Hexaaqua­magnesium(II) bis­{[2-(1-phenyl-1H-tetra­zol-5-yl)sulfan­yl]acetate}

The asymmetric unit of the title compound, [Mg(H₂O)₆](C₉H₇N₄O₂S)₂, contains one-half of a [Mg(H₂O)₆]²⁺ cation ( symmetry) and one uncoordinated 2-[(1-phenyl-1H-tetra­zol-5-yl)sulfan­yl]acetate anion. The Mg^II cation is coordinated by six water mol­ecules, exhibiting a slightly distorted octa­hedral coordination. A two-dimensional network parallel to (001) is formed via extensive hydrogen-bonding inter­actions involving the water mol­ecules as donors and the tetra­zole N and carboxyl­ate O atoms of the anion as acceptors. The shortest distance between two adjacent parallel benzene rings is 3.315 (2) Å. The dihedral angle between the benzene ring and the tetra­zole ring is 40.98 (2)°.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.122
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         10
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The design and synthesis of supramolecular complexes with a high-nuclearity and N-containing carboxylate ligands, especially tetrazole-containing ligands, has been a rapidly growing area of research due to their fascinating structures and interesting physical properties (He et al., 2005). Several transition metal and rare earths metal complexes with similar ligand systems were reported (Yang et al., 2008).

We are interested in the solid-state coordination chemistry of ligands derived from 2-(1-phenyl-1H-tetrazol-5-ylthio)acetic acid (HPsta). In order to understand the behavior of alkali earth metals with the HPsta ligand, we prepared the title compound, [Mg(H₂O)₆](Psta)₂, (I), the synthesis and structure of which are reported here.

As shown in Fig. 1, the asymmetric unit of (I) consists of one-half of a [Mg(H₂O)₆]²⁺ cation (site symmetry 1) and an uncoordinated 2-(1-phenyl-1H-tetrazol-5-ylthio)acetate monoanion. The Mg^II atom is coordinated by six water molecules in a slightly distorted octahedral coordination. The corresponding Mg—O distances (Table 1) are in agreement with similar complexes containing the [Mg(H₂O)]²⁺ cation (Zhang et al., 2006; Zhou et al., 2008). The dihedral angle between the benzene ring and the tetrazole ring is 40.98 (2) °. In the crystal structure, the two Psta groups are involved in a number of intermolecular hydrogen bonds (Table 2) involving the O and N atoms as acceptors and the coordinated water molecules as donor groups (Fig. 2; Table 2), leading to a layer structure extending parallel to (001). In addition, π—π stacking is observed with a shortest distance between two adjacent parallel benzene rings of 3.315 (2) Å.

Related literature

For general background, see: He et al. (2005); Yang et al. (2008). For synthetic details, see: D'Amico et al. (1957). For related structures with [Mg(H₂O)₆]²⁺ cations, see: Zhang et al. (2006); Zhou et al. (2008).

S2. Experimental

The ligand 2-(1-phenyl-1H-tetrazol-5-ylthio)acetic acid (HPsta) was synthesized according to the literature method (D'Amico et al., 1957). To prepare the title complex, the ligand HPsta (0.4 mmol,0.0944 g) was dissolved in methanol (6 ml) at 348 K and an aqueous solution (4 ml) containing MgCO₃ (0.0336 g, 0.4 mmol) was added. The resulting solution was stirred at 348 K for 4 h, then cooled to room temperature and filtered. Colorless, prismatic crystals suitable for X-ray diffraction were obtained by slow evaporation over several days, with a yield of 61%. Elemental analysis, found (%):C, 35.79; H, 4.38; O, 26.65; N, 18.52; S, 10.66 calc(%): 35.88; H, 4.32; O, 26.58; N, 18.60; S, 10.63.

S3. Refinement

Water H atoms were located in a difference Fourier map and refined freely. All other H atoms were placed in their calculated positions and refined as riding with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular moieties of (I), showing the atom-numbering scheme. Symmetry code: A -x+2,-y,-z+2. Probability function is drawn at the 50% level.
	Fig. 2. Packing of (I), viewed down the a axis. Hydrogen bonding interactions are shown by dashed lines.

Hexaaquamagnesium(II) bis{[2-(1-phenyl-1H-tetrazol-5-yl)sulfanyl]acetate}

Crystal data

[Mg(H2O)6](C9H7N4O2S)2	Z = 1
Mr = 602.92	F(000) = 314.0
Triclinic, P1	Dx = 1.481 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8380 (14) Å	Cell parameters from 1867 reflections
b = 7.5220 (15) Å	θ = 2.0–25.0°
c = 13.556 (3) Å	µ = 0.29 mm^−1
α = 92.57 (3)°	T = 293 K
β = 99.14 (3)°	Prism, colourless
γ = 100.07 (3)°	0.25 × 0.13 × 0.08 mm
V = 675.9 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2347 independent reflections
Radiation source: fine-focus sealed tube	1867 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
phi and ω scans	θmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→7
Tmin = 0.806, Tmax = 0.931	k = −8→8
3914 measured reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 0.250P] where P = (Fo^2 + 2Fc^2)/3
2347 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mg1	1.0000	0.0000	1.0000	0.0290 (3)
C1	0.5668 (4)	0.3487 (4)	0.8626 (2)	0.0316 (6)
C2	0.4066 (4)	0.4641 (4)	0.8376 (2)	0.0334 (7)
H2A	0.4655	0.5792	0.8155	0.040*
H2B	0.3472	0.4874	0.8962	0.040*
C3	0.0428 (4)	0.4804 (4)	0.72657 (19)	0.0292 (6)
C4	−0.1942 (4)	0.3060 (4)	0.5768 (2)	0.0321 (7)
C5	−0.1784 (4)	0.1299 (4)	0.5934 (2)	0.0393 (7)
H5	−0.1309	0.0985	0.6572	0.047*
C6	−0.2343 (4)	0.0001 (4)	0.5137 (3)	0.0491 (9)
H6A	−0.2206	−0.1191	0.5232	0.059*
C7	−0.3105 (5)	0.0470 (5)	0.4198 (2)	0.0503 (9)
H7A	−0.3477	−0.0407	0.3664	0.060*
C8	−0.3314 (5)	0.2215 (5)	0.4051 (2)	0.0526 (9)
H8A	−0.3861	0.2511	0.3420	0.063*
C9	−0.2721 (5)	0.3546 (4)	0.4831 (2)	0.0431 (8)
H9A	−0.2842	0.4740	0.4730	0.052*
N1	−0.1273 (3)	0.4464 (3)	0.65654 (16)	0.0326 (6)
N2	−0.2303 (4)	0.5835 (4)	0.66553 (19)	0.0449 (7)
N3	−0.1245 (4)	0.6943 (4)	0.73682 (19)	0.0465 (7)
N4	0.0470 (4)	0.6354 (3)	0.77710 (17)	0.0364 (6)
O1	0.5227 (3)	0.1854 (3)	0.83268 (16)	0.0427 (6)
O2	0.7301 (3)	0.4261 (3)	0.91271 (18)	0.0550 (7)
O3	1.0502 (3)	0.2699 (3)	0.97908 (17)	0.0371 (5)
O4	1.2154 (4)	−0.0513 (3)	0.91404 (18)	0.0453 (6)
O5	0.7751 (3)	−0.0466 (3)	0.87611 (17)	0.0465 (6)
S1	0.21753 (11)	0.33953 (10)	0.73900 (5)	0.0384 (2)
H5B	0.700 (5)	0.027 (5)	0.857 (2)	0.050 (10)*
H3B	1.122 (5)	0.338 (5)	1.016 (3)	0.048 (11)*
H5A	0.793 (6)	−0.110 (5)	0.827 (3)	0.069 (12)*
H4B	1.194 (6)	−0.160 (6)	0.877 (3)	0.088 (14)*
H4A	1.291 (6)	0.020 (5)	0.893 (3)	0.058 (13)*
H3A	0.935 (8)	0.313 (7)	0.944 (4)	0.13 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mg1	0.0306 (7)	0.0222 (6)	0.0334 (7)	0.0083 (5)	0.0007 (5)	−0.0019 (5)
C1	0.0297 (15)	0.0306 (15)	0.0319 (14)	0.0047 (12)	−0.0013 (12)	0.0008 (12)
C2	0.0324 (16)	0.0308 (14)	0.0343 (15)	0.0082 (12)	−0.0033 (12)	−0.0029 (12)
C3	0.0292 (15)	0.0322 (15)	0.0266 (13)	0.0097 (12)	0.0018 (11)	−0.0003 (12)
C4	0.0255 (15)	0.0358 (16)	0.0339 (15)	0.0065 (12)	0.0024 (11)	−0.0041 (12)
C5	0.0311 (16)	0.0384 (17)	0.0465 (17)	0.0091 (13)	−0.0016 (13)	0.0013 (14)
C6	0.0349 (18)	0.0360 (17)	0.073 (2)	0.0084 (14)	0.0021 (16)	−0.0108 (16)
C7	0.0375 (18)	0.057 (2)	0.053 (2)	0.0069 (15)	0.0059 (15)	−0.0239 (17)
C8	0.051 (2)	0.069 (2)	0.0327 (16)	0.0058 (17)	−0.0001 (14)	−0.0053 (16)
C9	0.0505 (19)	0.0411 (17)	0.0350 (16)	0.0109 (14)	−0.0037 (14)	0.0036 (14)
N1	0.0326 (13)	0.0342 (13)	0.0319 (12)	0.0148 (10)	−0.0002 (10)	−0.0021 (10)
N2	0.0429 (15)	0.0470 (15)	0.0463 (15)	0.0262 (12)	−0.0046 (12)	−0.0083 (13)
N3	0.0496 (16)	0.0457 (16)	0.0458 (15)	0.0250 (13)	−0.0013 (12)	−0.0113 (13)
N4	0.0380 (14)	0.0347 (13)	0.0375 (13)	0.0167 (11)	0.0007 (11)	−0.0051 (11)
O1	0.0356 (12)	0.0297 (11)	0.0581 (13)	0.0117 (9)	−0.0097 (10)	−0.0065 (10)
O2	0.0371 (13)	0.0327 (12)	0.0827 (17)	0.0054 (9)	−0.0239 (12)	−0.0032 (11)
O3	0.0390 (13)	0.0231 (10)	0.0454 (12)	0.0059 (9)	−0.0035 (10)	−0.0018 (10)
O4	0.0471 (15)	0.0331 (12)	0.0552 (14)	−0.0001 (11)	0.0188 (12)	−0.0099 (11)
O5	0.0509 (14)	0.0469 (14)	0.0413 (13)	0.0279 (11)	−0.0094 (10)	−0.0129 (11)
S1	0.0359 (4)	0.0357 (4)	0.0410 (4)	0.0180 (3)	−0.0097 (3)	−0.0103 (3)

Geometric parameters (Å, º)

Mg1—O3^i	2.039 (2)	C5—C6	1.383 (4)
Mg1—O3	2.039 (2)	C5—H5	0.9300
Mg1—O5^i	2.061 (2)	C6—C7	1.382 (5)
Mg1—O5	2.061 (2)	C6—H6A	0.9300
Mg1—O4	2.093 (2)	C7—C8	1.365 (5)
Mg1—O4^i	2.093 (2)	C7—H7A	0.9300
C1—O2	1.242 (3)	C8—C9	1.383 (4)
C1—O1	1.246 (3)	C8—H8A	0.9300
C1—C2	1.519 (4)	C9—H9A	0.9300
C2—S1	1.803 (3)	N1—N2	1.358 (3)
C2—H2A	0.9700	N2—N3	1.284 (3)
C2—H2B	0.9700	N3—N4	1.367 (3)
C3—N4	1.319 (3)	O3—H3B	0.75 (4)
C3—N1	1.358 (3)	O3—H3A	0.97 (6)
C3—S1	1.725 (3)	O4—H4B	0.91 (5)
C4—C5	1.373 (4)	O4—H4A	0.77 (4)
C4—C9	1.388 (4)	O5—H5B	0.84 (4)
C4—N1	1.438 (3)	O5—H5A	0.84 (4)
O3^i—Mg1—O3	180.000 (1)	C4—C5—H5	120.6
O3^i—Mg1—O5^i	90.36 (10)	C6—C5—H5	120.6
O3—Mg1—O5^i	89.64 (10)	C7—C6—C5	120.1 (3)
O3^i—Mg1—O5	89.64 (10)	C7—C6—H6A	119.9
O3—Mg1—O5	90.36 (10)	C5—C6—H6A	119.9
O5^i—Mg1—O5	180.000 (1)	C8—C7—C6	120.4 (3)
O3^i—Mg1—O4	87.11 (10)	C8—C7—H7A	119.8
O3—Mg1—O4	92.89 (10)	C6—C7—H7A	119.8
O5^i—Mg1—O4	88.33 (10)	C7—C8—C9	120.6 (3)
O5—Mg1—O4	91.67 (10)	C7—C8—H8A	119.7
O3^i—Mg1—O4^i	92.89 (10)	C9—C8—H8A	119.7
O3—Mg1—O4^i	87.11 (10)	C8—C9—C4	118.5 (3)
O5^i—Mg1—O4^i	91.67 (10)	C8—C9—H9A	120.8
O5—Mg1—O4^i	88.33 (10)	C4—C9—H9A	120.8
O4—Mg1—O4^i	180.000 (1)	N2—N1—C3	108.3 (2)
O2—C1—O1	125.7 (3)	N2—N1—C4	120.9 (2)
O2—C1—C2	116.6 (2)	C3—N1—C4	130.5 (2)
O1—C1—C2	117.6 (2)	N3—N2—N1	106.2 (2)
C1—C2—S1	107.16 (18)	N2—N3—N4	111.7 (2)
C1—C2—H2A	110.3	C3—N4—N3	105.8 (2)
S1—C2—H2A	110.3	Mg1—O3—H3B	123 (3)
C1—C2—H2B	110.3	Mg1—O3—H3A	115 (3)
S1—C2—H2B	110.3	H3B—O3—H3A	115 (4)
H2A—C2—H2B	108.5	Mg1—O4—H4B	119 (3)
N4—C3—N1	108.1 (2)	Mg1—O4—H4A	127 (3)
N4—C3—S1	129.0 (2)	H4B—O4—H4A	111 (4)
N1—C3—S1	122.93 (19)	Mg1—O5—H5B	125 (2)
C5—C4—C9	121.5 (3)	Mg1—O5—H5A	118 (3)
C5—C4—N1	120.5 (2)	H5B—O5—H5A	110 (3)
C9—C4—N1	118.0 (3)	C3—S1—C2	100.91 (12)
C4—C5—C6	118.9 (3)
O2—C1—C2—S1	164.8 (2)	C5—C4—N1—N2	−142.3 (3)
O1—C1—C2—S1	−16.2 (3)	C9—C4—N1—N2	38.4 (4)
C9—C4—C5—C6	2.6 (4)	C5—C4—N1—C3	44.2 (4)
N1—C4—C5—C6	−176.6 (3)	C9—C4—N1—C3	−135.0 (3)
C4—C5—C6—C7	−2.0 (5)	C3—N1—N2—N3	0.7 (3)
C5—C6—C7—C8	−0.1 (5)	C4—N1—N2—N3	−174.0 (3)
C6—C7—C8—C9	1.6 (5)	N1—N2—N3—N4	−0.5 (4)
C7—C8—C9—C4	−1.0 (5)	N1—C3—N4—N3	0.3 (3)
C5—C4—C9—C8	−1.1 (5)	S1—C3—N4—N3	178.7 (2)
N1—C4—C9—C8	178.1 (3)	N2—N3—N4—C3	0.1 (4)
N4—C3—N1—N2	−0.7 (3)	N4—C3—S1—C2	−0.9 (3)
S1—C3—N1—N2	−179.1 (2)	N1—C3—S1—C2	177.1 (2)
N4—C3—N1—C4	173.4 (3)	C1—C2—S1—C3	176.0 (2)
S1—C3—N1—C4	−5.0 (4)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2	0.97 (5)	1.77 (6)	2.711 (3)	164 (5)
O3—H3B···O2^ii	0.75 (4)	2.00 (4)	2.727 (3)	162 (4)
O4—H4A···O1^iii	0.77 (4)	2.13 (4)	2.899 (3)	172 (4)
O4—H4B···N4^iv	0.92 (4)	2.01 (4)	2.882 (3)	158 (4)
O5—H5A···N3^iv	0.84 (4)	2.08 (4)	2.896 (4)	164 (4)
O5—H5B···O1	0.84 (4)	1.85 (4)	2.682 (3)	172 (3)

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