Copper(II)-diethylenetriamine complexes with monodentate N-donor ligands : crystal and molecular structure of diethylenetriamine 2-cyanoguanidine copper(II) nitrate

Polyhedron

Pergamon PI1 : SO277-5387(%)00338-5

Vol. 16, No. 5, pp. 8OS813, 1997 Copyright 0 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0277-5387/97 $17.00+0.00

Copper(II)-diethylenetriamine complexes with monodentate N-donor ligands : crystal and molecular structure of diethylenetriamine 2-cyanoguanidine copper(I1) nitrate Michael J. Begley, Peter Hubberstey* and Jo Stroud Department

of Chemistry, Nottingham

University, Nottingham

NG7 2RD, U.K.

(Received 18 June 1996 ; accepted 8 July 1996)

Abstract-Mixed ligand copper(I1) complexes, [Cu(dien)(cnge)X,*nH,O] (X = NO;, NO; or O.SSO:-), containing diethylenetriamine (dien) and cyanoguanidine (cnge), have been prepared and characterized. Similar complexes, [Cu(dien)(ImH)X,-nHzO] (X = Cl-, NO;, NO; or 0.5SO:-), containing diethylenetriamine (dien) and imidazole (ImH), were prepared for comparison. Under identical reaction conditions, the corresponding pyridine complexes could not be isolated, the copper(II)dien complexes, [Cu(dien)X, - nH,O] (X = Br-, Cl-, NO;, NO; or O.SSO:-) being formed. The structure of [Cu(dien)(cnge)(ONO,)J (5) has been determined by single-crystal X-ray diffraction methods. It comprises discrete molecular units based on a tetragonally elon ated octahedral copper(I1) coordination sphere with equatorially bound dien (average Cu---N = 2.004 x ) and cnge (Cu-- -N = 1.945 A) and axially bound nitrate (Cu-- -0 = 2.517, 2.567 A). Marked shifts (- 25 cm-‘) to higher frequency in the v,,(NCN) band of cnge on coordination to copper(I1) in 5 and related complexes are shown to be consistent with strongly bound cnge, as evidenced by short Cu-N distances and near linear CuNC bond angles. FAB-MS studies gave comparable patterns for all complexes, inferring structural types similar to that for [Cu(dien)(cnge)(ONO&]. Copyright 0 1996 Elsevier Science Ltd Keywords: copper(I1) ; diethylenetriamine

; 2-cyanoguanidine.

2-Cyanoguanidine (cnge) readily coordinates later transition metals [l-8], complexes with copper(I) [l], copper(I1) [2-6] and cadmium(I1) [7] having been structurally characterized. In the absence of multidentate ligands, copper(I1) normally binds two translocated cnge ligands [2,3] ; in the presence of bidentate chelating 2,2’-bipyridine (bipy), it coordinates two cislocated cnge ligands [4]. In the presence of tridentate chelating I-(2-aminoethyl)biguanide (aebg), copper(I1) binds a single cnge ligand [5]. In all cases, the cnge molecules occupy equatorial positions of the tetragonally elongated copper(I1) (8) coordination sphere ; the only example of axially located cnge occurs in the unique tetrakis(acetato) bridged dinuclear copper(I1) complex [6]. We now describe the coordination of cnge to copper(I1) in a complex containing the tridentate chelating ligand, dietbylene-

*Author

to whom correspondence

should be addressed.

triamine [bis(2aminoethyl)amine, 3-azapentane-1,5diamine, dien]. Although mixed ligand complexes of copper(I1) containing dien have been known for many years [9111, structural data are limited. Of those which have been structurally characterized, very few contain dien and a monodentate ligand [IO] ; the majority contain dien and a bidentate ligand [ 111. The latter adopt fivecoordinate distorted square pyramidal geometries, with dien located equatorially and the bidentate ligand occupying one equatorial and one axial position ; anions are not coordinated [I 11. The former adopt six-coordinate tetragonally elongated octahedral geometries, with both ligands located equatorially and anions weakly bound axially [lo]. Surprisingly, analogous pentamethyldiethylenetriamine (Me,dien) complexes all adopt five-coordinate square pyramidal geometries [ 12,131. Those with Me,dien and a bidentate ligand are structurally analogous to the corresponding dien complexes [ 121; those with Me,dien and a monodentate ligand bind a

805

806

M. J. Begley et al.

third ligand (either solvent or anion) in the axial position [13]. RESULTS AND DISCUSSION Mixed ligand copper(I1) complexes, containing dien and either imidazole (ImH), 2-cyanoguanidine (cnge) or pyridine (py), were targeted. Anions varied from bromide through chloride, nitrate and nitrite to sulfate. The general synthetic route comprised treatment of an aqueous solution of the copper(I1) salt with an aqueous solution containing dien and the appropriate monodentate N-donor ligand. Of the 15 possible mixed ligand products only seven formed ; they are listed in Table 1. Imidazole was the most effective monodentate ligand, forming complexes l-4 with all anions except bromide ; cnge formed complexes 5-7 with the oxoanions, but not the halides, and pyridine did not form any complexes. The products of the other eight systems were the simple copper(II)dien complexes (812), which were also produced in the absence of the monodentate ligand. Of the 12 products, only eight (1,2,4,5,7-10) could be satisfactorily characterized by analytical and spectroscopic methods ; the other four (3,6,11,12) were so deliquescent that quantitative analysis was not attempted. Vibrational spectroscopy was used, however, to confirm the presence of dien, monodentate ligand and anion, as appropriate. Analytical and spectroscopic data are collated in Table 1. LJV-

vis spectra of all products were similar, comprising a single broad band with A,,,,, close to 660 nm. They had magnetic moments close to 1.7 B.M., typical of mononuclear copper(I1) d9 systems. Fast atomic bombardment mass spectroscopy (FAB-MS) studies of all 12 products, plus Cu(Me,dien)(cnge)(N0,)2 (13), were undertaken. Although the parent ions were not observed, the fragmentation and combination patterns were consistent with the proposed product identities.

X-ray crystal structure of [Cu(dien)(cnge)(ONO,),]

(5) After recrystallization, [Cu(dien)(ImH)Cl, - 2Hz0] (1) [Cu(dien)(ImH)(NO,), * Hz01 (2) and [Cu (dien)(cnge)(NO,),] (5) gave good quality crystals. However, structural analysis was only pursued for 5, the structure of the imidazole (ImH) and l-ethylimidazole (EtImH) complexes, [Cu(dien)(L) (OClO,),] [L = ImH (14) or EtImH (15)] having been determined previously [lo]. The molecular structure of 5 is shown in Fig. 1; selected interatomic distances and angles are given in Table 2. It comprises discrete molecular units based on a tetragonally elongated octahedral copper(I1) coordination sphere, typical of Jahn-Teller distorted d9 [(dz2)* (dx2_y2)1] systems, with strongly bonded N-donor ligands in the equatorial sites and weakly bonded

Table 1. Analytical and spectroscopic data for copper-&en complexes Analytical data C

Complex Cu(dien)(ImH)Cl,

- 2H,O

Cu(dien)(ImH)(NO,),

*H,O

1 2

Cu(dien)(ImH)(NO& *nH,O* Cu(dien)(ImH)(SO,) *2H20

3 4

Cu(dien)(cnge)(NO,),

5

Cu(dien)(cnge)(NO,), *nH20b Cu(dien)(cnge)(SO,) *3H20

6 7

Cu(dien)Br,

8

Cu(dien)Cl,

9

Cu(dien)(NO,),

10

Cu(dien)(NO& -nH,O* Cu(dien)(SOJ *nH20b

11

12

H

N

IR spectroscopic data (cn-I)’ Cu

24.4 6.4 20.4 17.2 (24.6) (6.2) (20.5) (18.6) 22.0 4.8 26.5 16.8 (22.3) (5.1) (26.0) (16.9) 24.9 6.3 20.9 18.6 (25.4) (5.2) (21.2) (19.4) 19.1 4.8 34.0 16.6 (19.3) (4.6) (33.7) (17.0) 17.6 (18.0) 14.6 (14.7) 20.6 (20.2) 16.7 (16.6)

6.1 (5.8) 4.1 (4.0) 5.9 (5.5) 4.5 (4.5)

24.8 (24.5) 12.9 (12.9) 18.0 (17.7) 24.0 (24.1)

15.7 (15.9) 19.2 (19.5) 25.5 (26.8) 20.8 (21.9)

dien

ligand

2917s 1597m

1733m, 1024m

2920s

1734m, 1024m

1383s

2885s, 1597m, 1459m 2927s, 1597m

1729m, 1024m 1730s 1020s

1265s 1118s

2922s

2235s 2191s

1380s

2919s, -, 1445m 2929s, 16OOm

219ls, 2148s 224Os, 2189s

1269s 1112s

anion

2939s, 1576m, 147Om 2923s, 16lOm, 154lm 292Os, 1599m, 1458m

1385s

2925s,1594m, 148Om 2927s 1599m, 1460m

1260s 1115s

a IR data for the free ligands and anions. dien : 293Os, 1598m, 1458m err-’ ; ImH : 1735s 1025s cm-’ ; cnge : 2209s, 2165s cm-‘; vJ(N09) 1390 cm-‘, v~(NOJ 1244s, cm-‘, v,(SOJ 1105 cm-‘. bAnalytical data are not available for these complexes due to their deliquescent nature.

Copper(II)-diethylenetriamine

complexes

Fig. 1. Molecular structure of [Cu(dien)(cnge)(ONO,),].

Table 2. Interatomic distances (A) and angles (“) in [Cu(dien)(cnge)(ONO,),] Copper coordination sphere Cu(l)-N(1 1) 1.945(4) Cu(l)-N(21) 2.006(4) Cu(l)-N(24) 1.988(4) Cu(l)-N(27) 2.019(4) Cu(l)-O(ll) 2.567(3) Cu(l)-0(22) 2.517(3)

Cyanoguanidine N(ll)-C(ll) C(ll)-N(12) N(12)-C(12) C(12)-N(13) C(12)-N(14)

nitrates EtImH located located for the

1.146(5) 1.287(5) 1.345(5) 1.313(5) 1.309(5)

in the axial sites. The analogous ImH and complexes are very similar, with equatorially dien and imidazole molecules and axially perchlorate anions. Pertinent structural data copper(I1) coordination spheres of all three

N(ll)-Cu(l)-N(21) N(21)-Cu(l)-N(24) N(24)-Cu(l)-N(27) N( 1l)-&(l)-N(27) N( 1I)-Cu( l)-N(24) N(21)-Cu(l)-N(27) N(ll)-Cu(l)-O(l1) N(21)-Cu(l)-O(I 1) N(24)-Cu(l)-O(ll) N(27)-Cu( l)-O( 11) N( 1l)-Cu( 1)-0(22) N(21)-Cu(l)-O(22) N(24)---&(1)-0(22) N(27)-Cu(l)-O(22)

95.2(2) 84.3(2) 84.0(2) 96.6(2) 179.4(2) 165.5(2) 9 1.0(2) 97.2(2) 89.4(2) 91.2(2) 88.7(2) 89.8(2) 91.0(2) 81.9(2)

Cu(l)-O(ll)-N(1) Cu(l)-0(22)-N(2)

110.9(3) 127.6(3)

N(ll)-C(ll)-N(12) C(ll)-N(12)-C(12) N(12)-C(12)-N(13) N(12)-C(12)-N(14) N(13)-C(12)-N(14)

174.6(5) 119.2(4) 123.2(4) 117.6(4) 119.2(4)

Cu(l)-N(1

176.4(4)

I)-C(11)

complexes are compared in Table 3. The most significant difference lies in the copper to anion distances, those to perchlorate being somewhat longer than those to nitrate. It is also interesting to note that the Cu-N distances increase in the sequence, cnge (1.945

M. J. Begley et al.

808 Table

3.

Structural parameters [Cu(dien)(cnge)(ONO,),]

[distances (A) and angles (S), [Cu(dien)(ImH)(OClO,)J

5

14”

15”

1.988-2.019 (2.004)b 1.945 2.517, 2.567 81.9-97.2d 84.0, 84.3 95.2, 96.6

2.006-2.012 (2.008)’ 1.970 2.571, 2.763 80.6101.8d 84.1 96.3

2.009-2.016 (2.012)h 1.971 2.570, 2.686 80.695.8“ 83.2, 83.6 96.1, 96.9

Cu- - -N(dien) Cu- - -N(L)’ Cu- - -0 (anion) O___Cu___N N(dien)-Cu-N(dien) N(dien)-Cu-N(L)’

(“)I in the copper coordination spheres (14) and [Cu(dien)(EtImH)(OClO,),] (15)

of

“Reference [lo]. ‘Range (average). ‘L = cnge, ImH or EtImH. d Range.

ImH (1.970 A) N EtImH (1.971 A) < dien (1.988-2.019 A), owing to the change from sp through sp* to sp3hybridization. The cnge molecule bonds to the copper(I1) ion in an equatorial position. As for other examples of cnge coordinated to copper(I1) [2-6], its geometry (Table 2) does not differ significantly from that for free cnge [14]. Although effectively planar [maximum deviation from the least squares mean plane = 0.047 A, C(l2)], the cnge molecule is twisted out of the plane formed by the four ligating nitrogen atoms (dihedral angle = 36.1”). The latter is slightly distorted, the trans-located terminal dien nitrogens lying above the mean plane [N(21), 0.073 A; N(27), 0.072 A] and the pivotal dien nitrogen and cnge nitrile nitrogen lying below the mean plane [N(24), -0.079 A; N(ll), -0.066 A]. The copper atom lies 0.077 A below the mean plane, between the pivotal dien and cnge nitrogens [N( 1l)-Cu-N(24) 179.4(2)]. The nitrate anions are planar and subtend dihedral angles of 20.0 [N(l)O;] and 67.4” lN(2)0;] with the N4 plane. The monodentate coordination of the nitrate anions in 5 differs from that of the nitrate anions in [Cu (dien)(NO,)](NO,) (16) [15] and [Cu(dien)2](N03)2 (17) [16]. In 16, one nitrate acts as a bidentate bridging ligand and the other is non-coordinated, as are both nitrates in 17. The distorted trigonal bipyramidal copper(I1) coordination sphere in 16 is completed by a single tridentate chelating dien molecule [ 151.The copper(I1) in 17 is surrounded by two tridentate chelating dien ligands, its six-coordinate geometry, the relatively rare, compressed tetragonally distorted octahedron, the alternative Jahn-Teller distorted & [&_,,2)* (&)i] system, being dictated by the steric requirements of the dien ligand [16]. The differing strength of nitrate binding in 5 and 17 can be traced to the copper(I1) coordination geometry. Whereas the nitrate anions bind weakly in the axial positions of the tetragonally elongated octahedron in 5 (Cu. . .O = 2.52, 2.57 A), it is much more strongly coordinated in the bridging equatorial positions of the distorted trigonal bipyramid in 16 (Cu . . .O = 2.12, 2.29 A). Nitrate binding in 16 is enhanced by secondary interactions, giving A) <

a pseudo-bidentate chelating coordination for both copper-nitrate contacts (Cu. . .O = 2.58,2.89 A) and hence a pseudo-seven-fold coordination geometry. The molecules of 5 are held in place in the crystal predominantly by hydrogen bonding interactions between the cnge amino moieties and the nitrate anions. Hydrogen bond contacts also occur between terminal dien amino groups and the nitrate anions. These interactions are shown in Fig. 2 and structural details for all possible hydrogen bond contacts are collected in Table 4. A marked increase in the frequency of the doublet assigned to v,,(NCN) [ 171is observed on coordination of cnge in [Cu(dien)(cnge)(ONO,),J (Table 1). This change is typical of coordinated cnge, as shown by comparison with data for the five previously structurally characterized copper(II)-cnge complexes (Table 5). Only one complex, [(p-OAc),{Cu(cnge)},], does not exhibit such a change in v,,(NCN). Although the marked shifts in v,,(NCN) cannot be related to trends in the geometry of the ligating nitrile moiety of the cnge molecule, they do appear to be sensitive to the cnge coordination geometry and the strength of the Cu---N coordinate bond. Marked increases in v,,(NCN) are consistent with short Cu. . N distances and near linear Cu-N-C bond angles, presumed indicative of strongly bound cnge. Virtually no change in v,,(NCN) occurs for [(p-OAc),{Cu(cnge)},], which has the longest Cu-- -N distance and smallest Cu-N-C angle (Table 5). Thus despite the increasing database on copper(II)+ige complexes, v,,(NCN) can only be used as a crude indicator of the strength of cnge bonding. Although coordination of cnge in Cu(dien) (cnge)(SO,) .3H20 (7) results in an increase in v,,(NCN) similar to that observed in 5, a decrease in for v,,(NCN) is observed Cu(dien)(cnge) (NO,),*nH,O (6) (Table 1). Hence, similar coordination geometries may be inferred for 5 and 7, but not 6. As 6 is the first copper(II)+nge complex for which a decrease has been observed and we have not been able to obtain a pure crystalline sample, an assessment of its structural chemistry is not possible.

Copper(II)-diethylenetriamine

809

complexes

Fig. 2. Hydrogen bonding interactions between centrosymmetrically related [Cu(dien)(cnge)(ON02)~

Table 4. Hydrogen bonding interactions in [Cu(dien)(cnge)(ONO&] Interaction N-H..

.X

N(l3)-H(l31)...0(21) N(l3)-H(l32)...0(13) N(l4)-H(141)...0(12) N(l4)-H(l42). . O(21) N(21)-H(211) N(21)-H(212) .0(23) N(24)-H(241)” N(27)-H(271) . . . O(21) N(27)-H(272)” *H

Symmetry of X

N-H

(l-x, l-y, -z) (1 -x, 2-Y, -z) (1 -x, 2-Y, -z) (2-x, 1 -Y, -z)

0.85(7) 0.78(7) 0.91(7) 0.87(6) 0.88(6) 0.95(7) 0.79(4) 0.88(6) 0.78(6)

(x, Y>r) (1 -x,

1 -y,

-z)

(A)

X contacts c 2.49 A do not occur with these amino hydrogen atoms.

N-X

(A)

molecules.

(5) H...X

(A)

NHX (“)

3.109(5) 2.899(5) 3.037(S) 3.003(5)

2.36(7) 2.14(8) 2.13(7) 2.13(8)

147(6) 166(7) 174(6) 178(6)

2.996(6)

2.14(7)

150(6)

3.144(5)

2.35(6)

151(5)

810

M. J. Begley et al. Table 5. Molecular

geometries

and IR spectroscopic

data for structurally

characterized

copper-cnge

Geometrical data

complexes IR spectroscopic data

Cu-N(1)

N(l)<(l)

C(l)-N(2)

Cu-N(I)--c(l)

N(l)-C(l)-N(2)

(A)

(A)

(A)

(“)

(“)

v,, (NCN) (cm-‘)

1.945(4) 1.931 2.136 1.92

1.169 1.146(5) 1.159 1.146 1.16

1.305 1.287(5) 1.309 1.300 1.29

176.4(4) 151.0 135.9 168.8

175.1 174.6(5) 174.7 175.1 173.2

220912165 2235/2191 223212209 220912168 2240/2200

1.92 1.96

1.16 1.17

1.29 1.28

164.9 h

170.6 172.6

2250/2200 h

Mass spectrometric studies of copper(dien plexes

com-

Complex

Free cnge” [Cu(dien)(cnge)(ONO,)J*

[Cu(bipy)(cnge),(FBF,),l’ [Cu,(O,CMe),(cnge),ld ]Cu(cnge)AH@)zl(NOJz 2HrO ]Cu(cnge)A%(HA%I’ [Cu(cnge)(aebg)]SO,

*

*H&Y

a Reference [ 141. “This work. ’Reference [4]. dReference [6]. eReference [2]. ‘Reference [3]. 9 Reference [5]. ‘Not quoted.

FAB-MS studies of copper(II)dien complexes have been particularly valuable, the spectra following a consistent pattern. The fragmentation and combination patterns for Cu(dien)X, and Cu(dien)LX, (L = ImH or cnge ; X = Br, Cl, NO3 or NOz) complexes are summarized in Schemes 1 and 2, respectively. The ions (minimum m/z values) observed for individual complexes are collated in Table 6. In neither case is the parent ion observed. In the absence of a mondentate N-donor ligand (Scheme l), however, loss of X- gives the observed [Cd’(dien)X]+ cation, which either loses X to form [Cu’(dien)]+ or combines with [Cu”(dien)X,] or [Cu’X] moieties to form species

which consecutively lose up to two HX fragments. For complexes containing a monodentate N-donor ligand (Scheme 2) a similar behaviour pattern emerges, loss of X- giving [Cu”(dien)LX]+, which either loses L to form [Cu’(dien)X]+ or combines with [Cu”(dien)X,] or [Cu’X] moieties to form species which exhibit HX loss. The formation of [Cu’ (dien)X] +, which could also arise from Cu(dien)LX, via Cu(dien)X, by sequential loss of L and X-, leads to those ions observed in the spectra of Cu(dien)X, (Scheme 1). The spectra for the sulfates (Schemes 1 and 2 ; Table 6) are analogous to those for the complexes containing singly charged ions, the only significant difference involving the formation of the pivotal ions, addition of H+ giving [Cu”(dien)(SO,H)]+ (Scheme 1) and

Cu’*(dien)Xz -A [C&iien)X]+ _-Hx

[Cunz(dien)2Xz-HI+ -‘ix 1 [C&(dien)sX-2H]’

tc&ti@x*t/

J-x

[C&lien)]+

Icun*W”)2X31+ cl’‘% G

v

[CQCur(dien)X~+ -Hx

[CGCut(dien)X-HJ+

J’ cu%kn~X* [Cu”&u’(dien)2&1+

-ax 1 [Curt@“(dien)2Xs-HI]+ Scheme 1.

-mf [Cun$3&lien~Xz-2H]t

Copper(II)diethylenetriamine

complexes Q+%Ias0~So4)

Cs+W&Xa

Scheme 2.

[Cu”(dien)L(SO,H)]+ (Scheme 2), which behave as [Cu”(dien)X] + and [Cu”(dien)LX] +, HSO; being the singly charged X- anion. EXPERIMENTAL Elemental analysis, mass spectrometry, IR and UV-vis spectroscopy and magnetic measurements were used to characterize all products, except for the highly deliquescent nitrites and sulfates, which were studied using spectroscopic methods only ; pertinent data are collated in Table 1. Carbon, nitrogen and hydrogen analyses (microanalysis) and copper analyses (atomic absorption spectroscopy) and mass spectral data acquisition were carried out in the University of Nottingham Chemistry Department by Mr T. J. Spencer, Mr M. Guyler and Mr T. Hollingworth, respectively. IR spectra were obtained as ICBr pressed pellets on either a Perkin-Elmer PE983G or PE 1600 series FTIR spectrophotometer and UV-vis spectra

on either a Perkin-Elmer

Lambda 5 or Unicam UV2100 spectrometer. Copper(I1) nitrite was prepared in situ by treatment of CuSO., * 5Hz0 with Ba(NO&. The other copper(I1) CuCl, - 2H20, salts [CuBr,, CWO,),. 3&O, CuS04 - 5Hz0] were obtained from Aldrich Chemical Company Ltd and recrystallized from deionized water prior to use. The N-donor ligands, dien, ImH, cnge and py, were obtained from Aldrich Chemical Company Ltd and used without further purification.

Preparation of bromide salts

An aqueous solution (50 cm3) of CuBr, (4.00 g, 17.9 mmol) was added to an aqueous solution (50 cm3) containing either dien (1.93 g, 18.0 mmol) alone or dien (1.39 g, 18.0 mmol) with either ImH (1.24 g, 18.2 mmol), cnge (1.50 g, 17.8 mmol) or py (1.43 g, 18.1 mmol). The resulting blue solution was heated to 90°C

Table 6. Ions (minimum m/z values) observed in the FAB mass spectra of Cu(dien)Br, @I), Cu(dien)Cl, (9), Cu(dien) (ImH)Cl,* 2H20 (I), Cu(dien)(NO,), (lo), Cu(dien)(ImH)(NO,),~ Hz0 (2), Cu(dien)(cnge)(NO,), (S), Cu(dien) (NO,), .nH20 (7), Cu(dien)(cnge)(NO,), *nHzO (6), Cu(dien)(SOJ *nH20 (12), Cu(dien)(ImH)(SO.,) *2H,O (4). Cu(dien) (cnge)(SO,) *3H20 (7) and Cu(Me,deta)(cnge)(NO& (13) NO;

CIAnion : Complex :

Br8

[Cu”(dien)X] + [Cuy (dien),X,]+ [Cu:I(dien),X,-H]+ [Cu!:(dien),X-2H]+ [Cu:‘Cu*(dien)&]+ [Cu:‘Cu’(dien),X~ - H] + [Cu:‘Cu’(dien),X, - 2H] + [Cu”Cu’(dien)X~ + [Cu”Cu’(dien)X - H] + [Cui(dien)] + [Cu”(dien)LX] + [Cu”Cu*(dien)LXd+ [Cu”Cu’(dien)LX - H] + [Cu:’(dien),LX,] +

245 -

Ion

307 166 -

so:-

NO;

9

1

10

2

5

11

6

12

4

7

13”

201 437 401 535 499 -

201 437 401 535 499 -

228 -

228 518 455 392 580

263

298

525 428 _

525 428 _

525 428 _

_

353 290 166 -

212 _ 166

263

299 263 166 269 367 331

212 _ 321 166

263

299 263 166 -

228 518 455 392 _ 166 312 437 374 -

-

-

587 423 325 166 -

587 423 325 166 331 490 393 -

587 423 325 166 347 506 409 _

236 382 507 444 -

-

‘For these ions read Me,dien for dien.

517 166 296 421 358 586

812

M. J. Begley et al.

for 30 min, before the solvent volume was reduced to yield a blue gum. For all four experiments, washing with ethanol gave a dark blue solid, which after recrystallization from aqueous ethanol was found to be Cu(dien)Br, (4.95 g, 15.2 mmol, 85%).

Preparation of chloride salts

An aqueous solution (60 cm3) of CuCl, *2H20 (5.00 g, 29.3 mmol) was added to an aqueous solution (60 cm3) containing either dien (3.10 g, 28.9 mmol) alone or dien (3.10 g, 28.9 mmol) with either ImH (1.95 g, 28.6 mmol), cnge (2.45 g, 29.1 mmol) or py (2.30 g, 29.1 mmol). The resulting blue solution was heated to 90°C for 30 min, solvent volume was reduced and ethanol added to yield a blue solid. Recrystallization from aqueous ethanol gave Cu(dien)Cl, (4.90 g, 20.6 mmol, 71%) or Cu(dien)(ImH)Cl,*2H,O (5.05 g, 14.8 mmol, 52%).

Preparation of sulfate salts

An aqueous solution (60 cm’) of CuSO, - 5H,O (8.00 g, 32.0 mmol) was added to an aqueous solution (60 cm3) containing either dien (3.45 g, 32.2 mmol) alone or dien (3.45 g, 32.2 mmol) with either ImH (2.15 g, 31.6 mmol), cnge (2.69 g, 32.0 mmol) or py (2.55 g, 32.2 mmol). The resulting blue solution was heated to 90°C for 30 min, solvent volume reduced, ethanol added and the mixture left at 5°C for 16 h. In the presence of ImH or cnge, highly deliquescent blue solids analysing for Cu(dien)(ImH)(SO,) * 2H,O (6.10 g, 16.6 mmol, 53%) and Cu(dien)(cnge)(SO,) - 3Hz0 (6.45 g, 16.1 mmol, 50%) were recovered. In the presence of py or with dien alone, precipitation did not occur. As for the nitrites, various solvent combinations (H,O-Pr’OH, MeCN-Et,O, MeCN-toluene) were tried but without success. A solid product could only be obtained by removal of all solvent in vacua.

Preparation of nitrate salts

X-ray crystallography

An aqueous solution (60 cm3) of Cu(NO,), - 3H20 (5.00 g, 20.7 mmol) was added to an aqueous solution (60 cm’) containing either dien (2.22 g, 20.7 mmol) alone or dien (2.22 g, 20.7 mmol) with either ImH (1.40 g, 20.6 mmol), cnge (1.75 g, 20.8 mmol) or py (1.65 g, 20.9 mmol). The resulting blue solution was heated to 90°C for 30 min, solvent volume reduced, ethanol added.and the mixture left at 5°C for 16 h. All four experiments gave blue solids, which after recrystallization from aqueous ethanol analysed for Cu(dien)(N03), (4.20 g, 14.5 mmol, 70%), Cu(dien) (ImH)(N03)z.Hz0 (6.25 g, 16.6 mmol, 80%) Cu(dien)(cnge)(N03)z (5.95 g, 15.8 mmol, 77%) and Cu(dien)(NO&*HZO (3.65 g, 11.8 mmol, 57%), respectively.

Oscillation and Weissenberg photographs revealed preliminary cell parameters for selected crystals of 5 (triclinic) mounted in Lindemann tubes under dry nitrogen. X-ray diffraction data for the refinement of cell parameters and structure determination were collected using a Hilger and Watts Y290 four-circle diffractometer. Crystal data. CSH1,CuN90e, M = 374.80, triclinic, Pi, a = 7.949(3), b = 10.217(4), space group c = 10.351(4) A, ~1= 66.08(5)“, p = 75.39(5)“, y = 85.45(5)“, U = 743.36 A3, Z = 2, F(OO0) = 386, D, (bromoform/hexane) = 1.68 g cmm3, D, = 1.67 g cmm3, MO-& radiation, Iz = 0.71073 A, pale = 15.15 cm-‘, crystal dimensions 0.08 x 0.20 x 0.25 mm3. One unique set of data (2199 reflections ; index ranges -9 30(Z)] with unit weights converged to R = 0.040 and R, = 0.042 for 257 parameters in space group residual Aptin = -0.513, Apmax= 0.619, Pi; (A/o),,,=~= 0.065.

Preparation of nitrite salts

An aqueous solution (30 cm’) of CuSO,* 5Hz0 (3.26 g, 13.1 mmol) was added to an aqueous solution (30 cm’) of Ba(NO& (3.00 g, 13.1 mmol). A white precipitate of BaSO,, which formed immediately, was filtered off to leave a lime green solution, which was then added to an aqueous solution (40 cm3) containing dien (1.35 g, 12.6 mmol) alone or dien (1.35 g, 12.6 mmol) with either ImH (0.86 g, 12.6 mmol), cnge (1.05 g, 12.5 mmol) or py (1.00 g, 12.6 mmol). The resulting blue solution was heated to 90°C for 30 min, solvent volume reduced, ethanol added and the mixture left at 5°C for 16 h. In none of the experiments did precipitation occur. Other diverse solvent combinations (H@--PtiOH, MeCN-Et,O, MeCN-toluene) were tried but without success. A solid product could only be obtained by removal of all solvent in vacua.

Copper(II)diethylenetriamine Atomic plete list observed deposited

coordinates, thermal parameters, a comof interatomic distances and angles, and and calculated structure factors have been with the Editor as supplementary material.

9.

Acknowledgement-We thank the EPSRC for a maintenance grant (to J.S.).

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