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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): m691–m692.
Published online 2010 May 22. doi:  10.1107/S1600536810017952
PMCID: PMC2979591

Poly[bis­(N,N-dimethyl­formamide-κO)(μ4-naphthalene-1,5-disulfonato)magnesium(II)]

Abstract

The structure of the title compound, [Mg(C10H6O6S2)(C3H7NO)2]n, consists of MgO6 octa­hedra (An external file that holds a picture, illustration, etc.
Object name is e-66-0m691-efi1.jpg symmetry) connected to naphthalene-1,5-disulfonate ligands (An external file that holds a picture, illustration, etc.
Object name is e-66-0m691-efi1.jpg symmetry) in the equatoral plane, forming a two-dimensional network propagating parallel to (010). The coordination sphere of the Mg atom is completed by the O atoms of two N,N-dimethyl­formamide (DMF) mol­ecules in the axial positions. The title compound represents the first time the naphthalene-1,5-disulfonate anion is bound directly to a Mg2+ atom. Disorder over two positions was found in the DMF mol­ecule in a 0.518 (8):0.482 (8) ratio.

Related literature

For background to metal-organic coordination polymers (CPs) and frameworks (MOFs), see: Cheetham et al. (2006 [triangle]); Kitagawa et al. (2004 [triangle]); Rosseinsky (2004 [triangle]); Rowsell & Yaghi (2004 [triangle]). For structures in which Mg2+ is not directly linked to naphthalene­disulfonate ligands but is surrounded by water mol­ecules, see: Cody & Hazel (1977 [triangle]); Morris et al. (2003 [triangle]); Shakeri & Haussühl (1992 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m691-scheme1.jpg

Experimental

Crystal data

  • [Mg(C10H6O6S2)(C3H7NO)2]
  • M r = 456.79
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m691-efi3.jpg
  • a = 5.1328 (2) Å
  • b = 9.3890 (4) Å
  • c = 10.4029 (4) Å
  • α = 85.158 (1)°
  • β = 75.638 (1)°
  • γ = 79.501 (1)°
  • V = 477.13 (3) Å3
  • Z = 1
  • Synchrotron radiation
  • λ = 0.41328 Å
  • μ = 0.08 mm−1
  • T = 100 K
  • 0.09 × 0.03 × 0.01 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.993, T max = 0.999
  • 8811 measured reflections
  • 1961 independent reflections
  • 1721 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.087
  • S = 1.04
  • 1961 reflections
  • 221 parameters
  • 6 restraints
  • Only H-atom coordinates refined
  • Δρmax = 0.61 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SIR2004 (Burla et al., 2005 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: CrystalMaker (CrystalMaker, 2009 [triangle]); software used to prepare material for publication: enCIFer (Allen et al., 2004 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017952/wm2328sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017952/wm2328Isup2.hkl

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

Acknowledgments

This work was supported by the National Science Foundation (DMR-0800415). The authors would like to thank Yu-Sheng Chen at ChemMatCARS, APS, for his assistance during the data collection. ChemMatCARS (APS, Sector 15) is principally supported by the National Science Foundation/Department of Energy under grant No. CHE-0535644. Use of the Advance Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE—AC02-06CH11357.

supplementary crystallographic information

Comment

Interest in metal organic coordination polymers (CPs) and frameworks (MOFs) arises due to the potential applications including size/shape catalysis and gas storage/separation (Cheetham et al., 2006; Kitagawa et al., 2004; Rosseinsky, 2004; Rowsell & Yaghi, 2004). This is owing to the fact that these materials have similar properties to zeolites with the added possiblity of structural design. Three factors need to be considered during the sythesis of CPs and MOFs; the coordination sphere of the metal center, the size, shape and functionality of the organic linker and the synthetic conditions.

Previous studies have looked at the interaction between a variety of metal atoms and 1,5-naphthalenedisulfonic acid. A search of the literature results in examples of direct bonding between this ligand and every alkali and alkali earth metal except Mg2+. Due to perodic trends we suspected that Mg2+ and naphthalene-1,5-disulfonate should have a direct bonding interaction, which indicates a change in synthetic conditions compared to the previous studies was needed. The previous efforts used water as the solvent resulting in structures where the Mg2+ atoms are bound solely to water molecules and interacted with 1,5-naphthalenedisulfonic acid through hydrogen bonds (Cody & Hazel, 1977; Morris et al., 2003; Shakeri & Haussühl, 1992). In our study we used N,N-dimethylformamide (DMF) as the solvent with the thought that DMF is a large solvent molecule and is unlikely to complete for the coordination sphere of the Mg2+ atom.

The title compound consists of MgO6 octahedra linked by 1,5- naphthalenedisulfonate ligands to form a two-dimensional network parallel to (010). The Mg2+ atom is bound to four O atoms from four separate naphthalene-1,5-disulfonate ligands in the equitorial plane and two O atoms from two symmetry equivalent N,N-dimethylformamide molecules in the axial positions (Figure 1). The average equitorial Mg—O bond length is 2.031 Å whereas the axial bond length is slightly longer at 2.156 Å (Table 1). The individual MgO6 octahedra are connected by the naphthalene-1,5-disulfonate linkers in a bridging bidentate fashion to form chains along the [100] direction, which are further connected by the linker molecules to form an overall 2-dimensional structure (Figure 2).

Experimental

All of the starting materials are available commercially and were used without any further purification. Magnesium nitrate hexahydrate (Mg(NO3)2.6H2O, 1.3 grams), 1,5-naphthalenedisulfonic acid tetrahydrate (C10H8S2O6 4H2O, 1.87 grams) and ammonium fluoride (NH4F, 0.021 grams) were dissolved in 15 grams of N,N-dimethylformamide (DMF). The solution was prepared in a 23 mL Teflon lined Parr bomb and stirred for three hours to achieve homogeneity. The resulting solution was heated statically at 373 K for three days. Colorless needle shaped crystals were recovered and were washed with ethanol.

Refinement

Disorder was found in the bound N,N-dimethylformamide molecules with the major component occupied 51.8 (8)% and the minor 48.2 (8)%, of which only the O atom does not have a second position. The disordered atoms were refined anisotropically without constraints. All of the hydrogen atoms were located in the Fourier difference map and their positions were allowed to refine independent of the C atoms with Uiso(H)=1.5Ueq(C) for the methyl groups and Uiso(H)=1.2Ueq (C) for all others. The highest peak (~0.6 e- A-3) can be found within 0.89 Å of C2 and the deepest hole (~-0.5 e- A-3) within 0.73 Å of S1. The near equal values of the highest peak and deepest hole indicate that there is not any remaining unmodelled electron density. The crystal remained stable throughout the low temperature data collection.

Figures

Fig. 1.
Polyhedral representation of a layer of the title compound. The DMF disorder and the H atoms were omitted for clarity. Color codes: blue octahedra Mg, red spheres O, light blue spheres N, and black lines C.

Crystal data

[Mg(C10H6O6S2)(C3H7NO)2]Z = 1
Mr = 456.79F(000) = 238
Triclinic, P1Dx = 1.590 Mg m3
Hall symbol: -P 1Synchrotron radiation, λ = 0.41328 Å
a = 5.1328 (2) ÅCell parameters from 4827 reflections
b = 9.3890 (4) Åθ = 2.4–17.1°
c = 10.4029 (4) ŵ = 0.08 mm1
α = 85.158 (1)°T = 100 K
β = 75.638 (1)°Needle, colorless
γ = 79.501 (1)°0.09 × 0.03 × 0.01 mm
V = 477.13 (3) Å3

Data collection

Bruker APEXII CCD diffractometer1961 independent reflections
Radiation source: APS Sector 151721 reflections with I > 2σ(I)
graphiteRint = 0.054
phi scansθmax = 15.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −6→6
Tmin = 0.993, Tmax = 0.999k = −11→11
8811 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087Only H-atom coordinates refined
S = 1.04w = 1/[σ2(Fo2) + (0.0481P)2 + 0.2091P] where P = (Fo2 + 2Fc2)/3
1961 reflections(Δ/σ)max < 0.001
221 parametersΔρmax = 0.61 e Å3
6 restraintsΔρmin = −0.51 e Å3

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.
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)

xyzUiso*/UeqOcc. (<1)
S10.07457 (7)0.11525 (4)0.80723 (4)0.00723 (15)
Mg10.50000.00001.00000.00731 (19)
O10.2916 (2)0.11924 (12)0.87562 (11)0.0100 (3)
O2−0.1359 (2)0.04071 (13)0.88296 (11)0.0117 (3)
O3−0.0320 (2)0.25885 (12)0.76873 (12)0.0123 (3)
O40.5528 (2)−0.18505 (12)0.88102 (12)0.0115 (3)
C10.4500 (3)0.04297 (17)0.56082 (16)0.0084 (3)
C20.2241 (3)0.00625 (17)0.65774 (15)0.0088 (3)
C30.1051 (3)−0.10819 (18)0.63682 (17)0.0113 (3)
H3−0.048 (4)−0.127 (2)0.698 (2)0.014*
C40.4211 (3)−0.16097 (18)0.42018 (17)0.0103 (3)
H40.474 (4)−0.216 (2)0.343 (2)0.012*
C50.2054 (4)−0.19167 (19)0.51598 (17)0.0135 (4)
H50.112 (4)−0.269 (2)0.503 (2)0.016*
C60.3941 (13)−0.2695 (7)0.8776 (6)0.0152 (12)0.518 (8)
H60.213 (9)−0.258 (4)0.935 (4)0.018*0.518 (8)
N10.4566 (15)−0.3857 (7)0.7960 (6)0.0128 (13)0.518 (8)
C70.2600 (9)−0.4804 (5)0.7982 (5)0.0269 (13)0.518 (8)
H7A0.355 (14)−0.580 (7)0.827 (7)0.040*0.518 (8)
H7B0.089 (11)−0.435 (6)0.866 (5)0.040*0.518 (8)
H7C0.224 (10)−0.489 (6)0.713 (6)0.040*0.518 (8)
C80.7147 (16)−0.4185 (7)0.6958 (6)0.0182 (13)0.518 (8)
H8A0.809 (13)−0.505 (9)0.686 (7)0.027*0.518 (8)
H8B0.683 (11)−0.383 (6)0.620 (5)0.027*0.518 (8)
H8C0.839 (10)−0.384 (5)0.721 (5)0.027*0.518 (8)
C6'0.4544 (12)−0.2955 (6)0.9149 (6)0.0098 (11)0.482 (8)
H6'0.362 (9)−0.313 (5)1.007 (5)0.012*0.482 (8)
N1'0.4704 (16)−0.4086 (8)0.8350 (7)0.0108 (13)0.482 (8)
C7'0.3529 (8)−0.5363 (4)0.8827 (4)0.0154 (13)0.482 (8)
H7A'0.228 (11)−0.544 (8)0.839 (6)0.023*0.482 (8)
H7B'0.500 (10)−0.625 (5)0.860 (5)0.023*0.482 (8)
H7C'0.279 (9)−0.520 (5)0.977 (5)0.023*0.482 (8)
C8'0.6042 (17)−0.4110 (8)0.6929 (6)0.0157 (14)0.482 (8)
H8A'0.751 (13)−0.511 (9)0.678 (7)0.024*0.482 (8)
H8B'0.674 (10)−0.320 (6)0.674 (5)0.024*0.482 (8)
H8C'0.469 (11)−0.418 (5)0.651 (5)0.024*0.482 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0075 (2)0.0079 (2)0.0062 (2)−0.00348 (15)−0.00026 (15)0.00097 (15)
Mg10.0080 (4)0.0073 (4)0.0069 (4)−0.0044 (3)−0.0006 (3)0.0014 (3)
O10.0109 (5)0.0108 (6)0.0091 (6)−0.0057 (4)−0.0027 (4)0.0039 (5)
O20.0097 (5)0.0156 (6)0.0103 (6)−0.0080 (5)0.0006 (4)0.0010 (5)
O30.0140 (6)0.0089 (6)0.0134 (6)−0.0014 (5)−0.0038 (5)0.0028 (5)
O40.0138 (6)0.0098 (6)0.0116 (6)−0.0058 (5)−0.0016 (5)0.0002 (5)
C10.0093 (7)0.0077 (8)0.0085 (8)−0.0017 (6)−0.0031 (6)0.0018 (6)
C20.0099 (7)0.0090 (8)0.0072 (8)−0.0012 (6)−0.0022 (6)0.0009 (6)
C30.0116 (8)0.0126 (8)0.0098 (8)−0.0062 (6)−0.0005 (6)0.0025 (6)
C40.0138 (8)0.0093 (8)0.0083 (8)−0.0051 (6)−0.0013 (6)−0.0007 (6)
C50.0173 (8)0.0120 (8)0.0134 (8)−0.0104 (7)−0.0019 (7)−0.0004 (7)
C60.016 (3)0.020 (3)0.012 (3)−0.0077 (19)−0.0046 (19)−0.001 (2)
N10.020 (2)0.010 (2)0.011 (3)−0.0105 (18)−0.004 (2)0.002 (2)
C70.032 (2)0.022 (2)0.031 (3)−0.0188 (19)−0.0045 (19)−0.0054 (19)
C80.020 (3)0.015 (3)0.017 (2)−0.001 (3)−0.002 (3)−0.0009 (16)
C6'0.010 (2)0.011 (2)0.010 (3)−0.0038 (18)−0.0023 (18)−0.004 (2)
N1'0.012 (2)0.008 (2)0.010 (3)−0.0034 (17)0.000 (2)0.002 (2)
C7'0.0156 (19)0.008 (2)0.022 (3)−0.0054 (14)−0.0012 (16)−0.0012 (16)
C8'0.018 (3)0.016 (2)0.014 (3)−0.004 (3)−0.003 (3)−0.0018 (16)

Geometric parameters (Å, °)

S1—O31.4234 (12)C5—H50.98 (2)
S1—O21.4276 (12)C6—N11.381 (8)
S1—O11.4701 (11)C6—H60.97 (4)
S1—C21.8560 (16)N1—C71.456 (7)
Mg1—O12.0193 (11)N1—C81.469 (9)
Mg1—O1i2.0193 (11)C7—H7A1.03 (7)
Mg1—O2ii2.0429 (11)C7—H7B1.03 (6)
Mg1—O2iii2.0429 (11)C7—H7C0.97 (6)
Mg1—O4i2.1562 (11)C8—H8A0.87 (9)
Mg1—O42.1562 (11)C8—H8B0.87 (5)
O2—Mg1iv2.0429 (11)C8—H8C0.87 (5)
O4—C6'1.223 (6)C6'—N1'1.382 (8)
O4—C61.244 (6)C6'—H6'0.97 (5)
C1—C21.409 (2)N1'—C7'1.436 (7)
C1—C4v1.440 (2)N1'—C8'1.468 (8)
C1—C1v1.488 (3)C7'—H7A'0.89 (6)
C2—C31.386 (2)C7'—H7B'1.02 (5)
C3—C51.469 (2)C7'—H7C'0.97 (5)
C3—H30.92 (2)C8'—H8A'1.09 (9)
C4—C51.350 (2)C8'—H8B'0.98 (5)
C4—C1v1.440 (2)C8'—H8C'0.92 (5)
C4—H40.95 (2)
O3—S1—O2111.65 (7)C3—C5—H5119.7 (12)
O3—S1—O1109.59 (7)O4—C6—N1124.7 (6)
O2—S1—O1113.33 (7)O4—C6—H6120 (2)
O3—S1—C2109.78 (7)N1—C6—H6115 (2)
O2—S1—C2104.07 (7)O4—C6—H6'94.7 (18)
O1—S1—C2108.22 (7)N1—C6—H6'111.8 (18)
O1—Mg1—O1i180.00 (4)H6—C6—H6'61 (3)
O1—Mg1—O2ii91.70 (5)C6—N1—C7121.5 (6)
O1i—Mg1—O2ii88.30 (5)C6—N1—C8123.5 (6)
O1—Mg1—O2iii88.30 (5)C7—N1—C8114.9 (6)
O1i—Mg1—O2iii91.70 (5)N1—C7—H7A103 (4)
O2ii—Mg1—O2iii180.0N1—C7—H7B104 (3)
O1—Mg1—O4i90.98 (5)H7A—C7—H7B115 (5)
O1i—Mg1—O4i89.02 (5)N1—C7—H7C114 (3)
O2ii—Mg1—O4i93.38 (5)H7A—C7—H7C108 (5)
O2iii—Mg1—O4i86.62 (4)H7B—C7—H7C112 (4)
O1—Mg1—O489.02 (5)N1—C8—H8A123 (5)
O1i—Mg1—O490.98 (5)N1—C8—H8B107 (4)
O2ii—Mg1—O486.62 (4)H8A—C8—H8B110 (6)
O2iii—Mg1—O493.38 (5)N1—C8—H8C108 (3)
O4i—Mg1—O4180.0H8A—C8—H8C94 (5)
S1—O1—Mg1141.82 (7)H8B—C8—H8C115 (5)
S1—O2—Mg1iv161.80 (8)N1'—C6'—H6'113 (2)
C6'—O4—Mg1126.6 (3)C6'—N1'—C7'123.1 (5)
C6—O4—Mg1130.9 (3)C6'—N1'—C8'124.2 (6)
C2—C1—C4v120.44 (15)C7'—N1'—C8'112.7 (6)
C2—C1—C1v118.31 (17)N1'—C7'—H7A'109 (5)
C4v—C1—C1v121.26 (18)N1'—C7'—H7B'109 (3)
C3—C2—C1119.08 (15)H7A'—C7'—H7B'106 (5)
C3—C2—S1120.03 (12)N1'—C7'—H7C'103 (3)
C1—C2—S1120.80 (12)H7A'—C7'—H7C'114 (5)
C2—C3—C5122.01 (15)H7B'—C7'—H7C'116 (4)
C2—C3—H3117.9 (12)N1'—C8'—H8A'107 (4)
C5—C3—H3119.9 (12)N1'—C8'—H8B'104 (3)
C5—C4—C1v118.10 (15)H8A'—C8'—H8B'118 (5)
C5—C4—H4118.1 (12)N1'—C8'—H8C'105 (3)
C1v—C4—H4123.7 (12)H8A'—C8'—H8C'107 (4)
C4—C5—C3121.24 (15)H8B'—C8'—H8C'115 (4)
C4—C5—H5119.0 (12)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2328).

References

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