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In the title compound, {[Na(H2O)4]2(C4H2N2O7)}n, the 1,5-dihydr­oxy-4,8,9-trioxa-2,6-diaza­bicyclo­[3.3.1]nona-2,6-diene-3,7-diolate anion lies across a twofold axis in the space group C2/c; there are two independent Na sites, one on a twofold axis and the other on a centre of inversion. Hydrogen bonds link the {[Na(H2O)4]+}n chains and diolate anions into a three-dimensional framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107001977/gd3082sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107001977/gd3082Isup2.hkl
Contains datablock I

CCDC reference: 609931

Comment top

The synthesis of organic compounds from common inorganic materials has long attracted attention because of its potential significance in pharmacology, agriculture and chemical industry (Gleix, 1954; Achille et al., 1998). To our knowledge, however, there have been no reports of the formation of heterobicyclic compounds from a metal carbonate with ammonia in a single-step process. Recently, we have synthesized from sodium carbonate and aqueous ammonia by a hydrothermal method the novel heterocyclic title compound, (I), whose structure is reported here.

The title compound crystallizes in the centrosymmetric space group C2/c with two independent Na sites, one on a twofold axis and one on an inversion centre, and a C4H2N2O7- anion located across a twofold axis (Fig. 1). Both Na sites are six-coordinated by O atoms from water molecules, forming distorted octahedra with Na—O distances in the range 2.395 (3)–2.458 (3) Å, which are comparable to those observed in Na2CO3·H2O (Harper, 1968) and in Na2CO3·7H2O (Betzel et al., 1982). Neighbouring sodium octahedra share edges via two water molecules, forming infinite chains parallel to [001] (Fig. 1). Similar arrangements of hydrated sodium ions are found in Na2C4O4·3H2O (Ranganathan & Kulkarni, 2002) and in NaHC4O4·H2O (Petrova et al., 2006).

The C4H2N2O72- anion contains a novel heterocyclic skeleton. All the bond length are in their normal ranges. The C—O single-bond lengths (C1—O1, C1—O2, C2—O3, C2—O4 and C2—O1A; symmetry code A is defined in Fig. 1) are between 1.366 (5) and 1.495 (4) Å, while the C1N1 and C2—N1 bond lengths are 1.384 (4) Å and 1.507 (4) Å, respectively. The O2—C1—O1, O2—C1—N1 and O1—C1—N1 angles are close to 120°, while the O3—C2—O4 and O1A—C2—N1 angles are 111.8 (3) and 108.3 (3)°. In the C4H2N2O72- anion, atoms N1, O1, N1A and O1A constitute an equatorial plane with a mean deviation from the mean plane of 0.0781 Å. Atoms O3, O4 and C2 are displaced above the plane at distances of 1.7111, 1.6691 and 0.8775 Å, and atoms O2 and C1 atoms are below the plane at distances of 0.9588 and 0.3207 Å, respectively.

All the H atoms of hydroxyl and water molecules contribute to the formation of a hydrogen-bond network (Table 1), and O—H···O and O—H···N hydrogen bonds link the C4H2N2O72- anions and the {[Na(H2O)4]+}n chains into a three-dimensional framework (Fig. 2).

Related literature top

For related literature, see: Achille et al. (1998); Betzel et al. (1982); Gleix (1954); Harper (1968); Petrova et al. (2006); Ranganathan & Kulkarni (2002).

Experimental top

Anhydrous sodium carbonate (0.318 g) and 18% aqueous ammonia (0.6 ml) in a molar ratio of 3:5 were dissolved in water (5 ml) with stirring at room temperature for 10 min. The solution was then transferred into a 15 ml teflon-lined bomb and heated at 413 K for 4 days. Colourless crystals were obtained in 42% yield after cooling to room temperature. Analysis found: C 12.6, H 4.8, N 7.4%; calculated for C4H18N2Na2O15: C 12.6, H 4.8, N 7.4% [found and calc. are identical; please confirm]. IR (KBr, cm-1): 3442 (s), 1795 (w), 1254 (m), 1106 (m), 873 (w), 816 (w).

Refinement top

All H atoms were located in difference maps and then treated as riding atoms (O—H = 0.81–0.85 Å). The Uiso(H) values were refined freely. The highest residual peak is located 0.98 Å from O2, 1.77 Å from N1 and 1.98 Å from C1. Please check changes to text.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The crystal structure of (I), showing 35% probability displacement ellipsoids. [Symmetry codes: (A) -x + 1, y, -z + 3/2; (B) -x, y, -z + 3/2; (C) -x, -y, -z + 1; (D) x, -y, 1/2 + z.] Please check use of symmetry codes in cation.
[Figure 2] Fig. 2. The crystal packing of (I), viewed along the b axis. Hydrogen bonds are shown as dashed lines.
bis(tetraaquasodium) 1,5-dihydroxy-4,8,9-trioxa-2,6-diazabicyclo[3.3.1]nona-2,6-diene-3,7-diolate top
Crystal data top
[Na(H2O)4]2(C4H2N2O7)F(000) = 792
Mr = 380.18Dx = 1.680 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 986 reflections
a = 11.935 (7) Åθ = 2.8–24.3°
b = 10.709 (6) ŵ = 0.22 mm1
c = 12.277 (7) ÅT = 298 K
β = 106.634 (8)°Block, colourless
V = 1503.5 (16) Å30.33 × 0.25 × 0.18 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1333 independent reflections
Radiation source: fine-focus sealed tube1146 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1414
Tmin = 0.932, Tmax = 0.962k = 1212
3719 measured reflectionsl = 1411
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.225Only H-atom displacement parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.1475P)2 + 3.8784P]
where P = (Fo2 + 2Fc2)/3
1333 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.96 e Å3
27 restraintsΔρmin = 0.81 e Å3
Crystal data top
[Na(H2O)4]2(C4H2N2O7)V = 1503.5 (16) Å3
Mr = 380.18Z = 4
Monoclinic, C2/cMo Kα radiation
a = 11.935 (7) ŵ = 0.22 mm1
b = 10.709 (6) ÅT = 298 K
c = 12.277 (7) Å0.33 × 0.25 × 0.18 mm
β = 106.634 (8)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1333 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
1146 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.962Rint = 0.026
3719 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.06627 restraints
wR(F2) = 0.225Only H-atom displacement parameters refined
S = 1.08Δρmax = 0.96 e Å3
1333 reflectionsΔρmin = 0.81 e Å3
116 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
xyzUiso*/Ueq
C10.4017 (3)0.0430 (3)0.6078 (3)0.0314 (8)
C20.5853 (3)0.1549 (3)0.7149 (3)0.0298 (8)
N10.51954 (19)0.0657 (2)0.62411 (19)0.0144 (6)
Na10.00000.15330 (19)0.75000.0353 (6)
Na20.00000.00000.50000.0325 (6)
O10.34573 (19)0.0802 (2)0.68557 (18)0.0257 (6)
O20.3384 (2)0.0165 (2)0.5113 (2)0.0346 (7)
O30.50000.2326 (3)0.75000.0226 (7)
O40.6607 (2)0.2288 (2)0.66778 (19)0.0306 (7)
H40.72850.22970.70940.039 (11)*
O50.1230 (2)0.0005 (2)0.6959 (2)0.0336 (7)
H5A0.12350.07750.70270.072 (14)*
H5B0.19280.02210.70040.050 (10)*
O60.1230 (2)0.1540 (2)0.5516 (2)0.0343 (7)
H6A0.18660.12510.55000.078 (13)*
H6B0.12840.19620.49210.058 (10)*
O70.1173 (2)0.2949 (3)0.6725 (2)0.0409 (7)
H7A0.10810.27190.60390.062 (9)*
H7B0.11120.37330.67180.058 (10)*
O80.1194 (2)0.1646 (2)0.4620 (2)0.0384 (7)
H8A0.08430.19390.39990.051 (9)*
H8B0.18290.13330.46140.050 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0281 (18)0.0358 (18)0.0320 (19)0.0002 (14)0.0113 (15)0.0006 (14)
C20.0271 (18)0.0343 (18)0.0273 (18)0.0025 (13)0.0069 (14)0.0024 (13)
N10.0084 (12)0.0230 (12)0.0135 (12)0.0037 (9)0.0057 (9)0.0065 (9)
Na10.0346 (12)0.0408 (12)0.0334 (12)0.0000.0142 (9)0.000
Na20.0313 (12)0.0366 (12)0.0297 (12)0.0011 (8)0.0088 (9)0.0013 (8)
O10.0198 (12)0.0356 (13)0.0233 (12)0.0032 (9)0.0088 (9)0.0059 (9)
O20.0240 (14)0.0506 (16)0.0299 (14)0.0110 (10)0.0088 (11)0.0162 (11)
O30.0241 (17)0.0226 (16)0.0214 (15)0.0000.0068 (12)0.000
O40.0237 (13)0.0419 (14)0.0253 (12)0.0070 (10)0.0057 (10)0.0070 (10)
O50.0276 (15)0.0332 (15)0.0401 (16)0.0010 (10)0.0100 (12)0.0000 (10)
O60.0272 (13)0.0416 (15)0.0336 (14)0.0013 (10)0.0077 (11)0.0047 (11)
O70.0394 (16)0.0392 (15)0.0406 (16)0.0007 (11)0.0056 (12)0.0053 (11)
O80.0329 (15)0.0460 (16)0.0343 (14)0.0045 (11)0.0066 (11)0.0113 (12)
Geometric parameters (Å, º) top
C1—O21.366 (5)Na2—O8iii2.395 (3)
C1—O11.373 (4)Na2—O6iii2.410 (3)
C1—N11.384 (4)Na2—O62.410 (3)
C2—O41.438 (4)Na2—O52.433 (3)
C2—O31.472 (4)Na2—O5iii2.433 (3)
C2—O1i1.495 (4)O4—H40.82
C2—N11.507 (4)O5—H5A0.83
Na1—O52.422 (3)O5—H5B0.85
Na1—O5ii2.422 (3)O6—H6A0.81
Na1—O72.435 (3)O6—H6B0.85
Na1—O7ii2.435 (3)O7—H7A0.85
Na1—O6ii2.458 (3)O7—H7B0.84
Na1—O62.458 (3)O8—H8A0.82
Na2—O82.395 (3)O8—H8B0.83
O2—C1—O1118.7 (3)O6—Na2—O5iii91.02 (9)
O2—C1—N1119.7 (3)O5—Na2—O5iii180.0
O1—C1—N1121.7 (3)O8—Na2—Na1iii91.46 (8)
O4—C2—O3111.8 (3)O8iii—Na2—Na1iii88.54 (8)
O4—C2—O1i111.2 (2)O6iii—Na2—Na1iii44.91 (6)
O3—C2—O1i109.1 (2)O6—Na2—Na1iii135.09 (6)
O4—C2—N1107.8 (2)O5—Na2—Na1iii135.93 (6)
O3—C2—N1108.5 (2)O5iii—Na2—Na1iii44.07 (6)
O1i—C2—N1108.3 (3)O8—Na2—H5A102.3
C1—N1—C2120.8 (2)O8iii—Na2—H5A77.7
O5—Na1—O5ii94.31 (14)O6iii—Na2—H5A79.3
O5—Na1—O781.67 (10)O6—Na2—H5A100.7
O5ii—Na1—O7172.80 (10)O5—Na2—H5A18.2
O5—Na1—O7ii172.80 (10)O5iii—Na2—H5A161.8
O5ii—Na1—O7ii81.67 (10)Na1iii—Na2—H5A122.9
O7—Na1—O7ii102.94 (16)O8—Na2—H6B76.9
O5—Na1—O6ii92.10 (9)O8iii—Na2—H6B103.1
O5ii—Na1—O6ii88.12 (9)O6iii—Na2—H6B160.9
O7—Na1—O6ii97.95 (10)O6—Na2—H6B19.1
O7ii—Na1—O6ii81.84 (9)O5—Na2—H6B102.8
O5—Na1—O688.12 (9)O5iii—Na2—H6B77.2
O5ii—Na1—O692.10 (9)Na1iii—Na2—H6B120.0
O7—Na1—O681.84 (9)H5A—Na2—H6B117.1
O7ii—Na1—O697.95 (10)C1—O1—C2i117.5 (3)
O6ii—Na1—O6179.67 (14)C2—O3—C2i111.2 (3)
O5—Na1—Na2ii94.24 (8)C2—O4—H4111.9
O5ii—Na1—Na2ii44.32 (7)Na1—O5—Na291.61 (9)
O7—Na1—Na2ii141.59 (6)Na1—O5—H5A129.5
O7ii—Na1—Na2ii78.70 (8)Na2—O5—H5A95.0
O6ii—Na1—Na2ii43.80 (6)Na1—O5—H5B116.5
O6—Na1—Na2ii136.42 (8)Na2—O5—H5B111.4
O8—Na2—O8iii180.00 (13)H5A—O5—H5B107.3
O8—Na2—O6iii90.64 (10)Na2—O6—Na191.28 (9)
O8iii—Na2—O6iii89.36 (10)Na2—O6—H6A111.6
O8—Na2—O689.36 (10)Na1—O6—H6A108.1
O8iii—Na2—O690.64 (10)Na2—O6—H6B92.3
O6iii—Na2—O6180.00 (11)Na1—O6—H6B137.2
O8—Na2—O588.27 (9)H6A—O6—H6B110.0
O8iii—Na2—O591.73 (9)Na1—O7—H7A106.2
O6iii—Na2—O591.02 (9)Na1—O7—H7B124.5
O6—Na2—O588.98 (9)H7A—O7—H7B107.0
O8—Na2—O5iii91.73 (9)Na2—O8—H8A106.8
O8iii—Na2—O5iii88.27 (9)Na2—O8—H8B107.4
O6iii—Na2—O5iii88.98 (9)H8A—O8—H8B111.7
O2—C1—N1—C2166.3 (3)O8—Na2—O5—Na189.70 (11)
O1—C1—N1—C212.9 (5)O8iii—Na2—O5—Na190.30 (11)
O4—C2—N1—C1138.1 (3)O6—Na2—O5—Na10.31 (9)
O3—C2—N1—C116.8 (4)O6iii—Na2—O5—Na1179.69 (9)
O1i—C2—N1—C1101.5 (3)Na1iii—Na2—O5—Na1180.0
O2—C1—O1—C2i174.8 (3)O8—Na2—O6—Na188.58 (10)
N1—C1—O1—C2i4.4 (5)O8iii—Na2—O6—Na191.42 (10)
O4—C2—O3—C2i173.2 (3)O5—Na2—O6—Na10.31 (9)
O1i—C2—O3—C2i63.34 (19)O5iii—Na2—O6—Na1179.69 (9)
N1—C2—O3—C2i54.45 (18)Na1iii—Na2—O6—Na1180.0
O5ii—Na1—O5—Na291.66 (9)O5ii—Na1—O6—Na293.94 (11)
O7—Na1—O5—Na282.33 (10)O5—Na1—O6—Na20.31 (9)
O6ii—Na1—O5—Na2179.94 (9)O7ii—Na1—O6—Na2175.81 (10)
O6—Na1—O5—Na20.30 (9)O7—Na1—O6—Na282.15 (11)
Na2ii—Na1—O5—Na2136.11 (7)Na2ii—Na1—O6—Na293.88 (12)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x, y, z+3/2; (iii) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O7i0.822.112.897 (4)160
O5—H5A···O4iv0.832.192.970 (4)157
O5—H5B···O10.851.992.833 (4)171
O6—H6A···O2iii0.812.102.869 (4)157
O6—H6B···O4v0.852.052.888 (4)169
O7—H7A···O80.852.122.943 (4)161
O7—H7B···N1vi0.842.333.118 (4)157
O8—H8A···O3v0.821.992.810 (3)179
O8—H8B···O20.832.403.171 (4)155
Symmetry codes: (i) x+1, y, z+3/2; (iii) x, y, z+1; (iv) x1/2, y1/2, z; (v) x+1/2, y+1/2, z+1; (vi) x1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[Na(H2O)4]2(C4H2N2O7)
Mr380.18
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)11.935 (7), 10.709 (6), 12.277 (7)
β (°) 106.634 (8)
V3)1503.5 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.33 × 0.25 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.932, 0.962
No. of measured, independent and
observed [I > 2σ(I)] reflections
3719, 1333, 1146
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.225, 1.08
No. of reflections1333
No. of parameters116
No. of restraints27
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)0.96, 0.81

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O7i0.822.112.897 (4)160
O5—H5A···O4ii0.832.192.970 (4)157
O5—H5B···O10.851.992.833 (4)171
O6—H6A···O2iii0.812.102.869 (4)157
O6—H6B···O4iv0.852.052.888 (4)169
O7—H7A···O80.852.122.943 (4)161
O7—H7B···N1v0.842.333.118 (4)157
O8—H8A···O3iv0.821.992.810 (3)179
O8—H8B···O20.832.403.171 (4)155
Symmetry codes: (i) x+1, y, z+3/2; (ii) x1/2, y1/2, z; (iii) x, y, z+1; (iv) x+1/2, y+1/2, z+1; (v) x1/2, y+1/2, z.
 

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