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In the title compound, {[Zn(C19H17N5O2)2(H2O)2](NO3)2}n, the ZnII cation is located at an inversion centre within a slightly distorted octa­hedron, ligated by four N atoms from four N2,N6-bis­[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxam­ide (L) ligands occupying a plane about the ZnII atom with the two water O atoms perpendicular to that. In the complex mol­ecule, the bidentate bridging L ligands display helical R and S conformers, and link the ZnII cations into a one-dimensional centrosymmetric double-chain structure con­taining 32-membered rings. The nitrate anions reside in these rings and are involved in multiple N-H...O hydrogen-bond inter­actions. On excitation at 390 nm, the title compound displays a strong blue emission centred at 449 nm. Investigation of the thermal stability shows that the network structure is stable up to 420 K.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112050214/sf3189sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112050214/sf3189Isup2.hkl
Contains datablock I

CCDC reference: 925255

Comment top

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).

Related literature top

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).

Experimental top

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).

Refinement top

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).

Computing details top

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).

Figures top
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.
catena-Poly[[[diaquazinc]-bis{µ-N2,N6- bis[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide}] dinitrate] top
Crystal data top
[Zn(C19H17N5O2)2(H2O)2](NO3)2Z = 1
Mr = 920.17F(000) = 476
Triclinic, P1Dx = 1.551 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.8956 (18) ÅCell parameters from 2618 reflections
b = 10.161 (2) Åθ = 2.3–24.9°
c = 11.233 (2) ŵ = 0.71 mm1
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
Data collection top
Siemens SMART CCD area-detector
diffractometer
3444 independent reflections
Radiation source: fine-focus sealed tube2955 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.815, Tmax = 0.898k = 1210
6816 measured reflectionsl = 1312
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-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 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Zn(C19H17N5O2)2(H2O)2](NO3)2γ = 84.80 (3)°
Mr = 920.17V = 984.9 (3) Å3
Triclinic, P1Z = 1
a = 8.8956 (18) ÅMo Kα radiation
b = 10.161 (2) ŵ = 0.71 mm1
c = 11.233 (2) ÅT = 293 K
α = 77.14 (3)°0.32 × 0.23 × 0.15 mm
β = 86.51 (3)°
Data collection top
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 = 0.898Rint = 0.018
6816 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.103H-atom parameters constrained
S = 1.05Δρmax = 0.62 e Å3
3444 reflectionsΔρmin = 0.35 e Å3
290 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
Zn10.00000.50000.50000.03553 (15)
O10.5417 (3)0.1385 (2)0.72284 (19)0.0620 (6)
O20.0601 (3)0.1740 (2)1.2035 (2)0.0695 (7)
O30.0799 (2)0.56867 (19)0.31878 (17)0.0449 (5)
O40.0545 (4)0.4225 (3)0.1427 (3)0.1000 (10)
O50.2861 (5)0.4455 (5)0.0915 (5)0.1547 (18)
O60.1656 (4)0.3118 (3)0.0191 (3)0.0958 (10)
N10.2843 (2)0.0198 (2)0.96892 (19)0.0365 (5)
N20.4102 (3)0.2471 (2)0.8568 (2)0.0417 (5)
N30.2140 (2)0.5325 (2)0.56442 (19)0.0336 (5)
N40.0914 (3)0.0479 (2)1.1531 (2)0.0428 (6)
N50.0844 (2)0.2841 (2)1.47590 (19)0.0375 (5)
N60.1717 (4)0.3910 (3)0.0864 (3)0.0729 (9)
C10.4518 (3)0.1386 (3)0.8109 (2)0.0422 (7)
C20.3812 (3)0.0105 (3)0.8749 (2)0.0381 (6)
C30.4196 (4)0.1103 (3)0.8389 (3)0.0492 (7)
H30.49110.11440.77320.059*
C40.3521 (4)0.2247 (3)0.9002 (3)0.0532 (8)
H4A0.37580.30870.87680.064*
C50.2497 (4)0.2155 (3)0.9961 (3)0.0459 (7)
H50.20040.29241.03890.055*
C60.2205 (3)0.0916 (3)1.0283 (2)0.0373 (6)
C70.1175 (3)0.0768 (3)1.1366 (2)0.0417 (6)
C80.4807 (3)0.3738 (3)0.8171 (3)0.0473 (7)
H8A0.58890.35310.79690.057*
H8B0.47510.42020.88610.057*
C90.4118 (3)0.4702 (3)0.7078 (2)0.0364 (6)
C100.4902 (3)0.5778 (3)0.6442 (3)0.0421 (6)
H100.58480.59400.67090.051*
C110.4286 (3)0.6613 (3)0.5411 (3)0.0428 (7)
H110.47890.73720.49750.051*
C120.2941 (3)0.6333 (3)0.5025 (2)0.0384 (6)
H120.25620.68770.42870.046*
C130.2720 (3)0.4551 (3)0.6672 (2)0.0344 (6)
H130.21370.38650.71440.041*
C140.0078 (3)0.0826 (3)1.2505 (3)0.0493 (7)
H14A0.06630.00421.28760.059*
H14B0.08060.15881.21500.059*
C150.0740 (3)0.1220 (3)1.3493 (2)0.0382 (6)
C160.1964 (3)0.0453 (3)1.4066 (3)0.0472 (7)
H160.23610.03541.38280.057*
C170.2595 (3)0.0885 (3)1.4987 (3)0.0504 (7)
H170.34340.03761.53970.060*
C180.2002 (3)0.2061 (3)1.5309 (3)0.0445 (7)
H180.24390.23331.59580.053*
C190.0246 (3)0.2396 (3)1.3869 (2)0.0386 (6)
H190.05820.29321.34660.046*
H3C0.07620.65140.27560.080 (12)*
H3B0.09370.51600.25670.093 (14)*
H20.33410.23980.92340.050 (8)*
H40.13540.11421.10040.050 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0354 (2)0.0346 (3)0.0342 (2)0.00360 (18)0.00071 (17)0.00225 (18)
O10.0689 (14)0.0602 (14)0.0480 (12)0.0047 (11)0.0171 (11)0.0023 (11)
O20.1059 (19)0.0364 (12)0.0606 (14)0.0140 (12)0.0246 (13)0.0032 (11)
O30.0592 (12)0.0375 (11)0.0352 (10)0.0075 (9)0.0055 (9)0.0027 (9)
O40.130 (3)0.096 (2)0.0725 (19)0.001 (2)0.0257 (18)0.0267 (17)
O50.117 (3)0.127 (3)0.245 (5)0.032 (3)0.032 (3)0.077 (3)
O60.140 (3)0.0563 (16)0.099 (2)0.0239 (16)0.0449 (19)0.0407 (16)
N10.0460 (12)0.0309 (12)0.0317 (11)0.0018 (10)0.0063 (9)0.0053 (9)
N20.0476 (13)0.0377 (13)0.0365 (12)0.0018 (10)0.0001 (10)0.0022 (10)
N30.0352 (11)0.0283 (11)0.0355 (11)0.0001 (9)0.0016 (9)0.0050 (9)
N40.0522 (14)0.0364 (13)0.0415 (13)0.0078 (11)0.0076 (11)0.0130 (11)
N50.0402 (12)0.0343 (12)0.0365 (12)0.0004 (10)0.0015 (9)0.0065 (10)
N60.104 (3)0.0398 (16)0.075 (2)0.0087 (17)0.0118 (19)0.0177 (15)
C10.0445 (15)0.0440 (17)0.0323 (14)0.0062 (13)0.0058 (12)0.0012 (12)
C20.0446 (15)0.0380 (15)0.0297 (13)0.0069 (12)0.0074 (11)0.0059 (11)
C30.0619 (18)0.0480 (18)0.0361 (15)0.0107 (14)0.0029 (13)0.0118 (13)
C40.077 (2)0.0387 (17)0.0452 (17)0.0114 (15)0.0068 (15)0.0175 (14)
C50.0659 (19)0.0325 (15)0.0391 (15)0.0015 (13)0.0107 (13)0.0073 (12)
C60.0491 (15)0.0311 (14)0.0314 (13)0.0013 (12)0.0096 (11)0.0057 (11)
C70.0551 (17)0.0325 (15)0.0369 (15)0.0041 (13)0.0047 (12)0.0057 (12)
C80.0515 (17)0.0443 (17)0.0432 (16)0.0076 (13)0.0107 (13)0.0004 (13)
C90.0403 (14)0.0323 (14)0.0359 (14)0.0013 (11)0.0004 (11)0.0074 (11)
C100.0399 (14)0.0417 (16)0.0454 (16)0.0084 (12)0.0006 (12)0.0095 (13)
C110.0446 (15)0.0346 (15)0.0465 (16)0.0106 (12)0.0067 (12)0.0028 (12)
C120.0423 (14)0.0313 (14)0.0381 (14)0.0001 (11)0.0026 (11)0.0023 (11)
C130.0376 (13)0.0289 (13)0.0354 (14)0.0027 (11)0.0033 (11)0.0055 (11)
C140.0452 (16)0.0543 (19)0.0534 (18)0.0072 (14)0.0082 (13)0.0237 (15)
C150.0378 (14)0.0360 (15)0.0396 (14)0.0064 (11)0.0105 (11)0.0073 (12)
C160.0519 (17)0.0359 (16)0.0524 (17)0.0030 (13)0.0069 (14)0.0113 (13)
C170.0479 (16)0.0460 (18)0.0544 (18)0.0085 (14)0.0066 (14)0.0087 (14)
C180.0474 (16)0.0424 (16)0.0446 (16)0.0009 (13)0.0043 (13)0.0118 (13)
C190.0376 (14)0.0385 (15)0.0376 (14)0.0011 (11)0.0031 (11)0.0067 (12)
Geometric parameters (Å, º) top
Zn1—O3i2.1017 (19)C3—H30.9500
Zn1—O32.1017 (19)C4—C51.382 (4)
Zn1—N32.155 (2)C4—H4A0.9500
Zn1—N3i2.155 (2)C5—C61.384 (4)
Zn1—N5ii2.321 (2)C5—H50.9500
Zn1—N5iii2.321 (2)C6—C71.505 (4)
O1—C11.234 (3)C8—C91.513 (4)
O2—C71.230 (3)C8—H8A0.9900
O3—H3C0.8709C8—H8B0.9900
O3—H3B0.9656C9—C131.383 (4)
O4—N61.240 (4)C9—C101.387 (4)
O5—N61.212 (5)C10—C111.385 (4)
O6—N61.228 (4)C10—H100.9500
N1—C61.335 (3)C11—C121.370 (4)
N1—C21.337 (3)C11—H110.9500
N2—C11.332 (4)C12—H120.9500
N2—C81.451 (4)C13—H130.9500
N2—H20.9726C14—C151.507 (4)
N3—C121.341 (3)C14—H14A0.9900
N3—C131.346 (3)C14—H14B0.9900
N4—C71.319 (3)C15—C191.380 (4)
N4—C141.448 (3)C15—C161.384 (4)
N4—H40.8946C16—C171.377 (4)
N5—C181.335 (4)C16—H160.9500
N5—C191.340 (3)C17—C181.375 (4)
N5—Zn1iv2.321 (2)C17—H170.9500
C1—C21.511 (4)C18—H180.9500
C2—C31.384 (4)C19—H190.9500
C3—C41.381 (4)
O3i—Zn1—O3180.0N1—C6—C5122.9 (3)
O3i—Zn1—N390.12 (8)N1—C6—C7116.1 (2)
O3—Zn1—N389.88 (8)C5—C6—C7121.0 (3)
O3i—Zn1—N3i89.88 (8)O2—C7—N4122.7 (3)
O3—Zn1—N3i90.12 (8)O2—C7—C6122.2 (3)
N3—Zn1—N3i180.0N4—C7—C6115.1 (2)
O3i—Zn1—N5ii86.39 (8)N2—C8—C9115.0 (2)
O3—Zn1—N5ii93.61 (8)N2—C8—H8A108.5
N3—Zn1—N5ii87.51 (8)C9—C8—H8A108.5
N3i—Zn1—N5ii92.50 (8)N2—C8—H8B108.5
O3i—Zn1—N5iii93.61 (8)C9—C8—H8B108.5
O3—Zn1—N5iii86.39 (8)H8A—C8—H8B107.5
N3—Zn1—N5iii92.49 (8)C13—C9—C10117.8 (2)
N3i—Zn1—N5iii87.50 (8)C13—C9—C8122.5 (2)
N5ii—Zn1—N5iii180.0C10—C9—C8119.8 (2)
Zn1—O3—H3C128.1C11—C10—C9119.0 (3)
Zn1—O3—H3B126.1C11—C10—H10120.5
H3C—O3—H3B102.3C9—C10—H10120.5
C6—N1—C2118.3 (2)C12—C11—C10119.3 (2)
C1—N2—C8122.7 (2)C12—C11—H11120.3
C1—N2—H2118.9C10—C11—H11120.3
C8—N2—H2118.3N3—C12—C11122.8 (2)
C12—N3—C13117.4 (2)N3—C12—H12118.6
C12—N3—Zn1120.23 (17)C11—C12—H12118.6
C13—N3—Zn1122.35 (16)N3—C13—C9123.5 (2)
C7—N4—C14123.1 (2)N3—C13—H13118.3
C7—N4—H4118.2C9—C13—H13118.3
C14—N4—H4118.7N4—C14—C15113.7 (2)
C18—N5—C19115.8 (2)N4—C14—H14A108.8
C18—N5—Zn1iv126.49 (19)C15—C14—H14A108.8
C19—N5—Zn1iv117.10 (17)N4—C14—H14B108.8
O5—N6—O6121.3 (4)C15—C14—H14B108.8
O5—N6—O4120.1 (4)H14A—C14—H14B107.7
O6—N6—O4118.5 (4)C19—C15—C16117.4 (3)
O1—C1—N2124.2 (3)C19—C15—C14119.1 (3)
O1—C1—C2120.5 (3)C16—C15—C14123.4 (3)
N2—C1—C2115.3 (2)C17—C16—C15118.6 (3)
N1—C2—C3122.5 (3)C17—C16—H16120.7
N1—C2—C1116.6 (2)C15—C16—H16120.7
C3—C2—C1120.9 (3)C18—C17—C16119.5 (3)
C4—C3—C2118.8 (3)C18—C17—H17120.3
C4—C3—H3120.6C16—C17—H17120.3
C2—C3—H3120.6N5—C18—C17123.5 (3)
C3—C4—C5119.1 (3)N5—C18—H18118.2
C3—C4—H4A120.4C17—C18—H18118.2
C5—C4—H4A120.4N5—C19—C15125.1 (3)
C4—C5—C6118.4 (3)N5—C19—H19117.4
C4—C5—H5120.8C15—C19—H19117.4
C6—C5—H5120.8
O3i—Zn1—N3—C12147.6 (2)C5—C6—C7—O23.0 (4)
O3—Zn1—N3—C1232.4 (2)N1—C6—C7—N46.0 (4)
N3i—Zn1—N3—C1272 (25)C5—C6—C7—N4175.9 (3)
N5ii—Zn1—N3—C1261.21 (19)C1—N2—C8—C987.7 (3)
N5iii—Zn1—N3—C12118.79 (19)N2—C8—C9—C1315.1 (4)
O3i—Zn1—N3—C1331.75 (19)N2—C8—C9—C10164.5 (3)
O3—Zn1—N3—C13148.25 (19)C13—C9—C10—C112.6 (4)
N3i—Zn1—N3—C13109 (25)C8—C9—C10—C11177.1 (3)
N5ii—Zn1—N3—C13118.13 (19)C9—C10—C11—C121.9 (4)
N5iii—Zn1—N3—C1361.87 (19)C13—N3—C12—C111.4 (4)
C8—N2—C1—O17.8 (4)Zn1—N3—C12—C11178.0 (2)
C8—N2—C1—C2172.0 (2)C10—C11—C12—N34.1 (4)
C6—N1—C2—C31.3 (4)C12—N3—C13—C93.4 (4)
C6—N1—C2—C1179.5 (2)Zn1—N3—C13—C9177.19 (19)
O1—C1—C2—N1179.5 (2)C10—C9—C13—N35.4 (4)
N2—C1—C2—N10.7 (3)C8—C9—C13—N3174.2 (2)
O1—C1—C2—C32.3 (4)C7—N4—C14—C15109.3 (3)
N2—C1—C2—C3177.5 (2)N4—C14—C15—C19130.7 (3)
N1—C2—C3—C41.9 (4)N4—C14—C15—C1650.1 (4)
C1—C2—C3—C4179.9 (3)C19—C15—C16—C171.4 (4)
C2—C3—C4—C50.6 (5)C14—C15—C16—C17177.8 (3)
C3—C4—C5—C61.1 (4)C15—C16—C17—C180.3 (4)
C2—N1—C6—C50.5 (4)C19—N5—C18—C171.5 (4)
C2—N1—C6—C7177.5 (2)Zn1iv—N5—C18—C17169.4 (2)
C4—C5—C6—N11.7 (4)C16—C17—C18—N51.3 (5)
C4—C5—C6—C7176.2 (3)C18—N5—C19—C150.2 (4)
C14—N4—C7—O20.6 (5)Zn1iv—N5—C19—C15171.5 (2)
C14—N4—C7—C6178.4 (2)C16—C15—C19—N51.2 (4)
N1—C6—C7—O2175.0 (3)C14—C15—C19—N5178.1 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+1, z+2; (iii) x, y, z1; (iv) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O40.971.822.755 (4)162
O3—H3C···O2v0.871.782.643 (3)173
N2—H2···O6iv0.971.972.877 (4)154
N4—H4···O6iv0.892.052.881 (4)155
Symmetry codes: (iv) x, y, z+1; (v) x, y+1, z1.

Experimental details

Crystal data
Chemical formula[Zn(C19H17N5O2)2(H2O)2](NO3)2
Mr920.17
Crystal system, space groupTriclinic, 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)
V3)984.9 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.71
Crystal size (mm)0.32 × 0.23 × 0.15
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.815, 0.898
No. of measured, independent and
observed [I > 2σ(I)] reflections
6816, 3444, 2955
Rint0.018
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.103, 1.05
No. of reflections3444
No. of parameters290
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.35

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Zn1—O32.1017 (19)Zn1—N5i2.321 (2)
Zn1—N32.155 (2)
O3ii—Zn1—O3180.0O3—Zn1—N5i93.61 (8)
O3ii—Zn1—N390.12 (8)N3—Zn1—N5i87.51 (8)
O3—Zn1—N389.88 (8)N3ii—Zn1—N5i92.50 (8)
N3—Zn1—N3ii180.0N5i—Zn1—N5iii180.0
O3ii—Zn1—N5i86.39 (8)
Symmetry codes: (i) x, y+1, z+2; (ii) x, y+1, z+1; (iii) x, y, z1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3B···O40.971.822.755 (4)161.8
O3—H3C···O2iv0.871.782.643 (3)173.2
N2—H2···O6v0.971.972.877 (4)153.7
N4—H4···O6v0.892.052.881 (4)154.6
Symmetry codes: (iv) x, y+1, z1; (v) x, y, z+1.
 

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