Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026402/cv2251sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026402/cv2251Isup2.hkl |
CCDC reference: 654702
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (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
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.
C-bound H atoms were geonetrically positioned (C—H = 0.96 Å) and treated as riding with Uiso(H) = 1.5Ueq(C).
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).
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.
[NaBr(C2H6OS)2] | F(000) = 520 |
Mr = 259.16 | Dx = 1.638 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7474 reflections |
a = 6.433 (3) Å | θ = 6.4–55.0° |
b = 9.969 (4) Å | µ = 4.30 mm−1 |
c = 16.430 (6) Å | T = 291 K |
β = 94.046 (17)° | Block, colourless |
V = 1051.0 (7) Å3 | 0.21 × 0.20 × 0.19 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 2401 independent reflections |
Radiation source: fine-focus sealed tube | 1772 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −8→8 |
Tmin = 0.461, Tmax = 0.491 | k = −12→12 |
10170 measured reflections | l = −21→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-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 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[NaBr(C2H6OS)2] | V = 1051.0 (7) Å3 |
Mr = 259.16 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.433 (3) Å | µ = 4.30 mm−1 |
b = 9.969 (4) Å | T = 291 K |
c = 16.430 (6) Å | 0.21 × 0.20 × 0.19 mm |
β = 94.046 (17)° |
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 = 0.491 | Rint = 0.051 |
10170 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.31 e Å−3 |
2401 reflections | Δρmin = −0.40 e Å−3 |
95 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.71849 (5) | 0.19369 (3) | −0.13185 (2) | 0.05075 (12) | |
C1 | 1.1343 (5) | 0.4654 (3) | 0.23986 (19) | 0.0531 (8) | |
H3A | 1.2370 | 0.3970 | 0.2335 | 0.080* | |
H3B | 1.0944 | 0.4652 | 0.2951 | 0.080* | |
H3C | 1.1916 | 0.5513 | 0.2275 | 0.080* | |
C2 | 0.7672 (6) | 0.5765 (4) | 0.1974 (2) | 0.0704 (11) | |
H2A | 0.8535 | 0.6549 | 0.1956 | 0.106* | |
H2B | 0.7207 | 0.5664 | 0.2513 | 0.106* | |
H2C | 0.6487 | 0.5860 | 0.1589 | 0.106* | |
C3 | 0.7631 (6) | 0.8295 (3) | −0.0050 (3) | 0.0635 (10) | |
H4A | 0.6740 | 0.8410 | 0.0389 | 0.095* | |
H4B | 0.8098 | 0.9157 | −0.0224 | 0.095* | |
H4C | 0.8813 | 0.7759 | 0.0132 | 0.095* | |
C4 | 0.4105 (6) | 0.8611 (3) | −0.0979 (2) | 0.0630 (10) | |
H1A | 0.3125 | 0.8304 | −0.1406 | 0.094* | |
H1B | 0.4597 | 0.9487 | −0.1111 | 0.094* | |
H1C | 0.3437 | 0.8650 | −0.0475 | 0.094* | |
Na1 | 0.74441 (16) | 0.42912 (10) | −0.02932 (6) | 0.0324 (2) | |
O2 | 0.5379 (3) | 0.62069 (18) | −0.05373 (12) | 0.0401 (5) | |
O1 | 0.9778 (3) | 0.4577 (2) | 0.08719 (11) | 0.0397 (5) | |
S1 | 0.91242 (12) | 0.43317 (7) | 0.17235 (4) | 0.03852 (18) | |
S2 | 0.62360 (12) | 0.74854 (7) | −0.08747 (5) | 0.04170 (19) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0597 (2) | 0.03973 (18) | 0.0550 (2) | −0.00658 (15) | 0.01907 (16) | −0.01221 (14) |
C1 | 0.060 (2) | 0.062 (2) | 0.0368 (17) | −0.0069 (17) | 0.0002 (16) | −0.0009 (15) |
C2 | 0.072 (3) | 0.085 (3) | 0.056 (2) | 0.025 (2) | 0.016 (2) | −0.005 (2) |
C3 | 0.048 (2) | 0.049 (2) | 0.092 (3) | −0.0068 (16) | −0.007 (2) | −0.0026 (19) |
C4 | 0.068 (2) | 0.0321 (16) | 0.085 (3) | 0.0036 (16) | −0.015 (2) | 0.0140 (17) |
Na1 | 0.0328 (6) | 0.0304 (5) | 0.0343 (6) | −0.0003 (4) | 0.0049 (5) | 0.0000 (4) |
O2 | 0.0406 (11) | 0.0259 (9) | 0.0552 (12) | 0.0003 (8) | 0.0135 (10) | 0.0082 (9) |
O1 | 0.0377 (11) | 0.0554 (12) | 0.0268 (10) | −0.0104 (9) | 0.0067 (8) | −0.0010 (9) |
S1 | 0.0432 (4) | 0.0430 (4) | 0.0301 (4) | −0.0122 (3) | 0.0079 (3) | −0.0019 (3) |
S2 | 0.0504 (5) | 0.0298 (4) | 0.0465 (4) | −0.0020 (3) | 0.0148 (4) | 0.0052 (3) |
Na1—Br1 | 2.8869 (13) | C4—H1A | 0.9600 |
C1—S1 | 1.774 (3) | C4—H1B | 0.9600 |
C1—H3A | 0.9600 | C4—H1C | 0.9600 |
C1—H3B | 0.9600 | Na1—O2 | 2.345 (2) |
C1—H3C | 0.9600 | Na1—O1 | 2.365 (2) |
C2—S1 | 1.772 (3) | Na1—O1i | 2.368 (2) |
C2—H2A | 0.9600 | Na1—O2ii | 2.399 (2) |
C2—H2B | 0.9600 | Na1—Na1ii | 3.639 (2) |
C2—H2C | 0.9600 | Na1—Na1i | 3.646 (2) |
C3—S2 | 1.767 (4) | O2—S2 | 1.5095 (19) |
C3—H4A | 0.9600 | O2—Na1ii | 2.399 (2) |
C3—H4B | 0.9600 | O1—S1 | 1.5093 (19) |
C3—H4C | 0.9600 | O1—Na1i | 2.368 (2) |
C4—S2 | 1.770 (3) | ||
S1—C1—H3A | 109.5 | O1i—Na1—O2ii | 161.75 (8) |
S1—C1—H3B | 109.5 | O2—Na1—Br1 | 123.62 (7) |
H3A—C1—H3B | 109.5 | O1—Na1—Br1 | 125.28 (6) |
S1—C1—H3C | 109.5 | O1i—Na1—Br1 | 99.62 (6) |
H3A—C1—H3C | 109.5 | O2ii—Na1—Br1 | 98.55 (6) |
H3B—C1—H3C | 109.5 | O2—Na1—Na1ii | 40.47 (5) |
S1—C2—H2A | 109.5 | O1—Na1—Na1ii | 104.47 (7) |
S1—C2—H2B | 109.5 | O1i—Na1—Na1ii | 127.73 (7) |
H2A—C2—H2B | 109.5 | O2ii—Na1—Na1ii | 39.36 (5) |
S1—C2—H2C | 109.5 | Br1—Na1—Na1ii | 117.05 (5) |
H2A—C2—H2C | 109.5 | O2—Na1—Na1i | 102.64 (7) |
H2B—C2—H2C | 109.5 | O1—Na1—Na1i | 39.66 (5) |
S2—C3—H4A | 109.5 | O1i—Na1—Na1i | 39.60 (5) |
S2—C3—H4B | 109.5 | O2ii—Na1—Na1i | 129.41 (7) |
H4A—C3—H4B | 109.5 | Br1—Na1—Na1i | 118.90 (5) |
S2—C3—H4C | 109.5 | Na1ii—Na1—Na1i | 124.03 (6) |
H4A—C3—H4C | 109.5 | S2—O2—Na1 | 122.25 (11) |
H4B—C3—H4C | 109.5 | S2—O2—Na1ii | 133.96 (11) |
S2—C4—H1A | 109.5 | Na1—O2—Na1ii | 100.17 (8) |
S2—C4—H1B | 109.5 | S1—O1—Na1 | 121.89 (11) |
H1A—C4—H1B | 109.5 | S1—O1—Na1i | 135.81 (12) |
S2—C4—H1C | 109.5 | Na1—O1—Na1i | 100.74 (8) |
H1A—C4—H1C | 109.5 | O1—S1—C2 | 105.70 (15) |
H1B—C4—H1C | 109.5 | O1—S1—C1 | 106.60 (13) |
O2—Na1—O1 | 111.08 (8) | C2—S1—C1 | 97.05 (18) |
O2—Na1—O1i | 88.73 (8) | O2—S2—C3 | 106.45 (15) |
O1—Na1—O1i | 79.26 (8) | O2—S2—C4 | 105.67 (15) |
O2—Na1—O2ii | 79.83 (8) | C3—S2—C4 | 97.61 (18) |
O1—Na1—O2ii | 91.58 (8) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [NaBr(C2H6OS)2] |
Mr | 259.16 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 291 |
a, b, c (Å) | 6.433 (3), 9.969 (4), 16.430 (6) |
β (°) | 94.046 (17) |
V (Å3) | 1051.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.30 |
Crystal size (mm) | 0.21 × 0.20 × 0.19 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.461, 0.491 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10170, 2401, 1772 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.072, 1.04 |
No. of reflections | 2401 |
No. of parameters | 95 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
Na1—Br1 | 2.8869 (13) | Na1—O1i | 2.368 (2) |
Na1—O2 | 2.345 (2) | Na1—O2ii | 2.399 (2) |
Na1—O1 | 2.365 (2) | ||
O2—Na1—O1 | 111.08 (8) | O1i—Na1—O2ii | 161.75 (8) |
O2—Na1—O1i | 88.73 (8) | O2—Na1—Br1 | 123.62 (7) |
O1—Na1—O1i | 79.26 (8) | O1—Na1—Br1 | 125.28 (6) |
O2—Na1—O2ii | 79.83 (8) | O1i—Na1—Br1 | 99.62 (6) |
O1—Na1—O2ii | 91.58 (8) | O2ii—Na1—Br1 | 98.55 (6) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z. |
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.