Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112050214/sf3189sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112050214/sf3189Isup2.hkl |
CCDC reference: 925255
For related literature, see: Adarsh & Dastidar (2011); Burchell et al. (2004); Guo et al. (2012); Li et al. (2009, 2012); Uemura et al. (2002); Wang et al. (2012); Wu et al. (2008, 2010); Yang (2012); Yao et al. (2012); Yue et al. (2005).
The ligand L was prepared according to the method of Yang et al. (2012). For the preparation of (I), a solution of L (69.4 mg, 0.2 mmol) in methanol (12 ml) was added dropwise to a solution of Zn(NO3)2.6H2O (29.7 mg, 0.1 mmol) in methanol (12 ml). After stirring for 30 min, the resulting mixture was filtered. The filtrate was allowed to evaporate at room temperature for one week, and colourless crystals of (I) were obtained in 72% yield. Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3256 (s), 3058 (w), 166 (v), 1549 (s), 1436 (m), 1380 (v), 1257(m), 745(m), 708 (m), 683 (m).
The H atoms of the coordinated water molecules and those on N atoms were located from difference Fourier maps and allowed to ride on their parent atoms. All other H atoms were generated geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.99 Å. [Please check added text] In all cases, Uiso(H) = 1.2Ueq(parent).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Fig. 1. The coordination environment of the ZnII cations in (I), with the
atom-numbering scheme. Displacement ellipsoids are drawn at the ??%
probability level. [Symmetry codes: (i) -x, -y + 1,
-z + 1; (ii) -x, -y + 1, -z + 2; (iii) x,
y, z - 1.] Fig. 2. (a) A view of the one-dimensional centrosymmetric double-chain structure of (I), based on 32-membered metallated macrocycles, showing the nitrate anions connected through multiple N—H···O hydrogen-bond interactions (dashed lines). (b) A space-filling view of the double-chain structure, consisting of two chiral chains individually constructed of S and R conformers bridging the metal centres. The encapsulated nitrate anions have been omitted for clarity. Fig. 3. A view of the two-dimensional supramolecular framework of (I), formed through interchain O—H···O hydrogen-bond interactions (dashed lines). Fig. 4. A view of the stacking of layers forming the three-dimensional supramolecular framework of (I) through weak interlayer C—H···O hydrogen-bond interactions (dashed lines). Fig. 5. The TGA curve for (I). Fig. 6. The solid-state photoluminescent spectra of (I) (upper line; red in the electronic version of the paper) and of the free ligand L (lower line; black) at room temperature. |
[Zn(C19H17N5O2)2(H2O)2](NO3)2 | Z = 1 |
Mr = 920.17 | F(000) = 476 |
Triclinic, P1 | Dx = 1.551 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8956 (18) Å | Cell parameters from 2618 reflections |
b = 10.161 (2) Å | θ = 2.3–24.9° |
c = 11.233 (2) Å | µ = 0.71 mm−1 |
α = 77.14 (3)° | T = 293 K |
β = 86.51 (3)° | Block, colourless |
γ = 84.80 (3)° | 0.32 × 0.23 × 0.15 mm |
V = 984.9 (3) Å3 |
Siemens SMART CCD area-detector diffractometer | 3444 independent reflections |
Radiation source: fine-focus sealed tube | 2955 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.815, Tmax = 0.898 | k = −12→10 |
6816 measured reflections | l = −13→12 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.648P] where P = (Fo2 + 2Fc2)/3 |
3444 reflections | (Δ/σ)max < 0.001 |
290 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[Zn(C19H17N5O2)2(H2O)2](NO3)2 | γ = 84.80 (3)° |
Mr = 920.17 | V = 984.9 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.8956 (18) Å | Mo Kα radiation |
b = 10.161 (2) Å | µ = 0.71 mm−1 |
c = 11.233 (2) Å | T = 293 K |
α = 77.14 (3)° | 0.32 × 0.23 × 0.15 mm |
β = 86.51 (3)° |
Siemens SMART CCD area-detector diffractometer | 3444 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2955 reflections with I > 2σ(I) |
Tmin = 0.815, Tmax = 0.898 | Rint = 0.018 |
6816 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.62 e Å−3 |
3444 reflections | Δρmin = −0.35 e Å−3 |
290 parameters |
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 | ||
Zn1 | 0.0000 | 0.5000 | 0.5000 | 0.03553 (15) | |
O1 | 0.5417 (3) | 0.1385 (2) | 0.72284 (19) | 0.0620 (6) | |
O2 | 0.0601 (3) | −0.1740 (2) | 1.2035 (2) | 0.0695 (7) | |
O3 | 0.0799 (2) | 0.56867 (19) | 0.31878 (17) | 0.0449 (5) | |
O4 | 0.0545 (4) | 0.4225 (3) | 0.1427 (3) | 0.1000 (10) | |
O5 | 0.2861 (5) | 0.4455 (5) | 0.0915 (5) | 0.1547 (18) | |
O6 | 0.1656 (4) | 0.3118 (3) | 0.0191 (3) | 0.0958 (10) | |
N1 | 0.2843 (2) | 0.0198 (2) | 0.96892 (19) | 0.0365 (5) | |
N2 | 0.4102 (3) | 0.2471 (2) | 0.8568 (2) | 0.0417 (5) | |
N3 | 0.2140 (2) | 0.5325 (2) | 0.56442 (19) | 0.0336 (5) | |
N4 | 0.0914 (3) | 0.0479 (2) | 1.1531 (2) | 0.0428 (6) | |
N5 | 0.0844 (2) | 0.2841 (2) | 1.47590 (19) | 0.0375 (5) | |
N6 | 0.1717 (4) | 0.3910 (3) | 0.0864 (3) | 0.0729 (9) | |
C1 | 0.4518 (3) | 0.1386 (3) | 0.8109 (2) | 0.0422 (7) | |
C2 | 0.3812 (3) | 0.0105 (3) | 0.8749 (2) | 0.0381 (6) | |
C3 | 0.4196 (4) | −0.1103 (3) | 0.8389 (3) | 0.0492 (7) | |
H3 | 0.4911 | −0.1144 | 0.7732 | 0.059* | |
C4 | 0.3521 (4) | −0.2247 (3) | 0.9002 (3) | 0.0532 (8) | |
H4A | 0.3758 | −0.3087 | 0.8768 | 0.064* | |
C5 | 0.2497 (4) | −0.2155 (3) | 0.9961 (3) | 0.0459 (7) | |
H5 | 0.2004 | −0.2924 | 1.0389 | 0.055* | |
C6 | 0.2205 (3) | −0.0916 (3) | 1.0283 (2) | 0.0373 (6) | |
C7 | 0.1175 (3) | −0.0768 (3) | 1.1366 (2) | 0.0417 (6) | |
C8 | 0.4807 (3) | 0.3738 (3) | 0.8171 (3) | 0.0473 (7) | |
H8A | 0.5889 | 0.3531 | 0.7969 | 0.057* | |
H8B | 0.4751 | 0.4202 | 0.8861 | 0.057* | |
C9 | 0.4118 (3) | 0.4702 (3) | 0.7078 (2) | 0.0364 (6) | |
C10 | 0.4902 (3) | 0.5778 (3) | 0.6442 (3) | 0.0421 (6) | |
H10 | 0.5848 | 0.5940 | 0.6709 | 0.051* | |
C11 | 0.4286 (3) | 0.6613 (3) | 0.5411 (3) | 0.0428 (7) | |
H11 | 0.4789 | 0.7372 | 0.4975 | 0.051* | |
C12 | 0.2941 (3) | 0.6333 (3) | 0.5025 (2) | 0.0384 (6) | |
H12 | 0.2562 | 0.6877 | 0.4287 | 0.046* | |
C13 | 0.2720 (3) | 0.4551 (3) | 0.6672 (2) | 0.0344 (6) | |
H13 | 0.2137 | 0.3865 | 0.7144 | 0.041* | |
C14 | −0.0078 (3) | 0.0826 (3) | 1.2505 (3) | 0.0493 (7) | |
H14A | −0.0663 | 0.0042 | 1.2876 | 0.059* | |
H14B | −0.0806 | 0.1588 | 1.2150 | 0.059* | |
C15 | 0.0740 (3) | 0.1220 (3) | 1.3493 (2) | 0.0382 (6) | |
C16 | 0.1964 (3) | 0.0453 (3) | 1.4066 (3) | 0.0472 (7) | |
H16 | 0.2361 | −0.0354 | 1.3828 | 0.057* | |
C17 | 0.2595 (3) | 0.0885 (3) | 1.4987 (3) | 0.0504 (7) | |
H17 | 0.3434 | 0.0376 | 1.5397 | 0.060* | |
C18 | 0.2002 (3) | 0.2061 (3) | 1.5309 (3) | 0.0445 (7) | |
H18 | 0.2439 | 0.2333 | 1.5958 | 0.053* | |
C19 | 0.0246 (3) | 0.2396 (3) | 1.3869 (2) | 0.0386 (6) | |
H19 | −0.0582 | 0.2932 | 1.3466 | 0.046* | |
H3C | 0.0762 | 0.6514 | 0.2756 | 0.080 (12)* | |
H3B | 0.0937 | 0.5160 | 0.2567 | 0.093 (14)* | |
H2 | 0.3341 | 0.2398 | 0.9234 | 0.050 (8)* | |
H4 | 0.1354 | 0.1142 | 1.1004 | 0.050 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0354 (2) | 0.0346 (3) | 0.0342 (2) | −0.00360 (18) | −0.00071 (17) | −0.00225 (18) |
O1 | 0.0689 (14) | 0.0602 (14) | 0.0480 (12) | 0.0047 (11) | 0.0171 (11) | −0.0023 (11) |
O2 | 0.1059 (19) | 0.0364 (12) | 0.0606 (14) | −0.0140 (12) | 0.0246 (13) | −0.0032 (11) |
O3 | 0.0592 (12) | 0.0375 (11) | 0.0352 (10) | −0.0075 (9) | 0.0055 (9) | −0.0027 (9) |
O4 | 0.130 (3) | 0.096 (2) | 0.0725 (19) | −0.001 (2) | 0.0257 (18) | −0.0267 (17) |
O5 | 0.117 (3) | 0.127 (3) | 0.245 (5) | −0.032 (3) | −0.032 (3) | −0.077 (3) |
O6 | 0.140 (3) | 0.0563 (16) | 0.099 (2) | −0.0239 (16) | 0.0449 (19) | −0.0407 (16) |
N1 | 0.0460 (12) | 0.0309 (12) | 0.0317 (11) | 0.0018 (10) | −0.0063 (9) | −0.0053 (9) |
N2 | 0.0476 (13) | 0.0377 (13) | 0.0365 (12) | −0.0018 (10) | −0.0001 (10) | −0.0022 (10) |
N3 | 0.0352 (11) | 0.0283 (11) | 0.0355 (11) | −0.0001 (9) | 0.0016 (9) | −0.0050 (9) |
N4 | 0.0522 (14) | 0.0364 (13) | 0.0415 (13) | −0.0078 (11) | 0.0076 (11) | −0.0130 (11) |
N5 | 0.0402 (12) | 0.0343 (12) | 0.0365 (12) | −0.0004 (10) | 0.0015 (9) | −0.0065 (10) |
N6 | 0.104 (3) | 0.0398 (16) | 0.075 (2) | −0.0087 (17) | 0.0118 (19) | −0.0177 (15) |
C1 | 0.0445 (15) | 0.0440 (17) | 0.0323 (14) | 0.0062 (13) | −0.0058 (12) | 0.0012 (12) |
C2 | 0.0446 (15) | 0.0380 (15) | 0.0297 (13) | 0.0069 (12) | −0.0074 (11) | −0.0059 (11) |
C3 | 0.0619 (18) | 0.0480 (18) | 0.0361 (15) | 0.0107 (14) | −0.0029 (13) | −0.0118 (13) |
C4 | 0.077 (2) | 0.0387 (17) | 0.0452 (17) | 0.0114 (15) | −0.0068 (15) | −0.0175 (14) |
C5 | 0.0659 (19) | 0.0325 (15) | 0.0391 (15) | 0.0015 (13) | −0.0107 (13) | −0.0073 (12) |
C6 | 0.0491 (15) | 0.0311 (14) | 0.0314 (13) | 0.0013 (12) | −0.0096 (11) | −0.0057 (11) |
C7 | 0.0551 (17) | 0.0325 (15) | 0.0369 (15) | −0.0041 (13) | −0.0047 (12) | −0.0057 (12) |
C8 | 0.0515 (17) | 0.0443 (17) | 0.0432 (16) | −0.0076 (13) | −0.0107 (13) | 0.0004 (13) |
C9 | 0.0403 (14) | 0.0323 (14) | 0.0359 (14) | −0.0013 (11) | 0.0004 (11) | −0.0074 (11) |
C10 | 0.0399 (14) | 0.0417 (16) | 0.0454 (16) | −0.0084 (12) | 0.0006 (12) | −0.0095 (13) |
C11 | 0.0446 (15) | 0.0346 (15) | 0.0465 (16) | −0.0106 (12) | 0.0067 (12) | −0.0028 (12) |
C12 | 0.0423 (14) | 0.0313 (14) | 0.0381 (14) | −0.0001 (11) | 0.0026 (11) | −0.0023 (11) |
C13 | 0.0376 (13) | 0.0289 (13) | 0.0354 (14) | −0.0027 (11) | 0.0033 (11) | −0.0055 (11) |
C14 | 0.0452 (16) | 0.0543 (19) | 0.0534 (18) | −0.0072 (14) | 0.0082 (13) | −0.0237 (15) |
C15 | 0.0378 (14) | 0.0360 (15) | 0.0396 (14) | −0.0064 (11) | 0.0105 (11) | −0.0073 (12) |
C16 | 0.0519 (17) | 0.0359 (16) | 0.0524 (17) | 0.0030 (13) | 0.0069 (14) | −0.0113 (13) |
C17 | 0.0479 (16) | 0.0460 (18) | 0.0544 (18) | 0.0085 (14) | −0.0066 (14) | −0.0087 (14) |
C18 | 0.0474 (16) | 0.0424 (16) | 0.0446 (16) | −0.0009 (13) | −0.0043 (13) | −0.0118 (13) |
C19 | 0.0376 (14) | 0.0385 (15) | 0.0376 (14) | 0.0011 (11) | 0.0031 (11) | −0.0067 (12) |
Zn1—O3i | 2.1017 (19) | C3—H3 | 0.9500 |
Zn1—O3 | 2.1017 (19) | C4—C5 | 1.382 (4) |
Zn1—N3 | 2.155 (2) | C4—H4A | 0.9500 |
Zn1—N3i | 2.155 (2) | C5—C6 | 1.384 (4) |
Zn1—N5ii | 2.321 (2) | C5—H5 | 0.9500 |
Zn1—N5iii | 2.321 (2) | C6—C7 | 1.505 (4) |
O1—C1 | 1.234 (3) | C8—C9 | 1.513 (4) |
O2—C7 | 1.230 (3) | C8—H8A | 0.9900 |
O3—H3C | 0.8709 | C8—H8B | 0.9900 |
O3—H3B | 0.9656 | C9—C13 | 1.383 (4) |
O4—N6 | 1.240 (4) | C9—C10 | 1.387 (4) |
O5—N6 | 1.212 (5) | C10—C11 | 1.385 (4) |
O6—N6 | 1.228 (4) | C10—H10 | 0.9500 |
N1—C6 | 1.335 (3) | C11—C12 | 1.370 (4) |
N1—C2 | 1.337 (3) | C11—H11 | 0.9500 |
N2—C1 | 1.332 (4) | C12—H12 | 0.9500 |
N2—C8 | 1.451 (4) | C13—H13 | 0.9500 |
N2—H2 | 0.9726 | C14—C15 | 1.507 (4) |
N3—C12 | 1.341 (3) | C14—H14A | 0.9900 |
N3—C13 | 1.346 (3) | C14—H14B | 0.9900 |
N4—C7 | 1.319 (3) | C15—C19 | 1.380 (4) |
N4—C14 | 1.448 (3) | C15—C16 | 1.384 (4) |
N4—H4 | 0.8946 | C16—C17 | 1.377 (4) |
N5—C18 | 1.335 (4) | C16—H16 | 0.9500 |
N5—C19 | 1.340 (3) | C17—C18 | 1.375 (4) |
N5—Zn1iv | 2.321 (2) | C17—H17 | 0.9500 |
C1—C2 | 1.511 (4) | C18—H18 | 0.9500 |
C2—C3 | 1.384 (4) | C19—H19 | 0.9500 |
C3—C4 | 1.381 (4) | ||
O3i—Zn1—O3 | 180.0 | N1—C6—C5 | 122.9 (3) |
O3i—Zn1—N3 | 90.12 (8) | N1—C6—C7 | 116.1 (2) |
O3—Zn1—N3 | 89.88 (8) | C5—C6—C7 | 121.0 (3) |
O3i—Zn1—N3i | 89.88 (8) | O2—C7—N4 | 122.7 (3) |
O3—Zn1—N3i | 90.12 (8) | O2—C7—C6 | 122.2 (3) |
N3—Zn1—N3i | 180.0 | N4—C7—C6 | 115.1 (2) |
O3i—Zn1—N5ii | 86.39 (8) | N2—C8—C9 | 115.0 (2) |
O3—Zn1—N5ii | 93.61 (8) | N2—C8—H8A | 108.5 |
N3—Zn1—N5ii | 87.51 (8) | C9—C8—H8A | 108.5 |
N3i—Zn1—N5ii | 92.50 (8) | N2—C8—H8B | 108.5 |
O3i—Zn1—N5iii | 93.61 (8) | C9—C8—H8B | 108.5 |
O3—Zn1—N5iii | 86.39 (8) | H8A—C8—H8B | 107.5 |
N3—Zn1—N5iii | 92.49 (8) | C13—C9—C10 | 117.8 (2) |
N3i—Zn1—N5iii | 87.50 (8) | C13—C9—C8 | 122.5 (2) |
N5ii—Zn1—N5iii | 180.0 | C10—C9—C8 | 119.8 (2) |
Zn1—O3—H3C | 128.1 | C11—C10—C9 | 119.0 (3) |
Zn1—O3—H3B | 126.1 | C11—C10—H10 | 120.5 |
H3C—O3—H3B | 102.3 | C9—C10—H10 | 120.5 |
C6—N1—C2 | 118.3 (2) | C12—C11—C10 | 119.3 (2) |
C1—N2—C8 | 122.7 (2) | C12—C11—H11 | 120.3 |
C1—N2—H2 | 118.9 | C10—C11—H11 | 120.3 |
C8—N2—H2 | 118.3 | N3—C12—C11 | 122.8 (2) |
C12—N3—C13 | 117.4 (2) | N3—C12—H12 | 118.6 |
C12—N3—Zn1 | 120.23 (17) | C11—C12—H12 | 118.6 |
C13—N3—Zn1 | 122.35 (16) | N3—C13—C9 | 123.5 (2) |
C7—N4—C14 | 123.1 (2) | N3—C13—H13 | 118.3 |
C7—N4—H4 | 118.2 | C9—C13—H13 | 118.3 |
C14—N4—H4 | 118.7 | N4—C14—C15 | 113.7 (2) |
C18—N5—C19 | 115.8 (2) | N4—C14—H14A | 108.8 |
C18—N5—Zn1iv | 126.49 (19) | C15—C14—H14A | 108.8 |
C19—N5—Zn1iv | 117.10 (17) | N4—C14—H14B | 108.8 |
O5—N6—O6 | 121.3 (4) | C15—C14—H14B | 108.8 |
O5—N6—O4 | 120.1 (4) | H14A—C14—H14B | 107.7 |
O6—N6—O4 | 118.5 (4) | C19—C15—C16 | 117.4 (3) |
O1—C1—N2 | 124.2 (3) | C19—C15—C14 | 119.1 (3) |
O1—C1—C2 | 120.5 (3) | C16—C15—C14 | 123.4 (3) |
N2—C1—C2 | 115.3 (2) | C17—C16—C15 | 118.6 (3) |
N1—C2—C3 | 122.5 (3) | C17—C16—H16 | 120.7 |
N1—C2—C1 | 116.6 (2) | C15—C16—H16 | 120.7 |
C3—C2—C1 | 120.9 (3) | C18—C17—C16 | 119.5 (3) |
C4—C3—C2 | 118.8 (3) | C18—C17—H17 | 120.3 |
C4—C3—H3 | 120.6 | C16—C17—H17 | 120.3 |
C2—C3—H3 | 120.6 | N5—C18—C17 | 123.5 (3) |
C3—C4—C5 | 119.1 (3) | N5—C18—H18 | 118.2 |
C3—C4—H4A | 120.4 | C17—C18—H18 | 118.2 |
C5—C4—H4A | 120.4 | N5—C19—C15 | 125.1 (3) |
C4—C5—C6 | 118.4 (3) | N5—C19—H19 | 117.4 |
C4—C5—H5 | 120.8 | C15—C19—H19 | 117.4 |
C6—C5—H5 | 120.8 | ||
O3i—Zn1—N3—C12 | −147.6 (2) | C5—C6—C7—O2 | 3.0 (4) |
O3—Zn1—N3—C12 | 32.4 (2) | N1—C6—C7—N4 | 6.0 (4) |
N3i—Zn1—N3—C12 | 72 (25) | C5—C6—C7—N4 | −175.9 (3) |
N5ii—Zn1—N3—C12 | −61.21 (19) | C1—N2—C8—C9 | 87.7 (3) |
N5iii—Zn1—N3—C12 | 118.79 (19) | N2—C8—C9—C13 | 15.1 (4) |
O3i—Zn1—N3—C13 | 31.75 (19) | N2—C8—C9—C10 | −164.5 (3) |
O3—Zn1—N3—C13 | −148.25 (19) | C13—C9—C10—C11 | −2.6 (4) |
N3i—Zn1—N3—C13 | −109 (25) | C8—C9—C10—C11 | 177.1 (3) |
N5ii—Zn1—N3—C13 | 118.13 (19) | C9—C10—C11—C12 | −1.9 (4) |
N5iii—Zn1—N3—C13 | −61.87 (19) | C13—N3—C12—C11 | −1.4 (4) |
C8—N2—C1—O1 | −7.8 (4) | Zn1—N3—C12—C11 | 178.0 (2) |
C8—N2—C1—C2 | 172.0 (2) | C10—C11—C12—N3 | 4.1 (4) |
C6—N1—C2—C3 | −1.3 (4) | C12—N3—C13—C9 | −3.4 (4) |
C6—N1—C2—C1 | −179.5 (2) | Zn1—N3—C13—C9 | 177.19 (19) |
O1—C1—C2—N1 | −179.5 (2) | C10—C9—C13—N3 | 5.4 (4) |
N2—C1—C2—N1 | 0.7 (3) | C8—C9—C13—N3 | −174.2 (2) |
O1—C1—C2—C3 | 2.3 (4) | C7—N4—C14—C15 | 109.3 (3) |
N2—C1—C2—C3 | −177.5 (2) | N4—C14—C15—C19 | 130.7 (3) |
N1—C2—C3—C4 | 1.9 (4) | N4—C14—C15—C16 | −50.1 (4) |
C1—C2—C3—C4 | 179.9 (3) | C19—C15—C16—C17 | 1.4 (4) |
C2—C3—C4—C5 | −0.6 (5) | C14—C15—C16—C17 | −177.8 (3) |
C3—C4—C5—C6 | −1.1 (4) | C15—C16—C17—C18 | −0.3 (4) |
C2—N1—C6—C5 | −0.5 (4) | C19—N5—C18—C17 | 1.5 (4) |
C2—N1—C6—C7 | 177.5 (2) | Zn1iv—N5—C18—C17 | −169.4 (2) |
C4—C5—C6—N1 | 1.7 (4) | C16—C17—C18—N5 | −1.3 (5) |
C4—C5—C6—C7 | −176.2 (3) | C18—N5—C19—C15 | −0.2 (4) |
C14—N4—C7—O2 | −0.6 (5) | Zn1iv—N5—C19—C15 | 171.5 (2) |
C14—N4—C7—C6 | 178.4 (2) | C16—C15—C19—N5 | −1.2 (4) |
N1—C6—C7—O2 | −175.0 (3) | C14—C15—C19—N5 | 178.1 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) x, y, z−1; (iv) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O4 | 0.97 | 1.82 | 2.755 (4) | 162 |
O3—H3C···O2v | 0.87 | 1.78 | 2.643 (3) | 173 |
N2—H2···O6iv | 0.97 | 1.97 | 2.877 (4) | 154 |
N4—H4···O6iv | 0.89 | 2.05 | 2.881 (4) | 155 |
Symmetry codes: (iv) x, y, z+1; (v) x, y+1, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C19H17N5O2)2(H2O)2](NO3)2 |
Mr | 920.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.8956 (18), 10.161 (2), 11.233 (2) |
α, β, γ (°) | 77.14 (3), 86.51 (3), 84.80 (3) |
V (Å3) | 984.9 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.32 × 0.23 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.815, 0.898 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6816, 3444, 2955 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.103, 1.05 |
No. of reflections | 3444 |
No. of parameters | 290 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.35 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Zn1—O3 | 2.1017 (19) | Zn1—N5i | 2.321 (2) |
Zn1—N3 | 2.155 (2) | ||
O3ii—Zn1—O3 | 180.0 | O3—Zn1—N5i | 93.61 (8) |
O3ii—Zn1—N3 | 90.12 (8) | N3—Zn1—N5i | 87.51 (8) |
O3—Zn1—N3 | 89.88 (8) | N3ii—Zn1—N5i | 92.50 (8) |
N3—Zn1—N3ii | 180.0 | N5i—Zn1—N5iii | 180.0 |
O3ii—Zn1—N5i | 86.39 (8) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x, −y+1, −z+1; (iii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3B···O4 | 0.97 | 1.82 | 2.755 (4) | 161.8 |
O3—H3C···O2iv | 0.87 | 1.78 | 2.643 (3) | 173.2 |
N2—H2···O6v | 0.97 | 1.97 | 2.877 (4) | 153.7 |
N4—H4···O6v | 0.89 | 2.05 | 2.881 (4) | 154.6 |
Symmetry codes: (iv) x, y+1, z−1; (v) x, y, z+1. |
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In recent decades, pyridinecarboxamides, as multidentate heterocyclic ligands, have been widely used as spacers to construct intriguing metal-containing assemblies in coordination chemistry (Yue et al., 2005; Adarsh & Dastidar, 2011; Uemura et al., 2002). Among them, the U-shaped symmetric bispyridine–bisamides, which combine rigidity with flexibility, play an important role in engineering metal-containing macrocycles, nanocages and porous frameworks (Burchell et al., 2004; Wu et al., 2008; Wang et al., 2012). In particular, the labile conformations of U-shaped symmetric bispyridine–bisamides, especially the nonplanar conformers, can be recognized and used to direct self-assembly with metal cations. For example, using N2,N6-bis(pyridin-3-yl)pyridine-2,6-dicarboxamide and N2,N6-bis[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide (L) ligands to assemble with NiII and AgI, a chiral tetragonal molecular cage (Li et al., 2012) and homochiral coordination polymers (Wu et al., 2010) have been obtained, respectively. In addition, the regular hydrogen bonding occurring from the amide groups of these ligands can further organize the resultant metal-containing arrays into higher-dimensional networks (Burchell et al., 2004), or it can anchor smaller guests in the cavities of the resulting frameworks (Guo et al., 2012). In this paper, we report the reaction of the multifunctional ligand L with zinc(II) cations, and report the title zinc(II) coordination polymer {[Zn(L)2(H2O)2](NO3)2}n, (I).
In (I), each ZnII centre is coordinated by four N atoms from the outer pyridine rings of four L ligands in the equatorial plane and by two water O atoms at the axial sites, and adopts a slightly distorted six-coordinate octahedral geometry with an inversion centre on the ZnII atom (Fig. 1). The Zn—N and Zn—O bond lengths cover the range 2.102 (2)–2.321 (2) Å (Table 1).
In (I), the U-shaped L ligands act as bidentate bridging ligands to link the Zn nodes into a one-dimensional centrosymmetric double-chain structure along the c axis (Fig. 2a), in contrast with the two-dimensional corrugated sheet of uniform (4,4)-connected topology found in the CoII and NiII polymers of L (Yao et al., 2012; Guo et al., 2012). Owing to coordination, the outer pyridine arms of the L ligands in (I) are twisted from the central pyridine ring [dihedral angles = 90.2 (0) and 87.8 (0)°]. As a result, L ligands lower the C2v symmetry to pseudo-C2 symmetry, and adopt helical conformations very similar to those in the CoII and NiII polymers (Yao et al., 2012; Guo et al., 2012).
The polymeric chain of (I) is based on 32-membered metallated macrocycles built from a pair of enantiomers (R and S conformers) sharing two communal ZnII cations. For each macrocycle there are two nitrate anions, which are involved in multiple N—H···O hydrogen-bond interactions (Fig. 2a and Table 2). The separation of adjacent Zn nodes bridged by L is 11.233 (0) Å. Interestingly, the double-chain structure consists of two chiral chains individually constructed of S and R conformers bridging the metal centres, as shown in Fig. 2.
In (I), the double-chain structures are extended into a two-dimensional supramolecular framework in the bc plane through interchain O—H···O hydrogen-bond interactions arising from the coordinated water and the carboxamide O atoms of L (Fig. 3 and Table 2). Through weak interlayer C—H···O hydrogen-bond interactions, the layers are linked into a three-dimensional supramolecular framework (Fig. 4).
Thermogravimetric analysis (TGA) of (I) was carried out in air from 303 to 957 K at a heating rate of 10 K min-1 using a crystalline sample. As shown in Fig. 5, (I) is stable up to 420 K. On heating, the compound suffers a continuous weight loss in a range 420–868 K, indicating the complete decomposition of the framework. The remaining 8.29% may be ZnO, in agreement with the theoretical value of 8.84%.
The solid-state photoluminescence behaviours of L and (I) were investigated at room temperature, and the results are presented in Fig. 6. The free ligand L displays strong luminescence, with a single broad band centred at 397 nm, corresponding to excitation at 352 nm. When excited at 390 nm, (I) displays a very intense emission with a peak maximum at 449 nm. In comparison with the fluorescence of the free ligand L, the emission of (I) is blue-shifted by 52 nm and its intensity is increased. The emission behaviour of complex (I) probably originates from a metal-perturbed intraligand transition, as reported for ZnII or other d10 metal complexes with N-donor ligands, based on the position and shape of the emission band (Li et al., 2009).