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Acta Cryst.(2002). E58, m513±m516 DOI: 10.1107/S1600536802015118 Savarimuthu Baskar Rajet al. [Na(C9H6NO4S)]

m513

metal-organic papers

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Metal-binding modes in sulfoxines:

supramolecular network in

(8-hydroxy-quinoline-5-sulfonato-N

1

,O

8

)sodium(I)

Savarimuthu Baskar Raj,a

Packianathan Thomas

Muthiah,a* Gabriele Bocelliband

Rita Ollab

aDepartment of Chemistry, Bharathidasan

University, Tiruchirappalli 620 024, Tamilnadu, India, andbIMEM-CNR, Palazzo

Chimico-Campus, Parco Area delle Scienze 17/a, I-43100 Parma, Italy

Correspondence e-mail: tommtrichy@yahoo.co.in

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.031

wRfactor = 0.091

Data-to-parameter ratio = 15.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

In the title compound, [Na(C9H6NO4S)], the sodium ion is

coordinated by the N and O atoms of the quinolinol moiety (usual bidentate chelation) and three O atoms from three different sulfonate groups. The quinolinol O atom and one of the sulfonate O atoms are in the axial positions and the ring N atom and two O atoms from two different sulfonate groups lie in the equatorial positions of the trigonal bipyramid around sodium. Unlike other metal sulfoxinates, the quinolinol O atom is not deprotonated, but is involved in hydrogen bonding. Moreover, all three sulfonate O atoms are involved in coordination, leading to a supramolecular three-dimen-sional network structure.

Comment

Oxine and its derivatives are well known analytical reagents and antiamoebic agents (Bambury, 1979). Oxine is a bidentate chelator forming complexes with many metal ions through the quinoline N and deprotonated quinolinol O atoms. Metal chelation has been implicated in the biological activity of oxine derivatives (Martel & Calvin, 1959). The incorporation of sulfonic acid in the oxine moiety provides additional metal-binding and potential hydrogen-bonding acceptor sites/modes. This type of ligand is called sulfoxine (sulfonic acid + oxine). In metal sulfoxinates, in addition to the usual bidentate chelation of the oxine moiety through the N and O atoms, sulfonic O atoms also coordinate to the metal. Hydrogen-bonding patterns and metal-binding modes of sulfoxinates are of current interest (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yaoet al., 2001; Cai, Chen, Fenget al., 2001). It has recently been demonstrated that the combination of coordi-nation and the sulfonate group can result in the formation of strong supramolecular aggregates through hydrogen bonding and this represents a new strategy for the design of SHG (second harmonic generation) materials (Xie et al., 2002). Information on the structural chemistry of metal sulfoxinates is relatively rare, due to the poor coordinating ability of sulfoxinates compared with that of phosphonates. Various remarkable structural features of metal sulfoxinates have prompted us to investigate systematically the structural chemistry of these compounds. The crystal structures of 7-iodo-8-hydroxyquinoline-5-sulfonic acid (ferron; Balasu-bramanian & Muthiah, 1996a), 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate (Balasubramanian & Muthiah, 1996b), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of 8-hydroxyquinoline-5-sulfonic acid (HQS; Baskar Raj et al., 2001), the nickel complex of ferron (Baskar Rajet al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997) have also been reported from our laboratory.

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metal-organic papers

m514

Savarimuthu Baskar Rajet al. [Na(C9H6NO4S)] Acta Cryst.(2002). E58, m513±m516 In metal sulfoxinates, the sulfonate motifs can be linked in

two ways. In one type, in addition to the usual bidentate chelation of the oxine motif, two centrosymmetrically related monomers are bridged by one of the sulfonate O atoms involved in the coordination, forming a cage-like dimer, as observed in the copper±sulfoxinate complexes (Petit, Coquerelet al., 1993; Petit, Ammoret al., 1993), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of ferron (Baskar Raj et al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997). In another type, in addition to the usual bidentate chelation, a sulfonic acid O atom of one molecule is coordinated to the metal atom of another molecule, leading to a one-dimensional polymeric arrangement, as observed in the copper±sulfoxinate complex (Petit, Coquerelet al., 1993).

In the sodium complex of HQS, (I), the coordination geometry around the sodium ion is distorted trigonal bipyr-amidal. In addition to the usual bidentate chelation involving the N and O atoms of the oxine moiety, three sulfonate O atoms from three different sulfonate groups are coordinated

to the sodium ion. The O atom of the quinolinol moiety and one of the O atoms (O3) from the sulfonate group bind to the Na+ion at the axial positions and two O atoms (O2 and O4)

from two different sulfonate groups and the ring N atom lie in the equatorial positions. A view of the complex unit of (I), with the atom-labelling scheme, is shown in Fig. 1. One of the sulfonate O atoms bridges the two inversion-related mono-mers, leading to a cage-like dimeric unit (Fig. 2). The distance between two neighbouring Na atoms is 5.4718 (15) AÊ. A view of the packing is shown in Fig. 3. The present sodium complex is quite different from other metal sulfoxinates reported in the literature (Balasubramanian, 1995; Murugesan & Muthiah, 1997; Petit, Coquerel et al., 1993; Petit, Ammor et al., 1993; Baskar Raj et al., 2001, 2002) in the sense that all three sulfonate O atoms are involved in the coordination, leading to a supramolecular network structure. The smaller NÐNaÐO bite angle in (I) may be the result of longer coordination bonds than those in the Co and Ni complexes. The NaÐ O(quinolinol) and NaÐN(ring) bond distances are not signi®cantly different from one another. The NaÐN(ring) distance [2.4418 (15) AÊ] in (I) agrees with the range of values [2.459 (7)±2.539 (6) AÊ] reported in the literature (Papadimi-triou et al., 1998). Also, the NaÐO(quinolinol) distance [2.4892 (14) AÊ] in (I) agrees with the corresponding distance [2.42 (9) AÊ] in small molecules (Harding, 2002) reported in the Cambridge Structural Database (Allen & Kennard, 1993). The NaÐO(sulfonate) distances agree with the corresponding distance reported in the literature (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yaoet al., 2001; Cai, Chen, Feng Figure 1

View of (I), with the atom-labelling scheme and 50% probability displacement ellipsoids.

Figure 2

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et al., 2001) and are signi®cantly shorter than the NaÐ O(quinolinol) distance (Table 1).

Unlike other sulfoxinates, the quinolinol O atom is not deprotonated, but is involved in a hydrogen bond with a symmetry-related O atom of the sulfonic acid group [O1Ð H1 O3i; symmetry code: (i) 1 +x, y, z]. Atoms C4 and C6 are

also involved in intramolecular hydrogen bonding with atoms O4 and O2 of the sulfonate group (Table 2), forming ®ve-membered rings on both sides of the SÐC bond. Intramole-cular hydrogen bonding involving atom C6 with one of the sulfonate O atoms has also been observed in both 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate (Balasub-ramanian & Muthiah, 1996b) and ferron (Balasubramanian & Muthiah, 1996a). There is also a glide-related CÐH

interaction [H Cg 2.6341 (6) AÊ and C2ÐH2 Cg

134.02 (5); atom C2 is in the pyridine ring and Cg is the phenyl-ring centroid]. Stacking interactions between the pyridine and phenyl rings in adjacent complex units are observed. The centroid-to-centroid and interplanar distances are 3.499 (9) and 3.303 (4) AÊ, respectively. The slip angle (angle between the centroid vector and the normal to the plane) is 20.73 (3).

Experimental

An aqueous solution of sodium diethyldithiocarbamate (0.113 g) and an aqueous solution of 8-hydroxyquinoline-5-sulfonic acid mono-hydrate were mixed and warmed over a water bath for 30 min. The product was then recrystallized from acetonitrile.

Crystal data

[Na(C9H6NO4S)] Mr= 247.21 Monoclinic,P21=c a= 8.284 (2) AÊ b= 10.488 (2) AÊ c= 10.916 (2) AÊ

= 103.25 (2)

V= 923.2 (3) AÊ3 Z= 4

Dx= 1.779 Mg mÿ3 MoKradiation Cell parameters from 50

re¯ections

= 3.0±29.6

= 0.39 mmÿ1 T= 293 (2) K Cuboid, colourless 0.340.260.17 mm

Data collection

Bruker AXS SMART CCD diffractometer

!scans

Absorption correction: multi-scan (SHELXTL-NT; Bruker, 1997) Tmin= 0.787,Tmax= 0.936 132 007 measured re¯ections

2662 independent re¯ections 2119 re¯ections withI> 2(I) Rint= 0.032

max= 30.6 h=ÿ11!11 k=ÿ14!14 l=ÿ14!14

Re®nement

Re®nement onF2 R[F2> 2(F2)] = 0.031 wR(F2) = 0.091 S= 1.01 2662 re¯ections 169 parameters

All H-atom parameters re®ned w= 1/[2(Fo2) + (0.0587P)2]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.003

max= 0.35 e AÊÿ3 min=ÿ0.29 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,).

SÐO2 1.4482 (12) SÐO3 1.4731 (12) SÐO4 1.4563 (12) SÐC5 1.7740 (15) NaÐO2 2.2979 (14) NaÐO4i 2.3357 (13)

NaÐO3ii 2.4175 (13) NaÐO1iii 2.4892 (14) NaÐN1iii 2.4418 (15) O1ÐC8 1.3551 (18) N1ÐC2 1.3213 (19) N1ÐC9 1.3735 (18)

O2ÐSÐO3 112.20 (7) O2ÐSÐO4 114.35 (7) O2ÐSÐC5 106.31 (7) O3ÐSÐO4 110.92 (7) O3ÐSÐC5 105.53 (7) O4ÐSÐC5 106.88 (7) O2ÐNaÐO4i 122.27 (5) O2ÐNaÐO3ii 91.71 (5) O1iiiÐNaÐO2 85.61 (5) O2ÐNaÐN1iii 131.41 (5) O3iiÐNaÐO4i 93.20 (5) O1iiiÐNaÐO4i 103.57 (5) O4iÐNaÐN1iii 102.47 (5) O1iiiÐNaÐO3ii 161.68 (5) O3iiÐNaÐN1iii 104.65 (5)

O1iiiÐNaÐN1iii 64.86 (4) NaivÐO1ÐC8 121.03 (9) SÐO2ÐNa 133.30 (7) SÐO3ÐNaii 139.97 (7) SÐO4ÐNav 140.35 (7) NaivÐN1ÐC2 121.33 (10) C2ÐN1ÐC9 117.40 (12) NaivÐN1ÐC9 121.24 (9) N1ÐC2ÐC3 123.97 (13) SÐC5ÐC10 120.01 (10) SÐC5ÐC6 119.61 (10) O1ÐC8ÐC9 115.68 (12) O1ÐC8ÐC7 124.04 (13) N1ÐC9ÐC10 122.93 (12) N1ÐC9ÐC8 117.16 (12) Symmetry codes: (i) 1ÿx;yÿ1

2;ÿ12ÿz; (ii) 1ÿx;ÿy;ÿz; (iii)xÿ1;12ÿy;zÿ12; (iv)

1‡x;1

2ÿy;12‡z; (v) 1ÿx;12‡y;ÿ12ÿz.

Table 2

Hydrogen-bonding geometry (AÊ,).

DÐH A DÐH H A D A DÐH A

O1ÐH1 O3i 0.805 (18) 1.902 (18) 2.7029 (17) 173.4 (17) C4ÐH4 O4 0.936 (17) 2.584 (18) 3.1235 (19) 117.1 (13) C6ÐH6 O2 0.972 (18) 2.381 (17) 2.8657 (19) 110.2 (12) Symmetry code: (i) 1‡x;y;z.

The H atoms were located in difference Fourier maps and re®ned with isotropic displacement parameters. The CÐH and OÐH bond lengths are 0.883 (18)-0.98 (3) and 0.805 (18) AÊ, respectively.

Acta Cryst.(2002). E58, m513±m516 Savarimuthu Baskar Rajet al. [Na(C9H6NO4S)]

m515

metal-organic papers

Figure 3

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metal-organic papers

m516

Savarimuthu Baskar Rajet al. [Na(C9H6NO4S)] Acta Cryst.(2002). E58, m513±m516 Data collection:SMART(Bruker, 1997); cell re®nement:SMART;

data reduction: SAINT (Bruker, 1997); program(s) used to solve structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

PLATON (Spek, 1997); software used to prepare material for publication:PLATON.

SBR thanks the Council of Scienti®c and Industrial Research, New Delhi, India, for the award of a Senior Research Fellowship [reference No. 9/475(103)2002 EMR-I].

References

Allen, F. H. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Balasubramanian, T. & Muthiah, P. T. (1996a).Acta Cryst.C52, 2072±2073. Balasubramanian, T. & Muthiah, P. T. (1996b).Acta Cryst.C52, 1017±1019. Balasubramanian, T. (1995). PhD thesis, Department of Chemistry,

Bhar-athidasan University, Tiruchirappalli, India.

Bambury, R. E. (1979).Burger's Medicinal Chemistry, edited by M. E. Wolff, pp. 41±48. New York: John Wiley.

Baskar Raj, S., Muthiah, P. T., Bocelli, G. & Righi, L. (2001).Acta Cryst.E57, m591±m594.

Baskar Raj. S., Muthiah, P. T., Rychlewska, U., WarzÇajtis. B., Bocelli, G. & Olla, R. (2002).Acta Cryst.C58. Submitted.

Bruker (1997). SAINT, SMART and SHELXTL-NT. Bruker Axs Inc., Madison, Wisconsin, USA.

Cai, J., Chen, C.-H., Feng, X.-L., Liao, C.-Z. & Chen, X.-M. (2001).J. Chem. Soc. Dalton Trans.pp. 2370±2375.

Cai, J., Chen, C.-H., Liao, C.-Z., Feng, X.-L. & Chen, X.-M. (2001).Acta Cryst. B57, 520±530.

Cai, J., Chen, C.-H., Liao, C.-Z., Yao, J.-H., Hu, X.-P. & Chen, X.-M. (2001).J. Chem. Soc. Dalton Trans.pp. 1137±1142.

Harding, M. M. (2002).Acta Cryst.D58, 872±874.

Martel, A. E. & Calvin, M. (1959).Chemistry of Metal Chelate Compounds. Englewood Cliffs: Prentice Hall.

Murugesan, S. & Muthiah, P. T. (1997). XXVIIIth National Seminar on Crystallography, Kottayam, India, September 24±26. (Deposited at CCDC, No. CCDC 166283.)

Papadimitriou, C., Veltsistas, P., Marek, J., Novosad, J., Slawin, A. M. Z. & Woollins, J. D. (1998).Inorg. Chem. Commun.1, 418±420.

Petit, S., Ammor, S., Coquerel, G., Mayer, C. & Perez, G. (1993).Eur. J. Solid State Inorg. Chem.30, 497±507.

Petit, S., Coquerel, G., Perez, G., Louer, D. & Lover, M. (1993).New. J. Chem. 17, 187±192.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.

Spek, A. L. (1997).PLATON.Utrecht University, The Netherlands. Xie, Y.-R., Xiong, R.-G., Xue, X., Chen, X.-T., Xue, Z. & You, X.-Z. (2002).

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supporting information

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Acta Cryst. (2002). E58, m513–m516

supporting information

Acta Cryst. (2002). E58, m513–m516 [doi:10.1107/S1600536802015118]

Metal-binding modes in sulfoxines: supramolecular network in

(8-hydroxy-quinoline-5-sulfonato-

N

1

,

O

8

)sodium(I)

Savarimuthu Baskar Raj, Packianathan Thomas Muthiah, Gabriele Bocelli and Rita Olla

S1. Comment

Oxine and its derivatives are well known analytical reagents and antiamoebic agents (Bambury, 1979). Oxine is a bidentate chelator forming complexes with many metal ions through the quinoline N and deprotonated quinolinol O atoms. Metal chelation has been implicated in the biological activity of oxine derivatives (Martel & Calvin, 1959). The incorporation of sulfonic acid in the oxine moiety provides additional metal-binding and potential hydrogen-bonding acceptor sites/modes. This type of ligand is called sulfoxine (sulfonic acid + oxine). In metal sulfoxinates, in addition to the usual bidentate chelation of the oxine moiety through the N and O atoms, sulfonic-O atoms also coordinate to the metal. Hydrogen-bonding patterns and metal-binding modes of sulfoxinates are of current interest (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yao et al., 2001; Cai, Chen, Feng et al., 2001). It has recently been demonstrated that the combination of coordination and the sulfonate group can result in the formation of strong supramolecular aggregates through hydrogen bonding and this represents a new strategy for the design of SHG (second harmonic generation) materials (Xie et al., 2002). Information on the structural chemistry of metal sulfoxinates is relatively rare due to the poor coordination strength of sulfoxinates compared with that of phosphonates. The various remarkable structural features of metal sulfoxinates have prompted us to investigate systematically the structural chemistry of these compounds. The crystal structures of 7-iodo-8-hydroxyquinoline-5-sulfonic acid (ferron; Balasubramanian & Muthiah, 1996a), 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate (Balasubramanian & Muthiah, 1996b), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of 8-hydroxyquinoline-5-sulfonic acid (HQS; Baskar Raj et al., 2001), the nickel complex of ferron (Baskar Raj et al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997) have also been reported from our laboratory.

In metal sulfoxinates, the sulfonate motifs can be linked in two ways. In one type, in addition to the usual bidentate chelation of the oxine motif, two centrosymmetrically related monomers are bridged by one of the sulfonate O atoms involved in the coordination, forming a cage-like dimer, as observed in the copper–sulfoxinate complexes (Petit, Coquerel et al., 1993; Petit, Ammor et al., 1993), the cobalt complex of ferron (Balasubramanian, 1995), the nickel complex of ferron (Baskar Raj et al., 2002) and the lithium complex of HQS (Murugesan & Muthiah, 1997). In another type, in addition to the usual bidentate chelation, a sulfonic acid O atom of one molecule is coordinated to the metal atom of another molecule, leading to a one-dimensional polymeric arrangement, as observed in the copper–sulfoxinate

complex (Petit, Coquerel et al., 1993).

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supporting information

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Acta Cryst. (2002). E58, m513–m516

two different sulfonate groups and the ring N atom lie in the equatorial positions. A view of the complex unit of (I), with the atom-labelling scheme, is shown in Fig. 1. One of the sulfonate O atoms bridges the two inversion-related monomers, leading to a cage-like dimeric unit (Fig. 2). The distance between two neighbouring Na atoms is 5.4718 (15) Å. A view of the packing is shown in Fig. 3. The present sodium complex is quite different from other metal sulfoxinates reported in the literature (Balasubramanian, 1996; Murugesan & Muthiah, 1997; Petit, Coquerel et al., 1993; Petit, Ammor et al., 1993; Baskar Raj et al., 2001, 2002) in the sense that all tthree sulfonate O atoms are involved in the coordination, leading to a supramolecular network structure. The smaller N—Na—O bite angle in (I) may be the result of longer coordination bonds than those in the Co and Ni complexes. The Na—O(quinolinol) and Na—N(ring) bond distances are not significantly different from one another. The Na—N(ring) distance [2.4418 (15) Å] in (I) agrees with the range of values [2.459 (7)–2.539 (6) Å] reported in the literature (Papadimitriou et al., 1998). Also, the Na—O(quinolinol) distance [2.4892 (14) Å] in (I) agrees with the corresponding distance [2.42 (9) Å] in small molecules (Harding, 2002) reported in the Cambridge Structural Database (Allen & Kennard, 1993). The Na—O(sulfonate) distances agree with the corresponding distance reported in the literature (Cai, Chen, Liao, Feng & Chen, 2001; Cai, Chen, Liao, Yao et al., 2001; Cai, Chen, Feng et al., 2001) and are significantly shorter than the Na—O(quinolinol) distance (Table 1).

Unlike other sulfoxinates, the quinolinol O atom is not deprotonated, but is involved in a hydrogen bond with a

symmetry-related O atom of the sulfonic acid group [O1—H1···O3i: symmetry code: (i) 1 + x, y, z]. Atoms C4 and C6 are

also involved in intramolecular hydrogen bonding with atoms O4 and O2 of the sulfonate group (Table 2), forming five-membered rings on both sides of the S—C bond. Intramolecular hydrogen bonding involving atom C6 with one of the sulfonate O atoms has also been observed in both 7-nitro-8-hydroxyquinoline-5-sulfonic acid monohydrate

(Balasubramanian & Muthiah, 1996b) and ferron (Balasubramanian & Muthiah, 1996a). There is also a glide-related C— H···π interaction [H···Cg 2.6341 (6) Å and C2—H2···Cg 134.02 (5)°; atoms C2 is in the pyridine ring and Cg is the phenyl-ring centroid]. Stacking interactions between the pyridine and phenyl rings in adjacent complex units is observed. The centroid-to-centroid and interplanar distances are 3.499 (9) and 3.303 (4) Å, respectively. The slip angles (angle between the centroid vector and the normal to the plane) is 20.73 (3)°.

S2. Experimental

An aqueous solution of sodium diethyldithiocarbomate (0.113 g) and an aqueous solution of 8-hydroxyquinoline-5-sulfonic acid monohydrate were mixed and warmed over a water bath for 30 min. The product was then recrystallized from acetonitrile.

S3. Refinement

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[image:7.610.127.487.68.426.2]

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Acta Cryst. (2002). E58, m513–m516

Figure 1

View of (I) with the atom-labelling scheme and 50% probability displacement ellipsoids.

Figure 2

[image:7.610.230.382.465.660.2]
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[image:8.610.121.488.68.480.2]

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Acta Cryst. (2002). E58, m513–m516

Figure 3

View of the packing diagram of (I), showing the dimeric arrangement in the bc plane.

(8-hydroxyquinoline-5-sulfonato-N1,O8)sodium(I)

Crystal data

[Na(C9H6NO4S)] Mr = 247.21

Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 8.284 (2) Å

b = 10.488 (2) Å

c = 10.916 (2) Å

β = 103.25 (2)°

V = 923.2 (3) Å3 Z = 4

F(000) = 504

Dx = 1.779 Mg m−3

Mo radiation, λ = 0.71069 Å Cell parameters from 50 reflections

θ = 3.0–29.6°

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Acta Cryst. (2002). E58, m513–m516

Data collection

Bruker AXS SMART with CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: ψ scan (SHELXTL-NT; Bruker, 1997)

Tmin = 0.787, Tmax = 0.936

132007 measured reflections 2662 independent reflections 2119 reflections with I > 2σ(I)

Rint = 0.032

θmax = 30.6°, θmin = 2.5° h = −11→11

k = −14→14

l = −14→14

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.031 wR(F2) = 0.091 S = 1.01 2662 reflections 169 parameters 0 restraints 0 constraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

All H-atom parameters refined

w = 1/[σ2(F

o2) + (0.0587P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.003

Δρmax = 0.35 e Å−3

Δρmin = −0.29 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

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Acta Cryst. (2002). E58, m513–m516

H6 0.918 (2) 0.0955 (18) −0.0790 (16) 0.035 (5)* H7 1.208 (2) 0.1434 (16) −0.0072 (15) 0.026 (4)*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

S 0.0180 (2) 0.0221 (2) 0.0238 (2) −0.0022 (1) 0.0020 (1) −0.0004 (1) Na 0.0246 (3) 0.0284 (3) 0.0305 (3) 0.0002 (2) −0.0002 (2) −0.0018 (2) O1 0.0169 (5) 0.0344 (6) 0.0404 (6) 0.0006 (4) 0.0027 (4) −0.0065 (5) O2 0.0269 (5) 0.0319 (6) 0.0407 (6) −0.0058 (4) 0.0025 (5) −0.0137 (5) O3 0.0248 (5) 0.0329 (5) 0.0308 (5) −0.0004 (4) 0.0099 (4) 0.0048 (4) O4 0.0246 (5) 0.0332 (6) 0.0329 (6) 0.0012 (4) −0.0023 (4) 0.0076 (4) N1 0.0239 (6) 0.0254 (6) 0.0229 (6) −0.0031 (4) 0.0020 (4) −0.0025 (5) C2 0.0305 (7) 0.0242 (7) 0.0249 (7) −0.0029 (5) 0.0044 (6) −0.0050 (5) C3 0.0279 (7) 0.0261 (7) 0.0284 (7) 0.0036 (5) 0.0076 (6) −0.0035 (6) C4 0.0209 (6) 0.0262 (7) 0.0255 (7) 0.0005 (5) 0.0049 (5) −0.0014 (5) C5 0.0189 (6) 0.0212 (6) 0.0203 (6) −0.0016 (5) 0.0023 (5) 0.0006 (5) C6 0.0238 (7) 0.0215 (6) 0.0269 (7) −0.0013 (5) 0.0048 (5) −0.0025 (5) C7 0.0219 (6) 0.0251 (7) 0.0312 (7) 0.0035 (5) 0.0064 (5) −0.0017 (6) C8 0.0179 (6) 0.0260 (7) 0.0222 (6) 0.0002 (5) 0.0020 (5) 0.0028 (5) C9 0.0199 (6) 0.0210 (6) 0.0192 (6) −0.0010 (5) 0.0028 (5) 0.0009 (5) C10 0.0194 (6) 0.0204 (6) 0.0184 (6) −0.0006 (4) 0.0033 (5) 0.0015 (5)

Geometric parameters (Å, º)

S—O2 1.4482 (12) C3—C4 1.366 (2) S—O3 1.4731 (12) C4—C10 1.423 (2) S—O4 1.4563 (12) C5—C10 1.4312 (18) S—C5 1.7740 (15) C5—C6 1.373 (2) Na—O2 2.2979 (14) C6—C7 1.416 (2) Na—O4i 2.3357 (13) C7—C8 1.3730 (19)

Na—O3ii 2.4175 (13) C8—C9 1.4304 (19)

Na—O1iii 2.4892 (14) C9—C10 1.4207 (19)

Na—N1iii 2.4418 (15) C2—H2 0.98 (2)

O1—C8 1.3551 (18) C3—H3 0.883 (18) O1—H1 0.805 (18) C4—H4 0.936 (17) N1—C2 1.3213 (19) C6—H6 0.972 (18) N1—C9 1.3735 (18) C7—H7 0.934 (17) C2—C3 1.407 (2)

S···H1iv 2.967 (18) C7···C3vi 3.423 (2)

S···H4 2.821 (17) C7···C2vi 3.500 (2)

O1···O3v 2.7029 (17) C8···C2vi 3.575 (2)

O1···N1 2.6445 (18) C8···C4vi 3.469 (2)

O1···C4vi 3.416 (2) C8···C3vi 3.252 (2)

O2···C3vii 3.415 (2) C9···C10vi 3.544 (2)

O3···C4 3.1943 (19) C9···C9vi 3.525 (2)

(11)

supporting information

sup-7

Acta Cryst. (2002). E58, m513–m516

O4···C4 3.1235 (19) C10···C9vi 3.544 (2)

O4···C3viii 3.343 (2) C2···H6x 3.027 (18)

O2···H6 2.381 (17) C3···H6x 3.008 (18)

O3···H1iv 1.902 (18) C5···H2xi 2.735 (18)

O3···H4 2.729 (17) C6···H6xii 3.097 (19)

O4···H4 2.584 (18) C6···H2xi 2.933 (18)

O4···H3viii 2.634 (17) C8···H3xi 3.046 (18)

N1···O1 2.6445 (18) C9···H2xi 3.025 (19)

N1···C10vi 3.3380 (19) C10···H2xi 2.791 (19)

C2···C5ix 3.551 (2) H1···Sv 2.967 (18)

C2···C6ix 3.483 (2) H1···O3v 1.902 (18)

C2···C5vi 3.545 (2) H1···H7 2.37 (2)

C2···C6vi 3.481 (2) H2···C5ix 2.735 (18)

C2···C7vi 3.500 (2) H2···C6ix 2.933 (18)

C2···C8vi 3.575 (2) H2···C9ix 3.025 (19)

C3···C8vi 3.252 (2) H2···C10ix 2.791 (19)

C3···O4viii 3.343 (2) H3···C8ix 3.046 (18)

C3···C7vi 3.423 (2) H3···O4viii 2.634 (17)

C3···O2x 3.415 (2) H4···S 2.821 (17)

C4···O4 3.1235 (19) H4···O3 2.729 (17) C4···O1vi 3.416 (2) H4···O4 2.584 (18)

C4···O3 3.1943 (19) H6···O2 2.381 (17) C4···C8vi 3.469 (2) H6···C6xii 3.097 (19)

C5···C2xi 3.551 (2) H6···C2vii 3.027 (18)

C5···C2vi 3.545 (2) H6···C3vii 3.008 (18)

C6···C2vi 3.481 (2) H7···H1 2.37 (2)

C6···C2xi 3.483 (2)

O2—S—O3 112.20 (7) C2—C3—C4 119.23 (14) O2—S—O4 114.35 (7) C3—C4—C10 119.54 (13) O2—S—C5 106.31 (7) C6—C5—C10 120.35 (13) O3—S—O4 110.92 (7) S—C5—C10 120.01 (10) O3—S—C5 105.53 (7) S—C5—C6 119.61 (10) O4—S—C5 106.88 (7) C5—C6—C7 121.29 (13) O2—Na—O4i 122.27 (5) C6—C7—C8 119.86 (13)

O2—Na—O3ii 91.71 (5) O1—C8—C9 115.68 (12)

O1iii—Na—O2 85.61 (5) O1—C8—C7 124.04 (13)

O2—Na—N1iii 131.41 (5) C7—C8—C9 120.28 (13)

O3ii—Na—O4i 93.20 (5) N1—C9—C10 122.93 (12)

O1iii—Na—O4i 103.57 (5) C8—C9—C10 119.89 (12)

O4i—Na—N1iii 102.47 (5) N1—C9—C8 117.16 (12)

O1iii—Na—O3ii 161.68 (5) C5—C10—C9 118.32 (12)

O3ii—Na—N1iii 104.65 (5) C4—C10—C5 124.75 (13)

O1iii—Na—N1iii 64.86 (4) C4—C10—C9 116.90 (12)

Naxiii—O1—C8 121.03 (9) N1—C2—H2 114.7 (10)

S—O2—Na 133.30 (7) C3—C2—H2 121.2 (10) S—O3—Naii 139.97 (7) C2—C3—H3 118.0 (12)

(12)

supporting information

sup-8

Acta Cryst. (2002). E58, m513–m516

Naxiii—O1—H1 127.8 (13) C3—C4—H4 117.5 (11)

C8—O1—H1 111.2 (13) C10—C4—H4 122.9 (11) Naxiii—N1—C2 121.33 (10) C5—C6—H6 115.5 (10)

C2—N1—C9 117.40 (12) C7—C6—H6 123.2 (10) Naxiii—N1—C9 121.24 (9) C6—C7—H7 119.1 (10)

N1—C2—C3 123.97 (13) C8—C7—H7 121.0 (10)

O3—S—C5—C10 −59.77 (12) Naxiii—O1—C8—C7 −179.42 (11)

O4—S—C5—C10 58.38 (12) Naxiii—O1—C8—C9 1.00 (16)

O3—S—O2—Na 70.79 (11) C2—N1—C9—C8 176.52 (12) O4—S—O2—Na −56.65 (11) Naxiii—N1—C9—C8 −1.68 (16)

C5—S—O2—Na −174.33 (9) C9—N1—C2—C3 1.2 (2) O2—S—C5—C6 −1.11 (13) Naxiii—N1—C2—C3 179.35 (11)

O2—S—O4—Naxiv −80.24 (12) Naxiii—N1—C9—C10 −179.89 (9)

O3—S—O4—Naxiv 151.67 (9) C2—N1—C9—C10 −1.69 (19)

C5—S—O4—Naxiv 37.11 (12) N1—C2—C3—C4 0.3 (2)

O2—S—O3—Naii 41.33 (12) C2—C3—C4—C10 −1.3 (2)

O4—S—O3—Naii 170.58 (9) C3—C4—C10—C5 −177.57 (13)

C5—S—O3—Naii −74.02 (11) C3—C4—C10—C9 0.79 (19)

O4—S—C5—C6 −123.64 (11) C10—C5—C6—C7 0.1 (2) O2—S—C5—C10 −179.09 (11) S—C5—C6—C7 −177.91 (11) O3—S—C5—C6 118.21 (11) C6—C5—C10—C9 −0.64 (19) O4i—Na—O2—S 164.24 (8) C6—C5—C10—C4 177.71 (13)

O3ii—Na—O2—S −100.90 (10) S—C5—C10—C9 177.32 (10)

O1—Naxiii—N1—C2 −176.60 (12) S—C5—C10—C4 −4.33 (18)

O2xiii—Naxiii—N1—C2 125.17 (11) C5—C6—C7—C8 0.1 (2)

O1—Naxiii—N1—C9 1.53 (10) C6—C7—C8—C9 0.3 (2)

O2xiii—Naxiii—N1—C9 −56.70 (12) C6—C7—C8—O1 −179.24 (13)

O1iii—Na—O2—S 60.95 (10) C7—C8—C9—C10 −0.9 (2)

N1iii—Na—O2—S 10.43 (13) C7—C8—C9—N1 −179.18 (13)

O2xiv—Naxiv—O4—S 166.12 (9) O1—C8—C9—N1 0.42 (18)

N1—Naxiii—O1—C8 −1.31 (10) O1—C8—C9—C10 178.68 (12)

O2xiii—Naxiii—O1—C8 138.94 (11) C8—C9—C10—C5 1.06 (19)

O2ii—Naii—O3—S −84.62 (11) N1—C9—C10—C4 0.74 (19)

O2xiii—Naxiii—O1—H1 −39.0 (16) N1—C9—C10—C5 179.22 (12)

N1—Naxiii—O1—H1 −179.2 (17) C8—C9—C10—C4 −177.42 (12)

Symmetry codes: (i) −x+1, y−1/2, −z−1/2; (ii) −x+1, −y, −z; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z; (v) x+1, y, z; (vi) −x+2, −y+1, −z; (vii) x, −y+1/2,

z−1/2; (viii) −x+1, −y+1, −z; (ix) −x+2, y+1/2, −z+1/2; (x) x, −y+1/2, z+1/2; (xi) −x+2, y−1/2, −z+1/2; (xii) −x+2, −y, −z; (xiii) x+1, −y+1/2, z+1/2; (xiv) −x+1, y+1/2, −z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O1—H1···O3v 0.805 (18) 1.902 (18) 2.7029 (17) 173.4 (17)

C4—H4···O4 0.936 (17) 2.584 (18) 3.1235 (19) 117.1 (13) C6—H6···O2 0.972 (18) 2.381 (17) 2.8657 (19) 110.2 (12)

Figure

Figure 1
Figure 3

References

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