



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810025195/xu2784sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810025195/xu2784Isup2.hkl |
CCDC reference: 745052
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean
(C-C) = 0.004 Å
- R factor = 0.042
- wR factor = 0.115
- Data-to-parameter ratio = 11.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.53 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5 - C6 ... 1.53 Ang. PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings Differ ?
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
A mixture of H2pyzdc (0.83 mmol, 140 mg), acridine (1.67 mmol, 300 mg), and Zn(NO3)2.4H2O (0.27 mmol, 80 mg) in distilled water (12 ml) was placed in a Teflon-lined stainless steel vessel, heated to 423 K for 4 days, and then cooled to room temperature over 12 h. Red block crystals were obtained after five months by slow evaporation of solvent with a yield of approximate 55% based on Zn.
N-bonded H atom was located in a difference Fourier map and refined with a distance restraint. Other H atoms were placed in calculated positions and refined in a riding mode. Uiso(H) = 1.2 Ueq(C,N).
H2pyzdc has proved to be well suited for the construction of multidimensional frameworks due to the presence of two adjacent carboxylate groups (O donor atoms) as substituents on the N-heterocyclic pyrazine ring (N donor atoms). In this paper, we report the hydrothermal synthesis, crystal and molecular structure of a pyrazinecarboxylate-based Zn atom supramolecular coordination compound as a novel inorganic polymer, for the first time. The hydrothermal reaction between H2pyzdc, acr, and zinc nitrate tetra-hydrate, resulted in the formation of {(C13H10N)2[Zn(C6H2N2O4)2]}n. This inorganic polymeric compound consists of an anionic complex, [Zn(pyzdc)2]2–, counter-ions, (acrH)+ molecules. In the title inorganic polymeric compound, two COOH protons have been transferred to non-coordinated pyridine rings of acr moieties. The central Zn1 atom is six-coordinated by N1 and O1 atoms in the equatorial plane from two (pyzdc)2– ligands and by two O4 atoms in the axial positions (Fig. 1). The coordination environment around the Zn atom may be considered as slightly distorted octahedral. The anionic complex lies on a crystallographic center of symmetry. The mean Zn–N and Zn–O bond lengths are 2.093 (2) and 2.138 (17) Å, respectively. In the structure of the title inorganic polymeric compound, (acrH)+ cations and [Zn(pyzdc)2]2- anions are linked together by classical N3–H3B···O3 and non-classical C13–H13···O2 and C16–H16···O3 hydrogen bonds. In the crystal structure of the title polymeric compound, the spaces between [Zn(pyzdc)2]2- fragments are filled with layers of (acrH)+ cations. Indeed, the arrangement of anionic layers to each other resulted in the making of suitable spaces for entering cationic parts. As a essential factor extensive π–π stacking interactions between parallel aromatic rings of the acridinium ions,(acrH)+, with face-to-face distances of 3.311 (3) and 3.267 (4) Å, caused to further stabilization of crystalline network.
It should be noted that most of the molecular structures consisting up dicarboxylate ligands incorporate water molecules of hydration which may lead to formation kind of (H2O)n clusters (Review article by Aghabozorg et al. 2010a). The used reaction conditions such as hydrothermal synthesis versus just normal synthesis in aqueous conditions play basic roles in this regard. Additionally, if water molecules are present, it may prevent polymerization because it will coordinate to the metal center and so, used dicarboxylate ligand can not play chelate role for connecting metal centers to each other. For example, herein, we have obtained an inorganic polymer because of applying hydrothermal condition. But, recently published work of our research group (Aghabozorg et al. 2010b) show that the reaction of cobalt(II) nitrate hexa-hydrate, acr, and H2pyzdc in aqueous solution and routine condition resulted in the formation of (acrH)2[Co(pyzdc)2(H2O)2]. 6H2O crystals as monomeric structure.
For structure of a related Co(II) complex with pyzdc ligands, see: Aghabozorg et al. (2010b). For the proton transfer of the carboxyl group, see: Aghabozorg et al. (2010a).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![]() | Fig. 1. A part of the title polymeric compound, thermal ellipsoids are shown at the 50% probability level. Symmetry code: (i): 2-x, 2-y, 1-z; (ii): x, 1+y, z; (iii): 2-x, 1-y, 1-z. |
(C13H10N)2[Zn(C6H2N2O4)2] | F(000) = 776 |
Mr = 758.00 | Dx = 1.663 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 600 reflections |
a = 13.2256 (12) Å | θ = 2.0–24.0° |
b = 6.8141 (6) Å | µ = 0.88 mm−1 |
c = 17.9889 (16) Å | T = 120 K |
β = 111.013 (2)° | Prism, red |
V = 1513.4 (2) Å3 | 0.27 × 0.15 × 0.13 mm |
Z = 2 |
Bruker SMART 1000 CCD area-detector diffractometer | 2720 independent reflections |
Radiation source: fine-focus sealed tube | 2292 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 25.2°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick 1998) | h = −15→15 |
Tmin = 0.845, Tmax = 0.891 | k = −8→8 |
15968 measured reflections | l = −21→21 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0644P)2 + 1.454P] where P = (Fo2 + 2Fc2)/3 |
2720 reflections | (Δ/σ)max = 0.001 |
244 parameters | Δρmax = 0.76 e Å−3 |
1 restraint | Δρmin = −0.47 e Å−3 |
(C13H10N)2[Zn(C6H2N2O4)2] | V = 1513.4 (2) Å3 |
Mr = 758.00 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.2256 (12) Å | µ = 0.88 mm−1 |
b = 6.8141 (6) Å | T = 120 K |
c = 17.9889 (16) Å | 0.27 × 0.15 × 0.13 mm |
β = 111.013 (2)° |
Bruker SMART 1000 CCD area-detector diffractometer | 2720 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick 1998) | 2292 reflections with I > 2σ(I) |
Tmin = 0.845, Tmax = 0.891 | Rint = 0.032 |
15968 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.76 e Å−3 |
2720 reflections | Δρmin = −0.47 e Å−3 |
244 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
Zn1 | 1.0000 | 1.0000 | 0.5000 | 0.02299 (17) | |
N1 | 0.97579 (16) | 0.7741 (3) | 0.41650 (12) | 0.0181 (4) | |
N2 | 0.92414 (17) | 0.4493 (3) | 0.31697 (13) | 0.0235 (5) | |
N3 | 0.56207 (16) | 0.2835 (3) | 0.40993 (12) | 0.0188 (4) | |
O1 | 0.90033 (14) | 0.8249 (3) | 0.53444 (11) | 0.0225 (4) | |
O2 | 0.81853 (16) | 0.5307 (3) | 0.51045 (12) | 0.0275 (5) | |
O3 | 0.71207 (14) | 0.3430 (3) | 0.34784 (11) | 0.0231 (4) | |
O4 | 0.84996 (14) | 0.1517 (3) | 0.41985 (10) | 0.0219 (4) | |
C1 | 0.87279 (19) | 0.6642 (4) | 0.49636 (15) | 0.0183 (5) | |
C2 | 0.91244 (18) | 0.6323 (4) | 0.42725 (14) | 0.0166 (5) | |
C3 | 1.0143 (2) | 0.7552 (4) | 0.35783 (15) | 0.0213 (5) | |
H3 | 1.0591 | 0.8517 | 0.3499 | 0.026* | |
C4 | 0.9879 (2) | 0.5930 (4) | 0.30892 (15) | 0.0234 (6) | |
H4 | 1.0158 | 0.5833 | 0.2684 | 0.028* | |
C5 | 0.88694 (19) | 0.4691 (4) | 0.37672 (15) | 0.0174 (5) | |
C6 | 0.8114 (2) | 0.3068 (4) | 0.38376 (15) | 0.0197 (5) | |
C7 | 0.4615 (2) | 0.3287 (3) | 0.35817 (15) | 0.0173 (5) | |
C8 | 0.4441 (2) | 0.3677 (4) | 0.27753 (15) | 0.0216 (5) | |
H8 | 0.5016 | 0.3642 | 0.2593 | 0.026* | |
C9 | 0.3419 (2) | 0.4107 (4) | 0.22648 (16) | 0.0233 (6) | |
H9 | 0.3300 | 0.4348 | 0.1731 | 0.028* | |
C10 | 0.2537 (2) | 0.4193 (4) | 0.25332 (15) | 0.0233 (6) | |
H10 | 0.1850 | 0.4504 | 0.2176 | 0.028* | |
C11 | 0.2682 (2) | 0.3826 (4) | 0.33062 (16) | 0.0229 (6) | |
H11 | 0.2095 | 0.3882 | 0.3475 | 0.027* | |
C12 | 0.3732 (2) | 0.3354 (4) | 0.38588 (15) | 0.0187 (5) | |
C13 | 0.3932 (2) | 0.2948 (3) | 0.46547 (15) | 0.0183 (5) | |
H13 | 0.3366 | 0.3014 | 0.4846 | 0.022* | |
C14 | 0.4961 (2) | 0.2445 (4) | 0.51706 (15) | 0.0183 (5) | |
C15 | 0.5195 (2) | 0.1983 (4) | 0.59890 (15) | 0.0219 (6) | |
H15 | 0.4644 | 0.2036 | 0.6196 | 0.026* | |
C16 | 0.6211 (2) | 0.1467 (4) | 0.64685 (16) | 0.0239 (6) | |
H16 | 0.6358 | 0.1182 | 0.7003 | 0.029* | |
C17 | 0.7049 (2) | 0.1364 (4) | 0.61494 (16) | 0.0237 (6) | |
H17 | 0.7738 | 0.0977 | 0.6480 | 0.028* | |
C18 | 0.6877 (2) | 0.1814 (4) | 0.53774 (15) | 0.0210 (5) | |
H18 | 0.7441 | 0.1759 | 0.5184 | 0.025* | |
C19 | 0.5823 (2) | 0.2368 (3) | 0.48739 (14) | 0.0180 (5) | |
H3N | 0.6133 (15) | 0.292 (4) | 0.3912 (15) | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0244 (3) | 0.0228 (3) | 0.0256 (3) | −0.00764 (17) | 0.0137 (2) | −0.00581 (17) |
N1 | 0.0126 (10) | 0.0220 (11) | 0.0196 (10) | 0.0012 (8) | 0.0058 (8) | 0.0009 (9) |
N2 | 0.0187 (11) | 0.0312 (12) | 0.0221 (11) | −0.0029 (9) | 0.0093 (9) | −0.0022 (9) |
N3 | 0.0152 (11) | 0.0215 (11) | 0.0217 (11) | −0.0001 (8) | 0.0090 (9) | 0.0011 (9) |
O1 | 0.0224 (9) | 0.0225 (9) | 0.0252 (10) | −0.0031 (7) | 0.0118 (8) | −0.0029 (7) |
O2 | 0.0303 (11) | 0.0281 (10) | 0.0318 (11) | −0.0089 (8) | 0.0205 (9) | −0.0043 (8) |
O3 | 0.0149 (9) | 0.0282 (10) | 0.0251 (10) | −0.0018 (7) | 0.0058 (8) | 0.0009 (8) |
O4 | 0.0209 (9) | 0.0198 (9) | 0.0234 (9) | −0.0017 (7) | 0.0059 (8) | −0.0002 (7) |
C1 | 0.0142 (12) | 0.0211 (13) | 0.0193 (13) | 0.0010 (10) | 0.0058 (10) | 0.0012 (10) |
C2 | 0.0120 (11) | 0.0199 (12) | 0.0177 (12) | 0.0017 (9) | 0.0051 (10) | 0.0034 (10) |
C3 | 0.0131 (12) | 0.0285 (13) | 0.0226 (13) | −0.0016 (10) | 0.0067 (10) | 0.0028 (11) |
C4 | 0.0181 (13) | 0.0320 (15) | 0.0226 (13) | 0.0014 (11) | 0.0102 (11) | −0.0014 (11) |
C5 | 0.0109 (11) | 0.0223 (12) | 0.0177 (12) | 0.0004 (9) | 0.0035 (10) | 0.0003 (10) |
C6 | 0.0164 (12) | 0.0248 (13) | 0.0182 (12) | −0.0031 (10) | 0.0065 (10) | −0.0050 (10) |
C7 | 0.0161 (12) | 0.0150 (11) | 0.0207 (13) | −0.0002 (9) | 0.0064 (10) | −0.0015 (9) |
C8 | 0.0201 (13) | 0.0250 (13) | 0.0226 (13) | 0.0016 (10) | 0.0110 (11) | 0.0003 (11) |
C9 | 0.0267 (14) | 0.0232 (13) | 0.0186 (13) | 0.0004 (11) | 0.0066 (11) | −0.0013 (10) |
C10 | 0.0156 (13) | 0.0259 (13) | 0.0233 (14) | 0.0011 (10) | 0.0009 (11) | 0.0021 (11) |
C11 | 0.0149 (12) | 0.0256 (13) | 0.0284 (14) | −0.0010 (10) | 0.0081 (11) | 0.0008 (11) |
C12 | 0.0165 (12) | 0.0188 (12) | 0.0224 (13) | −0.0008 (9) | 0.0088 (11) | −0.0016 (10) |
C13 | 0.0165 (12) | 0.0187 (12) | 0.0231 (13) | −0.0027 (10) | 0.0112 (10) | −0.0028 (10) |
C14 | 0.0177 (12) | 0.0158 (12) | 0.0223 (13) | −0.0035 (9) | 0.0083 (10) | −0.0022 (10) |
C15 | 0.0233 (13) | 0.0232 (13) | 0.0231 (13) | −0.0040 (11) | 0.0131 (11) | −0.0009 (10) |
C16 | 0.0250 (14) | 0.0257 (13) | 0.0203 (13) | −0.0065 (11) | 0.0073 (11) | 0.0017 (10) |
C17 | 0.0164 (13) | 0.0265 (13) | 0.0247 (14) | −0.0015 (10) | 0.0032 (11) | 0.0050 (11) |
C18 | 0.0152 (12) | 0.0232 (13) | 0.0252 (14) | −0.0020 (10) | 0.0080 (11) | 0.0010 (10) |
C19 | 0.0194 (13) | 0.0163 (11) | 0.0199 (12) | −0.0032 (10) | 0.0090 (10) | 0.0000 (10) |
Zn1—O1 | 2.0326 (17) | C7—C8 | 1.410 (4) |
Zn1—O1i | 2.0326 (17) | C7—C12 | 1.425 (3) |
Zn1—N1i | 2.093 (2) | C8—C9 | 1.366 (4) |
Zn1—N1 | 2.093 (2) | C8—H8 | 0.9300 |
Zn1—O4ii | 2.2435 (17) | C9—C10 | 1.414 (4) |
Zn1—O4iii | 2.2435 (17) | C9—H9 | 0.9300 |
N1—C3 | 1.332 (3) | C10—C11 | 1.357 (4) |
N1—C2 | 1.338 (3) | C10—H10 | 0.9300 |
N2—C4 | 1.333 (4) | C11—C12 | 1.425 (4) |
N2—C5 | 1.340 (3) | C11—H11 | 0.9300 |
N3—C7 | 1.358 (3) | C12—C13 | 1.387 (4) |
N3—C19 | 1.359 (3) | C13—C14 | 1.388 (4) |
N3—H3N | 0.86 (2) | C13—H13 | 0.9300 |
O1—C1 | 1.273 (3) | C14—C19 | 1.422 (3) |
O2—C1 | 1.240 (3) | C14—C15 | 1.427 (4) |
O3—C6 | 1.263 (3) | C15—C16 | 1.357 (4) |
O4—C6 | 1.249 (3) | C15—H15 | 0.9300 |
C1—C2 | 1.528 (3) | C16—C17 | 1.422 (4) |
C2—C5 | 1.399 (3) | C16—H16 | 0.9300 |
C3—C4 | 1.377 (4) | C17—C18 | 1.359 (4) |
C3—H3 | 0.9300 | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—C19 | 1.414 (4) |
C5—C6 | 1.526 (3) | C18—H18 | 0.9300 |
O1—Zn1—O1i | 180.0 | O3—C6—C5 | 114.1 (2) |
O1—Zn1—N1i | 99.32 (7) | N3—C7—C8 | 120.4 (2) |
O1i—Zn1—N1i | 80.68 (7) | N3—C7—C12 | 119.5 (2) |
O1—Zn1—N1 | 80.68 (7) | C8—C7—C12 | 120.1 (2) |
O1i—Zn1—N1 | 99.32 (7) | C9—C8—C7 | 119.3 (2) |
N1i—Zn1—N1 | 180.0 | C9—C8—H8 | 120.4 |
O1—Zn1—O4ii | 86.88 (7) | C7—C8—H8 | 120.4 |
O1i—Zn1—O4ii | 93.12 (7) | C8—C9—C10 | 121.2 (2) |
N1i—Zn1—O4ii | 89.71 (7) | C8—C9—H9 | 119.4 |
N1—Zn1—O4ii | 90.29 (7) | C10—C9—H9 | 119.4 |
O1—Zn1—O4iii | 93.12 (7) | C11—C10—C9 | 120.8 (2) |
O1i—Zn1—O4iii | 86.88 (7) | C11—C10—H10 | 119.6 |
N1i—Zn1—O4iii | 90.29 (7) | C9—C10—H10 | 119.6 |
N1—Zn1—O4iii | 89.71 (7) | C10—C11—C12 | 120.1 (2) |
O4ii—Zn1—O4iii | 180.000 (1) | C10—C11—H11 | 120.0 |
C3—N1—C2 | 118.8 (2) | C12—C11—H11 | 120.0 |
C3—N1—Zn1 | 129.49 (17) | C13—C12—C11 | 122.9 (2) |
C2—N1—Zn1 | 111.71 (16) | C13—C12—C7 | 118.5 (2) |
C4—N2—C5 | 116.2 (2) | C11—C12—C7 | 118.6 (2) |
C7—N3—C19 | 122.7 (2) | C12—C13—C14 | 121.2 (2) |
C7—N3—H3N | 115.6 (19) | C12—C13—H13 | 119.4 |
C19—N3—H3N | 121.6 (19) | C14—C13—H13 | 119.4 |
C1—O1—Zn1 | 115.63 (15) | C13—C14—C19 | 119.0 (2) |
C6—O4—Zn1iv | 145.70 (16) | C13—C14—C15 | 122.8 (2) |
O2—C1—O1 | 126.6 (2) | C19—C14—C15 | 118.2 (2) |
O2—C1—C2 | 117.0 (2) | C16—C15—C14 | 120.8 (2) |
O1—C1—C2 | 116.4 (2) | C16—C15—H15 | 119.6 |
N1—C2—C5 | 119.9 (2) | C14—C15—H15 | 119.6 |
N1—C2—C1 | 115.5 (2) | C15—C16—C17 | 119.6 (2) |
C5—C2—C1 | 124.7 (2) | C15—C16—H16 | 120.2 |
N1—C3—C4 | 120.1 (2) | C17—C16—H16 | 120.2 |
N1—C3—H3 | 119.9 | C18—C17—C16 | 122.1 (2) |
C4—C3—H3 | 119.9 | C18—C17—H17 | 118.9 |
N2—C4—C3 | 123.1 (2) | C16—C17—H17 | 118.9 |
N2—C4—H4 | 118.5 | C17—C18—C19 | 118.7 (2) |
C3—C4—H4 | 118.5 | C17—C18—H18 | 120.6 |
N2—C5—C2 | 121.9 (2) | C19—C18—H18 | 120.6 |
N2—C5—C6 | 115.7 (2) | N3—C19—C18 | 120.4 (2) |
C2—C5—C6 | 122.3 (2) | N3—C19—C14 | 119.1 (2) |
O4—C6—O3 | 126.0 (2) | C18—C19—C14 | 120.5 (2) |
O4—C6—C5 | 119.9 (2) | ||
O1—Zn1—N1—C3 | 179.3 (2) | N2—C5—C6—O4 | 83.9 (3) |
O1i—Zn1—N1—C3 | −0.7 (2) | C2—C5—C6—O4 | −98.6 (3) |
O4ii—Zn1—N1—C3 | 92.5 (2) | N2—C5—C6—O3 | −93.2 (3) |
O4iii—Zn1—N1—C3 | −87.5 (2) | C2—C5—C6—O3 | 84.3 (3) |
O1—Zn1—N1—C2 | −1.26 (16) | C19—N3—C7—C8 | −177.2 (2) |
O1i—Zn1—N1—C2 | 178.74 (16) | C19—N3—C7—C12 | 2.4 (4) |
O4ii—Zn1—N1—C2 | −88.05 (16) | N3—C7—C8—C9 | 179.3 (2) |
O4iii—Zn1—N1—C2 | 91.95 (16) | C12—C7—C8—C9 | −0.4 (4) |
N1i—Zn1—O1—C1 | −177.15 (17) | C7—C8—C9—C10 | 0.8 (4) |
N1—Zn1—O1—C1 | 2.85 (17) | C8—C9—C10—C11 | −0.8 (4) |
O4ii—Zn1—O1—C1 | 93.66 (17) | C9—C10—C11—C12 | 0.2 (4) |
O4iii—Zn1—O1—C1 | −86.34 (17) | C10—C11—C12—C13 | −179.4 (2) |
Zn1—O1—C1—O2 | 175.2 (2) | C10—C11—C12—C7 | 0.2 (4) |
Zn1—O1—C1—C2 | −3.8 (3) | N3—C7—C12—C13 | −0.1 (3) |
C3—N1—C2—C5 | −0.7 (3) | C8—C7—C12—C13 | 179.5 (2) |
Zn1—N1—C2—C5 | 179.80 (17) | N3—C7—C12—C11 | −179.8 (2) |
C3—N1—C2—C1 | 179.3 (2) | C8—C7—C12—C11 | −0.2 (3) |
Zn1—N1—C2—C1 | −0.2 (2) | C11—C12—C13—C14 | 178.3 (2) |
O2—C1—C2—N1 | −176.4 (2) | C7—C12—C13—C14 | −1.4 (4) |
O1—C1—C2—N1 | 2.7 (3) | C12—C13—C14—C19 | 0.7 (4) |
O2—C1—C2—C5 | 3.6 (4) | C12—C13—C14—C15 | −178.8 (2) |
O1—C1—C2—C5 | −177.4 (2) | C13—C14—C15—C16 | 178.9 (2) |
C2—N1—C3—C4 | 0.7 (4) | C19—C14—C15—C16 | −0.6 (4) |
Zn1—N1—C3—C4 | −179.85 (18) | C14—C15—C16—C17 | −0.7 (4) |
C5—N2—C4—C3 | −0.7 (4) | C15—C16—C17—C18 | 1.6 (4) |
N1—C3—C4—N2 | 0.0 (4) | C16—C17—C18—C19 | −1.2 (4) |
C4—N2—C5—C2 | 0.7 (4) | C7—N3—C19—C18 | 176.9 (2) |
C4—N2—C5—C6 | 178.2 (2) | C7—N3—C19—C14 | −3.1 (4) |
N1—C2—C5—N2 | −0.1 (4) | C17—C18—C19—N3 | 179.8 (2) |
C1—C2—C5—N2 | 179.9 (2) | C17—C18—C19—C14 | −0.2 (4) |
N1—C2—C5—C6 | −177.4 (2) | C13—C14—C19—N3 | 1.6 (3) |
C1—C2—C5—C6 | 2.6 (4) | C15—C14—C19—N3 | −178.9 (2) |
Zn1iv—O4—C6—O3 | −171.95 (18) | C13—C14—C19—C18 | −178.4 (2) |
Zn1iv—O4—C6—C5 | 11.3 (4) | C15—C14—C19—C18 | 1.1 (3) |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) x, y+1, z; (iii) −x+2, −y+1, −z+1; (iv) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O3 | 0.86 (2) | 1.78 (2) | 2.634 (3) | 172 (3) |
C13—H13···O2v | 0.93 | 2.38 | 3.211 (4) | 149 |
C16—H16···O3vi | 0.93 | 2.49 | 3.377 (3) | 159 |
Symmetry codes: (v) −x+1, −y+1, −z+1; (vi) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C13H10N)2[Zn(C6H2N2O4)2] |
Mr | 758.00 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 13.2256 (12), 6.8141 (6), 17.9889 (16) |
β (°) | 111.013 (2) |
V (Å3) | 1513.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.27 × 0.15 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick 1998) |
Tmin, Tmax | 0.845, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15968, 2720, 2292 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.115, 1.14 |
No. of reflections | 2720 |
No. of parameters | 244 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.76, −0.47 |
Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008).
Zn1—O1 | 2.0326 (17) | Zn1—O4i | 2.2435 (17) |
Zn1—N1 | 2.093 (2) |
Symmetry code: (i) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O3 | 0.86 (2) | 1.78 (2) | 2.634 (3) | 172 (3) |
C13—H13···O2ii | 0.93 | 2.38 | 3.211 (4) | 149 |
C16—H16···O3iii | 0.93 | 2.49 | 3.377 (3) | 159 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z+1/2. |
H2pyzdc has proved to be well suited for the construction of multidimensional frameworks due to the presence of two adjacent carboxylate groups (O donor atoms) as substituents on the N-heterocyclic pyrazine ring (N donor atoms). In this paper, we report the hydrothermal synthesis, crystal and molecular structure of a pyrazinecarboxylate-based Zn atom supramolecular coordination compound as a novel inorganic polymer, for the first time. The hydrothermal reaction between H2pyzdc, acr, and zinc nitrate tetra-hydrate, resulted in the formation of {(C13H10N)2[Zn(C6H2N2O4)2]}n. This inorganic polymeric compound consists of an anionic complex, [Zn(pyzdc)2]2–, counter-ions, (acrH)+ molecules. In the title inorganic polymeric compound, two COOH protons have been transferred to non-coordinated pyridine rings of acr moieties. The central Zn1 atom is six-coordinated by N1 and O1 atoms in the equatorial plane from two (pyzdc)2– ligands and by two O4 atoms in the axial positions (Fig. 1). The coordination environment around the Zn atom may be considered as slightly distorted octahedral. The anionic complex lies on a crystallographic center of symmetry. The mean Zn–N and Zn–O bond lengths are 2.093 (2) and 2.138 (17) Å, respectively. In the structure of the title inorganic polymeric compound, (acrH)+ cations and [Zn(pyzdc)2]2- anions are linked together by classical N3–H3B···O3 and non-classical C13–H13···O2 and C16–H16···O3 hydrogen bonds. In the crystal structure of the title polymeric compound, the spaces between [Zn(pyzdc)2]2- fragments are filled with layers of (acrH)+ cations. Indeed, the arrangement of anionic layers to each other resulted in the making of suitable spaces for entering cationic parts. As a essential factor extensive π–π stacking interactions between parallel aromatic rings of the acridinium ions,(acrH)+, with face-to-face distances of 3.311 (3) and 3.267 (4) Å, caused to further stabilization of crystalline network.
It should be noted that most of the molecular structures consisting up dicarboxylate ligands incorporate water molecules of hydration which may lead to formation kind of (H2O)n clusters (Review article by Aghabozorg et al. 2010a). The used reaction conditions such as hydrothermal synthesis versus just normal synthesis in aqueous conditions play basic roles in this regard. Additionally, if water molecules are present, it may prevent polymerization because it will coordinate to the metal center and so, used dicarboxylate ligand can not play chelate role for connecting metal centers to each other. For example, herein, we have obtained an inorganic polymer because of applying hydrothermal condition. But, recently published work of our research group (Aghabozorg et al. 2010b) show that the reaction of cobalt(II) nitrate hexa-hydrate, acr, and H2pyzdc in aqueous solution and routine condition resulted in the formation of (acrH)2[Co(pyzdc)2(H2O)2]. 6H2O crystals as monomeric structure.