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In the title compound, {[Zn(C8H4O5)(C12H8N2)]·H2O}n or {[Zn(OH-BDC)(phen)]·H2O}n (where OH-H2BDC is 5-hydroxy­isophthalic acid and phen is 1,10-phenanthroline), the Zn atoms are coordinated by two N atoms from the phen ligands and by four O atoms from hydroxy­isophthalate ligands in a highly distorted octahedral geometry, with Zn—O distances in the range 2.042 (4)–2.085 (5) Å and Zn—N distances of 2.133 (5) and 2.137 (5) Å. The {[Zn(OH-BDC)(phen)]·H2O}n infinite zigzag polymer forms a helical chain of [Zn2(OH-BDC)2]n units. Face-to-face π–π interactions (3.60–3.75 Å) occur between two phen rings belonging to the same helical chain. Consolidation of the packing structure is achieved by O—H...O hydrogen-bonding interactions between the carboxyl­ate O atoms, the hydroxyl group and the water mol­ecule, forming two-dimensional sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010401056X/ga1056sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010401056X/ga1056Isup2.hkl
Contains datablock I

CCDC reference: 245868

Comment top

Helical structures have attracted increasing attention in coordination and materials chemistry, being an essential element of living structures and also important in advanced materials, such as optical devices and asymmetric catalysis (Lehn, 1995). The design and synthesis of supramolecular coordination polymer networks, especially those constructed via hydrogen-bonding and ππ stacking interactions, has been a field of rapid growth because of their special physical properties and potential application in functional materials (Atwood et al., 1996; Barton et al., 1999). The coordination chemistry of aromatic polycarboxylate transition metal complexes has received considerable attention, due to the variety of bridging abilities of polycarboxylates in the formation of porous frameworks (Mori et al., 1997; Chui et al., 1999; Lo et al., 2000). 5-Hydroxyisophthalic acid, OH—H2BDC, like benzene-1,3,5-tricarboxylic acid, has two carboxylic acid groups arranged meta to each other, with a phenol hydroxyl group meta to both (Plate et al., 2001). The phenol hydroxyl group was intended as a mimic for the third carboxyl group, which remains protonated in other reported layered polymers (Foreman et al., 1999), as well as in this paper. As part of our research interests in new polycarboxylic acid-bridged polymeric complexes, the title complex, (I), was obtained by the hydrothermal reaction of OH—H2BDC with zinc acetate and phen, as a colourless solid in 67.3% yield. \sch

As shown in Fig. 1, the Zn atoms in (I) are six-coordinated, via two N atoms from the phen ligand and four O atoms from hydroxyisophthalate ligands in a highly distorted octahedral geometry, with Zn—O distances in the range 2.042 (4)–2.085 (5) Å and Zn—N distances of 2.133 (5) and 2.137 (5) Å. These values are similar to those found in [Zn(o-phen)MoO4] (Hagrman & Zubieta, 1999), [Zn2(bpy)2(MeC02)3]C104 (Chen & Tong, 1994) and in the closest relative catena-[(µ2-adipato-O,O',O'',O''')-(µ2-adipato-O,O') -diaqua-bis(1,10-phenanthroline)dizinc(II)] (Zheng et al., 2002). The closest Zn···Zn distance is 3.989 (4) Å, indicating no direct metal-metal interaction. The 5-hydroxyisophthalate acts as a tetradentate ligand in this structure, with one carboxylate group acting as bidentate to one Zn atom and the two remaining O atoms acting as monodentate ligands to two further Zn atoms. The asymmetric unit thus consists of one Zn atom, one phen ligand bound in a bidentate manner, one hydroxyisophthalate ligand and one water molecule. One-dimensional chains are formed by the Zn cations and the carboxylate ligands, so that (I) contains a [Zn2(OH-BDC)2]n helical structure which is composed of eight-membered and sixteen-membered rings (Fig. 2). The phen ligands are at approximately 90° to these latter rings. The smallest repeat distance of the helical chain is 17.451 (2) Å.

The chains of (I) are linked by an O—H···O hydrogen-bonding network, consisting of carboxylate O and hydroxy O interactions with the H atoms of the water molecule, resulting in two-dimensional sheets (Table 2). Additionally, there are face-to-face ππ interactions between phen ligands belonging to the same helical chain (Fig. 2a), with phen···phen distances in the range 3.595 (4)–3.748 (3) Å, close to the sum of the van der Waals radii of two C atoms (Bondi, 1964). The usual ππ interaction is offset or slipped stacking, i.e. the rings are parallel displaced; the face-to-face ππ alignment seen in (I), where most of the ring-plane area overlaps, is a rare phenomenon (Janiak, 2000).

Experimental top

A mixture of Zn(CH3CO2)2·2H2O (0.5 mmol), OH—H2BDC (0.5 mmol), phen (0.5 mmol), Na2CO3 (0.5 mmol) and water (16 ml) was sealed in a 25 ml stainless-steel reactor with a Teflon liner. The reaction system was heated at 433 K for 60 h. Slow cooling of the system to room temperature yielded colourless crystals of the title complex, which were collected by filtration.

Refinement top

All H atoms, except water atoms H1WA and H1WB, were positioned geometrically and refined using a riding model [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C), and O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O)]. No riding model was applied to H1WA and H1WB. Please give brief details of how these atoms were located and treated.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1996); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are plotted at the 60% probability level. H atoms and solvent water molecules have been omitted for clarity [symmetry codes: (a) 2 − x, 1 − y, 2 − z; (b) 3/2 − x, y, 3/2 − z; (c) 1/2 + x, 1 − y, 1/2 + z].
[Figure 2] Fig. 2. (a) A space-filling atomic diagram showing the zigzag chain of (I). (b) A space-filling plot of the [Zn2(OH-BDC)2]n double helix.
Poly[[[(1,10-phenanthroline-κ2N,N')zinc(II)]-µ3– 5-hydroxyisophthalato-κ4O'O':O'':O'''] monohydrate] top
Crystal data top
[Zn(C8H4O5)(C12H8N2)]·H2OF(000) = 904
Mr = 443.70Dx = 1.665 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
a = 8.7640 (4) ÅCell parameters from 3603 reflections
b = 12.1090 (6) Åθ = 1.7–25.0°
c = 17.0440 (8) ŵ = 1.43 mm1
β = 101.846 (1)°T = 293 K
V = 1770.24 (15) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
Make Model CCD area-detector
diffractometer
3087 independent reflections
Radiation source: fine-focus sealed tube2512 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ϕ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 109
Tmin = 0.578, Tmax = 0.751k = 1114
6008 measured reflectionsl = 2015
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.156H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0619P)2 + 7.1455P]
where P = (Fo2 + 2Fc2)/3
3087 reflections(Δ/σ)max = 0.004
268 parametersΔρmax = 0.46 e Å3
2 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Zn(C8H4O5)(C12H8N2)]·H2OV = 1770.24 (15) Å3
Mr = 443.70Z = 4
Monoclinic, P2/nMo Kα radiation
a = 8.7640 (4) ŵ = 1.43 mm1
b = 12.1090 (6) ÅT = 293 K
c = 17.0440 (8) Å0.40 × 0.30 × 0.20 mm
β = 101.846 (1)°
Data collection top
Make Model CCD area-detector
diffractometer
3087 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
2512 reflections with I > 2σ(I)
Tmin = 0.578, Tmax = 0.751Rint = 0.039
6008 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0552 restraints
wR(F2) = 0.156H atoms treated by a mixture of independent and constrained refinement
S = 1.14Δρmax = 0.46 e Å3
3087 reflectionsΔρmin = 0.45 e Å3
268 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
Zn10.94511 (7)0.29467 (5)0.83478 (3)0.0246 (2)
O1W1.0449 (6)0.5967 (4)0.8564 (3)0.0551 (13)
H1WB1.044 (11)0.574 (7)0.902 (2)0.083*
H1WA1.034 (11)0.547 (5)0.823 (4)0.083*
O11.2134 (5)0.2598 (4)0.9027 (3)0.0504 (12)
O21.0572 (5)0.3841 (3)0.9352 (2)0.0416 (10)
O31.2757 (4)0.6462 (3)1.1616 (2)0.0342 (9)
O41.4778 (5)0.5877 (3)1.2533 (2)0.0354 (9)
O51.7035 (5)0.2765 (3)1.1123 (3)0.0413 (10)
H5O1.78020.31721.12190.062*
N10.9890 (5)0.1561 (4)0.7646 (2)0.0284 (10)
N20.8726 (5)0.1572 (4)0.8977 (3)0.0298 (10)
C11.0513 (8)0.1581 (5)0.7002 (3)0.0385 (14)
H11.07150.22620.67870.046*
C21.0879 (9)0.0611 (5)0.6634 (4)0.0500 (18)
H21.13290.06510.61850.060*
C31.0576 (8)0.0394 (6)0.6933 (4)0.0494 (17)
H31.08170.10440.66890.059*
C40.9904 (7)0.0441 (5)0.7606 (3)0.0351 (13)
C50.9522 (8)0.1470 (5)0.7977 (4)0.0471 (17)
H50.97300.21470.77580.056*
C60.8879 (8)0.1455 (5)0.8625 (4)0.0434 (16)
H60.86310.21230.88420.052*
C70.8565 (7)0.0438 (5)0.8992 (4)0.0362 (13)
C80.7925 (8)0.0364 (5)0.9685 (4)0.0455 (16)
H80.76570.10040.99310.055*
C90.7700 (8)0.0659 (5)0.9995 (4)0.0447 (16)
H90.72760.07161.04520.054*
C100.8106 (7)0.1612 (5)0.9624 (3)0.0357 (13)
H100.79380.23000.98390.043*
C110.8933 (6)0.0570 (4)0.8658 (3)0.0274 (12)
C120.9588 (6)0.0563 (4)0.7946 (3)0.0261 (11)
C131.5492 (7)0.4270 (5)1.1465 (3)0.0341 (13)
H131.62750.44531.19040.041*
C141.4110 (6)0.4878 (4)1.1309 (3)0.0280 (12)
C151.2921 (6)0.4596 (4)1.0653 (3)0.0278 (12)
H151.19980.50031.05430.033*
C161.3844 (6)0.5802 (4)1.1852 (3)0.0284 (12)
C171.3130 (6)0.3705 (4)1.0169 (3)0.0283 (12)
C181.4532 (7)0.3112 (4)1.0330 (3)0.0311 (12)
H181.46750.25211.00000.037*
C191.5710 (6)0.3393 (4)1.0972 (3)0.0289 (12)
C201.1875 (7)0.3362 (5)0.9472 (3)0.0317 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0346 (4)0.0166 (3)0.0206 (3)0.0008 (3)0.0009 (2)0.0005 (2)
O1W0.062 (3)0.034 (3)0.066 (3)0.005 (2)0.006 (3)0.002 (2)
O10.056 (3)0.058 (3)0.036 (2)0.006 (2)0.006 (2)0.020 (2)
O20.045 (3)0.034 (2)0.038 (2)0.002 (2)0.0103 (19)0.0008 (18)
O30.035 (2)0.032 (2)0.033 (2)0.0144 (18)0.0005 (17)0.0025 (17)
O40.044 (2)0.029 (2)0.027 (2)0.0090 (18)0.0077 (17)0.0053 (17)
O50.031 (2)0.032 (2)0.059 (3)0.0065 (18)0.0042 (19)0.012 (2)
N10.037 (3)0.026 (2)0.022 (2)0.000 (2)0.0051 (19)0.0010 (18)
N20.039 (3)0.021 (2)0.029 (2)0.006 (2)0.006 (2)0.0041 (19)
C10.058 (4)0.035 (3)0.025 (3)0.006 (3)0.015 (3)0.005 (3)
C20.076 (5)0.043 (4)0.037 (3)0.013 (3)0.027 (3)0.001 (3)
C30.066 (5)0.039 (4)0.043 (4)0.011 (3)0.011 (3)0.013 (3)
C40.039 (3)0.027 (3)0.035 (3)0.003 (2)0.003 (3)0.005 (2)
C50.062 (4)0.022 (3)0.052 (4)0.005 (3)0.000 (3)0.005 (3)
C60.057 (4)0.016 (3)0.054 (4)0.003 (3)0.005 (3)0.007 (3)
C70.039 (3)0.025 (3)0.043 (3)0.001 (3)0.005 (3)0.008 (3)
C80.054 (4)0.031 (3)0.052 (4)0.007 (3)0.014 (3)0.017 (3)
C90.056 (4)0.040 (4)0.042 (4)0.001 (3)0.020 (3)0.012 (3)
C100.041 (3)0.035 (3)0.033 (3)0.004 (3)0.013 (3)0.001 (3)
C110.034 (3)0.020 (3)0.026 (3)0.002 (2)0.000 (2)0.005 (2)
C120.032 (3)0.020 (3)0.023 (3)0.000 (2)0.000 (2)0.002 (2)
C130.037 (3)0.029 (3)0.030 (3)0.004 (2)0.009 (2)0.004 (2)
C140.033 (3)0.025 (3)0.025 (3)0.002 (2)0.003 (2)0.001 (2)
C150.032 (3)0.025 (3)0.025 (3)0.004 (2)0.002 (2)0.000 (2)
C160.035 (3)0.024 (3)0.026 (3)0.003 (2)0.004 (2)0.002 (2)
C170.034 (3)0.026 (3)0.024 (3)0.003 (2)0.005 (2)0.004 (2)
C180.040 (3)0.027 (3)0.026 (3)0.000 (2)0.006 (2)0.006 (2)
C190.030 (3)0.022 (3)0.034 (3)0.001 (2)0.008 (2)0.002 (2)
C200.041 (3)0.030 (3)0.022 (3)0.007 (3)0.001 (2)0.001 (2)
Geometric parameters (Å, º) top
Zn1—O4i2.043 (4)C3—H30.9300
Zn1—O3ii2.071 (4)C4—C121.394 (8)
Zn1—O22.086 (4)C4—C51.460 (9)
Zn1—N12.133 (4)C5—C61.337 (10)
Zn1—N22.137 (4)C5—H50.9300
Zn1—O12.429 (5)C6—C71.427 (8)
Zn1—C202.594 (6)C6—H60.9300
O1W—H1WB0.82 (6)C7—C111.406 (7)
O1W—H1WA0.82 (6)C7—C81.408 (9)
O1—C201.241 (7)C8—C91.371 (9)
O2—C201.255 (7)C8—H80.9300
O3—C161.241 (6)C9—C101.391 (8)
O3—Zn1ii2.071 (4)C9—H90.9300
O4—C161.275 (6)C10—H100.9300
O4—Zn1iii2.043 (4)C11—C121.442 (8)
O5—C191.363 (7)C13—C191.386 (8)
O5—H5O0.8200C13—C141.391 (8)
N1—C11.319 (7)C13—H130.9300
N1—C121.354 (7)C14—C151.401 (7)
N2—C101.325 (7)C14—C161.495 (7)
N2—C111.350 (7)C15—C171.387 (7)
C1—C21.393 (8)C15—H150.9300
C1—H10.9300C17—C181.396 (8)
C2—C31.360 (9)C17—C201.499 (7)
C2—H20.9300C18—C191.381 (8)
C3—C41.391 (9)C18—H180.9300
O4i—Zn1—O3ii92.45 (16)C5—C6—C7121.6 (6)
O4i—Zn1—O295.16 (16)C5—C6—H6119.2
O3ii—Zn1—O294.69 (16)C7—C6—H6119.2
O4i—Zn1—N195.53 (16)C11—C7—C8116.5 (5)
O3ii—Zn1—N1124.22 (16)C11—C7—C6119.0 (5)
O2—Zn1—N1138.97 (17)C8—C7—C6124.5 (5)
O4i—Zn1—N2166.96 (17)C9—C8—C7119.5 (5)
O3ii—Zn1—N282.96 (16)C9—C8—H8120.3
O2—Zn1—N297.37 (17)C7—C8—H8120.3
N1—Zn1—N277.27 (17)C8—C9—C10119.9 (6)
O4i—Zn1—O1100.77 (16)C8—C9—H9120.1
O3ii—Zn1—O1149.37 (14)C10—C9—H9120.1
O2—Zn1—O156.94 (15)N2—C10—C9122.2 (6)
N1—Zn1—O182.16 (16)N2—C10—H10118.9
N2—Zn1—O189.13 (17)C9—C10—H10118.9
O4i—Zn1—C2099.17 (16)N2—C11—C7123.4 (5)
O3ii—Zn1—C20122.48 (17)N2—C11—C12116.8 (4)
O2—Zn1—C2028.58 (17)C7—C11—C12119.8 (5)
N1—Zn1—C20110.47 (18)N1—C12—C4123.0 (5)
N2—Zn1—C2093.57 (17)N1—C12—C11117.0 (4)
O1—Zn1—C2028.36 (16)C4—C12—C11120.0 (5)
H1WB—O1W—H1WA113 (9)C19—C13—C14120.5 (5)
C20—O1—Zn183.2 (4)C19—C13—H13119.7
C20—O2—Zn198.8 (3)C14—C13—H13119.7
C16—O3—Zn1ii150.2 (4)C13—C14—C15119.9 (5)
C16—O4—Zn1iii120.8 (3)C13—C14—C16120.9 (5)
C19—O5—H5O109.5C15—C14—C16119.2 (5)
C1—N1—C12118.4 (5)C17—C15—C14119.5 (5)
C1—N1—Zn1127.1 (4)C17—C15—H15120.2
C12—N1—Zn1114.4 (3)C14—C15—H15120.2
C10—N2—C11118.5 (5)O3—C16—O4123.6 (5)
C10—N2—Zn1127.0 (4)O3—C16—C14118.9 (5)
C11—N2—Zn1114.5 (3)O4—C16—C14117.5 (5)
N1—C1—C2122.0 (6)C15—C17—C18119.8 (5)
N1—C1—H1119.0C15—C17—C20121.2 (5)
C2—C1—H1119.0C18—C17—C20118.9 (5)
C3—C2—C1119.9 (6)C19—C18—C17120.7 (5)
C3—C2—H2120.0C19—C18—H18119.6
C1—C2—H2120.0C17—C18—H18119.6
C2—C3—C4119.4 (6)O5—C19—C18118.6 (5)
C2—C3—H3120.3O5—C19—C13121.8 (5)
C4—C3—H3120.3C18—C19—C13119.5 (5)
C3—C4—C12117.4 (6)O1—C20—O2121.1 (5)
C3—C4—C5124.3 (6)O1—C20—C17119.4 (5)
C12—C4—C5118.4 (5)O2—C20—C17119.6 (5)
C6—C5—C4121.2 (6)O1—C20—Zn168.4 (3)
C6—C5—H5119.4O2—C20—Zn152.6 (3)
C4—C5—H5119.4C17—C20—Zn1172.1 (4)
Symmetry codes: (i) x1/2, y+1, z1/2; (ii) x+2, y+1, z+2; (iii) x+1/2, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O20.82 (6)2.36 (8)2.883 (6)122 (8)
O1W—H1WA···O4i0.82 (6)2.01 (3)2.817 (6)169 (9)
O5—H5O···O1Wiv0.821.822.642 (7)178
Symmetry codes: (i) x1/2, y+1, z1/2; (iv) x+3, y+1, z+2.

Experimental details

Crystal data
Chemical formula[Zn(C8H4O5)(C12H8N2)]·H2O
Mr443.70
Crystal system, space groupMonoclinic, P2/n
Temperature (K)293
a, b, c (Å)8.7640 (4), 12.1090 (6), 17.0440 (8)
β (°) 101.846 (1)
V3)1770.24 (15)
Z4
Radiation typeMo Kα
µ (mm1)1.43
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerMake Model CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.578, 0.751
No. of measured, independent and
observed [I > 2σ(I)] reflections
6008, 3087, 2512
Rint0.039
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.156, 1.14
No. of reflections3087
No. of parameters268
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.46, 0.45

Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1996), XPREP in SHELXTL (Siemens, 1994), SHELXTL.

Selected geometric parameters (Å, º) top
Zn1—O4i2.043 (4)Zn1—N12.133 (4)
Zn1—O3ii2.071 (4)Zn1—N22.137 (4)
Zn1—O22.086 (4)Zn1—O12.429 (5)
O4i—Zn1—O3ii92.45 (16)O2—Zn1—N1138.97 (17)
O4i—Zn1—O295.16 (16)O4i—Zn1—N2166.96 (17)
O3ii—Zn1—O294.69 (16)O3ii—Zn1—N282.96 (16)
O4i—Zn1—N195.53 (16)O2—Zn1—N297.37 (17)
O3ii—Zn1—N1124.22 (16)N1—Zn1—N277.27 (17)
Symmetry codes: (i) x1/2, y+1, z1/2; (ii) x+2, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O20.82 (6)2.36 (8)2.883 (6)122 (8)
O1W—H1WA···O4i0.82 (6)2.01 (3)2.817 (6)169 (9)
O5—H5O···O1Wiii0.821.822.642 (7)178.0
Symmetry codes: (i) x1/2, y+1, z1/2; (iii) x+3, y+1, z+2.
 

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