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The tetranuclear dianion of the title compound, Na2[Zn4(C10H2O8)2(OH)2]·C4H4N2, forms a network framework in which the Zn atom exists in a tetrahedral environment, as it is coordinated by the carboxyl O atoms belonging to three different (C10H2O8)4- anions as well as by the bridging OH group. Adjacent OH groups are linked together through the uncoordinated heterocycle, which lies on a site of 2/m symmetry. The octahedrally coordinated Na ion, which lies on a site of 2 symmetry, interacts with one O atom of the carboxyl group of two anions and with two O atoms of the ortho-carboxyl groups of two other anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016921/bt6318sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016921/bt6318Isup2.hkl
Contains datablock I

CCDC reference: 222801

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.028
  • wR factor = 0.072
  • Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ..... 0.95
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .. ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .. ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by .......... 2.00 Ratio PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ..... ? PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct. 3 PLAT731_ALERT_1_C Bond Calc 0.93(3), Rep 0.930(10) .... 3.00 su-Ratio C4 -H4 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.93(3), Rep 0.930(10) .... 3.00 su-Ratio C7 -H7 1.555 1.555
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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

Comment top

The 4,4'-bipyridine spacer molecule has been used in the formation of a plethora of adducts with zinc carboxylates; however, the spacer was not incorporated in hydrated disodium dihydrogen 1,2,4,5-benzenetetracarboxylatozinc (Wu et al., 2001) when the synthesis was performed under acidic conditions. The use of pyrazine in the metathetical reaction of the sodium salt of this acid and a zinc salt did not lead to the formation of an N-coordinated Zn complex either. The title complex, (I), is formally a hydroxide (Fig. 1), and the heterocycle merely serves as a connector that links adjacent groups together.

The compound adopts a network framework in which the Zn atom exits in a tetrahedral geometry, the atom being covalently bonded to the carboxyl O atoms belonging to three different [C10H2O8]2− dianions and to the bridging OH group. Adjacent OH groups are linked together through the lattice heterocycle (Fig. 2). The octahedrally coordinated Na atom interacts with one O atom of the carboxyl group of two dianions and with two O atoms of the ortho-carboxyl groups of two other dianions (Fig. 3).

In the assembly of coordination polymers the use of sodium hydroxide to deprotonate the carboxylic acids sometimes furnishes compounds having sodium atoms incorporated into the crystal structure (Robl, 1992; Wu et al., 2001; Yang et al., 2002) because the Na+ cation is able to form strong bonds with carboxylate groups or with water. Furthermore, it serves to compensate for the negative charge of the frameworks.

Experimental top

1,2,4,5-Benzenetetracarboxylic acid anhydride (pyromellitic anhydride, 0.22 g, 1 mmol) and sodium hydroxide (0.16 g, 4 mmol) were dissolved in water (15 ml), and to the solution was added zinc dinitrate hexahydrate (0.59 g, 2 mmol) and pyrazine (0.16 g, 2 mmol) dissolved in water (5 ml). The mixturen was placed in a 20 ml Teflon-lined stainless-steel bomb, which was then heated to 453 K for 100 h. The bomb was cooled to room temperature at 5 k h−1. Block-shaped colorless crystals separated from the solution.

Refinement top

The diffraction measurements were of sufficiently high quality to allow for the refinement of the four H atoms, three of which lie on special positions, when restraints (O—H = 0.85±0.01 Å and C—H 0.93±0.01 Å) were applied.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) plot of a fragment of the structure of the title compound at the 75% probability level. H atoms are drawn as spheres of arbitrary radii. [Symmetry codes: (i) 1/2 − x, 1/2 − y, −z; (ii) 1/2 − x, 1/2 + y, 1 − z.]
[Figure 2] Fig. 2. ORTEPII (Johnson, 1976) plot illustrating the hydroxyl–pyrazine–hydroxyl hydrogen bonds.
[Figure 3] Fig. 3. ORTEPII (Johnson, 1976) plot illustrating the geometry of the Na atom. [Symmetry codes: (i) 1/2 − x, 3/2 − y, 1 − z; (ii) x − 1/2, 3/2 − y, z; (iii) −x, y, 1 − z.]
Disodium bis(1,2,4,5-benzenetetracarboxylato)dihydroxytetrazincate(II).pyrazine top
Crystal data top
Na2[Zn4(C10H2O8)2(OH)2]·C4H4N2F(000) = 908
Mr = 921.80Dx = 2.312 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
a = 10.4073 (5) ÅCell parameters from 5344 reflections
b = 17.8174 (8) Åθ = 2.3–28.3°
c = 7.5278 (4) ŵ = 3.71 mm1
β = 108.474 (1)°T = 298 K
V = 1324.0 (1) Å3Block, colorless
Z = 20.29 × 0.17 × 0.12 mm
Data collection top
Bruker APEX area-detector
diffractometer
1629 independent reflections
Radiation source: fine-focus sealed tube1470 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1313
Tmin = 0.463, Tmax = 0.641k = 2323
7636 measured reflectionsl = 99
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)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072All H-atom parameters refined
S = 1.03 w = 1/[σ2(Fo2) + (0.0429P)2]
where P = (Fo2 + 2Fc2)/3
1629 reflections(Δ/σ)max = 0.001
130 parametersΔρmax = 0.51 e Å3
4 restraintsΔρmin = 0.40 e Å3
Crystal data top
Na2[Zn4(C10H2O8)2(OH)2]·C4H4N2V = 1324.0 (1) Å3
Mr = 921.80Z = 2
Monoclinic, C2/mMo Kα radiation
a = 10.4073 (5) ŵ = 3.71 mm1
b = 17.8174 (8) ÅT = 298 K
c = 7.5278 (4) Å0.29 × 0.17 × 0.12 mm
β = 108.474 (1)°
Data collection top
Bruker APEX area-detector
diffractometer
1629 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1470 reflections with I > 2σ(I)
Tmin = 0.463, Tmax = 0.641Rint = 0.035
7636 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0284 restraints
wR(F2) = 0.072All H-atom parameters refined
S = 1.03Δρmax = 0.51 e Å3
1629 reflectionsΔρmin = 0.40 e Å3
130 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.15965 (3)0.72269 (1)0.15033 (4)0.0163 (1)
Na10.00000.75322 (8)0.50000.0244 (3)
O10.3100 (2)0.8655 (1)0.0101 (2)0.0237 (4)
O20.3018 (2)0.8000 (1)0.2381 (2)0.0178 (3)
O30.1603 (2)0.8468 (1)0.5297 (3)0.0310 (4)
O40.3824 (2)0.8303 (1)0.6467 (2)0.0197 (4)
O50.00000.7703 (1)0.00000.0296 (6)
N10.00000.9230 (2)0.00000.0398 (9)
C10.3293 (3)1.00000.1793 (5)0.0156 (6)
C20.3180 (2)0.9321 (1)0.2629 (3)0.0140 (4)
C30.3013 (2)0.9322 (1)0.4399 (3)0.0139 (4)
C40.2956 (3)1.00000.5262 (4)0.0167 (7)
C50.3108 (2)0.8609 (1)0.1562 (3)0.0154 (4)
C60.2767 (2)0.8633 (1)0.5403 (3)0.0171 (5)
C70.0164 (3)0.9616 (2)0.1415 (5)0.0390 (7)
H50.00000.8176 (6)0.00000.03 (1)*
H10.339 (3)1.00000.061 (2)0.02 (1)*
H40.284 (4)1.00000.644 (3)0.03 (1)*
H70.026 (3)0.933 (2)0.239 (3)0.04 (1)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0225 (2)0.0114 (2)0.0152 (2)0.0009 (1)0.0064 (1)0.0001 (1)
Na10.0209 (7)0.0196 (7)0.0354 (8)0.0000.0125 (6)0.000
O10.043 (1)0.013 (1)0.018 (1)0.002 (1)0.013 (1)0.002 (1)
O20.023 (1)0.011 (1)0.017 (1)0.003 (1)0.004 (1)0.000 (1)
O30.026 (1)0.023 (1)0.048 (1)0.002 (1)0.017 (1)0.009 (1)
O40.027 (1)0.016 (1)0.017 (1)0.004 (1)0.009 (1)0.005 (1)
O50.025 (1)0.013 (1)0.040 (2)0.0000.006 (1)0.000
N10.033 (2)0.018 (2)0.057 (2)0.0000.003 (2)0.000
C10.020 (2)0.014 (2)0.014 (2)0.0000.007 (1)0.000
C20.016 (2)0.011 (1)0.014 (1)0.000 (1)0.004 (1)0.001 (1)
C30.014 (1)0.012 (1)0.016 (1)0.000 (1)0.004 (1)0.002 (1)
C40.023 (2)0.017 (2)0.012 (2)0.0000.008 (1)0.000
C50.016 (1)0.012 (1)0.017 (1)0.000 (1)0.005 (1)0.002 (1)
C60.027 (1)0.012 (1)0.015 (1)0.002 (1)0.010 (1)0.002 (1)
C70.032 (2)0.030 (2)0.046 (2)0.000 (1)0.000 (1)0.006 (1)
Geometric parameters (Å, º) top
Zn1—O1i1.973 (2)N1—C7v1.324 (4)
Zn1—O21.975 (2)N1—C71.324 (4)
Zn1—O4ii1.960 (2)C1—C2vi1.386 (3)
Zn1—O51.890 (1)C1—C21.386 (3)
Na1—O2ii2.542 (2)C2—C31.398 (3)
Na1—O2iii2.542 (2)C2—C51.490 (3)
Na1—O32.319 (2)C3—C41.382 (3)
Na1—O3iv2.319 (2)C3—C61.505 (3)
Na1—O4ii2.406 (2)C4—C3vi1.382 (3)
Na1—O4iii2.406 (2)C7—C7vi1.370 (6)
O1—C51.252 (3)O5—H50.84 (1)
O2—C51.266 (3)C1—H10.93 (1)
O3—C61.224 (3)C4—H40.93 (1)
O4—C61.279 (3)C7—H70.93 (1)
O1i—Zn1—O2120.3 (1)C6—O4—Na1ii117.3 (1)
O1i—Zn1—O4ii98.5 (1)Zn1ii—O4—Na1ii109.4 (1)
O1i—Zn1—O5107.3 (1)Zn1v—O5—Zn1126.6 (1)
O2—Zn1—O4ii113.8 (1)C7v—N1—C7117.4 (4)
O2—Zn1—O5108.1 (1)C2vi—C1—C2121.7 (3)
O4ii—Zn1—O5108.2 (1)C1—C2—C3119.1 (2)
O2ii—Na1—O2iii136.2 (1)C1—C2—C5119.7 (2)
O2ii—Na1—O379.1 (1)C3—C2—C5121.0 (2)
O2ii—Na1—O3iv136.5 (1)C4—C3—C2119.1 (2)
O2ii—Na1—O4ii73.7 (1)C4—C3—C6116.0 (2)
O2ii—Na1—O4iii79.6 (1)C2—C3—C6124.7 (2)
O2iii—Na1—O3136.5 (1)C3—C4—C3vi121.9 (3)
O2iii—Na1—O3iv79.1 (1)O1—C5—O2124.4 (2)
O2iii—Na1—O4ii79.6 (1)O1—C5—C2117.8 (2)
O2iii—Na1—O4iii73.7 (1)O2—C5—C2117.8 (2)
O3—Na1—O3iv88.1 (1)O3—C6—O4124.6 (2)
O3—Na1—O4ii91.9 (1)O3—C6—C3118.9 (2)
O3—Na1—O4iii148.8 (1)O4—C6—C3116.1 (2)
O3iv—Na1—O4ii148.8 (1)N1—C7—C7vi121.3 (2)
O3iv—Na1—O4iii91.9 (1)Zn1v—O5—H5116.7 (1)
O4ii—Na1—O4iii103.6 (1)Zn1—O5—H5116.7 (1)
C5—O1—Zn1i122.1 (2)C2vi—C1—H1119.1 (2)
C5—O2—Zn1126.7 (2)C2—C1—H1119.1 (2)
C5—O2—Na1ii122.0 (1)C3—C4—H4119.0 (2)
Zn1—O2—Na1ii109.7 (1)C3vi—C4—H4119 (3)
C6—O3—Na1147.7 (2)N1—C7—H7115 (2)
C6—O4—Zn1ii110.5 (1)C7vi—C7—H7124 (2)
O5—Zn1—O2—C527.6 (2)Zn1i—O1—C5—O215.7 (3)
O4ii—Zn1—O2—C5147.8 (2)Zn1i—O1—C5—C2166.5 (1)
O1i—Zn1—O2—C596.0 (2)Zn1—O2—C5—O153.5 (3)
O5—Zn1—O2—Na1ii166.6 (1)Na1ii—O2—C5—O1110.7 (2)
O4ii—Zn1—O2—Na1ii46.5 (1)Zn1—O2—C5—C2124.3 (2)
O1i—Zn1—O2—Na1ii69.9 (1)Na1ii—O2—C5—C271.5 (2)
O3iv—Na1—O3—C6172.9 (4)C1—C2—C5—O12.7 (3)
O4ii—Na1—O3—C624.1 (3)C3—C2—C5—O1171.5 (2)
O4iii—Na1—O3—C696.6 (3)C1—C2—C5—O2179.3 (2)
O2iii—Na1—O3—C6101.0 (3)C3—C2—C5—O26.5 (3)
O2ii—Na1—O3—C648.9 (3)Na1—O3—C6—O447.0 (5)
O4ii—Zn1—O5—Zn1v66.3 (1)Na1—O3—C6—C3140.4 (2)
O1i—Zn1—O5—Zn1v39.0 (1)Zn1ii—O4—C6—O320.4 (3)
O2—Zn1—O5—Zn1v170.1 (1)Na1ii—O4—C6—O3105.8 (2)
C2vi—C1—C2—C33.1 (5)Zn1ii—O4—C6—C3152.4 (2)
C2vi—C1—C2—C5171.2 (2)Na1ii—O4—C6—C381.4 (2)
C1—C2—C3—C40.4 (4)C4—C3—C6—O378.2 (3)
C5—C2—C3—C4173.8 (2)C2—C3—C6—O396.5 (3)
C1—C2—C3—C6174.9 (2)C4—C3—C6—O495.1 (3)
C5—C2—C3—C60.7 (3)C2—C3—C6—O490.3 (3)
C2—C3—C4—C3vi2.3 (5)C7v—N1—C7—C7vi0.0 (1)
C6—C3—C4—C3vi172.7 (2)
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x+1/2, y+3/2, z+1; (iii) x1/2, y+3/2, z; (iv) x, y, z+1; (v) x, y, z; (vi) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···N10.84 (1)1.88 (1)2.720 (4)180 (?)

Experimental details

Crystal data
Chemical formulaNa2[Zn4(C10H2O8)2(OH)2]·C4H4N2
Mr921.80
Crystal system, space groupMonoclinic, C2/m
Temperature (K)298
a, b, c (Å)10.4073 (5), 17.8174 (8), 7.5278 (4)
β (°) 108.474 (1)
V3)1324.0 (1)
Z2
Radiation typeMo Kα
µ (mm1)3.71
Crystal size (mm)0.29 × 0.17 × 0.12
Data collection
DiffractometerBruker APEX area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.463, 0.641
No. of measured, independent and
observed [I > 2σ(I)] reflections
7636, 1629, 1470
Rint0.035
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.03
No. of reflections1629
No. of parameters130
No. of restraints4
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.51, 0.40

Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
Zn1—O1i1.973 (2)Na1—O2ii2.542 (2)
Zn1—O21.975 (2)Na1—O32.319 (2)
Zn1—O4ii1.960 (2)Na1—O4ii2.406 (2)
Zn1—O51.890 (1)
O1i—Zn1—O2120.3 (1)O2ii—Na1—O3iv136.5 (1)
O1i—Zn1—O4ii98.5 (1)O2ii—Na1—O4ii73.7 (1)
O1i—Zn1—O5107.3 (1)O2ii—Na1—O4iii79.6 (1)
O2—Zn1—O4ii113.8 (1)O3—Na1—O3iv88.1 (1)
O2—Zn1—O5108.1 (1)O3—Na1—O4ii91.9 (1)
O4ii—Zn1—O5108.2 (1)O3—Na1—O4iii148.8 (1)
O2ii—Na1—O2iii136.2 (1)O4ii—Na1—O4iii103.6 (1)
O2ii—Na1—O379.1 (1)
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x+1/2, y+3/2, z+1; (iii) x1/2, y+3/2, z; (iv) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5···N10.84 (1)1.88 (1)2.720 (4)180(?)
 

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