Paper

Hydrogen bonded 1,10-diammoniodecane – an example of an

organo-template for the crystal engineering of polymeric polyiodides

Guido J. Reiß* and Judith S. Engel

Institut fur Anorganische Chemie und Strukturchemie, Heinrich-Heine-UniversitatDusseldorf, Universitatsstraße 1, D-40225 Dusseldorf, Germany.E-mail: reissg@uni-duesseldorf.de

Received 10th April 2002, Accepted 9th May 2002

Published on the Web 13th June 2002

Using the rod-like 1,10-diammoniodecane (dadH2) as a template it is possible to synthesize and crystallize the

two polyiodide compounds (dadH2)2I2[I3]2 (1) and dadH2[I3]2?I2?2H2O (2). Compound 1 crystallizes in the polar

monoclinic space group P21 with eight iodine atoms and two all-trans conformated 1,10-diammoniodecanes in

the asymmetric unit. The structure is built by the dications and the two iodide anions forming a hydrogen

bonded framework in which channels contain the two crystallographically independent I32 anions. These I3

2

anions are interconnected via extremely weak I…I interactions to a one-dimensional polymer with the I32 units

linked to each other. They do not form hydrogen bonds of reasonable strength to the host framework.

Compound 2 crystallizes in the centrosymmetric space group P21/n. The 1,10-diammonioalkane cations are

lying on centres of symmetry and are showing an all-trans conformation. These cations form a sub-structure

that is built by hydrogen bonded ribbons of 1,10-diammoniodecanes and water molecules in the ratio 1 : 2.

These ribbons act as polymeric templates for the formation of a iodine–iodide framework. This anionic sub-

structure is best described as a three-dimensional framework built by I2 molecules and I32 anions showing the

habit of a herring-bone motif. Neglecting the weak I…I interactions of ca. 4 A the polyiodide framework can

be separated into outstretched, Z-shaped [I3…I2

…I3]22 sub-units lying on centres of symmetry. In the

structures of the compounds 1 and 2 the 1,10-diammoniodecane cations form hydrogen bonded ring motifs that

may be classified to Etter’s rules as R24(30) with the iodide anions in 1 and water molecules in 2 acting as

hydrogen bond acceptors. The crystal structure of the 1,10-diaminodecane (3) has been determined. This ‘soft

as butter’ material crystallizes in the centrosymmetric space group Pbca with the molecules lying on a centre of

symmetry and shows nearly ideal all-trans conformation. Only weak N–H…N hydrogen bonds occur between

neighbouring molecules to form a layered structure. The molecules are arranged in the ac plane to form a

herring-bone motif with the building ring motifs classified according Etter’s rules with the symbol R44(30).

Introduction

A fine control by the use of organic templates for the synthesisof new inorganic frameworks of a tailored topology is offundamental interest for the design of micro-porous solids (i.e.zeolites). It seems to be common sense that the interplay ofweak and subtle interactions plays a decisive role in crystalpacking and the formation of three-dimensional interconnectedstructures. For a template-controlled synthesis, two main pro-perties of the template demonstrate their ability to act as astructure-directing agent. On the one hand is the principalshape of the template, and the shapes of all stable conformers;on the other hand the chemical functionality plays animportant role. In most cases a compromise between bothdetermines the principal features of the solid-state structuresobtained with these compounds.1

Much of the current research in crystal engineering, however,is focused on attempts to create multi-component supramole-cular architectures based on intermolecular interactions, andinvolves the optimised formation of hydrogen bonds as theprimary design strategy.2 Rod like, flexible a,v-diammonioalk-anes3 and a,v-diaminoalkanes4 are already known to be potenttemplates used in crystal engineering to generate typicallylayered structures. For their flexibility the a,v-diammonioalk-anes have also been used for the crystal engineering of ions withan unusual topology, trapped in special organic–inorganicframeworks,5 whereas in combination with tetrahalogeno-metallates they form layered compounds showing a large

variety of phase transitions6 which are governed by thedynamics of the cations. At last these diammonioalkanecations have proved to be potent templates for the synthesisof a wide variety of layered aluminium phosphates.7

Iodine-rich iodides are very numerous and a great variety ofthem have been structurally characterized8 by X-ray diffractionmethods up to an I/I2-relation of 9.66.9 Raman spectroscopyhas also been successfully used to identify the structuralfragments of the polyiodides.10 Solid materials containingpolyiodides have earned much attention as these compoundsshow electric conduction ranging from values typical ofinsulators to those of typical metals.11 Conductivity is intro-duced in these materials by the electron-acceptor properties ofI2 molecules removing electron density from donor molecules.This property implicates future applications of such materialsin the areas of electronic and electrochemical technology.12

Most iodine–iodides are built up by the well known I32 anion

and discrete I2 molecules linked together by medium-strong toweak triiodide–iodine and triiodide–triiodide interactions. It isalso well known that the construction and stability of complexiodine–iodide anions and polymers are dependent upon theshape of the corresponding counter cations or correspondingtemplates.13,14

In the present study we show the ability of the 1,10-diammoniodecane cation to act as a template for a new tailoredpolyiodide framework and for the formation of a one-dimensional polymeric triiodide species accommodated withina hydrogen bonded channel structure.

DOI: 10.1039/b203499a CrystEngComm, 2002, 4(28), 155–161 155

This journal is # The Royal Society of Chemistry 2002

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Results and discussion

During the course of our study on the structural chemistry ofhydrogen bonded alkylammonium iodide salts we obtainedin the system 1,10-diammoniodecane (dadH2)/iodide/diiodine/water two compounds that can be formulated according tothe species that build the structure as: (dadH2)2I2[I3]2 (1), anddadH2[I3]2?I2?2H2O (2). As the solid-state structure of theneutral 1,10-diaminodecane is as yet unknown and it may be ofinterest in relation to the protonated species in 1 and 2 that wealso determined the crystal structure of this compound.

The structure of 1,10-diammoniodecane iodide triiodide (1)

The structure of 1 may be divided into two sub-systems. Thereis on the one hand the hydrogen bonded host framework builtby the dications and the iodide anions. On the other hand thereare triiodide anions which are situated in the channels of thisframework.

The two crystallographically independent dadH2 cationsboth show, in principle, an all-trans conformation (Table 1). Adetailed view on the conformtion parameters shows that bothcations show significant deviations from the ideal 180u angle tofill the needs of the hydrogen bonding in the structure of 1.

Both cations donate hydrogen bonds of medium strength tothe neighbouring iodide anions (Table 2) to form hydrogenbonded wavy layers in the ac plane (Fig. 1), while the distancesbetween ammonium groups and triiodide anions are signifi-cantly longer. Each iodide anion accepts four hydrogen bondswhile each ammonium group acts vice versa as a donor for twohydrogen bonds. The resulting two different ring motifs may be

classified according to Etter’s rules15 with the symbols R24(8)

and R24(30). These corrugated iron-like layers, not connected via

hydrogen bonds, are stacked in a manner such that the crests ofthe waves face each other directly. This arrangement createschannels in the [2 0 25] direction accommodating the I3

2

anions (Fig. 2). Both crystallographically independent I32

anions show the typical geometry with the central iodineatoms located off-centre and having a bond angle near 180u(Table 1). The distances between the I3

2 anions are with4.135(2) and 4.168(2) A in the vicinity of van der Waalscontacts. They may be interpreted, according to values givenin the literature, as weak I…I interactions to give kinkedpolymeric chains (Fig. 1). In many structures polymersconceived of I3

2 anions are found.16 Distances betweendiscrete I3

2 anions and the corresponding molecular symmetryof these ions have been determined by Bragg diffraction as wellas by diffuse scattering. Some of these compounds show aserious disorder of the anions in these polymers. The distancesbetween I3

2 anions found in the structures of these compoundsare significantly shorter than those found in 1.

Hydrogen bonding between these I32 anions and the

diammonioalkane cations of the hydrogen bonded frameworkare according to the shortest I…H distances weaker than thosewithin the layers discussed before. A detailed description of thestructural features of this compound is complicated by thepseudo-symmetry effects introducing parameter correlations ofatomic coordinates and displacement parameters.

The structure of 1,10-diammoniodecane bis-triiodide iodinedihydrate (2)

The structure of the complex salt 1,10-diammoniodecane-diiodide/diiodine/water (1 : 3 : 2) may also be divided into theiodine–iodide and a hydrogen bonded 1,10-diammoniodecane–water sub-structure. This is not only useful for a betterunderstanding of this complex structure, there are also nosignificant interactions between them other than van der Waalsinteractions.

The 1,10-diammoniodecane is found to be in principle in anall-trans conformation, lying on a centre of symmetry. In detail,the flexibility of the a,v-diammonioalkane is expressed bytorsion angles of the (CH2)n chain. This semi-flexible dicationshows its most significant deviation from the above-mentionedall-trans conformation in the vicinity of the ammonium groups.The angle between the planes defined by the atoms N1–C1–C2–C3 and C2–C3–C4–C5 is found to be 7.5(7)u while the atoms

Table 1 Bond lengths (A), angles and torsion angles (u) for 1–3

Compound 1I3–I4 3.0229(17) I4–I5 2.8822(19)I6–I7 2.8593(17) I7–I8 3.0485(18)I3–I8i 4.1630(18) I5–I6 4.1319(19)C–N distances 1.434(13)–

1.492(15)C–C distances 1.489(10)–

1.521(10)C–C–C–C and

C–C–C–Ntorsion angles

169.2(11)–179.9(14)

I3–I4–I5 176.79(4) I6–I7–I8 178.82(5)I4–I5–I6 167.27(4) I5–I6–I7 173.78(5)

Compound 2I2–I3 2.8888(11) I1–I2 2.9686(10)I4–I4ii 2.7319(14) I3–I4 3.5098(11)I2–I1iii 4.1304 (11) I3–I4iv 4.2295 (13)N1–C1 1.487(9) C1–C2 1.510(10)C2–C3 1.517(10) C3–C4 1.509(10)C4–C5 1.511(10) C5–C5v 1.515(14)I1–I2–I3 176.01(3) I2–I3–I4 121.60(3)N1–C1–C2 111.6(5) C1–C2–C3 112.4(5)C2–C3–C4 112.8(5)C3–C4–C5 114.3(5) C4–C5–C5v 114.7(7)N1–C1–C2–C3 174.3(6) C1–C2–C3–C4 176.4(6)C2–C3–C4–C5 177.5(7) C3–C4–C5–C5v 174.5(8)I2–I3–I4–I4ii 165.6(3)

Compound 3N1–C1 1.4660(18) C1–C2 1.5148(18)C2–C3 1.5221(17) C3–C4 1.5198(18)C4–C5 1.5215(16) C5–C5vi 1.515(3)N1–C1–C2 115.57(13) C1–C2–C3 114.23(12)C2–C3–C4 113.49(11) C3–C4–C5 114.26(11)C4–C5–C5vi 113.92(14)N1–C1–C2–C3 178.10(13) C1–C2–C3–C4 2179.47(12)C2–C3–C4–C5 178.90(12) C3–C4–C5–C5vi 2179.73(14)

Symmetry codes: i ~ 1 1 x, y, 21 1 z; ii ~ 2x, 2y, 1 2 z; iii ~0.5 1 x, 0.5 2 y, 0.5 1 z; iv ~ x 1 1, y, z; v ~ 1 2 x, 2y, 2z;vi ~ 1 2 x, 1 2 y, 2 2 z.

Table 2 Hydrogen bonding data for 1–3

d(D–H)/A d(H…A)/A d(D…A)/A /(DHA)/u

Compound 1N11–H111…I1 0.89 2.79 3.660(12) 166.7N11–H112…I2 0.89 2.64 3.520(10) 170.5N12–H121…I1i 0.89 2.85 3.573(9) 139.2N12ii–H122ii…I2iii 0.89 2.70 3.513(9) 152.6N21–H212…I1 0.89 2.72 3.584(9) 164.0N21–H213…I2iii 0.89 2.81 3.668(11) 161.0N22–H222…I1iv 0.89 2.68 3.556(10) 168.8N22–H223…I2iv 0.89 2.87 3.584(10) 138.4N22–H221…I8 0.89 2.85 3.726(11) 167.8

Compound 2O1–H1O…I3v 0.80(7) 3.10(6) 3.779(6) 144(9)O1–H2O…I1vi 0.80(5) 3.17(7) 3.850(6) 144(10)N1–H11…O1 0.89(2) 2.06(2) 2.913(9) 162(3)N1–H11…O1vii 0.89(2) 2.04(2) 2.926(8) 175(3)

Compound 3N1–H12…N1viii 0.937(14) 2.257(14) 3.1893(14) 172.9(16)

Symmetry codes: i ~ x, y, 1 1 z; ii ~ x, y, 21 1 z; iii ~ 21 1 x,y, z; iv ~ 21 1 x, y, 1 1 z; v ~ x 2 1, y, z; vi ~ 0.5 1 x, 0.5 2

y, 0.5 2 z; vii ~ x 1 1, y, z; viii ~ 0.5 1 x, 1.5 2 y, 2 2 z.

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C1 to C5 are lying nearly exactly within a plane (Fig. 3). Allother bond lengths and bond angles are in the expected range(Table 1). Hydrogen bonding of reasonable strength onlyoccurs between the 1,10-diammoniodecane cations, that act ashydrogen bonding donors and the water molecules that acts asacceptors (Fig. 3). The shortest N–H…I distances are 3.10(6) Awhile similar values occur for hydrogen atoms of the methylenegroup of the diamonioalkane. According to values known astypical H…I distances, N–H…I hydrogen bonds are notpresent in this structure.17

The cations and the water molecules form ribbons along the[100] direction (Fig. 3). Ring motifs are formed by twodiammonioalkane cations each acting twice as hydrogenbond donor – as for each ring four H-donors are counted –and two water molecules only acting as acceptors resulting inthe notation R2

4(30). The hydrogen bonded chain motif defined

by the ammonium groups and water molecules at the edges ofthe ribbon can be classified according this notation as C4. Itseems to be worth mentioning that the ring motif R2

4(30) foundin the structure of 2 (Fig. 3) is the same as the one present in 1(Fig. 1), replacing the water molecules by iodide anions as thehydrogen bond acceptors.

For the iodine–iodide sub-structure there are differentdescriptions that can be used depending on the criterionwhich is used for the discussion of the I…I interactions. If weonly mention the medium-strong I…I interactions, those whichare indicated by I…I distances between ca. 2.7 and 3.8 A, wehave to describe the motif that forms this structure as Z-shaped

Fig. 1 (Upper part) One hydrogen bonded layer of dadH2I (iodide atoms coloured light violet) in relation to the polymeric I32 species (iodide atoms

coloured dark violet) arranged in the channels built by neighbouring layers in the structure of 1; click image or here to access a 3D representation.(Lower part) Details of hydrogen bonding (atom radii are drawn at arbitrary size).

Fig. 2 View along the I32 chains accommodated by the hydrogen

bonded wavy layers in 1 with view direction [2 0 –5].

Fig. 3 Hydrogen bonded ribbons of dadH2 cations and watermolecules stacked along the a direction in 2 (displacement ellipsoidsare drawn at the 50% probability level; the radii of the hydrogen atomsare chosen to be arbitrary).

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entities of two I32 ions [2.888(1) and 2.969(1) A] attached to

one central I2 molecule [I–I: 2.732(1) A] interconnected bymedium-strong bonding interactions (Fig. 4). The polyiodidesub-system may be described therefore as the packing ofoctaiodide anions. This I8

22 motif has been found in a varietyof compounds, as in 2, lying on a centre of symmetry to forman outstretched Z-shaped entity (Fig. 4).18,19

An interpretation of the I…I distances as bonding interac-tions in the vicinity of 4 A for a linear configuration have beenreported previously13 with the reservation that this discussion isstrongly dependent on the structural features. A decision ifthese I…I distances correspond to bonding interactions only onthe basis of the distances is very delicate as these values are onlya few picometres shorter than the corresponding van der Waalsdistances.20 If these distances are accepted to be significantconcerning a bonding interaction, the anionic sub-structure isbest described as a three-dimensional framework built by I2

molecules and I32 anions showing the habit of a herring-bone

motif with channels in the [100] direction (Fig. 5) accommo-dating the polymeric template discussed before.

The principles of crystal engineering of a polyiodideframework discussed here may be related to systems wheremolecular cryptand–metal complexes,14 which are used astemplates for the synthesis of corresponding iodine-richpolyiodide frameworks. But in contrast to these investigationsthe use of the stick-shaped, conformationally flexible, hydrogen

bonded 1,10-diammonioalkane as a template for the generationof polyiodides it is most probable that aggregates are formed,which fit in with the length of these bifunctional cations.

The structure of 1,10-diaminodecane (3)

This ‘soft as butter’ material crystallizes in the centrosymmetricspace group Pbca. The molecules forming the structure lie oncentres of symmetry. Therefore, there is one half of themolecule in the asymmetric unit as Z ~ 4. The diaminodecanemolecules show nearly ideal all-trans conformation (Table 1).All C–C and C–N distances found are as expected for aliphaticdiamines. According to typical N–H…N hydrogen bonds,donor–acceptor distances between 2.7 and 3.2 A are com-mon,21 therefore the hydrogen bonds between amino groups ofneighbouring molecules in 3 can be classified as weak. Eachamino group accepts and donates one weak hydrogen bond(Table 2), while the second hydrogen atom is not involved inany hydrogen bonding (Fig. 6). This structural feature was alsofound for the homologous, isostructural a,v-diaminoalkanes[H2N–(CH2)n–NH2, n~ 4–8]22 and for an aromatic amine.23 Itis further known for hydrogen bonded amino groups that theirconformation can be fixed by two hydrogen bonds. Each aminogroup donates and accepts one hydrogen bond while thesecond hydrogen atom is oriented such that no hydrogenbonding can occur. Such a situation has been discussed in detailfor an analogous amine–water system.24

Cutting through one column of parallel diaminodecanemolecules and investigating the stacking within this layer(viewing along [21 10 0]) the pseudo-hexagonal stacking isobvious (Fig. 7). The result of the herring-bone arrangement ofthe molecules is that the b-CH2 groups fit into the gaps formedby the CH2–N…H grouping (Fig. 6).

The ideal all-trans conformation in combination with weakhydrogen bonds makes it plausible that this structure is acompromise between hydrogen bonding of the amino groupsand the hydrophobic interactions of the aliphatic chains(Fig. 7). This is plausible since for the above-mentioned a,v-diaminoalkanes it has been shown that the structures of thediscussed diamines are dominated by van der Waals interac-tions.20

Fig. 4 Z-shaped centrosymmetrical [I3…I2

…I3]22 unit building thepolyiodide subsystem of 2 (displacement ellipsoids are drawn at the50% probability level).

Fig. 5 Packing of 2 along [100]. Dotted lines mark I…I distances in the vicinity of the van der Waals region.

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The softness of this material is also in good agreement withthe weak intermolecular interactions between the moleculesderived from the crystal structure.

Conclusions

It has been shown that hydrogen bonded 1,10-diammonio-decane is a potent template for the formation of tailoredpolyiodides. For compound 1 the dications and iodide anionsform the hydrogen bonded framework with channels accom-modating I3

2 anions interconnected via extremely weak I…Iinteractions. The hydrogen bonded dadH2/water template in 2forms an iodine-rich polyiodide framework.

Stick-shaped a,v-diammonioalkanes in general seem to beable to act as hydrogen bonded polymeric templates for thesynthesis of new polyiodides that fit with the moleculardimensions of the used cations. The semi-flexibility of thea,v-diammonioalkane is found in a conformation that fits bestthe needs of hydrogen bonding, while the pure amine 3 has aconformation that compromises the most stable moleculargeometry with an additional stabilisation by weak hydrogenbonding. A detailed view on the physical properties and thetemperature dependent phase relations of the compounds 1 and2 is in progress.

Experimental

Synthesis

1,10-Diammoniodecane reacts with an iodine-saturated solu-tion of concentrated hydroiodic acid and a stoichiometricamount of iodine giving a dark solution. Crystals of 1 and 2grow within several weeks at ambient temperature. Themajority of crystals which grow under these conditions areneedle-shaped, black crystals of 2. Besides the bulk phase some

small orange-brown platelets of 1 grow. Crystals of both phaseshave been harvested from the mother liquor and sealed with aninert oil (RS2000, ABCR-Chemicals).

Crystals of 3 are obtained by sublimation. The material issoft as butter and tends to form multiple twins. To obtaincrystals of suitable quality for the diffraction study we had tocut pieces from a bigger crystal, and investigated them with apolarisation microscope.

Crystallographic study

Bis(1,10-diammoniodecane) diiodide bis-triiodide (1). A pla-telet with the dimensions 0.3 6 0.2 6 0.03 mm was mountedon a Stoe four-circle diffractometer equipped with a CCDdetector. For the data collection 16 v-runs (scan width: 0.75u),with different x, w and 2h settings, a detector-to-crystal distanceof 60 mm and an exposure time of 22 s, were measured.25

Standard integration procedures using variable integrationmasks and an integration width of 0.75u yielded a datacompleteness of 99.3%.26 A numerical absorption correctionusing indexed faces of the measured crystal (Tmin/Tmax: 0.212/0.832)27 has been undertaken. The unit cell constants have beenrefined from 5000 quasi-centred reflections extracted from thewhole dataset. Structure solution by direct methods28 in thepolar space group P21 and secondary structure solution bydifference Fourier synthesis succeeded.29 After refinement of allnon-hydrogen atoms using anisotropic displacement para-meters, all H atom positions can be obtained from successivedifference Fourier synthesis. To achieve convergence of therefinement of this pseudo-symmetric structure the H atomsattached to C atoms were included using a riding model and theanisotropic displacement parameters have been restrainedusing the ISOR option of the SHELX system. The H atomsof the ammonium group were refined using a riding model withthe NH3 group being allowed to rotate by the C–C bond. For asummary of the crystallographic data for 1, see Table 3.

Pseudo-symmetry effects are introduced in the structuredetermination by the fact that the hydrogen bonded layers canbe described – including most of the hydrogen atom positions –in the centrosymmetric space group P21/a with the same cellsetting. As it is dubious at first sight to refine a structure in thelower symmetric space group P21 when a higher symmetrypossibility exists for most of the atom sites,30 we checked thisfact by comparative refinements.

Starting with only one dadH2 dication and two iodide anionsin the asymmetric unit, using the higher symmetric arrange-ment, representing the exact centrosymmetrical host frame-work refined well. But the difference electron density calculatedfrom Fourier synthesis for the remaining I3

2 located in thechannels of the host system documents an artificial disorder.The additional centres of symmetry are not consistent with anordered distribution of the I3

2 anions. Finally, it should be

Fig. 6 Arrangement of the molecules in the crystal structure of 3 in the ac plane to form a layered structure with the building ring motifs classifiedaccording Etter’s rules as R4

4(30). Click image or here to access a 3D representation.

Fig. 7 Stacking of the 1,10-diaminodecane molecules in the crystalstructure of 3 with view direction [21 10 0].

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noted that the serious violations of systematic absences (themedium I/s for all 655 measured h0l reflections is 4.6, and 155of them are larger than 4s) for the additional a glide plane areplausible and are caused by heavy I3

2 ‘solvent’ anions breakingthe symmetry.

1,10-Diammoniodecane bis-triiodide iodine dihydrate (2).After inspection of some crystals of the title compound usingan optical microscope a platelet with the dimensions 0.4 60.2 6 0.03 mm, was sealed in a thin walled glass capillary andmounted on a Stoe one circle diffractometer IPDS I (ImagePlate Diffraction System).31 Data collection was achieved at acrystal detector distance of 70 mm and a w range of 0–222u for159 exposures with an exposure time of 4 min for each. Datareduction included a Lorentz- and a polarisation-correction aswell as a numerical absorption correction using indexed facesof the measured crystal (Tmin/Tmax: 0.0810/0.7767).27 The unitcell constants were refined from 5000 quasi-centred reflectionsextracted from the whole dataset. Structure solution by directmethods28 in the centrosymmetric space group P21/n andsecondary structure solution by difference Fourier synthesissucceeded.29 After refinement of all non-hydrogen atoms usinganisotropic displacement parameters, all H atom positionswere obtained from successive difference Fourier synthesis. Toachieve convergence in the final stages of the refinement the Hatoms attached to C atoms were included using a riding model.The H atoms of the water molecule and the ammonium groupwere refined with their O–H and N–H distances restrained toplausible values. One common Uiso value has been refined forthe H atoms of each CH2 and NH3 group and the watermolecule. See Table 3 for a summary of the crystallographicdata for 2.

1,10-Diaminodecane (3). An isometric crystal with thedimensions 0.4 6 0.3 6 0.2 mm was mounted on a Stoefour-circle diffractometer equipped with a CCD detector. Forthe data collection, 30 v-runs (scan width: 0.5u) with differentx, w and 2h settings, a detector-to-crystal distance of 80 mm andan exposure time of 25 s were measured. Standard integration

procedures using variable integration masks and an integrationwidth of 0.9u yielded a data completeness of 99.7%. The unitcell constants were refined from 1200 quasi-centred reflectionsextracted from the whole dataset. The structure solution bydirect methods28 in the centrosymmetric space group Pbca anda secondary structure solution by difference Fourier synthesissucceeded.29 After refinement of all non-hydrogen atoms usinganisotropic displacement parameters, all H atom positionswere obtained from successive difference Fourier synthesis. Toachieve convergence of the refinement the H atoms attached toC atoms were included using a riding model (AFIX 23). The Hatoms of the amino groups were refined free with individualUiso values and the N–H distances softly restained to onecommon value. See Table 3 for a summary of the crystal-lographic data for 3.

Vibrational spectroscopy

C10H30I8N2O2 (2). Infrared spectroscopy. The infraredspectra were recorded on a Bio-Rad FTS-3500 FT-IR-spectrometer with a resolution of 8 cm21. A single crystal ofdimensions 0.1 6 0.2 6 1 mm was squeezed on the ZnSe plateof the single reflection ATR (attenuated total reflectance)accessory unit (MIRacle, PIKE-Technologies, Madison).

Scan range 4000–650 cm21: 3400(br), 3080(br), 2920, 2850,2391, 1876(br), 1618, 1564, 1466, 1433, 1386, 1315, 1127, 1043,967, 914, 874, 786, 736, 721.Raman spectroscopy. A single crystal sample was used, FT-

Raman Accessory (BioRad, Krefeld, Germany) attached toIR-Spectrometer FTS3500, 1283 mW, YAG-laser, liquidnitrogen cooled germanium detector, range 20–3400 cm21:101, 150, 204, 1300, 1465, 1556, 2900.

In measuring the Raman spectrum at a laser power thatdestroys the single crystal, the Raman effect at 150 cm21

increases relative to that found at 101 cm21. This effect hasbeen observed earlier and is related to so-called ‘hot bands’which should occur as a consequence of exited electronicstates.32

Table 3 Summary of crystallographic data for 1–3a

Parameter 1 2 3

Formula C20H52I8N4 C10H30I8N2O2 C10H24N2

M 1363.86 1225.56 172.31Crystal system Monoclinic Monoclinic OrthorhombicSpace group P21 P21/n Pbcaa/A 10.0811(7) 4.9700(10) 5.6451(10)b/A 12.0991(9) 31.580(6) 28.124(4)c/A 16.3805(14) 9.240(2) 7.1248(11)b/u 95.223(7) 91.10(3) 90V/A3 1989.7(3) 1450.0(5) 1131.1(3)Z 2 2 4Dc/g cm23 2.276 2.807 1.012m(MoKa)/cm21 62.5 85.63 0.06Reflections measured, Rint 17 134, 0.0471 8860, 0.0491 18 636, 0.0612hmax/u 50.1 50.1 50.0Index ranges 212 ¡ h ¡ 12 25 ¡ h ¡ 5 26 ¡ h ¡ 6

214 ¡ k ¡ 14 237 ¡ k ¡ 37 233 ¡ k ¡ 33219 ¡ l ¡ 19 210 ¡ l ¡ 10 28 ¡ l ¡ 8

Unique reflections 6939 2369 1000Observed reflections [F2

w 2s(F2)] 5323 2053 952Refinement method Full-matrix, least squares on F2 Full-matrix, least squares on F2 Full-matrix, least squares on F2

Parameters refined 297 122 65wR2 0.0966 0.0794 0.0829R1

b 0.0473 0.0363 0.0520GoF 1.039 1.089 1.006s/sumax 0.005 0.01 0.001Drmin/max

c/e A23 20.75/1.50 20.649/0.911 20.10/0.14aClick here for full crystallographic data (CCDC 184191–184193). bFor 1: w ~ 1/[s2(Fo

2) 1 (0.03P)2 1 3P] where P ~ (Fo2 1 2Fc

2)/3; for 2:w ~ 1/[s2(Fo

2) 1 (0.012P)2 1 9.2357P] where P ~ (Fo2 1 2Fc

2)/3; for 3: w ~ 1/[s2(Fo2) 1 0.55P] where P ~ (Fo

2 1 2Fc2)/3. cFor 1:

Drmax 1.11 A apart from I4.

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C10H24N2 (3). IR spectroscopy. BioRAD, FTS3500, ATR-Accessory, 4000–400 cm21: 3362, 3330, 3252, 3165, 2918, 2849,1648, 1605, 1581, 1470, 1462, 1391, 1362, 1320, 1198, 1093,1057, 1007, 981, 922, 897, 884, 818, 778, 733, 720.Raman spectroscopy. Single crystal sample, FT-Raman

Accessory (BioRad, Krefeld, Germany) attached to IR-Spectrometer FTS3500, 480 mW, YAG-laser, liquid nitrogencooled germanium detector, resolution 8 cm21, range 20–3400 cm21: 127, 198, 473, 1058, 1118, 1292, 1414, 1442, 1608,2716, 2846, 2881, 3164, 3238, 3329.

In particular, Raman spectroscopy, as stated before,10 canan be used to determine the type of polyiodide fragmentspresent in a newly synthesized material by the investigation ofthe characteristic bands in the far-IR region.

Acknowledgements

We thank E. Hammes for the IR and Raman spectralmeasurements and Dr W. Poll for useful discussions andproof reading of the manuscript.

Notes and references

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3 G. Ning, L. Yong-Hua, Z. Guang-Fu and X. Shi-Quan, ActaCrystallogr., Sect. C, 1992, 48, 650; R. J. Francis, P. S.Halasyamani and D. O’Hare, Angew. Chem., Int. Ed., 1998,110, 2336; S. Phan Thanh, J. Renaudin and V. Maisonneuve, SolidState Sci., 2000, 2, 143.

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17 For example: G. J. Reiß, K. Hegetschweiler and J. Sander, ActaCrystallogr., Sect. C, 1999, 55, 123.

18 P. K. Hon, C. V. Mak and J. Trotter, Inorg. Chem., 1979, 18, 2916and refs. cited therein.

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20 A. Bondi, J. Phys. Chem., 1964, 68, 441; N. Alcock, Adv. Inorg.Chem. Radiochem., 1972, 15, 1.

21 An enquiry was made to the Cambridge Crystallographic DataFile for intermolecular N–H…N interactions (donor–acceptordistance: 2.7–3.2 A) that yielded more than 3000 hits.

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23 P. J. Cox, Acta Crystallogr., Sect. E, 2001, 57, o1203.24 S. Janeda and D. Mootz, Z. Naturforsch., Sect. B, 1999, 54, 103.25 Kuma Diffraction (2000a). CrysAlis 1.166, CCD data collection

user interface, Kuma Diffraction Instruments, Wroclaw, Poland.26 Kuma Diffraction (2000b). CrysAlis RED 1.166, CCD data

reduction user interface, Kuma Diffraction Instruments, Wroclaw,Poland.

27 Stoe & Cie, X-Red, Ver. 1.12, Program for Data Reduction,Darmstadt, Germany, 1998.

28 G. M. Sheldrick, SHELXS-97, Program for the Solution ofCrystal Structures, University of Gottingen, Germany, 1997.

29 G. M. Sheldrick, SHELXL-97, Program for the Refinement ofCrystal Structures, University of Gottingen, Germany, 1997.

30 R. E. Marsh, M. Kapon, S. Hu and F. H. Herbstein, ActaCrystallogr., Sect. B, 2002, 58, 62.

31 Stoe & Cie, IPDS-Data Collection and Reduction Software, Ver.2.87, Darmstadt, Germany, 1998.

32 P. H. Svensson and L. Kloo, J. Chem Soc., Dalton Trans., 2000,2449.

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