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Acta Cryst. (2007). E63, m1722-m1723    [ doi:10.1107/S1600536807024610 ]

catena-Poly[[[triaquabarium(II)]-di-[mu]-2,4,6-trinitrophenolato-[kappa]3O:O',O'';[kappa]3O,O':O''] benzimidazole disolvate]

D.-Y. Ma and G.-H. Deng

Abstract top

In the title complex, {[Ba(C6H2N3O7)2(H2O)3]·2C7H6N2}n, the BaII coordination polyhedron is defined by six O atoms from four 2,4,6-trinitrophenolate ligands and three water molecules, displaying a distorted monocapped square-antiprismatic geometry. Both the Ba atom and one of the coordinated water molecules lie on a twofold axis. The compound forms an infinite chain parallel to the c axis through [kappa]3-bridging 2,4,6-trinitrophenolate ligands to the metal atoms. A supramolecular network is formed via hydrogen bonding and [pi]-[pi] interactions involving both the chains and benzimidazole solvent molecules. The face-to-face and centroid- centroid distances between parallel 2,4,6-trinitrophenolate and benzimidazole rings of neighboring complexes are 3.509 (3) and 3.613 (2) Å, respectively.

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Tao et al., 2000; Choi & Jeon, 2003). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metal ions and the bridging building blocks, as well as on the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. In this sense, 2,4,6-trinitrophenolate is an excellent candidante for the construction of supramolecular complexes, since it not only displays multiple coordination modes but also can form regular hydrogen bonds by functioning both as hydrogen-bond donor and acceptor (Gu et al., 2004). In the present paper, we report the novel title Ba polymer (I).

Fig. 1 shows its molecular diagram: the BaII atom lies on a two fold axis and presents a distorted mono-capped square antiprism geometry, defined by six O atoms from four 2,4,6-trinitrophenolate ligands, and three water molecules, one of which is also bisected by the diad. The compound forms an infinite chain parallel to the c axis through κ3 bridging 2,4,6-trinitrophenolate ligands to the metal atoms, with the adjacent Ba···Ba distance being 8.362 (3) /%A. Inter/intramolecular (O—H···O and N—H···O) hydrogen bonding (Table 2) and π···π interactions involving both the chains and independent benzimidazole molecules stabilize the supramolecular network (Fig. 2). The face-to-face and centroid-centroid distances between parallel 2,4,6-trinitrophenolate and benzimidazole of neighboring complexes are 3.509 (3) and 3.613 (2) Å, respectively.

Related literature top

For related literature, see: Choi & Jeon (2003); Gu et al. (2004); Tao et al. (2000).

Experimental top

The title complex was prepared by the addition of a stoichiometric amount of barium chloride (20 mmol) and benzimidazole (20 mmol) to a hot aqueous solution(25 ml) of 2,4,6-trinitrophenolate (20 mmol). the PH was then adjusted to 7.0 to 8.0 with NaOH (30 mmol).The resulting solution was filtered, and yellow single crystals were obtained at room temperature over several days. (yield, 58%).

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. Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 (1) Å and H···H = 1.29 (1) Å. In all cases, Uiso(H) = 1.2 Ueq(Host).

Computing details top

Data collection: APEXII (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: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown as 30% probability displacement ellipsoids. Symmetry code: (i) -x, y, 1/2 - z; (ii) x, 1 - y, -1/2 + z; (iii) -x, 1 - y, 1 - z.
[Figure 2] Fig. 2. A packing view of (I), Hydrogen bonds are shown as dashed lines.
catena-Poly[[[triaquabarium(II)]-di-µ-2,4,6-trinitrophenolato- κ3O,O':O'';κ3O:O',O''] benzimidazole disolvate] top
Crystal data top
[Ba(C6H2N3O7)2(H2O)3].2C7H6N2F(000) = 1756
Mr = 882.87Dx = 1.804 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3200 reflections
a = 30.4215 (6) Åθ = 1.7–28.0°
b = 6.7394 (1) ŵ = 1.32 mm−1
c = 16.6695 (3) ÅT = 293 K
β = 107.950 (1)°Block, yellow
V = 3251.27 (10) Å30.20 × 0.18 × 0.18 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		3176 independent reflections
Radiation source: fine-focus sealed tube2965 reflections with I > 2σ(I)
graphiteRint = 0.024
φ and ω scansθmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −37→37
Tmin = 0.779, Tmax = 0.797k = −8→8
11230 measured reflectionsl = −20→19
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)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0238P)2 + 2.8124P]
where P = (Fo2 + 2Fc2)/3
3176 reflections(Δ/σ)max = 0.001
254 parametersΔρmax = 0.31 e Å−3
4 restraintsΔρmin = −0.30 e Å−3
Crystal data top
[Ba(C6H2N3O7)2(H2O)3].2C7H6N2V = 3251.27 (10) Å3
Mr = 882.87Z = 4
Monoclinic, C2/cMo Kα radiation
a = 30.4215 (6) ŵ = 1.32 mm−1
b = 6.7394 (1) ÅT = 293 K
c = 16.6695 (3) Å0.20 × 0.18 × 0.18 mm
β = 107.950 (1)°
Data collection top
Bruker APEXII area-detector
diffractometer		3176 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2965 reflections with I > 2σ(I)
Tmin = 0.779, Tmax = 0.797Rint = 0.024
11230 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049Δρmax = 0.31 e Å−3
S = 1.03Δρmin = −0.30 e Å−3
3176 reflectionsAbsolute structure: ?
254 parametersFlack parameter: ?
4 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*/UeqOcc. (<1)
Ba10.00000.54969 (3)0.25000.02678 (6)
C10.12475 (6)0.8786 (3)0.04517 (13)0.0305 (4)
C20.09690 (7)0.8776 (3)−0.03851 (14)0.0385 (5)
H20.06490.8729−0.05230.046*
C30.11831 (9)0.8839 (4)−0.10030 (15)0.0479 (6)
H30.10030.8835−0.15660.058*
C40.16600 (10)0.8909 (4)−0.08066 (17)0.0533 (6)
H40.17910.8943−0.12420.064*
C50.19433 (8)0.8930 (4)0.00113 (18)0.0493 (6)
H50.22630.89860.01400.059*
C60.17305 (7)0.8863 (3)0.06404 (14)0.0359 (5)
C70.15304 (9)0.8749 (4)0.17941 (15)0.0477 (6)
H70.15580.87140.23650.057*
C80.08615 (6)0.6307 (3)0.46576 (12)0.0271 (4)
C90.08875 (6)0.6439 (3)0.55372 (12)0.0272 (4)
C100.12886 (6)0.6317 (3)0.61992 (12)0.0292 (4)
H100.12820.63470.67530.035*
C110.17024 (6)0.6148 (3)0.60218 (12)0.0315 (4)
C120.17172 (6)0.6059 (3)0.52008 (13)0.0313 (4)
H120.19990.59630.50960.038*
C130.13161 (6)0.6113 (3)0.45470 (12)0.0279 (4)
N10.11318 (6)0.8717 (3)0.11972 (11)0.0399 (4)
N20.18963 (6)0.8836 (3)0.15040 (12)0.0473 (5)
H2A0.21820.88690.18050.057*
N30.04662 (5)0.6730 (3)0.57559 (10)0.0339 (4)
N40.21295 (6)0.6097 (3)0.67093 (12)0.0424 (5)
N50.13605 (6)0.6021 (3)0.37039 (11)0.0360 (4)
O30.10196 (6)0.5831 (3)0.30871 (10)0.0606 (5)
O40.17466 (6)0.6120 (3)0.36322 (11)0.0598 (5)
O50.04921 (5)0.6328 (3)0.40711 (9)0.0435 (4)
O60.01290 (5)0.7470 (3)0.52530 (10)0.0633 (6)
O70.04724 (6)0.6278 (3)0.64730 (10)0.0519 (4)
O80.21155 (6)0.6352 (3)0.74293 (10)0.0619 (5)
O90.24904 (5)0.5800 (4)0.65494 (12)0.0718 (6)
O1W0.00000.1516 (4)0.25000.0525 (6)
H1W0.010 (2)0.076 (7)0.224 (3)0.063*0.50
O2W−0.03027 (5)0.8540 (3)0.33929 (9)0.0395 (3)
H2W−0.0537 (6)0.862 (4)0.3550 (14)0.047*
H3W−0.0098 (6)0.828 (4)0.3817 (12)0.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba10.02865 (9)0.03324 (10)0.01903 (9)0.0000.00817 (6)0.000
C10.0307 (9)0.0268 (10)0.0341 (11)−0.0013 (8)0.0100 (8)0.0007 (9)
C20.0359 (10)0.0342 (11)0.0396 (12)−0.0017 (9)0.0032 (9)0.0005 (10)
C30.0684 (16)0.0406 (13)0.0320 (12)0.0008 (12)0.0115 (11)0.0007 (10)
C40.0746 (17)0.0451 (14)0.0534 (16)0.0002 (13)0.0391 (14)0.0019 (12)
C50.0383 (12)0.0454 (14)0.0713 (18)−0.0008 (10)0.0275 (12)0.0008 (13)
C60.0314 (10)0.0311 (11)0.0421 (12)0.0003 (8)0.0068 (9)0.0010 (9)
C70.0648 (15)0.0461 (14)0.0298 (12)−0.0031 (12)0.0113 (11)0.0018 (11)
C80.0278 (9)0.0288 (10)0.0240 (9)−0.0007 (8)0.0071 (7)−0.0014 (8)
C90.0287 (9)0.0290 (10)0.0253 (9)−0.0015 (8)0.0103 (7)0.0002 (8)
C100.0345 (10)0.0312 (10)0.0212 (9)−0.0022 (8)0.0077 (8)0.0011 (8)
C110.0279 (9)0.0356 (11)0.0262 (10)−0.0016 (8)0.0013 (8)0.0015 (9)
C120.0277 (9)0.0356 (11)0.0319 (11)0.0001 (8)0.0111 (8)−0.0001 (9)
C130.0319 (9)0.0304 (10)0.0221 (9)0.0000 (8)0.0095 (8)0.0002 (8)
N10.0440 (10)0.0407 (10)0.0374 (10)−0.0024 (9)0.0162 (8)0.0013 (9)
N20.0378 (10)0.0503 (12)0.0425 (11)−0.0018 (9)−0.0044 (8)0.0017 (10)
N30.0321 (8)0.0442 (11)0.0277 (9)−0.0011 (8)0.0125 (7)−0.0029 (8)
N40.0318 (9)0.0544 (12)0.0343 (10)−0.0038 (8)0.0001 (8)0.0048 (9)
N50.0399 (9)0.0436 (11)0.0277 (9)0.0011 (8)0.0150 (8)0.0003 (8)
O30.0454 (9)0.1133 (18)0.0223 (8)−0.0046 (10)0.0093 (7)−0.0052 (9)
O40.0453 (9)0.1017 (16)0.0418 (9)−0.0006 (10)0.0271 (8)−0.0007 (10)
O50.0289 (7)0.0726 (11)0.0250 (7)0.0029 (7)0.0024 (6)−0.0088 (8)
O60.0397 (8)0.1134 (17)0.0381 (9)0.0293 (10)0.0138 (7)0.0088 (10)
O70.0503 (9)0.0778 (12)0.0364 (9)0.0007 (9)0.0266 (7)0.0122 (9)
O80.0438 (9)0.1064 (16)0.0276 (9)−0.0049 (10)−0.0006 (7)0.0031 (10)
O90.0275 (8)0.130 (2)0.0517 (11)0.0076 (10)0.0033 (8)−0.0012 (11)
O1W0.0769 (17)0.0340 (13)0.0618 (17)0.0000.0435 (14)0.000
O2W0.0390 (8)0.0474 (9)0.0345 (8)0.0063 (7)0.0152 (6)0.0028 (8)
Geometric parameters (Å, °) top
Ba1—O52.6451 (14)C8—O51.242 (2)
Ba1—O5i2.6451 (14)C8—C91.447 (3)
Ba1—O1W2.683 (2)C8—C131.456 (3)
Ba1—O7ii2.8184 (15)C9—C101.372 (3)
Ba1—O7iii2.8184 (15)C9—N31.450 (2)
Ba1—O2Wi2.8484 (16)C10—C111.384 (3)
Ba1—O2W2.8484 (16)C10—H100.9300
Ba1—O32.9596 (17)C11—C121.384 (3)
Ba1—O3i2.9596 (17)C11—N41.444 (2)
C1—C21.391 (3)C12—C131.363 (3)
C1—N11.393 (3)C12—H120.9300
C1—C61.406 (3)C13—N51.454 (2)
C2—C31.379 (3)N2—H2A0.8600
C2—H20.9300N3—O61.214 (2)
C3—C41.386 (4)N3—O71.228 (2)
C3—H30.9300N4—O91.223 (2)
C4—C51.370 (4)N4—O81.226 (2)
C4—H40.9300N5—O41.219 (2)
C5—C61.393 (3)N5—O31.221 (2)
C5—H50.9300O7—Ba1iii2.8184 (15)
C6—N21.371 (3)O1W—H1W0.80 (2)
C7—N11.310 (3)O2W—H2W0.83 (2)
C7—N21.345 (3)O2W—H3W0.80 (2)
C7—H70.9300
O5—Ba1—O5i155.56 (8)C2—C3—H3119.1
O5—Ba1—O1W102.22 (4)C4—C3—H3119.1
O5i—Ba1—O1W102.22 (4)C5—C4—C3121.8 (2)
O5—Ba1—O7ii116.89 (5)C5—C4—H4119.1
O5i—Ba1—O7ii74.18 (5)C3—C4—H4119.1
O1W—Ba1—O7ii64.88 (4)C4—C5—C6116.9 (2)
O5—Ba1—O7iii74.18 (5)C4—C5—H5121.5
O5i—Ba1—O7iii116.89 (5)C6—C5—H5121.5
O1W—Ba1—O7iii64.88 (4)N2—C6—C5133.3 (2)
O7ii—Ba1—O7iii129.77 (8)N2—C6—C1104.79 (19)
O5—Ba1—O2Wi100.92 (5)C5—C6—C1122.0 (2)
O5i—Ba1—O2Wi60.38 (5)N1—C7—N2113.7 (2)
O1W—Ba1—O2Wi136.05 (3)N1—C7—H7123.1
O7ii—Ba1—O2Wi71.38 (5)N2—C7—H7123.1
O7iii—Ba1—O2Wi158.50 (5)O5—C8—C9123.43 (17)
O5—Ba1—O2W60.38 (5)O5—C8—C13124.44 (17)
O5i—Ba1—O2W100.92 (5)C9—C8—C13112.11 (16)
O1W—Ba1—O2W136.05 (3)C10—C9—C8124.65 (17)
O7ii—Ba1—O2W158.50 (5)C10—C9—N3116.22 (16)
O7iii—Ba1—O2W71.38 (5)C8—C9—N3119.13 (16)
O2Wi—Ba1—O2W87.90 (6)C9—C10—C11118.37 (17)
O5—Ba1—O356.00 (4)C9—C10—H10120.8
O5i—Ba1—O3121.80 (4)C11—C10—H10120.8
O1W—Ba1—O394.37 (4)C10—C11—C12121.58 (17)
O7ii—Ba1—O363.55 (5)C10—C11—N4119.20 (18)
O7iii—Ba1—O3120.67 (5)C12—C11—N4119.21 (18)
O2Wi—Ba1—O369.10 (5)C13—C12—C11119.69 (17)
O2W—Ba1—O3104.30 (5)C13—C12—H12120.2
O5—Ba1—O3i121.80 (4)C11—C12—H12120.2
O5i—Ba1—O3i56.00 (4)C12—C13—N5116.40 (16)
O1W—Ba1—O3i94.37 (4)C12—C13—C8123.52 (17)
O7ii—Ba1—O3i120.67 (5)N5—C13—C8120.06 (16)
O7iii—Ba1—O3i63.55 (5)C7—N1—C1104.35 (18)
O2Wi—Ba1—O3i104.30 (5)C7—N2—C6107.51 (18)
O2W—Ba1—O3i69.10 (5)C7—N2—H2A126.2
O3—Ba1—O3i171.26 (9)C6—N2—H2A126.2
O5—Ba1—H3W44.8 (3)O6—N3—O7122.01 (17)
O5i—Ba1—H3W116.3 (3)O6—N3—C9120.42 (16)
O1W—Ba1—H3W129.2 (5)O7—N3—C9117.50 (16)
O7ii—Ba1—H3W154.5 (4)O9—N4—O8122.71 (18)
O7iii—Ba1—H3W68.5 (5)O9—N4—C11118.65 (19)
O2Wi—Ba1—H3W93.0 (5)O8—N4—C11118.64 (18)
O2W—Ba1—H3W15.7 (3)O4—N5—O3121.14 (18)
O3—Ba1—H3W92.3 (3)O4—N5—C13118.16 (17)
O3i—Ba1—H3W82.1 (3)O3—N5—C13120.70 (16)
C2—C1—N1130.62 (18)N5—O3—Ba1144.86 (13)
C2—C1—C6119.76 (19)C8—O5—Ba1151.16 (13)
N1—C1—C6109.62 (18)N3—O7—Ba1iii147.01 (14)
C3—C2—C1117.8 (2)Ba1—O1W—H1W130 (4)
C3—C2—H2121.1Ba1—O2W—H2W131.0 (19)
C1—C2—H2121.1Ba1—O2W—H3W90.9 (18)
C2—C3—C4121.7 (2)H2W—O2W—H3W104.2 (19)
Symmetry codes: (i) −x, y, −z+1/2; (ii) x, −y+1, z−1/2; (iii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2Wiv0.80 (2)2.02 (2)2.816 (2)171 (6)
O2W—H2W···N1i0.83 (2)1.98 (2)2.812 (2)174 (2)
O2W—H3W···O50.80 (2)2.16 (2)2.768 (2)133 (2)
O2W—H3W···O60.80 (2)2.34 (2)3.058 (2)148 (2)
N2—H2A···O8v0.862.132.987 (2)174
Symmetry codes: (iv) −x, y−1, −z+1/2; (i) −x, y, −z+1/2; (v) −x+1/2, −y+3/2, −z+1.
Table 1
Selected geometric parameters (Å) top
Ba1—O52.6451 (14)Ba1—O2W2.8484 (16)
Ba1—O1W2.683 (2)Ba1—O32.9596 (17)
Ba1—O7i2.8184 (15)
Symmetry codes: (i) x, −y+1, z−1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2Wii0.80 (2)2.02 (2)2.816 (2)171 (6)
O2W—H2W···N1iii0.83 (2)1.98 (2)2.812 (2)174 (2)
O2W—H3W···O50.80 (2)2.16 (2)2.768 (2)133 (2)
O2W—H3W···O60.80 (2)2.34 (2)3.058 (2)148 (2)
N2—H2A···O8iv0.862.132.987 (2)174
Symmetry codes: (ii) −x, y−1, −z+1/2; (iii) −x, y, −z+1/2; (iv) −x+1/2, −y+3/2, −z+1.
Acknowledgements top

The authors acknowledge South China University of Technology for supporting this work.

references
References top

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