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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1562.
Published online 2009 November 11. doi:  10.1107/S160053680904687X
PMCID: PMC2971790

Bis[2-(ethoxy­carbonyl­amino)ethan­aminium] hexa­bromidostannate

Abstract

In the title salt, (C5H13N2O2)2[SnBr6], the Sn atom (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-65-m1562-efi3.jpg) exists in a slightly distorted octa­hedral geometry. The cation is non-planar as the terminal CH2NH3 + residue lies below the plane defined by the remaining non-H atoms. In the crystal, cations associate via N—H(...)O hydrogen bonds involving the ammonium and carbonyl residues, forming a 14-membered {(...)HNC2NCO}2 synthon. The cations and anions are arranged in alternating layers arranged along the a-axis direction, the major association between them being N—H(...)Br contacts.

Related literature

For background to the synthesis of the title salt, see: Duschinsky (1950 [triangle]); Kita et al. (1980 [triangle]); Smith et al. (1998 [triangle]); Tavridou et al. (1995 [triangle]); Wilson & Nowick (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1562-scheme1.jpg

Experimental

Crystal data

  • (C5H13N2O2)2[SnBr6]
  • M r = 864.48
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1562-efi4.jpg
  • a = 21.8907 (5) Å
  • b = 7.4428 (2) Å
  • c = 15.5318 (4) Å
  • β = 105.934 (2)°
  • V = 2433.34 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 10.92 mm−1
  • T = 120 K
  • 0.38 × 0.32 × 0.22 mm

Data collection

  • Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.355, T max = 0.746
  • 15137 measured reflections
  • 2777 independent reflections
  • 2450 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.070
  • S = 1.12
  • 2777 reflections
  • 120 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.87 e Å−3
  • Δρmin = −1.35 e Å−3

Data collection: COLLECT (Hooft, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904687X/hb5214sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904687X/hb5214Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from FAPEMIG (Brazil).

supplementary crystallographic information

Comment

Tin halides react with 2-imidazolidone, 1 (Scheme 2), in non-protic solvents such as dichloromethane, to form solid complexes [R2SnCl2(1-O)2] (R = Me, Bu or Ph), [MeSnCl3(1-O)2] and [SnX4(1-O)2] (X = Cl, Br or I) (Tavridou et al., 1995); 1-O is the O-bound form of 1. As reported herein, 2-imidazolidone reacts with SnBr4 in EtOH to form ethyl (2-ammonioethyl)carbamate hexabromostannate, (I), Fig. 4. The combination of SnBr4 and EtOH proved to have sufficient Brønsted acidity to open the 2-imidazidone ring. Ring opening reactions of 2-imidazolidone derivatives have been variously reported using bases, e.g. N-(2-nitrobenzenesulfonyl)-2-imidazolidon by a secondary amine, R R'NH (Wilson & Nowick, 1998) and acids, e.g., ring opening of 1-methyl-3–3-hydroxyphenyl-2-imidaxolidone by concentrated HCl to give MeNHCH2CH2NHC6H4OH-m (Duschinsky, 1950). With reduced acidity, co-crystallization can occur instead as shown by the isolation of a 1:1 adduct of 2-imidazolidone and 5-nitrosalicylic acid (Smith et al., 1998). The free base of 2 has been reported from the reaction of H2NCH2CH2NH2 with EtO2CO(MeO)CCH2 (Kita et al., 1980).

The structure of (I) comprises ethyl (2-ammonioethyl)carbamate cations and SnBr6 dianions in the ratio 2:1; the Sn atom is located on a crystallographic centre of inversion so that the asymmetric unit is defined by one cation and half an anion, Fig. 1. The cation is not planar. While the RMS deviation of the O1, O2, N1 and C1—C4 atoms is 0.019 Å, the C5 atom lies 1.410 (5) Å out of this plane; the C3/N1/C4/C5 torsion angle of 96.4 (4)°. In the anion, the Sn—Br2 bond distance of 2.5820 (4) Å is significantly shorter than the Sn–Br1 and Sn–Br3 bond distances of 2.6075 (4) and 2.6053 (4) Å, respectively, an observation rationalized in terms of the pattern of intermolecular interactions,see below. The carbonyl-O1 atom forms a hydrogen bond with an ammonium-H atom to form a dimeric aggregate, Table 1 and Fig. 2. The resulting 14-membered {···HNC2NCO}2 synthon has twofold symmetry. The remaining acidic H atoms form contacts to the Br1 and Br3 atoms, Table 1, explaining the variation of the Sn–Br bond distances, whereby the Br2 atom not engaged in a significant intermolecular contact forms the shorter of the Sn–Br bonds. Globally, the crystal packing comprises alternating layers of cations and anions stacking along the a direction.

Experimental

A solution of 2-imidazolidone (0.86 g) and SnBr4 (2.20 g) in EtOH (10 ml) was heated to 323 K for 15 minutes, cooled and maintained at room temperature to slowly form crystals of (I); m. pt. 459–463 K. IR(KBr) = 1692 cm-1.

Refinement

All H atoms were located from a difference map but, were geometrically placed (C–H = 0.98–0.99 Å, and N–H = 0.88–0.91 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C, N). The maximum and minimum residual electron density peaks of 0.85 and 1.26 e Å-3, respectively, were located 1.81 Å and 0.82 Å from the S1 and Sn atoms, respectively.

Figures

Fig. 1.
Molecular structure of (I) showing displacement ellipsoids at the 70% probability level. Unlabelled bromide ions are generated by the symmetry operation 1/2 - x, 1/2 - y, 1 - z.
Fig. 2.
Supramolecular dimer in (I) mediated by N–H···O hydrogen bonds (orange dashed lines).
Fig. 3.
Unit-cell contents for (I) viewed in projection down the c axis. The N–H···O hydrogen bonds (orange dashed lines) and N–H···Br contacts (blue dashed lines) indicate the mode of asscoiated ...
Fig. 4.
The formation of the title compound.

Crystal data

(C5H13N2O2)2[SnBr6]F(000) = 1624
Mr = 864.48Dx = 2.360 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 11507 reflections
a = 21.8907 (5) Åθ = 2.9–27.5°
b = 7.4428 (2) ŵ = 10.92 mm1
c = 15.5318 (4) ÅT = 120 K
β = 105.934 (2)°Block, light-yellow
V = 2433.34 (11) Å30.38 × 0.32 × 0.22 mm
Z = 4

Data collection

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer2777 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2450 reflections with I > 2σ(I)
graphiteRint = 0.051
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
[var phi] and ω scansh = −28→28
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)k = −9→9
Tmin = 0.355, Tmax = 0.746l = −20→20
15137 measured reflections

Refinement

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) = 0.070H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.0263P)2 + 9.0406P] where P = (Fo2 + 2Fc2)/3
2777 reflections(Δ/σ)max = 0.001
120 parametersΔρmax = 0.87 e Å3
1 restraintΔρmin = −1.35 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
Sn0.25000.25000.50000.01268 (10)
Br10.220893 (18)0.02595 (5)0.61162 (3)0.02190 (11)
Br20.135158 (17)0.22636 (5)0.39826 (3)0.02122 (11)
Br30.284421 (16)−0.01941 (5)0.41692 (3)0.01712 (11)
O1−0.02161 (12)0.3062 (4)0.6285 (2)0.0235 (6)
O20.01221 (13)0.2554 (4)0.5051 (2)0.0224 (6)
N10.08208 (14)0.3322 (5)0.6316 (2)0.0200 (7)
H1N0.10730.32590.59630.024*
N20.14598 (16)0.2592 (4)0.8785 (2)0.0183 (7)
H2N0.17490.35010.89050.027*
H3N0.16270.16060.91110.027*
H4N0.11030.29420.89310.027*
C1−0.0502 (2)0.1802 (6)0.3600 (3)0.0277 (10)
H1A−0.03230.28570.33790.042*
H1B−0.09330.15840.32190.042*
H1C−0.02350.07510.35840.042*
C2−0.05232 (18)0.2130 (6)0.4539 (3)0.0212 (9)
H2A−0.08120.31430.45610.025*
H2B−0.06770.10470.47850.025*
C30.02071 (18)0.2985 (5)0.5912 (3)0.0163 (8)
C40.10453 (17)0.3786 (5)0.7254 (3)0.0187 (8)
H4A0.06930.43150.74550.022*
H4B0.13870.46950.73390.022*
C50.1296 (2)0.2146 (6)0.7810 (3)0.0227 (9)
H5A0.09710.11850.76740.027*
H5B0.16790.16950.76570.027*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn0.01042 (17)0.01213 (17)0.0158 (2)0.00012 (12)0.00415 (14)−0.00043 (13)
Br10.0233 (2)0.01857 (19)0.0286 (2)0.00387 (15)0.01518 (17)0.00774 (16)
Br20.01230 (18)0.0248 (2)0.0236 (2)0.00109 (15)−0.00008 (16)−0.00413 (16)
Br30.01406 (18)0.01542 (18)0.0230 (2)−0.00038 (14)0.00701 (15)−0.00511 (15)
O10.0150 (13)0.0372 (16)0.0200 (16)−0.0028 (12)0.0075 (11)−0.0051 (13)
O20.0141 (13)0.0355 (17)0.0170 (15)0.0003 (11)0.0034 (12)−0.0037 (12)
N10.0116 (14)0.0328 (19)0.0161 (18)−0.0009 (14)0.0046 (13)0.0002 (15)
N20.0125 (14)0.0211 (16)0.0195 (18)0.0017 (12)0.0016 (13)−0.0030 (13)
C10.031 (2)0.026 (2)0.023 (2)0.0041 (19)0.0008 (18)−0.0024 (18)
C20.0159 (18)0.026 (2)0.017 (2)0.0009 (16)−0.0038 (16)−0.0016 (17)
C30.0164 (18)0.0160 (17)0.016 (2)0.0001 (15)0.0044 (15)−0.0005 (15)
C40.0158 (17)0.0199 (18)0.019 (2)−0.0042 (15)0.0034 (15)−0.0015 (16)
C50.0205 (19)0.028 (2)0.017 (2)0.0045 (17)−0.0002 (16)−0.0079 (17)

Geometric parameters (Å, °)

Sn—Br2i2.5820 (4)N2—H3N0.9100
Sn—Br22.5820 (4)N2—H4N0.9100
Sn—Br32.6053 (4)C1—C21.493 (6)
Sn—Br3i2.6053 (4)C1—H1A0.9800
Sn—Br1i2.6075 (4)C1—H1B0.9800
Sn—Br12.6075 (4)C1—H1C0.9800
O1—C31.222 (5)C2—H2A0.9900
O2—C31.339 (5)C2—H2B0.9900
O2—C21.453 (5)C4—C51.509 (6)
N1—C31.341 (5)C4—H4A0.9900
N1—C41.445 (5)C4—H4B0.9900
N1—H1N0.8800C5—H5A0.9900
N2—C51.494 (5)C5—H5B0.9900
N2—H2N0.9100
Br2i—Sn—Br2180.000 (10)C2—C1—H1B109.5
Br2i—Sn—Br389.437 (12)H1A—C1—H1B109.5
Br2—Sn—Br390.563 (12)C2—C1—H1C109.5
Br2i—Sn—Br3i90.563 (12)H1A—C1—H1C109.5
Br2—Sn—Br3i89.437 (12)H1B—C1—H1C109.5
Br3—Sn—Br3i180.0O2—C2—C1106.4 (3)
Br2i—Sn—Br1i89.357 (13)O2—C2—H2A110.4
Br2—Sn—Br1i90.643 (13)C1—C2—H2A110.4
Br3—Sn—Br1i90.355 (12)O2—C2—H2B110.4
Br3i—Sn—Br1i89.645 (12)C1—C2—H2B110.4
Br2i—Sn—Br190.643 (13)H2A—C2—H2B108.6
Br2—Sn—Br189.357 (13)O1—C3—O2124.8 (3)
Br3—Sn—Br189.646 (12)O1—C3—N1124.2 (4)
Br3i—Sn—Br190.354 (12)O2—C3—N1111.0 (3)
Br1i—Sn—Br1180.000 (16)N1—C4—C5110.7 (3)
C3—O2—C2116.5 (3)N1—C4—H4A109.5
C3—N1—C4122.4 (3)C5—C4—H4A109.5
C3—N1—H1N114.7N1—C4—H4B109.5
C4—N1—H1N122.9C5—C4—H4B109.5
C5—N2—H2N109.5H4A—C4—H4B108.1
C5—N2—H3N109.5N2—C5—C4110.4 (3)
H2N—N2—H3N109.5N2—C5—H5A109.6
C5—N2—H4N109.5C4—C5—H5A109.6
H2N—N2—H4N109.5N2—C5—H5B109.6
H3N—N2—H4N109.5C4—C5—H5B109.6
C2—C1—H1A109.5H5A—C5—H5B108.1
C3—O2—C2—C1176.8 (3)C4—N1—C3—O2−178.8 (3)
C2—O2—C3—O1−0.8 (6)C3—N1—C4—C596.4 (4)
C2—O2—C3—N1179.1 (3)N1—C4—C5—N2−173.7 (3)
C4—N1—C3—O11.1 (6)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1n···Br3i0.882.833.501 (3)134
N2—H2n···Br1ii0.912.643.495 (3)157
N2—H3n···Br3iii0.912.843.425 (3)123
N2—H4n···O1iv0.911.882.717 (5)152

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, −y, z+1/2; (iv) −x, y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5214).

References

  • Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Duschinsky, R. (1950). Chem. Abstr. 44, 56460.
  • Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
  • Kita, K., Haruta, J-I., Tagawa, H. & Tamura, Y. (1980). J. Org. Chem. 45, 4519–4522.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smith, G., Lynch, D. E. & Bott, R. C. (1998). Aust. J. Chem. 51?, 159–164.
  • Tavridou, P., Russo, U., Marton, D., Valle, G. & Kovala-Demertzi, D. (1995). Inorg. Chim. Acta, 231, 139–145.
  • Wilson, M. E. & Nowick, J. S. (1998). Tetrahedron Lett. 39, 6613–6616.

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