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Структура, влияние, синтез водородной связи полимерных материалов.

Структура управления и вияние водородной связи полимерных материалов. Синтез, координации новых переходных металлов с разной композицией.

The Structure Directing Effect of Hydrogen Bonding in the Novel Polymeric Thioantimonate Mn2(H2N(CH2)2NH2)2Sb2S5. Michael Schura and Wolfgang Benschb a Fritz Haber Institut der Max Plank Gesellschaft, Faradayweg 4-6, D-14195 Berlin b Institut f¨ur Anorganische Chemie, Christian-Albrechts-Universit¨at Kiel, Olshausenstrasse 40, D-24098 Kiel Reprint requests to Prof. Dr. Wolfgang Bensch. Z. Naturforsch. 5 7 b, 1–7 (2002); received November 5, 2001 Thioantimonates, Solvothermal Synthesis, Coordination Polymer A new transition metal thioantimonate(III) with composition Mn2(H2N(CH2)2NH2)Sb2S5 has been synthesised under solvothermal conditions.

Two trigonal SbSb3 pyramids and two octahedrally coordinated Mn atoms are interconnected to form Mn2Sb2S4 heterocubanes as secondary building units (SBU’s). The SBU’s are covalently linked into linear infinite onedimensional rods. Long Sb-S bonds connect the rods to form layers. The two N atoms of the ethylenediamine molecule (en) are chelating one Mn(II) ion. The amino hydrogen atoms of the en ligand are engaged in hydrogen bonding which is responsible for the different structure pattern of the title compound compared to a previously reported series of Mn-amino-thioantimonates(III) with analogous stoichiometry built up from different amino ligands.

Introduction. Syntheses under solvothermal conditions employed for the preparation of novel solids have seen a dramatic evolution in the past few years. The low temperature regime and the dedicated use of suitable solvents is thought to retain complex building units and facilitate their controlled linkage. A wide variety of inorganic materials was processed accordingly and the majority of them in the presence of organic amines to provide space filling or structure directing cations for the assessment of new framework structures. In practice, however, the result of a new synthesis is barely predictable and obviously strongly influenced by a multitude of reaction parameters. A very prominent one, which is often discussed, is the structure directing influence of the organic counterpart. Among the various classes of solids that were manufactured according to the aforementioned ideas the main group chalcogenidometallates such as thiogermanates, -stannates, -indates and -antimonates have attracted special attention. This is due to the semiconducting properties of their binary compounds which is retained in the novel frameworks and will hopefully produce useful and interesting combinations in the resulting materials. Accordingly, a number of new compounds were successfully synthesised often with the aid of large alkylammonium ions. We have focused our research onto thioantimonates(III) with their versatile SbSx units which readily form polymeric anions displaying an intriguing complex structural chemistry with networks of all dimensionalities [19 — 25]. The large structural diversity is due to the variable coordination geometry of Sb(III) as a result of both the stereochemically active lone pair and the tendency of Sb (III) to extend its  oordination number beyond three to form ÿ-SbS4 trigonal bipyramids or ÿ-SbS5 octahedra. In addition, the resulting thioantimonate (III) frameworks are strongly affected by the pronounced structure directing effects exerted by the size, shape and charge of the organic countercation. However, up to now only coarse rules are at hand to describe the interplay between the properties of the so-called template and the structural features of the final framework.

The most prominent
effect exerted onto the final product is called the size effect. With increasing size of the charge compensating cation more probably lower dimensionalities of the frameworks result. In addition, we have

identified a distinct structure directing effect within a number of ‘templated’ thioantimonates through hydrogen bonding from the amino groups of the amines used. However, it has emerged that a strong tendency of the thioantimonates prevails
to form one-dimensional or two-dimensional polymers in contrast to the desired three-dimensional ones. In order to extend the framework forming capabilities of thioantimonates(III) and, in addition, to tune the properties of the resulting phases, we have introduced transition metals (M) to combine the MSy polyhedra with the SbSx building blocks.

A series of polymeric manganese thioantimonates of the general formula Mn2(L)Sb2S5 with L = two monodentate amines as methyl- (MA), ethyl- (EA) or propylamine (PA) or a bidentate one like diaminopropane (DAP), N-methylaminopropane (MDAP) were synthesised and characterised. In contrast to all other related thioantimonate frameworks these are charge neutral. The structures of the compounds obtained so far are constituted of topologically identical two-dimensional porous Mn2Sb2S5 frameworks with the alkylamines ligated to half of the Mn atoms providing both space filling of the pores and separation of the sheets. The MnSbSframework is flexible enough to fulfil the steric requirements of the amines. To further elucidate the structure directing effects of the amines we have used ethylenediamine (en) as the smallest possible chelating ligand to study its effect onto product formation. In this communication we report on the synthesis and crystal structure of the new compound Mn2 (en)Sb2S5. The structure of the title compound is compared with that of compounds Mn2(L)Sb2S5 with an analogous composition but a significantly different crystal structure.

Table 1. Technical details of data acquisition and selected refinement results for Mn2(NH2CH2CH2NH2)Sb2S5.
a [A˚ ] 5.6496(10)
b [A˚ ] 10.3720(18)
c [˚A] 11.175(2) ˚A
ÿ [ÿ] 76.21(2)
þ [ÿ] 84.30(2)
ý [ÿ] 75.40(2)
V [˚A3] 614.9(2)
Z 4
ü [mmþ1] 7.158
MG [g/mol] 573.78
Space group P¯1
Density (calc) [g/cm3] 3.099
2û-Range 3ÿ ÿ 2û ÿ 55ÿ
Data collected 3256
Unique data 2836
Data used (Fo > 4 .0 ú(Fo)) 2338
Min./max. transmission 0.56757 / 0.75908
Weighting schemea y: a = 0.0664, b = 0.5654
ùø [e/˚A3] 1.88 / –1.86 e/˚A3
R1 Fo > 4ú(Fo) 0.0339
wR2 (Fo > 4ú(Fo) 0.0901
wR2 all Refln. 0.0968
Goodness of fit (all R.) 1.078
Extinction x: 0.0021(5) b
a y = 1/[ú
2(Fo
2) + (aP)2 + bP]; P = (Max(Fo
2, 0) + 2 þ
Fc
2) / 3; b F* = kFc þ [1 + 0.001 þ x þ Fc
2
þ ÷
3 / sin(2ö)]0:25;
k = scale factor.

emental Mn, Sb and S (ratio: 1:1:2.5 mmol) were reacted for 5 d in 10 ml of an aqueous solution (50 Vol%) of ethylenediamine at 130 ÿC. The synthesis was carried out in stainless autoclaves with teflon liners of 50 ml inner volume. After the reactions the samples were cooled to room temperature within 3 h and the solid products were filtered off and washed with ethanol. This procedure produced variable amounts (up to 50%) of the title compound besides Mn(en)3Sb4S7 as spherical aggregates composed of fine needles smaller than 0.3mmin length and 0.01mm in diameter.

Single crystals suitable for X-ray work were obtained from Sb2S3, Mn, and S as starting materials in a molar ratio 1:1:1 as dark red lath-like crystals with dimensions up to 1.0 þ 0.3 þ 0.1 mm3. The compound is stable on air for several months. An energy dispersive analysis of X-rays (EDAX) yields Mn : Sb : S = 1.01(1) : 1.0(1) : 2.48(2). It is noteworthy that Mn2(en)Sb2S5 is not formed when the slurry is stirred during reaction. This is in contrast to the other Mn2(L)Sb2S5 phases where these conditions have proved beneficial for product purity. This observation is another strong hint for the kinetic factors influencing the product speciation of this type of reaction.

Table 2. Atomic coordinates [þ 104] and isotropic displacement parameters Ueq [˚A2 þ 103] for Mn2(NH2CH2-CH2NH2)Sb2S5. Estimated standard deviations are given in parentheses. Ueq is defined as one third of the trace of the orthogonalised Uij tensor.

Atom x y z Ueq
Sb(1) 7301(1) 6184(1) 10701(1) 17(1)
Sb(2) 3608(1) 3922(1) 12851(1) 16(1)
Mn(1) 1512(2) 7993(1) 12075(1) 22(1)
Mn(2) 7197(2) 6095(1) 13991(1) 23(1)
S(1) 2219(2) 5797(1) 13925(1) 16(1)
S(2) 6881(2) 7915(1) 11931(1) 18(1)
S(3) 7884(2) 4305(1) 12623(1) 18(1)
S(4) 4087(2) 2198(1) 14714(1) 20(1)
S(5) 2984(2) 6668(2) 10426(1) 21(1)
N(1) 1336(9) 10199(5) 11103(4) 26(1)
N(2) 682(10) 9065(5) 13613(4) 25(1)
C(1) 1704(13) 10929(6) 12032(6) 31(1)
C(2) 48(12) 10557(6) 13143(6) 30(1)

Single crystal work Intensity data were collected using a STOE AED-4 four-circle diffractometer with graphite monochromated Mo-Kÿ radiation (÷ = 0.7107 ˚A). The lattice parameters were refined using 54re flections in the range 25ÿ ÿ 2û ÿ 50ÿ. Crystal stability was monitored with 4standar d reflections measured every 2 h. No significant decay could be observed. Lorentz, polarisation as well as an empirical absorption correction with psi scans were applied. The structure was solved with direct methods using the program SHELXS-86 [34] and refined (full matrix) with SHELXL-93 [35]. All hydrogen atoms were placed in idealised geometry and refined as riding atoms. Technical details of data acquisition and some selected refinement results are summarised in Table 1.Atomic coordinates are compiled in Table 2, interatomic distances and selected angles are given in Table 3. Thermal decomposition was investigated on a NETZSCH STA 449 device under an Ar flow (5 ml / min) with a heating rate of 3 K/min with sample masses of 10 mg.

Results. The primary building units of the crystal structure of Mn2(en)Sb2S5 are two trigonal SbSb3 pyramids and two octahedrally coordinated Mn atoms. The Mn2 atom is in a distorted octahedral environment of six sulfur atoms with Mn-S distances spreading from 2.475(2) to 2.915(2) ˚A (average Mn-S distance: 2.67 A˚ ) (Table 3). In contrast, Mn1 is surrounded by four S atoms and the two N atoms of Table 3. Selected interatomic distances [A˚ ] and angles [ÿ] for Mn2(NH2CH2CH2NH2)Sb2S5.

Estimated standard
deviations are given in parentheses.
Sb1-S5 2.398(1) Mn2-S4''' 2.475(2)
Sb1-S2 2.463(2) Mn2-S2 2.595(2)
Sb1-S3 2.518(2) Mn2-S3 2.608(2)
Sb1-S5'' 3.347(2) Mn2-S1''' 2.652(2)
Sb1-S5'''' 3.524(2) Mn2-S1'' 2.771(2)
Sb2-S42. 387(1) Mn2-S1 2.915(2)
Sb2-S1 2.449(1) Mn1-S1 2.662(2)
Sb2-S3 2.525(1) Mn1-S2' 2.660(2)
Sb2-S3' 3.185(2) Mn1-S2 3.003(2)
Sb2-S5 3.403(2) Mn1-S5 2.510(2)
Mn1-N1 2.268(5) Mn1-N2 2.213(5)
N1-C1 1.481(8) N2-C2 1.473(8)
C1-C2 1.513(9)
S(5)-Sb(1)-S(2) 93.59(5) S(2)'-Mn(1)-S(1) 91.56(5)
S(5)-Sb(1)-S(3) 102.75(5) S(4)'''-Mn(2)-S(1)'' 99.33(6)
S(2)-Sb(1)-S(3) 90.77(5) S(2)-Mn(2)-S(1)'' 90.54(5)
S(4)-Sb(2)-S(1) 93.72(5) S(3)-Mn(2)-S(1)'' 88.89(5)
S(4)-Sb(2)-S(3) 98.11(5) S(1)'''-Mn(2)-S(1)'' 86.41(5)
S(1)-Sb(2)-S(3) 90.16(5) S(4)'''-Mn(2)-S(2) 94.14(5)
N(2)-Mn(1)-N(1) 77.3(2) S(4)'''-Mn(2)-S(3) 171.78(6)
N(2)-Mn(1)-S(5) 172.9(2) S(2)-Mn(2)-S(3) 85.93(5)
N(1)-Mn(1)-S(5) 104.58(13) S(4)'''-Mn(2)-S(1)''' 86.95(5)
N(2)-Mn(1)-S(2)' 93.67(14) S(2)-Mn(2)-S(1)''' 176.89(5)
N(1)-Mn(1)-S(2)' 99.93(14) S(3)-Mn(2)-S(1)''' 93.41(5)
S(5)-Mn(1)-S(2)' 92.79(5) C(1)-N(1)-Mn(1) 107.7(3)
N(2)-Mn(1)-S(1) 82.16(13) C(2)-N(2)-Mn(1) 110.9(4)
N(1)-Mn(1)-S(1) 156.95(14) N(2)-C(2)-C(1) 109.2(5)
S(5)-Mn(1)-S(1) 94.65(5) N(1)-C(1)-C(2) 107.2(5)
Symmetry codes: ': x – 1, y, z; '': x + 1, y, z; ''': 1 – x, 1 – y, 3 – z;
'''': 1 – x, 1 – y, 2 – z.

Fig. 1. The heterocubane unit in Mn2(en)Sb2S5 together with atom labelling. The symmetry codes for the marked atoms are given in Table 3. The ellipsoids are drawn at the 50% probability level. Note: Broken lines represent the long Sb-S contacts. the en ligand with an N-Mn-N bite angle of 77.3ÿ. The environment of Mn2 features a remarkably long

Fig. 2. Interconnection of the heterocubane units in Mn2(en)- Sb2S5. Selected symmetry related atoms are labelled (codes: see Table 3). C atoms are omitted for clarity. Two H-S4contacts are shown. distance to the S2 atom of 3.003(2) ˚A resulting in a strongly distorted coordination (Table 3). The two crystallographically independent Sb atoms form trigonal pyramids with the three nearest sulfur atoms at distances of 2.387(2) — 2.525(2) ˚A (see Table 3). These are linked through S3 to form a dinuclear Sb2S5 4þ anion. Both Sb atoms have two next-nearest S atoms at 3.347(2) and 3.524(2) ˚A (Sb1) and 3.185(2) and 3.403(2) ˚A (Sb2) located in trans position to the short bonds resulting in a ÿ-octahedral environment with ÿ being the electron lone pair. The primary units are joined to form a heterocubane-like assembly depicted in Fig. 1. One of the long Sb-S contacts thereby forms one edge of the hetereocubane. This arrangement may be regarded as a secondary building unit (SBU). The SBU’s are joined via two Mn2-S1 bonds (Mn2'-S1 and Mn2-S1'') and two long Sb2-S3 contacts (Sb2-S3' and Sb2''-S3) and arranged with parallel aligned faces forming chains extending infinitely along [100] as displayed in Fig. 2. Pairs of these chains are linked again through Mn2-S1 bonds of heterocubanes with aligned edges (Mn2-S1''') and bridging S4''' atoms into double-strings. Interestingly, the S4''' atoms which are not part of the cubane units have no other bonds to theMn-Sb-S framework. The bridging angle Sb2-S4'''-Mn2''' amounts to 92.44(1)ÿ. Within the rods, chains of Mn2S6 octahedra linked by edge and corner sharing are formed. Interconnection of Sb(III) atoms via the longer Sb-S contacts yields an infinite double-chain-like thioantimonate(III) substructure (see Fig. 4). The linkage between the chains (Sb1-S5: 3.524 A˚ ) is weaker than within the chains. The en ligands are situated at the outer region of the rods thereby separating them parallel to [010]. A quasi-two-dimensional arrangement with layers in the (010) plane is achieved through the long Sb1-S5 contacts that join the Sb-S chains (Fig. 4). The sheets are separated by the en ligands and, only van-der-Waals contacts are found between them. The individual rods are charge neutral. The most striking feature of the arrangement of the en ligands is the location of the amino hydrogen atoms. Both amino hydrogen atoms of N2 point directly and in a nearly symmetrical manner towards the S4at oms linking the heterocubane framework. The HÿÿÿS distances of 2.562(5) and 2.582(5) ˚A and angles of 170.6(1)ÿ and 172.2(1)ÿ are indicative of strong hydrogen bonding. This arrangement is also depicted in Fig. 2. Upon heating in an inert atmosphere a single step decomposition with an onset temperature of approximately 280 ÿC is observed for the title compound. The mass loss of 8.2 % agrees fairly well with the calculated value for the total removal of the en ligands of 10.5%. It is assumed that part of the ligand decomposes to yield non-volatile coke. The resulting material forms a mixture of MnS (Alabandin) and an unidentified crystalline com.

Fig. 3. View of a section of the layer of interconnected heterocubanes found in Mn2(DAP)Sb2S5. The SþþþH contacts are represented as dotted lines. Note: C atoms are omitted for clarity. pound with nominal composition MnSb2S4. Compared with the other Mn2(L)Sb2S5 compounds the onset for the decomposition is at significantly higher temperatures for the title compound than for those with chelating ligands DAP (260 ÿC) and MDAP (275 ÿC) and, expectedly, far higher than for the compounds with monodentate amines MA or EA. The latter exhibits two not well resolved decomposition steps starting at temperatures below 200 ÿC.

Discussion. The title compound represents another example of a polymeric transition metal thioantimonate(III). Its structure exhibits similar primary and secondary building units as the formerly reported Mn2(L)Sb2S5 compounds [29, 30], however with a distinctly different connection scheme. The compounds reported earlier possess a distinct two-dimensional linkage and are therefore called ‘2Dcompounds’ in the following discussion, whereas the title compound exhibits primarily a one-dimensional arrangement. The 2D-compounds comprise similar heterocubanes as the title compound. A significantly elongated Mn-S bond in cis position to the two amino ligands is also found, however, with a different arrangement of one of the amino ligands. The heterocubanes are interconnected in a way that pores with the size of two by two cubanes are created with two amines being located within the pores (Fig. 3). One hydrogen atom of each of these amino groups has a short contact to a neighbouring sulfur atom. The distances are comparable to the one found in the title compound. For example for L = DAP the distance is 2.542 ˚A and indicates a stabilising contribution to the 2D-structures. It seems reasonable that the small N-Mn-N angle inMn2(en)Sb2S5 forced by the en ligand prevents an effective hydrogen bonding of the configuration observed in the 2D-compounds. As a result the framework of the title compound is obtained with two nearly equally strong hydrogen bonds instead ofone. The different topology of the Mn-Sb-S framework in the title compound compared to the 2DMn2(L)Sb2S5 compounds is obviously the result of the hydrogen bonding pattern. The very long Mn1-S2 distance also observed in the 2D-compounds isthus likely to be due to other than pure steric or electronic effects. Another issue of the differing structures is the linkage of the thioantimonate substructures shown in Fig. 4. Taking the secondary Sb-S bonds into account, single 1 1[Sb2S5] chains result for the 2D-compounds in contrast to the double 1 1[Sb2S5] chains of the title compound. The different connectivities of the thioantimonate framework of Mn2(en)Sb2S5 is also evident comparing the optical properties. The decrease of the optical band-gap with increasing connectivity within the thioantimonate(III) framework is a well known phenomenon. In contrast to

Fig. 4. The thioantimonate substructures in Mn2(en)Sb2S5 (top) and the 2D-Mn2 (L)Sb2S5 compounds. Note that each of the Sb-S chains in Mn2 (en)Sb2S5 belongs to an individual Mn-Sb-S framework. the dark red colour of the title compound the crystals of the 2D-compounds are bright yellow. The isolation of the title compound thus shows that hydrogen bonding plays a vital role in the structure forming process. It seems that the size of the structure directing amine is less important than in other compounds, which is in part due to the special structure of these Mn-Sb-S compounds allowing to adopt a variety of different amines. Apart from the structural considerations the observation of similar building units in Mn2(en)Sb2S5 and Mn2(L)Sb2S5 suggests that they are all formed via a similar reaction path. In addition, one may speculate that they have a common molecular Mn-Sb-S species as a precursor to the polymeric structures. The precursors are then joined according to the structure directing effect of hydrogen bonding exerted already in the early stages of product formation. In this context it seems noteworthy that primary building units may also be effectively stabilised by hydrogen bonding as we have shown with the use of less polar solvents preventing the further polymerisation of Sb2S4 2þ, which is stabilised by extensive hydrogen bonding from methylammonium [27]. The results of further systematic research on syntheses and structures may eventually help to identify the reaction pathways and the intermediate species of either antimony or manganese. Acknowledgements Financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (DFG) is gratefully acknowledged.

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