Download citation
Download citation
link to html
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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026700/hb2440sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026700/hb2440Isup2.hkl
Contains datablock I

CCDC reference: 654703

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.029
  • wR factor = 0.076
  • Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of Tmax/Tmin expected RT(exp) is > 1.10 Absorption corrections should be applied. Tmin and Tmax expected: 0.775 0.877 RT(exp) = 1.132 PLAT057_ALERT_3_C Correction for Absorption Required RT(exp) ... 1.13 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N5
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.91
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check

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).

Structure description 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).

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).

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]F(000) = 1792
Mr = 437.78Dx = 1.521 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5531 reflections
a = 14.4330 (4) Åθ = 2.8–23.6°
b = 16.0837 (4) ŵ = 1.31 mm1
c = 16.4677 (5) ÅT = 273 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)
Graphite monochromatorRint = 0.036
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1717
Tmin = 0.779, Tmax = 0.880k = 1918
22267 measured reflectionsl = 1918
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0317P)2 + 1.8397P]
where P = (Fo2 + 2Fc2)/3
3338 reflections(Δ/σ)max = 0.001
262 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
[Zn(N3)2(C9H8N2)2]V = 3822.75 (18) Å3
Mr = 437.78Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.4330 (4) ŵ = 1.31 mm1
b = 16.0837 (4) ÅT = 273 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)] = 0.0290 restraints
wR(F2) = 0.077H-atom parameters constrained
S = 1.02Δρmax = 0.27 e Å3
3338 reflectionsΔρmin = 0.28 e Å3
262 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
Zn10.94645 (2)0.032733 (17)0.680773 (16)0.04710 (11)
C10.89609 (17)0.02149 (15)0.85389 (15)0.0470 (6)
H10.86160.02390.83640.056*
C20.89393 (16)0.04197 (14)0.93744 (14)0.0435 (6)
C30.83983 (19)0.00398 (18)0.99208 (17)0.0609 (7)
H30.80460.04880.97420.073*
C40.8399 (2)0.01836 (18)1.07239 (17)0.0651 (8)
H40.80370.01121.10920.078*
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, º) 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, º) 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) x1/2, y+1/2, z+1; (iii) x+1/2, y, z+3/2; (iv) x+2, y, z+2.

Experimental details

Crystal data
Chemical formula[Zn(N3)2(C9H8N2)2]
Mr437.78
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)273
a, b, c (Å)14.4330 (4), 16.0837 (4), 16.4677 (5)
V3)3822.75 (18)
Z8
Radiation typeMo Kα
µ (mm1)1.31
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.779, 0.880
No. of measured, independent and
observed [I > \2s(I)] reflections
22267, 3338, 2560
Rint0.036
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.077, 1.02
No. of reflections3338
No. of parameters262
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.28

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000), SHELXTL.

Selected geometric parameters (Å, º) 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, º) 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) x1/2, y+1/2, z+1; (iii) x+1/2, y, z+3/2; (iv) x+2, y, z+2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds