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Structural chemistry of naphthalenedisulfonate salts
Inorganica
Chimica
Acta 258 ( 1997) 237-246
Structuralchemistry of naphthalenedisulfonate salts Brian J. Gunclerman ‘, Ian D. Kabell a, Philip J. Squattrito &*, Sure&a Received
12 July 1996, accepted
15 October
N. Dubey b
1996
Salts of naphthalenedisulfonrte anions with several different metal cations have heen crystallized and their stmcmms (H,HC,~H,(S0,)2),.4H,0: triclinic, space groupP1, Z= 1. o=- 12.779(3). b= 12.984(4). c y= 114.58(2)3 V-803.8(4) A3.R(F)==0.038 for 269 variables and 2305 observations (I
b-6.874(5), c=21.509(4) A, cobalt analog of the nickel corn anions in which the aromatic tin are between these layers and se coordinated octahedrally to six water molecules with no direct coordination to the suifonate oxygen atoms. The sodi three sulfonate oxygen atoms andthree water moleculesin a somewhatdistorted octahedron.The barium cation is of two sulfonate oxygen atoms and six water molecules. The coordination trends and layering patterns of these those of previously repotted monosulfonatesalts. Keywords:
Crystal
struc~ums;
Sulfonate
salts; Nickel
complexes:
Barium
compleaes;
1. Introduction Compounds with structures composed of alternating inorganic and organic layers have been of interest in recent years for their potential to act as host structures forvariouschemical processes [ 1]. Among the most widely studied have been metal phosphonate salts of the general formula M(OxPR) . xHzO in wi 7 is an aliphatic or aromatic organic group. The oxygen ,.oms of the phosphonate group coordinate to the metal ion, sometimes along with some water molecules. Most commonly, a two-dimensional metal-oxygen-phosphorus framework is formed [2-141, though chains and three-dimensional structures are also known [ B-191. In all these materials. the R groups act as spacers between the inorganic parts. The resulting structures have rigid covalent inorganic frameworks separated by weakly interacting organic domains. The use of different organic groups alters the size * Comspondiag
author.
0020.1693/97/$17.00 0 1997 EIsevier PllSOO20-1693(96)05534-X
Science
.%A. All rights msewed
Sodium complexes
and nature of the organic region, and hence the physical properties of the mater% In particuhu, the in of polar or ionic Rmctional groups on the organic moiety offers the potential for size- and shape-selective ion-f~xcbange or intercalation. Sulfonation of the attempted in the past to create ion those found in inorganic layered conimo phosphate [ 201. Moreover, selves are widely used industrially as surfactants and dyes. Recently, they have been studied as potential liquid crystalline [21] and no&ear optical materials [22J3], and as complexing agents in the form of sulfonated macmcycfes [ 241. We have undertaken asystematic of metal organosulfonate salts 125-29 structuraltrendsthatmaypmvideinsi cations for this class of compounds. Previously. metal benzenesulfonate [25-281 and napbthalenesuffonate [29] salts have been examined. As an extension of this study, we have synthesized and structurally characterized salts of two iso-
238
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merit disuifonated naphthalenes, 3-aminonaphthalene-l,Sdisulfonate (I) and 6aminonaphthalene- 1,3disulfonate (II) (Scheme 1). The compounds were prepared by metathesis reactions of the metal chloride or nitrate with the sodium sulfonate salt in aqueous solution. We report here the structures of these compounds and discuss their relationships to each other and to previously reported sulfonates.
2.1.3. Na,(HflC&Is(SO,),)* SHzO A 1.00 g ( 1.73 mmol) sample of disodium 3-aminonaphthalene-1 &disulfonate was dissolved in 50 ml of water with heating and stirring. To the brown solution was added 0.010 g (0.25 mmol) of NaOH, which dissolved quickly raising the pH of the resulting solution to about 7. The solution was allowed to stand in an open container until the solvent had completely evaporated. A total of 0.65 g of brown needle-like crystals were recovered, an 86% yield based on themaction2Na” +H2NC,eH,(SOs)22+5H2b*Na2(H2NC,&(SO,),) .5H20. Awl. Found: C, 24.81; H, 4.20; N,
2. Experimental
2. I. Syntheses 2.1. I. [Ni(HzO),l{H,NC,d-r,(SO,),),. 4H,O A 4.01 g (6.93 mmol) sample of disodium 3-aminonaphthalene-1,5disulfonate (Eastman, technical grade 60%) was placed in 200 ml of distilled water. The mixture was heated and stirred until the solid dissolved completely to form a clear brown solution. Then, 1.65 g (6.94 mmol) of NiCla.6HaO was added to the solution. The resulting solution, brown with a slight greenish tint, was set out at room temperature in an open container. Upon evaporation of the water, a mixture of large, clear light brown flattened needleshaped crystals and small darker brown clumps of fine needles formed. The larger crystals, which are the nickel salt, were separated by hand from the smaller crystals, which are a reported sodium 3-ammonionaphthalene-l ,S-disulfonate salt [ 291. A total of 2.24 g of nickel sulfonate crystals were recovered, a 76% yield based on the reaction Ni*” + 2HaNCteH,(SO~)a*+2Ha0++8HaO+ [Ni(H,O),](H3NCu,H~(S03)2)2~4H20. As no acid was added to this reaction, we assume the natural acidity of the transition metal cation led to the protonation of the amine group on the anion. Anal. (National Chemical Consulting, Tenafly, NJ) Found: C, 27.13; H, 4.04; N, 2.80. Calc.: C, 28.48; H, 4.30; N, 3.32.
A 4.00 g (6.91 mmol) sample of disodium 3-aminonaphthalene- 1.5disulfonate was dissolved in 200 ml of water with heating and stirring. To the brown solution was added 1.65 g (6.93 mmol) of CoCl, . 6H20 which dissolved leaving the color unchanged. The solution was allowed to stand at room temperature in an open container. After the water bad evaporated, a product distribution similar to that of the mckel reaction was obtained. A total of 2.46 g ( 84% yield) of brown crystals of [Co(H,O),] (HSNC,~H,(S0,)2)2.4H20 were isolated.
2.2. Crystallographic
studies
All of the single-crystal X-ray diffraction measurements were done at room temperature on a Rigaku AFC6S fourcircle diffractometer (graphite-monochromated 2.0 kW MO Ka X-ray source; A = 0.7 1069 A> operated by the MSCAFC Diffractometer Control software [ 301. All crystals were cut from larger fragments and were mounted on glass fibers with silicone cement. Unit cell parameters were obtained by indexing 25 reflections found during a search of reciprocal space and were refined by a least-squares analysis of the setting angles of 19-21 reflections ( 18’< 28(Mo Ka) < 50“) in which the appropriate cell angles were constrained to 90”. Intensity data in the range 3-50” 28 were collected with ~28 scans of 8” mitt- ’ for the nickel crystal and w scans of 4” min - ’ for the sodium and barium crystals. Reflections were measured at a constant scan rate with multiple scans (up to four) for weaker data (those withZ< low(Z)). The intensities of three standard reflections measured after every 150 data showed no significant variations. All crystallographic calculations were performed on a VAXStation 3100/76 computer with the TEXSAN [31] series of programs. Atomic scattering factors [ 321 and anomalous
B.J. Gunderman
et al. /Inor8anica
Chimka
Acta 258 (1997) 237-26
dispersion terms [ 331 were from standard sources. Datawere corrected for Lorentx and polarization effects. A secondary extinction correction [34] was made for the data of the Ni compound, while the data of the Ba compound were corrected for both absorption ( 9 scans) and extinction. Space groups were assigned either uniquely based on systematic absences (Z&n, O&Z.n, Z&O,h+k+2tr, hOZ,Z+2n), by acombination of systematic absences and intensity statistics ( CWc. Z&Z, h +k# 2n. hOI, I# 2n). or by intensity statistics alone (Pi), and were confirmed by successful refinements. The structures were solved by direct methods: MITHRIL [35] for the heavy atoms (Ni. Ba, S and Na) and I?H?LX!J [36] for the lighter non-hydrogen atoms (0, N and C). Most of the hydrogen atoms were located on difference electron density maps and their positions were refined in the Ni and Ba structures. Hydrogen atoms were included as fixed scatterers for the Na compound. The B,, value of each H atom was set at 1.2 times the Bog value of the attached atom at the time of its inclusion. Final refinements included anisotropicdisplacement parameters for all non-hydrogen atoms and were performed on those data having Z>3a(Z). There were no unusual variations in F,,- F, as a function of (sin 6) /A, Miller indices, or F,. Crystallographic data for the three compounds are summarized in Table 1. Final positional and equivalent isotropic displacement parameters are listed in Table 2.
Empiricalformula Formulaweight Ctystai system a (A)
b(A)
c(A) a (9 B (9 Y0 V(P) SP=egroup zvahle Du* (8 cm-‘) WOO) c (cm-‘) Transmissionfactors l?.mmiua coefficient Pemngefordata(“1 Detacoketed Totaldata Numberof uniquedata RI, Numberofdata/>3cr(/) Numberof variables RU3:R.V~ (I>3o(I)) Goudaessof fit LarpestpeaksinfinaiAF(eA-3)
Cd%&hWi 843.43 tlichic 12.779(3) 12.984(4) 5.473(1) 102.17(2) 89.65(2) 114.58(2) e3.8(4) PI (No. 2) 1.73 438 9.45 EiX IO-’ 3-H) +h. ctk. *I 2956 2818 0.049 2305 269 0.038;0.040 2.18 057; -0.45
monoclinic 25.864(3) 6.874(S) 21.509(4) 90 116.825(IO) 90 3412(2) CL/c (No. IS) 4 1.79 1864 14.83 0.82-1.00 0.246x lo-” 3-m +h. +L *I 3359 3218 0.028 2249 274 0.028;0.029
I.70 0.90; - 0.62
12.755(4) 5.890(3) 23203(3) 90 90 90 1743(I ) F&n (No.60) 4 1.67 904 3.95 mme izi +h.
4-L. +1
1817 1817 ET 123 0.04%0.046 2.19 0.31: -0.33
B.J. Gunderman
Table 2 Positional Atom
ef ai. /Inorganica
S(2) O(2)
O(I)
O(3) O(4) O(S)
O(6) ‘38)
O(7)
O(9) O( IO) O(ll) N(l) C(l) (32) C(3) C(4) C(5)
‘36)
C(7) C(8) C(9) C(lO) H(l)
H(2)
H(3) H(4) H(5)
H(6) H(7) H(8) H(9) H(l0) H(ll)
W12) H(13) H(l4) H(15) H(
16)
andequivalentisotropicthermalparameters
x
Y
O(2) O(3) Or41 O(5)
O(6) Nb C(l)
C(2) C(3) C(4) C(5) H(1)
H(2)
0 0.20556(9) 0.3202!(S) 0.1213(3) 0.3257(2) 0.1826(3) 0.4116(2) 0.2041(2) 0.3360(2) 0.0818(3) -0.1647(3) -0.0032(2) 0.4193(S) 0.3433(4) OAid8(3) 0.1943(3) 0.3385(3) 0.4020(3) 0.3969(3) 0.3239(3) 0.1762(3) 0.1116(3) 0.1202(3) 0.2626(3) 0.2542(3) 0.528(3) 0.435(3) 0.523(3) 0.339(3) 0.439(3) 0.167(3) 0.063(3) 0.078(3) 0.114(3) 0.055(4) -0.211(4) -0.181(4) -0.064(3) 0.038(3) 0.408 0.351(6)
0 0.76607(9) 0.32321(8) 0.7581(2) 0.8349(2) 0.8057(3) 0.3389(2) 0.2.526(2) 0.281312) -0.0546(3) -0.1046(3) - 0.1183(2) 0.0501(4) 0X1428(4) 0.7522(3) 0.6232(3) 0.6876(3) 0.6610(3) 0.5497(3) 0.4637(3) 0.3995(?) 0.4245(3) 0.5376(4) 0.6007(.3) 0.4858(3) 0.813(4) 0.783(3) 0.728(3) 0.759(3) 0.534(3) 0.324(3) 0.370(3) 0.554(3) -0.104(3) -O&9(4) -0.144(4) -0.138(4) -0.162(3) -0.155(3) 0.067 0.052(6)
NaAHJ’JC,,Ps(SO,M s 0.5799(l) Na O(l)
Acfa 258 (I 997) 237-246
Table 2 (continued) parameters
Atom
.?
fNitHP),1(H~NCldtStSO~)~)~.4H~0 Ni S(I)
Chimica
0.8228(2) 0.4762(3) O&07(3) 0.6055(4) 0.6974(3) 0.8008(4) 0.6866(9) 0.5719(S) 0.6293(5) 0.6236(S) 0.5582(5) 0.5025(5) 0.693 0.552
.5H
0 0.1916(2) -0.2133(2) 0.3360(5) 0.3294(5) -0.0549(5) --0.3409(5) -0.3702(S) 0.0328(5) -0.2148(5) -0.2127(5) 0.2592(5) 0.056(l) 0.5762(9) -0.3879(7) 0.1432(7) -0.1264(7) -0.2604(7) -0.2843(7) -0.1682(7) 0.0980(7) 0.2330(8) 0.2583(8) -0.0022(7) -0.275(7) -0.499(7) -0.459(7) -0.116(6) -0.387(6) 0.086(7) 0.330(7) 0.349(7) -0.157(7) -0.363(8) -0.138(g) -0.325(g) 0.275(7) 0.280(7) -0.107 0.12(!)
1.84(2) 2.32(3) 1.85(3) 3.2(l) 3.1(l) 3.5(l) 2.9( 1) 2.4(l) 2.5(l) 3.1(l) 2.7(l) 2.3(l) 10.6(3) 9.4( 2) 2.3(l) 2.0(l) 2.0(l) 1.8(l) 1.9(l) 1.7(l) 2.3(l) 2.5(l) 2.5(l) 1.7(l) 1.8(l) 3.0 2.6 2.6 2.3 2.3 2.8 2.9 3.0 3.4 3.4 3.0 3.0 2.6 2.6 12.3 II.3
120 0.0290(3) -0.0173(S) -0.019( I ) -0.1114(8) 0.2677(8) -0.2168(g) -0.292(l) -0.127(l) -0.503(2) -0.064(I) -0.252(l) -0.344(l) -0.240(l) 0.046(l) -0.340 -0.326
0.64166(7) 0.2116(l) 0.6666(2) 0.6684(2) 0.6415(2) 0.2775(2) 0.3831(2) 114 0.4809(S) 0.5687(3) 0.5538(3) 0.4972(3) 0.4575(3) 0.5281(3) 0.582 0.420
2.25(S) 2.7(l) 3.0(2) 2.6(2) 3.3(3) 2.7(2) 5.1(3) 4.1(4) 3.5(6) 2.2(3) 3.0(4) 3.0(4) 2.7(4) 2.1(3) 2.8 3.1 wnrinued)
H(3) H(4) H(5)
.?
x 0.733 0.655 0.995
[ W WW BZl S(l)
S(2) O(I) O(2) O(3) O(4) O(5)
O(6) O(8) O(7)
O(9) O( 10) O(11) N(1) C(l)
C(2) C(3) C(4) C(5)
C(6) C(7) C(8) C(9) C( 10) WI)
H(2)
H(3) H(4) H(5)
H(6)
H(7) H(8) H(9) W 10) H(ll) W H(l3) H(14) H(l5) W W 17)
12) 16)
-0.268 -0.107 -0.041
oHs(S~I)Z)Z(HZ~)~I~~H~O l/2 0.25675(7) 0.34887(5) 0.0231(2) 0.11629(5) 0.0198(2) 0.3875(l) 0.1695(5) 0.3747(l) -0.1704(S) 0.3261(l) 0.0756(S) 0.0720(l) O.OlOO(6) 0.1154(l) 0.1998(4) 0.1166(l) -0.1509(4) 0.4995(2) -0.0977(6) 0.4323(2) 0.X63(6) 0.4811(2) 0.3570(8) 0.3023(2) 0.4878(6) 0.4970(2) 0.1425(8) 0.3092(2) -0.0216(6) 0.2882(2) 0.0127(6) 0.2343(21 0.0205(7) 0.1844(2) 0.0169(7) 0.1888(2) 0.0088(7) 0.2491(2) -0.0062(7) 0.3024(2) -0.0166(6) 0.3533(2) -0.0202(7) 0.3496(2) -0.0129(7) 0.2953(2) -0.0004(6) 0.2441(2) O.OOOl(6) 0.231(2) 0.026(6) 0.160(2) 0.004(6) 0.216(2) 0.002(6) 0.387(2) -0.031(6) 0.383(2) -0.023(6) 0.330(2) -0.152(6) 0.330(2) 0.081(6) 0.277(2) -0.017(7) 0.498(2) -0.092(8) 0.470(2) -0.129(8) 0.411(2) 0.633(8) 0.444(3) 0.645(8) 0.452(2) 0.339(8) 0.505(3) 0.37(l) 0.329(2) 0.391(8) 0.316(2) 0.601(8) 0.526(3) 0.06( 1)
C’ 0.315 0.287 0.287
3.1 3.1 4.6
314 0.71259(5) 0.56205(6) 0.7082(2) 0.7257(2) 0.7603(2) 0.4906(2) 0.5973(2) 0.6026(2) 0.8220(2) 0.6762(2) 0.8611(2) 0.2375(2) 1.0488(2) 0.3759(2) 0.6281(2) 0.6253(2) 0.x04(2) 0.4999(2) 0.4377(2) 0.4403(2) 0.5037(2) 0.56.51(2) 0.5603(2) 0.5010(2) 0.666(2) 0.463<2) 0.396(2) 0.502(2) 0.606(2) 0.374(2) 0.374(2) 0.342(2) 0.861(3) 0.794(3) 0.694( 3) 0.669(3) 0.873(3) 0.895(3) 0.242(3) 0.247(3) 1.063(4)
1.98(2) 1.91(4) 1.88(4) 3.2(l) 3.3(l) 3.0(l) 3.7(2) 3.1(l) 2.6(l) 3.4(Z) 3.9(2) 5.3(2) 3.6(2) 6.2(2) 2.0(2) 1.4(l) l.7(2) 1.5(2) 1.7(2) 1.7(2) 1.7(2) 2.0(2) 1.8(2) U(2) 1.5(l) 2.0 2.0 1.9 2.3 1.9 2.1 2.1 2.1 3.7 3.7 4.3 4.3 5.4 5.4 4.1 4.1 7.3
‘B,=~4~3~~o2P,,+b’&~+~*~,+~~bcosy~~,~+(2ac~~~~)~,,+ (~cos~~h,l. boccupivlcy=0.5.
The compound adopts a structure in which layers of anions alternate with layers of cations. Each anion layer contains a single plane of cofacial naphthalene rings sitting vertically so that the SO,- and NH,+ groups are directed to opposite sides of the layer. The position of the ammonium group is inverted on adjacent anions. Between the anion layers are the hexaaquanickel cations. The layers are held together by a strong networkof N-Ha*-OandO-Ha a. hydrogen bonds involving the ammonium, water and sulfonate groups (Table 5). This
B.J. Gundemun
et al. /Inorganico
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Acta 258 (1997) 237-246
Table3 Weeted bonddisra~~~~(A)
~N~~H~O),I(H,NC,~JI,(S~)~)Z.~HZO Pig. I. ORTEP diagramof the molecularsbuctme of [Ni(H,O),](H,NC,~s(SO~),),.4H, showingatom labellingscheme.Symmetry equivalentwatermoleculeshavebeenincludedfo showtheoctahedralcoor-
figuresareshownat the50%probabilitylevel.exceptfor theseof hydrogen whichareshownasisotmpicspheresof arbitrary size. structural motif is typical of transition metal sulfonate salts. Due to the 2: I stoichiometry and the large size of the anions, there are holes in the cation layer which are occupied by the two free water molecules. It is evident from the displacement parameters of the oxygen atoms that these water molecules are rather loosely bound in these sites. The presence of channels containing uncomplexed water distinguishes these compounds from most of the benzenesulfonate salts we have studied [ 25-281. The cobalt analog is isostructural (unit cell dimensions u= 12.750(3), b= 12.981(4), c=5.501(2) A. a= 102.16(3)q /3=89.56(3)“, y=114.63(2)3 +805.6(S) A’), indicating that this is a general structure type for the divalent first row transition metals. 3.2. Na,(HflC,,,H&O&~SH,O The molecular structure is shown in Fig. 3 while a packing view of the unit cell is presented in Fig. 4. Important bond distances and angles are given in Tables 3-5. This compound is the dibasic salt of the parent disulfonic acid. The amine group is not protonated. The asymmetric unit contains one cation, half of an anion and two and a half water molecules. The anion sits on an inversion center which forces the amine group to be disordered between two equivalent positions. The N atom was included at half-occupancy in the refinement. Consequently, the amine H atoms could not be located and the C-N distance is anomalously short. Otherwise, the geometry of the anion is similar to that observed in the nickel salt. Of the five water molecules in the empirical formula, four are
Ni-O(7) N&O(8) N&O(9)
S(1)-al) St 1 S(IkO(3)
ko(2)
Na2WJ-GWXM2) s-o(l)
s-o(2) g-O(3) s-c(l)
N+W) M-W)
2.038(J) 2.075(3) 2.061(3) 1.450(3) l&5(3) 1.454(3) .SH,O 1.472(4) 1.459(4) 1.444(51 1.781(6) 2.421(5) 2.415(6)
S(l)-al)
WbOW sCO-a5) %WW) s1wa5) N(lbC(3) Na-O(3) Na-o(4) Na-O(4)
Na-a6) N-c(3)
IB~(H~NC,~S(~~)~)Z(HZ~)~I-~HZ~ 2.698(3) Ba-CNl) .%1)-c(I) Ba-O(7) 2.891(4) s(2)*(4) 2.759(4) BaQ(Q 2.736(4) Bit-a(9) 1.450(3) S(lbo(l) 1.458(4) s(tbo(2) N( 1.442(3) S(lbO(3)
sc?)-a5) WMW) SCW.X3) IF36)
1.7n7(4) l&44(2) 1.793(3) l&g(4) 2376(S) 2-W) 2.353(5) 2.513(3) 1.%1)
1.789(4) l.446(3) 1.779(4) 1.472(S)
attached to sodium cations and one is free. All of tbe H atoms on the coordinated water molecules as well as those on the carbon atoms were located, though their positions were not refined. The sodium cation is in a fairly regular oc&edml coordination of three water molecules and three oxygen atoms from different anions. The presence bonding between the cation and sulfonate group is collsistent with what we have found in other Often. the sodium coordination en in oxoanion salts, but modestly dis that reported here have been observed in several sodium sulfonates [25.26.28.29]. In these structures there is ao clear distinction between the Na-O%and Na-O~distaaces as the ranges (2.293(6)-2.555(6) and 2.353(S)2.696(6) A, respectively) overlap. The Na-0 distances in the present compound are consistent with this observation. It
242
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et al. /Inorganica
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Acta 258 (1997) 237-246
Table4 Sekcteu
Lxmd angles (9
[Ni(H,O),I(H,NC,~H,(SO,),),.4H;O O(7)-NiXI@) 93.5(l) 94.4(l) 0(7)-N&O(9) 0(8)-N&O(9) 86.2(I) 112.6(2) O( 1)-a 1 113.2(2) O(I)-%~)-o(3) 106.7(2) 0(1)-%1)-C(1) 111.2(2) O(2)-% 1W(3) 105.4(2) 0(2)-q I bet 1) 107.1(2) 0(3)-.9(1)-C(l) 112.2(2) 0(4)-S(2)*(5)
)-o(2)
NMWCIOHS(SO~)Z) O( 1 0(1)-S-O(3) 0(1)-S-C(1)
G-o(2)
OG!)-S-O(3) 0c9-s-c( I) 0(3)-S-C(1) O(2)-Na-O(2) O(2)-Na-O(3) O(2)-Ne-O(4) 0(2)-N&(4) O(2)-Na-O(6) O(2)-Na-O(3)
.5&O 111.0(3) 113.0(3) 105.3(3) 113.2(3) 105.7(3) 108.0(3) 100.7(2) 81.5(2) 81.6(2) 86.6(2) 174.7(2) 104.0(2)
0(4)-.%2)-O(6) 0(4)-S(2)-C(5) 0(5)-%2)-o(6)
O(5Pww35) 3(6bWbC(5)
SC1)-C( 1)-C(8) S(I)-aI)49)
SW-W)-c(4) SG+W)~:(lW
0(2)-N&O(4) O(2)-Ne-O(4) O(2)-NttO(6) O(3)-Nti(4) 0(3)-N&O(4) O(3)-Ne-O(6) 0(4)-N&O(4) 0(4)-N&O(6) 0(4)-N&O(6)
S-c(~Mxo
S-aI)-w)
IBa(H,NC,,H,(SO~)2)2(H,0),1 .4H20 O(l)-Be-O(l) 1X3(2) O( 1)-S( 1W(2) 74.1(l) 0(1)-B&(7) O(l)-S(lkO(3) 0(1)-B&O(7) 84.2(l) O(l)-S(I)-C(l~ 70.7(1) 0(1)-B&O(8) O(2)-% 1)-O(3) Of 1)-B&O(8) 132.3(1) 0(2)-S(l)-C(l) O( I )-Be-O(9) 75.9(l) 0(3)-S(l)-C(l) O( 1)-B&(9) 110.9(I ) 0(4kS(2)-0(5) O(7)-Be-O(7) 65.1(2) 0(4)-S(2)-O(6) O(7)-Be-O(8) 143.5(l) 0(7)-B&O(8) 119.8(1) O(7)-Be-O(9) 72.4(I) 0(7)-B&O(9) 136.6(1) O(8)-Ba-O(8) 79.0(2) s(lw(lba2) O(8)-Be-O(9) 89.5(2) S( 1)-c( 1)-C(9) 0(8)-B&O(9) 67.7( I) O(9)-Be-O(g) 150.8(2)
0(4bWkC(3) OW-WbO(6) O(5bWkW) O(6bWbCW WMX3bW) S(2)43)-c(4)
114.2(2) 10X9(2) 111.5(2) 105.1(2) 107.2(2) 117.5(3) 120.8(3) 116.1(3) 122.5(3)
83.4(2) 163.9(2) 80.5(2) 162.5(2) 91.3(2) 93.2(2) 83.5(2) 103.7(2) 93.6(2) 117.2(5) 121.2(S)
112.1(2) 112.8(2) 106.0(2) 113.0(2) 106.0(2) 106.3(2) 113.7(2) 112.6(2) 107.2(2) 111.7(2) 105.6(2) 105.3(2) 116.9(3) 121.8(3) 116.9(3) 122.2(3)
appears that the sodium ion does not exert a strong directing influence on the structure in order to form a regular coordination polyhedron. but rather fits into holes in the packing of
the large sulfonate anions. This compound also forms a layered structure with slabs of anions sandwiching cations and water molecules. The aromatic rings are approximately perpendicular to the plane of the layer and the sulfonate groups are on the faces of the layer. Within the layer there are columns of anions running parallel to the b axis. In each column the rings are cofacial. The columns are related along the a axis by mirror symmetry so the naphthatene grout~s of adjacent columns are canted rather than parallel. The SOa- groups on adjacent columnsahemate between being on the upper side or the lower side of the layer.
Fig. 3. ORTRP diagramof the meleculatstmctme of Naz(HINC,cHs(SO,),) 95H,Oshowingatomlabellingscheme.Symmetryequivalentwater moleculesandsulfonek 0 atomshavebeenincludedto showthedistorted octahedralenvimnmentof theNa+ ion. The amine N etomis dismdeted betweentwo sitesrelatedby invenionthroughthecenterof thenaphtbelene unit.
The sodium ions are near the neighboring SOa- groups so that they too alternate positions within the layer. This is a different arrangement than in the nickel salt, in which the anions within a layer are all parallel to one another, the sul-
fonate groups are evenly spaced and the metal ions are both evenly spaced and coplanar. A feature common to the two structures is the presence of holes, in this case between the pairs of widely spaced SOs- groups, filled by uncomplexed water molecules. The structure of the monobasic salt Na(H,NC,&(SO,),)~HzO is also known [29]. The ammoniodisulfonate anions stack in cofacial columns, but with the sodium ions and attached water molecules interspersed in such a way that segregated organic layers are not formed.
The molecular structure is depicted in Fig. 5 and the unit cell is shown in Fig. 6. Bond distances and angles may be found in Tables 3-5. This compound is compositionally analogous to the nickel salt. in that it contains a divafent cation, two protonated ammoniodisulfonate anions, and ten water molecules. The anion used in this case is 6-aminonaphthalene-13-disulfonate, an isomer of the anion in the previous compounds. It was selected because crystals of the barium 1,5-disulfonate compound were not readily obtained and we were interested to see whether the barium ion would be chelated by oxygens from sulfonate groups in the 1 and 3 positions. The barium ion is bonded to six water molecules and
E.J. Gundennan .?I al. /Inorganica
Chimica
243
Acta 258 (1997) 237-244
Table5 SeIectedhydrogenbondingintemctions(A. “) D
H
A
[Ni(H~O),l(H~NC,dWgO~)~)~~4H~O N(I) H(l) O( 10) N(I) O(4) N(I) H(3) D(7) H(9) O(3) O(9) D(7) W 10)
H(2)
O(2)
O(8) OW
Wll)
O(6)
D(9) O(9)
H( 13) W 14)
I-U12)
O(5)
O(5) O(I)
Na2~H,NC,J4H,(S03)2) .SH,O O(4) H(3) O(5) O(I) D(4) H(4)
[Ba(H,NC,,H,(SO,),),(H,0),1.4H,O N(I) H(6) O(6) N(l) N(l) D(7) D(7)
O(8) O(8)
O(9) D(9)
O( 10)
O( 101
H(7)
H(8)
H(9) W 10) WII) W
12)
H( 13) W 14) W 15) H(
16)
O(5) WIO)
O(11)
O(2) O(2) D(7) O(6) O(4) O(2) O(3)
d(D...A)
A@ (D-H...A)
1.91(4) 1.88(4) 1.91(4) 1.76(4) 2.05(4) 2.02(4) 2.11(4) 1.89(4) 1.83(4)
2.774(6) 2.809(4) 2.805(4) 2.665(4) 2X47(4) 2.780(4) 2.794(4) 2.655(4) 2.667(4)
159(4) 167(3) W(3) 176(4) !74(4) l62(4) lW5) 170(4) l76(4)
1--x, l-y. -z ry,r-I I-x.1-y.-I-r x- 1.y.r
0.81
1.84 2.12
2X58(6) 2.917(6)
167 I51
LY.Z I-x. -y. l-z
lM(4) 0.90(4) 0.84(4) 0.86(5) 0.76(5) 0.92(5) 0.67(5) 0.91(5) 0.72(6) 0.93(5) 0.84(S)
1.83(4) l.%(S) 1.98(4) 1.92(S) 2.24(5) 1.94(5) 2.25(6) 2.06(5) 2.16(6) 2.05(S) 2.24(S)
2.857(Z) 2.831(S) 2.815(6) 2.755(6) 2.986(5) 2.838(5) 2.897(6) 2.%3(5) uw(5) 2.960(6) 3.058(6)
162(3) 161(4) l77(4) l%(5)
112-r -y-IL?, I-r 112-x. 112-y. l-z l/2-ry-l/2 112-z l-r. -y,2-z
&D-H)
d(
O.%(4) O.%(4) 0.91(4) 0.91(4) 0.80(4) 0.79(4) 0.69(4) 0.78(4) 0.&?4(4) 1.03
H...A)
two sulfonate 0( 1) atoms related by symmetry. There is no interaction between the oxygen atoms of the other SOSgroup and the Ba” ion. thus it is not a chelate complex. The geometry is irregular and perhaps best described as a distorted square antiprism. Square-antiprismatic eight-fold coordination of Ba*’ is found in other oxoanion salts such as Ba( OH) 2 * 8H20 [ 391, in which eight water molecules form the coordination sphere with Ba-0 distances ranging loom 2.69 to 2.77 A. In barium 4aminobenzenesulfonate, [Ba(H2NC,&SOj),(H20)] -2.5H20 [40]. the Ba*’ ion is coordinated to eight sulfonate 0 atoms in a distorted cube (Ba-0 range 2.68-3.07 A) with one face capped by a water molecule at 2.83 A. The distances in the present compound (Table 3) show a smaller variation than in the Caminobenzenesulfonate. and the distribution of sulfonate and water 0 atoms in the coordination sphere is essentially reversed. The structural features of the anion are similar to those of the 3aminonaphthalene- 1,S-disulfonate. The SOS- groups are bent sightly towards each other. One oxygen atom on the free sulfonate group eclipses the C-ring (torsion angle 0(4)S(2)-C(3)4(4) 0.7(S)“) while the sulfonate group that coordinates the Ba*’ ion is rotated somewhat relative to the naphthalene unit (torsion angle 0( 3)S( I)-C( 1)-C(2) - 10.7(4)0).TheC-Ndistance (1.472(S) A) isagainindicative of the presence of the ammonium group. All hydrogen
W6)
l66(5) 163(8) 170(5)
l=(8) M(5) 164(S)
&Y.Pl -x. -y.
-z
-x. -y. -1-r -1. -y. -z x-l.Y.2
iY.Z x.y+I.z
I-x.y+1.3/2-z 112-x. 112+y.3/2-z 1/2+x. 112-y. 1/2+z r. -y.z- 112 L I-y.z-I12
atoms except one on 0( 1 I ) were located and theii positions refined. The packing diagram shows that this compound has a htyered structure with many similarities to those of the 13. disulfonate anion. The 6- ammonionaphthaIene-l&disulfonate anions occur as inverted pairs positioned veikally in their layer with the rings cofacial and the s&mate groups on opposite faces of the layer. The Ba*’ ions and most of the water molecules are between the anion layers The cations hold the anion layers together by bonding to st&nategroups in neighboring layers. There is also an extensive network of hydrogen bonds involving the water molecules, NH, + , and SO*-. As m the nickel salt, two of the five crystallogrrtphitally independent water molecules are not bonded to the metal cation, however in this case the ir1ocationsared One, represented by 0( IO). is in the interior of the anion layer where it is hydrogen bonded to the ammonium 8roup. ~eother,representeabyO(ll).sitsinthespacesbetweea the cations in the inorganic layer, as do the uncomplexed water molecules in the nickel sah. The displacement parametersofthelattermolecukindicatesomeenhancedfbeedom of movement, though it is not as pronounced as in the nickel compound. This suggests that the holes in the barium iayer are smaller than those in the nickel layer. As evidence oae may note that the metal-metal distance is 12.98 A between
B.J. Gunderman
et al. /Inorganica
Chimica
Acta 258 (1997) 237-246
Fig. 5. ORTEPdiagramof the molecularstmctute of [Ba(H3NC10Hs(SO,),),(H,O),] .4H,O showingthe atomlabellingscheme.Symmetty equivalentwater moleculesandsulfonate0 atomshave beenincludedto show theeight-foldcoordinationof theBa” ion.
e
’ FI
Fig.4.ORTEPpackingdiagramof Nq( H,NC,Jis( SO&). SH,Oshowing theoutlineof the unit cell.View is alongtheb axis.TheNa andS atomsate shownwith octatttshadingand the Na-0 bondshave beenomitted.The opencircles with noattachedatomsaretheuncomplexedwatermolecules. ions and 11.60 A between Ba*+ ions. Since the metalcoordinated water distances are longer for Ba*‘, the actual amount of space available for the additional water molecules will be a lesser proportion of this separation for the barium salt than for the nickel salt.
Fig. 6. ORTEP packing diagramof [Ba(H,NC,~s(SOs)2)2(H20)61 * 4H20showingtheoutlineof the unit cell.View is approximatelyalongthe b axis. TheBa aad S atomsare shownwith Octaatshading.
Ni*’
4. Discussion The naphthalenedisulfonate salts reported here follow the pattern of the benzene- and naphthalenemonosulfonate salts studied previously [ 25-291 in forming structures with segregated organic and inorganic layers. The anions are arranged with the aromatic rings facing one another and the polar groups directed to the surfaces of the layer. Anions in inverted orientations are interleaved so that alternating anions have the SOs- groups on opposite faces of the same layer. This interleaving is in contrast to the structures of monophosphonate salts [ 2-141 which typically have the anions further
segregated in double layers of opposite orientations. In that sense, the sulfonate structures are denser and the layers are more strongly bonded together, making them perhaps less good candidates for intercalation chemistry. Nevertheless, some sulfonate salts do adopt noninterleaved structures [ 26 28) and others have been shown to convert from interleaved to noninterleaved on dehydration [41]. Recently, several diphosphonate salts have been reported [42] which have single layers of interleaved anions similar to the layers in the disulfonate salts. The trends in coordination behavior of the different metal ions toward the sulfonate groups closely parallels what was found for benzenesulfonate salts [ 25,261. The divalent transition metal ions do not bond directly to sulfonate oxygen atoms in the presence of water. All such salts crystallized directly from aqueous solutions contain hexaaquacations [ 25.26.431. The sulfonate can be forced to coordinate to these metal ions if the water is driven out of the structure. however
B.J. Gunderman
et al. /InorgMico
such materials are very hygroscopic and mhydrate quickly on exposure to humid air 1411. This tendency not to form strong complexes contributes to the efficacy of alkylsulfonates as anionic surfactants in hard water and of polystyrenesulfonates as ion-exchangers. The alkaline earth cation Ba*’ shows a greater tendency to bond to the sulfonate. The coordination spheres of alkaline earths, as well as of trivalent lanthanides, in sulfonate salts typically contain one or two oxygens from SOB- with the balance of the ligands being water molecules [ 2644-461. This is in contrast to the behavior of phosphonates which readily coordinate to these metals in the presence of water [2-141. The Na+ ion forms even more interactions with sulfonate oxygen atoms. Alkali metals [27,29] show the greatest tendency to bond to SOs- , with a majority of the coordination environment made up of sulfonate oxygen atoms. These salts typically contain much less water than those of other metals. Some differences in the anion layers occur between the reported naphthalene monosulfonate compounds [ 291 and the disulfonate materials. The monosulfonate anions pack with the long axis of the naphthalene perpendicular to the plane of the layer while the disulfonates have the long axis parallel to the layer. Thus the monosulfonate anion slabs are somewhat thicker. The monosulfonate salts showed some tendency to crystallize in noncentrosymmetric space groups. a useful property for nonlinear optical applications, however the disulfonate salts prepared so far have all been centrosymmetric. The disulfonate compounds form structures with open spaces containing uncomplexed water molecules to a greater degree than monosulfonate salts. This raises the question of whether other molecules could be included in the lattice and if such guest species would have any effects on the structure of the salt. Experiments addressing this issue are in progress. 5. Supplementary
material
Complete tables of bond distances and angles have been deposited with the Cambridge Crystallographic DataCentm. 12 Union Road, Cambridge CB2 1EZ. UK. Additional crystallographic data can be obtained from the authors (P.J.S.). Acknowledgements The support of the Herbert H. and Grace A. Dow Foundation. The Dow Chemical Company Foundation and Central Michigan University in the establishment of the CMU X-ray Crystallography Laboratory is gratefully acknowledged. The Center for International Education and College of Arts and Sciences at Central Michigan University provided funding to support SND’s stay at CMU. References [I] M. Thompson, Chcm Mater.. 6 (1994) 1168. [2]G.Cao.V.Lyttch.J.SwinneaandT.Mall0uk.lnorgC~m..29(199O) 2112.
Chimica
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243
131 G. Cao and T. hawk. fmwg. Chcm.. 30 (1991) 1434. [4] K.Frink.R.Wat&J.C&ttmtdA.fIka&M,/w~.C~m..3O(1991) 1438. IS] Y. Zbaag and A. Ckarlkkl. Inorg. Ckem.. 31( 1992) 2821. ]6] R.Weng.Y.Zhan&H.He,R.FrsoHo+edA.Ckrrhdd.C~Morcr.. 4 (1992) 864. f7] G. Httm. A. Jacahsm I. Johnson and D. G&tmt, Chem. Muter.. 4 (1992) 661. [ 81 G. Albetti. M. Casciil9. U. Costmaiao. A. Rx&o ad E. SolidState kmics. SO (1992) 315. [9]G.Albeni.M.CsrciolaM.PalombnriandA.Pcnio 58 ( 1992) 339. [IO] G. Cao. R. HausMter and K. .%&ma&, Inorg. Cb.. 32 ( 1993) 127. [II]Q.ChcnJ.Sal~~J.Zubiap.Inorg.C~m..~(1993)4485. [ 1211. Le Bidea, 9. Bujoli. A. Jousnaesra. C.Payat,P.PalvadeassadJ. Rouxel, Inorg. Chem.. 32 ( 1993) 4617. [ 131 D. Poojaty, H. Hu. F. Cam@eU and A. Cbfidd, Acra Cryabgr.. Sect. B. 49 ( 1993) 9%. II41 M. Lutz aud G. Mulkr. Iwg. Chinr Acro.232 ( 1995) 189. 1151 V.Scghmonian.Q.Chcw,R. H&tt.&b~J.Ztd!iC@~gCt%C7M ht. Ed ERgI.. 34 ( 1995) 223. [ 1611. Le Bii. C. Payeat, P. Falvadeau atd B. Bttjoli. fmwg. Cfmm..33 (1994) 4885. [ 171 K. Ibfzda, 1. Akimoto. Y. Kiyozwtd and F. Mindat& J. ckrrr S&z., them. c( 1995) 1033. [18]S.DNmel.P.Jaav~.DD.DeaiaudrtldB.Bajdi.J.CAcnr~.CAarr commnn. (1995) 1051. [ 191 D. Pwjaty, D. Gmhoi and A. tZle&cld, Angm. C/tea ha Ed Et& 34 (1995) 1508. [20] A. ckarfietd, 1. Waa~. Y. Two. E. stein and C. Bbatdw& 1. S&f State C&m.. 117 (1995) 275. [21] Q. Hue. D. Margoksc. U. Cii D. Demadt, P. Fat&T. Gia, P. Siga. A. Fd. 8. Chmelka F. SchttUt attd G. Stecky, C&m. Marer...6(1994) 1176. [U] S. Marder, 1. Perry and C. Yakymyskyn Cbt. Mer.. 6 (1994) 1137. [23] V. Russell. hf. Etter and M. Ward. CRcm. Mater., 6 (1994) 1206. ]24] 1. Steed. C. Jobsott. C. Banes. R. Jwteja 1. m S. R&y. R. Hdlis. P. Smith sad D. Clark, 1. Aa Cbaa Sac.. 117 (1995) 11426. [U] E. Kasnic, E. McClymutt. R. Hoddu attd P. Sqawito. Inog Cl& Acm, 2oI( 1992) 143. [26] A. Shubacll. E. Kosnic attd P. Sqwtbito. fnor& C&a Acts. 216 (1994) 101. ]27] 9. Gwkmmn and P. Sqtwtito. Iaorg. Ckem.. 33 ( 1994) 2924. [ 281 P. Squatttito. AC& CrusroUogr.. Seer. C. 51( 199% 1282. 12.919. Gundeaun and P. Squawto, fnorg. them.. 34 ( 1995) [M] [email protected]. shuctutcCorpontioa.TltcWoodbads.TXUSA.1988. [31] TEXSAN, Ttwaystrw~analyti~~ge.Vvcrdoa5.0.~ smtcturecorpontDMa.ThewoodLpdsTx.uSA.1991. [32] D. Cattd 1. Waber. Issawbml Tables jbr X-my Crystallogrqshy. The Kyttoch Ress, BinniagaaaS Esgtsd 1974. Vol. tV. Tabbz 2.2A. [33] D. Cmtwr. Iiuematiomzl Tabks for X-my Cw. lk Kynocb Press. Bimtin@attt. Eitplattd. 1974. Vol. Iv. Table 2.3.1. [ 341 W. %chw&m. Acm CryssnuOer.. Sect A. 24 ( 1968) 212 [ 351 C. Gi, 1. &I. CrJlsMuog.. 17 ( 1984) 42. [ 361 P. Beutskuts. DIRDIF: Direct Methis* Difemwe Stxmtzs, 1~ automaticglmccdaforpbarecxtensionrudrrsscrsepofdarcrrrre suochne f’actm, Teck Rep. IWI, w Laba~ny. Toutuwivcki, 6525 ED Nijmcsm. Ned&?&. 1984. ]37]F.A.Cottor~L.Daai&.C.MtttilbantlJ.Qtw&~..m..32 (1993)4861.
246
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[ 381A. Shabnell andP. Sqaatbito. AcraCryskzllogr Sect. C, SO ( 1994)1296. [39] H. ManoharandS. Ramaseshan. 2 Krisrallogr.. 119 (1964) 357. [40] V. ShakeriandS. HaassuN.2 KrismlIogr., 198 (1992) 297. 1411S. Resio.J. Londo. B. Ganderman.M. Leonardand P. Squattrito, unpublishedresults. [42] D. Poojary,B. Zhang.P. Bellinghaasenand A. Cleartield.lnorg. Chem., 35 (1996) 4942.
Chrmica
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[431 C. Couldwell.K. Prout,D. Robey.R. Taylor and F. Rossotti,A~ro Ctystallogr..Sect.E. 34 (1978) 1491. [Ml Y. Ohki. Y. Suzuki.M. Nakamura.M. Shimoiand A. Ouchi. Bull. Chem. Sot. Jpn.. 58 ( 1985) 2968.
[451 Y. Ohki. Y. Suzuki.T. TakeachiandA. Ouchi.Bull. Chem SOC. 61 (1988) 393. [461 P. Statynowicz.Acra Crysfallogr.. Seer. C, 48 ( 1992) 1414.
Jpn.,
Chimica
Acta 258 ( 1997) 237-246
Structuralchemistry of naphthalenedisulfonate salts Brian J. Gunclerman ‘, Ian D. Kabell a, Philip J. Squattrito &*, Sure&a Received
12 July 1996, accepted
15 October
N. Dubey b
1996
Salts of naphthalenedisulfonrte anions with several different metal cations have heen crystallized and their stmcmms (H,HC,~H,(S0,)2),.4H,0: triclinic, space groupP1, Z= 1. o=- 12.779(3). b= 12.984(4). c y= 114.58(2)3 V-803.8(4) A3.R(F)==0.038 for 269 variables and 2305 observations (I
b-6.874(5), c=21.509(4) A, cobalt analog of the nickel corn anions in which the aromatic tin are between these layers and se coordinated octahedrally to six water molecules with no direct coordination to the suifonate oxygen atoms. The sodi three sulfonate oxygen atoms andthree water moleculesin a somewhatdistorted octahedron.The barium cation is of two sulfonate oxygen atoms and six water molecules. The coordination trends and layering patterns of these those of previously repotted monosulfonatesalts. Keywords:
Crystal
struc~ums;
Sulfonate
salts; Nickel
complexes:
Barium
compleaes;
1. Introduction Compounds with structures composed of alternating inorganic and organic layers have been of interest in recent years for their potential to act as host structures forvariouschemical processes [ 1]. Among the most widely studied have been metal phosphonate salts of the general formula M(OxPR) . xHzO in wi 7 is an aliphatic or aromatic organic group. The oxygen ,.oms of the phosphonate group coordinate to the metal ion, sometimes along with some water molecules. Most commonly, a two-dimensional metal-oxygen-phosphorus framework is formed [2-141, though chains and three-dimensional structures are also known [ B-191. In all these materials. the R groups act as spacers between the inorganic parts. The resulting structures have rigid covalent inorganic frameworks separated by weakly interacting organic domains. The use of different organic groups alters the size * Comspondiag
author.
0020.1693/97/$17.00 0 1997 EIsevier PllSOO20-1693(96)05534-X
Science
.%A. All rights msewed
Sodium complexes
and nature of the organic region, and hence the physical properties of the mater% In particuhu, the in of polar or ionic Rmctional groups on the organic moiety offers the potential for size- and shape-selective ion-f~xcbange or intercalation. Sulfonation of the attempted in the past to create ion those found in inorganic layered conimo phosphate [ 201. Moreover, selves are widely used industrially as surfactants and dyes. Recently, they have been studied as potential liquid crystalline [21] and no&ear optical materials [22J3], and as complexing agents in the form of sulfonated macmcycfes [ 241. We have undertaken asystematic of metal organosulfonate salts 125-29 structuraltrendsthatmaypmvideinsi cations for this class of compounds. Previously. metal benzenesulfonate [25-281 and napbthalenesuffonate [29] salts have been examined. As an extension of this study, we have synthesized and structurally characterized salts of two iso-
238
B.J.Gundermanet al. /Inorganica ChimicaActa 2S8(1997)237-246
merit disuifonated naphthalenes, 3-aminonaphthalene-l,Sdisulfonate (I) and 6aminonaphthalene- 1,3disulfonate (II) (Scheme 1). The compounds were prepared by metathesis reactions of the metal chloride or nitrate with the sodium sulfonate salt in aqueous solution. We report here the structures of these compounds and discuss their relationships to each other and to previously reported sulfonates.
2.1.3. Na,(HflC&Is(SO,),)* SHzO A 1.00 g ( 1.73 mmol) sample of disodium 3-aminonaphthalene-1 &disulfonate was dissolved in 50 ml of water with heating and stirring. To the brown solution was added 0.010 g (0.25 mmol) of NaOH, which dissolved quickly raising the pH of the resulting solution to about 7. The solution was allowed to stand in an open container until the solvent had completely evaporated. A total of 0.65 g of brown needle-like crystals were recovered, an 86% yield based on themaction2Na” +H2NC,eH,(SOs)22+5H2b*Na2(H2NC,&(SO,),) .5H20. Awl. Found: C, 24.81; H, 4.20; N,
2. Experimental
2. I. Syntheses 2.1. I. [Ni(HzO),l{H,NC,d-r,(SO,),),. 4H,O A 4.01 g (6.93 mmol) sample of disodium 3-aminonaphthalene-1,5disulfonate (Eastman, technical grade 60%) was placed in 200 ml of distilled water. The mixture was heated and stirred until the solid dissolved completely to form a clear brown solution. Then, 1.65 g (6.94 mmol) of NiCla.6HaO was added to the solution. The resulting solution, brown with a slight greenish tint, was set out at room temperature in an open container. Upon evaporation of the water, a mixture of large, clear light brown flattened needleshaped crystals and small darker brown clumps of fine needles formed. The larger crystals, which are the nickel salt, were separated by hand from the smaller crystals, which are a reported sodium 3-ammonionaphthalene-l ,S-disulfonate salt [ 291. A total of 2.24 g of nickel sulfonate crystals were recovered, a 76% yield based on the reaction Ni*” + 2HaNCteH,(SO~)a*+2Ha0++8HaO+ [Ni(H,O),](H3NCu,H~(S03)2)2~4H20. As no acid was added to this reaction, we assume the natural acidity of the transition metal cation led to the protonation of the amine group on the anion. Anal. (National Chemical Consulting, Tenafly, NJ) Found: C, 27.13; H, 4.04; N, 2.80. Calc.: C, 28.48; H, 4.30; N, 3.32.
A 4.00 g (6.91 mmol) sample of disodium 3-aminonaphthalene- 1.5disulfonate was dissolved in 200 ml of water with heating and stirring. To the brown solution was added 1.65 g (6.93 mmol) of CoCl, . 6H20 which dissolved leaving the color unchanged. The solution was allowed to stand at room temperature in an open container. After the water bad evaporated, a product distribution similar to that of the mckel reaction was obtained. A total of 2.46 g ( 84% yield) of brown crystals of [Co(H,O),] (HSNC,~H,(S0,)2)2.4H20 were isolated.
2.2. Crystallographic
studies
All of the single-crystal X-ray diffraction measurements were done at room temperature on a Rigaku AFC6S fourcircle diffractometer (graphite-monochromated 2.0 kW MO Ka X-ray source; A = 0.7 1069 A> operated by the MSCAFC Diffractometer Control software [ 301. All crystals were cut from larger fragments and were mounted on glass fibers with silicone cement. Unit cell parameters were obtained by indexing 25 reflections found during a search of reciprocal space and were refined by a least-squares analysis of the setting angles of 19-21 reflections ( 18’< 28(Mo Ka) < 50“) in which the appropriate cell angles were constrained to 90”. Intensity data in the range 3-50” 28 were collected with ~28 scans of 8” mitt- ’ for the nickel crystal and w scans of 4” min - ’ for the sodium and barium crystals. Reflections were measured at a constant scan rate with multiple scans (up to four) for weaker data (those withZ< low(Z)). The intensities of three standard reflections measured after every 150 data showed no significant variations. All crystallographic calculations were performed on a VAXStation 3100/76 computer with the TEXSAN [31] series of programs. Atomic scattering factors [ 321 and anomalous
B.J. Gunderman
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Acta 258 (1997) 237-26
dispersion terms [ 331 were from standard sources. Datawere corrected for Lorentx and polarization effects. A secondary extinction correction [34] was made for the data of the Ni compound, while the data of the Ba compound were corrected for both absorption ( 9 scans) and extinction. Space groups were assigned either uniquely based on systematic absences (Z&n, O&Z.n, Z&O,h+k+2tr, hOZ,Z+2n), by acombination of systematic absences and intensity statistics ( CWc. Z&Z, h +k# 2n. hOI, I# 2n). or by intensity statistics alone (Pi), and were confirmed by successful refinements. The structures were solved by direct methods: MITHRIL [35] for the heavy atoms (Ni. Ba, S and Na) and I?H?LX!J [36] for the lighter non-hydrogen atoms (0, N and C). Most of the hydrogen atoms were located on difference electron density maps and their positions were refined in the Ni and Ba structures. Hydrogen atoms were included as fixed scatterers for the Na compound. The B,, value of each H atom was set at 1.2 times the Bog value of the attached atom at the time of its inclusion. Final refinements included anisotropicdisplacement parameters for all non-hydrogen atoms and were performed on those data having Z>3a(Z). There were no unusual variations in F,,- F, as a function of (sin 6) /A, Miller indices, or F,. Crystallographic data for the three compounds are summarized in Table 1. Final positional and equivalent isotropic displacement parameters are listed in Table 2.
Empiricalformula Formulaweight Ctystai system a (A)
b(A)
c(A) a (9 B (9 Y0 V(P) SP=egroup zvahle Du* (8 cm-‘) WOO) c (cm-‘) Transmissionfactors l?.mmiua coefficient Pemngefordata(“1 Detacoketed Totaldata Numberof uniquedata RI, Numberofdata/>3cr(/) Numberof variables RU3:R.V~ (I>3o(I)) Goudaessof fit LarpestpeaksinfinaiAF(eA-3)
Cd%&hWi 843.43 tlichic 12.779(3) 12.984(4) 5.473(1) 102.17(2) 89.65(2) 114.58(2) e3.8(4) PI (No. 2) 1.73 438 9.45 EiX IO-’ 3-H) +h. ctk. *I 2956 2818 0.049 2305 269 0.038;0.040 2.18 057; -0.45
monoclinic 25.864(3) 6.874(S) 21.509(4) 90 116.825(IO) 90 3412(2) CL/c (No. IS) 4 1.79 1864 14.83 0.82-1.00 0.246x lo-” 3-m +h. +L *I 3359 3218 0.028 2249 274 0.028;0.029
I.70 0.90; - 0.62
12.755(4) 5.890(3) 23203(3) 90 90 90 1743(I ) F&n (No.60) 4 1.67 904 3.95 mme izi +h.
4-L. +1
1817 1817 ET 123 0.04%0.046 2.19 0.31: -0.33
B.J. Gunderman
Table 2 Positional Atom
ef ai. /Inorganica
S(2) O(2)
O(I)
O(3) O(4) O(S)
O(6) ‘38)
O(7)
O(9) O( IO) O(ll) N(l) C(l) (32) C(3) C(4) C(5)
‘36)
C(7) C(8) C(9) C(lO) H(l)
H(2)
H(3) H(4) H(5)
H(6) H(7) H(8) H(9) H(l0) H(ll)
W12) H(13) H(l4) H(15) H(
16)
andequivalentisotropicthermalparameters
x
Y
O(2) O(3) Or41 O(5)
O(6) Nb C(l)
C(2) C(3) C(4) C(5) H(1)
H(2)
0 0.20556(9) 0.3202!(S) 0.1213(3) 0.3257(2) 0.1826(3) 0.4116(2) 0.2041(2) 0.3360(2) 0.0818(3) -0.1647(3) -0.0032(2) 0.4193(S) 0.3433(4) OAid8(3) 0.1943(3) 0.3385(3) 0.4020(3) 0.3969(3) 0.3239(3) 0.1762(3) 0.1116(3) 0.1202(3) 0.2626(3) 0.2542(3) 0.528(3) 0.435(3) 0.523(3) 0.339(3) 0.439(3) 0.167(3) 0.063(3) 0.078(3) 0.114(3) 0.055(4) -0.211(4) -0.181(4) -0.064(3) 0.038(3) 0.408 0.351(6)
0 0.76607(9) 0.32321(8) 0.7581(2) 0.8349(2) 0.8057(3) 0.3389(2) 0.2.526(2) 0.281312) -0.0546(3) -0.1046(3) - 0.1183(2) 0.0501(4) 0X1428(4) 0.7522(3) 0.6232(3) 0.6876(3) 0.6610(3) 0.5497(3) 0.4637(3) 0.3995(?) 0.4245(3) 0.5376(4) 0.6007(.3) 0.4858(3) 0.813(4) 0.783(3) 0.728(3) 0.759(3) 0.534(3) 0.324(3) 0.370(3) 0.554(3) -0.104(3) -O&9(4) -0.144(4) -0.138(4) -0.162(3) -0.155(3) 0.067 0.052(6)
NaAHJ’JC,,Ps(SO,M s 0.5799(l) Na O(l)
Acfa 258 (I 997) 237-246
Table 2 (continued) parameters
Atom
.?
fNitHP),1(H~NCldtStSO~)~)~.4H~0 Ni S(I)
Chimica
0.8228(2) 0.4762(3) O&07(3) 0.6055(4) 0.6974(3) 0.8008(4) 0.6866(9) 0.5719(S) 0.6293(5) 0.6236(S) 0.5582(5) 0.5025(5) 0.693 0.552
.5H
0 0.1916(2) -0.2133(2) 0.3360(5) 0.3294(5) -0.0549(5) --0.3409(5) -0.3702(S) 0.0328(5) -0.2148(5) -0.2127(5) 0.2592(5) 0.056(l) 0.5762(9) -0.3879(7) 0.1432(7) -0.1264(7) -0.2604(7) -0.2843(7) -0.1682(7) 0.0980(7) 0.2330(8) 0.2583(8) -0.0022(7) -0.275(7) -0.499(7) -0.459(7) -0.116(6) -0.387(6) 0.086(7) 0.330(7) 0.349(7) -0.157(7) -0.363(8) -0.138(g) -0.325(g) 0.275(7) 0.280(7) -0.107 0.12(!)
1.84(2) 2.32(3) 1.85(3) 3.2(l) 3.1(l) 3.5(l) 2.9( 1) 2.4(l) 2.5(l) 3.1(l) 2.7(l) 2.3(l) 10.6(3) 9.4( 2) 2.3(l) 2.0(l) 2.0(l) 1.8(l) 1.9(l) 1.7(l) 2.3(l) 2.5(l) 2.5(l) 1.7(l) 1.8(l) 3.0 2.6 2.6 2.3 2.3 2.8 2.9 3.0 3.4 3.4 3.0 3.0 2.6 2.6 12.3 II.3
120 0.0290(3) -0.0173(S) -0.019( I ) -0.1114(8) 0.2677(8) -0.2168(g) -0.292(l) -0.127(l) -0.503(2) -0.064(I) -0.252(l) -0.344(l) -0.240(l) 0.046(l) -0.340 -0.326
0.64166(7) 0.2116(l) 0.6666(2) 0.6684(2) 0.6415(2) 0.2775(2) 0.3831(2) 114 0.4809(S) 0.5687(3) 0.5538(3) 0.4972(3) 0.4575(3) 0.5281(3) 0.582 0.420
2.25(S) 2.7(l) 3.0(2) 2.6(2) 3.3(3) 2.7(2) 5.1(3) 4.1(4) 3.5(6) 2.2(3) 3.0(4) 3.0(4) 2.7(4) 2.1(3) 2.8 3.1 wnrinued)
H(3) H(4) H(5)
.?
x 0.733 0.655 0.995
[ W WW BZl S(l)
S(2) O(I) O(2) O(3) O(4) O(5)
O(6) O(8) O(7)
O(9) O( 10) O(11) N(1) C(l)
C(2) C(3) C(4) C(5)
C(6) C(7) C(8) C(9) C( 10) WI)
H(2)
H(3) H(4) H(5)
H(6)
H(7) H(8) H(9) W 10) H(ll) W H(l3) H(14) H(l5) W W 17)
12) 16)
-0.268 -0.107 -0.041
oHs(S~I)Z)Z(HZ~)~I~~H~O l/2 0.25675(7) 0.34887(5) 0.0231(2) 0.11629(5) 0.0198(2) 0.3875(l) 0.1695(5) 0.3747(l) -0.1704(S) 0.3261(l) 0.0756(S) 0.0720(l) O.OlOO(6) 0.1154(l) 0.1998(4) 0.1166(l) -0.1509(4) 0.4995(2) -0.0977(6) 0.4323(2) 0.X63(6) 0.4811(2) 0.3570(8) 0.3023(2) 0.4878(6) 0.4970(2) 0.1425(8) 0.3092(2) -0.0216(6) 0.2882(2) 0.0127(6) 0.2343(21 0.0205(7) 0.1844(2) 0.0169(7) 0.1888(2) 0.0088(7) 0.2491(2) -0.0062(7) 0.3024(2) -0.0166(6) 0.3533(2) -0.0202(7) 0.3496(2) -0.0129(7) 0.2953(2) -0.0004(6) 0.2441(2) O.OOOl(6) 0.231(2) 0.026(6) 0.160(2) 0.004(6) 0.216(2) 0.002(6) 0.387(2) -0.031(6) 0.383(2) -0.023(6) 0.330(2) -0.152(6) 0.330(2) 0.081(6) 0.277(2) -0.017(7) 0.498(2) -0.092(8) 0.470(2) -0.129(8) 0.411(2) 0.633(8) 0.444(3) 0.645(8) 0.452(2) 0.339(8) 0.505(3) 0.37(l) 0.329(2) 0.391(8) 0.316(2) 0.601(8) 0.526(3) 0.06( 1)
C’ 0.315 0.287 0.287
3.1 3.1 4.6
314 0.71259(5) 0.56205(6) 0.7082(2) 0.7257(2) 0.7603(2) 0.4906(2) 0.5973(2) 0.6026(2) 0.8220(2) 0.6762(2) 0.8611(2) 0.2375(2) 1.0488(2) 0.3759(2) 0.6281(2) 0.6253(2) 0.x04(2) 0.4999(2) 0.4377(2) 0.4403(2) 0.5037(2) 0.56.51(2) 0.5603(2) 0.5010(2) 0.666(2) 0.463<2) 0.396(2) 0.502(2) 0.606(2) 0.374(2) 0.374(2) 0.342(2) 0.861(3) 0.794(3) 0.694( 3) 0.669(3) 0.873(3) 0.895(3) 0.242(3) 0.247(3) 1.063(4)
1.98(2) 1.91(4) 1.88(4) 3.2(l) 3.3(l) 3.0(l) 3.7(2) 3.1(l) 2.6(l) 3.4(Z) 3.9(2) 5.3(2) 3.6(2) 6.2(2) 2.0(2) 1.4(l) l.7(2) 1.5(2) 1.7(2) 1.7(2) 1.7(2) 2.0(2) 1.8(2) U(2) 1.5(l) 2.0 2.0 1.9 2.3 1.9 2.1 2.1 2.1 3.7 3.7 4.3 4.3 5.4 5.4 4.1 4.1 7.3
‘B,=~4~3~~o2P,,+b’&~+~*~,+~~bcosy~~,~+(2ac~~~~)~,,+ (~cos~~h,l. boccupivlcy=0.5.
The compound adopts a structure in which layers of anions alternate with layers of cations. Each anion layer contains a single plane of cofacial naphthalene rings sitting vertically so that the SO,- and NH,+ groups are directed to opposite sides of the layer. The position of the ammonium group is inverted on adjacent anions. Between the anion layers are the hexaaquanickel cations. The layers are held together by a strong networkof N-Ha*-OandO-Ha a. hydrogen bonds involving the ammonium, water and sulfonate groups (Table 5). This
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Acta 258 (1997) 237-246
Table3 Weeted bonddisra~~~~(A)
~N~~H~O),I(H,NC,~JI,(S~)~)Z.~HZO Pig. I. ORTEP diagramof the molecularsbuctme of [Ni(H,O),](H,NC,~s(SO~),),.4H, showingatom labellingscheme.Symmetry equivalentwatermoleculeshavebeenincludedfo showtheoctahedralcoor-
figuresareshownat the50%probabilitylevel.exceptfor theseof hydrogen whichareshownasisotmpicspheresof arbitrary size. structural motif is typical of transition metal sulfonate salts. Due to the 2: I stoichiometry and the large size of the anions, there are holes in the cation layer which are occupied by the two free water molecules. It is evident from the displacement parameters of the oxygen atoms that these water molecules are rather loosely bound in these sites. The presence of channels containing uncomplexed water distinguishes these compounds from most of the benzenesulfonate salts we have studied [ 25-281. The cobalt analog is isostructural (unit cell dimensions u= 12.750(3), b= 12.981(4), c=5.501(2) A. a= 102.16(3)q /3=89.56(3)“, y=114.63(2)3 +805.6(S) A’), indicating that this is a general structure type for the divalent first row transition metals. 3.2. Na,(HflC,,,H&O&~SH,O The molecular structure is shown in Fig. 3 while a packing view of the unit cell is presented in Fig. 4. Important bond distances and angles are given in Tables 3-5. This compound is the dibasic salt of the parent disulfonic acid. The amine group is not protonated. The asymmetric unit contains one cation, half of an anion and two and a half water molecules. The anion sits on an inversion center which forces the amine group to be disordered between two equivalent positions. The N atom was included at half-occupancy in the refinement. Consequently, the amine H atoms could not be located and the C-N distance is anomalously short. Otherwise, the geometry of the anion is similar to that observed in the nickel salt. Of the five water molecules in the empirical formula, four are
Ni-O(7) N&O(8) N&O(9)
S(1)-al) St 1 S(IkO(3)
ko(2)
Na2WJ-GWXM2) s-o(l)
s-o(2) g-O(3) s-c(l)
N+W) M-W)
2.038(J) 2.075(3) 2.061(3) 1.450(3) l&5(3) 1.454(3) .SH,O 1.472(4) 1.459(4) 1.444(51 1.781(6) 2.421(5) 2.415(6)
S(l)-al)
WbOW sCO-a5) %WW) s1wa5) N(lbC(3) Na-O(3) Na-o(4) Na-O(4)
Na-a6) N-c(3)
IB~(H~NC,~S(~~)~)Z(HZ~)~I-~HZ~ 2.698(3) Ba-CNl) .%1)-c(I) Ba-O(7) 2.891(4) s(2)*(4) 2.759(4) BaQ(Q 2.736(4) Bit-a(9) 1.450(3) S(lbo(l) 1.458(4) s(tbo(2) N( 1.442(3) S(lbO(3)
sc?)-a5) WMW) SCW.X3) IF36)
1.7n7(4) l&44(2) 1.793(3) l&g(4) 2376(S) 2-W) 2.353(5) 2.513(3) 1.%1)
1.789(4) l.446(3) 1.779(4) 1.472(S)
attached to sodium cations and one is free. All of tbe H atoms on the coordinated water molecules as well as those on the carbon atoms were located, though their positions were not refined. The sodium cation is in a fairly regular oc&edml coordination of three water molecules and three oxygen atoms from different anions. The presence bonding between the cation and sulfonate group is collsistent with what we have found in other Often. the sodium coordination en in oxoanion salts, but modestly dis that reported here have been observed in several sodium sulfonates [25.26.28.29]. In these structures there is ao clear distinction between the Na-O%and Na-O~distaaces as the ranges (2.293(6)-2.555(6) and 2.353(S)2.696(6) A, respectively) overlap. The Na-0 distances in the present compound are consistent with this observation. It
242
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et al. /Inorganica
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Acta 258 (1997) 237-246
Table4 Sekcteu
Lxmd angles (9
[Ni(H,O),I(H,NC,~H,(SO,),),.4H;O O(7)-NiXI@) 93.5(l) 94.4(l) 0(7)-N&O(9) 0(8)-N&O(9) 86.2(I) 112.6(2) O( 1)-a 1 113.2(2) O(I)-%~)-o(3) 106.7(2) 0(1)-%1)-C(1) 111.2(2) O(2)-% 1W(3) 105.4(2) 0(2)-q I bet 1) 107.1(2) 0(3)-.9(1)-C(l) 112.2(2) 0(4)-S(2)*(5)
)-o(2)
NMWCIOHS(SO~)Z) O( 1 0(1)-S-O(3) 0(1)-S-C(1)
G-o(2)
OG!)-S-O(3) 0c9-s-c( I) 0(3)-S-C(1) O(2)-Na-O(2) O(2)-Na-O(3) O(2)-Ne-O(4) 0(2)-N&(4) O(2)-Na-O(6) O(2)-Na-O(3)
.5&O 111.0(3) 113.0(3) 105.3(3) 113.2(3) 105.7(3) 108.0(3) 100.7(2) 81.5(2) 81.6(2) 86.6(2) 174.7(2) 104.0(2)
0(4)-.%2)-O(6) 0(4)-S(2)-C(5) 0(5)-%2)-o(6)
O(5Pww35) 3(6bWbC(5)
SC1)-C( 1)-C(8) S(I)-aI)49)
SW-W)-c(4) SG+W)~:(lW
0(2)-N&O(4) O(2)-Ne-O(4) O(2)-NttO(6) O(3)-Nti(4) 0(3)-N&O(4) O(3)-Ne-O(6) 0(4)-N&O(4) 0(4)-N&O(6) 0(4)-N&O(6)
S-c(~Mxo
S-aI)-w)
IBa(H,NC,,H,(SO~)2)2(H,0),1 .4H20 O(l)-Be-O(l) 1X3(2) O( 1)-S( 1W(2) 74.1(l) 0(1)-B&(7) O(l)-S(lkO(3) 0(1)-B&O(7) 84.2(l) O(l)-S(I)-C(l~ 70.7(1) 0(1)-B&O(8) O(2)-% 1)-O(3) Of 1)-B&O(8) 132.3(1) 0(2)-S(l)-C(l) O( I )-Be-O(9) 75.9(l) 0(3)-S(l)-C(l) O( 1)-B&(9) 110.9(I ) 0(4kS(2)-0(5) O(7)-Be-O(7) 65.1(2) 0(4)-S(2)-O(6) O(7)-Be-O(8) 143.5(l) 0(7)-B&O(8) 119.8(1) O(7)-Be-O(9) 72.4(I) 0(7)-B&O(9) 136.6(1) O(8)-Ba-O(8) 79.0(2) s(lw(lba2) O(8)-Be-O(9) 89.5(2) S( 1)-c( 1)-C(9) 0(8)-B&O(9) 67.7( I) O(9)-Be-O(g) 150.8(2)
0(4bWkC(3) OW-WbO(6) O(5bWkW) O(6bWbCW WMX3bW) S(2)43)-c(4)
114.2(2) 10X9(2) 111.5(2) 105.1(2) 107.2(2) 117.5(3) 120.8(3) 116.1(3) 122.5(3)
83.4(2) 163.9(2) 80.5(2) 162.5(2) 91.3(2) 93.2(2) 83.5(2) 103.7(2) 93.6(2) 117.2(5) 121.2(S)
112.1(2) 112.8(2) 106.0(2) 113.0(2) 106.0(2) 106.3(2) 113.7(2) 112.6(2) 107.2(2) 111.7(2) 105.6(2) 105.3(2) 116.9(3) 121.8(3) 116.9(3) 122.2(3)
appears that the sodium ion does not exert a strong directing influence on the structure in order to form a regular coordination polyhedron. but rather fits into holes in the packing of
the large sulfonate anions. This compound also forms a layered structure with slabs of anions sandwiching cations and water molecules. The aromatic rings are approximately perpendicular to the plane of the layer and the sulfonate groups are on the faces of the layer. Within the layer there are columns of anions running parallel to the b axis. In each column the rings are cofacial. The columns are related along the a axis by mirror symmetry so the naphthatene grout~s of adjacent columns are canted rather than parallel. The SOa- groups on adjacent columnsahemate between being on the upper side or the lower side of the layer.
Fig. 3. ORTRP diagramof the meleculatstmctme of Naz(HINC,cHs(SO,),) 95H,Oshowingatomlabellingscheme.Symmetryequivalentwater moleculesandsulfonek 0 atomshavebeenincludedto showthedistorted octahedralenvimnmentof theNa+ ion. The amine N etomis dismdeted betweentwo sitesrelatedby invenionthroughthecenterof thenaphtbelene unit.
The sodium ions are near the neighboring SOa- groups so that they too alternate positions within the layer. This is a different arrangement than in the nickel salt, in which the anions within a layer are all parallel to one another, the sul-
fonate groups are evenly spaced and the metal ions are both evenly spaced and coplanar. A feature common to the two structures is the presence of holes, in this case between the pairs of widely spaced SOs- groups, filled by uncomplexed water molecules. The structure of the monobasic salt Na(H,NC,&(SO,),)~HzO is also known [29]. The ammoniodisulfonate anions stack in cofacial columns, but with the sodium ions and attached water molecules interspersed in such a way that segregated organic layers are not formed.
The molecular structure is depicted in Fig. 5 and the unit cell is shown in Fig. 6. Bond distances and angles may be found in Tables 3-5. This compound is compositionally analogous to the nickel salt. in that it contains a divafent cation, two protonated ammoniodisulfonate anions, and ten water molecules. The anion used in this case is 6-aminonaphthalene-13-disulfonate, an isomer of the anion in the previous compounds. It was selected because crystals of the barium 1,5-disulfonate compound were not readily obtained and we were interested to see whether the barium ion would be chelated by oxygens from sulfonate groups in the 1 and 3 positions. The barium ion is bonded to six water molecules and
E.J. Gundennan .?I al. /Inorganica
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243
Acta 258 (1997) 237-244
Table5 SeIectedhydrogenbondingintemctions(A. “) D
H
A
[Ni(H~O),l(H~NC,dWgO~)~)~~4H~O N(I) H(l) O( 10) N(I) O(4) N(I) H(3) D(7) H(9) O(3) O(9) D(7) W 10)
H(2)
O(2)
O(8) OW
Wll)
O(6)
D(9) O(9)
H( 13) W 14)
I-U12)
O(5)
O(5) O(I)
Na2~H,NC,J4H,(S03)2) .SH,O O(4) H(3) O(5) O(I) D(4) H(4)
[Ba(H,NC,,H,(SO,),),(H,0),1.4H,O N(I) H(6) O(6) N(l) N(l) D(7) D(7)
O(8) O(8)
O(9) D(9)
O( 10)
O( 101
H(7)
H(8)
H(9) W 10) WII) W
12)
H( 13) W 14) W 15) H(
16)
O(5) WIO)
O(11)
O(2) O(2) D(7) O(6) O(4) O(2) O(3)
d(D...A)
A@ (D-H...A)
1.91(4) 1.88(4) 1.91(4) 1.76(4) 2.05(4) 2.02(4) 2.11(4) 1.89(4) 1.83(4)
2.774(6) 2.809(4) 2.805(4) 2.665(4) 2X47(4) 2.780(4) 2.794(4) 2.655(4) 2.667(4)
159(4) 167(3) W(3) 176(4) !74(4) l62(4) lW5) 170(4) l76(4)
1--x, l-y. -z ry,r-I I-x.1-y.-I-r x- 1.y.r
0.81
1.84 2.12
2X58(6) 2.917(6)
167 I51
LY.Z I-x. -y. l-z
lM(4) 0.90(4) 0.84(4) 0.86(5) 0.76(5) 0.92(5) 0.67(5) 0.91(5) 0.72(6) 0.93(5) 0.84(S)
1.83(4) l.%(S) 1.98(4) 1.92(S) 2.24(5) 1.94(5) 2.25(6) 2.06(5) 2.16(6) 2.05(S) 2.24(S)
2.857(Z) 2.831(S) 2.815(6) 2.755(6) 2.986(5) 2.838(5) 2.897(6) 2.%3(5) uw(5) 2.960(6) 3.058(6)
162(3) 161(4) l77(4) l%(5)
112-r -y-IL?, I-r 112-x. 112-y. l-z l/2-ry-l/2 112-z l-r. -y,2-z
&D-H)
d(
O.%(4) O.%(4) 0.91(4) 0.91(4) 0.80(4) 0.79(4) 0.69(4) 0.78(4) 0.&?4(4) 1.03
H...A)
two sulfonate 0( 1) atoms related by symmetry. There is no interaction between the oxygen atoms of the other SOSgroup and the Ba” ion. thus it is not a chelate complex. The geometry is irregular and perhaps best described as a distorted square antiprism. Square-antiprismatic eight-fold coordination of Ba*’ is found in other oxoanion salts such as Ba( OH) 2 * 8H20 [ 391, in which eight water molecules form the coordination sphere with Ba-0 distances ranging loom 2.69 to 2.77 A. In barium 4aminobenzenesulfonate, [Ba(H2NC,&SOj),(H20)] -2.5H20 [40]. the Ba*’ ion is coordinated to eight sulfonate 0 atoms in a distorted cube (Ba-0 range 2.68-3.07 A) with one face capped by a water molecule at 2.83 A. The distances in the present compound (Table 3) show a smaller variation than in the Caminobenzenesulfonate. and the distribution of sulfonate and water 0 atoms in the coordination sphere is essentially reversed. The structural features of the anion are similar to those of the 3aminonaphthalene- 1,S-disulfonate. The SOS- groups are bent sightly towards each other. One oxygen atom on the free sulfonate group eclipses the C-ring (torsion angle 0(4)S(2)-C(3)4(4) 0.7(S)“) while the sulfonate group that coordinates the Ba*’ ion is rotated somewhat relative to the naphthalene unit (torsion angle 0( 3)S( I)-C( 1)-C(2) - 10.7(4)0).TheC-Ndistance (1.472(S) A) isagainindicative of the presence of the ammonium group. All hydrogen
W6)
l66(5) 163(8) 170(5)
l=(8) M(5) 164(S)
&Y.Pl -x. -y.
-z
-x. -y. -1-r -1. -y. -z x-l.Y.2
iY.Z x.y+I.z
I-x.y+1.3/2-z 112-x. 112+y.3/2-z 1/2+x. 112-y. 1/2+z r. -y.z- 112 L I-y.z-I12
atoms except one on 0( 1 I ) were located and theii positions refined. The packing diagram shows that this compound has a htyered structure with many similarities to those of the 13. disulfonate anion. The 6- ammonionaphthaIene-l&disulfonate anions occur as inverted pairs positioned veikally in their layer with the rings cofacial and the s&mate groups on opposite faces of the layer. The Ba*’ ions and most of the water molecules are between the anion layers The cations hold the anion layers together by bonding to st&nategroups in neighboring layers. There is also an extensive network of hydrogen bonds involving the water molecules, NH, + , and SO*-. As m the nickel salt, two of the five crystallogrrtphitally independent water molecules are not bonded to the metal cation, however in this case the ir1ocationsared One, represented by 0( IO). is in the interior of the anion layer where it is hydrogen bonded to the ammonium 8roup. ~eother,representeabyO(ll).sitsinthespacesbetweea the cations in the inorganic layer, as do the uncomplexed water molecules in the nickel sah. The displacement parametersofthelattermolecukindicatesomeenhancedfbeedom of movement, though it is not as pronounced as in the nickel compound. This suggests that the holes in the barium iayer are smaller than those in the nickel layer. As evidence oae may note that the metal-metal distance is 12.98 A between
B.J. Gunderman
et al. /Inorganica
Chimica
Acta 258 (1997) 237-246
Fig. 5. ORTEPdiagramof the molecularstmctute of [Ba(H3NC10Hs(SO,),),(H,O),] .4H,O showingthe atomlabellingscheme.Symmetty equivalentwater moleculesandsulfonate0 atomshave beenincludedto show theeight-foldcoordinationof theBa” ion.
e
’ FI
Fig.4.ORTEPpackingdiagramof Nq( H,NC,Jis( SO&). SH,Oshowing theoutlineof the unit cell.View is alongtheb axis.TheNa andS atomsate shownwith octatttshadingand the Na-0 bondshave beenomitted.The opencircles with noattachedatomsaretheuncomplexedwatermolecules. ions and 11.60 A between Ba*+ ions. Since the metalcoordinated water distances are longer for Ba*‘, the actual amount of space available for the additional water molecules will be a lesser proportion of this separation for the barium salt than for the nickel salt.
Fig. 6. ORTEP packing diagramof [Ba(H,NC,~s(SOs)2)2(H20)61 * 4H20showingtheoutlineof the unit cell.View is approximatelyalongthe b axis. TheBa aad S atomsare shownwith Octaatshading.
Ni*’
4. Discussion The naphthalenedisulfonate salts reported here follow the pattern of the benzene- and naphthalenemonosulfonate salts studied previously [ 25-291 in forming structures with segregated organic and inorganic layers. The anions are arranged with the aromatic rings facing one another and the polar groups directed to the surfaces of the layer. Anions in inverted orientations are interleaved so that alternating anions have the SOs- groups on opposite faces of the same layer. This interleaving is in contrast to the structures of monophosphonate salts [ 2-141 which typically have the anions further
segregated in double layers of opposite orientations. In that sense, the sulfonate structures are denser and the layers are more strongly bonded together, making them perhaps less good candidates for intercalation chemistry. Nevertheless, some sulfonate salts do adopt noninterleaved structures [ 26 28) and others have been shown to convert from interleaved to noninterleaved on dehydration [41]. Recently, several diphosphonate salts have been reported [42] which have single layers of interleaved anions similar to the layers in the disulfonate salts. The trends in coordination behavior of the different metal ions toward the sulfonate groups closely parallels what was found for benzenesulfonate salts [ 25,261. The divalent transition metal ions do not bond directly to sulfonate oxygen atoms in the presence of water. All such salts crystallized directly from aqueous solutions contain hexaaquacations [ 25.26.431. The sulfonate can be forced to coordinate to these metal ions if the water is driven out of the structure. however
B.J. Gunderman
et al. /InorgMico
such materials are very hygroscopic and mhydrate quickly on exposure to humid air 1411. This tendency not to form strong complexes contributes to the efficacy of alkylsulfonates as anionic surfactants in hard water and of polystyrenesulfonates as ion-exchangers. The alkaline earth cation Ba*’ shows a greater tendency to bond to the sulfonate. The coordination spheres of alkaline earths, as well as of trivalent lanthanides, in sulfonate salts typically contain one or two oxygens from SOB- with the balance of the ligands being water molecules [ 2644-461. This is in contrast to the behavior of phosphonates which readily coordinate to these metals in the presence of water [2-141. The Na+ ion forms even more interactions with sulfonate oxygen atoms. Alkali metals [27,29] show the greatest tendency to bond to SOs- , with a majority of the coordination environment made up of sulfonate oxygen atoms. These salts typically contain much less water than those of other metals. Some differences in the anion layers occur between the reported naphthalene monosulfonate compounds [ 291 and the disulfonate materials. The monosulfonate anions pack with the long axis of the naphthalene perpendicular to the plane of the layer while the disulfonates have the long axis parallel to the layer. Thus the monosulfonate anion slabs are somewhat thicker. The monosulfonate salts showed some tendency to crystallize in noncentrosymmetric space groups. a useful property for nonlinear optical applications, however the disulfonate salts prepared so far have all been centrosymmetric. The disulfonate compounds form structures with open spaces containing uncomplexed water molecules to a greater degree than monosulfonate salts. This raises the question of whether other molecules could be included in the lattice and if such guest species would have any effects on the structure of the salt. Experiments addressing this issue are in progress. 5. Supplementary
material
Complete tables of bond distances and angles have been deposited with the Cambridge Crystallographic DataCentm. 12 Union Road, Cambridge CB2 1EZ. UK. Additional crystallographic data can be obtained from the authors (P.J.S.). Acknowledgements The support of the Herbert H. and Grace A. Dow Foundation. The Dow Chemical Company Foundation and Central Michigan University in the establishment of the CMU X-ray Crystallography Laboratory is gratefully acknowledged. The Center for International Education and College of Arts and Sciences at Central Michigan University provided funding to support SND’s stay at CMU. References [I] M. Thompson, Chcm Mater.. 6 (1994) 1168. [2]G.Cao.V.Lyttch.J.SwinneaandT.Mall0uk.lnorgC~m..29(199O) 2112.
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