Poly[tetra­aqua­bis(μ2-2,4,6-trinitro­phenolato)barium(II)]

Vesta, C.; Uthrakumar, R.; Jerome Das, S.; Varghese, B.

doi:10.1107/S1600536808002961

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Pages m451-m452

doi:10.1107/S1600536808002961

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Poly[tetraaquabis(μ₂-2,4,6-trinitrophenolato)barium(II)]

C. Vesta,^a R. Uthrakumar,^a S. Jerome Das ^a and Babu Varghese ^b ^*

^aDepartment of Physics, Loyola College, Chennai 600 034, India, and ^bSophisticated Analytical Instruments Facility, Indian Institute of Technology Madras, Chennai 600 036, India
^*Correspondence e-mail: varghese@iitm.ac.in

(Received 17 December 2007; accepted 26 January 2008; online 6 February 2008)

The asymmetric unit of the title compound, [Ba(C₆H₂N₃O₇)₂(H₂O)₄]_n, consists of a barium ion coordinated by two nitrophenolate ligands and four water molecules. Barium is decacoordinated by O atoms. These units are linked together through bridging nitro groups to form a one-dimensional polymeric chain. The three-dimensional packing is facilitated through hydrogen-bonding interactions mediated through water molecules. The coordination distances around Ba vary from 2.728 (4) to 3.138 (5) Å. The crystal sample, on exposure to air at room temperature for many days, slowly loses the water and peels out as filaments.

Related literature

For related literature, see: Brahadeeswaran et al. (1998 , 1999 ); Jonie Varjula et al. (2007 ); Milton Boaz et al. (2005 ); Vesta et al. (2007 ).

Experimental

Crystal data

[Ba(C₆H₂N₃O₇)₂(H₂O)₄]
M_r = 665.62
Monoclinic, P 2₁ /c
a = 11.6765 (4) Å
b = 6.6878 (2) Å
c = 27.0324 (9) Å
β = 95.608 (2)°
V = 2100.86 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.00 mm⁻¹
T = 293 (2) K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEX2 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.652, T_max = 0.723
20976 measured reflections
3674 independent reflections
3552 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.084
S = 1.42
3674 reflections
360 parameters
234 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O15—H15A⋯O7ⁱ	0.85 (4)	2.20 (4)	2.939 (6)	145 (6)
O15—H15A⋯O6ⁱ	0.85 (4)	2.33 (4)	3.030 (7)	140 (5)
O15—H15B⋯O9ⁱⁱ	0.85 (4)	2.103 (6)	2.953 (6)	179 (7)
O16—H16A⋯O4ⁱⁱⁱ	0.85 (3)	2.08 (4)	2.806 (6)	142 (5)
O16—H16B⋯O15^iv	0.85 (6)	2.11 (3)	2.906 (7)	156 (6)
O17—H17A⋯O12^v	0.85 (4)	2.45 (3)	3.258 (8)	158 (6)
O17—H17B⋯O18^v	0.85 (5)	1.969 (17)	2.805 (7)	168 (7)
O18—H18A⋯O16ⁱ	0.85 (4)	2.04 (3)	2.822 (7)	153 (7)
O18—H18B⋯O1^vi	0.85 (5)	2.47 (3)	3.241 (7)	151 (6)
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z; (iii) x-1, y, z; (iv) x, y+1, z; (v) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002961/sg2220sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002961/sg2220Isup2.hkl

checkCIF report

Comment top

Nitrophenol family of crystals are found to have high laser damage threshold, wide transparency windows, and high NLO co-efficients ((Brahadeeswaran et al., 1998, 1999), (Milton Boaz et al., 2005), (Vesta et al., 2007), (Jonie Varjula et al., 2007)). Nitrophenol groups are found to be good proton acceptors from the metallic hydroxide complexes. The title compound was synthesized as part of our ongoing research for synthesizing and characterizing new optically active materials. In the present work, the crystal structure of the compound (BaC₁₂H₄N₆O₁₄.4H₂O) is reported for the first time.The reported compound is not optically active.

The title compound crystallizes in monoclinic system with space group P2₁/c. ORTEP representation of the molecule with 50% anisotropic ellipsoids are shown in figure1.The asymmetric unit consists of two nitrophenolate moieties coordinated to barium through phenolate O atoms O7 and O14 and one nitro oxygen each from nitrophenolate moieties (O1 and O8), on one side. Four water molecules of the asymmetric unit coordinates to other side. The asymmetric unit and its inversion are linked to each other through nitro oxygen O5(symm: 2 - x, 2 - y, -z) coordinating to metal. The centrosymmetric pair and its a-translations are joined to each other through nitro O atoms O11 (symm: x - 1, y, z) to form an one dimensional infinite polymeric chain parallel to a axis (Fig.2).Thus, Barium is coordinated with 10 O atoms. The coordination distances around Ba vary from 2.728 Å to 3.138 Å. The one dimensional chains are further linked to each other (along b and c directions) through water mediated O—H···O hydrogen bonds (Fig.3). The crystal sample, on exposure to air at room temperature for many days, slowly looses the water and peels out as filaments.

Related literature top

For related literature, see: Brahadeeswaran et al. (1998, 1999); Jonie Varjula et al. (2007); Milton Boaz et al. (2005); Vesta et al. (2007).

Experimental top

Picric acid (99%, 5.73 g ms) was dissolved in deionized water (100 ml) and then Ba(OH)2 (97%, 3.94 g ms) was added slowly with stirring to obtain saturated solution. The saturated solution kept at 305 K yielded fine yellow crystals in three days through spontaneous nucleation. The sample was purified further through recrystallization.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2/SAINT (Bruker, 2004); data reduction: SAINT/XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The ORTEP representation of the molecule with 50% probability anisotropic ellipsoid.
	Fig. 2. One dimensional polymeric chain of the title compound formed by a-translation of the asymmetric unit and its inversion.
	Fig. 3. Packing of molecules in the unit cell viewed down b axis. Hydrogen bonds are shown with dotted lines.

Poly[tetraaquabis(µ₂-2,4,6-trinitrophenolato)barium(II)] top

Crystal data top

[Ba(C₆H₂N₃O₇)₂(H₂O)₄]	F(000) = 1304
M_r = 665.62	D_x = 2.104 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 6588 reflections
a = 11.6765 (4) Å	θ = 2.4–25.0°
b = 6.6878 (2) Å	µ = 2.00 mm⁻¹
c = 27.0324 (9) Å	T = 293 K
β = 95.608 (2)°	Plate, yellow
V = 2100.86 (12) Å³	0.20 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker Kappa APEX2 diffractometer	3674 independent reflections
Radiation source: fine-focus sealed tube	3552 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −13→13
T_min = 0.652, T_max = 0.723	k = −7→7
20976 measured reflections	l = −32→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.42	w = 1/[σ²(F_o²) + 9.4089P] where P = (F_o² + 2F_c²)/3
3674 reflections	(Δ/σ)_max = 0.002
360 parameters	Δρ_max = 0.58 e Å⁻³
234 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Ba(C₆H₂N₃O₇)₂(H₂O)₄]	V = 2100.86 (12) Å³
M_r = 665.62	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6765 (4) Å	µ = 2.00 mm⁻¹
b = 6.6878 (2) Å	T = 293 K
c = 27.0324 (9) Å	0.20 × 0.20 × 0.15 mm
β = 95.608 (2)°

Data collection top

Bruker Kappa APEX2 diffractometer	3674 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	3552 reflections with I > 2σ(I)
T_min = 0.652, T_max = 0.723	R_int = 0.020
20976 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	234 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.42	Δρ_max = 0.58 e Å⁻³
3674 reflections	Δρ_min = −0.53 e Å⁻³
360 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

	x	y	z	U_iso*/U_eq
C1	1.2555 (4)	1.1054 (8)	0.13511 (18)	0.0242 (11)
C2	1.1690 (4)	1.1014 (7)	0.09309 (19)	0.0238 (10)
C3	1.2195 (4)	1.1225 (7)	0.04666 (18)	0.0255 (11)
C4	1.3344 (4)	1.1314 (8)	0.04212 (19)	0.0280 (11)
H4	1.3617	1.1369	0.0110	0.034*
C5	1.4101 (4)	1.1319 (8)	0.0851 (2)	0.0271 (11)
C6	1.3720 (4)	1.1214 (7)	0.13149 (19)	0.0258 (11)
H6	1.4238	1.1251	0.1599	0.031*
C7	1.3226 (4)	0.6198 (7)	0.09934 (18)	0.0246 (11)
C8	1.4352 (4)	0.6309 (8)	0.0885 (2)	0.0280 (12)
H8	1.4527	0.6363	0.0557	0.034*
C9	1.5217 (4)	0.6338 (8)	0.12707 (19)	0.0268 (11)
C10	1.4971 (4)	0.6212 (8)	0.1761 (2)	0.0301 (12)
H10	1.5561	0.6187	0.2018	0.036*
C11	1.3855 (5)	0.6125 (8)	0.18597 (19)	0.0291 (12)
C12	1.2861 (4)	0.6108 (8)	0.1489 (2)	0.0270 (11)
N1	1.2203 (4)	1.0954 (7)	0.18515 (16)	0.0324 (10)
N2	1.5322 (4)	1.1492 (8)	0.0809 (2)	0.0409 (12)
N3	1.1438 (4)	1.1353 (7)	0.00065 (17)	0.0339 (11)
N4	1.2374 (4)	0.6143 (7)	0.05641 (16)	0.0284 (10)
N5	1.6402 (4)	0.6485 (8)	0.11597 (19)	0.0384 (12)
N6	1.3656 (4)	0.6031 (9)	0.23850 (18)	0.0426 (12)
O1	1.1282 (4)	1.0179 (7)	0.19220 (15)	0.0450 (11)
O2	1.2845 (4)	1.1681 (8)	0.21915 (15)	0.0524 (12)
O3	1.5656 (4)	1.1695 (9)	0.03987 (19)	0.0671 (15)
O4	1.5960 (4)	1.1459 (10)	0.1193 (2)	0.0709 (16)
O5	1.1760 (4)	1.0643 (9)	−0.03692 (16)	0.0604 (14)
O6	1.0527 (4)	1.2218 (8)	0.00097 (17)	0.0616 (14)
O7	1.0641 (3)	1.0833 (6)	0.09589 (14)	0.0359 (9)
O8	1.1364 (3)	0.6458 (8)	0.06148 (16)	0.0566 (13)
O9	1.2699 (4)	0.5776 (7)	0.01567 (14)	0.0467 (11)
O10	1.6600 (4)	0.6531 (9)	0.07262 (19)	0.0672 (15)
O11	1.7160 (3)	0.6578 (8)	0.15020 (18)	0.0573 (13)
O12	1.2822 (5)	0.6819 (10)	0.25207 (18)	0.0770 (17)
O13	1.4367 (4)	0.5156 (8)	0.26667 (17)	0.0616 (14)
O14	1.1854 (3)	0.5971 (7)	0.15895 (15)	0.0419 (10)
O15	0.9006 (4)	0.4119 (7)	0.07251 (15)	0.0403 (10)
O16	0.8349 (4)	1.1003 (8)	0.13919 (18)	0.0522 (12)
O17	0.9062 (4)	0.8444 (9)	0.22439 (17)	0.0601 (13)
O18	0.9301 (5)	0.4269 (8)	0.19520 (18)	0.0639 (14)
Ba	0.96482 (2)	0.74829 (6)	0.130390 (11)	0.02924 (11)
H15A	0.955 (3)	0.334 (7)	0.067 (2)	0.07 (3)*
H15B	0.852 (4)	0.415 (11)	0.0470 (14)	0.08 (3)*
H16A	0.7657 (17)	1.072 (11)	0.144 (3)	0.080*
H16B	0.835 (5)	1.182 (10)	0.115 (2)	0.080*
H17A	0.852 (3)	0.930 (6)	0.222 (2)	0.080*
H17B	0.948 (5)	0.866 (11)	0.2514 (15)	0.080*
H18A	0.925 (6)	0.318 (5)	0.179 (2)	0.080*
H18B	0.901 (6)	0.410 (10)	0.2224 (15)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.030 (3)	0.020 (2)	0.023 (2)	0.002 (2)	0.003 (2)	0.002 (2)
C2	0.019 (2)	0.017 (2)	0.035 (3)	−0.002 (2)	0.003 (2)	0.001 (2)
C3	0.031 (3)	0.017 (3)	0.028 (3)	−0.004 (2)	0.000 (2)	0.001 (2)
C4	0.033 (3)	0.023 (3)	0.030 (3)	−0.004 (2)	0.010 (2)	−0.003 (2)
C5	0.023 (3)	0.021 (3)	0.038 (3)	0.002 (2)	0.004 (2)	−0.003 (2)
C6	0.024 (3)	0.019 (3)	0.033 (3)	0.003 (2)	−0.003 (2)	−0.002 (2)
C7	0.026 (3)	0.018 (2)	0.029 (3)	0.000 (2)	−0.004 (2)	0.000 (2)
C8	0.027 (3)	0.025 (3)	0.032 (3)	−0.001 (2)	0.006 (2)	0.002 (2)
C9	0.019 (2)	0.024 (3)	0.038 (3)	0.000 (2)	0.003 (2)	0.002 (2)
C10	0.026 (3)	0.027 (3)	0.036 (3)	−0.002 (2)	−0.007 (2)	0.003 (2)
C11	0.030 (3)	0.030 (3)	0.027 (3)	0.000 (2)	0.001 (2)	−0.001 (2)
C12	0.022 (3)	0.021 (3)	0.037 (3)	0.000 (2)	0.001 (2)	0.001 (2)
N1	0.031 (2)	0.036 (3)	0.030 (2)	−0.001 (2)	0.0047 (19)	−0.002 (2)
N2	0.028 (2)	0.042 (3)	0.054 (3)	0.001 (2)	0.008 (2)	−0.004 (2)
N3	0.033 (3)	0.036 (3)	0.032 (2)	−0.010 (2)	−0.0009 (19)	0.005 (2)
N4	0.027 (2)	0.023 (2)	0.034 (2)	0.0018 (19)	−0.0030 (18)	−0.0015 (19)
N5	0.023 (2)	0.041 (3)	0.051 (3)	−0.002 (2)	0.005 (2)	0.003 (2)
N6	0.035 (3)	0.054 (3)	0.039 (3)	−0.001 (3)	0.004 (2)	0.000 (3)
O1	0.040 (2)	0.058 (3)	0.039 (2)	−0.016 (2)	0.0174 (18)	−0.002 (2)
O2	0.050 (3)	0.075 (3)	0.032 (2)	−0.011 (2)	0.0019 (19)	−0.015 (2)
O3	0.042 (3)	0.095 (4)	0.069 (3)	−0.010 (3)	0.029 (2)	−0.006 (3)
O4	0.023 (2)	0.115 (4)	0.073 (3)	0.002 (3)	−0.004 (2)	0.008 (3)
O5	0.046 (3)	0.102 (4)	0.033 (2)	−0.012 (3)	0.0025 (19)	−0.013 (3)
O6	0.058 (3)	0.064 (3)	0.058 (3)	0.024 (3)	−0.019 (2)	0.002 (3)
O7	0.0214 (19)	0.039 (2)	0.047 (2)	−0.0024 (17)	0.0017 (16)	0.0081 (19)
O8	0.025 (2)	0.091 (4)	0.051 (3)	0.015 (2)	−0.0070 (18)	−0.014 (3)
O9	0.042 (2)	0.070 (3)	0.028 (2)	−0.006 (2)	0.0009 (17)	0.003 (2)
O10	0.040 (3)	0.106 (4)	0.059 (3)	0.001 (3)	0.019 (2)	0.013 (3)
O11	0.022 (2)	0.081 (3)	0.068 (3)	−0.007 (2)	−0.003 (2)	−0.003 (3)
O12	0.070 (3)	0.117 (5)	0.047 (3)	0.026 (3)	0.019 (2)	−0.006 (3)
O13	0.065 (3)	0.077 (4)	0.040 (2)	−0.001 (3)	−0.008 (2)	0.015 (2)
O14	0.024 (2)	0.055 (3)	0.047 (2)	0.0024 (19)	0.0071 (17)	0.003 (2)
O15	0.040 (2)	0.039 (2)	0.040 (2)	0.004 (2)	−0.0036 (19)	−0.0070 (19)
O16	0.033 (2)	0.054 (3)	0.069 (3)	0.006 (2)	0.004 (2)	−0.005 (2)
O17	0.060 (3)	0.084 (4)	0.038 (2)	−0.006 (3)	0.008 (2)	−0.001 (2)
O18	0.082 (4)	0.059 (3)	0.048 (3)	−0.010 (3)	−0.007 (3)	0.011 (2)
Ba	0.02237 (16)	0.03288 (18)	0.03255 (17)	−0.00217 (15)	0.00312 (11)	0.00155 (16)

Geometric parameters (Å, º) top

C1—C6	1.378 (7)	N3—O6	1.211 (6)
C1—C2	1.444 (7)	N3—O5	1.214 (6)
C1—N1	1.453 (6)	N4—O8	1.218 (6)
C2—O7	1.241 (6)	N4—O9	1.224 (6)
C2—C3	1.445 (7)	N5—O10	1.216 (6)
C3—C4	1.360 (7)	N5—O11	1.218 (6)
C3—N3	1.457 (7)	N6—O12	1.196 (7)
C4—C5	1.388 (7)	N6—O13	1.220 (7)
C4—H4	0.9300	O1—Ba	3.010 (4)
C5—C6	1.374 (7)	O5—Baⁱ	3.138 (5)
C5—N2	1.446 (7)	O7—Ba	2.728 (4)
C6—H6	0.9300	O8—Ba	2.947 (4)
C7—C8	1.377 (7)	O11—Baⁱⁱ	3.065 (4)
C7—C12	1.446 (7)	O14—Ba	2.805 (4)
C7—N4	1.453 (6)	O15—Ba	2.801 (4)
C8—C9	1.379 (7)	O15—H15A	0.85 (4)
C8—H8	0.9300	O15—H15B	0.85 (4)
C9—C10	1.385 (7)	O16—Ba	2.823 (5)
C9—N5	1.448 (6)	O16—H16A	0.85 (3)
C10—C11	1.356 (7)	O16—H16B	0.85 (6)
C10—H10	0.9300	O17—Ba	2.771 (4)
C11—C12	1.458 (7)	O17—H17A	0.85 (4)
C11—N6	1.463 (7)	O17—H17B	0.85 (5)
C12—O14	1.236 (6)	O18—Ba	2.827 (5)
N1—O1	1.225 (6)	O18—H18A	0.85 (4)
N1—O2	1.228 (6)	O18—H18B	0.85 (5)
N2—O3	1.218 (6)	Ba—O11ⁱⁱⁱ	3.065 (4)
N2—O4	1.218 (7)	Ba—O5ⁱ	3.138 (5)

C6—C1—C2	124.4 (4)	C12—O14—Ba	141.3 (4)
C6—C1—N1	116.1 (4)	Ba—O15—H15A	116 (3)
C2—C1—N1	119.5 (4)	Ba—O15—H15B	124 (5)
O7—C2—C1	124.9 (5)	H15A—O15—H15B	109 (5)
O7—C2—C3	123.5 (5)	Ba—O16—H16A	111 (5)
C1—C2—C3	111.6 (4)	Ba—O16—H16B	116 (5)
C4—C3—C2	124.9 (5)	H16A—O16—H16B	109 (6)
C4—C3—N3	116.3 (5)	Ba—O17—H17A	109 (5)
C2—C3—N3	118.8 (4)	Ba—O17—H17B	131 (5)
C3—C4—C5	118.5 (5)	H17A—O17—H17B	108 (6)
C3—C4—H4	120.7	Ba—O18—H18A	110 (4)
C5—C4—H4	120.7	Ba—O18—H18B	137 (5)
C6—C5—C4	121.8 (5)	H18A—O18—H18B	109 (6)
C6—C5—N2	119.1 (5)	O7—Ba—O17	105.91 (15)
C4—C5—N2	119.1 (5)	O7—Ba—O15	124.63 (12)
C5—C6—C1	118.6 (5)	O17—Ba—O15	128.47 (15)
C5—C6—H6	120.7	O7—Ba—O14	88.90 (12)
C1—C6—H6	120.7	O17—Ba—O14	97.68 (14)
C8—C7—C12	125.0 (5)	O15—Ba—O14	93.02 (13)
C8—C7—N4	115.1 (4)	O7—Ba—O16	66.02 (13)
C12—C7—N4	119.9 (4)	O17—Ba—O16	63.03 (16)
C7—C8—C9	118.9 (5)	O15—Ba—O16	126.89 (13)
C7—C8—H8	120.5	O14—Ba—O16	139.82 (13)
C9—C8—H8	120.5	O7—Ba—O18	158.07 (13)
C8—C9—C10	121.1 (5)	O17—Ba—O18	62.93 (17)
C8—C9—N5	119.2 (5)	O15—Ba—O18	71.85 (14)
C10—C9—N5	119.6 (5)	O14—Ba—O18	74.86 (15)
C11—C10—C9	119.0 (5)	O16—Ba—O18	118.10 (16)
C11—C10—H10	120.5	O7—Ba—O8	68.72 (14)
C9—C10—H10	120.5	O17—Ba—O8	151.36 (13)
C10—C11—C12	125.5 (5)	O15—Ba—O8	67.76 (13)
C10—C11—N6	116.1 (5)	O14—Ba—O8	55.05 (12)
C12—C11—N6	118.4 (5)	O16—Ba—O8	130.63 (15)
O14—C12—C7	125.4 (5)	O18—Ba—O8	111.25 (17)
O14—C12—C11	124.0 (5)	O7—Ba—O1	55.28 (11)
C7—C12—C11	110.5 (4)	O17—Ba—O1	63.37 (13)
O1—N1—O2	122.1 (5)	O15—Ba—O1	155.78 (13)
O1—N1—C1	119.7 (4)	O14—Ba—O1	63.12 (13)
O2—N1—C1	118.1 (4)	O16—Ba—O1	76.72 (13)
O3—N2—O4	123.7 (5)	O18—Ba—O1	103.48 (13)
O3—N2—C5	119.1 (5)	O8—Ba—O1	93.27 (12)
O4—N2—C5	117.2 (5)	O7—Ba—O11ⁱⁱⁱ	131.55 (13)
O6—N3—O5	122.5 (5)	O17—Ba—O11ⁱⁱⁱ	64.06 (14)
O6—N3—C3	118.8 (5)	O15—Ba—O11ⁱⁱⁱ	74.48 (13)
O5—N3—C3	118.6 (5)	O14—Ba—O11ⁱⁱⁱ	137.85 (13)
O8—N4—O9	121.6 (4)	O16—Ba—O11ⁱⁱⁱ	67.90 (14)
O8—N4—C7	120.0 (4)	O18—Ba—O11ⁱⁱⁱ	62.99 (16)
O9—N4—C7	118.3 (4)	O8—Ba—O11ⁱⁱⁱ	141.18 (13)
O10—N5—O11	122.6 (5)	O1—Ba—O11ⁱⁱⁱ	125.55 (12)
O10—N5—C9	118.4 (5)	O7—Ba—O5ⁱ	66.63 (12)
O11—N5—C9	119.0 (5)	O17—Ba—O5ⁱ	119.27 (15)
O12—N6—O13	123.0 (6)	O15—Ba—O5ⁱ	77.31 (14)
O12—N6—C11	119.4 (5)	O14—Ba—O5ⁱ	139.51 (12)
O13—N6—C11	117.6 (5)	O16—Ba—O5ⁱ	59.42 (14)
N1—O1—Ba	133.3 (3)	O18—Ba—O5ⁱ	134.99 (15)
N3—O5—Baⁱ	109.7 (4)	O8—Ba—O5ⁱ	85.35 (12)
C2—O7—Ba	123.8 (3)	O1—Ba—O5ⁱ	117.49 (13)
N4—O8—Ba	146.8 (3)	O11ⁱⁱⁱ—Ba—O5ⁱ	77.80 (13)
N5—O11—Baⁱⁱ	120.5 (4)

C6—C1—C2—O7	178.6 (5)	C10—C11—N6—O12	146.4 (6)
N1—C1—C2—O7	−2.5 (8)	C12—C11—N6—O12	−33.9 (9)
C6—C1—C2—C3	−1.8 (7)	C10—C11—N6—O13	−32.8 (8)
N1—C1—C2—C3	177.2 (4)	C12—C11—N6—O13	146.9 (6)
O7—C2—C3—C4	−176.1 (5)	O2—N1—O1—Ba	−164.9 (4)
C1—C2—C3—C4	4.2 (7)	C1—N1—O1—Ba	15.9 (8)
O7—C2—C3—N3	3.8 (8)	O6—N3—O5—Baⁱ	17.7 (7)
C1—C2—C3—N3	−175.8 (4)	C3—N3—O5—Baⁱ	−160.0 (3)
C2—C3—C4—C5	−3.9 (8)	C1—C2—O7—Ba	−65.4 (6)
N3—C3—C4—C5	176.2 (5)	C3—C2—O7—Ba	115.0 (5)
C3—C4—C5—C6	0.8 (8)	O9—N4—O8—Ba	−178.2 (5)
C3—C4—C5—N2	−177.6 (5)	C7—N4—O8—Ba	1.9 (10)
C4—C5—C6—C1	1.5 (8)	O10—N5—O11—Baⁱⁱ	7.9 (8)
N2—C5—C6—C1	179.9 (5)	C9—N5—O11—Baⁱⁱ	−171.3 (4)
C2—C1—C6—C5	−0.9 (8)	C7—C12—O14—Ba	−42.3 (9)
N1—C1—C6—C5	−179.8 (5)	C11—C12—O14—Ba	140.1 (5)
C12—C7—C8—C9	0.0 (8)	C2—O7—Ba—O17	105.6 (4)
N4—C7—C8—C9	−179.1 (5)	C2—O7—Ba—O15	−85.0 (4)
C7—C8—C9—C10	1.5 (8)	C2—O7—Ba—O14	7.9 (4)
C7—C8—C9—N5	−179.1 (5)	C2—O7—Ba—O16	155.6 (4)
C8—C9—C10—C11	−2.2 (8)	C2—O7—Ba—O18	49.6 (6)
N5—C9—C10—C11	178.4 (5)	C2—O7—Ba—O8	−44.7 (4)
C9—C10—C11—C12	1.5 (9)	C2—O7—Ba—O1	65.4 (4)
C9—C10—C11—N6	−178.9 (5)	C2—O7—Ba—O11ⁱⁱⁱ	174.8 (4)
C8—C7—C12—O14	−178.6 (5)	C2—O7—Ba—O5ⁱ	−138.9 (4)
N4—C7—C12—O14	0.5 (8)	C12—O14—Ba—O7	−25.0 (6)
C8—C7—C12—C11	−0.7 (7)	C12—O14—Ba—O17	−130.9 (6)
N4—C7—C12—C11	178.4 (4)	C12—O14—Ba—O15	99.6 (6)
C10—C11—C12—O14	177.9 (6)	C12—O14—Ba—O16	−74.3 (6)
N6—C11—C12—O14	−1.8 (8)	C12—O14—Ba—O18	169.9 (6)
C10—C11—C12—C7	0.0 (8)	C12—O14—Ba—O8	39.5 (6)
N6—C11—C12—C7	−179.7 (5)	C12—O14—Ba—O1	−76.1 (6)
C6—C1—N1—O1	−156.2 (5)	C12—O14—Ba—O11ⁱⁱⁱ	169.6 (5)
C2—C1—N1—O1	24.8 (7)	C12—O14—Ba—O5ⁱ	25.7 (7)
C6—C1—N1—O2	24.6 (7)	N4—O8—Ba—O7	85.4 (8)
C2—C1—N1—O2	−154.4 (5)	N4—O8—Ba—O17	1.1 (10)
C6—C5—N2—O3	−176.0 (6)	N4—O8—Ba—O15	−129.7 (8)
C4—C5—N2—O3	2.4 (8)	N4—O8—Ba—O14	−18.9 (7)
C6—C5—N2—O4	2.7 (8)	N4—O8—Ba—O16	110.0 (8)
C4—C5—N2—O4	−178.9 (6)	N4—O8—Ba—O18	−71.1 (8)
C4—C3—N3—O6	−144.6 (5)	N4—O8—Ba—O1	34.8 (8)
C2—C3—N3—O6	35.4 (7)	N4—O8—Ba—O11ⁱⁱⁱ	−144.0 (7)
C4—C3—N3—O5	33.1 (7)	N4—O8—Ba—O5ⁱ	152.1 (8)
C2—C3—N3—O5	−146.9 (5)	N1—O1—Ba—O7	−45.6 (5)
C8—C7—N4—O8	−164.9 (5)	N1—O1—Ba—O17	178.3 (6)
C12—C7—N4—O8	15.9 (7)	N1—O1—Ba—O15	52.7 (7)
C8—C7—N4—O9	15.2 (7)	N1—O1—Ba—O14	63.4 (5)
C12—C7—N4—O9	−164.0 (5)	N1—O1—Ba—O16	−115.5 (5)
C8—C9—N5—O10	−1.7 (8)	N1—O1—Ba—O18	128.4 (5)
C10—C9—N5—O10	177.7 (6)	N1—O1—Ba—O8	15.6 (5)
C8—C9—N5—O11	177.6 (5)	N1—O1—Ba—O11ⁱⁱⁱ	−165.4 (5)
C10—C9—N5—O11	−3.0 (8)	N1—O1—Ba—O5ⁱ	−70.9 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15A···O7^iv	0.85 (4)	2.20 (4)	2.939 (6)	145 (6)
O15—H15A···O6^iv	0.85 (4)	2.33 (4)	3.030 (7)	140 (5)
O15—H15B···O9^v	0.85 (4)	2.10 (1)	2.953 (6)	179 (7)
O16—H16A···O4ⁱⁱⁱ	0.85 (3)	2.08 (4)	2.806 (6)	142 (5)
O16—H16B···O15^vi	0.85 (6)	2.11 (3)	2.906 (7)	156 (6)
O17—H17A···O12^vii	0.85 (4)	2.45 (3)	3.258 (8)	158 (6)
O17—H17B···O18^vii	0.85 (5)	1.97 (2)	2.805 (7)	168 (7)
O18—H18A···O16^iv	0.85 (4)	2.04 (3)	2.822 (7)	153 (7)
O18—H18B···O1^viii	0.85 (5)	2.47 (3)	3.241 (7)	151 (6)

Symmetry codes: (iii) x−1, y, z; (iv) x, y−1, z; (v) −x+2, −y+1, −z; (vi) x, y+1, z; (vii) −x+2, y+1/2, −z+1/2; (viii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Ba(C₆H₂N₃O₇)₂(H₂O)₄]
M_r	665.62
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.6765 (4), 6.6878 (2), 27.0324 (9)
β (°)	95.608 (2)
V (Å³)	2100.86 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.00
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEX2 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.652, 0.723
No. of measured, independent and observed [I > 2σ(I)] reflections	20976, 3674, 3552
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.084, 1.42
No. of reflections	3674
No. of parameters	360
No. of restraints	234
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.53

Computer programs: APEX2 (Bruker, 2004), APEX2/SAINT (Bruker, 2004), SAINT/XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Bruno et al., 2002).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O15—H15A···O7ⁱ	0.85 (4)	2.20 (4)	2.939 (6)	145 (6)
O15—H15A···O6ⁱ	0.85 (4)	2.33 (4)	3.030 (7)	140 (5)
O15—H15B···O9ⁱⁱ	0.85 (4)	2.103 (6)	2.953 (6)	179 (7)
O16—H16A···O4ⁱⁱⁱ	0.85 (3)	2.08 (4)	2.806 (6)	142 (5)
O16—H16B···O15^iv	0.85 (6)	2.11 (3)	2.906 (7)	156 (6)
O17—H17A···O12^v	0.85 (4)	2.45 (3)	3.258 (8)	158 (6)
O17—H17B···O18^v	0.85 (5)	1.969 (17)	2.805 (7)	168 (7)
O18—H18A···O16ⁱ	0.85 (4)	2.04 (3)	2.822 (7)	153 (7)
O18—H18B···O1^vi	0.85 (5)	2.47 (3)	3.241 (7)	151 (6)

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

Acknowledgements

The authors thank the Sophisticated Analytical Instruments Facility, Indian Institute of Technology Madras, Chennai, for the X-ray data collection.

References

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