A novel inorganic-organic hybrid borate, poly{[Na(2)(C(4)H(2)O(4))(H(3)BO(3))(H(2)O)(4)]·H(3)BO(3)}.

The structure of the title compound, catena-poly[[[di-μ-aqua-μ-fumarato-μ-(boric acid)-disodium]-di-μ-aqua] boric acid monosolvate], contains two crystallographically independent Na(+) cations, each being six-coordinated by one fumarate O atom, one boric acid O atom and four water O atoms in a distorted octa-hedral geometry. Adjacent [NaO(2)(OH(2))(4)] units share edges and are linked into chains propagating parallel to [100]. The free boric acid mol-ecules are connected to the chains through strong inter-molecular O-H⋯O hydrogen bonds. Additional O-H⋯O hydrogen bonds between the water mol-ecules, the free and coordinated boric acid mol-ecules and the fumarate anion lead to the formation of a three-dimensional supra-molecular structure. With the exception of the two water mol-ecules, all other atoms lie on mirror planes.

Related literature

For the synthesis of organic ammonium borates, see: Li et al. (2006 ▶); Wang et al. (2004 ▶); Liu et al. (2008 ▶). For the synthesis of metal borates with neutral amines, see: Sung et al. (2000 ▶); Zhang et al. (2004 ▶); Liu et al. (2006 ▶); Wang et al. (2005 ▶). For borates involving organic acids, see: Tombul et al. (2007 ▶); Wu et al. (2009 ▶). For typical Na—O bond lengths, see: Yi et al. (2005 ▶); Huang et al. (2005 ▶); for B—O bond lengths, see: Li et al. (1999 ▶); Andrews et al. (1983 ▶); Roy et al. (2002 ▶).

Experimental

Crystal data

[Na2(C4H2O4)(H3BO3)(H2O)4]·H3BO3

M = 355.77

Orthorhombic,

a = 14.116 (3) Å

b = 6.9347 (14) Å

c = 14.997 (3) Å

V = 1468.1 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 295 K

0.39 × 0.26 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.924, T max = 0.950

13772 measured reflections

1806 independent reflections

1460 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.103

S = 1.10

1806 reflections

127 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.23 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg & Putz, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810041358/wm2409sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041358/wm2409Isup2.hkl

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

[Na2(C4H2O4)(H3BO3)(H2O)4]·H3BO3	F(000) = 736
Mr = 355.77	Dx = 1.610 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 10305 reflections
a = 14.116 (3) Å	θ = 3.1–27.4°
b = 6.9347 (14) Å	µ = 0.21 mm−1
c = 14.997 (3) Å	T = 295 K
V = 1468.1 (5) Å3	Block, colorless
Z = 4	0.39 × 0.26 × 0.25 mm

Rigaku R-AXIS RAPID diffractometer	1806 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
graphite	Rint = 0.023
ω scans	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −18→18
Tmin = 0.924, Tmax = 0.950	k = −8→8
13772 measured reflections	l = −19→19

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0595P)2 + 0.2607P] where P = (Fo2 + 2Fc2)/3
1806 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.23 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
Na1	0.62506 (5)	0.2500	0.69475 (5)	0.0291 (2)
Na2	0.37214 (5)	0.2500	0.74696 (5)	0.0329 (2)
B1	0.54673 (15)	0.2500	0.91475 (15)	0.0306 (5)
B2	0.34246 (15)	0.2500	1.10354 (14)	0.0272 (4)
C1	0.58145 (12)	0.2500	0.48138 (12)	0.0239 (4)
C2	0.48259 (12)	0.2500	0.51652 (12)	0.0285 (4)
H2A	0.4753	0.2500	0.5795	0.034*
C3	0.40513 (13)	0.2500	0.46889 (13)	0.0315 (4)
H3A	0.4111	0.2500	0.4058	0.038*
C4	0.30740 (12)	0.2500	0.50783 (13)	0.0269 (4)
O1	0.64692 (9)	0.2500	0.53758 (9)	0.0352 (4)
O2	0.59437 (9)	0.2500	0.39758 (8)	0.0287 (3)
O3	0.24072 (9)	0.2500	0.45118 (9)	0.0367 (4)
O4	0.29720 (9)	0.2500	0.59059 (9)	0.0374 (4)
O5	0.61770 (9)	0.2500	0.85300 (10)	0.0401 (4)
H5A	0.6759	0.2500	0.8732	0.050*
O6	0.45594 (10)	0.2500	0.88318 (10)	0.0481 (5)
H6A	0.4145	0.2500	0.9289	0.050*
O7	0.56202 (8)	0.2500	1.00406 (9)	0.0402 (4)
H7A	0.6218	0.2500	1.0174	0.050*
O8	0.32662 (9)	0.2500	1.01491 (10)	0.0423 (4)
H8A	0.2683	0.2500	0.9977	0.050*
O9	0.27009 (9)	0.2500	1.16470 (9)	0.0315 (3)
H9A	0.2178	0.2500	1.1379	0.047*
O10	0.43302 (9)	0.2500	1.13675 (9)	0.0366 (4)
H10A	0.4719	0.2500	1.0943	0.055*
O11	0.49721 (7)	0.01436 (15)	0.71463 (6)	0.0354 (3)
H11B	0.4694	−0.0581	0.6800	0.050*
H11A	0.5038	−0.0341	0.7696	0.050*
O12	0.75426 (7)	0.02208 (15)	0.69870 (6)	0.0358 (3)
H12B	0.7608	−0.0362	0.6419	0.050*
H12A	0.7415	−0.0522	0.7374	0.050*

	U11	U22	U33	U12	U13	U23
Na1	0.0239 (4)	0.0398 (4)	0.0238 (4)	0.000	−0.0013 (3)	0.000
Na2	0.0238 (4)	0.0429 (5)	0.0321 (5)	0.000	−0.0002 (3)	0.000
B1	0.0218 (10)	0.0481 (13)	0.0219 (10)	0.000	−0.0013 (8)	0.000
B2	0.0218 (9)	0.0366 (11)	0.0231 (10)	0.000	−0.0009 (8)	0.000
C1	0.0207 (8)	0.0298 (9)	0.0211 (8)	0.000	−0.0003 (6)	0.000
C2	0.0206 (8)	0.0431 (10)	0.0218 (9)	0.000	0.0024 (7)	0.000
C3	0.0213 (8)	0.0503 (12)	0.0230 (9)	0.000	0.0040 (7)	0.000
C4	0.0175 (8)	0.0367 (10)	0.0266 (9)	0.000	0.0022 (7)	0.000
O1	0.0185 (6)	0.0632 (10)	0.0239 (7)	0.000	−0.0020 (5)	0.000
O2	0.0210 (6)	0.0441 (8)	0.0210 (6)	0.000	−0.0005 (5)	0.000
O3	0.0186 (6)	0.0645 (10)	0.0270 (7)	0.000	0.0007 (5)	0.000
O4	0.0231 (7)	0.0661 (10)	0.0231 (7)	0.000	0.0019 (5)	0.000
O5	0.0186 (6)	0.0795 (11)	0.0223 (7)	0.000	−0.0008 (5)	0.000
O6	0.0194 (7)	0.1019 (14)	0.0229 (7)	0.000	−0.0010 (5)	0.000
O7	0.0175 (6)	0.0822 (12)	0.0208 (7)	0.000	−0.0013 (5)	0.000
O8	0.0172 (6)	0.0852 (11)	0.0243 (7)	0.000	−0.0002 (5)	0.000
O9	0.0206 (6)	0.0504 (8)	0.0235 (7)	0.000	−0.0002 (5)	0.000
O10	0.0206 (6)	0.0642 (10)	0.0248 (7)	0.000	−0.0012 (5)	0.000
O11	0.0378 (5)	0.0379 (5)	0.0303 (5)	−0.0042 (4)	−0.0043 (4)	−0.0039 (4)
O12	0.0384 (5)	0.0371 (5)	0.0318 (5)	−0.0006 (4)	0.0005 (4)	0.0004 (4)

Na1—O5	2.3756 (17)	C1—O1	1.251 (2)
Na1—O1	2.3771 (17)	C1—O2	1.270 (2)
Na1—O12i	2.4140 (12)	C1—C2	1.492 (2)
Na1—O12	2.4140 (12)	C2—C3	1.306 (3)
Na1—O11	2.4529 (12)	C2—H2A	0.9500
Na1—O11i	2.4529 (12)	C3—C4	1.498 (2)
Na1—Na2ii	3.5955 (12)	C3—H3A	0.9500
Na1—Na2	3.6552 (12)	C4—O4	1.250 (2)
Na2—O6	2.3606 (16)	C4—O3	1.268 (2)
Na2—O12iii	2.4353 (12)	O5—H5A	0.8756
Na2—O12iv	2.4353 (12)	O6—H6A	0.9013
Na2—O11i	2.4541 (12)	O7—H7A	0.8673
Na2—O11	2.4541 (12)	O8—H8A	0.8627
Na2—O4	2.5727 (17)	O9—H9A	0.8400
Na2—Na1iii	3.5955 (12)	O10—H10A	0.8400
B1—O7	1.357 (3)	O11—H11B	0.8224
B1—O5	1.364 (3)	O11—H11A	0.8951
B1—O6	1.366 (3)	O12—Na2ii	2.4353 (12)
B2—O8	1.348 (3)	O12—H12B	0.9473
B2—O10	1.372 (2)	O12—H12A	0.7967
B2—O9	1.373 (2)
O5—Na1—O1	175.05 (6)	O1—C1—O2	124.12 (17)
O5—Na1—O12i	90.49 (4)	O1—C1—C2	116.94 (17)
O1—Na1—O12i	85.77 (4)	O2—C1—C2	118.94 (16)
O5—Na1—O12	90.49 (4)	C3—C2—C1	126.15 (18)
O1—Na1—O12	85.77 (4)	C3—C2—H2A	116.9
O12i—Na1—O12	81.80 (5)	C1—C2—H2A	116.9
O5—Na1—O11	81.16 (4)	C2—C3—C4	123.90 (18)
O1—Na1—O11	102.48 (4)	C2—C3—H3A	118.1
O12i—Na1—O11	171.52 (5)	C4—C3—H3A	118.1
O12—Na1—O11	96.70 (4)	O4—C4—O3	125.46 (16)
O5—Na1—O11i	81.16 (4)	O4—C4—C3	119.56 (16)
O1—Na1—O11i	102.48 (4)	O3—C4—C3	114.98 (16)
O12i—Na1—O11i	96.70 (4)	C1—O1—Na1	124.91 (12)
O12—Na1—O11i	171.52 (5)	C4—O4—Na2	149.11 (12)
O11—Na1—O11i	83.55 (5)	B1—O5—Na1	135.26 (12)
O6—Na2—O12iii	93.03 (4)	B1—O5—H5A	117.0
O6—Na2—O12iv	93.03 (4)	Na1—O5—H5A	107.7
O12iii—Na2—O12iv	80.93 (5)	B1—O6—Na2	140.35 (13)
O6—Na2—O11i	79.08 (4)	B1—O6—H6A	110.2
O12iii—Na2—O11i	171.82 (5)	Na2—O6—H6A	109.5
O12iv—Na2—O11i	97.21 (4)	B1—O7—H7A	112.5
O6—Na2—O11	79.08 (4)	B2—O8—H8A	117.0
O12iii—Na2—O11	97.21 (4)	B2—O9—H9A	109.5
O12iv—Na2—O11	171.82 (5)	B2—O10—H10A	109.5
O11i—Na2—O11	83.50 (5)	Na1—O11—Na2	96.30 (4)
O6—Na2—O4	174.20 (6)	Na1—O11—H11B	133.0
O12iii—Na2—O4	91.38 (4)	Na2—O11—H11B	100.9
O12iv—Na2—O4	91.38 (4)	Na1—O11—H11A	106.6
O11i—Na2—O4	96.64 (4)	Na2—O11—H11A	98.2
O11—Na2—O4	96.64 (4)	H11B—O11—H11A	113.7
O7—B1—O5	123.60 (18)	Na1—O12—Na2ii	95.71 (4)
O7—B1—O6	119.43 (18)	Na1—O12—H12B	109.3
O5—B1—O6	116.97 (18)	Na2ii—O12—H12B	120.7
O8—B2—O10	120.84 (18)	Na1—O12—H12A	105.7
O8—B2—O9	122.36 (17)	Na2ii—O12—H12A	109.3
O10—B2—O9	116.80 (17)	H12B—O12—H12A	113.7

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O8	0.90	1.79	2.690 (2)	177
O10—H10A···O7	0.84	1.86	2.6973 (19)	178
O5—H5A···O4ii	0.88	1.80	2.6713 (19)	177
O7—H7A···O3ii	0.87	1.74	2.6104 (18)	178
O12—H12B···O3v	0.95	2.04	2.9355 (15)	157.8
O12—H12A···O9vi	0.80	2.02	2.8063 (14)	171.5
O11—H11B···O2v	0.82	1.98	2.8042 (14)	175.5
O11—H11A···O10vi	0.90	2.24	3.0494 (15)	150.5
O8—H8A···O1iii	0.86	1.79	2.6559 (19)	180
O9—H9A···O2iii	0.84	1.82	2.6504 (19)	168

Na1—O5	2.3756 (17)
Na1—O1	2.3771 (17)
Na1—O12	2.4140 (12)
Na1—O11	2.4529 (12)
Na2—O6	2.3606 (16)
Na2—O12i	2.4353 (12)
Na2—O11	2.4541 (12)
Na2—O4	2.5727 (17)
B1—O7	1.357 (3)
B1—O5	1.364 (3)
B1—O6	1.366 (3)
B2—O8	1.348 (3)
B2—O10	1.372 (2)
B2—O9	1.373 (2)

O7—B1—O5	123.60 (18)
O7—B1—O6	119.43 (18)
O5—B1—O6	116.97 (18)
O8—B2—O10	120.84 (18)
O8—B2—O9	122.36 (17)
O10—B2—O9	116.80 (17)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O8	0.90	1.79	2.690 (2)	177
O10—H10A⋯O7	0.84	1.86	2.6973 (19)	178
O5—H5A⋯O4ii	0.88	1.80	2.6713 (19)	177
O7—H7A⋯O3ii	0.87	1.74	2.6104 (18)	178
O12—H12B⋯O3iii	0.95	2.04	2.9355 (15)	157.8
O12—H12A⋯O9iv	0.80	2.02	2.8063 (14)	171.5
O11—H11B⋯O2iii	0.82	1.98	2.8042 (14)	175.5
O11—H11A⋯O10iv	0.90	2.24	3.0494 (15)	150.5
O8—H8A⋯O1i	0.86	1.79	2.6559 (19)	180
O9—H9A⋯O2i	0.84	1.82	2.6504 (19)	168

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .