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The asymmetric unit of {[4,7-bis(2-amino­ethyl)-1,4,7-tri­aza­cyclo­nonan-1-yl]acetato}zinc(II) triaqua{μ-[4,7-bis(2-amino­ethyl)-1,4,7-tri­aza­cyclo­nonan-1-yl]acetato}lithium(I)zinc(II) chloride diperchlorate, [Zn(C12H26N5O2)][LiZn(C12H26N5O2)(H2O)3]Cl(ClO4)2, obtained from the reaction between the lithium salt of 4,7-bis(2-amino­ethyl)-1,4,7-tri­aza­cyclo­nonane-1-acetate and Zn(ClO4)2, contains two ZnII complexes in which each ZnII ion is six-coordinated by five N-atom donors and one O-­atom donor from the ligand. One carboxyl­ate O-atom donor is not involved in coordination to a ZnII atom, but coordinates to an Li+ ion, the tetrahedral geometry of Li+ being completed by three water mol­ecules. The two complexes are linked via a hydrogen bond between a primary amine N—H group and the carboxyl­ate-O atom not involved in coordination to a metal.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102021947/gd1237sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102021947/gd1237Isup2.hkl
Contains datablock I

CCDC reference: 205291

Comment top

The synthesis of novel polyaza macrocyclic ligands containing functional pendant arms has received much attention because of the effects exerted by these functional groups on the co-ordination geometry and chemical properties of the resulting complexes (Bernhardt & Lawrence, 1990; Wainwright, 1997; Haines, 2001; Costamagna et al., 2000; Wainwright, 2001). Among the metal complexes with polyazamacrocycles, those with the small tridentate macrocycle 1,4,7-triazacyclononane ([9]aneN3) have been widely studied, for example for the mimicry of metalloenzymes (Chaudhuri & Wieghardt, 1987; Wieghardt, 1989; Tolman, 1997) and for the catalysis of oxidative organic transformations (De Vos et al., 1999; Bolm et al., 2000; Grenz et al., 2001). Many derivatives of [9]aneN3 containing four, five or six donor atoms have been synthesized and studies of their co-ordination chemistry with a wide range of transition metal ions in different oxidation states have been reported (Bernhardt & Lawrence, 1990; Wainwright, 1997; Haines, 2001; Costamagna et al., 2000; Wainwright, 2001). Less work has been done on the synthesis of [9]aneN3 derivatives having different pendant donor groups, reflecting the increased synthetic difficulty encountered for these types of ligands. However, they are of major interest because they can be used for the construction of multifunctional materials such as dendrimers (Beer & De Gao, 2000), and their complexes exhibit useful chemical properties (Stockheim et al., 1996; Di Vaira et al., 1998) and have practical applications including radio-labelling (André et al., 1998) and selective cation binding (Huskens & Sherry, 1996).

Recently, we reported a new synthetic route to the asymmetric functionalization of [9]aneN3, the synthesis of the MnII complexes of these new ligands and the trigonal prismatic crystal structures of two of them (Tei et al., 2002). In an attempt to explore further the reactivity of one of these new ligands, namely 1-carboxymethyl-4,7- bis(2-aminoethyl)-1,4,7-triazacyclononane (HL), its lithium salt [Li(L)] was reacted with one molar equivalent of Zn(ClO4)2 in MeOH. Diffraction quality colourless crystals were obtained by slow diffusion of Et2O vapour into a MeCN solution of the complex. A single-crystal X-ray structural determination shows two ZnII complexes in the asymmetric unit: in both of these the ZnII ion is co-ordinated by five N-donors and one O-donor from the ligand (Figure 1). No major difference has been detected between the co-ordination environment at the two independent ZnII complexes, as can be seen from Table 1. The only difference between the two complexes is that in one of them a Li+ ion is co-ordinated by the oxygen of the carboxylate group not involved in co-ordination of the metal (O3C), and to three water molecules, giving a tetrahedral geometry [Li—O 1.921 (9)–1.978 (9) Å; O—Li—O 102.5 (4)–117.6 (4)°]. A hydrogen bond between a primary amine N–H (N3B) in this complex and the carboxylate oxygen (O3C') not involved in co-ordination to the other metal connects the two complex cations (H···O 2.13 Å; N—H···O 174°; see Figure 1). In contrast to the MnII complex with Li(L), where the geometry around the metal centre is a rather regular trigonal prism (Tei et al., 2002), [Zn(L)]+ does not adopt a specific ideal geometry around the ZnII centre in either of the complex cations: twist angles between the triangular faces defined by the macrocyclic N-donors and the pendant arm donors are 37.0 and 36.6°, intermediate between an octahedron and a trigonal prism. This absence of a specific co-ordination polyhedron around the ZnII ion is not surprising considering that a d10 metal ion does not have any electronically preferred geometry and therefore the disposition of the donor atoms is regulated only by steric factors. While the Zn—O bond lengths involving O4C and O4C' are 2.098 (3) and 2.102 (3) Å, respectively, the Zn—N(primary amine) bond lengths lie in the range 2.116 (4)–2.145 (4) Å, shorter than the Zn—N(tertiary amine) bonds which are in the range 2.180 (4)–2.231 (4) Å. These differences in Zn—N bond lengths are expected due to the increased steric repulsion at the tertiary amines and the lower donor ability of tertiary amino groups compared to primary ones. Of the numerous [9]aneN3 pendant arms functionalized ligands, Mani and co-workers have reported (Di Vaira et al., 1998) a comparable ZnII complex with the [9]aneN3 derivative containing one carboxylate and two imidazole pendant co-ordinating groups where the bond lengths between the metal and the macrocyclic N-donors are quite long [2.224 (2)–2.339 (2) Å] with the ZnII ion shifted towards the N– and O-donors of the pendant arms [range 2.074 (3)–2.081 (2) Å] within a distorted trigonal prismatic geometry.

Experimental top

Zn(ClO4)2·6H2O (34.6 mg, 0.093 mmol) in MeOH (10 cm3) was added to a solution of Li(L) (26.0 mg, 0.093 mmol) in MeOH (10 cm3). The resulting solution was stirred for 3 h at room temperature. The solvent was removed under reduced pressure and the residue dissolved in MeCN. Single crystals suitable for X-ray structural analysis were obtained by diffusion of Et2O vapour into the MeCN solution of the complex (35.0 mg, 0.074 mmol, 79.3% yield). Mass spectrum (electrospray): m/z = 336 (M+ [Zn(L)]+). Elemental analysis: found (calc. for C24H60Cl3LiN10O15Zn2): C 30.12 (29.63), H 6.47 (6.22), N 14.58% (14.40%). IR spectrum (KBr disc) (ν/cm−1): 3293 (s), 3161 (m), 2966 (w), 2919 (w), 2858 (w), 1609 (s), 1474 (w), 1400 (w), 1325 (w), 1121 (s), 1051 (m), 1006 (m), 799 (w), 634 (m).

Refinement top

One carbon atom (C2A') of one pendant arm and one oxygen atom (O8) belonging to a perchlorate anion were found to be disordered. The disorder was modelled by a partial occupancy model over two sites for C2A'/C2A" with occupancy factors of 0.85/0.15, respectively, and over three sites for O8, with occupancy factors of 0.50/0.30/0.20 for O8/O8'/O8". Appropriate restraints were applied to all bond distances and angles involving disordered atoms.

Methylene and amine hydrogen atoms, after location from ΔF syntheses, were placed geometrically and refined with a riding model for which the C—H and N—H distances were constrained to be 0.99 Å and 0.92 Å, respectively, and Uiso(H) = 1.2 Ueq(C, N). Our attempts to locate the water H atoms were uniformly unsuccessful. They are therefore not included in the refinement model, but they are accounted for in the chemical formula. It is possible to identify possible O—H···O hydrogen bonds from short O···O distances.

Computing details top

Data collection: Bruker SMART version 5.054 (Bruker, 1998); cell refinement: Bruker SAINT version 6.02a (Bruker, 2000); data reduction: Bruker SAINT; Bruker SHELXTL (Bruker, 1997); program(s) used to solve structure: Bruker SHELXTL; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: SHELXL97; PLATON (Spek, 2002).

Figures top
[Figure 1] Fig. 1. Structure of the title compound showing the atom numbering scheme adopted. Only the hydrogen atoms on primary amines are shown, the others have been omitted for clarity. Displacement ellipsoids are drawn at 50% probability.
(I) top
Crystal data top
[Zn(C12H32N5O)LiO4][Zn(C12H26N5O2].Cl.2(ClO4)F(000) = 2024
Mr = 970.85Dx = 1.612 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4413 reflections
a = 15.6382 (12) Åθ = 2.4–25.4°
b = 8.8403 (7) ŵ = 1.48 mm1
c = 29.595 (2) ÅT = 150 K
β = 103.672 (2)°Column, colourless
V = 3975.5 (5) Å30.26 × 0.08 × 0.08 mm
Z = 4
Data collection top
Bruker SMART1000 CCD area detector with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986)
diffractometer
9917 independent reflections
Radiation source: normal-focus sealed tube5504 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω scansθmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 2113
Tmin = 0.722, Tmax = 0.888k = 1211
24884 measured reflectionsl = 3740
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)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0606P)2
where P = (Fo2 + 2Fc2)/3
9356 reflections(Δ/σ)max = 0.008
498 parametersΔρmax = 0.88 e Å3
32 restraintsΔρmin = 1.01 e Å3
Crystal data top
[Zn(C12H32N5O)LiO4][Zn(C12H26N5O2].Cl.2(ClO4)V = 3975.5 (5) Å3
Mr = 970.85Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.6382 (12) ŵ = 1.48 mm1
b = 8.8403 (7) ÅT = 150 K
c = 29.595 (2) Å0.26 × 0.08 × 0.08 mm
β = 103.672 (2)°
Data collection top
Bruker SMART1000 CCD area detector with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986)
diffractometer
9917 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
5504 reflections with I > 2σ(I)
Tmin = 0.722, Tmax = 0.888Rint = 0.063
24884 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05832 restraints
wR(F2) = 0.139H-atom parameters constrained
S = 1.00Δρmax = 0.88 e Å3
9356 reflectionsΔρmin = 1.01 e Å3
498 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.25470 (3)0.23587 (6)0.181291 (17)0.01776 (14)
N10.2523 (3)0.2352 (4)0.10624 (13)0.0206 (8)
C20.3439 (3)0.2319 (6)0.10024 (17)0.0271 (11)
H2A0.35950.33360.09070.032*
H2B0.34710.16020.07500.032*
C30.4103 (3)0.1851 (5)0.14426 (16)0.0264 (11)
H3A0.40650.07450.14860.032*
H3B0.47040.20860.14090.032*
N40.3949 (3)0.2635 (4)0.18556 (13)0.0213 (8)
C50.4179 (3)0.4258 (5)0.18560 (18)0.0267 (11)
H5A0.42760.45330.15480.032*
H5B0.47370.44350.20910.032*
C60.3461 (3)0.5280 (5)0.19645 (17)0.0256 (11)
H6A0.34810.52280.23010.031*
H6B0.35720.63400.18880.031*
N70.2580 (2)0.4817 (4)0.16964 (13)0.0202 (9)
C80.2460 (3)0.5106 (5)0.11895 (16)0.0244 (11)
H8A0.30380.53360.11240.029*
H8B0.20770.60010.11010.029*
C90.2054 (3)0.3766 (5)0.08991 (16)0.0235 (11)
H9A0.14300.36680.09130.028*
H9B0.20700.39430.05710.028*
C1A0.2012 (3)0.0994 (5)0.08697 (16)0.0274 (12)
H1A10.21040.07750.05570.033*
H1A20.13770.11870.08380.033*
C2A0.2292 (3)0.0345 (5)0.11810 (16)0.0256 (11)
H2A10.19190.12300.10610.031*
H2A20.29110.06080.11890.031*
N3A0.2204 (3)0.0038 (4)0.16527 (13)0.0261 (9)
H3AA0.25660.05780.18660.031*
H3AB0.16340.01280.16730.031*
C1B0.4387 (3)0.1879 (6)0.22939 (17)0.0292 (12)
H1B10.50220.21300.23720.035*
H1B20.43270.07690.22550.035*
C2B0.3979 (3)0.2382 (6)0.26873 (17)0.0307 (12)
H2B10.42200.17680.29680.037*
H2B20.41270.34560.27640.037*
N3B0.3017 (3)0.2200 (4)0.25465 (13)0.0260 (9)
H3BA0.27530.29350.26870.031*
H3BB0.28650.12730.26450.031*
C1C0.1873 (3)0.5434 (5)0.18874 (17)0.0238 (11)
H1C10.16360.63490.17090.029*
H1C20.21230.57470.22130.029*
C2C0.1118 (3)0.4331 (5)0.18785 (15)0.0208 (10)
O3C0.0436 (2)0.4815 (4)0.19639 (12)0.0266 (8)
O4C0.1238 (2)0.2942 (3)0.17913 (11)0.0225 (7)
Zn20.20025 (4)0.79445 (6)0.393961 (18)0.02163 (15)
N1'0.1999 (3)0.6778 (5)0.45953 (14)0.0275 (10)
C2'0.2477 (3)0.7690 (6)0.49895 (16)0.0299 (12)
H2'10.30580.72230.51190.036*
H2'20.21460.76850.52360.036*
C3'0.2610 (3)0.9327 (6)0.48539 (17)0.0296 (12)
H3'10.20450.98780.48070.035*
H3'20.30390.98260.51110.035*
N4'0.2933 (3)0.9413 (4)0.44262 (13)0.0247 (9)
C5'0.3845 (3)0.8857 (6)0.44886 (18)0.0307 (12)
H5'10.40300.83640.47970.037*
H5'20.42400.97300.44850.037*
C6'0.3947 (3)0.7729 (6)0.41113 (17)0.0279 (11)
H6'10.39390.82820.38190.033*
H6'20.45220.72090.42100.033*
N7'0.3240 (3)0.6607 (4)0.40267 (13)0.0231 (9)
C8'0.3309 (3)0.5563 (6)0.44214 (17)0.0290 (12)
H8'10.37420.59710.46940.035*
H8'20.35320.45760.43410.035*
C9'0.2432 (4)0.5319 (6)0.45533 (18)0.0337 (13)
H9'10.20420.46910.43130.040*
H9'20.25340.47700.48530.040*
C1A'0.1061 (4)0.6571 (7)0.4591 (2)0.0426 (15)
H1A30.08130.57490.43720.051*0.85
H1A40.10070.62670.49050.051*0.85
H1AA0.09220.71930.48440.051*0.15
H1AB0.09580.55040.46640.051*0.15
C2A'0.0559 (4)0.7950 (7)0.4453 (2)0.0340 (15)0.85
H2A30.07530.87440.46910.041*0.85
H2A40.00750.77550.44260.041*0.85
C2A"0.0442 (16)0.699 (2)0.4160 (8)0.037 (9)*0.15
H2AA0.01590.70620.42130.045*0.15
H2AB0.04380.62000.39220.045*0.15
N3A'0.0702 (3)0.8472 (5)0.39922 (15)0.0339 (11)
H3AC0.06140.95000.39640.041*0.85
H3AD0.03020.80070.37550.041*0.85
H3AE0.03450.87380.37100.041*0.15
H3AF0.06980.92300.42050.041*0.15
C1B'0.2796 (4)1.0915 (6)0.42110 (18)0.0343 (13)
H1B30.32761.15990.43670.041*
H1B40.22331.13400.42510.041*
C2B'0.2777 (4)1.0827 (6)0.36984 (18)0.0358 (13)
H2B30.26181.18270.35520.043*
H2B40.33681.05530.36580.043*
N3B'0.2131 (3)0.9686 (4)0.34694 (14)0.0312 (10)
H3BC0.23090.92760.32210.037*
H3BD0.15931.01420.33580.037*
C1C'0.3149 (3)0.5812 (5)0.35798 (16)0.0242 (11)
H1C30.34970.48660.36340.029*
H1C40.33950.64550.33680.029*
C2C'0.2200 (3)0.5428 (5)0.33471 (17)0.0238 (11)
O3C'0.2065 (2)0.4445 (4)0.30385 (12)0.0295 (8)
O4C'0.1590 (2)0.6153 (4)0.34719 (11)0.0267 (8)
Cl10.46479 (8)0.77052 (14)0.09591 (4)0.0297 (3)
O10.4327 (3)0.8929 (5)0.06482 (15)0.0626 (13)
O20.5576 (3)0.7714 (5)0.11004 (16)0.0542 (12)
O30.4348 (3)0.6273 (4)0.07571 (14)0.0488 (11)
O40.4316 (3)0.7911 (5)0.13734 (15)0.0559 (12)
Cl20.01147 (9)0.24834 (16)0.43313 (5)0.0419 (4)
O50.0499 (3)0.1332 (6)0.4354 (2)0.0963 (19)
O60.0697 (4)0.1964 (6)0.4072 (2)0.100 (2)
O70.0677 (4)0.2747 (8)0.4783 (2)0.119 (2)*
O80.0325 (5)0.3832 (8)0.4164 (3)0.054 (2)*0.50
O8'0.0171 (10)0.3557 (14)0.3949 (4)0.054 (4)*0.30
O8"0.0246 (13)0.3698 (17)0.4533 (7)0.051 (5)*0.20
Li0.0181 (5)0.6614 (9)0.2279 (3)0.029 (2)
O1S0.1012 (2)0.8273 (4)0.23460 (14)0.0394 (9)
O2S0.0843 (2)0.7402 (4)0.18520 (12)0.0337 (8)
O3S0.0093 (2)0.6046 (4)0.28756 (11)0.0279 (8)
Cl30.31550 (8)0.85005 (12)0.26751 (4)0.0205 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0182 (3)0.0186 (3)0.0179 (3)0.0001 (2)0.0069 (2)0.0001 (2)
N10.021 (2)0.023 (2)0.020 (2)0.0008 (17)0.0093 (17)0.0031 (16)
C20.029 (3)0.032 (3)0.025 (3)0.002 (2)0.017 (2)0.004 (2)
C30.023 (3)0.027 (3)0.033 (3)0.001 (2)0.014 (2)0.003 (2)
N40.021 (2)0.020 (2)0.022 (2)0.0014 (17)0.0050 (17)0.0002 (16)
C50.020 (3)0.025 (3)0.035 (3)0.007 (2)0.006 (2)0.004 (2)
C60.022 (3)0.022 (3)0.032 (3)0.005 (2)0.004 (2)0.004 (2)
N70.018 (2)0.020 (2)0.025 (2)0.0015 (16)0.0087 (18)0.0010 (16)
C80.025 (3)0.022 (2)0.027 (3)0.001 (2)0.009 (2)0.0073 (19)
C90.025 (3)0.028 (3)0.017 (2)0.004 (2)0.005 (2)0.0079 (19)
C1A0.028 (3)0.031 (3)0.021 (3)0.002 (2)0.003 (2)0.006 (2)
C2A0.026 (3)0.022 (3)0.028 (3)0.000 (2)0.006 (2)0.006 (2)
N3A0.028 (3)0.024 (2)0.027 (2)0.0020 (18)0.006 (2)0.0031 (17)
C1B0.024 (3)0.030 (3)0.031 (3)0.002 (2)0.000 (2)0.003 (2)
C2B0.032 (3)0.034 (3)0.022 (3)0.003 (2)0.001 (2)0.001 (2)
N3B0.033 (3)0.026 (2)0.019 (2)0.0018 (19)0.0074 (19)0.0032 (16)
C1C0.024 (3)0.020 (2)0.029 (3)0.002 (2)0.009 (2)0.002 (2)
C2C0.022 (3)0.025 (3)0.016 (2)0.003 (2)0.004 (2)0.0025 (18)
O3C0.0212 (19)0.0264 (18)0.034 (2)0.0017 (15)0.0096 (16)0.0069 (15)
O4C0.0190 (18)0.0205 (17)0.0303 (18)0.0001 (14)0.0104 (15)0.0008 (14)
Zn20.0211 (3)0.0257 (3)0.0180 (3)0.0028 (2)0.0045 (2)0.0019 (2)
N1'0.024 (2)0.039 (3)0.022 (2)0.0009 (19)0.0107 (19)0.0011 (18)
C2'0.031 (3)0.046 (3)0.016 (2)0.005 (2)0.011 (2)0.002 (2)
C3'0.026 (3)0.043 (3)0.020 (3)0.003 (2)0.005 (2)0.008 (2)
N4'0.024 (2)0.029 (2)0.021 (2)0.0008 (18)0.0050 (19)0.0047 (17)
C5'0.026 (3)0.037 (3)0.030 (3)0.009 (2)0.009 (2)0.008 (2)
C6'0.023 (3)0.037 (3)0.025 (3)0.001 (2)0.008 (2)0.006 (2)
N7'0.025 (2)0.025 (2)0.020 (2)0.0005 (18)0.0083 (18)0.0011 (16)
C8'0.036 (3)0.028 (3)0.022 (3)0.008 (2)0.006 (2)0.005 (2)
C9'0.046 (4)0.033 (3)0.024 (3)0.002 (3)0.013 (3)0.007 (2)
C1A'0.032 (3)0.063 (4)0.036 (3)0.006 (3)0.015 (3)0.004 (3)
C2A'0.025 (4)0.045 (4)0.035 (4)0.003 (3)0.012 (3)0.001 (3)
N3A'0.022 (2)0.042 (3)0.035 (3)0.004 (2)0.001 (2)0.004 (2)
C1B'0.043 (4)0.024 (3)0.038 (3)0.004 (2)0.013 (3)0.007 (2)
C2B'0.049 (4)0.027 (3)0.034 (3)0.002 (3)0.015 (3)0.002 (2)
N3B'0.042 (3)0.029 (2)0.024 (2)0.008 (2)0.010 (2)0.0003 (18)
C1C'0.026 (3)0.025 (3)0.023 (3)0.006 (2)0.010 (2)0.001 (2)
C2C'0.028 (3)0.020 (2)0.025 (3)0.000 (2)0.009 (2)0.0035 (19)
O3C'0.034 (2)0.0285 (19)0.0290 (19)0.0070 (16)0.0135 (17)0.0097 (15)
O4C'0.026 (2)0.0288 (19)0.0258 (19)0.0017 (15)0.0066 (16)0.0049 (14)
Cl10.0225 (7)0.0310 (7)0.0331 (7)0.0018 (5)0.0020 (6)0.0027 (5)
O10.076 (4)0.049 (3)0.048 (3)0.004 (2)0.013 (3)0.017 (2)
O20.025 (2)0.058 (3)0.077 (3)0.010 (2)0.007 (2)0.003 (2)
O30.055 (3)0.042 (2)0.043 (2)0.018 (2)0.002 (2)0.0098 (19)
O40.065 (3)0.056 (3)0.056 (3)0.010 (2)0.033 (2)0.004 (2)
Cl20.0344 (8)0.0441 (8)0.0515 (9)0.0082 (7)0.0186 (7)0.0175 (7)
O50.067 (4)0.089 (4)0.132 (5)0.050 (3)0.023 (4)0.006 (4)
O60.102 (5)0.095 (4)0.127 (5)0.026 (4)0.073 (4)0.000 (4)
O1S0.030 (2)0.031 (2)0.058 (3)0.0032 (16)0.012 (2)0.0064 (18)
O2S0.028 (2)0.033 (2)0.039 (2)0.0023 (16)0.0063 (17)0.0021 (16)
O3S0.030 (2)0.0269 (18)0.0277 (19)0.0006 (15)0.0093 (16)0.0040 (14)
Li0.022 (5)0.030 (5)0.038 (5)0.000 (4)0.011 (4)0.003 (4)
Cl30.0247 (6)0.0187 (5)0.0195 (6)0.0007 (5)0.0080 (5)0.0022 (4)
Geometric parameters (Å, º) top
Zn1—N12.212 (4)Li—O3C1.932 (9)
Zn1—N42.180 (4)Li—O1S1.939 (9)
Zn1—N72.203 (4)Li—O2S1.921 (9)
Zn1—N3A2.145 (4)Li—O3S1.978 (9)
Zn1—N3B2.126 (4)C2—H2A0.99
Zn1—O4C2.098 (3)C2—H2B0.99
N1—C91.472 (6)C3—H3A0.99
N1—C1A1.480 (6)C3—H3B0.99
N1—C21.485 (6)C5—H5A0.99
C2—C31.519 (7)C5—H5B0.99
C3—N41.474 (6)C6—H6A0.99
N4—C1B1.476 (6)C6—H6B0.99
N4—C51.479 (6)C8—H8A0.99
C5—C61.534 (7)C8—H8B0.99
C6—N71.476 (6)C9—H9A0.99
N7—C1C1.460 (6)C9—H9B0.99
N7—C81.489 (6)C1A—H1A10.99
C8—C91.512 (6)C1A—H1A20.99
C1A—C2A1.501 (7)C2A—H2A10.99
C2A—N3A1.474 (6)C2A—H2A20.99
C1B—C2B1.520 (7)N3A—H3AA0.92
C2B—N3B1.473 (6)N3A—H3AB0.92
C1C—C2C1.527 (6)C1B—H1B10.99
C2C—O3C1.230 (5)C1B—H1B20.99
C2C—O4C1.277 (5)C2B—H2B10.99
Zn2—N1'2.199 (4)C2B—H2B20.99
Zn2—N4'2.210 (4)N3B—H3BA0.92
Zn2—N7'2.231 (4)N3B—H3BB0.92
Zn2—N3B'2.116 (4)C1C—H1C10.99
Zn2—N3A'2.127 (4)C1C—H1C20.99
Zn2—O4C'2.102 (3)C2'—H2'10.99
N1'—C2'1.469 (6)C2'—H2'20.99
N1'—C1A'1.475 (6)C3'—H3'10.99
N1'—C9'1.476 (6)C3'—H3'20.99
C2'—C3'1.529 (7)C5'—H5'10.99
C3'—N4'1.471 (6)C5'—H5'20.99
N4'—C1B'1.467 (6)C6'—H6'10.99
N4'—C5'1.478 (6)C6'—H6'20.99
C5'—C6'1.533 (6)C8'—H8'10.99
C6'—N7'1.462 (6)C8'—H8'20.99
N7'—C8'1.473 (6)C9'—H9'10.99
N7'—C1C'1.475 (6)C9'—H9'20.99
C8'—C9'1.527 (7)C1A'—H1A30.99
C1A'—C2A"1.455 (12)C1A'—H1A40.99
C1A'—C2A'1.455 (8)C1A'—H1AA0.99
C2A'—N3A'1.507 (7)C1A'—H1AB0.99
C2A"—N3A'1.493 (12)C2A'—H2A30.99
C1B'—C2B'1.512 (7)C2A'—H2A40.99
C2B'—N3B'1.474 (7)C2A"—H2AA0.99
C1C'—C2C'1.520 (7)C2A"—H2AB0.99
C2C'—O3C'1.242 (5)N3A'—H3AC0.92
C2C'—O4C'1.274 (5)N3A'—H3AD0.92
Cl1—O11.432 (4)N3A'—H3AE0.92
Cl1—O21.413 (4)N3A'—H3AF0.92
Cl1—O31.432 (4)C1B'—H1B30.99
Cl1—O41.451 (4)C1B'—H1B40.99
Cl2—O51.411 (4)C2B'—H2B30.99
Cl2—O61.399 (4)C2B'—H2B40.99
Cl2—O71.435 (5)N3B'—H3BC0.92
Cl2—O81.406 (6)N3B'—H3BD0.92
Cl2—O8'1.464 (7)C1C'—H1C30.99
Cl2—O8"1.409 (8)C1C'—H1C40.99
N1—Zn1—N480.61 (14)C6—C5—H5A109.1
N1—Zn1—N780.85 (13)N4—C5—H5B109.1
N1—Zn1—N3A80.29 (14)C6—C5—H5B109.1
N1—Zn1—N3B160.89 (15)H5A—C5—H5B107.8
N1—Zn1—O4C100.67 (13)N7—C6—H6A109.4
N4—Zn1—N780.68 (14)C5—C6—H6A109.4
N4—Zn1—N3A108.39 (15)N7—C6—H6B109.4
N4—Zn1—N3B81.27 (15)C5—C6—H6B109.4
N4—Zn1—O4C159.28 (13)H6A—C6—H6B108.0
N7—Zn1—N3A157.34 (15)N7—C8—H8A109.2
N7—Zn1—N3B102.12 (15)C9—C8—H8A109.2
N7—Zn1—O4C79.13 (13)N7—C8—H8B109.2
N3A—Zn1—N3B99.82 (15)C9—C8—H8B109.2
N3A—Zn1—O4C92.13 (14)H8A—C8—H8B107.9
N3B—Zn1—O4C98.42 (14)N1—C9—H9A109.3
C9—N1—C1A112.4 (4)C8—C9—H9A109.3
C9—N1—C2113.4 (4)N1—C9—H9B109.3
C1A—N1—C2112.7 (4)C8—C9—H9B109.3
C9—N1—Zn1102.5 (3)H9A—C9—H9B107.9
C1A—N1—Zn1105.6 (3)N1—C1A—H1A1109.5
C2—N1—Zn1109.4 (3)C2A—C1A—H1A1109.5
N1—C2—C3112.7 (4)N1—C1A—H1A2109.5
N4—C3—C2111.7 (4)C2A—C1A—H1A2109.5
C3—N4—C1B112.5 (4)H1A1—C1A—H1A2108.1
C3—N4—C5111.7 (4)N3A—C2A—H2A1109.9
C1B—N4—C5112.1 (4)C1A—C2A—H2A1109.9
C3—N4—Zn1105.0 (3)N3A—C2A—H2A2109.9
C1B—N4—Zn1104.5 (3)C1A—C2A—H2A2109.9
C5—N4—Zn1110.5 (3)H2A1—C2A—H2A2108.3
N4—C5—C6112.4 (4)C2A—N3A—H3AA109.5
N7—C6—C5111.2 (4)Zn1—N3A—H3AA109.5
C1C—N7—C6112.6 (4)C2A—N3A—H3AB109.5
C1C—N7—C8113.5 (4)Zn1—N3A—H3AB109.5
C6—N7—C8111.9 (4)H3AA—N3A—H3AB108.1
C1C—N7—Zn1105.1 (3)N4—C1B—H1B1109.6
C6—N7—Zn1104.0 (3)C2B—C1B—H1B1109.6
C8—N7—Zn1109.0 (3)N4—C1B—H1B2109.6
N7—C8—C9112.0 (4)C2B—C1B—H1B2109.6
N1—C9—C8111.7 (4)H1B1—C1B—H1B2108.1
N1—C1A—C2A110.5 (4)N3B—C2B—H2B1109.7
N3A—C2A—C1A108.7 (4)C1B—C2B—H2B1109.7
C2A—N3A—Zn1110.8 (3)N3B—C2B—H2B2109.7
N4—C1B—C2B110.5 (4)C1B—C2B—H2B2109.7
N3B—C2B—C1B109.7 (4)H2B1—C2B—H2B2108.2
C2B—N3B—Zn1111.4 (3)C2B—N3B—H3BA109.3
N7—C1C—C2C114.1 (4)Zn1—N3B—H3BA109.3
O3C—C2C—O4C123.5 (4)C2B—N3B—H3BB109.3
O3C—C2C—C1C118.6 (4)Zn1—N3B—H3BB109.3
O4C—C2C—C1C117.9 (4)H3BA—N3B—H3BB108.0
C2C—O3C—Li132.4 (4)N7—C1C—H1C1108.7
C2C—O4C—Zn1114.8 (3)C2C—C1C—H1C1108.7
N1'—Zn2—N4'80.74 (15)N7—C1C—H1C2108.7
N1'—Zn2—N7'80.37 (14)C2C—C1C—H1C2108.7
N1'—Zn2—N3A'80.57 (16)H1C1—C1C—H1C2107.6
N1'—Zn2—N3B'160.40 (16)N1'—C2'—H2'1109.0
N1'—Zn2—O4C'99.39 (14)C3'—C2'—H2'1109.0
N4'—Zn2—N7'79.41 (14)N1'—C2'—H2'2109.0
N4'—Zn2—N3A'108.47 (16)C3'—C2'—H2'2109.0
N4'—Zn2—N3B'81.44 (15)H2'1—C2'—H2'2107.8
N4'—Zn2—O4C'157.52 (14)N4'—C3'—H3'1109.3
N7'—Zn2—N3A'157.84 (16)C2'—C3'—H3'1109.3
N7'—Zn2—N3B'104.28 (15)N4'—C3'—H3'2109.3
N7'—Zn2—O4C'78.46 (13)C2'—C3'—H3'2109.3
N3A'—Zn2—N3B'97.44 (17)H3'1—C3'—H3'2107.9
N3B'—Zn2—O4C'100.20 (14)N4'—C5'—H5'1109.0
N3A'—Zn2—O4C'93.63 (15)C6'—C5'—H5'1109.0
C2'—N1'—C1A'113.1 (4)N4'—C5'—H5'2109.0
C2'—N1'—C9'112.9 (4)C6'—C5'—H5'2109.0
C1A'—N1'—C9'111.5 (4)H5'1—C5'—H5'2107.8
C2'—N1'—Zn2109.6 (3)N7'—C6'—H6'1109.4
C1A'—N1'—Zn2105.1 (3)C5'—C6'—H6'1109.4
C9'—N1'—Zn2103.8 (3)N7'—C6'—H6'2109.4
N1'—C2'—C3'112.8 (4)C5'—C6'—H6'2109.4
N4'—C3'—C2'111.7 (4)H6'1—C6'—H6'2108.0
C1B'—N4'—C3'112.1 (4)N7'—C8'—H8'1109.0
C1B'—N4'—C5'113.1 (4)C9'—C8'—H8'1109.0
C3'—N4'—C5'113.1 (4)N7'—C8'—H8'2109.0
C1B'—N4'—Zn2104.1 (3)C9'—C8'—H8'2109.0
C3'—N4'—Zn2102.9 (3)H8'1—C8'—H8'2107.8
C5'—N4'—Zn2110.7 (3)N1'—C9'—H9'1109.5
N4'—C5'—C6'112.9 (4)C8'—C9'—H9'1109.5
N7'—C6'—C5'111.2 (4)N1'—C9'—H9'2109.5
C6'—N7'—C8'112.3 (4)C8'—C9'—H9'2109.5
C6'—N7'—C1C'112.7 (4)H9'1—C9'—H9'2108.1
C8'—N7'—C1C'112.7 (4)C2A'—C1A'—H1A3109.3
C6'—N7'—Zn2105.1 (3)N1'—C1A'—H1A3109.3
C8'—N7'—Zn2108.8 (3)C2A'—C1A'—H1A4109.3
C1C'—N7'—Zn2104.6 (3)N1'—C1A'—H1A4109.3
N7'—C8'—C9'113.0 (4)H1A3—C1A'—H1A4108.0
N1'—C9'—C8'110.9 (4)C2A"—C1A'—H1AA108.1
C2A'—C1A'—N1'111.6 (5)N1'—C1A'—H1AA108.4
C1A'—C2A'—N3A'108.9 (5)C2A"—C1A'—H1AB108.6
C1A'—C2A"—N3A'109.7 (9)N1'—C1A'—H1AB108.5
C2A"—N3A'—Zn299.9 (13)H1AA—C1A'—H1AB107.5
C2A'—N3A'—Zn2110.4 (3)C1A'—C2A'—H2A3109.9
N4'—C1B'—C2B'110.8 (4)N3A'—C2A'—H2A3109.9
N3B'—C2B'—C1B'110.2 (4)C1A'—C2A'—H2A4109.9
C2B'—N3B'—Zn2110.9 (3)N3A'—C2A'—H2A4109.9
N7'—C1C'—C2C'112.9 (4)H1AA—C2A'—H2A4101.7
O3C'—C2C'—O4C'123.8 (5)H2A3—C2A'—H2A4108.3
O3C'—C2C'—C1C'117.8 (4)C1A'—C2A'—H3AF132.9
O4C'—C2C'—C1C'118.3 (4)H2A4—C2A'—H3AF112.2
C2C'—O4C'—Zn2115.8 (3)C1A'—C2A"—H2AA109.7
O2—Cl1—O3109.9 (3)N3A'—C2A"—H2AA109.7
O2—Cl1—O1111.4 (3)C1A'—C2A"—H2AB109.7
O3—Cl1—O1111.7 (3)N3A'—C2A"—H2AB109.7
O2—Cl1—O4107.3 (3)H2AA—C2A"—H2AB108.2
O3—Cl1—O4108.4 (3)C2A'—N3A'—H3AC109.6
O1—Cl1—O4107.9 (3)Zn2—N3A'—H3AC109.6
O6—Cl2—O8114.4 (5)C2A'—N3A'—H3AD109.6
O6—Cl2—O8"149.2 (9)Zn2—N3A'—H3AD109.6
O6—Cl2—O5109.1 (4)H3AC—N3A'—H3AD108.1
O8—Cl2—O5110.3 (4)C2A"—N3A'—H3AE111.8
O8"—Cl2—O5100.7 (9)Zn2—N3A'—H3AE112.0
O6—Cl2—O7103.2 (4)C2A"—N3A'—H3AF111.5
O8—Cl2—O7109.3 (4)Zn2—N3A'—H3AF111.8
O8"—Cl2—O772.5 (9)H3AE—N3A'—H3AF109.6
O5—Cl2—O7110.3 (4)N4'—C1B'—H1B3109.5
O6—Cl2—O8'84.8 (7)C2B'—C1B'—H1B3109.5
O5—Cl2—O8'114.7 (7)N4'—C1B'—H1B4109.5
O7—Cl2—O8'128.5 (7)C2B'—C1B'—H1B4109.5
O3C—Li—O1S117.6 (4)H1B3—C1B'—H1B4108.1
O3C—Li—O2S102.5 (4)N3B'—C2B'—H2B3109.6
O3C—Li—O3S109.5 (4)C1B'—C2B'—H2B3109.6
O1S—Li—O2S103.2 (4)N3B'—C2B'—H2B4109.6
O1S—Li—O3S112.4 (4)C1B'—C2B'—H2B4109.6
O2S—Li—O3S110.9 (4)H2B3—C2B'—H2B4108.1
N1—C2—H2A109.0C2B'—N3B'—H3BC109.5
C3—C2—H2A109.0Zn2—N3B'—H3BC109.5
N1—C2—H2B109.0C2B'—N3B'—H3BD109.5
C3—C2—H2B109.0Zn2—N3B'—H3BD109.5
H2A—C2—H2B107.8H3BC—N3B'—H3BD108.0
N4—C3—H3A109.3N7'—C1C'—H1C3109.0
C2—C3—H3A109.3C2C'—C1C'—H1C3109.0
N4—C3—H3B109.3N7'—C1C'—H1C4109.0
C2—C3—H3B109.3C2C'—C1C'—H1C4109.0
H3A—C3—H3B107.9H1C3—C1C'—H1C4107.8
N4—C5—H5A109.1
C9—N1—C2—C3130.1 (4)C2'—C3'—N4'—C5'69.1 (5)
C1A—N1—C2—C3100.7 (4)C1B'—N4'—C5'—C6'100.2 (5)
N1—C2—C3—N445.2 (5)C3'—N4'—C5'—C6'131.1 (4)
C2—C3—N4—C1B162.0 (4)N4'—C5'—C6'—N7'45.3 (6)
C2—C3—N4—C570.9 (5)C5'—C6'—N7'—C8'69.2 (5)
C3—N4—C5—C6132.6 (4)C5'—C6'—N7'—C1C'162.2 (4)
C1B—N4—C5—C6100.1 (5)C6'—N7'—C8'—C9'134.0 (4)
N4—C5—C6—N745.6 (5)C1C'—N7'—C8'—C9'97.4 (5)
C5—C6—N7—C1C162.4 (4)C2'—N1'—C9'—C8'67.3 (5)
C5—C6—N7—C868.3 (5)C1A'—N1'—C9'—C8'164.0 (4)
C1C—N7—C8—C997.4 (5)N7'—C8'—C9'—N1'48.6 (6)
C6—N7—C8—C9133.8 (4)C2'—N1'—C1A'—C2A"126.7 (13)
C1A—N1—C9—C8164.9 (4)C9'—N1'—C1A'—C2A"104.7 (13)
C2—N1—C9—C865.8 (5)C2'—N1'—C1A'—C2A'73.5 (6)
N7—C8—C9—N150.4 (5)C9'—N1'—C1A'—C2A'157.9 (5)
C9—N1—C1A—C2A155.6 (4)C2A"—C1A'—C2A'—N3A'51.0 (13)
C2—N1—C1A—C2A74.7 (5)N1'—C1A'—C2A'—N3A'54.5 (6)
N1—C1A—C2A—N3A55.6 (5)C2A'—C1A'—C2A"—N3A'52.0 (13)
C3—N4—C1B—C2B161.2 (4)N1'—C1A'—C2A"—N3A'45 (3)
C5—N4—C1B—C2B71.9 (5)C1A'—C2A"—N3A'—C2A'51.2 (13)
N4—C1B—C2B—N3B51.7 (5)C1A'—C2A'—N3A'—C2A"50.9 (14)
C6—N7—C1C—C2C140.4 (4)C3'—N4'—C1B'—C2B'157.0 (4)
C8—N7—C1C—C2C91.1 (5)C5'—N4'—C1B'—C2B'73.7 (5)
N7—C1C—C2C—O3C168.9 (4)N4'—C1B'—C2B'—N3B'52.9 (6)
N7—C1C—C2C—O4C12.5 (6)C6'—N7'—C1C'—C2C'145.1 (4)
O4C—C2C—O3C—Li158.6 (5)C8'—N7'—C1C'—C2C'86.6 (5)
C1C—C2C—O3C—Li20.0 (7)N7'—C1C'—C2C'—O3C'162.0 (4)
C1A'—N1'—C2'—C3'100.9 (5)N7'—C1C'—C2C'—O4C'19.5 (6)
C9'—N1'—C2'—C3'131.3 (4)C2C—O3C—Li—O2S131.1 (5)
N1'—C2'—C3'—N4'46.9 (6)C2C—O3C—Li—O1S18.8 (8)
C2'—C3'—N4'—C1B'161.6 (4)C2C—O3C—Li—O3S111.1 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H3AA···Cl3i0.922.493.330 (7)152
N3B—H3BA···O3C0.922.133.050 (8)174
N3B—H3BB···Cl3i0.922.493.294 (7)146
N3A—H3AD···O4Cii0.922.563.387 (9)149
N3A—H3AE···O3Cii0.922.283.188 (10)170
N3A—H3AC···O6iii0.922.203.096 (15)164
N3B—H3BC···Cl30.922.423.312 (7)164
N3B—H3BD···O2Sii0.922.333.134 (10)146
Symmetry codes: (i) x, y1, z; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Zn(C12H32N5O)LiO4][Zn(C12H26N5O2].Cl.2(ClO4)
Mr970.85
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)15.6382 (12), 8.8403 (7), 29.595 (2)
β (°) 103.672 (2)
V3)3975.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.48
Crystal size (mm)0.26 × 0.08 × 0.08
Data collection
DiffractometerBruker SMART1000 CCD area detector with Oxford Cryosystems open-flow cryostat (Cosier & Glazer, 1986)
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.722, 0.888
No. of measured, independent and
observed [I > 2σ(I)] reflections
24884, 9917, 5504
Rint0.063
(sin θ/λ)max1)0.683
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.139, 1.00
No. of reflections9356
No. of parameters498
No. of restraints32
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.88, 1.01

Computer programs: Bruker SMART version 5.054 (Bruker, 1998), Bruker SAINT version 6.02a (Bruker, 2000), Bruker SAINT; Bruker SHELXTL (Bruker, 1997), Bruker SHELXTL, SHELXL97 (Sheldrick, 1997), SHELXL97; PLATON (Spek, 2002).

Selected geometric parameters (Å, º) top
Zn1—N12.212 (4)Zn2—N7'2.231 (4)
Zn1—N42.180 (4)Zn2—N3B'2.116 (4)
Zn1—N72.203 (4)Zn2—N3A'2.127 (4)
Zn1—N3A2.145 (4)Zn2—O4C'2.102 (3)
Zn1—N3B2.126 (4)Li—O3C1.932 (9)
Zn1—O4C2.098 (3)Li—O1S1.939 (9)
Zn2—N1'2.199 (4)Li—O2S1.921 (9)
Zn2—N4'2.210 (4)Li—O3S1.978 (9)
N1—Zn1—N480.61 (14)N1'—Zn2—N3B'160.40 (16)
N1—Zn1—N780.85 (13)N1'—Zn2—O4C'99.39 (14)
N1—Zn1—N3A80.29 (14)N4'—Zn2—N7'79.41 (14)
N1—Zn1—N3B160.89 (15)N4'—Zn2—N3A'108.47 (16)
N1—Zn1—O4C100.67 (13)N4'—Zn2—N3B'81.44 (15)
N4—Zn1—N780.68 (14)N4'—Zn2—O4C'157.52 (14)
N4—Zn1—N3A108.39 (15)N7'—Zn2—N3A'157.84 (16)
N4—Zn1—N3B81.27 (15)N7'—Zn2—N3B'104.28 (15)
N4—Zn1—O4C159.28 (13)N7'—Zn2—O4C'78.46 (13)
N7—Zn1—N3A157.34 (15)N3A'—Zn2—N3B'97.44 (17)
N7—Zn1—N3B102.12 (15)N3B'—Zn2—O4C'100.20 (14)
N7—Zn1—O4C79.13 (13)N3A'—Zn2—O4C'93.63 (15)
N3A—Zn1—N3B99.82 (15)O3C—Li—O1S117.6 (4)
N3A—Zn1—O4C92.13 (14)O3C—Li—O2S102.5 (4)
N3B—Zn1—O4C98.42 (14)O3C—Li—O3S109.5 (4)
N1'—Zn2—N4'80.74 (15)O1S—Li—O2S103.2 (4)
N1'—Zn2—N7'80.37 (14)O1S—Li—O3S112.4 (4)
N1'—Zn2—N3A'80.57 (16)O2S—Li—O3S110.9 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3A—H3AA···Cl3i0.922.493.330 (7)152
N3B—H3BA···O3C'0.922.133.050 (8)174
N3B—H3BB···Cl3i0.922.493.294 (7)146
N3A'—H3AD···O4Cii0.922.563.387 (9)149
N3A'—H3AE···O3Cii0.922.283.188 (10)170
N3A'—H3AC···O6iii0.922.203.096 (15)164
N3B'—H3BC···Cl30.922.423.312 (7)164
N3B'—H3BD···O2Sii0.922.333.134 (10)146
Symmetry codes: (i) x, y1, z; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z.
 

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