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The title compound, [Zn2(C17H13N2O)2(N3)2], is an azide-bridged dinuclear zinc(II) complex which has inversion symmetry. The ZnII atom is five-coordinated in a square-pyramidal configuration by one O and two N atoms of one Schiff base ligand [Zn-O = 1.902 (2) Å and Zn-N = 1.938 (2) and 2.002 (2) Å] and by one terminal N atom [Zn-N = 1.985 (2) Å] of a bridging azide ligand defining the basal plane, and by another terminal N atom of another bridging azide ligand [Zn-N = 2.554 (2) Å] occupying the apical position.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105026260/ob1242sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105026260/ob1242Isup2.hkl
Contains datablock I

CCDC reference: 285649

Comment top

Metal–organic complexes containing bridging ligands are of current interest because of their interesting molecular topologies and crystal packing motifs, as well as the fact that they may be designed with specific functionalities (Supriya et al., 2005; Batten & Robson, 1998; Colacio et al., 2005; Abourahma et al., 2002; Konar et al., 2002). In addition to being robust and thermally stable, some possess photoluminescent properties, a feature that has contributed to d10 metal polynuclear complexes being investigated in the search for new materials (Weidenbruch et al., 1989; Kunkely & Vogler, 1990; Bertoncello et al., 1992). Among the ZnII and CdII complexes of this class, most possess photoluminescent properties (Sang & Xu, 2005; Wang et al., 2003).

Due to the versatile coordination modes of the ambidentate azide ligand, this pseudohalide ligand has become one of the most extensively studied building blocks in the field of polynuclear complexes (Woodward et al., 2005; Mukherjee et al., 2001; Goher et al., 2002). A major obstacle to a more comprehensive study of such azide-based complexes is the lack of rational synthetic procedures since, with the present state of knowledge, it is hardly possible to determine which coordination mode will be adopted by the azide ligand and whether the sought-after alternating chain structure will finally be formed (Tercero et al., 2002; Ribas et al., 1999; Liu et al., 2003).

Our work is aimed at obtaining polynuclear complexes. Based on the above considerations, the author has already reported an azide-bridged polynuclear copper(II) complex, viz. catena-poly[{4-bromo-2-[2-(dimethylamino)ethyliminomethyl]phenolato} (µ-azido)copper(II)], [Cu(bdmp)(N3)]n, (II) (You, 2005). In (II), the bridging azide ligand coordinates to two metal atoms via the same terminal N atom. The [Cu(bdmp)] moieties are linked by the bridging azide ligands, forming polymeric chains. In order to study the effects of Schiff base ligands in the construction of polynuclear complexes with the azide ligand, we have designed and synthesized a rigid tridentate ligand, 1-(pyridin-2-ylmethyliminomethyl)naphthalen-2-ol (Hpmmn), which is different from the flexible tridentate ligand, 4-bromo-2-[2-(dimethylamino)ethyliminomethyl]phenol (Hbdmp), used in the preparation of (II). The title complex, [Zn2(pmmn)2(N3)2], (I), formed by the reaction of Hpmmn, sodium azide, and zinc(II) acetate, is reported here.

Complex (I) is an azide-bridged dinuclear zinc(II) compound (Fig. 1) which has inversion symmetry. The ZnII atom is in a square-pyramidal coordination, with atoms O1, N1 and N2 of the pmmn ligand and the terminal N atom (N3) of a bridging azide ligand defining the basal plane, and one terminal N atom (N3i) of another bridging azide ligand occupying the apical position [symmetry code: (i) 1 − x, −y, 1 − z]. These are similar to the coordination modes of the Schiff base ligand and the bridging azide anion observed in (II). However, (I) and (II) are dinuclear and polynuclear complexes, respectively. The difference between the two structures is very likely caused by the hindrance effects of the Schiff bases. In (I), the rigid pmmn ligand is kept almost coplanar when coordinated to the metal ions, with a mean deviation from the plane of 0.057 (3) Å. The basal least-squares planes of the two adjacent ZnII centres are parallel to each other, making it possible for the two azide anions to be coordinated to the same two zinc(II) atoms. In contrast, in (II), the bdmp is a flexible Schiff base ligand. The basal least-squares planes of the two adjacent CuII centres in (II) are not parallel to each other and form a dihedral angle of 43.5 (2)°. This configuration makes it difficult for the other azide ligand to coordinate to the same two metal atoms as the first azide ligand from the other side. However, the other bridging azide has no choice but to coordinate to the third metal atom via the low-hindrance side of (II). Thus, complex (II) forms an infinite chain structure. The bond lengths around the metal centre are comparable in (I) and (II), although the metal centres are ZnII and CuII, respectively. The different configurations lead to an M—N—M bond angle of 95.44 (10)° in (I), much smaller than the corresponding value of 129.1 (2)° observed in (II), and the M···M distance in (I) [3.380 (2) Å] is much shorter than the corresponding value [4.196 (2) Å] in (II).

The bond lengths subtended at atom Zn1 in the basal plane are comparable with those observed in other Schiff base zinc(II) complexes (Gross & Vahrenkamp, 2005; Chen et al., 2005), and as expected, the bond involving the pyridine atom N2 [2.003 (2) Å] is longer than that involving the imino atom N1 [1.938 (2) Å] (Mondal et al., 2001). The bridging NNN group is nearly linear and shows bent coordination modes with the metal atoms (Table 1).

Experimental top

2-Hydroxy-1-naphthaldehyde (0.1 mmol, 17.2 mg) and 2-aminomethylpyridine (0.1 mmol, 10.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution. To this solution was added an aqueous solution (3 ml) of NaN3 (0.1 mmol, 6.5 mg) and an MeOH solution (5 ml) of Zn(CH3COO)2·4H2O (0.1 mmol, 25.6 mg), with stirring. The mixture was stirred for another 10 min at room temperature. After keeping the filtrate in air for 17 d, colourless block-shaped crystals of (I) were formed (yield 72.3%, on the basis of the Schiff base used).

Refinement top

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); 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 drawn at the 30% probability level. Atoms labelled with the suffix A or unlabelled are at the symmetry position (1 − x, −y, 1 − z).
Di-µ-azido-bis{[1-(pyridin-2-ylmethyliminomethyl)-2-naphtholato]zinc(II)} top
Crystal data top
[Zn2(C17H13N2O)2(N3)2]F(000) = 752
Mr = 737.39Dx = 1.600 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.587 (1) ÅCell parameters from 2253 reflections
b = 14.746 (2) Åθ = 2.7–23.4°
c = 13.692 (2) ŵ = 1.62 mm1
β = 92.53 (2)°T = 298 K
V = 1530.3 (4) Å3Block, colourless
Z = 20.25 × 0.21 × 0.17 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3406 independent reflections
Radiation source: fine-focus sealed tube2491 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.688, Tmax = 0.770k = 1913
8467 measured reflectionsl = 1715
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0656P)2]
where P = (Fo2 + 2Fc2)/3
3406 reflections(Δ/σ)max < 0.001
217 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Zn2(C17H13N2O)2(N3)2]V = 1530.3 (4) Å3
Mr = 737.39Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.587 (1) ŵ = 1.62 mm1
b = 14.746 (2) ÅT = 298 K
c = 13.692 (2) Å0.25 × 0.21 × 0.17 mm
β = 92.53 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3406 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2491 reflections with I > 2σ(I)
Tmin = 0.688, Tmax = 0.770Rint = 0.031
8467 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.03Δρmax = 0.55 e Å3
3406 reflectionsΔρmin = 0.25 e Å3
217 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
Zn10.28270 (5)0.02511 (2)0.48926 (3)0.03900 (15)
O10.2176 (3)0.05608 (14)0.58940 (15)0.0421 (5)
N10.1394 (3)0.12139 (16)0.54036 (18)0.0374 (6)
N20.3156 (3)0.11495 (18)0.38190 (17)0.0377 (6)
N30.4231 (3)0.07074 (17)0.42703 (18)0.0399 (6)
N40.3887 (3)0.1492 (2)0.43811 (18)0.0418 (6)
N50.3600 (5)0.2250 (2)0.4454 (2)0.0694 (10)
C10.0354 (4)0.04268 (19)0.6822 (2)0.0344 (7)
C20.1264 (4)0.03955 (19)0.6652 (2)0.0358 (7)
C30.1202 (4)0.1095 (2)0.7363 (2)0.0460 (8)
H30.18050.16340.72620.055*
C40.0293 (5)0.1000 (2)0.8179 (2)0.0505 (8)
H40.03150.14680.86350.061*
C50.1698 (5)0.0125 (3)0.9213 (3)0.0590 (10)
H50.17090.06010.96580.071*
C60.2633 (5)0.0629 (3)0.9387 (3)0.0630 (10)
H60.32710.06720.99500.076*
C70.2644 (5)0.1340 (3)0.8726 (3)0.0575 (9)
H70.32880.18620.88460.069*
C80.1703 (4)0.1274 (2)0.7895 (2)0.0470 (8)
H80.17430.17540.74530.056*
C90.0686 (4)0.0511 (2)0.7689 (2)0.0376 (7)
C100.0692 (5)0.0211 (2)0.8363 (2)0.0444 (8)
C110.0467 (4)0.1168 (2)0.6175 (2)0.0384 (7)
H110.01950.16780.63180.046*
C120.1348 (5)0.2054 (2)0.4849 (2)0.0508 (8)
H12A0.18010.25450.52590.061*
H12B0.01390.21960.46470.061*
C130.2437 (4)0.1971 (2)0.3965 (2)0.0409 (7)
C140.2656 (4)0.2675 (2)0.3328 (3)0.0505 (8)
H140.21560.32380.34460.061*
C150.3632 (4)0.2542 (3)0.2505 (2)0.0527 (9)
H150.38050.30140.20690.063*
C160.4326 (5)0.1710 (3)0.2351 (2)0.0549 (9)
H160.49550.16020.17950.066*
C170.4100 (4)0.1029 (2)0.3015 (2)0.0456 (8)
H170.46130.04670.29090.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0439 (2)0.0327 (2)0.0410 (2)0.00130 (16)0.00916 (16)0.00069 (15)
O10.0507 (13)0.0288 (10)0.0481 (12)0.0037 (10)0.0178 (10)0.0009 (10)
N10.0434 (14)0.0309 (13)0.0385 (14)0.0023 (11)0.0093 (11)0.0036 (11)
N20.0379 (13)0.0399 (15)0.0354 (13)0.0008 (11)0.0019 (11)0.0046 (11)
N30.0506 (15)0.0285 (13)0.0416 (14)0.0001 (12)0.0129 (12)0.0010 (11)
N40.0465 (15)0.0480 (17)0.0319 (13)0.0064 (13)0.0123 (11)0.0061 (12)
N50.109 (3)0.0324 (17)0.069 (2)0.0026 (17)0.0337 (19)0.0023 (15)
C10.0335 (15)0.0335 (16)0.0367 (15)0.0030 (12)0.0054 (12)0.0028 (12)
C20.0362 (16)0.0298 (16)0.0418 (16)0.0055 (12)0.0058 (13)0.0020 (12)
C30.0533 (19)0.0293 (16)0.056 (2)0.0035 (14)0.0119 (16)0.0036 (15)
C40.062 (2)0.0397 (19)0.0505 (19)0.0017 (16)0.0154 (17)0.0100 (15)
C50.072 (3)0.065 (2)0.041 (2)0.002 (2)0.0169 (18)0.0048 (17)
C60.068 (2)0.079 (3)0.044 (2)0.002 (2)0.0219 (18)0.008 (2)
C70.059 (2)0.061 (2)0.053 (2)0.0122 (19)0.0111 (17)0.0167 (19)
C80.0523 (19)0.0439 (19)0.0456 (18)0.0058 (16)0.0096 (15)0.0045 (15)
C90.0372 (16)0.0384 (17)0.0372 (16)0.0036 (13)0.0023 (13)0.0072 (14)
C100.0483 (19)0.0428 (19)0.0423 (18)0.0065 (15)0.0057 (14)0.0013 (15)
C110.0393 (16)0.0302 (15)0.0459 (17)0.0027 (13)0.0050 (13)0.0057 (13)
C120.064 (2)0.0346 (18)0.055 (2)0.0090 (16)0.0150 (16)0.0091 (15)
C130.0399 (17)0.0405 (18)0.0421 (17)0.0019 (14)0.0006 (13)0.0071 (14)
C140.0491 (19)0.044 (2)0.059 (2)0.0034 (16)0.0015 (16)0.0158 (16)
C150.0514 (19)0.055 (2)0.052 (2)0.0012 (17)0.0010 (16)0.0225 (18)
C160.052 (2)0.075 (3)0.0378 (17)0.0045 (19)0.0079 (15)0.0159 (18)
C170.0454 (18)0.050 (2)0.0416 (17)0.0006 (15)0.0044 (14)0.0038 (15)
Geometric parameters (Å, º) top
Zn1—O11.902 (2)C5—H50.9300
Zn1—N11.938 (2)C6—C71.384 (5)
Zn1—N22.003 (2)C6—H60.9300
Zn1—N31.985 (2)C7—C81.373 (5)
Zn1—N3i2.554 (2)C7—H70.9300
O1—C21.296 (4)C8—C91.401 (4)
N1—C111.297 (4)C8—H80.9300
N1—C121.452 (4)C9—C101.409 (4)
N2—C131.347 (4)C11—H110.9300
N2—C171.352 (4)C12—C131.500 (4)
N3—N41.197 (4)C12—H12A0.9700
C1—C111.412 (4)C12—H12B0.9700
C1—C21.420 (4)C13—C141.371 (4)
C1—C91.459 (4)C14—C151.389 (5)
C2—C31.421 (4)C14—H140.9300
C3—C41.345 (4)C15—C161.355 (5)
C3—H30.9300C15—H150.9300
C4—C101.412 (5)C16—C171.370 (4)
C4—H40.9300C16—H160.9300
C5—C61.345 (6)C17—H170.9300
C5—C101.425 (5)N4—N51.144 (4)
O1—Zn1—N191.89 (10)C8—C7—C6120.0 (3)
O1—Zn1—N391.30 (10)C8—C7—H7120.0
N1—Zn1—N3175.74 (10)C6—C7—H7120.0
O1—Zn1—N2172.02 (10)C7—C8—C9122.3 (3)
N1—Zn1—N282.55 (10)C7—C8—H8118.8
N3—Zn1—N293.98 (11)C9—C8—H8118.8
O1—Zn1—N3i95.28 (10)C8—C9—C10117.2 (3)
N1—Zn1—N3i97.94 (11)C8—C9—C1123.7 (3)
N2—Zn1—N3i91.17 (11)C10—C9—C1119.1 (3)
N3—Zn1—N3i84.56 (11)C9—C10—C4119.2 (3)
Zn1—N3—Zn1i95.44 (10)C9—C10—C5119.0 (3)
C2—O1—Zn1128.62 (19)C4—C10—C5121.8 (3)
C11—N1—C12118.0 (3)N1—C11—C1127.0 (3)
C11—N1—Zn1126.1 (2)N1—C11—H11116.5
C12—N1—Zn1115.90 (19)C1—C11—H11116.5
C13—N2—C17118.2 (3)N1—C12—C13110.6 (3)
C13—N2—Zn1114.9 (2)N1—C12—H12A109.5
C17—N2—Zn1126.8 (2)C13—C12—H12A109.5
N4—N3—Zn1120.6 (2)N1—C12—H12B109.5
N4—N3—Zn1i112.9 (2)C13—C12—H12B109.5
C11—C1—C2121.0 (3)H12A—C12—H12B108.1
C11—C1—C9119.6 (3)N2—C13—C14121.6 (3)
C2—C1—C9119.4 (3)N2—C13—C12115.7 (3)
O1—C2—C1124.9 (3)C14—C13—C12122.6 (3)
O1—C2—C3116.6 (3)C13—C14—C15119.6 (3)
C1—C2—C3118.5 (3)C13—C14—H14120.2
C4—C3—C2121.8 (3)C15—C14—H14120.2
C4—C3—H3119.1C16—C15—C14118.6 (3)
C2—C3—H3119.1C16—C15—H15120.7
C3—C4—C10122.0 (3)C14—C15—H15120.7
C3—C4—H4119.0C15—C16—C17120.0 (3)
C10—C4—H4119.0C15—C16—H16120.0
C6—C5—C10121.6 (4)C17—C16—H16120.0
C6—C5—H5119.2N2—C17—C16122.0 (3)
C10—C5—H5119.2N2—C17—H17119.0
C5—C6—C7119.9 (3)C16—C17—H17119.0
C5—C6—H6120.1N5—N4—N3177.1 (3)
C7—C6—H6120.1
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula[Zn2(C17H13N2O)2(N3)2]
Mr737.39
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.587 (1), 14.746 (2), 13.692 (2)
β (°) 92.53 (2)
V3)1530.3 (4)
Z2
Radiation typeMo Kα
µ (mm1)1.62
Crystal size (mm)0.25 × 0.21 × 0.17
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.688, 0.770
No. of measured, independent and
observed [I > 2σ(I)] reflections
8467, 3406, 2491
Rint0.031
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.120, 1.03
No. of reflections3406
No. of parameters217
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.55, 0.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top
Zn1—O11.902 (2)Zn1—N31.985 (2)
Zn1—N11.938 (2)Zn1—N3i2.554 (2)
Zn1—N22.003 (2)
O1—Zn1—N191.89 (10)N1—Zn1—N3i97.94 (11)
O1—Zn1—N391.30 (10)N2—Zn1—N3i91.17 (11)
N1—Zn1—N3175.74 (10)N3—Zn1—N3i84.56 (11)
O1—Zn1—N2172.02 (10)Zn1—N3—Zn1i95.44 (10)
N1—Zn1—N282.55 (10)N4—N3—Zn1120.6 (2)
N3—Zn1—N293.98 (11)N4—N3—Zn1i112.9 (2)
O1—Zn1—N3i95.28 (10)N5—N4—N3177.1 (3)
Symmetry code: (i) x+1, y, z+1.
 

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