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Acta Cryst. (2007). E63, m1808    [ doi:10.1107/S1600536807026700 ]

Bis(5-aminoisoquinoline)diazidozinc(II)

Z.-X. Miao, M. Shao and M.-X. Li

Abstract top

The solution reaction of Zn2+ with 5-aminoisoquinoline and NaN3 afforded the mononuclear title complex, [Zn(N3)2(C9H8N2)2]. The azide anions and the 5-aminoisoquinoline molecules act as monodentate ligands, resulting in a slightly distorted ZnN4 tetrahedron. A network of weak N-H...N hydrogen bonds helps to consolidate the crystal packing.

Comment top

Intense attention has been received to azide complexes due to their diverse structural topologies from discrete molecules to three-dimensional networks and their potential applications in functional materials (Robin & Fromm, 2006; Yaghi et al., 2003). The azido group can act as a monodentate ligand as well as bridging ligand which adopting end-on or end-to-end bridging modes to generate many complexes with interesting structures (Liu et al., 2004; Gao et al., 2006). Here we report a new azide complex using 5-aminoisoquinoline as co-ligand, Zn(C9H8N2)2(N3)2 (I). To our knowledge, no other structurally characterized example of a 5-aminoisoquinoline complex has been documented.

As shown in Figure 1, the Zn(II) atom of (I) is coordinated tetrahedrally by four nitrogen atoms, of which two N-donor atoms are from azide groups and the others are from 5-aminoisoquinoline ligands (Table 1). The Zn—N—N bond angles in (I) compare well to equivalent values in related structures (Li et al., 2006; Miao et al., 2006). The 5-aminoisoquinoline aromatic planes are nearly perpendicular to one another with a dihedral angle of 82.106(x)°. A network of weak N—H···N hydrogen bonds (Table 2) completes the structure (Fig. 2).

Related literature top

For related structures, see: Liu et al. (2004); Gao et al. (2006); Li et al. (2006); Miao et al. (2006).

For related literature, see: Robin & Fromm (2006); Yaghi et al. (2003).

Experimental top

Complex (I) was synthesized in a solution reaction. NaN3 (0.2 mmol) dissolved in 2 ml water was added to 5 ml aqueous solution of Zn(CH3COO)22H2O (0.1 mmol) with stirring. Then an ethanol solution (5 ml) of 5-aminoisoquinoline (0.2 mmol) was added into the solution and stirred for 5 h. The mixture was filtered and the clear solution was kept at room temperature to evaporate slowly·After one week, light-yellow single crystals suitable for X-ray diffraction were obtained.

Refinement top

The H atoms were geometrically placed (C—H = 0.93 Å, N—H = 0.86 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity
[Figure 2] Fig. 2. A packing diagram for (I).
Bis(5-aminoisoquinoline)diazidozinc(II) top
Crystal data top
[Zn(N3)2(C9H8N2)2]F000 = 1792
Mr = 437.78Dx = 1.521 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5531 reflections
a = 14.4330 (4) Åθ = 2.8–23.6º
b = 16.0837 (4) ŵ = 1.31 mm−1
c = 16.4677 (5) ÅT = 273 (2) K
V = 3822.75 (18) Å3Block, light-yellow
Z = 80.20 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD
diffractometer		3338 independent reflections
Radiation source: fine-focus sealed tube2560 reflections with I > \2s(I)
Monochromator: graphiteRint = 0.036
T = 273(2) Kθmax = 25.0º
ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→17
Tmin = 0.779, Tmax = 0.880k = −19→18
22267 measured reflectionsl = −19→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.077  w = 1/[σ2(Fo2) + (0.0317P)2 + 1.8397P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3338 reflectionsΔρmax = 0.27 e Å−3
262 parametersΔρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(N3)2(C9H8N2)2]V = 3822.75 (18) Å3
Mr = 437.78Z = 8
Orthorhombic, PbcaMo Kα
a = 14.4330 (4) ŵ = 1.31 mm−1
b = 16.0837 (4) ÅT = 273 (2) K
c = 16.4677 (5) Å0.20 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD
diffractometer		3338 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2560 reflections with I > \2s(I)
Tmin = 0.779, Tmax = 0.880Rint = 0.036
22267 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029262 parameters
wR(F2) = 0.077H-atom parameters constrained
S = 1.02Δρmax = 0.27 e Å−3
3338 reflectionsΔρmin = −0.28 e Å−3
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.94645 (2)0.032733 (17)0.680773 (16)0.04710 (11)
C10.89609 (17)0.02149 (15)0.85389 (15)0.0470 (6)
H10.8616−0.02390.83640.056*
C20.89393 (16)0.04197 (14)0.93744 (14)0.0435 (6)
C30.83983 (19)−0.00398 (18)0.99208 (17)0.0609 (7)
H30.8046−0.04880.97420.073*
C40.8399 (2)0.01836 (18)1.07239 (17)0.0651 (8)
H40.8037−0.01121.10920.078*
C50.89341 (19)0.08466 (17)1.09951 (16)0.0574 (7)
H50.89230.09811.15440.069*
C60.94764 (17)0.13088 (15)1.04849 (15)0.0490 (6)
C70.94798 (16)0.11029 (14)0.96325 (14)0.0415 (5)
C80.99863 (18)0.15350 (15)0.90421 (15)0.0507 (6)
H81.03460.19900.91920.061*
C90.99554 (19)0.12939 (15)0.82568 (15)0.0517 (6)
H91.02980.15910.78770.062*
C100.80985 (18)0.16731 (15)0.64571 (14)0.0496 (6)
H100.79980.16620.70150.060*
C110.76044 (17)0.22168 (14)0.60011 (14)0.0457 (6)
H110.71840.25730.62500.055*
C120.77234 (16)0.22461 (13)0.51551 (13)0.0393 (5)
C130.72056 (17)0.27742 (14)0.46242 (14)0.0435 (6)
C140.73427 (19)0.26955 (16)0.38043 (15)0.0558 (7)
H140.69970.30250.34530.067*
C150.7983 (2)0.21394 (17)0.34800 (16)0.0631 (8)
H150.80480.21020.29190.076*
C160.85134 (19)0.16508 (16)0.39660 (15)0.0557 (7)
H160.89550.12960.37450.067*
C170.83801 (16)0.16920 (14)0.48121 (13)0.0412 (5)
C180.88677 (17)0.11636 (14)0.53447 (15)0.0474 (6)
H180.93090.08080.51240.057*
N10.89962 (19)−0.08021 (14)0.66187 (14)0.0667 (7)
N20.91573 (16)−0.13681 (14)0.70470 (13)0.0548 (6)
N30.9294 (2)−0.19444 (16)0.74305 (16)0.0981 (11)
N41.07524 (17)0.04730 (15)0.64174 (15)0.0639 (6)
N51.13908 (18)0.03513 (14)0.68614 (14)0.0574 (6)
N61.2017 (2)0.0247 (2)0.72680 (17)0.0886 (9)
N70.94411 (13)0.06303 (12)0.79965 (12)0.0447 (5)
N80.99928 (17)0.19602 (15)1.07584 (13)0.0684 (7)
H8A0.99830.20911.12650.082*
H8B1.03280.22411.04250.082*
N90.87372 (14)0.11419 (11)0.61346 (11)0.0447 (5)
N100.65323 (15)0.32964 (13)0.49322 (13)0.0568 (6)
H10A0.61890.35800.46080.068*
H10B0.64560.33380.54490.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0574 (2)0.04234 (17)0.04158 (18)0.00293 (13)−0.00621 (13)0.00430 (12)
C10.0435 (14)0.0449 (14)0.0526 (16)−0.0007 (11)−0.0049 (12)0.0029 (11)
C20.0377 (13)0.0431 (13)0.0495 (15)0.0018 (11)0.0000 (11)0.0102 (11)
C30.0577 (17)0.0577 (16)0.0674 (19)−0.0124 (14)0.0064 (14)0.0087 (14)
C40.0646 (19)0.0693 (19)0.0614 (19)−0.0035 (15)0.0146 (15)0.0156 (15)
C50.0613 (17)0.0665 (18)0.0443 (15)0.0104 (15)0.0089 (13)0.0099 (13)
C60.0482 (14)0.0503 (15)0.0484 (15)0.0069 (12)−0.0036 (12)0.0027 (12)
C70.0375 (12)0.0429 (13)0.0442 (14)0.0045 (11)−0.0029 (10)0.0052 (10)
C80.0554 (16)0.0467 (14)0.0502 (16)−0.0116 (12)−0.0006 (12)0.0022 (12)
C90.0615 (17)0.0483 (15)0.0454 (15)−0.0086 (13)0.0026 (12)0.0048 (12)
C100.0606 (16)0.0529 (15)0.0353 (13)0.0029 (13)0.0003 (12)0.0017 (11)
C110.0507 (15)0.0467 (14)0.0397 (13)0.0051 (11)0.0006 (11)−0.0031 (11)
C120.0409 (13)0.0364 (12)0.0405 (13)−0.0052 (10)−0.0026 (10)0.0010 (10)
C130.0470 (14)0.0418 (13)0.0418 (14)−0.0032 (11)−0.0027 (11)0.0012 (11)
C140.0693 (18)0.0540 (16)0.0440 (15)0.0074 (14)−0.0073 (13)0.0095 (12)
C150.089 (2)0.0653 (18)0.0347 (14)0.0120 (16)0.0043 (14)0.0037 (13)
C160.0677 (18)0.0547 (16)0.0448 (15)0.0113 (13)0.0079 (13)0.0024 (12)
C170.0467 (14)0.0388 (13)0.0382 (13)−0.0028 (11)−0.0007 (11)0.0024 (10)
C180.0510 (15)0.0436 (14)0.0477 (15)0.0036 (11)0.0006 (11)0.0014 (11)
N10.0943 (19)0.0471 (14)0.0588 (14)−0.0042 (13)−0.0196 (13)0.0005 (12)
N20.0735 (15)0.0459 (13)0.0449 (13)−0.0026 (11)0.0015 (11)−0.0107 (11)
N30.184 (3)0.0486 (15)0.0620 (16)0.0097 (18)−0.0026 (19)0.0045 (14)
N40.0618 (15)0.0745 (16)0.0554 (15)0.0016 (13)0.0062 (12)0.0147 (12)
N50.0574 (15)0.0640 (15)0.0506 (14)−0.0022 (12)0.0126 (13)0.0046 (12)
N60.0590 (17)0.138 (3)0.0689 (18)0.0028 (17)0.0005 (14)0.0083 (17)
N70.0482 (12)0.0424 (11)0.0435 (11)0.0007 (9)−0.0049 (9)0.0042 (9)
N80.0839 (18)0.0761 (16)0.0451 (13)−0.0167 (14)−0.0014 (12)−0.0071 (12)
N90.0529 (12)0.0421 (11)0.0391 (12)0.0009 (9)−0.0047 (9)0.0039 (9)
N100.0636 (14)0.0598 (13)0.0471 (12)0.0182 (11)−0.0054 (11)0.0047 (10)
Geometric parameters (Å, °) top
Zn1—N11.963 (2)C10—H100.9300
Zn1—N41.981 (2)C11—C121.404 (3)
Zn1—N92.0118 (19)C11—H110.9300
Zn1—N72.018 (2)C12—C171.418 (3)
C1—N71.313 (3)C12—C131.430 (3)
C1—C21.415 (3)C13—C141.370 (3)
C1—H10.9300C13—N101.381 (3)
C2—C31.402 (3)C14—C151.392 (4)
C2—C71.413 (3)C14—H140.9300
C3—C41.370 (4)C15—C161.358 (4)
C3—H30.9300C15—H150.9300
C4—C51.391 (4)C16—C171.408 (3)
C4—H40.9300C16—H160.9300
C5—C61.368 (3)C17—C181.409 (3)
C5—H50.9300C18—N91.315 (3)
C6—N81.362 (3)C18—H180.9300
C6—C71.442 (3)N1—N21.175 (3)
C7—C81.401 (3)N2—N31.139 (3)
C8—C91.351 (3)N4—N51.193 (3)
C8—H80.9300N5—N61.137 (3)
C9—N71.369 (3)N8—H8A0.8600
C9—H90.9300N8—H8B0.8600
C10—C111.356 (3)N10—H10A0.8600
C10—N91.364 (3)N10—H10B0.8600
N1—Zn1—N4112.41 (11)C12—C11—H11119.8
N1—Zn1—N9109.61 (9)C11—C12—C17117.1 (2)
N4—Zn1—N9103.52 (9)C11—C12—C13124.2 (2)
N1—Zn1—N7111.81 (9)C17—C12—C13118.6 (2)
N4—Zn1—N7107.58 (9)C14—C13—N10121.3 (2)
N9—Zn1—N7111.63 (8)C14—C13—C12118.2 (2)
N7—C1—C2123.7 (2)N10—C13—C12120.3 (2)
N7—C1—H1118.2C13—C14—C15122.2 (2)
C2—C1—H1118.2C13—C14—H14118.9
C3—C2—C7121.6 (2)C15—C14—H14118.9
C3—C2—C1120.9 (2)C16—C15—C14121.3 (2)
C7—C2—C1117.5 (2)C16—C15—H15119.3
C4—C3—C2118.8 (3)C14—C15—H15119.3
C4—C3—H3120.6C15—C16—C17118.6 (2)
C2—C3—H3120.6C15—C16—H16120.7
C3—C4—C5120.7 (3)C17—C16—H16120.7
C3—C4—H4119.6C16—C17—C18121.3 (2)
C5—C4—H4119.6C16—C17—C12121.0 (2)
C6—C5—C4122.5 (3)C18—C17—C12117.7 (2)
C6—C5—H5118.7N9—C18—C17124.1 (2)
C4—C5—H5118.7N9—C18—H18118.0
N8—C6—C5121.9 (2)C17—C18—H18118.0
N8—C6—C7119.8 (2)N2—N1—Zn1123.62 (19)
C5—C6—C7118.4 (2)N3—N2—N1176.3 (3)
C8—C7—C2117.7 (2)N5—N4—Zn1120.44 (19)
C8—C7—C6124.3 (2)N6—N5—N4177.9 (3)
C2—C7—C6118.0 (2)C1—N7—C9118.0 (2)
C9—C8—C7120.3 (2)C1—N7—Zn1123.09 (17)
C9—C8—H8119.8C9—N7—Zn1118.89 (16)
C7—C8—H8119.8C6—N8—H8A120.0
C8—C9—N7122.8 (2)C6—N8—H8B120.0
C8—C9—H9118.6H8A—N8—H8B120.0
N7—C9—H9118.6C18—N9—C10117.7 (2)
C11—C10—N9122.9 (2)C18—N9—Zn1119.19 (16)
C11—C10—H10118.5C10—N9—Zn1123.08 (15)
N9—C10—H10118.5C13—N10—H10A120.0
C10—C11—C12120.5 (2)C13—N10—H10B120.0
C10—C11—H11119.8H10A—N10—H10B120.0
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N10—H10B···N1i0.862.463.225 (3)148
N10—H10A···N4ii0.862.363.182 (3)160
N8—H8B···N10iii0.862.503.294 (3)154
N8—H8A···N3iv0.862.403.155 (4)147
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, y, −z+3/2; (iv) −x+2, −y, −z+2.
Selected geometric parameters (Å, °) top
Zn1—N11.963 (2)Zn1—N92.0118 (19)
Zn1—N41.981 (2)Zn1—N72.018 (2)
N2—N1—Zn1123.62 (19)N5—N4—Zn1120.44 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N10—H10B···N1i0.862.463.225 (3)148
N10—H10A···N4ii0.862.363.182 (3)160
N8—H8B···N10iii0.862.503.294 (3)154
N8—H8A···N3iv0.862.403.155 (4)147
Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) x−1/2, −y+1/2, −z+1; (iii) x+1/2, y, −z+3/2; (iv) −x+2, −y, −z+2.
Acknowledgements top

The project was supported by the Development Foundation of Shanghai Municipal Education Commission, China

references
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