrogen bonding is shown as dashed lines.

Tetraaquabis(tetrazolido-κN¹)magnesium top

Crystal data top

[Mg(CHN₄)₂(H₂O)₄]	F(000) = 244
M_r = 234.49	D_x = 1.694 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1468 reflections
a = 5.7570 (19) Å	θ = 3.5–26.9°
b = 11.638 (4) Å	µ = 0.21 mm⁻¹
c = 6.963 (2) Å	T = 173 K
β = 99.785 (5)°	Block, colorless
V = 459.7 (3) Å³	0.36 × 0.28 × 0.22 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	792 independent reflections
Radiation source: fine-focus sealed tube	709 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
phi and ω scans	θ_max = 25.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −5→6
T_min = 0.929, T_max = 0.955	k = −13→12
1806 measured reflections	l = −7→8

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0716P)² + 0.1838P] where P = (F_o² + 2F_c²)/3
792 reflections	(Δ/σ)_max < 0.001
86 parameters	Δρ_max = 0.35 e Å⁻³
6 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Mg(CHN₄)₂(H₂O)₄]	V = 459.7 (3) Å³
M_r = 234.49	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.7570 (19) Å	µ = 0.21 mm⁻¹
b = 11.638 (4) Å	T = 173 K
c = 6.963 (2) Å	0.36 × 0.28 × 0.22 mm
β = 99.785 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	792 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	709 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.955	R_int = 0.015
1806 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	6 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.35 e Å⁻³
792 reflections	Δρ_min = −0.25 e Å⁻³
86 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
Mg1	0.5000	0.5000	0.0000	0.0139 (3)
N1	0.8863 (2)	0.31027 (12)	0.0878 (2)	0.0188 (4)
N2	0.6554 (2)	0.32630 (12)	0.02230 (19)	0.0154 (4)
C1	0.5683 (3)	0.22168 (15)	−0.0099 (2)	0.0184 (4)
H1	0.4070	0.2058	−0.0575	0.022*
N4	0.7331 (2)	0.14132 (12)	0.0322 (2)	0.0199 (4)
O1	0.2683 (2)	0.45460 (11)	0.18011 (19)	0.0187 (3)
O2	0.7258 (2)	0.54196 (11)	0.25064 (18)	0.0196 (4)
N3	0.9328 (3)	0.20068 (12)	0.0938 (2)	0.0200 (4)
H2A	0.729 (4)	0.4945 (18)	0.341 (3)	0.033 (6)*
H1A	0.256 (4)	0.5042 (18)	0.260 (3)	0.037 (7)*
H1B	0.136 (4)	0.417 (2)	0.150 (3)	0.043 (7)*
H2B	0.819 (4)	0.594 (2)	0.293 (4)	0.045 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0152 (4)	0.0058 (5)	0.0200 (5)	−0.0001 (3)	0.0007 (3)	−0.0002 (3)
N1	0.0187 (8)	0.0104 (8)	0.0262 (8)	0.0028 (6)	0.0011 (6)	0.0006 (6)
N2	0.0170 (7)	0.0095 (8)	0.0194 (8)	0.0003 (6)	0.0017 (6)	−0.0003 (5)
C1	0.0192 (8)	0.0115 (9)	0.0235 (9)	−0.0005 (7)	0.0006 (7)	−0.0002 (7)
N4	0.0242 (8)	0.0090 (8)	0.0255 (9)	0.0007 (6)	0.0015 (6)	−0.0007 (6)
O1	0.0201 (7)	0.0106 (7)	0.0260 (7)	−0.0027 (5)	0.0053 (5)	−0.0036 (5)
O2	0.0237 (7)	0.0105 (7)	0.0221 (7)	−0.0051 (5)	−0.0034 (5)	0.0019 (5)
N3	0.0227 (8)	0.0108 (7)	0.0256 (8)	0.0026 (6)	0.0014 (6)	−0.0002 (6)

Geometric parameters (Å, º) top

Mg1—O1ⁱ	2.0492 (13)	N2—C1	1.321 (2)
Mg1—O1	2.0492 (13)	C1—N4	1.329 (2)
Mg1—O2ⁱ	2.0499 (13)	C1—H1	0.9500
Mg1—O2	2.0499 (13)	N4—N3	1.347 (2)
Mg1—N2	2.2053 (15)	O1—H1A	0.812 (19)
Mg1—N2ⁱ	2.2053 (15)	O1—H1B	0.876 (19)
N1—N3	1.302 (2)	O2—H2A	0.83 (2)
N1—N2	1.343 (2)	O2—H2B	0.83 (2)

O1ⁱ—Mg1—O1	180.00 (7)	N3—N1—N2	109.45 (13)
O1ⁱ—Mg1—O2ⁱ	85.69 (6)	C1—N2—N1	104.74 (13)
O1—Mg1—O2ⁱ	94.31 (6)	C1—N2—Mg1	134.05 (11)
O1ⁱ—Mg1—O2	94.31 (6)	N1—N2—Mg1	121.16 (10)
O1—Mg1—O2	85.69 (6)	N2—C1—N4	112.04 (15)
O2ⁱ—Mg1—O2	180.00 (7)	N2—C1—H1	124.0
O1ⁱ—Mg1—N2	88.91 (5)	N4—C1—H1	124.0
O1—Mg1—N2	91.09 (5)	C1—N4—N3	104.34 (15)
O2ⁱ—Mg1—N2	91.86 (5)	Mg1—O1—H1A	112.3 (16)
O2—Mg1—N2	88.14 (5)	Mg1—O1—H1B	128.1 (16)
O1ⁱ—Mg1—N2ⁱ	91.09 (5)	H1A—O1—H1B	110 (2)
O1—Mg1—N2ⁱ	88.91 (5)	Mg1—O2—H2A	114.5 (16)
O2ⁱ—Mg1—N2ⁱ	88.14 (5)	Mg1—O2—H2B	139.2 (17)
O2—Mg1—N2ⁱ	91.86 (5)	H2A—O2—H2B	106 (2)
N2—Mg1—N2ⁱ	180.0	N1—N3—N4	109.42 (14)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N3ⁱⁱ	0.83 (2)	1.96 (2)	2.7797 (19)	173 (2)
O1—H1B···N1ⁱⁱⁱ	0.88 (2)	1.89 (2)	2.755 (2)	169 (2)
O1—H1A···N4^iv	0.81 (2)	2.15 (2)	2.956 (2)	173 (2)
O2—H2A···N4^v	0.83 (2)	2.06 (2)	2.892 (2)	171 (2)

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

Experimental details

Crystal data
Chemical formula	[Mg(CHN₄)₂(H₂O)₄]
M_r	234.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	5.7570 (19), 11.638 (4), 6.963 (2)
β (°)	99.785 (5)
V (Å³)	459.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.36 × 0.28 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.929, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	1806, 792, 709
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.097, 1.01
No. of reflections	792
No. of parameters	86
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
O2—H2B···N3ⁱ	0.83 (2)	1.96 (2)	2.7797 (19)	173 (2)
O1—H1B···N1ⁱⁱ	0.876 (19)	1.889 (19)	2.755 (2)	169 (2)
O1—H1A···N4ⁱⁱⁱ	0.812 (19)	2.149 (19)	2.956 (2)	173 (2)
O2—H2A···N4^iv	0.83 (2)	2.06 (2)	2.892 (2)	171 (2)

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

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
He, X., Lu, C.-Z. & Yuan, D.-Q. (2006). Inorg. Chem. 15, 5760–5766. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, X.-M., Zhao, Y.-F., Zhang, W.-X. & Chen, X.-M. (2007). Adv. Mater. 19, 2843–2846. Web of Science CSD CrossRef CAS Google Scholar