Poly[[penta-aqua-bis-(μ3-hydrogen squarato)barium] monohydrate].

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 mol-ecules 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 = 471.53

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.013

wR(F 2) = 0.034

S = 1.06

2550 reflections

264 parameters

All H-atom parameters refined

Δρmax = 0.53 e Å−3

Δρmin = −0.25 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813014736/lh5617sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014736/lh5617Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ba(C4HO4)2(H2O)5]·H2O	F(000) = 920
Mr = 471.53	Dx = 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

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

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(Fo2) + (0.0174P)2 + 0.8037P] where P = (Fo2 + 2Fc2)/3
2550 reflections	(Δ/σ)max = 0.003
264 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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—Ba1iv	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—Ba1iv	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—Ba1iv	−43.2 (2)
C4—C3—C2—O2	−178.13 (17)	C3—C4—O4—Ba1iv	138.94 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O4Wv	0.74 (3)	2.13 (2)	2.8448 (19)	162 (3)
O1W—H1B···O8vi	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···O7vii	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···O11Wiv	0.79 (3)	2.05 (2)	2.8160 (17)	165 (2)
O4W—H4A···O7viii	0.77 (3)	2.07 (3)	2.7916 (16)	156 (2)
O4W—H4B···O5ix	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···O8vi	0.75 (2)	1.93 (2)	2.6730 (17)	169 (2)
O11W—H11B···O5Wx	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)

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) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O4W iii	0.74 (3)	2.13 (2)	2.8448 (19)	162 (3)
O1W—H1B⋯O8iv	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⋯O7vi	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⋯O7viii	0.77 (3)	2.07 (3)	2.7916 (16)	156 (2)
O4W—H4B⋯O5ix	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⋯O8iv	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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .