Di­aqua­tetra­kis­(1H-imidazole-κN ³)magnesium dichloride

Abstract

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,

• a = 12.3826 (6) Å

• b = 11.0048 (4) Å

• c = 14.4485 (6) Å

• β = 107.037 (1)°

• V = 1882.47 (14) ų

• 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[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

1. Comment

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).

2. Experimental

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%).

3. Refinement

Carbon-bound H atoms were placed at calculated positions and treated as riding on the parent atom, with, C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C). The O-bound and N-bound H atoms were located in a difference Fourier map and refined freely.

Figures

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.

Crystal data

[Mg(C3H4N2)4(H2O)2]Cl2	F(000) = 840
Mr = 403.57	Dx = 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

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

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068	w = 1/[σ2(Fo2) + (0.0327P)2 + 1.0653P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1854 reflections	Δρmax = 0.17 e Å−3
132 parameters	Δρmin = −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)

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	0.29321 (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 (Ų)

	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)

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)

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···Cl1iv	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.