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Acta Cryst. (2008). E64, m551    [ doi:10.1107/S1600536808006338 ]

Poly[[[mu]2-aqua-aqua([mu]3-3,5-dinitrosalicylato)barium(II)] monohydrate]

W.-D. Song, R.-Z. Fan, C.-S. Gu and X.-M. Hao

Abstract top

In the title coordination polymer, {[Ba(C7H2N2O7)(H2O)2]·H2O}n, the BaII atom is ten-coordinated by seven O atoms from four 3,5-dinitrosalicylatate ligands, two [mu]2-bridging aqua ligands and one water molecule. The coordination mode is best described as a bicapped square-antiprismatic geometry. The 3,5-dinitrosalicylatate ligands bridge three Ba atoms. Centrosymmetrically related dinuclear barium units, with a Ba...Ba separation of 4.767 (5) Å, form infinite chains, which are further self-assembled into a supramolecular network through intermolecular O-H...O hydrogen-bonding interactions between O atoms of 3,5-dinitrosalicylatate ligands and water molecules.

Comment top

In the structural investigation of 3,5-dinitrosalicylatato complexes, it has been found that the 3,5-dinitrosalicylatato moiety functions as a multidentate ligand (Song et al., 2007) with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Ba complex obtained by the reaction of 3,5-dinitrosalicylic acid and barium chloride in alkaline aqueous solution.

As illustrated in Figure 1, the BaII atom displays a bicapped square antiprismatic coordination environment, defined by seven O atoms from four 3,5-dinitrosalicylatato ligands, two µ2-bridging aqua ligands and one water molecule. The 3,5-dinitrosalicylatato ligands link barium ions to form infinite chains, which are further self-assembled into a supramolecular network through intermolecular O—H···O hydrogen bonding interactions (Table 1) involving the uncoordinating water molecules, coordinating water molecules as donors and O atoms of 3,5-dinitrosalicylatato ligands as acceptors (Fig. 2).

Related literature top

For related literature, see: Song et al. (2007).

Experimental top

A mixture of barium chloride (1 mmol), 3,5-dinitrosalicylic acid (1 mmol), NaOH (1.5 mmol) and H2O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h-1. The obtained crystals obtained were washed with water and dryed in air.

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 = 0.84 Å and H···H = 1.39 Å, each within a standard deviation of 0.01 Å, and with Uiso(H) = 1.5 Ueq(O)

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. A packing view of the title compound. The intermolecluar hydrogen bonds are shown as dashed lines.
Poly[[µ2-aqua-aqua(µ3-3,5-dinitrosalicylato)barium(II)] monohydrate] top
Crystal data top
[Ba(C7H2N2O7)(H2O)2]·H2OF000 = 800
Mr = 417.49Dx = 2.246 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5837 reflections
a = 11.9649 (6) Åθ = 2.8–27.9º
b = 4.1866 (2) ŵ = 3.27 mm−1
c = 26.121 (1) ÅT = 296 (2) K
β = 109.332 (3)ºBlock, yellow
V = 1234.7 (1) Å30.30 × 0.26 × 0.23 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2374 independent reflections
Radiation source: fine-focus sealed tube2189 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.041
T = 296(2) Kθmax = 26.0º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.392, Tmax = 0.472k = −4→4
8615 measured reflectionsl = −31→32
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.067  w = 1/[σ2(Fo2) + (0.0339P)2 + 1.4739P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2374 reflectionsΔρmax = 1.03 e Å−3
199 parametersΔρmin = −1.30 e Å−3
9 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ba(C7H2N2O7)(H2O)2]·H2OV = 1234.7 (1) Å3
Mr = 417.49Z = 4
Monoclinic, P21/cMo Kα
a = 11.9649 (6) ŵ = 3.27 mm−1
b = 4.1866 (2) ÅT = 296 (2) K
c = 26.121 (1) Å0.30 × 0.26 × 0.23 mm
β = 109.332 (3)º
Data collection top
Bruker APEXII area-detector
diffractometer		2374 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2189 reflections with I > 2σ(I)
Tmin = 0.392, Tmax = 0.472Rint = 0.041
8615 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0269 restraints
wR(F2) = 0.067H atoms treated by a mixture of
independent and constrained refinement
S = 1.05Δρmax = 1.03 e Å−3
2374 reflectionsΔρmin = −1.30 e Å−3
199 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
xyzUiso*/Ueq
Ba10.698106 (16)0.59849 (4)0.002749 (8)0.01250 (10)
O10.7177 (2)0.1028 (5)0.06998 (10)0.0150 (5)
O20.5320 (2)−0.3574 (6)0.05297 (11)0.0211 (6)
O30.4012 (2)−0.0694 (6)0.07602 (11)0.0190 (6)
O40.5934 (3)0.0066 (8)0.28282 (12)0.0311 (7)
O50.7491 (3)0.3054 (8)0.31157 (12)0.0359 (7)
O60.9954 (3)0.3764 (8)0.19294 (14)0.0416 (9)
O70.8915 (2)0.5460 (7)0.11347 (12)0.0251 (6)
N10.6755 (3)0.1544 (8)0.27501 (14)0.0245 (7)
N20.9007 (3)0.4015 (7)0.15565 (14)0.0205 (7)
C10.5067 (3)−0.1530 (8)0.08248 (14)0.0116 (7)
C20.6052 (3)−0.0051 (9)0.12815 (14)0.0129 (7)
C30.5950 (3)0.0128 (9)0.17862 (15)0.0167 (7)
H30.5270−0.06290.18440.020*
C40.6874 (3)0.1461 (9)0.22201 (15)0.0178 (8)
C50.7878 (3)0.2691 (9)0.21433 (15)0.0191 (8)
H50.84880.35520.24310.023*
C60.7951 (3)0.2603 (9)0.16271 (14)0.0158 (7)
C70.7074 (3)0.1200 (8)0.11687 (15)0.0146 (8)
O1W0.8608 (2)0.1295 (6)0.00092 (12)0.0205 (6)
H2W0.922 (2)0.101 (10)0.0272 (9)0.031*
H1W0.881 (3)0.137 (10)−0.0265 (9)0.031*
O2W0.7483 (2)0.6467 (6)−0.09980 (12)0.0223 (6)
H3W0.688 (2)0.758 (8)−0.1068 (17)0.033*
H4W0.732 (3)0.484 (6)−0.1189 (16)0.033*
O3W0.0565 (2)0.9715 (8)0.08622 (12)0.0255 (6)
H5W0.110 (3)1.093 (8)0.1033 (15)0.038*
H6W0.047 (4)0.837 (8)0.1074 (13)0.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.01402 (13)0.01055 (14)0.01455 (15)−0.00009 (7)0.00690 (10)−0.00038 (8)
O10.0191 (13)0.0156 (14)0.0133 (13)−0.0010 (9)0.0091 (11)−0.0007 (10)
O20.0199 (13)0.0222 (15)0.0235 (15)−0.0031 (10)0.0105 (12)−0.0089 (11)
O30.0142 (12)0.0185 (15)0.0238 (15)0.0005 (10)0.0055 (11)−0.0015 (11)
O40.0331 (16)0.0413 (17)0.0244 (16)−0.0037 (14)0.0167 (13)0.0019 (15)
O50.0411 (18)0.0464 (19)0.0186 (16)−0.0102 (15)0.0077 (14)−0.0100 (15)
O60.0227 (16)0.066 (3)0.033 (2)−0.0138 (14)0.0056 (15)0.0021 (16)
O70.0248 (14)0.0226 (15)0.0300 (17)−0.0044 (11)0.0117 (12)0.0052 (13)
N10.0296 (18)0.0263 (18)0.0184 (18)0.0037 (14)0.0089 (15)−0.0003 (14)
N20.0151 (15)0.0223 (19)0.0230 (19)−0.0046 (12)0.0049 (14)−0.0040 (14)
C10.0132 (16)0.0130 (18)0.0082 (17)−0.0010 (13)0.0030 (14)0.0023 (13)
C20.0163 (16)0.0102 (17)0.0128 (18)0.0025 (14)0.0056 (14)0.0018 (14)
C30.0178 (17)0.0153 (18)0.0178 (19)0.0006 (15)0.0071 (15)0.0015 (16)
C40.0214 (18)0.021 (2)0.0116 (18)0.0022 (14)0.0060 (15)−0.0015 (15)
C50.0190 (17)0.018 (2)0.0166 (19)−0.0003 (15)0.0013 (15)−0.0030 (16)
C60.0129 (16)0.016 (2)0.0181 (19)−0.0012 (14)0.0042 (14)−0.0002 (15)
C70.0184 (18)0.0121 (19)0.0146 (19)0.0044 (13)0.0074 (15)0.0040 (13)
O1W0.0156 (13)0.0291 (16)0.0186 (15)0.0036 (10)0.0079 (11)0.0005 (12)
O2W0.0290 (15)0.0188 (15)0.0222 (15)0.0010 (11)0.0126 (13)−0.0019 (11)
O3W0.0206 (14)0.0334 (17)0.0235 (16)−0.0020 (12)0.0086 (12)0.0046 (13)
Geometric parameters (Å, °) top
Ba1—O12.678 (2)O5—N11.237 (4)
Ba1—O1i2.706 (2)O6—N21.230 (5)
Ba1—O2i2.726 (3)O7—N21.230 (4)
Ba1—O1W2.777 (3)N1—C41.438 (5)
Ba1—O3ii2.813 (3)N2—C61.462 (4)
Ba1—O2iii2.840 (3)C1—C21.505 (5)
Ba1—O2W2.940 (3)C1—Ba1iii3.290 (3)
Ba1—O1Wi2.966 (3)C2—C31.366 (5)
Ba1—O3iii2.989 (3)C2—C71.447 (5)
Ba1—O73.056 (3)C3—C41.410 (5)
Ba1—C1iii3.290 (3)C3—H30.9300
Ba1—Ba1i4.18660 (19)C4—C51.382 (5)
Ba1—H3W2.90 (5)C5—C61.380 (5)
O1—C71.273 (4)C5—H50.9300
O1—Ba1iv2.706 (2)C6—C71.431 (5)
O2—C11.254 (4)O1W—Ba1iv2.966 (3)
O2—Ba1iv2.726 (3)O1W—H2W0.83 (4)
O2—Ba1iii2.840 (3)O1W—H1W0.83 (4)
O3—C11.266 (4)O2W—H3W0.83 (4)
O3—Ba1ii2.813 (3)O2W—H4W0.83 (4)
O3—Ba1iii2.989 (3)O3W—H5W0.82 (4)
O4—N11.233 (4)O3W—H6W0.83 (4)
O1—Ba1—O1i102.07 (8)O7—Ba1—Ba1i94.12 (5)
O1—Ba1—O2i69.92 (8)C1iii—Ba1—Ba1i124.53 (6)
O1i—Ba1—O2i63.59 (7)O1—Ba1—H3W142.3 (6)
O1—Ba1—O1W63.49 (7)O1i—Ba1—H3W115.3 (6)
O1i—Ba1—O1W130.70 (8)O2i—Ba1—H3W131.3 (3)
O2i—Ba1—O1W133.10 (8)O1W—Ba1—H3W86.9 (3)
O1—Ba1—O3ii161.23 (8)O3ii—Ba1—H3W41.2 (3)
O1i—Ba1—O3ii81.53 (7)O2iii—Ba1—H3W81.9 (7)
O2i—Ba1—O3ii96.08 (8)O2W—Ba1—H3W16.3 (6)
O1W—Ba1—O3ii127.72 (8)O1Wi—Ba1—H3W68.0 (7)
O1—Ba1—O2iii85.43 (8)O3iii—Ba1—H3W67.3 (7)
O1i—Ba1—O2iii118.10 (7)O7—Ba1—H3W136.2 (6)
O2i—Ba1—O2iii62.17 (9)C1iii—Ba1—H3W71.6 (7)
O1W—Ba1—O2iii107.83 (7)Ba1i—Ba1—H3W76.7 (6)
O3ii—Ba1—O2iii76.78 (8)C7—O1—Ba1124.9 (2)
O1—Ba1—O2W130.60 (7)C7—O1—Ba1iv130.8 (2)
O1i—Ba1—O2W122.52 (7)Ba1—O1—Ba1iv102.07 (8)
O2i—Ba1—O2W146.64 (8)C1—O2—Ba1iv134.8 (2)
O1W—Ba1—O2W71.15 (8)C1—O2—Ba1iii99.6 (2)
O3ii—Ba1—O2W56.60 (7)Ba1iv—O2—Ba1iii117.83 (9)
O2iii—Ba1—O2W90.76 (8)C1—O3—Ba1ii116.9 (2)
O1—Ba1—O1Wi132.52 (7)C1—O3—Ba1iii92.2 (2)
O1i—Ba1—O1Wi60.61 (7)Ba1ii—O3—Ba1iii92.33 (8)
O2i—Ba1—O1Wi122.95 (7)N2—O7—Ba1134.3 (2)
O1W—Ba1—O1Wi93.55 (7)O4—N1—O5122.1 (3)
O3ii—Ba1—O1Wi65.38 (7)O4—N1—C4119.0 (3)
O2iii—Ba1—O1Wi142.04 (8)O5—N1—C4118.9 (3)
O2W—Ba1—O1Wi66.46 (8)O7—N2—O6122.5 (3)
O1—Ba1—O3iii78.80 (7)O7—N2—C6119.2 (3)
O1i—Ba1—O3iii162.60 (7)O6—N2—C6118.3 (3)
O2i—Ba1—O3iii101.22 (7)O2—C1—O3122.7 (3)
O1W—Ba1—O3iii65.50 (7)O2—C1—C2118.9 (3)
O3ii—Ba1—O3iii92.33 (8)O3—C1—C2118.5 (3)
O2iii—Ba1—O3iii44.50 (7)O2—C1—Ba1iii58.32 (18)
O2W—Ba1—O3iii65.05 (7)O3—C1—Ba1iii65.18 (18)
O1Wi—Ba1—O3iii131.14 (7)C2—C1—Ba1iii169.1 (2)
O1—Ba1—O756.58 (7)C3—C2—C7121.9 (3)
O1i—Ba1—O764.28 (8)C3—C2—C1119.4 (3)
O2i—Ba1—O789.64 (8)C7—C2—C1118.7 (3)
O1W—Ba1—O769.50 (8)C2—C3—C4120.0 (3)
O3ii—Ba1—O7138.31 (7)C2—C3—H3120.0
O2iii—Ba1—O7139.60 (8)C4—C3—H3120.0
O2W—Ba1—O7123.25 (7)C5—C4—C3121.3 (3)
O1Wi—Ba1—O776.92 (7)C5—C4—N1119.9 (3)
O3iii—Ba1—O7127.03 (7)C3—C4—N1118.8 (3)
O1—Ba1—C1iii83.60 (8)C6—C5—C4118.1 (3)
O1i—Ba1—C1iii140.04 (8)C6—C5—H5121.0
O2i—Ba1—C1iii82.29 (8)C4—C5—H5121.0
O1W—Ba1—C1iii87.53 (8)C5—C6—C7124.2 (3)
O3ii—Ba1—C1iii82.12 (8)C5—C6—N2116.7 (3)
O2iii—Ba1—C1iii22.07 (8)C7—C6—N2119.1 (3)
O2W—Ba1—C1iii75.72 (8)O1—C7—C6123.4 (3)
O1Wi—Ba1—C1iii139.44 (8)O1—C7—C2122.2 (3)
O3iii—Ba1—C1iii22.61 (8)C6—C7—C2114.4 (3)
O7—Ba1—C1iii139.53 (8)Ba1—O1W—Ba1iv93.55 (7)
O1—Ba1—Ba1i140.79 (5)Ba1—O1W—H2W121 (3)
O1i—Ba1—Ba1i38.72 (5)Ba1iv—O1W—H2W107 (3)
O2i—Ba1—Ba1i86.11 (5)Ba1—O1W—H1W113 (3)
O1W—Ba1—Ba1i135.00 (5)Ba1iv—O1W—H1W115 (3)
O3ii—Ba1—Ba1i45.50 (5)H2W—O1W—H1W106.4 (17)
O2iii—Ba1—Ba1i110.82 (5)Ba1—O2W—H3W79 (3)
O2W—Ba1—Ba1i86.06 (5)Ba1—O2W—H4W114 (4)
O1Wi—Ba1—Ba1i41.45 (5)H3W—O2W—H4W108 (4)
O3iii—Ba1—Ba1i137.83 (5)H5W—O3W—H6W108 (4)
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z; (iii) −x+1, −y, −z; (iv) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H6W···O7v0.82 (3)2.27 (3)2.916 (4)135 (4)
O3W—H5W···O5vi0.82 (4)2.60 (4)2.985 (4)110 (3)
O3W—H5W···O2Wvii0.82 (4)2.04 (3)2.755 (4)145 (4)
O2W—H4W···N1viii0.83 (3)2.69 (4)3.340 (4)137 (4)
O2W—H4W···O4viii0.83 (3)2.55 (4)3.080 (4)123 (3)
O2W—H4W···O5viii0.83 (3)2.25 (3)2.993 (4)150 (5)
O2W—H3W···O3ii0.83 (3)2.01 (2)2.730 (4)145 (4)
O1W—H1W···O3Wii0.83 (3)1.991 (16)2.798 (4)164 (4)
O1W—H2W···O3Wix0.83 (3)1.90 (3)2.725 (4)171 (4)
Symmetry codes: (v) x−1, y, z; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y+2, −z; (viii) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (ix) x+1, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3W—H6W···O7i0.82 (3)2.27 (3)2.916 (4)135 (4)
O3W—H5W···O5ii0.82 (4)2.60 (4)2.985 (4)110 (3)
O3W—H5W···O2Wiii0.82 (4)2.04 (3)2.755 (4)145 (4)
O2W—H4W···N1iv0.83 (3)2.69 (4)3.340 (4)137 (4)
O2W—H4W···O4iv0.83 (3)2.55 (4)3.080 (4)123 (3)
O2W—H4W···O5iv0.83 (3)2.25 (3)2.993 (4)150 (5)
O2W—H3W···O3v0.83 (3)2.01 (2)2.730 (4)145 (4)
O1W—H1W···O3Wv0.83 (3)1.991 (16)2.798 (4)164 (4)
O1W—H2W···O3Wvi0.83 (3)1.90 (3)2.725 (4)171 (4)
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z; (iv) x, −y+1/2, z−1/2; (v) −x+1, −y+1, −z; (vi) x+1, y−1, z.
Acknowledgements top

The authors acknowledge Guang Dong Ocean University for supporting this work.

references
References top

Bruker (2004). APEX2 (Version 7.23A) and SAINT (Version 7.23A). Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Song, W.-D., Guo, X.-X. & Zhang, C.-H. (2007). Acta Cryst. E63, m399–m401.