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In the title compound, [NaBr(C2H6OS)2]n, each NaI cation is coordinated by four O atoms from four dimethyl sulfoxide ligands and by one Br anion in a distorted pyramidal geometry. Each O atom coordinates two NaI cations, leading to the formation of polymeric coordination chains parallel to the a axis with protruding Br anions and methyl groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026402/cv2251sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026402/cv2251Isup2.hkl
Contains datablock I

CCDC reference: 654702

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](a-O) = 0.002 Å
  • R factor = 0.034
  • wR factor = 0.072
  • Data-to-parameter ratio = 25.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.90 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.36 Ratio
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.900 Tmax scaled 0.442 Tmin scaled 0.415
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Dimethyl sulfoxide has been widely used to build up supramolecular structures (Chiarella et al., 2006; Gao et al., 1993; Nieuwenhuyzen et al., 1993; Schrauzer et al., 1990). In our attempt to synthesize nickel complex with malonic acid, we obtained two types of crystals differently coloured - green (Zhu et al., 2007) and colourless. We herein report the crystal structure of the colourless one, the title compound, (I).

In the asymmetric unit of (I), there are two dimethyl sulfoxide ligands, one sodium ion and one bromide anion (Fig.1). The sodium ion is five-coordinated in a distorted pyramid by four oxygen atoms from four dimethyl sulfoxide ligands and one bromide anion (Table 1). Every oxygen atom is used as bridge unit to link sodium ions to form an infinite chain along a axis.

Related literature top

For the crystal structures of analogues of the title compound, see: Chiarella et al. (2006); Gao et al. (1993); Nieuwenhuyzen et al. (1993); Schrauzer et al. (1990). For the crystal structure of a nickel complex formed in the same synthesis as the title compound, see: Zhu et al. (2007).

Experimental top

Malonic acid and NiBr2.6H2O of analytical grade were used without further purification. Malonic acid (1.04 g, 10 mmol) dissolved in dimethyl sulfoxide (10 ml) and NiBr2.6H2O (1.64 g, 5 mmol) dissolved in water (10 ml) were mixed and the pH was adjusted to about 5 by using NaOH solution (0.1 M) with stirring. The mixture was heated with stirring for half an hour and then cooled to room temperature. The filtrate was allowed to stand over a night, to generate two types of block crystals, one was colourless and another one was green.

Refinement top

C-bound H atoms were geonetrically positioned (C—H = 0.96 Å) and treated as riding with Uiso(H) = 1.5Ueq(C).

Structure description top

Dimethyl sulfoxide has been widely used to build up supramolecular structures (Chiarella et al., 2006; Gao et al., 1993; Nieuwenhuyzen et al., 1993; Schrauzer et al., 1990). In our attempt to synthesize nickel complex with malonic acid, we obtained two types of crystals differently coloured - green (Zhu et al., 2007) and colourless. We herein report the crystal structure of the colourless one, the title compound, (I).

In the asymmetric unit of (I), there are two dimethyl sulfoxide ligands, one sodium ion and one bromide anion (Fig.1). The sodium ion is five-coordinated in a distorted pyramid by four oxygen atoms from four dimethyl sulfoxide ligands and one bromide anion (Table 1). Every oxygen atom is used as bridge unit to link sodium ions to form an infinite chain along a axis.

For the crystal structures of analogues of the title compound, see: Chiarella et al. (2006); Gao et al. (1993); Nieuwenhuyzen et al. (1993); Schrauzer et al. (1990). For the crystal structure of a nickel complex formed in the same synthesis as the title compound, see: Zhu et al. (2007).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Part of the structure of the title complex, with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been ommited. [Symmetry codes: (i) 2 - x, 3/2 + y, 1/2 - x; (ii) -1 + x, y, z; (iii) 1 - x, 3/2 + y, 1/2 - z; (iv) 1 + x, y, z.]
catena-Poly[[bromidosodium(I)]-bis(µ-dimethyl sulfoxide-κ2O:O)] top
Crystal data top
[NaBr(C2H6OS)2]F(000) = 520
Mr = 259.16Dx = 1.638 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7474 reflections
a = 6.433 (3) Åθ = 6.4–55.0°
b = 9.969 (4) ŵ = 4.30 mm1
c = 16.430 (6) ÅT = 291 K
β = 94.046 (17)°Block, colourless
V = 1051.0 (7) Å30.21 × 0.20 × 0.19 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2401 independent reflections
Radiation source: fine-focus sealed tube1772 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 88
Tmin = 0.461, Tmax = 0.491k = 1212
10170 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0286P)2 + 0.2048P]
where P = (Fo2 + 2Fc2)/3
2401 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[NaBr(C2H6OS)2]V = 1051.0 (7) Å3
Mr = 259.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.433 (3) ŵ = 4.30 mm1
b = 9.969 (4) ÅT = 291 K
c = 16.430 (6) Å0.21 × 0.20 × 0.19 mm
β = 94.046 (17)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2401 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
1772 reflections with I > 2σ(I)
Tmin = 0.461, Tmax = 0.491Rint = 0.051
10170 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.04Δρmax = 0.31 e Å3
2401 reflectionsΔρmin = 0.40 e Å3
95 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.71849 (5)0.19369 (3)0.13185 (2)0.05075 (12)
C11.1343 (5)0.4654 (3)0.23986 (19)0.0531 (8)
H3A1.23700.39700.23350.080*
H3B1.09440.46520.29510.080*
H3C1.19160.55130.22750.080*
C20.7672 (6)0.5765 (4)0.1974 (2)0.0704 (11)
H2A0.85350.65490.19560.106*
H2B0.72070.56640.25130.106*
H2C0.64870.58600.15890.106*
C30.7631 (6)0.8295 (3)0.0050 (3)0.0635 (10)
H4A0.67400.84100.03890.095*
H4B0.80980.91570.02240.095*
H4C0.88130.77590.01320.095*
C40.4105 (6)0.8611 (3)0.0979 (2)0.0630 (10)
H1A0.31250.83040.14060.094*
H1B0.45970.94870.11110.094*
H1C0.34370.86500.04750.094*
Na10.74441 (16)0.42912 (10)0.02932 (6)0.0324 (2)
O20.5379 (3)0.62069 (18)0.05373 (12)0.0401 (5)
O10.9778 (3)0.4577 (2)0.08719 (11)0.0397 (5)
S10.91242 (12)0.43317 (7)0.17235 (4)0.03852 (18)
S20.62360 (12)0.74854 (7)0.08747 (5)0.04170 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0597 (2)0.03973 (18)0.0550 (2)0.00658 (15)0.01907 (16)0.01221 (14)
C10.060 (2)0.062 (2)0.0368 (17)0.0069 (17)0.0002 (16)0.0009 (15)
C20.072 (3)0.085 (3)0.056 (2)0.025 (2)0.016 (2)0.005 (2)
C30.048 (2)0.049 (2)0.092 (3)0.0068 (16)0.007 (2)0.0026 (19)
C40.068 (2)0.0321 (16)0.085 (3)0.0036 (16)0.015 (2)0.0140 (17)
Na10.0328 (6)0.0304 (5)0.0343 (6)0.0003 (4)0.0049 (5)0.0000 (4)
O20.0406 (11)0.0259 (9)0.0552 (12)0.0003 (8)0.0135 (10)0.0082 (9)
O10.0377 (11)0.0554 (12)0.0268 (10)0.0104 (9)0.0067 (8)0.0010 (9)
S10.0432 (4)0.0430 (4)0.0301 (4)0.0122 (3)0.0079 (3)0.0019 (3)
S20.0504 (5)0.0298 (4)0.0465 (4)0.0020 (3)0.0148 (4)0.0052 (3)
Geometric parameters (Å, º) top
Na1—Br12.8869 (13)C4—H1A0.9600
C1—S11.774 (3)C4—H1B0.9600
C1—H3A0.9600C4—H1C0.9600
C1—H3B0.9600Na1—O22.345 (2)
C1—H3C0.9600Na1—O12.365 (2)
C2—S11.772 (3)Na1—O1i2.368 (2)
C2—H2A0.9600Na1—O2ii2.399 (2)
C2—H2B0.9600Na1—Na1ii3.639 (2)
C2—H2C0.9600Na1—Na1i3.646 (2)
C3—S21.767 (4)O2—S21.5095 (19)
C3—H4A0.9600O2—Na1ii2.399 (2)
C3—H4B0.9600O1—S11.5093 (19)
C3—H4C0.9600O1—Na1i2.368 (2)
C4—S21.770 (3)
S1—C1—H3A109.5O1i—Na1—O2ii161.75 (8)
S1—C1—H3B109.5O2—Na1—Br1123.62 (7)
H3A—C1—H3B109.5O1—Na1—Br1125.28 (6)
S1—C1—H3C109.5O1i—Na1—Br199.62 (6)
H3A—C1—H3C109.5O2ii—Na1—Br198.55 (6)
H3B—C1—H3C109.5O2—Na1—Na1ii40.47 (5)
S1—C2—H2A109.5O1—Na1—Na1ii104.47 (7)
S1—C2—H2B109.5O1i—Na1—Na1ii127.73 (7)
H2A—C2—H2B109.5O2ii—Na1—Na1ii39.36 (5)
S1—C2—H2C109.5Br1—Na1—Na1ii117.05 (5)
H2A—C2—H2C109.5O2—Na1—Na1i102.64 (7)
H2B—C2—H2C109.5O1—Na1—Na1i39.66 (5)
S2—C3—H4A109.5O1i—Na1—Na1i39.60 (5)
S2—C3—H4B109.5O2ii—Na1—Na1i129.41 (7)
H4A—C3—H4B109.5Br1—Na1—Na1i118.90 (5)
S2—C3—H4C109.5Na1ii—Na1—Na1i124.03 (6)
H4A—C3—H4C109.5S2—O2—Na1122.25 (11)
H4B—C3—H4C109.5S2—O2—Na1ii133.96 (11)
S2—C4—H1A109.5Na1—O2—Na1ii100.17 (8)
S2—C4—H1B109.5S1—O1—Na1121.89 (11)
H1A—C4—H1B109.5S1—O1—Na1i135.81 (12)
S2—C4—H1C109.5Na1—O1—Na1i100.74 (8)
H1A—C4—H1C109.5O1—S1—C2105.70 (15)
H1B—C4—H1C109.5O1—S1—C1106.60 (13)
O2—Na1—O1111.08 (8)C2—S1—C197.05 (18)
O2—Na1—O1i88.73 (8)O2—S2—C3106.45 (15)
O1—Na1—O1i79.26 (8)O2—S2—C4105.67 (15)
O2—Na1—O2ii79.83 (8)C3—S2—C497.61 (18)
O1—Na1—O2ii91.58 (8)
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[NaBr(C2H6OS)2]
Mr259.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)291
a, b, c (Å)6.433 (3), 9.969 (4), 16.430 (6)
β (°) 94.046 (17)
V3)1051.0 (7)
Z4
Radiation typeMo Kα
µ (mm1)4.30
Crystal size (mm)0.21 × 0.20 × 0.19
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.461, 0.491
No. of measured, independent and
observed [I > 2σ(I)] reflections
10170, 2401, 1772
Rint0.051
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.072, 1.04
No. of reflections2401
No. of parameters95
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.40

Computer programs: RAPID-AUTO (Rigaku, 1998), RAPID-AUTO, CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Selected geometric parameters (Å, º) top
Na1—Br12.8869 (13)Na1—O1i2.368 (2)
Na1—O22.345 (2)Na1—O2ii2.399 (2)
Na1—O12.365 (2)
O2—Na1—O1111.08 (8)O1i—Na1—O2ii161.75 (8)
O2—Na1—O1i88.73 (8)O2—Na1—Br1123.62 (7)
O1—Na1—O1i79.26 (8)O1—Na1—Br1125.28 (6)
O2—Na1—O2ii79.83 (8)O1i—Na1—Br199.62 (6)
O1—Na1—O2ii91.58 (8)O2ii—Na1—Br198.55 (6)
Symmetry codes: (i) x+2, y+1, z; (ii) x+1, y+1, z.
 

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