Hexa-aqua-bis-[3,5-bis-(hy-droxy-imino)-1-methyl-2,4,6-trioxo-cyclo-hexa-nido-κ(2) N (3),O (4)]barium tetrahydrate.

In the title compound, [Ba(C7H5N2O5)2(H2O)6]·4H2O, the Ba(2+) cation lies on a twofold rotation axis and is ten-coordinated by two 3,5-bis-(hy-droxy-imino)-1-methyl-2,4,6-trioxo-cyclo-hexa-n-ide oxo O atoms [Ba-O = 2.8715 (17) Å], two hy-droxy-imino N atoms [Ba-N = 3.036 (2) Å], and six water mol-ecules [Ba-O = 2.847 (2), 2.848 (2), and 2.880 (2) Å]. The 3,5-bis-(hy-droxy-imino)-1-methyl-2,4,6-trioxo-cyclo-hexa-nide monoanions act in a bidentate chelating manner, coordinating through an N atom of the non-deprotonated hy-droxy-imino group and an O atom of the neighboring oxo group. Two lattice water mol-ecules are located in the cavities of the framework and are involved in hydrogen bonding to O atoms of one of the coordinating water mol-ecules and the O atom of a keto group of the ligand. As a result, a three-dimensional network is formed.

Related literature

For the synthesis and crystal structure of sodium 3,5-bis­(hy­droxy­imino)-1-methyl-2,4,6- trioxo­cyclo­hexa­nide, see: Kovalchukova et al. (2012 ▶). For related structures of metal complexes with 1,2-benzo(naphto)quinone-1-oximes, see: Chakravorty (1974 ▶); Charalambous et al. (1993 ▶, 1995 ▶, 1996 ▶); Adatia et al. (1996 ▶); Basu & Chakravorty (1992 ▶); McPartlin (1973 ▶); Djinovic et al. (1992 ▶); Liu et al. (2010 ▶). For applications of related complexes as catalysts, see: Gharah et al. (2009 ▶).

Experimental

Crystal data

[Ba(C7H5N2O5)2(H2O)6]·4H2O

M = 711.76

Monoclinic,

a = 17.235 (3) Å

b = 6.736 (1) Å

c = 23.074 (5) Å

β = 108.61 (3)°

V = 2538.7 (9) Å3

Z = 4

Mo Kα radiation

μ = 1.66 mm−1

T = 293 K

0.33 × 0.12 × 0.07 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ▶) T min = 0.370, T max = 0.780

2429 measured reflections

2346 independent reflections

1755 reflections with I > 2σ(I)

R int = 0.019

3 standard reflections every 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.048

S = 0.98

2346 reflections

216 parameters

17 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.90 e Å−3

Data collection: CAD-4-PC (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4-PC; data reduction: CAD-4-PC; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CIFTAB97 (Sheldrick, 2008 ▶) and SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813027761/bv2225sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027761/bv2225Isup2.hkl

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

[Ba(C7H5N2O5)2(H2O)6]·4H2O	F(000) = 1432
Mr = 711.76	Dx = 1.862 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 17.235 (3) Å	θ = 9.2–11.7°
b = 6.736 (1) Å	µ = 1.66 mm−1
c = 23.074 (5) Å	T = 293 K
β = 108.61 (3)°	Plate, red
V = 2538.7 (9) Å3	0.33 × 0.12 × 0.07 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1755 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
β-filter monochromator	θmax = 25.5°, θmin = 1.9°
ω/2θ scans	h = 0→20
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −8→0
Tmin = 0.370, Tmax = 0.780	l = −27→26
2429 measured reflections	3 standard reflections every 60 min
2346 independent reflections	intensity decay: none

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)] = 0.018	Hydrogen site location: difference Fourier map
wR(F2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0317P)2] where P = (Fo2 + 2Fc2)/3
2346 reflections	(Δ/σ)max = 0.001
216 parameters	Δρmax = 0.47 e Å−3
17 restraints	Δρmin = −0.90 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	0.5000	0.24104 (3)	0.7500	0.02124 (7)
O1	0.56648 (10)	0.2550 (3)	0.65071 (7)	0.0332 (4)
O3	0.54847 (10)	0.3322 (3)	0.44397 (7)	0.0317 (4)
O5	0.32241 (10)	0.0962 (3)	0.49495 (7)	0.0349 (4)
O11	0.48141 (12)	0.6073 (3)	0.68255 (8)	0.0377 (4)
O12	0.59225 (10)	−0.1143 (3)	0.75770 (9)	0.0368 (4)
O13	0.32986 (11)	0.3326 (3)	0.70959 (8)	0.0371 (4)
O14	0.24224 (11)	−0.0492 (3)	0.70127 (9)	0.0447 (5)
O15	0.80288 (12)	0.0550 (3)	0.60419 (10)	0.0486 (5)
O21	0.67935 (10)	0.3795 (3)	0.52748 (8)	0.0335 (4)
O61	0.33722 (12)	0.0432 (3)	0.60383 (8)	0.0443 (5)
N2	0.64131 (11)	0.3306 (3)	0.56837 (9)	0.0259 (4)
N6	0.41475 (12)	0.1133 (3)	0.61886 (9)	0.0317 (4)
C1	0.52814 (12)	0.2383 (3)	0.59644 (9)	0.0226 (4)
C2	0.56427 (13)	0.2839 (3)	0.54772 (10)	0.0212 (4)
C3	0.51345 (14)	0.2780 (3)	0.48228 (10)	0.0214 (4)
C4	0.43167 (14)	0.2147 (3)	0.46508 (9)	0.0230 (4)
C5	0.39533 (13)	0.1576 (3)	0.50912 (10)	0.0235 (4)
C6	0.44222 (13)	0.1663 (3)	0.57513 (10)	0.0222 (4)
C7	0.38032 (15)	0.2124 (4)	0.39871 (10)	0.0314 (5)
H71	0.3245	0.2422	0.3951	0.038*
H72	0.3831	0.0834	0.3818	0.038*
H73	0.4005	0.3101	0.3769	0.038*
H21	0.646 (2)	0.360 (7)	0.4916 (14)	0.077 (4)*
H61	0.321 (2)	0.050 (6)	0.5645 (14)	0.077 (4)*
H111	0.470 (2)	0.606 (6)	0.6438 (5)	0.077 (4)*
H112	0.4404 (16)	0.664 (6)	0.6874 (16)	0.077 (4)*
H121	0.6431 (8)	−0.096 (6)	0.7668 (16)	0.077 (4)*
H122	0.582 (2)	−0.198 (5)	0.7293 (14)	0.077 (4)*
H131	0.302 (2)	0.228 (4)	0.7002 (17)	0.077 (4)*
H132	0.315 (2)	0.399 (5)	0.6766 (10)	0.077 (4)*
H141	0.217 (2)	−0.083 (6)	0.7256 (12)	0.077 (4)*
H142	0.2137 (19)	−0.102 (6)	0.6680 (9)	0.077 (4)*
H151	0.7660 (19)	0.008 (5)	0.5737 (12)	0.077 (4)*
H152	0.794 (3)	0.1784 (18)	0.6008 (18)	0.077 (4)*

	U11	U22	U33	U12	U13	U23
Ba1	0.02168 (10)	0.02131 (10)	0.02071 (9)	0.000	0.00676 (6)	0.000
O1	0.0286 (8)	0.0467 (10)	0.0227 (7)	−0.0042 (8)	0.0059 (6)	−0.0036 (8)
O3	0.0325 (9)	0.0387 (9)	0.0265 (8)	−0.0059 (8)	0.0131 (7)	0.0014 (7)
O5	0.0256 (8)	0.0448 (10)	0.0327 (9)	−0.0101 (8)	0.0070 (7)	−0.0014 (8)
O11	0.0491 (11)	0.0352 (10)	0.0281 (8)	0.0063 (8)	0.0116 (8)	0.0013 (7)
O12	0.0292 (8)	0.0334 (9)	0.0473 (10)	−0.0028 (8)	0.0114 (8)	−0.0080 (8)
O13	0.0344 (9)	0.0388 (10)	0.0347 (9)	0.0039 (8)	0.0062 (8)	0.0012 (8)
O14	0.0308 (9)	0.0582 (13)	0.0432 (10)	−0.0059 (9)	0.0092 (8)	0.0087 (10)
O15	0.0353 (10)	0.0522 (12)	0.0471 (11)	−0.0040 (10)	−0.0025 (8)	0.0100 (10)
O21	0.0273 (8)	0.0412 (10)	0.0351 (9)	−0.0068 (8)	0.0145 (7)	0.0002 (8)
O61	0.0343 (9)	0.0687 (14)	0.0310 (9)	−0.0242 (10)	0.0120 (8)	−0.0031 (9)
N2	0.0267 (10)	0.0223 (9)	0.0292 (10)	−0.0008 (8)	0.0097 (8)	−0.0012 (8)
N6	0.0294 (10)	0.0372 (12)	0.0293 (10)	−0.0115 (9)	0.0105 (8)	−0.0031 (9)
C1	0.0246 (10)	0.0187 (9)	0.0241 (9)	0.0008 (9)	0.0073 (8)	−0.0011 (9)
C2	0.0235 (10)	0.0137 (11)	0.0263 (10)	0.0013 (8)	0.0078 (8)	−0.0025 (8)
C3	0.0269 (10)	0.0138 (11)	0.0242 (9)	0.0021 (8)	0.0092 (8)	0.0000 (8)
C4	0.0293 (11)	0.0156 (11)	0.0226 (10)	0.0022 (8)	0.0064 (8)	0.0005 (8)
C5	0.0229 (11)	0.0180 (10)	0.0277 (11)	−0.0004 (9)	0.0054 (8)	−0.0018 (9)
C6	0.0250 (11)	0.0174 (9)	0.0244 (10)	0.0001 (9)	0.0082 (9)	−0.0011 (8)
C7	0.0352 (12)	0.0301 (13)	0.0245 (10)	−0.0031 (9)	0.0033 (9)	0.0003 (9)

Ba1—O13	2.8467 (19)	O15—H151	0.846 (10)
Ba1—O13i	2.8467 (19)	O15—H152	0.845 (10)
Ba1—O12	2.8475 (19)	O21—N2	1.350 (3)
Ba1—O12i	2.8475 (19)	O21—H21	0.86 (3)
Ba1—O1i	2.8715 (17)	O61—N6	1.354 (3)
Ba1—O1	2.8715 (17)	O61—H61	0.86 (3)
Ba1—O11i	2.8799 (19)	N2—C2	1.298 (3)
Ba1—O11	2.8799 (19)	N6—C6	1.294 (3)
Ba1—N6	3.036 (2)	C1—C2	1.481 (3)
Ba1—N6i	3.036 (2)	C1—C6	1.485 (3)
O1—C1	1.220 (3)	C2—C3	1.485 (3)
O3—C3	1.273 (3)	C3—O3	1.273 (3)
O5—C5	1.263 (3)	C3—C4	1.403 (3)
O11—H111	0.851 (10)	C4—C5	1.407 (3)
O11—H112	0.841 (10)	C4—C7	1.504 (3)
O12—H121	0.842 (10)	C5—O5	1.263 (3)
O12—H122	0.841 (10)	C5—C6	1.480 (3)
O13—H131	0.847 (10)	C7—H71	0.9600
O13—H132	0.847 (10)	C7—H72	0.9600
O14—H141	0.851 (10)	C7—H73	0.9600
O14—H142	0.849 (10)
O13—Ba1—O13i	154.98 (9)	Ba1—O11—H111	121 (3)
O13—Ba1—O12	134.33 (6)	Ba1—O11—H112	106 (3)
O13i—Ba1—O12	70.45 (6)	H111—O11—H112	103 (2)
O13—Ba1—O12i	70.45 (6)	Ba1—O12—H121	114 (3)
O13i—Ba1—O12i	134.33 (5)	Ba1—O12—H122	123 (3)
O12—Ba1—O12i	65.59 (7)	H121—O12—H122	104 (2)
O13—Ba1—O1i	67.83 (5)	Ba1—O13—H131	111 (3)
O13i—Ba1—O1i	111.29 (5)	Ba1—O13—H132	113 (3)
O12—Ba1—O1i	109.55 (5)	H131—O13—H132	103 (2)
O12i—Ba1—O1i	73.76 (5)	H141—O14—H142	102 (2)
O13—Ba1—O1	111.30 (5)	H151—O15—H152	103 (2)
O13i—Ba1—O1	67.83 (5)	N2—O21—H21	108 (3)
O12—Ba1—O1	73.76 (5)	N6—O61—H61	102 (3)
O12i—Ba1—O1	109.55 (5)	C2—N2—O21	118.06 (19)
O1i—Ba1—O1	176.25 (8)	C6—N6—O61	118.25 (19)
O13—Ba1—O11i	85.23 (6)	C6—N6—Ba1	121.19 (14)
O13i—Ba1—O11i	73.27 (6)	O61—N6—Ba1	118.58 (13)
O12—Ba1—O11i	136.29 (6)	O1—C1—C2	122.60 (19)
O12i—Ba1—O11i	135.85 (5)	O1—C1—C6	121.73 (19)
O1i—Ba1—O11i	62.92 (5)	C2—C1—C6	115.65 (18)
O1—Ba1—O11i	113.53 (5)	N2—C2—C1	113.59 (19)
O13—Ba1—O11	73.27 (6)	N2—C2—C3	125.6 (2)
O13i—Ba1—O11	85.23 (6)	C1—C2—C3	120.79 (19)
O12—Ba1—O11	135.85 (5)	O3—C3—C4	123.2 (2)
O12i—Ba1—O11	136.29 (5)	O3—C3—C4	123.2 (2)
O1i—Ba1—O11	113.53 (5)	O3—C3—C2	116.23 (19)
O1—Ba1—O11	62.92 (5)	O3—C3—C2	116.23 (19)
O11i—Ba1—O11	62.11 (7)	C4—C3—C2	120.62 (19)
O13—Ba1—N6	67.33 (6)	C3—C4—C5	121.15 (19)
O13i—Ba1—N6	120.54 (6)	C3—C4—C7	120.2 (2)
O12—Ba1—N6	84.66 (6)	C5—C4—C7	118.7 (2)
O12i—Ba1—N6	67.46 (6)	O5—C5—C4	122.6 (2)
O1i—Ba1—N6	127.95 (5)	O5—C5—C4	122.6 (2)
O1—Ba1—N6	53.38 (5)	O5—C5—C6	116.8 (2)
O11i—Ba1—N6	135.75 (6)	O5—C5—C6	116.8 (2)
O11—Ba1—N6	76.65 (6)	C4—C5—C6	120.64 (19)
O13—Ba1—N6i	120.54 (6)	N6—C6—C5	125.2 (2)
O13i—Ba1—N6i	67.33 (6)	N6—C6—C1	113.97 (19)
O12—Ba1—N6i	67.46 (6)	C5—C6—C1	120.87 (19)
O12i—Ba1—N6i	84.66 (6)	C4—C7—H71	109.5
O1i—Ba1—N6i	53.38 (5)	C4—C7—H72	109.5
O1—Ba1—N6i	127.96 (5)	H71—C7—H72	109.5
O11i—Ba1—N6i	76.65 (6)	C4—C7—H73	109.5
O11—Ba1—N6i	135.76 (6)	H71—C7—H73	109.5
N6—Ba1—N6i	147.08 (8)	H72—C7—H73	109.5
C1—O1—Ba1	126.33 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O3	0.86 (3)	1.70 (3)	2.476 (3)	150 (4)
O61—H61···O5	0.86 (3)	1.64 (3)	2.469 (2)	160 (4)
O11—H111···O3ii	0.85 (1)	1.99 (1)	2.827 (2)	167 (4)
O11—H112···O12iii	0.84 (1)	2.15 (3)	2.854 (3)	142 (4)
O12—H121···O14i	0.84 (1)	1.90 (1)	2.739 (3)	172 (4)
O12—H122···O11iv	0.84 (1)	2.17 (3)	2.839 (3)	137 (3)
O13—H131···O14	0.85 (1)	2.13 (1)	2.957 (3)	165 (4)
O13—H132···O15v	0.85 (1)	1.93 (1)	2.766 (3)	169 (4)
O14—H141···O13vi	0.85 (1)	1.99 (1)	2.835 (3)	173 (4)
O15—H151···O5vii	0.85 (1)	1.94 (1)	2.789 (3)	177 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O21—H21⋯O3	0.86 (3)	1.70 (3)	2.476 (3)	150 (4)
O61—H61⋯O5	0.86 (3)	1.64 (3)	2.469 (2)	160 (4)
O11—H111⋯O3i	0.85 (1)	1.99 (1)	2.827 (2)	167 (4)
O11—H112⋯O12ii	0.84 (1)	2.15 (3)	2.854 (3)	142 (4)
O12—H121⋯O14iii	0.84 (1)	1.90 (1)	2.739 (3)	172 (4)
O12—H122⋯O11iv	0.84 (1)	2.17 (3)	2.839 (3)	137 (3)
O13—H131⋯O14	0.85 (1)	2.13 (1)	2.957 (3)	165 (4)
O13—H132⋯O15v	0.85 (1)	1.93 (1)	2.766 (3)	169 (4)
O14—H141⋯O13vi	0.85 (1)	1.99 (1)	2.835 (3)	173 (4)
O15—H151⋯O5vii	0.85 (1)	1.94 (1)	2.789 (3)	177 (4)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .