catena-Poly[[[triaqua­barium(II)]-di-μ-2,4,6-trinitro­phenolato-κ³O:O′,O′′;κ³O,O′:O′′] benz­imidazole disolvate]

In the title complex, {[Ba(C₆H₂N₃O₇)₂(H₂O)₃]·2C₇H₆N₂}_n, the Ba^II 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 κ³-bridging 2,4,6-trinitro­phenolate ligands to the metal atoms. A supra­molecular network is formed via hydrogen bonding and π–π 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.020
• wR factor = 0.049
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ba1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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 Ba^II 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

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

S2. Experimental

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%).

S3. Refinement

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, U_iso(H) = 1.2 U_eq(Host).

Computing details

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

	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.
	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]

Crystal data

[Ba(C6H2N3O7)2(H2O)3].2C7H6N2	F(000) = 1756
Mr = 882.87	Dx = 1.804 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3200 reflections
a = 30.4215 (6) Å	θ = 1.7–28.0°
b = 6.7394 (1) Å	µ = 1.32 mm^−1
c = 16.6695 (3) Å	T = 293 K
β = 107.950 (1)°	Block, yellow
V = 3251.27 (10) Å^3	0.20 × 0.18 × 0.18 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	3176 independent reflections
Radiation source: fine-focus sealed tube	2965 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −37→37
Tmin = 0.779, Tmax = 0.797	k = −8→8
11230 measured reflections	l = −20→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0238P)^2 + 2.8124P] where P = (Fo^2 + 2Fc^2)/3
3176 reflections	(Δ/σ)max = 0.001
254 parameters	Δρmax = 0.31 e Å^−3
4 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ba1	0.0000	0.54969 (3)	0.2500	0.02678 (6)
C1	0.12475 (6)	0.8786 (3)	0.04517 (13)	0.0305 (4)
C2	0.09690 (7)	0.8776 (3)	−0.03851 (14)	0.0385 (5)
H2	0.0649	0.8729	−0.0523	0.046*
C3	0.11831 (9)	0.8839 (4)	−0.10030 (15)	0.0479 (6)
H3	0.1003	0.8835	−0.1566	0.058*
C4	0.16600 (10)	0.8909 (4)	−0.08066 (17)	0.0533 (6)
H4	0.1791	0.8943	−0.1242	0.064*
C5	0.19433 (8)	0.8930 (4)	0.00113 (18)	0.0493 (6)
H5	0.2263	0.8986	0.0140	0.059*
C6	0.17305 (7)	0.8863 (3)	0.06404 (14)	0.0359 (5)
C7	0.15304 (9)	0.8749 (4)	0.17941 (15)	0.0477 (6)
H7	0.1558	0.8714	0.2365	0.057*
C8	0.08615 (6)	0.6307 (3)	0.46576 (12)	0.0271 (4)
C9	0.08875 (6)	0.6439 (3)	0.55372 (12)	0.0272 (4)
C10	0.12886 (6)	0.6317 (3)	0.61992 (12)	0.0292 (4)
H10	0.1282	0.6347	0.6753	0.035*
C11	0.17024 (6)	0.6148 (3)	0.60218 (12)	0.0315 (4)
C12	0.17172 (6)	0.6059 (3)	0.52008 (13)	0.0313 (4)
H12	0.1999	0.5963	0.5096	0.038*
C13	0.13161 (6)	0.6113 (3)	0.45470 (12)	0.0279 (4)
N1	0.11318 (6)	0.8717 (3)	0.11972 (11)	0.0399 (4)
N2	0.18963 (6)	0.8836 (3)	0.15040 (12)	0.0473 (5)
H2A	0.2182	0.8869	0.1805	0.057*
N3	0.04662 (5)	0.6730 (3)	0.57559 (10)	0.0339 (4)
N4	0.21295 (6)	0.6097 (3)	0.67093 (12)	0.0424 (5)
N5	0.13605 (6)	0.6021 (3)	0.37039 (11)	0.0360 (4)
O3	0.10196 (6)	0.5831 (3)	0.30871 (10)	0.0606 (5)
O4	0.17466 (6)	0.6120 (3)	0.36322 (11)	0.0598 (5)
O5	0.04921 (5)	0.6328 (3)	0.40711 (9)	0.0435 (4)
O6	0.01290 (5)	0.7470 (3)	0.52530 (10)	0.0633 (6)
O7	0.04724 (6)	0.6278 (3)	0.64730 (10)	0.0519 (4)
O8	0.21155 (6)	0.6352 (3)	0.74293 (10)	0.0619 (5)
O9	0.24904 (5)	0.5800 (4)	0.65494 (12)	0.0718 (6)
O1W	0.0000	0.1516 (4)	0.2500	0.0525 (6)
H1W	0.010 (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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.02865 (9)	0.03324 (10)	0.01903 (9)	0.000	0.00817 (6)	0.000
C1	0.0307 (9)	0.0268 (10)	0.0341 (11)	−0.0013 (8)	0.0100 (8)	0.0007 (9)
C2	0.0359 (10)	0.0342 (11)	0.0396 (12)	−0.0017 (9)	0.0032 (9)	0.0005 (10)
C3	0.0684 (16)	0.0406 (13)	0.0320 (12)	0.0008 (12)	0.0115 (11)	0.0007 (10)
C4	0.0746 (17)	0.0451 (14)	0.0534 (16)	0.0002 (13)	0.0391 (14)	0.0019 (12)
C5	0.0383 (12)	0.0454 (14)	0.0713 (18)	−0.0008 (10)	0.0275 (12)	0.0008 (13)
C6	0.0314 (10)	0.0311 (11)	0.0421 (12)	0.0003 (8)	0.0068 (9)	0.0010 (9)
C7	0.0648 (15)	0.0461 (14)	0.0298 (12)	−0.0031 (12)	0.0113 (11)	0.0018 (11)
C8	0.0278 (9)	0.0288 (10)	0.0240 (9)	−0.0007 (8)	0.0071 (7)	−0.0014 (8)
C9	0.0287 (9)	0.0290 (10)	0.0253 (9)	−0.0015 (8)	0.0103 (7)	0.0002 (8)
C10	0.0345 (10)	0.0312 (10)	0.0212 (9)	−0.0022 (8)	0.0077 (8)	0.0011 (8)
C11	0.0279 (9)	0.0356 (11)	0.0262 (10)	−0.0016 (8)	0.0013 (8)	0.0015 (9)
C12	0.0277 (9)	0.0356 (11)	0.0319 (11)	0.0001 (8)	0.0111 (8)	−0.0001 (9)
C13	0.0319 (9)	0.0304 (10)	0.0221 (9)	0.0000 (8)	0.0095 (8)	0.0002 (8)
N1	0.0440 (10)	0.0407 (10)	0.0374 (10)	−0.0024 (9)	0.0162 (8)	0.0013 (9)
N2	0.0378 (10)	0.0503 (12)	0.0425 (11)	−0.0018 (9)	−0.0044 (8)	0.0017 (10)
N3	0.0321 (8)	0.0442 (11)	0.0277 (9)	−0.0011 (8)	0.0125 (7)	−0.0029 (8)
N4	0.0318 (9)	0.0544 (12)	0.0343 (10)	−0.0038 (8)	0.0001 (8)	0.0048 (9)
N5	0.0399 (9)	0.0436 (11)	0.0277 (9)	0.0011 (8)	0.0150 (8)	0.0003 (8)
O3	0.0454 (9)	0.1133 (18)	0.0223 (8)	−0.0046 (10)	0.0093 (7)	−0.0052 (9)
O4	0.0453 (9)	0.1017 (16)	0.0418 (9)	−0.0006 (10)	0.0271 (8)	−0.0007 (10)
O5	0.0289 (7)	0.0726 (11)	0.0250 (7)	0.0029 (7)	0.0024 (6)	−0.0088 (8)
O6	0.0397 (8)	0.1134 (17)	0.0381 (9)	0.0293 (10)	0.0138 (7)	0.0088 (10)
O7	0.0503 (9)	0.0778 (12)	0.0364 (9)	0.0007 (9)	0.0266 (7)	0.0122 (9)
O8	0.0438 (9)	0.1064 (16)	0.0276 (9)	−0.0049 (10)	−0.0006 (7)	0.0031 (10)
O9	0.0275 (8)	0.130 (2)	0.0517 (11)	0.0076 (10)	0.0033 (8)	−0.0012 (11)
O1W	0.0769 (17)	0.0340 (13)	0.0618 (17)	0.000	0.0435 (14)	0.000
O2W	0.0390 (8)	0.0474 (9)	0.0345 (8)	0.0063 (7)	0.0152 (6)	0.0028 (8)

Geometric parameters (Å, º)

Ba1—O5	2.6451 (14)	C8—O5	1.242 (2)
Ba1—O5^i	2.6451 (14)	C8—C9	1.447 (3)
Ba1—O1W	2.683 (2)	C8—C13	1.456 (3)
Ba1—O7^ii	2.8184 (15)	C9—C10	1.372 (3)
Ba1—O7^iii	2.8184 (15)	C9—N3	1.450 (2)
Ba1—O2W^i	2.8484 (16)	C10—C11	1.384 (3)
Ba1—O2W	2.8484 (16)	C10—H10	0.9300
Ba1—O3	2.9596 (17)	C11—C12	1.384 (3)
Ba1—O3^i	2.9596 (17)	C11—N4	1.444 (2)
C1—C2	1.391 (3)	C12—C13	1.363 (3)
C1—N1	1.393 (3)	C12—H12	0.9300
C1—C6	1.406 (3)	C13—N5	1.454 (2)
C2—C3	1.379 (3)	N2—H2A	0.8600
C2—H2	0.9300	N3—O6	1.214 (2)
C3—C4	1.386 (4)	N3—O7	1.228 (2)
C3—H3	0.9300	N4—O9	1.223 (2)
C4—C5	1.370 (4)	N4—O8	1.226 (2)
C4—H4	0.9300	N5—O4	1.219 (2)
C5—C6	1.393 (3)	N5—O3	1.221 (2)
C5—H5	0.9300	O7—Ba1^iii	2.8184 (15)
C6—N2	1.371 (3)	O1W—H1W	0.80 (2)
C7—N1	1.310 (3)	O2W—H2W	0.83 (2)
C7—N2	1.345 (3)	O2W—H3W	0.80 (2)
C7—H7	0.9300
O5—Ba1—O5^i	155.56 (8)	C2—C3—H3	119.1
O5—Ba1—O1W	102.22 (4)	C4—C3—H3	119.1
O5^i—Ba1—O1W	102.22 (4)	C5—C4—C3	121.8 (2)
O5—Ba1—O7^ii	116.89 (5)	C5—C4—H4	119.1
O5^i—Ba1—O7^ii	74.18 (5)	C3—C4—H4	119.1
O1W—Ba1—O7^ii	64.88 (4)	C4—C5—C6	116.9 (2)
O5—Ba1—O7^iii	74.18 (5)	C4—C5—H5	121.5
O5^i—Ba1—O7^iii	116.89 (5)	C6—C5—H5	121.5
O1W—Ba1—O7^iii	64.88 (4)	N2—C6—C5	133.3 (2)
O7^ii—Ba1—O7^iii	129.77 (8)	N2—C6—C1	104.79 (19)
O5—Ba1—O2W^i	100.92 (5)	C5—C6—C1	122.0 (2)
O5^i—Ba1—O2W^i	60.38 (5)	N1—C7—N2	113.7 (2)
O1W—Ba1—O2W^i	136.05 (3)	N1—C7—H7	123.1
O7^ii—Ba1—O2W^i	71.38 (5)	N2—C7—H7	123.1
O7^iii—Ba1—O2W^i	158.50 (5)	O5—C8—C9	123.43 (17)
O5—Ba1—O2W	60.38 (5)	O5—C8—C13	124.44 (17)
O5^i—Ba1—O2W	100.92 (5)	C9—C8—C13	112.11 (16)
O1W—Ba1—O2W	136.05 (3)	C10—C9—C8	124.65 (17)
O7^ii—Ba1—O2W	158.50 (5)	C10—C9—N3	116.22 (16)
O7^iii—Ba1—O2W	71.38 (5)	C8—C9—N3	119.13 (16)
O2W^i—Ba1—O2W	87.90 (6)	C9—C10—C11	118.37 (17)
O5—Ba1—O3	56.00 (4)	C9—C10—H10	120.8
O5^i—Ba1—O3	121.80 (4)	C11—C10—H10	120.8
O1W—Ba1—O3	94.37 (4)	C10—C11—C12	121.58 (17)
O7^ii—Ba1—O3	63.55 (5)	C10—C11—N4	119.20 (18)
O7^iii—Ba1—O3	120.67 (5)	C12—C11—N4	119.21 (18)
O2W^i—Ba1—O3	69.10 (5)	C13—C12—C11	119.69 (17)
O2W—Ba1—O3	104.30 (5)	C13—C12—H12	120.2
O5—Ba1—O3^i	121.80 (4)	C11—C12—H12	120.2
O5^i—Ba1—O3^i	56.00 (4)	C12—C13—N5	116.40 (16)
O1W—Ba1—O3^i	94.37 (4)	C12—C13—C8	123.52 (17)
O7^ii—Ba1—O3^i	120.67 (5)	N5—C13—C8	120.06 (16)
O7^iii—Ba1—O3^i	63.55 (5)	C7—N1—C1	104.35 (18)
O2W^i—Ba1—O3^i	104.30 (5)	C7—N2—C6	107.51 (18)
O2W—Ba1—O3^i	69.10 (5)	C7—N2—H2A	126.2
O3—Ba1—O3^i	171.26 (9)	C6—N2—H2A	126.2
O5—Ba1—H3W	44.8 (3)	O6—N3—O7	122.01 (17)
O5^i—Ba1—H3W	116.3 (3)	O6—N3—C9	120.42 (16)
O1W—Ba1—H3W	129.2 (5)	O7—N3—C9	117.50 (16)
O7^ii—Ba1—H3W	154.5 (4)	O9—N4—O8	122.71 (18)
O7^iii—Ba1—H3W	68.5 (5)	O9—N4—C11	118.65 (19)
O2W^i—Ba1—H3W	93.0 (5)	O8—N4—C11	118.64 (18)
O2W—Ba1—H3W	15.7 (3)	O4—N5—O3	121.14 (18)
O3—Ba1—H3W	92.3 (3)	O4—N5—C13	118.16 (17)
O3^i—Ba1—H3W	82.1 (3)	O3—N5—C13	120.70 (16)
C2—C1—N1	130.62 (18)	N5—O3—Ba1	144.86 (13)
C2—C1—C6	119.76 (19)	C8—O5—Ba1	151.16 (13)
N1—C1—C6	109.62 (18)	N3—O7—Ba1^iii	147.01 (14)
C3—C2—C1	117.8 (2)	Ba1—O1W—H1W	130 (4)
C3—C2—H2	121.1	Ba1—O2W—H2W	131.0 (19)
C1—C2—H2	121.1	Ba1—O2W—H3W	90.9 (18)
C2—C3—C4	121.7 (2)	H2W—O2W—H3W	104.2 (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, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2W^iv	0.80 (2)	2.02 (2)	2.816 (2)	171 (6)
O2W—H2W···N1^i	0.83 (2)	1.98 (2)	2.812 (2)	174 (2)
O2W—H3W···O5	0.80 (2)	2.16 (2)	2.768 (2)	133 (2)
O2W—H3W···O6	0.80 (2)	2.34 (2)	3.058 (2)	148 (2)
N2—H2A···O8^v	0.86	2.13	2.987 (2)	174

Symmetry codes: (i) −x, y, −z+1/2; (iv) −x, y−1, −z+1/2; (v) −x+1/2, −y+3/2, −z+1.