Di­aqua­tetra­kis­(1H-imidazole-κN3)magnesium dichloride

Kayalvizhi, M.; Vasuki, G.; Kaabi, K.; Ben Nasr, C.

doi:10.1107/S1600536813021478

metal-organic compounds

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Volume 69| Part 9| September 2013| Page m481

doi:10.1107/S1600536813021478

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Diaquatetrakis(1H-imidazole-κN³)magnesium dichloride

M. Kayalvizhi,^a G. Vasuki,^a ^* Kamel Kaabi ^b and Cherif Ben Nasr ^b

^aDepartment of Physics, Kunthavai Naachiar Government Arts College (W) (Autonomous), Thanjavur-7, India, and ^bLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia
^*Correspondence e-mail: vasuki.arasi@yahoo.com

(Received 17 July 2013; accepted 1 August 2013; online 10 August 2013)

In the title compound, [Mg(C₃H₃N₂)₄(H₂O)₂]Cl₂, the Mg^II cation lies on a crystallographic inversion centre and is coordinated by two water molecules and four N-atom donors from monodentate imidazole ligands, giving a slightly distorted octahedral stereochemistry. In the crystal, water O—H⋯Cl and imidazole N—H⋯Cl hydrogen bonds give rise to a three-dimensional structure.

Related literature

For a similar structure, see: Reiss et al. (2011 ).

Experimental

Crystal data

[Mg(C₃H₃N₂)₄(H₂O)₂]Cl₂
M_r = 403.57
Monoclinic, C 2/c
a = 12.3826 (6) Å
b = 11.0048 (4) Å
c = 14.4485 (6) Å
β = 107.037 (1)°
V = 1882.47 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.889, T_max = 0.924
8496 measured reflections
1854 independent reflections
1695 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.068
S = 1.05
1854 reflections
132 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

Mg1—N1	2.2281 (10)
Mg1—N3	2.1611 (10)
Mg1—O1	2.0923 (9)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯Cl1ⁱ	0.84 (1)	2.30 (1)	3.1361 (9)	172 (2)
O1—H2W⋯Cl1	0.84 (1)	2.30 (1)	3.1337 (10)	176 (2)
N2—H2A⋯Cl1ⁱⁱ	0.89 (1)	2.47 (1)	3.3165 (12)	160 (2)
N4—H4A⋯Cl1ⁱⁱⁱ	0.89 (1)	2.43 (1)	3.2585 (13)	155 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813021478/zs2271sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021478/zs2271Isup2.hkl

checkCIF report

Comment top

In the title compound, [Mg(C₃H₃N₂)₄(H₂O)₂] . 2Cl, the Mg^II cation lies on a crystallographic inversion centre and is coordinated by two water molecules and four N-atom donors from monodentate imidazole ligands, (Fig. 1), giving a slightly distorted octahedral geometry (Table 1). In the crystal, O—H···Cl and N—H···Cl hydrogen bonds between both the aqua ligands and the imidazole ligands and the chloride counter-anions (Table 2) generate a three-dimensional structure (Fig. 2). These water–chloride hydrogen-bonding interactions are in the typical range as observed in the redetermined structure of diaquatetrakis(dimethylformamide-κO)magnesium dichloride (Reiss et al., 2011).

Related literature top

For a similar structure, see: Reiss et al. (2011).

Experimental top

A solution of MgCl₂ (0.2 mmol) in water (6 ml) was added dropwise to a solution of imidazole (0.8 mmol) in ethanol. After stirring for 30 min, the mixture was filtered. Crystals suitable for X-ray analysis were obtained by evaporating the filtrate at room temperature (yield 56%).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing atom numbering, with displacement ellipsoids drawn at the 40% probability level. For symmetry code (i): -x + 1/2, -y + 3/2, -z + 1.
	Fig. 2. Crystal packing of the title compound viewed along the c axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

Diaquatetrakis(1H-imidazole-κN³)magnesium dichloride top

Crystal data top

[Mg(C₃H₄N₂)₄(H₂O)₂]Cl₂	F(000) = 840
M_r = 403.57	D_x = 1.424 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8496 reflections
a = 12.3826 (6) Å	θ = 2.1–26.0°
b = 11.0048 (4) Å	µ = 0.40 mm⁻¹
c = 14.4485 (6) Å	T = 296 K
β = 107.037 (1)°	Block, colourless
V = 1882.47 (14) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1854 independent reflections
Radiation source: fine-focus sealed tube	1695 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and ϕ scan	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −15→14
T_min = 0.889, T_max = 0.924	k = −13→13
8496 measured reflections	l = −17→16

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0327P)² + 1.0653P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1854 reflections	Δρ_max = 0.17 e Å⁻³
132 parameters	Δρ_min = −0.25 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0093 (6)

Crystal data top

[Mg(C₃H₄N₂)₄(H₂O)₂]Cl₂	V = 1882.47 (14) Å³
M_r = 403.57	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.3826 (6) Å	µ = 0.40 mm⁻¹
b = 11.0048 (4) Å	T = 296 K
c = 14.4485 (6) Å	0.30 × 0.25 × 0.20 mm
β = 107.037 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1854 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	1695 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.924	R_int = 0.026
8496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	4 restraints
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.17 e Å⁻³
1854 reflections	Δρ_min = −0.25 e Å⁻³
132 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	0.29321 (12)	0.73665 (13)	0.29376 (10)	0.0376 (3)
H1	0.3423	0.6718	0.3154	0.045*
C2	0.19291 (13)	0.87405 (14)	0.19885 (10)	0.0440 (4)
H2	0.1594	0.9221	0.1451	0.053*
C3	0.17954 (11)	0.88354 (12)	0.28794 (9)	0.0366 (3)
H3	0.1340	0.9406	0.3059	0.044*
C4	0.01955 (12)	0.63009 (13)	0.37687 (10)	0.0393 (3)
H4	−0.0098	0.7052	0.3525	0.047*
C5	−0.03394 (12)	0.52348 (14)	0.35343 (11)	0.0462 (4)
H5	−0.1058	0.5111	0.3112	0.055*
C6	0.13086 (11)	0.49423 (12)	0.45568 (11)	0.0385 (3)
H6	0.1931	0.4549	0.4967	0.046*
N1	0.24289 (8)	0.79672 (9)	0.34828 (7)	0.0298 (2)
N2	0.26524 (11)	0.78024 (12)	0.20364 (8)	0.0434 (3)
N3	0.12407 (9)	0.61208 (9)	0.44212 (7)	0.0298 (2)
N4	0.03796 (11)	0.43755 (11)	0.40368 (10)	0.0429 (3)
O1	0.37963 (8)	0.62540 (8)	0.50646 (7)	0.0355 (2)
Mg1	0.2500	0.7500	0.5000	0.02385 (15)
Cl1	0.41012 (3)	0.35283 (3)	0.57173 (3)	0.04135 (14)
H1W	0.4370 (11)	0.6384 (16)	0.4884 (12)	0.057 (5)*
H2A	0.2880 (16)	0.7492 (16)	0.1556 (10)	0.069 (6)*
H2W	0.3849 (15)	0.5529 (10)	0.5253 (12)	0.056 (5)*
H4A	0.0289 (15)	0.3576 (9)	0.4011 (13)	0.058 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0447 (7)	0.0340 (7)	0.0385 (7)	0.0014 (6)	0.0188 (6)	−0.0019 (6)
C2	0.0528 (8)	0.0486 (9)	0.0284 (7)	−0.0021 (7)	0.0084 (6)	0.0050 (6)
C3	0.0413 (7)	0.0359 (7)	0.0336 (7)	0.0034 (6)	0.0125 (6)	0.0017 (6)
C4	0.0389 (7)	0.0341 (7)	0.0413 (8)	−0.0016 (6)	0.0062 (6)	0.0048 (6)
C5	0.0416 (7)	0.0472 (9)	0.0460 (8)	−0.0129 (7)	0.0071 (6)	−0.0033 (7)
C6	0.0357 (7)	0.0278 (7)	0.0535 (8)	0.0005 (5)	0.0157 (6)	0.0041 (6)
N1	0.0356 (5)	0.0277 (5)	0.0288 (5)	−0.0026 (4)	0.0138 (4)	−0.0002 (4)
N2	0.0558 (7)	0.0484 (7)	0.0325 (6)	−0.0074 (6)	0.0233 (5)	−0.0088 (5)
N3	0.0326 (5)	0.0251 (5)	0.0337 (6)	−0.0023 (4)	0.0130 (4)	0.0007 (4)
N4	0.0485 (7)	0.0261 (6)	0.0594 (8)	−0.0110 (5)	0.0244 (6)	−0.0065 (5)
O1	0.0360 (5)	0.0257 (5)	0.0523 (6)	0.0056 (4)	0.0248 (4)	0.0073 (4)
Mg1	0.0275 (3)	0.0196 (3)	0.0275 (3)	−0.0003 (2)	0.0126 (2)	0.0008 (2)
Cl1	0.0432 (2)	0.0314 (2)	0.0584 (2)	0.00885 (13)	0.02879 (17)	0.01331 (14)

Geometric parameters (Å, º) top

C1—N1	1.3166 (16)	C6—N3	1.3107 (17)
C1—N2	1.3347 (18)	C6—N4	1.3306 (19)
C1—H1	0.9300	C6—H6	0.9300
C2—C3	1.3491 (19)	Mg1—N1	2.2281 (10)
C2—N2	1.355 (2)	N2—H2A	0.890 (9)
C2—H2	0.9300	Mg1—N3	2.1611 (10)
C3—N1	1.3738 (17)	N4—H4A	0.887 (9)
C3—H3	0.9300	Mg1—O1	2.0923 (9)
C4—C5	1.341 (2)	O1—H1W	0.838 (9)
C4—N3	1.3741 (17)	O1—H2W	0.839 (9)
C4—H4	0.9300	Mg1—O1ⁱ	2.0923 (9)
C5—N4	1.355 (2)	Mg1—N3ⁱ	2.1612 (10)
C5—H5	0.9300	Mg1—N1ⁱ	2.2281 (10)

N1—C1—N2	111.72 (13)	C6—N3—C4	104.57 (11)
N1—C1—H1	124.1	C6—N3—Mg1	129.03 (9)
N2—C1—H1	124.1	C4—N3—Mg1	126.30 (9)
C3—C2—N2	105.92 (12)	C6—N4—C5	107.41 (12)
C3—C2—H2	127.0	C6—N4—H4A	124.5 (12)
N2—C2—H2	127.0	C5—N4—H4A	128.0 (12)
C2—C3—N1	110.17 (12)	Mg1—O1—H1W	125.7 (12)
C2—C3—H3	124.9	Mg1—O1—H2W	128.6 (12)
N1—C3—H3	124.9	H1W—O1—H2W	105.6 (17)
C5—C4—N3	110.08 (13)	O1ⁱ—Mg1—O1	179.999 (1)
C5—C4—H4	125.0	O1ⁱ—Mg1—N3	89.19 (4)
N3—C4—H4	125.0	O1—Mg1—N3	90.81 (4)
C4—C5—N4	106.08 (12)	O1ⁱ—Mg1—N3ⁱ	90.81 (4)
C4—C5—H5	127.0	O1—Mg1—N3ⁱ	89.19 (4)
N4—C5—H5	127.0	N3—Mg1—N3ⁱ	180.0
N3—C6—N4	111.86 (13)	O1ⁱ—Mg1—N1ⁱ	90.22 (4)
N3—C6—H6	124.1	O1—Mg1—N1ⁱ	89.78 (4)
N4—C6—H6	124.1	N3—Mg1—N1ⁱ	91.99 (4)
C1—N1—C3	104.59 (11)	N3ⁱ—Mg1—N1ⁱ	88.01 (4)
C1—N1—Mg1	125.70 (9)	O1ⁱ—Mg1—N1	89.78 (4)
C3—N1—Mg1	129.45 (8)	O1—Mg1—N1	90.22 (4)
C1—N2—C2	107.60 (12)	N3—Mg1—N1	88.01 (4)
C1—N2—H2A	124.8 (12)	N3ⁱ—Mg1—N1	91.99 (4)
C2—N2—H2A	127.5 (12)	N1ⁱ—Mg1—N1	180.0

N2—C2—C3—N1	0.07 (16)	C4—N3—Mg1—O1ⁱ	33.40 (11)
N3—C4—C5—N4	−0.57 (17)	C6—N3—Mg1—O1	29.08 (12)
N2—C1—N1—C3	−0.09 (15)	C4—N3—Mg1—O1	−146.60 (11)
N2—C1—N1—Mg1	174.52 (9)	C6—N3—Mg1—N1ⁱ	−60.73 (12)
C2—C3—N1—C1	0.01 (15)	C4—N3—Mg1—N1ⁱ	123.59 (11)
C2—C3—N1—Mg1	−174.32 (9)	C6—N3—Mg1—N1	119.27 (12)
N1—C1—N2—C2	0.13 (17)	C4—N3—Mg1—N1	−56.41 (11)
C3—C2—N2—C1	−0.12 (16)	C1—N1—Mg1—O1ⁱ	−168.58 (11)
N4—C6—N3—C4	−0.12 (16)	C3—N1—Mg1—O1ⁱ	4.66 (11)
N4—C6—N3—Mg1	−176.52 (9)	C1—N1—Mg1—O1	11.42 (11)
C5—C4—N3—C6	0.43 (16)	C3—N1—Mg1—O1	−175.34 (11)
C5—C4—N3—Mg1	176.96 (10)	C1—N1—Mg1—N3	−79.38 (11)
N3—C6—N4—C5	−0.23 (17)	C3—N1—Mg1—N3	93.85 (11)
C4—C5—N4—C6	0.48 (17)	C1—N1—Mg1—N3ⁱ	100.62 (11)
C6—N3—Mg1—O1ⁱ	−150.92 (12)	C3—N1—Mg1—N3ⁱ	−86.14 (11)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Cl1ⁱⁱ	0.84 (1)	2.30 (1)	3.1361 (9)	172 (2)
O1—H2W···Cl1	0.84 (1)	2.30 (1)	3.1337 (10)	176 (2)
N2—H2A···Cl1ⁱⁱⁱ	0.89 (1)	2.47 (1)	3.3165 (12)	160 (2)
N4—H4A···Cl1^iv	0.89 (1)	2.43 (1)	3.2585 (13)	155 (2)

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

Selected bond lengths (Å) top

Mg1—N1	2.2281 (10)	Mg1—O1	2.0923 (9)
Mg1—N3	2.1611 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Cl1ⁱ	0.838 (9)	2.304 (10)	3.1361 (9)	171.8 (17)
O1—H2W···Cl1	0.839 (9)	2.296 (10)	3.1337 (10)	175.8 (17)
N2—H2A···Cl1ⁱⁱ	0.890 (9)	2.468 (11)	3.3165 (12)	159.6 (17)
N4—H4A···Cl1ⁱⁱⁱ	0.887 (9)	2.431 (11)	3.2585 (13)	155.4 (16)

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

Acknowledgements

The authors thank the Sophisticated Analytical Instrument Facility, IIT-Madras, Chennai, for the data collection.

References

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