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Acta Cryst. (2007). E63, m2296    [ doi:10.1107/S1600536807038159 ]

Poly[[tetra-[mu]2-aqua-diaqua-[mu]6-oxalato-barium(II)] 2,4,6-trinitrophenolate monohydrate]

P.-Z. Hong, W.-D. Song and Z.-H. Wu

Abstract top

In the title coordination polymer, {[Ba(C2O4)(H2O)6]C6H2N3O7·H2O}n, each BaII ion is nine-coordinated by three O atoms from two oxalate ligands, two O atoms from two water molecules and four O atoms from [mu]2-bridging aqua ligands, and displays a distorted tricapped trigonal-prismatic geometry. The [mu]6-bridging oxalate ligands and [mu]2-aqua ligands link BaII ions to form a neutral layer. The coordinated water molecules link the 2,4,6-trinitrophenolate anions to form a supramolecular network via hydrogen-bonding interactions.

Comment top

2,4,6-trinitrophenolic acid have afforded a large number of O-chelated metal derivates, such as barium (Pierce-Butler, 1982), potassium (Li, et al. 2003), sodium (Ward, et al., 1984) and so on.

As illustrated in Fig. 1, in the asymmetric unit of (I) each BaII centre is nine-coordinated by three carboxyl O atoms from two oxalato ligands, two O atoms from two water molecules and four O atoms from /m2 bridging aqua ligands, and displaying a distorted tricapped trigonal prism geometry. All geometries are general. Via a Ba···Ba interaction between symmetrically related moieties the compound forms polymer structures with a Ba···Ba separation of 6.957 (3) Å that are further extended to a supramolecular network through intermolecular hydrogen bonding interaction among the cationic units, 2,4,6-trinitrophenolate anions and uncoordinated molecules (Table 1 and Fig. 2).

Related literature top

For related literature, see: Li et al. (2003); Pierce-Butler (1982); Ward et al. (1984).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of barium chloride (4.16 g, 20 mmol) and oxalic acid (1.80 g, 20 mmol) to a hot aqueous solution (25 ml) of 2,4,6-trinitrophenolic acid (4.58 g, 30 mmol). The pH was then adjusted to 7.0 to 8.0 with NaOH (1.2 g, 30 mmol). The resulting solution was filtered, and yellow crystals were obtained at room temperature on slow evaporation of the solvent over several days.

Refinement top

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å, and with Uiso(H) = 1.2 Ueq(C); Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 or 0.85 Å and H···H = 1.29 or 1.39 Å, each within a standard deviation of 0.01 Å. Other H atoms with Uiso(H) = 1.5 Ueq(O). The highest peak in the difference map is 0.84 (1) Å from Ba1 and the largest hole is 1.13 (2) Å from Ba1.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level for non-H atoms. [Symmetry codes:(i)-x, 1 - y, -z; (ii) -x, -y, -z; (iii) -x, y + 1/2, 1/2 - z; (iv) -x, y - 1/2, 1/2 - z.]
[Figure 2] Fig. 2. The unit-cell packing diagram of (I). Hydrogen bonds are shown as dashed lines.
Poly[[di-µ2-aqua-diaqua-hemi-µ6-oxalato-barium(II)] 2,4,6-trinitrophenolate monohydrate] top
Crystal data top
[Ba(C2O4)0.5(H2O)4]C6H2N3O7·H2OF(000) = 972
Mr = 499.54Dx = 2.180 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ybcCell parameters from 3600 reflections
a = 15.1489 (2) Åθ = 1.7–28.0°
b = 6.5736 (1) ŵ = 2.70 mm−1
c = 15.3111 (2) ÅT = 293 K
β = 93.557 (1)°Block, yellow
V = 1521.78 (4) Å30.19 × 0.18 × 0.16 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		3654 independent reflections
Radiation source: fine-focus sealed tube3126 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→19
Tmin = 0.608, Tmax = 0.650k = −8→8
13176 measured reflectionsl = −20→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0277P)2 + 0.4903P]
where P = (Fo2 + 2Fc2)/3
3654 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.57 e Å−3
14 restraintsΔρmin = −0.53 e Å−3
Crystal data top
[Ba(C2O4)0.5(H2O)4]C6H2N3O7·H2OV = 1521.78 (4) Å3
Mr = 499.54Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.1489 (2) ŵ = 2.70 mm−1
b = 6.5736 (1) ÅT = 293 K
c = 15.3111 (2) Å0.19 × 0.18 × 0.16 mm
β = 93.557 (1)°
Data collection top
Bruker APEXII area-detector
diffractometer		3654 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3126 reflections with I > 2σ(I)
Tmin = 0.608, Tmax = 0.650Rint = 0.028
13176 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.056Δρmax = 0.57 e Å−3
S = 1.03Δρmin = −0.53 e Å−3
3654 reflectionsAbsolute structure: ?
256 parametersFlack parameter: ?
14 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Ba0.009199 (10)0.090317 (19)0.144062 (9)0.02169 (6)
C10.53089 (19)0.0665 (4)0.32517 (18)0.0287 (6)
H10.51520.05580.38280.034*
C20.61794 (18)0.0706 (4)0.30611 (17)0.0272 (6)
C30.64955 (18)0.0795 (4)0.21936 (17)0.0264 (6)
C40.57696 (19)0.0866 (4)0.15341 (17)0.0286 (6)
C50.48959 (19)0.0906 (4)0.17056 (18)0.0291 (6)
H50.44620.10120.12510.035*
C60.46645 (18)0.0786 (4)0.25682 (18)0.0266 (6)
C7−0.00848 (17)0.4258 (3)−0.03987 (16)0.0215 (5)
H1WA0.182 (2)−0.021 (3)0.4331 (19)0.026*
H1WB0.2387 (13)0.113 (4)0.4163 (19)0.026*
H2WA0.0900 (16)−0.317 (4)0.1881 (15)0.026*
H2WB0.1540 (11)−0.240 (4)0.2382 (17)0.026*
H3WA0.1313 (16)0.224 (4)0.3221 (14)0.026*
H3WB0.1543 (15)0.353 (4)0.2658 (17)0.026*
H4WA0.2140 (16)0.102 (4)0.1052 (16)0.026*
H4WB0.1765 (18)0.208 (3)0.0395 (15)0.026*
H5WA−0.2039 (15)0.144 (4)0.1023 (15)0.026*
H5WB−0.1725 (18)0.123 (4)0.0273 (12)0.026*
N10.68199 (17)0.0555 (4)0.38123 (16)0.0374 (6)
N20.37473 (16)0.0789 (3)0.27700 (17)0.0349 (6)
N30.59676 (18)0.0979 (4)0.06088 (16)0.0386 (6)
O10.73001 (13)0.0796 (3)0.20391 (13)0.0393 (5)
O20.75026 (17)0.1514 (5)0.38100 (16)0.0711 (8)
O30.66196 (17)−0.0536 (4)0.44163 (15)0.0607 (7)
O40.35790 (16)0.0651 (4)0.35365 (16)0.0553 (7)
O50.31768 (15)0.0929 (4)0.21685 (17)0.0556 (7)
O60.54645 (17)0.1997 (4)0.01244 (15)0.0593 (7)
O70.65884 (16)0.0004 (5)0.03584 (15)0.0611 (7)
O8−0.00452 (12)0.2386 (2)−0.02508 (10)0.0256 (4)
O90.02537 (13)0.4939 (3)0.11302 (11)0.0311 (4)
O1W0.18547 (15)0.1042 (4)0.42656 (16)0.0439 (5)
O2W0.10105 (13)−0.2370 (3)0.22765 (12)0.0294 (4)
O3W0.11131 (13)0.2932 (3)0.28179 (13)0.0322 (4)
O4W0.17396 (15)0.1144 (3)0.07199 (16)0.0432 (5)
O5W−0.16202 (14)0.1761 (4)0.07469 (14)0.0397 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba0.02843 (10)0.01617 (8)0.02048 (9)0.00071 (6)0.00166 (6)0.00054 (5)
C10.0330 (16)0.0297 (13)0.0233 (13)0.0002 (11)0.0024 (11)0.0015 (10)
C20.0257 (14)0.0299 (13)0.0256 (13)−0.0018 (11)−0.0009 (11)0.0010 (10)
C30.0251 (14)0.0293 (13)0.0251 (13)−0.0010 (11)0.0024 (11)0.0016 (10)
C40.0313 (15)0.0329 (14)0.0218 (13)−0.0024 (11)0.0033 (11)0.0007 (10)
C50.0278 (15)0.0323 (14)0.0266 (13)−0.0010 (11)−0.0040 (11)0.0004 (11)
C60.0232 (14)0.0258 (13)0.0311 (14)0.0010 (11)0.0039 (11)0.0021 (10)
C70.0238 (13)0.0196 (12)0.0210 (12)−0.0016 (10)0.0005 (10)0.0006 (9)
N10.0300 (14)0.0570 (16)0.0251 (12)0.0012 (12)0.0001 (10)0.0040 (11)
N20.0250 (13)0.0368 (13)0.0430 (15)0.0013 (10)0.0034 (11)0.0021 (10)
N30.0366 (15)0.0548 (16)0.0241 (12)−0.0148 (13)0.0011 (11)−0.0023 (11)
O10.0242 (11)0.0616 (14)0.0322 (11)−0.0026 (10)0.0033 (9)0.0011 (9)
O20.0423 (15)0.128 (2)0.0418 (14)−0.0344 (16)−0.0089 (12)0.0092 (15)
O30.0463 (15)0.097 (2)0.0383 (13)−0.0038 (13)−0.0067 (11)0.0281 (13)
O40.0367 (14)0.0888 (19)0.0424 (14)0.0053 (12)0.0174 (11)0.0069 (12)
O50.0272 (12)0.0817 (19)0.0568 (15)0.0000 (11)−0.0067 (11)0.0038 (12)
O60.0700 (18)0.0735 (17)0.0332 (12)−0.0032 (14)−0.0053 (12)0.0162 (12)
O70.0420 (15)0.107 (2)0.0355 (13)0.0007 (15)0.0117 (11)−0.0187 (14)
O80.0371 (11)0.0156 (8)0.0241 (9)−0.0007 (8)0.0018 (8)−0.0003 (6)
O90.0480 (13)0.0202 (9)0.0241 (9)−0.0037 (8)−0.0060 (8)0.0018 (7)
O1W0.0266 (12)0.0562 (14)0.0490 (13)0.0089 (11)0.0037 (10)0.0072 (11)
O2W0.0300 (11)0.0311 (10)0.0269 (10)0.0046 (9)−0.0011 (8)−0.0014 (8)
O3W0.0325 (12)0.0333 (11)0.0304 (10)−0.0008 (9)−0.0016 (9)0.0039 (8)
O4W0.0305 (12)0.0545 (14)0.0440 (14)0.0009 (10)−0.0018 (10)0.0108 (10)
O5W0.0306 (12)0.0619 (14)0.0270 (11)−0.0074 (11)0.0042 (9)−0.0005 (10)
Geometric parameters (Å, º) top
Ba—O92.709 (2)C5—C61.390 (4)
Ba—O82.763 (2)C5—H50.9300
Ba—O4W2.795 (2)C6—N21.442 (4)
Ba—O5W2.799 (2)C7—O9iv1.250 (3)
Ba—O2W2.825 (2)C7—O81.252 (3)
Ba—O8i2.826 (2)C7—C7iv1.571 (5)
Ba—O3W2.866 (2)N1—O21.212 (3)
Ba—O2Wii2.888 (2)N1—O31.223 (3)
Ba—O3Wiii2.949 (2)N2—O41.220 (3)
Ba—Ba6.957 (3)N2—O51.227 (3)
Ba—Bai4.5603 (3)N3—O71.219 (3)
Ba—Baii4.6386 (2)N3—O61.228 (3)
Ba—Baiii4.6386 (2)O1W—H1WA0.832 (17)
C1—C21.368 (4)O1W—H1WB0.834 (17)
C1—C61.388 (4)O2W—H2WA0.810 (16)
C1—H10.9300O2W—H2WB0.809 (16)
C2—C31.441 (4)O3W—H3WA0.808 (16)
C2—N11.461 (3)O3W—H3WB0.813 (16)
C3—O11.256 (3)O4W—H4WA0.771 (16)
C3—C41.447 (4)O4W—H4WB0.796 (16)
C4—C51.366 (4)O5W—H5WA0.812 (16)
C4—N31.468 (4)O5W—H5WB0.812 (16)
O9—Ba—O859.49 (5)O3W—Ba—O3Wiii110.10 (3)
O9—Ba—O4W77.44 (6)O2Wii—Ba—O3Wiii66.46 (5)
O8—Ba—O4W68.10 (6)C2—C1—C6118.7 (3)
O9—Ba—O5W80.09 (6)C1—C2—C3125.3 (2)
O8—Ba—O5W63.84 (6)C1—C2—N1115.6 (2)
O4W—Ba—O5W131.91 (6)C3—C2—N1119.1 (2)
O9—Ba—O2W141.07 (6)O1—C3—C2123.7 (2)
O8—Ba—O2W134.40 (5)O1—C3—C4125.0 (3)
O4W—Ba—O2W78.19 (6)C2—C3—C4111.3 (2)
O5W—Ba—O2W138.08 (6)C5—C4—C3124.8 (3)
O9—Ba—O8i129.44 (5)C5—C4—N3116.3 (2)
O8—Ba—O8i70.63 (5)C3—C4—N3118.9 (3)
O4W—Ba—O8i77.07 (6)C4—C5—C6119.1 (2)
O5W—Ba—O8i85.63 (6)C1—C6—C5120.8 (3)
O2W—Ba—O8i72.61 (5)C1—C6—N2118.7 (3)
O9—Ba—O3W67.85 (5)C5—C6—N2120.5 (2)
O8—Ba—O3W122.09 (5)O9iv—C7—O8125.6 (2)
O4W—Ba—O3W79.03 (6)O9iv—C7—C7iv116.6 (2)
O5W—Ba—O3W129.11 (6)O8—C7—C7iv117.8 (2)
O2W—Ba—O3W78.05 (5)O2—N1—O3124.0 (3)
O8i—Ba—O3W145.21 (5)O2—N1—C2119.2 (2)
O9—Ba—O2Wii78.28 (6)O3—N1—C2116.8 (2)
O8—Ba—O2Wii119.06 (5)O4—N2—O5123.2 (3)
O4W—Ba—O2Wii144.51 (6)O4—N2—C6117.9 (2)
O5W—Ba—O2Wii67.51 (6)O5—N2—C6118.9 (3)
O2W—Ba—O2Wii106.29 (4)O7—N3—O6123.9 (3)
O8i—Ba—O2Wii138.31 (5)O7—N3—C4119.0 (3)
O3W—Ba—O2Wii67.99 (5)O6—N3—C4117.0 (3)
O9—Ba—O3Wiii141.37 (6)H1WA—O1W—H1WB99 (3)
O8—Ba—O3Wiii125.61 (5)H2WA—O2W—H2WB107 (2)
O4W—Ba—O3Wiii141.16 (6)H3WA—O3W—H3WB104 (2)
O5W—Ba—O3Wiii72.43 (6)H4WA—O4W—H4WB116 (2)
O2W—Ba—O3Wiii67.69 (6)H5WA—O5W—H5WB104 (2)
O8i—Ba—O3Wiii75.52 (5)
Symmetry codes: (i) −x, −y, −z; (ii) −x, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, −y+1, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O40.83 (2)2.12 (2)2.915 (3)159 (3)
O1W—H1WA···O5Wiii0.83 (2)2.02 (2)2.837 (3)169 (3)
O2W—H2WB···O1v0.81 (2)2.25 (2)2.961 (3)146 (3)
O2W—H2WB···O2v0.81 (2)2.50 (3)2.974 (3)118 (2)
O2W—H2WA···O9vi0.81 (2)1.92 (2)2.697 (3)160 (3)
O3W—H3WB···O1vii0.81 (2)2.32 (2)3.051 (3)149 (3)
O3W—H3WA···O1W0.81 (2)1.92 (2)2.722 (3)170 (3)
O4W—H4WA···O50.77 (2)2.25 (2)3.013 (3)171 (3)
O4W—H4WB···O1Wviii0.80 (2)2.13 (2)2.908 (3)164 (3)
O5W—H5WA···O1ix0.81 (2)1.95 (2)2.719 (3)158 (3)
O5W—H5WA···O7ix0.81 (2)2.45 (2)2.975 (3)124 (2)
O5W—H5WB···O4Wi0.81 (2)2.18 (2)2.945 (3)158 (3)
Symmetry codes: (i) −x, −y, −z; (iii) −x, y−1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x, y−1, z; (vii) −x+1, y+1/2, −z+1/2; (viii) x, −y+1/2, z−1/2; (ix) x−1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O40.834 (17)2.12 (2)2.915 (3)159 (3)
O1W—H1WA···O5Wi0.832 (17)2.016 (18)2.837 (3)169 (3)
O2W—H2WB···O1ii0.809 (16)2.25 (2)2.961 (3)146 (3)
O2W—H2WB···O2ii0.809 (16)2.50 (3)2.974 (3)118 (2)
O2W—H2WA···O9iii0.810 (16)1.922 (16)2.697 (3)160 (3)
O3W—H3WB···O1iv0.813 (16)2.32 (2)3.051 (3)149 (3)
O3W—H3WA···O1W0.808 (16)1.922 (17)2.722 (3)170 (3)
O4W—H4WA···O50.771 (16)2.250 (17)3.013 (3)171 (3)
O4W—H4WB···O1Wv0.796 (16)2.134 (17)2.908 (3)164 (3)
O5W—H5WA···O1vi0.812 (16)1.948 (17)2.719 (3)158 (3)
O5W—H5WA···O7vi0.812 (16)2.45 (2)2.975 (3)124 (2)
O5W—H5WB···O4Wvii0.812 (16)2.178 (18)2.945 (3)158 (3)
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+1/2, z−1/2; (vi) x−1, y, z; (vii) −x, −y, −z.
Acknowledgements top

The authors thank the Scientific and Technical Key Leading Project of Guangdong Province of China (grant No. B05119) and Guangdong Ocean University for supporting this study.

references
References top

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