Poly[[μ₂-aqua-aqua­(μ₃-3,5-dinitro­salicylato)barium(II)] monohydrate]

In the title coordination polymer, {[Ba(C₇H₂N₂O₇)(H₂O)₂]·H₂O}_n, the Ba^II atom is ten-coordinated by seven O atoms from four 3,5-dinitro­salicylatate ligands, two μ₂-bridging aqua ligands and one water mol­ecule. The coordination mode is best described as a bicapped square-anti­prismatic geometry. The 3,5-dinitrosalicylatate ligands bridge three Ba atoms. Centrosymmetrically related dinuclear barium units, with a Ba...Ba separation of 4.767 (5) Å, form infinite chains, which are further self-assembled into a supra­molecular network through inter­molecular O—H...O hydrogen-bonding inter­actions between O atoms of 3,5-dinitro­salicylatate ligands and water mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.026
• wR factor = 0.068
• Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O2W    -   H3W    ...          ?

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.75 Ratio
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4W    ..  N1      ..       2.69 Ang.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.35 Ratio

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the structural investigation of 3,5-dinitrosalicylatato complexes, it has been found that the 3,5-dinitrosalicylatato moiety functions as a multidentate ligand (Song et al., 2007) with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound, (I), a new Ba complex obtained by the reaction of 3,5-dinitrosalicylic acid and barium chloride in alkaline aqueous solution.

As illustrated in Figure 1, the Ba^II atom displays a bicapped square antiprismatic coordination environment, defined by seven O atoms from four 3,5-dinitrosalicylatato ligands, two µ₂-bridging aqua ligands and one water molecule. The 3,5-dinitrosalicylatato ligands link barium ions to form infinite chains, which are further self-assembled into a supramolecular network through intermolecular O—H···O hydrogen bonding interactions (Table 1) involving the uncoordinating water molecules, coordinating water molecules as donors and O atoms of 3,5-dinitrosalicylatato ligands as acceptors (Fig. 2).

Related literature

For related literature, see: Song et al. (2007).

S2. Experimental

A mixture of barium chloride (1 mmol), 3,5-dinitrosalicylic acid (1 mmol), NaOH (1.5 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The obtained crystals obtained were washed with water and dryed in air.

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, and with U_iso(H) = 1.2 U_eq(C). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.84 Å and H···H = 1.39 Å, each within a standard deviation of 0.01 Å, and with U_iso(H) = 1.5 U_eq(O)

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids.
	Fig. 2. A packing view of the title compound. The intermolecluar hydrogen bonds are shown as dashed lines.

Poly[[µ₂-aqua-aqua(µ₃-3,5-dinitrosalicylato)barium(II)] monohydrate]

Crystal data

[Ba(C7H2N2O7)(H2O)2]·H2O	F(000) = 800
Mr = 417.49	Dx = 2.246 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5837 reflections
a = 11.9649 (6) Å	θ = 2.8–27.9°
b = 4.1866 (2) Å	µ = 3.27 mm^−1
c = 26.121 (1) Å	T = 296 K
β = 109.332 (3)°	Block, yellow
V = 1234.7 (1) Å^3	0.30 × 0.26 × 0.23 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	2374 independent reflections
Radiation source: fine-focus sealed tube	2189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ϕ and ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.392, Tmax = 0.472	k = −4→4
8615 measured reflections	l = −31→32

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 1.4739P] where P = (Fo^2 + 2Fc^2)/3
2374 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 1.03 e Å^−3
9 restraints	Δρmin = −1.30 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
Ba1	0.698106 (16)	0.59849 (4)	0.002749 (8)	0.01250 (10)
O1	0.7177 (2)	0.1028 (5)	0.06998 (10)	0.0150 (5)
O2	0.5320 (2)	−0.3574 (6)	0.05297 (11)	0.0211 (6)
O3	0.4012 (2)	−0.0694 (6)	0.07602 (11)	0.0190 (6)
O4	0.5934 (3)	0.0066 (8)	0.28282 (12)	0.0311 (7)
O5	0.7491 (3)	0.3054 (8)	0.31157 (12)	0.0359 (7)
O6	0.9954 (3)	0.3764 (8)	0.19294 (14)	0.0416 (9)
O7	0.8915 (2)	0.5460 (7)	0.11347 (12)	0.0251 (6)
N1	0.6755 (3)	0.1544 (8)	0.27501 (14)	0.0245 (7)
N2	0.9007 (3)	0.4015 (7)	0.15565 (14)	0.0205 (7)
C1	0.5067 (3)	−0.1530 (8)	0.08248 (14)	0.0116 (7)
C2	0.6052 (3)	−0.0051 (9)	0.12815 (14)	0.0129 (7)
C3	0.5950 (3)	0.0128 (9)	0.17862 (15)	0.0167 (7)
H3	0.5270	−0.0629	0.1844	0.020*
C4	0.6874 (3)	0.1461 (9)	0.22201 (15)	0.0178 (8)
C5	0.7878 (3)	0.2691 (9)	0.21433 (15)	0.0191 (8)
H5	0.8488	0.3552	0.2431	0.023*
C6	0.7951 (3)	0.2603 (9)	0.16271 (14)	0.0158 (7)
C7	0.7074 (3)	0.1200 (8)	0.11687 (15)	0.0146 (8)
O1W	0.8608 (2)	0.1295 (6)	0.00092 (12)	0.0205 (6)
H2W	0.922 (2)	0.101 (10)	0.0272 (9)	0.031*
H1W	0.881 (3)	0.137 (10)	−0.0265 (9)	0.031*
O2W	0.7483 (2)	0.6467 (6)	−0.09980 (12)	0.0223 (6)
H3W	0.688 (2)	0.758 (8)	−0.1068 (17)	0.033*
H4W	0.732 (3)	0.484 (6)	−0.1189 (16)	0.033*
O3W	0.0565 (2)	0.9715 (8)	0.08622 (12)	0.0255 (6)
H5W	0.110 (3)	1.093 (8)	0.1033 (15)	0.038*
H6W	0.047 (4)	0.837 (8)	0.1074 (13)	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01402 (13)	0.01055 (14)	0.01455 (15)	−0.00009 (7)	0.00690 (10)	−0.00038 (8)
O1	0.0191 (13)	0.0156 (14)	0.0133 (13)	−0.0010 (9)	0.0091 (11)	−0.0007 (10)
O2	0.0199 (13)	0.0222 (15)	0.0235 (15)	−0.0031 (10)	0.0105 (12)	−0.0089 (11)
O3	0.0142 (12)	0.0185 (15)	0.0238 (15)	0.0005 (10)	0.0055 (11)	−0.0015 (11)
O4	0.0331 (16)	0.0413 (17)	0.0244 (16)	−0.0037 (14)	0.0167 (13)	0.0019 (15)
O5	0.0411 (18)	0.0464 (19)	0.0186 (16)	−0.0102 (15)	0.0077 (14)	−0.0100 (15)
O6	0.0227 (16)	0.066 (3)	0.033 (2)	−0.0138 (14)	0.0056 (15)	0.0021 (16)
O7	0.0248 (14)	0.0226 (15)	0.0300 (17)	−0.0044 (11)	0.0117 (12)	0.0052 (13)
N1	0.0296 (18)	0.0263 (18)	0.0184 (18)	0.0037 (14)	0.0089 (15)	−0.0003 (14)
N2	0.0151 (15)	0.0223 (19)	0.0230 (19)	−0.0046 (12)	0.0049 (14)	−0.0040 (14)
C1	0.0132 (16)	0.0130 (18)	0.0082 (17)	−0.0010 (13)	0.0030 (14)	0.0023 (13)
C2	0.0163 (16)	0.0102 (17)	0.0128 (18)	0.0025 (14)	0.0056 (14)	0.0018 (14)
C3	0.0178 (17)	0.0153 (18)	0.0178 (19)	0.0006 (15)	0.0071 (15)	0.0015 (16)
C4	0.0214 (18)	0.021 (2)	0.0116 (18)	0.0022 (14)	0.0060 (15)	−0.0015 (15)
C5	0.0190 (17)	0.018 (2)	0.0166 (19)	−0.0003 (15)	0.0013 (15)	−0.0030 (16)
C6	0.0129 (16)	0.016 (2)	0.0181 (19)	−0.0012 (14)	0.0042 (14)	−0.0002 (15)
C7	0.0184 (18)	0.0121 (19)	0.0146 (19)	0.0044 (13)	0.0074 (15)	0.0040 (13)
O1W	0.0156 (13)	0.0291 (16)	0.0186 (15)	0.0036 (10)	0.0079 (11)	0.0005 (12)
O2W	0.0290 (15)	0.0188 (15)	0.0222 (15)	0.0010 (11)	0.0126 (13)	−0.0019 (11)
O3W	0.0206 (14)	0.0334 (17)	0.0235 (16)	−0.0020 (12)	0.0086 (12)	0.0046 (13)

Geometric parameters (Å, º)

Ba1—O1	2.678 (2)	O5—N1	1.237 (4)
Ba1—O1^i	2.706 (2)	O6—N2	1.230 (5)
Ba1—O2^i	2.726 (3)	O7—N2	1.230 (4)
Ba1—O1W	2.777 (3)	N1—C4	1.438 (5)
Ba1—O3^ii	2.813 (3)	N2—C6	1.462 (4)
Ba1—O2^iii	2.840 (3)	C1—C2	1.505 (5)
Ba1—O2W	2.940 (3)	C1—Ba1^iii	3.290 (3)
Ba1—O1W^i	2.966 (3)	C2—C3	1.366 (5)
Ba1—O3^iii	2.989 (3)	C2—C7	1.447 (5)
Ba1—O7	3.056 (3)	C3—C4	1.410 (5)
Ba1—C1^iii	3.290 (3)	C3—H3	0.9300
Ba1—Ba1^i	4.1866 (2)	C4—C5	1.382 (5)
Ba1—H3W	2.90 (5)	C5—C6	1.380 (5)
O1—C7	1.273 (4)	C5—H5	0.9300
O1—Ba1^iv	2.706 (2)	C6—C7	1.431 (5)
O2—C1	1.254 (4)	O1W—Ba1^iv	2.966 (3)
O2—Ba1^iv	2.726 (3)	O1W—H2W	0.83 (4)
O2—Ba1^iii	2.840 (3)	O1W—H1W	0.83 (4)
O3—C1	1.266 (4)	O2W—H3W	0.83 (4)
O3—Ba1^ii	2.813 (3)	O2W—H4W	0.83 (4)
O3—Ba1^iii	2.989 (3)	O3W—H5W	0.82 (4)
O4—N1	1.233 (4)	O3W—H6W	0.83 (4)
O1—Ba1—O1^i	102.07 (8)	O7—Ba1—Ba1^i	94.12 (5)
O1—Ba1—O2^i	69.92 (8)	C1^iii—Ba1—Ba1^i	124.53 (6)
O1^i—Ba1—O2^i	63.59 (7)	O1—Ba1—H3W	142.3 (6)
O1—Ba1—O1W	63.49 (7)	O1^i—Ba1—H3W	115.3 (6)
O1^i—Ba1—O1W	130.70 (8)	O2^i—Ba1—H3W	131.3 (3)
O2^i—Ba1—O1W	133.10 (8)	O1W—Ba1—H3W	86.9 (3)
O1—Ba1—O3^ii	161.23 (8)	O3^ii—Ba1—H3W	41.2 (3)
O1^i—Ba1—O3^ii	81.53 (7)	O2^iii—Ba1—H3W	81.9 (7)
O2^i—Ba1—O3^ii	96.08 (8)	O2W—Ba1—H3W	16.3 (6)
O1W—Ba1—O3^ii	127.72 (8)	O1W^i—Ba1—H3W	68.0 (7)
O1—Ba1—O2^iii	85.43 (8)	O3^iii—Ba1—H3W	67.3 (7)
O1^i—Ba1—O2^iii	118.10 (7)	O7—Ba1—H3W	136.2 (6)
O2^i—Ba1—O2^iii	62.17 (9)	C1^iii—Ba1—H3W	71.6 (7)
O1W—Ba1—O2^iii	107.83 (7)	Ba1^i—Ba1—H3W	76.7 (6)
O3^ii—Ba1—O2^iii	76.78 (8)	C7—O1—Ba1	124.9 (2)
O1—Ba1—O2W	130.60 (7)	C7—O1—Ba1^iv	130.8 (2)
O1^i—Ba1—O2W	122.52 (7)	Ba1—O1—Ba1^iv	102.07 (8)
O2^i—Ba1—O2W	146.64 (8)	C1—O2—Ba1^iv	134.8 (2)
O1W—Ba1—O2W	71.15 (8)	C1—O2—Ba1^iii	99.6 (2)
O3^ii—Ba1—O2W	56.60 (7)	Ba1^iv—O2—Ba1^iii	117.83 (9)
O2^iii—Ba1—O2W	90.76 (8)	C1—O3—Ba1^ii	116.9 (2)
O1—Ba1—O1W^i	132.52 (7)	C1—O3—Ba1^iii	92.2 (2)
O1^i—Ba1—O1W^i	60.61 (7)	Ba1^ii—O3—Ba1^iii	92.33 (8)
O2^i—Ba1—O1W^i	122.95 (7)	N2—O7—Ba1	134.3 (2)
O1W—Ba1—O1W^i	93.55 (7)	O4—N1—O5	122.1 (3)
O3^ii—Ba1—O1W^i	65.38 (7)	O4—N1—C4	119.0 (3)
O2^iii—Ba1—O1W^i	142.04 (8)	O5—N1—C4	118.9 (3)
O2W—Ba1—O1W^i	66.46 (8)	O7—N2—O6	122.5 (3)
O1—Ba1—O3^iii	78.80 (7)	O7—N2—C6	119.2 (3)
O1^i—Ba1—O3^iii	162.60 (7)	O6—N2—C6	118.3 (3)
O2^i—Ba1—O3^iii	101.22 (7)	O2—C1—O3	122.7 (3)
O1W—Ba1—O3^iii	65.50 (7)	O2—C1—C2	118.9 (3)
O3^ii—Ba1—O3^iii	92.33 (8)	O3—C1—C2	118.5 (3)
O2^iii—Ba1—O3^iii	44.50 (7)	O2—C1—Ba1^iii	58.32 (18)
O2W—Ba1—O3^iii	65.05 (7)	O3—C1—Ba1^iii	65.18 (18)
O1W^i—Ba1—O3^iii	131.14 (7)	C2—C1—Ba1^iii	169.1 (2)
O1—Ba1—O7	56.58 (7)	C3—C2—C7	121.9 (3)
O1^i—Ba1—O7	64.28 (8)	C3—C2—C1	119.4 (3)
O2^i—Ba1—O7	89.64 (8)	C7—C2—C1	118.7 (3)
O1W—Ba1—O7	69.50 (8)	C2—C3—C4	120.0 (3)
O3^ii—Ba1—O7	138.31 (7)	C2—C3—H3	120.0
O2^iii—Ba1—O7	139.60 (8)	C4—C3—H3	120.0
O2W—Ba1—O7	123.25 (7)	C5—C4—C3	121.3 (3)
O1W^i—Ba1—O7	76.92 (7)	C5—C4—N1	119.9 (3)
O3^iii—Ba1—O7	127.03 (7)	C3—C4—N1	118.8 (3)
O1—Ba1—C1^iii	83.60 (8)	C6—C5—C4	118.1 (3)
O1^i—Ba1—C1^iii	140.04 (8)	C6—C5—H5	121.0
O2^i—Ba1—C1^iii	82.29 (8)	C4—C5—H5	121.0
O1W—Ba1—C1^iii	87.53 (8)	C5—C6—C7	124.2 (3)
O3^ii—Ba1—C1^iii	82.12 (8)	C5—C6—N2	116.7 (3)
O2^iii—Ba1—C1^iii	22.07 (8)	C7—C6—N2	119.1 (3)
O2W—Ba1—C1^iii	75.72 (8)	O1—C7—C6	123.4 (3)
O1W^i—Ba1—C1^iii	139.44 (8)	O1—C7—C2	122.2 (3)
O3^iii—Ba1—C1^iii	22.61 (8)	C6—C7—C2	114.4 (3)
O7—Ba1—C1^iii	139.53 (8)	Ba1—O1W—Ba1^iv	93.55 (7)
O1—Ba1—Ba1^i	140.79 (5)	Ba1—O1W—H2W	121 (3)
O1^i—Ba1—Ba1^i	38.72 (5)	Ba1^iv—O1W—H2W	107 (3)
O2^i—Ba1—Ba1^i	86.11 (5)	Ba1—O1W—H1W	113 (3)
O1W—Ba1—Ba1^i	135.00 (5)	Ba1^iv—O1W—H1W	115 (3)
O3^ii—Ba1—Ba1^i	45.50 (5)	H2W—O1W—H1W	106.4 (17)
O2^iii—Ba1—Ba1^i	110.82 (5)	Ba1—O2W—H3W	79 (3)
O2W—Ba1—Ba1^i	86.06 (5)	Ba1—O2W—H4W	114 (4)
O1W^i—Ba1—Ba1^i	41.45 (5)	H3W—O2W—H4W	108 (4)
O3^iii—Ba1—Ba1^i	137.83 (5)	H5W—O3W—H6W	108 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H6W···O7^v	0.82 (3)	2.27 (3)	2.916 (4)	135 (4)
O3W—H5W···O5^vi	0.82 (4)	2.60 (4)	2.985 (4)	110 (3)
O3W—H5W···O2W^vii	0.82 (4)	2.04 (3)	2.755 (4)	145 (4)
O2W—H4W···N1^viii	0.83 (3)	2.69 (4)	3.340 (4)	137 (4)
O2W—H4W···O4^viii	0.83 (3)	2.55 (4)	3.080 (4)	123 (3)
O2W—H4W···O5^viii	0.83 (3)	2.25 (3)	2.993 (4)	150 (5)
O2W—H3W···O3^ii	0.83 (3)	2.01 (2)	2.730 (4)	145 (4)
O1W—H1W···O3W^ii	0.83 (3)	1.99 (2)	2.798 (4)	164 (4)
O1W—H2W···O3W^ix	0.83 (3)	1.90 (3)	2.725 (4)	171 (4)

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