Hexaaqua­magnesium bis­{4-[(5-bromo-2-hy­droxy­benzyl­idene)amino]­benzene­sulfonate} dihydrate

Tai, X.-S.

doi:10.1107/S1600536810053717

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page m132

doi:10.1107/S1600536810053717

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Hexaaquamagnesium bis{4-[(5-bromo-2-hydroxybenzylidene)amino]benzenesulfonate} dihydrate

Xi-Shi Tai ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 20 December 2010; accepted 21 December 2010; online 8 January 2011)

In the title hydrated molecular salt, [Mg(H₂O)₆](C₁₃H₉BrNO₄S)₂·2H₂O, the Mg²⁺ ion (site symmetry $[\overline{1}]$ ) adopts a near regular MgO₆ octahedral coordination geometry. In the anion, the dihedral angle between the aromatic rings is 2.5 (2)° and an intramolecular O—H⋯N hydrogen bond generates an S(6) ring. In the crystal, the components are linked by O—H⋯O and O—H⋯Br hydrogen bonds.

Related literature

For background to Schiff bases as ligands, see: Tai et al. (2003 ).

Experimental

Crystal data

[Mg(H₂O)₆](C₁₃H₉BrNO₄S)₂·2H₂O
M_r = 878.80
Monoclinic, P 2₁ /c
a = 18.7737 (14) Å
b = 6.2837 (5) Å
c = 15.7591 (12) Å
β = 108.668 (1)°
V = 1761.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 2.51 mm⁻¹
T = 291 K
0.30 × 0.26 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.48, T_max = 0.55
9144 measured reflections
3446 independent reflections
2473 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.131
S = 1.03
3446 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected bond lengths (Å)

Mg1—O12	2.031 (3)
Mg1—O11	2.065 (3)
Mg1—O13	2.077 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.96	1.73	2.570 (5)	144
O5—H5D⋯O3ⁱ	0.85	2.00	2.854 (4)	180
O5—H5A⋯O4ⁱⁱ	0.85	2.08	2.892 (4)	160
O11—H11A⋯Br1ⁱⁱⁱ	0.96	2.60	3.539 (3)	166
O11—H11C⋯O3ⁱⁱ	0.96	1.94	2.710 (4)	136
O12—H12A⋯O2^iv	0.96	2.04	2.747 (4)	129
O12—H12B⋯O5	0.96	1.90	2.729 (4)	143
O13—H13C⋯O4^v	0.96	1.88	2.763 (4)	152
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) -x+1, -y+2, -z; (v) x-1, y-1, z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053717/hb5780sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810053717/hb5780Isup2.hkl

checkCIF report

Related literature top

For background to Schiff bases as ligands, see: Tai et al. (2003).

Experimental top

1 mmol of magnesium perchlorate was added to a solution of 5-bromosalicylaldehyde-4-aminobenzene sulfonic acid (1 mmol) in 10 ml of 95% ethanol. The mixture was stirred for 3 h at refluxing temperature. Evaporating some ethanol, clear blocks of (I) were obtained after two weeks.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 (I) showing 50% displacement ellipsoids. Symmetry code: (i) –x, 1–y, –z.

Hexaaquamagnesium bis{4-[(5-bromo-2-hydroxybenzylidene)amino]benzenesulfonate} dihydrate top

Crystal data top

[Mg(H₂O)₆](C₁₃H₉BrNO₄S)₂·2H₂O	F(000) = 892
M_r = 878.80	D_x = 1.657 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1852 reflections
a = 18.7737 (14) Å	θ = 2.3–22.6°
b = 6.2837 (5) Å	µ = 2.51 mm⁻¹
c = 15.7591 (12) Å	T = 291 K
β = 108.668 (1)°	Block, colourless
V = 1761.3 (2) Å³	0.30 × 0.26 × 0.24 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	3446 independent reflections
Radiation source: sealed tube	2473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −21→22
T_min = 0.48, T_max = 0.55	k = −7→7
9144 measured reflections	l = −18→19

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.06P)² + 1.22P] where P = (F_o² + 2F_c²)/3
3446 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Mg(H₂O)₆](C₁₃H₉BrNO₄S)₂·2H₂O	V = 1761.3 (2) Å³
M_r = 878.80	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.7737 (14) Å	µ = 2.51 mm⁻¹
b = 6.2837 (5) Å	T = 291 K
c = 15.7591 (12) Å	0.30 × 0.26 × 0.24 mm
β = 108.668 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3446 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2473 reflections with I > 2σ(I)
T_min = 0.48, T_max = 0.55	R_int = 0.044
9144 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.03	Δρ_max = 0.29 e Å⁻³
3446 reflections	Δρ_min = −0.46 e Å⁻³
223 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
Br1	0.22648 (3)	1.13983 (10)	0.17778 (4)	0.0651 (2)
C1	0.3958 (3)	0.6851 (8)	0.1070 (3)	0.0477 (11)
C2	0.3228 (3)	0.6150 (9)	0.1013 (4)	0.0604 (13)
H2	0.3074	0.4775	0.0821	0.072*
C3	0.2748 (2)	0.7509 (8)	0.1242 (3)	0.0481 (11)
H3	0.2271	0.7041	0.1213	0.058*
C4	0.2961 (2)	0.9538 (8)	0.1511 (3)	0.0448 (10)
C5	0.3665 (2)	1.0246 (8)	0.1571 (3)	0.0450 (10)
H5	0.3805	1.1626	0.1767	0.054*
C6	0.4171 (2)	0.8944 (7)	0.1345 (3)	0.0397 (9)
C7	0.4892 (2)	0.9756 (8)	0.1354 (3)	0.0482 (11)
H7	0.5018	1.1160	0.1523	0.058*
C8	0.6080 (2)	0.9353 (7)	0.1133 (3)	0.0387 (9)
C9	0.6512 (3)	0.7946 (8)	0.0856 (4)	0.0563 (13)
H9	0.6325	0.6601	0.0658	0.068*
C10	0.7223 (3)	0.8507 (8)	0.0870 (3)	0.0513 (12)
H10	0.7512	0.7546	0.0671	0.062*
C11	0.7506 (2)	1.0454 (7)	0.1170 (3)	0.0403 (10)
C12	0.7072 (2)	1.1915 (7)	0.1430 (3)	0.0457 (11)
H12	0.7257	1.3271	0.1611	0.055*
C13	0.6353 (2)	1.1350 (8)	0.1421 (3)	0.0476 (12)
H13	0.6059	1.2315	0.1608	0.057*
Mg1	0.0000	0.5000	0.0000	0.0372 (4)
N1	0.53591 (18)	0.8598 (6)	0.1135 (2)	0.0436 (9)
O1	0.44163 (19)	0.5502 (6)	0.0844 (3)	0.0727 (12)
H1A	0.4853	0.6268	0.0825	0.109*
O2	0.85670 (16)	1.0353 (5)	0.04402 (18)	0.0401 (7)
O3	0.89136 (16)	0.9951 (6)	0.20297 (19)	0.0522 (8)
O4	0.85143 (17)	1.3394 (5)	0.1372 (2)	0.0450 (7)
O5	0.04046 (16)	0.9650 (5)	0.19393 (18)	0.0438 (7)
H5D	−0.0040	0.9738	0.1965	0.053*
H5A	0.0679	0.8973	0.2393	0.066*
O11	0.04471 (18)	0.3651 (5)	0.12539 (18)	0.0486 (8)
H11A	0.0911	0.2950	0.1291	0.073*
H11C	0.0542	0.4746	0.1701	0.073*
O12	0.05566 (19)	0.7759 (5)	0.0447 (2)	0.0503 (8)
H12A	0.1036	0.7722	0.0349	0.075*
H12B	0.0631	0.7904	0.1076	0.075*
O13	−0.08843 (18)	0.6110 (5)	0.0402 (2)	0.0506 (8)
H13A	−0.1230	0.6882	−0.0083	0.076*
H13C	−0.1138	0.4923	0.0560	0.076*
S1	0.84436 (5)	1.11031 (16)	0.12566 (6)	0.0322 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0464 (3)	0.0689 (4)	0.0887 (4)	0.0068 (2)	0.0338 (3)	0.0030 (3)
C1	0.040 (2)	0.047 (3)	0.055 (3)	−0.007 (2)	0.014 (2)	−0.003 (2)
C2	0.046 (3)	0.048 (3)	0.087 (4)	−0.018 (2)	0.021 (3)	−0.005 (3)
C3	0.028 (2)	0.058 (3)	0.056 (3)	−0.003 (2)	0.0105 (19)	0.013 (2)
C4	0.030 (2)	0.051 (3)	0.053 (3)	−0.0018 (19)	0.0128 (19)	0.004 (2)
C5	0.039 (2)	0.039 (3)	0.059 (3)	0.0022 (19)	0.019 (2)	0.002 (2)
C6	0.029 (2)	0.043 (3)	0.046 (2)	0.0004 (17)	0.0107 (17)	0.0030 (19)
C7	0.038 (2)	0.046 (3)	0.063 (3)	−0.003 (2)	0.018 (2)	−0.003 (2)
C8	0.0305 (19)	0.040 (2)	0.047 (2)	−0.0055 (17)	0.0137 (18)	−0.0009 (18)
C9	0.050 (3)	0.035 (2)	0.093 (4)	−0.020 (2)	0.035 (3)	−0.028 (2)
C10	0.048 (3)	0.049 (3)	0.062 (3)	−0.008 (2)	0.025 (2)	−0.025 (2)
C11	0.038 (2)	0.048 (3)	0.035 (2)	−0.0006 (19)	0.0116 (18)	0.0036 (18)
C12	0.041 (2)	0.039 (3)	0.067 (3)	−0.0133 (19)	0.031 (2)	−0.026 (2)
C13	0.047 (2)	0.049 (3)	0.063 (3)	−0.015 (2)	0.041 (2)	−0.031 (2)
Mg1	0.0380 (10)	0.0361 (11)	0.0405 (10)	0.0008 (8)	0.0166 (8)	−0.0003 (8)
N1	0.0279 (17)	0.048 (2)	0.054 (2)	−0.0080 (16)	0.0114 (15)	−0.0044 (18)
O1	0.0431 (18)	0.057 (2)	0.124 (3)	−0.0094 (17)	0.035 (2)	−0.026 (2)
O2	0.0475 (16)	0.0432 (17)	0.0386 (14)	−0.0031 (13)	0.0264 (13)	−0.0058 (13)
O3	0.0353 (16)	0.078 (2)	0.0378 (16)	0.0083 (16)	0.0042 (13)	0.0168 (16)
O4	0.0482 (17)	0.0379 (18)	0.0560 (18)	−0.0109 (14)	0.0267 (15)	−0.0102 (14)
O5	0.0436 (16)	0.0509 (19)	0.0358 (15)	0.0081 (14)	0.0111 (13)	0.0089 (13)
O11	0.063 (2)	0.0476 (19)	0.0329 (15)	0.0076 (15)	0.0119 (14)	0.0015 (13)
O12	0.065 (2)	0.0463 (19)	0.0510 (17)	−0.0202 (16)	0.0340 (16)	−0.0143 (14)
O13	0.0584 (19)	0.0361 (18)	0.072 (2)	0.0118 (15)	0.0415 (17)	0.0130 (15)
S1	0.0313 (5)	0.0350 (6)	0.0320 (5)	−0.0036 (4)	0.0123 (4)	0.0004 (4)

Geometric parameters (Å, º) top

Br1—C4	1.899 (5)	C11—S1	1.770 (4)
C1—O1	1.334 (6)	C12—C13	1.390 (6)
C1—C6	1.402 (6)	C12—H12	0.9300
C1—C2	1.415 (6)	C13—H13	0.9300
C2—C3	1.370 (7)	Mg1—O12ⁱ	2.031 (3)
C2—H2	0.9300	Mg1—O12	2.031 (3)
C3—C4	1.362 (7)	Mg1—O11	2.065 (3)
C3—H3	0.9300	Mg1—O11ⁱ	2.065 (3)
C4—C5	1.367 (6)	Mg1—O13ⁱ	2.077 (3)
C5—C6	1.385 (6)	Mg1—O13	2.077 (3)
C5—H5	0.9300	O1—H1A	0.9600
C6—C7	1.443 (6)	O2—S1	1.457 (3)
C7—N1	1.268 (6)	O3—S1	1.449 (3)
C7—H7	0.9300	O4—S1	1.452 (3)
C8—C9	1.362 (6)	O5—H5D	0.8501
C8—C13	1.376 (6)	O5—H5A	0.8500
C8—N1	1.436 (5)	O11—H11A	0.9600
C9—C10	1.373 (6)	O11—H11C	0.9600
C9—H9	0.9300	O12—H12A	0.9601
C10—C11	1.358 (6)	O12—H12B	0.9599
C10—H10	0.9300	O13—H13A	0.9599
C11—C12	1.374 (6)	O13—H13C	0.9600

O1—C1—C6	122.3 (4)	C8—C13—C12	119.6 (4)
O1—C1—C2	118.6 (4)	C8—C13—H13	120.2
C6—C1—C2	119.1 (4)	C12—C13—H13	120.2
C3—C2—C1	119.6 (5)	O12ⁱ—Mg1—O12	180.0
C3—C2—H2	120.2	O12ⁱ—Mg1—O11	89.32 (13)
C1—C2—H2	120.2	O12—Mg1—O11	90.68 (13)
C4—C3—C2	120.9 (4)	O12ⁱ—Mg1—O11ⁱ	90.68 (13)
C4—C3—H3	119.6	O12—Mg1—O11ⁱ	89.32 (13)
C2—C3—H3	119.6	O11—Mg1—O11ⁱ	180.0
C3—C4—C5	120.5 (4)	O12ⁱ—Mg1—O13ⁱ	88.86 (13)
C3—C4—Br1	119.4 (3)	O12—Mg1—O13ⁱ	91.14 (13)
C5—C4—Br1	120.1 (4)	O11—Mg1—O13ⁱ	91.94 (13)
C4—C5—C6	121.1 (4)	O11ⁱ—Mg1—O13ⁱ	88.06 (13)
C4—C5—H5	119.4	O12ⁱ—Mg1—O13	91.14 (13)
C6—C5—H5	119.4	O12—Mg1—O13	88.86 (13)
C5—C6—C1	118.8 (4)	O11—Mg1—O13	88.06 (13)
C5—C6—C7	120.5 (4)	O11ⁱ—Mg1—O13	91.94 (13)
C1—C6—C7	120.6 (4)	O13ⁱ—Mg1—O13	180.0
N1—C7—C6	121.5 (4)	C7—N1—C8	123.0 (4)
N1—C7—H7	119.3	C1—O1—H1A	108.7
C6—C7—H7	119.3	H5D—O5—H5A	109.5
C9—C8—C13	120.0 (4)	Mg1—O11—H11A	109.3
C9—C8—N1	116.4 (4)	Mg1—O11—H11C	109.3
C13—C8—N1	123.6 (4)	H11A—O11—H11C	109.5
C8—C9—C10	120.2 (4)	Mg1—O12—H12A	109.1
C8—C9—H9	119.9	Mg1—O12—H12B	109.2
C10—C9—H9	119.9	H12A—O12—H12B	109.5
C11—C10—C9	120.4 (4)	Mg1—O13—H13A	109.3
C11—C10—H10	119.8	Mg1—O13—H13C	109.2
C9—C10—H10	119.8	H13A—O13—H13C	109.5
C10—C11—C12	120.2 (4)	O3—S1—O4	112.5 (2)
C10—C11—S1	120.2 (4)	O3—S1—O2	110.78 (19)
C12—C11—S1	119.6 (3)	O4—S1—O2	113.44 (18)
C11—C12—C13	119.5 (4)	O3—S1—C11	105.83 (19)
C11—C12—H12	120.3	O4—S1—C11	106.7 (2)
C13—C12—H12	120.3	O2—S1—C11	107.05 (19)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.96	1.73	2.570 (5)	144
O5—H5D···O3ⁱⁱ	0.85	2.00	2.854 (4)	180
O5—H5A···O4ⁱⁱⁱ	0.85	2.08	2.892 (4)	160
O11—H11A···Br1^iv	0.96	2.60	3.539 (3)	166
O11—H11C···O3ⁱⁱⁱ	0.96	1.94	2.710 (4)	136
O12—H12A···O2^v	0.96	2.04	2.747 (4)	129
O12—H12B···O5	0.96	1.90	2.729 (4)	143
O13—H13C···O4^vi	0.96	1.88	2.763 (4)	152

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

Experimental details

Crystal data
Chemical formula	[Mg(H₂O)₆](C₁₃H₉BrNO₄S)₂·2H₂O
M_r	878.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	18.7737 (14), 6.2837 (5), 15.7591 (12)
β (°)	108.668 (1)
V (Å³)	1761.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.51
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.48, 0.55
No. of measured, independent and observed [I > 2σ(I)] reflections	9144, 3446, 2473
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.131, 1.03
No. of reflections	3446
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.46

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mg1—O12	2.031 (3)	Mg1—O13	2.077 (3)
Mg1—O11	2.065 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.96	1.73	2.570 (5)	144
O5—H5D···O3ⁱ	0.85	2.00	2.854 (4)	180
O5—H5A···O4ⁱⁱ	0.85	2.08	2.892 (4)	160
O11—H11A···Br1ⁱⁱⁱ	0.96	2.60	3.539 (3)	166
O11—H11C···O3ⁱⁱ	0.96	1.94	2.710 (4)	136
O12—H12A···O2^iv	0.96	2.04	2.747 (4)	129
O12—H12B···O5	0.96	1.90	2.729 (4)	143
O13—H13C···O4^v	0.96	1.88	2.763 (4)	152

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (20671073), NingXia Natural Gas Transfering Key Laboratory (2004007), the Science and Technology Foundation of Weifang and Weifang University for research grants.

References

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