Poly[[penta­aqua­bis­(μ3-hydrogen squarato)barium] monohydrate]

Trifa, C.; Bouhali, A.; Bouacida, S.; Boudaren, C.; Merazig, H.

doi:10.1107/S1600536813014736

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m366-m367

https://doi.org/10.1107/S1600536813014736

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Poly[[pentaaquabis(μ₃-hydrogen squarato)barium] monohydrate]

Chahrazed Trifa,^a Amira Bouhali,^a Sofiane Bouacida,^a,^b ^* Chaouki Boudaren ^a and Hocine Merazig ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine, 25000 , Algeria, and ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 13 May 2013; accepted 28 May 2013; online 8 June 2013)

The crystal structure of the title compound, {[Ba(C₄HO₄)₂(H₂O)₅]·H₂O}_n, consists of discrete double chains propagating along [010]. The chains are formed by Ba^II ions linked by bridging hydrogen squarate ligands in a trans-bis-monodentate mode. In addition, the bridging hydrogen squarate ligands connect the chains into a ladder structure via a third coordinating O atom. The remaining coordination sites are occupied by five aqua ligands and a second mondendate hydrogen squarate ligand, forming a slightly distorted tricapped trigonal–prismatic geometry. O—H⋯O hydrogen bonds link the chains and solvent water molecules into a three-dimensional network.

Related literature

For the synthesis and applications of cyclic oxocarbons, see: Cohen et al. (1959 ); Bertolasi et al. (2001 ). For crystal structures of hydrogen squarate complexes, see: Brach et al. (1987 ); Uçar et al. (2005 ); Lee et al. (1996 ). For related alkaline earth squarates, see: Robl & Weiss (1986a ,b ); Koferstein & Robl (2002 ). For other related structures, see: Trifa et al. (2011 ); Bouhali et al. (2011 ). For the bond-valence method, see: Hormillosa et al. (1993 ).

Experimental

Crystal data

[Ba(C₄HO₄)₂(H₂O)₅]·H₂O
M_r = 471.53
Monoclinic, P 2₁ /c
a = 11.1522 (11) Å
b = 9.0268 (8) Å
c = 14.3025 (14) Å
β = 94.009 (5)°
V = 1436.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.84 mm⁻¹
T = 150 K
0.12 × 0.1 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ) T_min = 0.731, T_max = 1.000
12082 measured reflections
2550 independent reflections
2471 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.013
wR(F²) = 0.034
S = 1.06
2550 reflections
264 parameters
All H-atom parameters refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

Ba1—O1	2.6857 (10)
Ba1—O3W	2.7032 (12)
Ba1—O5W	2.7358 (11)
Ba1—O1W	2.7500 (12)
Ba1—O2W	2.7791 (12)
Ba1—O6	2.7851 (11)
Ba1—O4W	2.8356 (14)
Ba1—O3ⁱ	2.7983 (10)
Ba1—O4ⁱⁱ	2.9630 (11)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O4Wⁱⁱⁱ	0.74 (3)	2.13 (2)	2.8448 (19)	162 (3)
O1W—H1B⋯O8^iv	0.86 (3)	1.93 (3)	2.7854 (16)	175 (2)
O2W—H2A⋯O11W^v	0.78 (3)	2.22 (3)	2.9431 (17)	156 (2)
O2W—H2B⋯O7^vi	0.86 (3)	1.98 (3)	2.8451 (17)	178 (3)
O3W—H3A⋯O4ⁱ	0.85 (3)	1.94 (3)	2.7724 (16)	165 (2)
O3W—H3B⋯O11W^vii	0.79 (3)	2.05 (2)	2.8160 (17)	165 (2)
O4W—H4A⋯O7^viii	0.77 (3)	2.07 (3)	2.7916 (16)	156 (2)
O4W—H4B⋯O5^ix	0.80 (2)	2.37 (3)	3.1245 (17)	156 (2)
O5W—H5A⋯O11W	0.84 (3)	1.96 (3)	2.7941 (16)	177 (3)
O5W—H5B⋯O1ⁱⁱ	0.85 (2)	1.87 (2)	2.7176 (15)	173 (3)
O11W—H11A⋯O8^iv	0.75 (2)	1.93 (2)	2.6730 (17)	169 (2)
O11W—H11B⋯O5W^x	0.85 (2)	1.94 (3)	2.7711 (16)	165 (2)
O2—H21⋯O6	0.86 (3)	1.77 (3)	2.6207 (15)	178 (2)
O5—H51⋯O3ⁱ	0.87 (2)	1.71 (2)	2.5795 (15)	176 (3)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+2, -y+1, -z+1; (v) x, y+1, z; (vi) -x+2, -y+2, -z+1; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ix) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (x) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813014736/lh5617sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813014736/lh5617Isup2.hkl

checkCIF report

Comment top

Squaric acid, H₂C₄O₄ (3,4-dihydroxycyclobut-3-ene-1,2-dione, Sq), was synthesized for the first time by Cohen et al. in 1959 and has attracted interest because of its cyclic structure and possible aromaticity. It belongs to the series of cyclic oxocarbons of formula H₂C_nO_n (n = 3–6 for deltic, squaric, croconic and rhodizonic acids, respectively). It and its anions (Hsq- and sq^2-) are also a useful tools for constructing crystalline architectures and they possess proton donating and accepting capabilities for hydrogen bonding (Cohen et al.1959; Bertolasi et al. 2001). The molecule presents high degree of electron delocalization, which is very important in crystal packing (Brach et al. 1987; Ucar et al. 2005; Lee et al. 1996). The crystal structure of alkaline earth squarates (Robl et al. 1986a,b; Koferstein & Robl. 2002) have already been published. Recently, we reported the crystal structures of a hemihydrate barium strontium hydrogen squarate (Trifa et al. 2011) and strontium hydrogen squarate (Bouhali et al. 2011). This paper describes the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I) consists of one Ba^II ion, two hydrogen squarate anions, five coordinated water molecules and one solvent water molecule (Fig. 1). Each Ba^II ion displays a slightly-distorted tricapped trigonal prismatic geometry, defined by four O atoms of two hydrogen squarate anions and five water molecules. The mean value deduced from the Ba–O bonding interactions taken in the range 2.6857 (10)–2.9630 (11) Å agrees with that calculated from the program VALENCE (Hormillosa et al. 1993). The C—O bond lengths indicate that the degree of delocalization in the HSQ– ion in (I) is comparable with literature values (Bertolasi et al. 2001). The structure of (I) consists of infinite linear chains with composition [Ba(HC₄O₄)₂(H₂O)₅]_n running along [010] (Fig. 2). The bridging squarate groups adopt two coordination modes, µ-1monodentate and µ-2 trans bis monodentate. In the crystal, O—H···O hydrogen bonds link the one-dimenaional chains and solvent water molecules into a three-dimensional network (Fig. 3).

It is particularly interesting to compare the crystal structure of this compound with that of its corresponding hemi hydrate barium strontium hydrogen squarate, [Ba_0.35Sr_0.65(HC₄O₄)₂(H₂O)₅], 0.5H₂O (Trifa et al. 2011). Indeed both structures can be described by chains connected by hydrogen squarate group, However, we can note the following important differences: the presence of Ba/SrO₉ polyhedra in the barium strontium hydrogen squarate and a different space group (C2/c) and lattice parameters. Moreover, due to the higher symmetry, the structure is built from dimers of edge-sharing monocapped square antiprisms [(Ba/Sr)O₃(H₂O)₆].

Related literature top

For the synthesis and applications of cyclic oxocarbons, see: Cohen et al. (1959); Bertolasi et al. (2001). For crystal structures of hydrogen squarate complexes, see: Brach et al. (1987); Uçar et al. (2005); Lee et al. (1996). For related alkaline earth squarates, see: Robl & Weiss (1986a,b); Koferstein & Robl (2002). For other related structures, see: Trifa et al. (2011); Bouhali et al. (2011). For the bond-valence method, see: Hormillosa et al. (1993).

Experimental top

All chemicals were purchased from commercial sources and used as received without further purification. The title compound, was synthesized by using a hydrothermal method. Typically a mixture of BaCl₂.2H₂O (0.112 g) and H₂C₄O₄ (0.114 g) were suspended in H₂O (ca 9 ml). The mixture was then placed in a Teflon lined autoclave, sealed and heated to 393K for 4 days followed by cooling in a water bath. The yellow crystals suitable for X-ray diffraction were filtered, washed with water and dried in air.

Structure description top

For the synthesis and applications of cyclic oxocarbons, see: Cohen et al. (1959); Bertolasi et al. (2001). For crystal structures of hydrogen squarate complexes, see: Brach et al. (1987); Uçar et al. (2005); Lee et al. (1996). For related alkaline earth squarates, see: Robl & Weiss (1986a,b); Koferstein & Robl (2002). For other related structures, see: Trifa et al. (2011); Bouhali et al. (2011). For the bond-valence method, see: Hormillosa et al. (1993).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP-3 (Farrugia, 2012) drawing of the asymmetric unit (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A View of a single chain in (I) along [010].
	Fig. 3. Projection of the structure along the b axis. Dashed lines denote hydrogen bonds.

Poly[[pentaaquabis(µ₃-hydrogen squarato)barium] monohydrate] top

Crystal data top

[Ba(C₄HO₄)₂(H₂O)₅]·H₂O	F(000) = 920
M_r = 471.53	D_x = 2.181 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9365 reflections
a = 11.1522 (11) Å	θ = 2.3–25.1°
b = 9.0268 (8) Å	µ = 2.84 mm⁻¹
c = 14.3025 (14) Å	T = 150 K
β = 94.009 (5)°	Bloc, yellow
V = 1436.3 (2) Å³	0.12 × 0.1 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2550 independent reflections
Radiation source: sealed tube	2471 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.1°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −13→13
T_min = 0.731, T_max = 1.000	k = −10→10
12082 measured reflections	l = −17→17

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)] = 0.013	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.034	All H-atom parameters refined
S = 1.06	w = 1/[σ²(F_o²) + (0.0174P)² + 0.8037P] where P = (F_o² + 2F_c²)/3
2550 reflections	(Δ/σ)_max = 0.003
264 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Ba(C₄HO₄)₂(H₂O)₅]·H₂O	V = 1436.3 (2) Å³
M_r = 471.53	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.1522 (11) Å	µ = 2.84 mm⁻¹
b = 9.0268 (8) Å	T = 150 K
c = 14.3025 (14) Å	0.12 × 0.1 × 0.09 mm
β = 94.009 (5)°

Data collection top

Bruker APEXII CCD diffractometer	2550 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	2471 reflections with I > 2σ(I)
T_min = 0.731, T_max = 1.000	R_int = 0.022
12082 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.013	0 restraints
wR(F²) = 0.034	All H-atom parameters refined
S = 1.06	Δρ_max = 0.53 e Å⁻³
2550 reflections	Δρ_min = −0.25 e Å⁻³
264 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
Ba1	0.676848 (7)	0.760410 (9)	0.685367 (6)	0.00657 (5)
O4W	0.83608 (12)	0.75740 (13)	0.84885 (10)	0.0117 (3)
O1	0.67679 (9)	1.02235 (11)	0.77441 (7)	0.0100 (2)
C3	0.76489 (13)	1.36306 (16)	0.72323 (10)	0.0076 (3)
O6	0.90411 (9)	0.87276 (11)	0.65721 (7)	0.0098 (2)
C4	0.66220 (13)	1.30175 (17)	0.77342 (10)	0.0075 (3)
C1	0.70789 (13)	1.14962 (16)	0.75478 (10)	0.0077 (3)
O3W	0.56965 (11)	0.65706 (14)	0.83609 (8)	0.0139 (2)
O2	0.89727 (9)	1.16255 (12)	0.66655 (8)	0.0103 (2)
O5	0.99133 (10)	0.52766 (11)	0.61707 (8)	0.0114 (2)
C2	0.80471 (14)	1.21456 (17)	0.70706 (11)	0.0080 (3)
O2W	0.65618 (12)	0.97776 (13)	0.54757 (8)	0.0154 (2)
O7	1.13514 (9)	0.98991 (11)	0.55422 (7)	0.0107 (2)
O1W	0.73539 (11)	0.64714 (14)	0.51598 (9)	0.0155 (3)
O8	1.20517 (9)	0.64982 (11)	0.50651 (8)	0.0112 (2)
C7	1.09085 (13)	0.86799 (16)	0.56650 (10)	0.0075 (3)
C5	1.02281 (13)	0.66277 (17)	0.59606 (11)	0.0083 (3)
C6	0.98586 (13)	0.81173 (17)	0.61497 (10)	0.0074 (3)
O3	0.79995 (9)	1.49094 (11)	0.70579 (7)	0.0093 (2)
C8	1.12363 (14)	0.71099 (17)	0.54615 (11)	0.0083 (3)
O4	0.57822 (9)	1.35215 (11)	0.81426 (7)	0.0103 (2)
O11W	0.56817 (12)	0.28422 (13)	0.52709 (8)	0.0116 (2)
O5W	0.51886 (10)	0.54413 (12)	0.62332 (8)	0.0111 (2)
H4A	0.860 (2)	0.681 (3)	0.8658 (15)	0.022 (6)*
H11A	0.634 (2)	0.293 (2)	0.5207 (14)	0.016 (5)*
H1B	0.7564 (19)	0.556 (3)	0.5121 (15)	0.030 (6)*
H1A	0.750 (2)	0.685 (3)	0.4720 (18)	0.033 (7)*
H4B	0.892 (2)	0.813 (3)	0.8462 (16)	0.034 (7)*
H3A	0.5667 (19)	0.563 (3)	0.8392 (15)	0.031 (6)*
H5A	0.535 (2)	0.465 (3)	0.5962 (17)	0.040 (7)*
H5B	0.458 (2)	0.529 (3)	0.6545 (16)	0.037 (6)*
H3B	0.542 (2)	0.690 (3)	0.8807 (18)	0.035 (7)*
H11B	0.535 (2)	0.323 (3)	0.4773 (17)	0.032 (6)*
H2A	0.616 (2)	1.046 (3)	0.5350 (17)	0.043 (7)*
H2B	0.720 (3)	0.985 (3)	0.5169 (18)	0.045 (7)*
H51	0.925 (2)	0.518 (3)	0.6447 (18)	0.049 (7)*
H21	0.901 (2)	1.068 (3)	0.6630 (17)	0.049 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.00723 (7)	0.00479 (6)	0.00797 (7)	−0.00014 (3)	0.00246 (4)	−0.00034 (3)
O4W	0.0108 (6)	0.0094 (6)	0.0149 (7)	−0.0005 (5)	0.0006 (5)	0.0027 (4)
O1	0.0121 (5)	0.0052 (5)	0.0133 (6)	−0.0007 (4)	0.0048 (4)	0.0005 (4)
C3	0.0077 (7)	0.0086 (7)	0.0062 (7)	−0.0005 (6)	−0.0015 (6)	0.0002 (5)
O6	0.0091 (5)	0.0085 (5)	0.0124 (5)	0.0008 (4)	0.0046 (4)	−0.0009 (4)
C4	0.0082 (7)	0.0072 (7)	0.0068 (7)	−0.0008 (6)	−0.0015 (6)	0.0003 (6)
C1	0.0076 (7)	0.0096 (8)	0.0059 (7)	0.0010 (6)	−0.0008 (6)	−0.0007 (6)
O3W	0.0198 (6)	0.0093 (6)	0.0136 (6)	−0.0004 (5)	0.0085 (5)	−0.0006 (5)
O2	0.0086 (5)	0.0075 (5)	0.0155 (6)	0.0014 (4)	0.0060 (4)	−0.0002 (4)
O5	0.0095 (6)	0.0067 (5)	0.0187 (6)	−0.0007 (4)	0.0062 (5)	0.0012 (4)
C2	0.0077 (8)	0.0085 (7)	0.0074 (8)	−0.0004 (6)	−0.0014 (6)	−0.0004 (6)
O2W	0.0157 (6)	0.0129 (6)	0.0186 (6)	0.0038 (5)	0.0078 (5)	0.0049 (5)
O7	0.0114 (5)	0.0084 (5)	0.0126 (6)	−0.0025 (4)	0.0031 (4)	−0.0007 (4)
O1W	0.0251 (7)	0.0096 (6)	0.0128 (6)	0.0018 (5)	0.0088 (5)	0.0011 (5)
O8	0.0091 (5)	0.0096 (5)	0.0154 (6)	0.0011 (4)	0.0053 (4)	−0.0019 (4)
C7	0.0070 (7)	0.0097 (7)	0.0057 (7)	−0.0003 (6)	−0.0011 (6)	0.0002 (6)
C5	0.0071 (7)	0.0093 (8)	0.0082 (7)	0.0004 (6)	−0.0010 (6)	−0.0010 (6)
C6	0.0059 (7)	0.0094 (7)	0.0067 (7)	−0.0007 (6)	−0.0013 (6)	0.0006 (6)
O3	0.0101 (5)	0.0058 (5)	0.0124 (5)	−0.0004 (4)	0.0033 (4)	0.0003 (4)
C8	0.0083 (8)	0.0081 (7)	0.0082 (7)	−0.0004 (6)	−0.0020 (6)	−0.0001 (6)
O4	0.0098 (5)	0.0082 (5)	0.0136 (6)	0.0006 (4)	0.0050 (4)	−0.0010 (4)
O11W	0.0085 (6)	0.0140 (6)	0.0125 (6)	−0.0003 (5)	0.0031 (5)	0.0018 (5)
O5W	0.0113 (6)	0.0105 (6)	0.0121 (6)	−0.0010 (4)	0.0049 (5)	−0.0018 (4)

Geometric parameters (Å, º) top

Ba1—O1	2.6857 (10)	O3W—H3A	0.85 (3)
Ba1—O3W	2.7032 (12)	O3W—H3B	0.79 (3)
Ba1—O5W	2.7358 (11)	O2—C2	1.3058 (19)
Ba1—O1W	2.7500 (12)	O2—H21	0.85 (3)
Ba1—O2W	2.7791 (12)	O5—C5	1.3099 (19)
Ba1—O6	2.7851 (11)	O5—H51	0.86 (3)
Ba1—O4W	2.8356 (14)	O2W—H2A	0.77 (3)
Ba1—O3ⁱ	2.7983 (10)	O2W—H2B	0.86 (3)
Ba1—O4ⁱⁱ	2.9630 (11)	O7—C7	1.2241 (18)
O3—Ba1ⁱⁱⁱ	2.7983 (10)	O1W—H1B	0.86 (3)
O4—Ba1^iv	2.9630 (11)	O1W—H1A	0.75 (3)
O4W—H4A	0.77 (2)	O8—C8	1.2351 (19)
O4W—H4B	0.80 (3)	C7—C6	1.491 (2)
O1—C1	1.2380 (18)	C7—C8	1.497 (2)
C3—O3	1.2496 (18)	C5—C6	1.438 (2)
C3—C2	1.436 (2)	C5—C8	1.441 (2)
C3—C4	1.499 (2)	O11W—H11A	0.75 (2)
O6—C6	1.2557 (19)	O11W—H11B	0.85 (3)
C4—O4	1.2255 (19)	O5W—H5A	0.84 (3)
C4—C1	1.495 (2)	O5W—H5B	0.85 (3)
C1—C2	1.442 (2)

O1—Ba1—O3W	84.89 (4)	O3—C3—C4	134.17 (14)
O1—Ba1—O5W	139.52 (3)	C2—C3—C4	89.30 (12)
O3W—Ba1—O5W	72.64 (4)	C6—O6—Ba1	127.48 (9)
O1—Ba1—O1W	138.85 (4)	O4—C4—C1	135.01 (14)
O3W—Ba1—O1W	136.03 (4)	O4—C4—C3	136.55 (14)
O5W—Ba1—O1W	68.66 (4)	C1—C4—C3	88.42 (11)
O1—Ba1—O2W	73.26 (3)	O1—C1—C2	135.70 (14)
O3W—Ba1—O2W	142.17 (4)	O1—C1—C4	135.04 (14)
O5W—Ba1—O2W	104.72 (4)	C2—C1—C4	89.25 (12)
O1W—Ba1—O2W	69.56 (4)	Ba1—O3W—H3A	114.0 (14)
O1—Ba1—O6	77.19 (3)	Ba1—O3W—H3B	137.3 (18)
O3W—Ba1—O6	134.32 (3)	H3A—O3W—H3B	109 (2)
O5W—Ba1—O6	141.71 (3)	C2—O2—H21	115.5 (17)
O1W—Ba1—O6	74.54 (3)	C5—O5—H51	116.6 (17)
O2W—Ba1—O6	70.83 (3)	O2—C2—C3	132.07 (14)
O1—Ba1—O3ⁱ	137.07 (3)	O2—C2—C1	134.86 (14)
O3W—Ba1—O3ⁱ	81.83 (3)	C3—C2—C1	93.04 (12)
O5W—Ba1—O3ⁱ	73.36 (3)	Ba1—O2W—H2A	137.9 (18)
O1W—Ba1—O3ⁱ	67.90 (4)	Ba1—O2W—H2B	112.5 (17)
O2W—Ba1—O3ⁱ	134.70 (3)	H2A—O2W—H2B	108 (2)
O6—Ba1—O3ⁱ	83.50 (3)	Ba1—O1W—H1B	119.7 (15)
O1—Ba1—O4W	68.80 (3)	Ba1—O1W—H1A	131 (2)
O3W—Ba1—O4W	68.01 (4)	H1B—O1W—H1A	108 (2)
O5W—Ba1—O4W	127.78 (3)	O7—C7—C6	135.31 (14)
O1W—Ba1—O4W	123.32 (4)	O7—C7—C8	135.78 (14)
O2W—Ba1—O4W	127.42 (4)	C6—C7—C8	88.76 (11)
O6—Ba1—O4W	66.36 (3)	O5—C5—C6	137.96 (14)
O3ⁱ—Ba1—O4W	68.36 (3)	O5—C5—C8	128.76 (14)
O1—Ba1—O4ⁱⁱ	73.80 (3)	C6—C5—C8	93.13 (12)
O3W—Ba1—O4ⁱⁱ	67.47 (3)	O6—C6—C5	136.74 (15)
O5W—Ba1—O4ⁱⁱ	66.64 (3)	O6—C6—C7	133.99 (14)
O1W—Ba1—O4ⁱⁱ	113.11 (3)	C5—C6—C7	89.21 (12)
O2W—Ba1—O4ⁱⁱ	76.82 (3)	C3—O3—Ba1ⁱⁱⁱ	131.74 (9)
O6—Ba1—O4ⁱⁱ	141.44 (3)	O8—C8—C5	135.85 (15)
O3ⁱ—Ba1—O4ⁱⁱ	134.97 (3)	O8—C8—C7	135.24 (14)
O4W—Ba1—O4ⁱⁱ	123.17 (3)	C5—C8—C7	88.86 (11)
Ba1—O4W—H4A	116.7 (16)	C4—O4—Ba1^iv	131.52 (9)
Ba1—O4W—H4B	113.6 (17)	H11A—O11W—H11B	103 (2)
H4A—O4W—H4B	109 (3)	Ba1—O5W—H5A	127.3 (16)
C1—O1—Ba1	134.44 (9)	Ba1—O5W—H5B	117.8 (16)
O3—C3—C2	136.52 (14)	H5A—O5W—H5B	108 (2)

O3W—Ba1—O1—C1	−176.77 (14)	O3—C3—C2—C1	178.50 (18)
O5W—Ba1—O1—C1	−121.24 (13)	C4—C3—C2—C1	−0.12 (12)
O1W—Ba1—O1—C1	−1.98 (16)	O1—C1—C2—O2	−0.4 (3)
O2W—Ba1—O1—C1	−28.01 (13)	C4—C1—C2—O2	178.04 (18)
O6—Ba1—O1—C1	45.53 (13)	O1—C1—C2—C3	−178.29 (18)
O3ⁱ—Ba1—O1—C1	111.03 (13)	C4—C1—C2—C3	0.12 (12)
O4W—Ba1—O1—C1	114.86 (14)	Ba1—O6—C6—C5	−27.9 (2)
O4ⁱⁱ—Ba1—O1—C1	−108.77 (14)	Ba1—O6—C6—C7	155.81 (13)
O1—Ba1—O6—C6	178.40 (12)	O5—C5—C6—O6	−3.4 (3)
O3W—Ba1—O6—C6	108.87 (12)	C8—C5—C6—O6	−178.92 (18)
O5W—Ba1—O6—C6	−15.47 (14)	O5—C5—C6—C7	173.96 (19)
O1W—Ba1—O6—C6	−31.82 (11)	C8—C5—C6—C7	−1.56 (11)
O2W—Ba1—O6—C6	−105.11 (12)	O7—C7—C6—O6	3.1 (3)
O3ⁱ—Ba1—O6—C6	37.00 (12)	C8—C7—C6—O6	178.98 (17)
O4W—Ba1—O6—C6	106.18 (12)	O7—C7—C6—C5	−174.39 (18)
O4ⁱⁱ—Ba1—O6—C6	−139.67 (11)	C8—C7—C6—C5	1.50 (11)
O3—C3—C4—O4	−0.1 (3)	C2—C3—O3—Ba1ⁱⁱⁱ	155.33 (14)
C2—C3—C4—O4	178.63 (18)	C4—C3—O3—Ba1ⁱⁱⁱ	−26.6 (2)
O3—C3—C4—C1	−178.57 (17)	O5—C5—C8—O8	3.0 (3)
C2—C3—C4—C1	0.12 (11)	C6—C5—C8—O8	179.15 (18)
Ba1—O1—C1—C2	−38.1 (3)	O5—C5—C8—C7	−174.60 (16)
Ba1—O1—C1—C4	144.19 (13)	C6—C5—C8—C7	1.55 (11)
O4—C4—C1—O1	−0.2 (3)	O7—C7—C8—O8	−3.3 (3)
C3—C4—C1—O1	178.31 (17)	C6—C7—C8—O8	−179.12 (18)
O4—C4—C1—C2	−178.67 (18)	O7—C7—C8—C5	174.36 (18)
C3—C4—C1—C2	−0.12 (11)	C6—C7—C8—C5	−1.50 (11)
O3—C3—C2—O2	0.5 (3)	C1—C4—O4—Ba1^iv	−43.2 (2)
C4—C3—C2—O2	−178.13 (17)	C3—C4—O4—Ba1^iv	138.94 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O4W^v	0.74 (3)	2.13 (2)	2.8448 (19)	162 (3)
O1W—H1B···O8^vi	0.86 (3)	1.93 (3)	2.7854 (16)	175 (2)
O2W—H2A···O11Wⁱⁱⁱ	0.78 (3)	2.22 (3)	2.9431 (17)	156 (2)
O2W—H2B···O7^vii	0.86 (3)	1.98 (3)	2.8451 (17)	178 (3)
O3W—H3A···O4ⁱ	0.85 (3)	1.94 (3)	2.7724 (16)	165 (2)
O3W—H3B···O11W^iv	0.79 (3)	2.05 (2)	2.8160 (17)	165 (2)
O4W—H4A···O7^viii	0.77 (3)	2.07 (3)	2.7916 (16)	156 (2)
O4W—H4B···O5^ix	0.80 (2)	2.37 (3)	3.1245 (17)	156 (2)
O5W—H5A···O11W	0.84 (3)	1.96 (3)	2.7941 (16)	177 (3)
O5W—H5B···O1ⁱⁱ	0.85 (2)	1.87 (2)	2.7176 (15)	173 (3)
O11W—H11A···O8^vi	0.75 (2)	1.93 (2)	2.6730 (17)	169 (2)
O11W—H11B···O5W^x	0.85 (2)	1.94 (3)	2.7711 (16)	165 (2)
O2—H21···O6	0.86 (3)	1.77 (3)	2.6207 (15)	178 (2)
O5—H51···O3ⁱ	0.87 (2)	1.71 (2)	2.5795 (15)	176 (3)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y+1, z; (iv) −x+1, y+1/2, −z+3/2; (v) x, −y+3/2, z−1/2; (vi) −x+2, −y+1, −z+1; (vii) −x+2, −y+2, −z+1; (viii) −x+2, y−1/2, −z+3/2; (ix) −x+2, y+1/2, −z+3/2; (x) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Ba(C₄HO₄)₂(H₂O)₅]·H₂O
M_r	471.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	11.1522 (11), 9.0268 (8), 14.3025 (14)
β (°)	94.009 (5)
V (Å³)	1436.3 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.84
Crystal size (mm)	0.12 × 0.1 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2002)
T_min, T_max	0.731, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12082, 2550, 2471
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.034, 1.06
No. of reflections	2550
No. of parameters	264
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.25

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 2012).

Selected bond lengths (Å) top

Ba1—O1	2.6857 (10)	Ba1—O6	2.7851 (11)
Ba1—O3W	2.7032 (12)	Ba1—O4W	2.8356 (14)
Ba1—O5W	2.7358 (11)	Ba1—O3ⁱ	2.7983 (10)
Ba1—O1W	2.7500 (12)	Ba1—O4ⁱⁱ	2.9630 (11)
Ba1—O2W	2.7791 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O4Wⁱⁱⁱ	0.74 (3)	2.13 (2)	2.8448 (19)	162 (3)
O1W—H1B···O8^iv	0.86 (3)	1.93 (3)	2.7854 (16)	175 (2)
O2W—H2A···O11W^v	0.78 (3)	2.22 (3)	2.9431 (17)	156 (2)
O2W—H2B···O7^vi	0.86 (3)	1.98 (3)	2.8451 (17)	178 (3)
O3W—H3A···O4ⁱ	0.85 (3)	1.94 (3)	2.7724 (16)	165 (2)
O3W—H3B···O11W^vii	0.79 (3)	2.05 (2)	2.8160 (17)	165 (2)
O4W—H4A···O7^viii	0.77 (3)	2.07 (3)	2.7916 (16)	156 (2)
O4W—H4B···O5^ix	0.80 (2)	2.37 (3)	3.1245 (17)	156 (2)
O5W—H5A···O11W	0.84 (3)	1.96 (3)	2.7941 (16)	177 (3)
O5W—H5B···O1ⁱⁱ	0.85 (2)	1.87 (2)	2.7176 (15)	173 (3)
O11W—H11A···O8^iv	0.75 (2)	1.93 (2)	2.6730 (17)	169 (2)
O11W—H11B···O5W^x	0.85 (2)	1.94 (3)	2.7711 (16)	165 (2)
O2—H21···O6	0.86 (3)	1.77 (3)	2.6207 (15)	178 (2)
O5—H51···O3ⁱ	0.87 (2)	1.71 (2)	2.5795 (15)	176 (3)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y+3/2, z−1/2; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z; (vi) −x+2, −y+2, −z+1; (vii) −x+1, y+1/2, −z+3/2; (viii) −x+2, y−1/2, −z+3/2; (ix) −x+2, y+1/2, −z+3/2; (x) −x+1, −y+1, −z+1.

Acknowledgements

We are grateful to all personal of the Unité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Constantine, for their assistance. Thanks are due to MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algérie) for financial support.

References

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