supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers buy article online

Acta Cryst. (2007). E63, m2987-m2988    [ doi:10.1107/S1600536807056243 ]

Poly[dimethylammonium [bis(dimethylamine)tri-[mu]4-terephthalato-sodium(I)dizinc(II)]]

L.-N. Zhu, S. Gao and S. W. Ng

Abstract top

The three terephthalate groups in the title polymeric coordination compound, {(C2H8N)[NaZn2(C8H4O4)3(C2H7N)2]}n, lie on inversion centers. One functions as a bridge to two Na and two Zn atoms. The O atoms of the other two terephthalate groups bind to only one Zn atom. The Zn atom is additionally coordinated by a dimethylamine molecule; together with bonding from the O atoms of the three terephthalate groups, the geometry is tetrahedral. The manner of bridging of the terephalate groups gives rise to a polyanionic honeycomb sheet motif; the sheets are held into a three-dimensional network through the Na atoms. The cavities in the network are occupied by the dimethylammonium cations. The organic cation is disordered about a centre of inversion.

Related literature top

A similar compound, bis(µ5-terephthalato)(µ4-terephthalato)bis(dimethyformamide)sodiumzinc, was synthesized by using a conventional preparation; the DMF is incorporated into the crystal structure (see Yang et al., 2002). Under hydrothermal conditions, the DMF is decomposed into dimethylamine, which coordinates to zinc in the title compound.

Experimental top

Zinc formate (1.55 g, 1 mmol) and terephthalic acid (1.66 g, 1 mmol) in dissolved in DMF (10 ml). The solution was heated in a 25-ml, Teflon-lined stainless-steel Parr bomb at 433 K for five days. The bomb was allowed to cool to room temperature. Several colorless prisms were picked out by hand.

Refinement top

Carbon- and nitrogen-bound H atoms were placed in calculated positions [C—H 0.93–0.97 Å and Uiso(H) 1.2–1.5Ueq(C)], and were included in the refinement in the riding-model approximation.

The dimethylammonium cation is disordered about an inversion site, and was refined as a half-occupancy species, subject to distance restraints of C–N 1.45±01 and C···C 2.37±0.01 Å. Their anisotropic temperature factors were restrained to be nearly isotropic.

The refinement initially assumed two independent zinc atoms in the asymmetric unit; however, the difference Fourier consistently had a deep hole near that atom on the inversion site. The occupancy of the zinc atom at (1/2, 1/2, 1/2) refined to 0.188, an occupancy consistent with sodium. The refinement with magnesium in place of sodium led to worse convergence. Furthermore, the octahedral environment of oxygen atoms at distances of 2.3 to 2.5 Å is consistent with this assumption. Sodium could have come from the water used to clean the containers, or the terephthalic acid was contaminated with unknown amounts of the sodium salt.

The final difference Fourier map had a large peak at 2.66 Å from H13a; this peak could not be refined as an oxygen atom.

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of a portion of the polymeric structure; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius. (Symmetry code is given in Table 1.)
[Figure 2] Fig. 2. Layer structure of the zinc-terepthalate network as illustrated by OLEX (Dolomanov et al., 2003).
Poly[dimethylammonium [bis(dimethylamine)tri-µ4-terephthalato-sodium(I)dizinc(II)]] top
Crystal data top
(C2H8N)[NaZn2(C8H4O4)3(C2H7N)2]Z = 1
Mr = 782.33F(000) = 402
Triclinic, P1Dx = 1.461 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.7893 (4) ÅCell parameters from 8042 reflections
b = 10.3641 (4) Åθ = 3.1–27.5°
c = 10.6649 (4) ŵ = 1.42 mm−1
α = 111.801 (1)°T = 295 K
β = 100.498 (1)°Prism, colorless
γ = 109.257 (1)°0.32 × 0.26 × 0.20 mm
V = 889.29 (6) Å3
Data collection top
Rigaku RAXIS-RAPID
diffractometer		4032 independent reflections
Radiation source: fine-focus sealed tube3743 reflections with I > 2σ(I)
graphiteRint = 0.019
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω–scansh = −12→12
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −13→13
Tmin = 0.500, Tmax = 0.764l = −13→13
8744 measured reflections
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0891P)2 + 0.691P]
where P = (Fo2 + 2Fc2)/3
4032 reflections(Δ/σ)max = 0.001
232 parametersΔρmax = 1.52 e Å−3
21 restraintsΔρmin = −0.37 e Å−3
Crystal data top
(C2H8N)[NaZn2(C8H4O4)3(C2H7N)2]γ = 109.257 (1)°
Mr = 782.33V = 889.29 (6) Å3
Triclinic, P1Z = 1
a = 9.7893 (4) ÅMo Kα radiation
b = 10.3641 (4) ŵ = 1.42 mm−1
c = 10.6649 (4) ÅT = 295 K
α = 111.801 (1)°0.32 × 0.26 × 0.20 mm
β = 100.498 (1)°
Data collection top
Rigaku RAXIS-RAPID
diffractometer		4032 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3743 reflections with I > 2σ(I)
Tmin = 0.500, Tmax = 0.764Rint = 0.019
8744 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.134Δρmax = 1.52 e Å−3
S = 1.08Δρmin = −0.37 e Å−3
4032 reflectionsAbsolute structure: ?
232 parametersFlack parameter: ?
21 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.59102 (3)0.46809 (3)0.79701 (3)0.02569 (13)
Na10.50000.50000.50000.0244 (3)
O10.5534 (4)0.7060 (3)0.7200 (3)0.0504 (6)
O20.5491 (3)0.6447 (2)0.8990 (2)0.0373 (5)
O30.3246 (3)0.3460 (3)0.5606 (3)0.0487 (6)
O40.4059 (2)0.2685 (3)0.7140 (3)0.0442 (5)
O50.6919 (2)0.4596 (3)0.6530 (2)0.0385 (5)
O60.9088 (3)0.6470 (3)0.8285 (3)0.0530 (6)
N10.7009 (3)0.4443 (3)0.9649 (3)0.0379 (6)
H10.62970.39850.99100.045*
C10.5425 (3)0.7297 (3)0.8384 (3)0.0337 (6)
C20.5199 (3)0.8695 (3)0.9231 (3)0.0314 (5)
C30.4778 (4)0.9489 (3)0.8546 (3)0.0368 (6)
H30.46320.91470.75720.044*
C40.5425 (4)0.9221 (3)1.0700 (3)0.0354 (6)
H40.57110.87031.11680.042*
C50.3034 (3)0.2560 (3)0.6121 (3)0.0357 (6)
C60.1461 (4)0.1213 (4)0.5529 (4)0.0409 (7)
C70.0188 (4)0.1272 (4)0.4790 (5)0.0598 (11)
H70.03110.21260.46400.072*
C80.1269 (4)−0.0070 (5)0.5731 (5)0.0597 (11)
H80.2121−0.01270.62180.072*
C90.8376 (3)0.5484 (4)0.7029 (3)0.0352 (6)
C100.9209 (3)0.5225 (3)0.5965 (3)0.0307 (5)
C110.8412 (3)0.4176 (4)0.4516 (4)0.0367 (6)
H110.73450.36230.41870.044*
C121.0806 (3)0.6048 (4)0.6438 (3)0.0365 (6)
H121.13500.67550.74050.044*
C130.7748 (5)0.3415 (5)0.9174 (5)0.0580 (10)
H13A0.70190.24780.83320.087*
H13B0.80920.31800.99290.087*
H13C0.86160.39170.89520.087*
C140.8095 (4)0.5905 (5)1.0944 (4)0.0552 (9)
H14A0.75820.65511.12340.083*
H14B0.89610.64241.07300.083*
H14C0.84480.56891.17110.083*
N20.972 (2)0.971 (5)0.987 (3)0.208 (10)0.50
H2A0.90500.87620.93520.249*0.50
H2B0.92521.02880.99830.249*0.50
C151.083 (2)1.0104 (17)0.9171 (17)0.113 (5)0.50
H15A1.03031.00280.82740.170*0.50
H15B1.12960.94040.89910.170*0.50
H15C1.16091.11400.97850.170*0.50
C161.059 (3)0.994 (2)1.1262 (18)0.156 (8)0.50
H16A0.99060.97611.17830.235*0.50
H16B1.13851.09811.18020.235*0.50
H16C1.10500.92341.11190.235*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02318 (18)0.02679 (19)0.03174 (19)0.01195 (14)0.01341 (13)0.01542 (14)
Na10.0289 (7)0.0256 (6)0.0254 (6)0.0119 (6)0.0155 (6)0.0155 (5)
O10.0838 (19)0.0400 (12)0.0462 (13)0.0368 (13)0.0382 (13)0.0227 (10)
O20.0492 (12)0.0339 (10)0.0431 (11)0.0273 (10)0.0229 (10)0.0209 (9)
O30.0360 (12)0.0443 (12)0.0695 (16)0.0084 (10)0.0204 (11)0.0372 (12)
O40.0278 (10)0.0414 (12)0.0447 (12)0.0001 (9)0.0018 (9)0.0197 (10)
O50.0313 (10)0.0482 (12)0.0497 (12)0.0206 (9)0.0278 (10)0.0272 (10)
O60.0454 (13)0.0672 (16)0.0425 (13)0.0212 (13)0.0245 (11)0.0203 (12)
N10.0275 (11)0.0504 (15)0.0457 (14)0.0167 (11)0.0150 (11)0.0312 (12)
C10.0375 (15)0.0268 (12)0.0382 (14)0.0157 (12)0.0157 (12)0.0138 (11)
C20.0400 (15)0.0262 (12)0.0303 (12)0.0168 (11)0.0141 (11)0.0124 (10)
C30.0530 (18)0.0327 (14)0.0283 (12)0.0219 (13)0.0154 (12)0.0142 (11)
C40.0465 (16)0.0312 (13)0.0341 (14)0.0205 (13)0.0133 (12)0.0178 (11)
C50.0279 (13)0.0331 (14)0.0386 (14)0.0049 (11)0.0121 (12)0.0162 (12)
C60.0295 (14)0.0379 (15)0.0431 (16)−0.0006 (12)0.0024 (12)0.0247 (13)
C70.0374 (18)0.048 (2)0.088 (3)0.0028 (16)0.0022 (18)0.049 (2)
C80.0351 (17)0.053 (2)0.079 (3)0.0040 (16)−0.0043 (18)0.043 (2)
C90.0346 (14)0.0458 (16)0.0438 (15)0.0244 (13)0.0245 (13)0.0279 (14)
C100.0281 (13)0.0396 (14)0.0397 (14)0.0192 (12)0.0204 (11)0.0254 (12)
C110.0251 (12)0.0440 (16)0.0494 (16)0.0160 (12)0.0203 (12)0.0257 (14)
C120.0286 (14)0.0452 (16)0.0389 (14)0.0165 (13)0.0169 (12)0.0200 (13)
C130.051 (2)0.065 (2)0.086 (3)0.038 (2)0.028 (2)0.049 (2)
C140.0416 (18)0.067 (2)0.0456 (18)0.0172 (18)0.0061 (15)0.0246 (18)
N20.214 (13)0.208 (15)0.197 (12)0.074 (10)0.097 (10)0.095 (9)
C150.114 (8)0.088 (7)0.127 (8)0.023 (5)0.066 (7)0.046 (6)
C160.159 (11)0.128 (10)0.161 (11)0.047 (8)0.053 (9)0.061 (8)
Geometric parameters (Å, °) top
Zn1—O51.963 (2)C6—C81.383 (5)
Zn1—O21.970 (2)C7—C8iii1.386 (5)
Zn1—O41.982 (2)C7—H70.9300
Zn1—N12.056 (3)C8—C7iii1.386 (5)
Na1—O32.297 (2)C8—H80.9300
Na1—O3i2.297 (2)C9—C101.510 (4)
Na1—O12.331 (2)C10—C111.390 (4)
Na1—O1i2.331 (2)C10—C121.393 (4)
Na1—O52.505 (2)C11—C12iv1.378 (4)
Na1—O5i2.505 (2)C11—H110.9300
O1—C11.226 (4)C12—C11iv1.378 (4)
O2—C11.282 (4)C12—H120.9300
O3—C51.229 (4)C13—H13A0.9600
O4—C51.271 (4)C13—H13B0.9600
O5—C91.288 (4)C13—H13C0.9600
O6—C91.224 (4)C14—H14A0.9600
N1—C131.468 (5)C14—H14B0.9600
N1—C141.477 (5)C14—H14C0.9600
N1—H10.8600N2—C151.455 (10)
C1—C21.509 (4)N2—C161.458 (10)
C2—C31.393 (4)N2—H2A0.8600
C2—C41.400 (4)N2—H2B0.8600
C3—C4ii1.382 (4)C15—H15A0.9600
C3—H30.9300C15—H15B0.9600
C4—C3ii1.382 (4)C15—H15C0.9600
C4—H40.9300C16—H16A0.9600
C5—C61.514 (4)C16—H16B0.9600
C6—C71.381 (5)C16—H16C0.9600
O5—Zn1—O2122.49 (9)C7—C6—C5119.5 (3)
O5—Zn1—O4107.71 (10)C8—C6—C5121.3 (3)
O2—Zn1—O4111.96 (10)C6—C7—C8iii120.5 (3)
O5—Zn1—N1114.27 (10)C6—C7—H7119.7
O2—Zn1—N1101.73 (10)C8iii—C7—H7119.7
O4—Zn1—N195.35 (10)C6—C8—C7iii120.2 (3)
O3—Na1—O3i180.00 (12)C6—C8—H8119.9
O3—Na1—O187.36 (10)C7iii—C8—H8119.9
O3i—Na1—O192.64 (10)O6—C9—O5123.9 (3)
O3—Na1—O1i92.64 (10)O6—C9—C10120.2 (3)
O3i—Na1—O1i87.36 (10)O5—C9—C10115.8 (3)
O1—Na1—O1i180.0C11—C10—C12119.0 (3)
O3—Na1—O583.95 (8)C11—C10—C9121.3 (3)
O3i—Na1—O596.05 (8)C12—C10—C9119.7 (3)
O1—Na1—O582.33 (9)C12iv—C11—C10120.4 (3)
O1i—Na1—O597.67 (9)C12iv—C11—H11119.8
O3—Na1—O5i96.05 (8)C10—C11—H11119.8
O3i—Na1—O5i83.95 (8)C11iv—C12—C10120.5 (3)
O1—Na1—O5i97.67 (9)C11iv—C12—H12119.7
O1i—Na1—O5i82.33 (9)C10—C12—H12119.7
O5—Na1—O5i180.0N1—C13—H13A109.5
C1—O1—Na1139.5 (2)N1—C13—H13B109.5
C1—O2—Zn1116.88 (18)H13A—C13—H13B109.5
C5—O3—Na1144.9 (2)N1—C13—H13C109.5
C5—O4—Zn1110.7 (2)H13A—C13—H13C109.5
C9—O5—Zn1115.7 (2)H13B—C13—H13C109.5
C9—O5—Na1121.97 (19)N1—C14—H14A109.5
Zn1—O5—Na194.39 (8)N1—C14—H14B109.5
C13—N1—C14111.2 (3)H14A—C14—H14B109.5
C13—N1—Zn1111.3 (2)N1—C14—H14C109.5
C14—N1—Zn1115.2 (2)H14A—C14—H14C109.5
C13—N1—H1106.1H14B—C14—H14C109.5
C14—N1—H1106.2C15—N2—C16107.3 (10)
Zn1—N1—H1106.1C15—N2—H2A110.3
O1—C1—O2125.3 (3)C16—N2—H2A110.3
O1—C1—C2118.9 (3)C15—N2—H2B110.3
O2—C1—C2115.7 (2)C16—N2—H2B110.3
C3—C2—C4119.3 (3)H2A—N2—H2B108.5
C3—C2—C1119.6 (3)N2—C15—H15A109.5
C4—C2—C1121.1 (2)N2—C15—H15B109.5
C4ii—C3—C2120.7 (3)H15A—C15—H15B109.5
C4ii—C3—H3119.7N2—C15—H15C109.5
C2—C3—H3119.7H15A—C15—H15C109.5
C3ii—C4—C2120.0 (3)H15B—C15—H15C109.5
C3ii—C4—H4120.0N2—C16—H16A109.5
C2—C4—H4120.0N2—C16—H16B109.5
O3—C5—O4124.1 (3)H16A—C16—H16B109.5
O3—C5—C6119.0 (3)N2—C16—H16C109.5
O4—C5—C6116.9 (3)H16A—C16—H16C109.5
C7—C6—C8119.3 (3)H16B—C16—H16C109.5
O3—Na1—O1—C122.2 (4)Na1—Zn1—N1—C1492.3 (4)
O3i—Na1—O1—C1−157.8 (4)Na1—O1—C1—O229.8 (6)
O5—Na1—O1—C1−62.1 (4)Na1—O1—C1—C2−150.5 (3)
O5i—Na1—O1—C1117.9 (4)Zn1—O2—C1—O13.3 (4)
O5—Zn1—O2—C122.2 (3)Zn1—O2—C1—C2−176.43 (19)
O4—Zn1—O2—C1−108.0 (2)O1—C1—C2—C314.2 (5)
N1—Zn1—O2—C1151.2 (2)O2—C1—C2—C3−166.0 (3)
O1—Na1—O3—C5−96.9 (4)O1—C1—C2—C4−165.0 (3)
O1i—Na1—O3—C583.1 (4)O2—C1—C2—C414.8 (4)
O5—Na1—O3—C5−14.4 (4)C4—C2—C3—C4ii−0.3 (5)
O5i—Na1—O3—C5165.6 (4)C1—C2—C3—C4ii−179.5 (3)
Zn1—Na1—O3—C5−40.3 (4)C3—C2—C4—C3ii0.3 (5)
Zn1i—Na1—O3—C5139.7 (4)C1—C2—C4—C3ii179.5 (3)
O5—Zn1—O4—C5−69.6 (2)Na1—O3—C5—O435.7 (6)
O2—Zn1—O4—C567.9 (2)Na1—O3—C5—C6−144.7 (3)
N1—Zn1—O4—C5172.8 (2)Zn1—O4—C5—O38.7 (4)
O2—Zn1—O5—C973.2 (2)Zn1—O4—C5—C6−170.9 (2)
O4—Zn1—O5—C9−154.8 (2)O3—C5—C6—C7−20.8 (5)
N1—Zn1—O5—C9−50.3 (2)O4—C5—C6—C7158.9 (4)
O2—Zn1—O5—Na1−55.59 (12)O3—C5—C6—C8160.1 (4)
O4—Zn1—O5—Na176.39 (10)O4—C5—C6—C8−20.3 (5)
N1—Zn1—O5—Na1−179.06 (9)C8—C6—C7—C8iii0.8 (8)
O3—Na1—O5—C9−162.0 (2)C5—C6—C7—C8iii−178.4 (4)
O3i—Na1—O5—C918.0 (2)C7—C6—C8—C7iii−0.8 (8)
O1—Na1—O5—C9−73.9 (2)C5—C6—C8—C7iii178.4 (4)
O1i—Na1—O5—C9106.1 (2)Zn1—O5—C9—O6−8.9 (4)
O3—Na1—O5—Zn1−37.89 (10)Na1—O5—C9—O6104.7 (3)
O3i—Na1—O5—Zn1142.11 (10)Zn1—O5—C9—C10169.76 (18)
O1—Na1—O5—Zn150.25 (9)Na1—O5—C9—C10−76.6 (3)
O1i—Na1—O5—Zn1−129.75 (9)O6—C9—C10—C11−176.2 (3)
O5—Zn1—N1—C13−33.0 (3)O5—C9—C10—C115.1 (4)
O2—Zn1—N1—C13−167.0 (2)O6—C9—C10—C123.8 (4)
O4—Zn1—N1—C1379.2 (2)O5—C9—C10—C12−174.9 (3)
Na1—Zn1—N1—C13−35.5 (4)C12—C10—C11—C12iv0.2 (5)
O5—Zn1—N1—C1494.8 (3)C9—C10—C11—C12iv−179.8 (3)
O2—Zn1—N1—C14−39.2 (3)C11—C10—C12—C11iv−0.2 (5)
O4—Zn1—N1—C14−153.0 (2)C9—C10—C12—C11iv179.8 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+2; (iii) −x, −y, −z+1; (iv) −x+2, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2v0.862.293.122 (3)162
Symmetry codes: (v) −x+1, −y+1, −z+2.
Acknowledgements top

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this work.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Dolomanov, O. V., Blake, A. J., Champness, N. R. & Schröder, M. (2003). J. Appl. Cryst. 36, 1283–1284.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku Corporation (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.

Yang, S.-Y., Sun, initials?, Z-, G., Long, L.-S., Huang, R.-B. & Zheng, L.-S. (2002). Main Group Met. Chem. 25, 579–580.