(2-Amido­ethyl-κ2C,O)trichloro­(3-chloro­propionamide-κO)stannane

Tiekink, E.R.T.; Wardell, J.L.; Wardell, S.M.S.V.

doi:10.1107/S1600536806010543

metal-organic compounds

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ISSN: 2056-9890

Volume 62| Part 5| May 2006| Pages m971-m973

https://doi.org/10.1107/S1600536806010543

(2-Amidoethyl-κ²C,O)trichloro(3-chloropropionamide-κO)stannane

Edward R. T. Tiekink,^a ^* James L. Wardell ^b,^c and Solange M. S. V. Wardell ^d ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, 6900 North Loop 1604 West, San Antonio, Texas 78249-0698, USA, ^bDepartment of Chemistry, University of Aberdeen, Old Aberdeen, AB24 3UE, Scotland, ^cInstituto de Química, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, and ^dComplexo Tecnológico de Medicamentos Farmanguinhos, Av. Comandante Guaranys 447, Jacarepaguá - Rio de Janeiro, RJ, Brazil
^*Correspondence e-mail: Edward.Tiekink@utsa.edu, solangewardell@yahoo.co.uk

(Received 21 March 2006; accepted 22 March 2006; online 7 April 2006)

The Sn atom in the title compound, [Sn(C₃H₆NO)Cl₃(C₃H₆ClNO)], exists within a fac-CCl₃O₂ donor set that defines an octahedral geometry and features a negatively charged chelating 2-amidoethyl ligand as well as a neutral 3-chloropropionamide ligand that coordinates exclusively via the carbonyl-O atom. Extensive N—H⋯O and N—H⋯Cl hydrogen bonding leads to a layer structure.

Comment

Functionally substituted organotin compounds, X₃SnCR₂CH₂COY (1) and the less well studied X₂Sn(CR₂CH₂COY)₂ (2), for X = halide, R = H or alkyl, and Y = alkyl, aryl, alkoxy or NH₂, are readily available from reactions of R₂C=CHCOY, HX and SnX₂ (generally for 1) or Sn (generally for 2) (Hutton & Oakes, 1976 ; Hutton et al., 1978 ; Burley et al., 1979 ). Original interest in these compounds was primarily involved with their industrial potential as precursors of PVC stabilizers, but much attention was also paid to their coordination chemistry (Milne et al., 2005 , and references therein). The title compound (I) was an unexpected product isolated from the reaction between Sn, H₂C=CHCONH₂ and HCl in diethyl ether solution.

The structure of (I) (Fig. 1 and Table 1) features an Sn atom within a disorted octahedral geometry defined by three Cl atoms, arranged facially, C and O of the chelating 2-amidoethyl ligand and carbonyl-O from 3-chloropropionamide. The 2-amidoethyl ligand in (I) coordinates in a similar fashion to that found in the only other structure of an amidotin compound, viz. Cl₂Sn(CH₂CH₂CONH₂)₂ (Harrison et al., 1979 ; also see Marsh (1997 ) for space-group revision).

The crystal structure is stabilized by hydrogen-bonding interactions as summarized in Table 2. Adjacent molecules form inversion-related dimers with an eight-membered {⋯H—N—C=O}₂ ring via N1—H1a⋯O1 hydrogen bonds shown as `(a)' in Fig. 2. These pairs associate with adjacent pairs via N—H⋯Cl3ⁱⁱ interactions involving the second N1—H amide H atom so as to form a double chain aligned along the a axis, `(b)' in Fig. 2. N2—H1a forms an intramolecular hydrogen bond to Cl2 and N2—H1b forms an interaction with Cl3ⁱⁱⁱ so that this Cl atom forms two hydrogen bonds. As these latter interactions extend in the b-axis direction, a 2-dimensional supramolecular array is formed. Connections between layers are made primarily via C4—H4a⋯Cl^iv interactions. It is the nature of the Cl⋯H interactions that readily accounts for the disparity in the Sn—Cl distances that span the range 2.3730 (11) to 2.4735 (10) Å. The Sn—Cl bond distances systematically elongate in accord with the number of such interactions so that Sn—Cl1, with the Cl1 atom forming only a weak C—H⋯Cl contact, is significantly shorter than the Sn—Cl2 bond, with the Cl2 atom forming a single N—H⋯Cl contact, which in turn is significantly shorter than the Sn—Cl3 bond, with the Cl3 atom involved in two N—H⋯Cl contacts.

Figure 1
The molecular structure of (I)

, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Figure 2
Packing diagram for (I)

, viewed down the b axis. Colour code: Sn (brown), Cl (pink), O (red), N (blue), C (grey) & H (green). Hydrogen bonds are shown as dashed lines.

Experimental

The title compound (I) was isolated from a reaction between Sn, acrylonitrile and HCl in diethyl ether solution following a general procedure (Hutton & Oakes, 1976). HCl was bubbled through a well stirred suspension of granulated Sn (0.1 mol) and H₂C=CHCONH₂ (0.22 mol) in Et₂O (40 ml), maintained at 273–283 K until all the Sn had reacted. The reaction mixture was stirred for a further 2 h and all volatiles removed under vacuum. The thick oily liquid was extracted into CH₂Cl₂ and hexane (1:) added. On leaving the mixture at 268 K, a small amount of crystalline (I) was initially deposited, m. p. 524–528 K (decomposition).

Crystal data

[Sn(C₃H₆NO)Cl₃(C₃H₆ClNO)]
M_r = 404.67
Triclinic, $[P \overline 1]$
a = 7.3582 (3) Å
b = 9.0387 (5) Å
c = 10.4342 (6) Å
α = 92.005 (2)°
β = 104.529 (3)°
γ = 96.222 (3)°
V = 666.42 (6) Å³
Z = 2
D_x = 2.017 Mg m⁻³
Mo Kα radiation
Cell parameters from 2904 reflections
θ = 2.9–27.5°
μ = 2.70 mm⁻¹
T = 120 (2) K
Needle, colourless
0.14 × 0.04 × 0.02 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.704, T_max = 0.948
13278 measured reflections
3086 independent reflections
2721 reflections with I > 2σ(I)
R_int = 0.068
θ_max = 27.8°
h = −9 → 8
k = −11 → 11
l = −13 → 13

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.09
3086 reflections
136 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0474P)² + 1.4199P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max <0.001
Δρ_max = 1.11 e Å⁻³
Δρ_min = −1.54 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sn—Cl1	2.3730 (11)
Sn—Cl2	2.4038 (11)
Sn—Cl3	2.4735 (10)
Sn—O1	2.239 (3)
Sn—O2	2.240 (3)
Sn—C1	2.138 (4)
Cl4—C4	1.786 (5)
O1—C3	1.263 (5)
O2—C6	1.257 (5)
N1—C3	1.313 (5)
N2—C6	1.307 (6)

Cl1—Sn—Cl2	93.44 (4)
Cl1—Sn—Cl3	90.04 (4)
Cl1—Sn—O1	84.52 (8)
Cl1—Sn—O2	83.93 (9)
Cl1—Sn—C1	162.38 (13)
Cl2—Sn—Cl3	93.97 (4)
Cl2—Sn—O1	177.51 (8)
Cl2—Sn—O2	96.20 (8)
Cl2—Sn—C1	102.37 (12)
Cl3—Sn—O1	87.47 (8)
Cl3—Sn—O2	168.47 (9)
Cl3—Sn—C1	96.48 (13)
O1—Sn—O2	82.18 (11)
O1—Sn—C1	79.47 (14)
O2—Sn—C1	86.66 (16)
Sn—O1—C3	112.5 (3)
Sn—O2—C6	135.8 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1a⋯O1ⁱ	0.88	2.06	2.924 (5)	167
N1—H1b⋯Cl3ⁱⁱ	0.88	2.47	3.326 (4)	166
N2—H2a⋯Cl2	0.88	2.40	3.227 (4)	156
N2—H2b⋯Cl3ⁱⁱⁱ	0.88	2.40	3.250 (4)	163
C4—H4a⋯Cl1^iv	0.99	2.79	3.742 (5)	163
C4—H4b⋯O2	0.99	2.59	2.923 (6)	100
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x+1, y, z; (iii) x, y-1, z; (iv) -x+1, -y+1, -z+1.

All H atoms were allowed to ride on their parent atoms in the riding-model approximation at distances of 0.99 (C—H) and 0.88 Å (N—H), and with U_iso(H) values of 1.2U_eq(C,N). The maximum residual electron density peak was located 1.26 Å from the Sn atom and the deepest hole was located 0.77 Å also from the Sn atom.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT (Otwinowski & Minor, 1997 ); data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Crystal Impact, 2006 ).; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806010543/sj2023sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806010543/sj2023Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT (Otwinowski & Minor, 1997); data reduction: DENZO & COLLECT; program(s) used to solve structure: SHELXS97; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND(Crystal Impact, 2006).; software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

[Sn(C₃H₆ClNO)(C₃H₆NO)Cl₃]	Z = 2
M_r = 404.67	F(000) = 392
Triclinic, P1	D_x = 2.017 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3582 (3) Å	Cell parameters from 2904 reflections
b = 9.0387 (5) Å	θ = 2.9–27.5°
c = 10.4342 (6) Å	µ = 2.70 mm⁻¹
α = 92.005 (2)°	T = 120 K
β = 104.529 (3)°	Plate, colourless
γ = 96.222 (3)°	0.14 × 0.04 × 0.02 mm
V = 666.42 (6) Å³

Data collection top

Bruker-Nonius 95mm CCD camera on a κ-goniostat diffractometer	3086 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	2721 reflections with I > 2σ(I)
10cm confocal mirrors monochromator	R_int = 0.068
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.8°, θ_min = 2.9°
φ and ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
T_min = 0.704, T_max = 0.948	l = −13→13
13278 measured reflections

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0474P)² + 1.4199P] where P = (F_o² + 2F_c²)/3
3086 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 1.11 e Å⁻³
0 restraints	Δρ_min = −1.54 e Å⁻³

Special details top

Experimental. IR (CsI, cm^-1): ν 3396, 3254, 1652, 1576, 1409, 1295, 1166, 970. 740, 666, 616, 584, 480, 367, 314.

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

	x	y	z	U_iso*/U_eq
Sn	0.10766 (4)	0.75079 (3)	0.23109 (3)	0.01770 (12)
Cl1	−0.00142 (15)	0.72255 (13)	0.42547 (11)	0.0257 (2)
Cl2	−0.16772 (15)	0.60455 (12)	0.09151 (12)	0.0266 (3)
Cl3	−0.02963 (15)	0.98881 (11)	0.19741 (11)	0.0243 (2)
Cl4	0.5294 (2)	0.26714 (17)	0.17569 (13)	0.0413 (3)
O1	0.3632 (4)	0.8805 (3)	0.3682 (3)	0.0197 (6)
O2	0.2650 (4)	0.5578 (3)	0.3009 (3)	0.0251 (7)
N1	0.6626 (5)	0.9740 (4)	0.3833 (4)	0.0227 (8)
H1A	0.6735	1.0141	0.4633	0.027*
H1B	0.7590	0.9852	0.3474	0.027*
N2	0.0551 (6)	0.3494 (4)	0.2481 (4)	0.0297 (9)
H2A	−0.0356	0.3990	0.2056	0.036*
H2B	0.0331	0.2524	0.2532	0.036*
C1	0.2878 (6)	0.7847 (5)	0.1001 (4)	0.0234 (9)
H1C	0.2785	0.6926	0.0434	0.028*
H1D	0.2486	0.8659	0.0418	0.028*
C2	0.4886 (7)	0.8253 (6)	0.1821 (5)	0.0281 (10)
H2C	0.5566	0.8945	0.1336	0.034*
H2D	0.5525	0.7339	0.1931	0.034*
C3	0.5025 (6)	0.8973 (5)	0.3175 (4)	0.0173 (8)
C4	0.5541 (7)	0.3544 (6)	0.3364 (5)	0.0283 (10)
H4A	0.6551	0.3132	0.4018	0.034*
H4B	0.5918	0.4628	0.3353	0.034*
C5	0.3718 (7)	0.3298 (5)	0.3779 (5)	0.0265 (10)
H5A	0.3978	0.3566	0.4741	0.032*
H5B	0.3224	0.2226	0.3627	0.032*
C6	0.2227 (6)	0.4197 (5)	0.3038 (4)	0.0226 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.01735 (18)	0.01386 (17)	0.02147 (19)	0.00121 (11)	0.00494 (12)	−0.00209 (11)
Cl1	0.0240 (5)	0.0293 (6)	0.0262 (6)	0.0040 (4)	0.0102 (4)	0.0052 (4)
Cl2	0.0222 (5)	0.0192 (5)	0.0339 (6)	0.0013 (4)	0.0003 (4)	−0.0066 (4)
Cl3	0.0262 (5)	0.0149 (5)	0.0345 (6)	0.0035 (4)	0.0125 (4)	0.0021 (4)
Cl4	0.0492 (8)	0.0498 (8)	0.0325 (7)	0.0197 (6)	0.0182 (6)	0.0047 (6)
O1	0.0161 (14)	0.0207 (15)	0.0216 (15)	−0.0011 (11)	0.0061 (12)	−0.0067 (12)
O2	0.0208 (15)	0.0153 (15)	0.0381 (19)	0.0038 (12)	0.0046 (13)	0.0029 (13)
N1	0.0200 (18)	0.0232 (19)	0.025 (2)	−0.0005 (14)	0.0090 (15)	−0.0054 (15)
N2	0.030 (2)	0.0147 (18)	0.039 (2)	0.0007 (15)	0.0000 (18)	0.0020 (16)
C1	0.027 (2)	0.026 (2)	0.020 (2)	0.0012 (18)	0.0121 (18)	−0.0029 (17)
C2	0.028 (2)	0.028 (2)	0.028 (3)	−0.0013 (19)	0.012 (2)	−0.009 (2)
C3	0.0157 (19)	0.0165 (19)	0.020 (2)	0.0027 (15)	0.0052 (16)	0.0006 (15)
C4	0.026 (2)	0.027 (2)	0.031 (3)	0.0083 (18)	0.004 (2)	0.0024 (19)
C5	0.033 (3)	0.021 (2)	0.027 (2)	0.0085 (19)	0.009 (2)	0.0050 (18)
C6	0.029 (2)	0.018 (2)	0.026 (2)	0.0051 (17)	0.0173 (19)	0.0007 (17)

Geometric parameters (Å, º) top

Sn—Cl1	2.3730 (11)	N2—H2B	0.8800
Sn—Cl2	2.4038 (11)	C1—C2	1.509 (6)
Sn—Cl3	2.4735 (10)	C1—H1C	0.9900
Sn—O1	2.239 (3)	C1—H1D	0.9900
Sn—O2	2.240 (3)	C2—C3	1.510 (6)
Sn—C1	2.138 (4)	C2—H2C	0.9900
Cl4—C4	1.786 (5)	C2—H2D	0.9900
O1—C3	1.263 (5)	C4—C5	1.506 (7)
O2—C6	1.257 (5)	C4—H4A	0.9900
N1—C3	1.313 (5)	C4—H4B	0.9900
N1—H1A	0.8800	C5—C6	1.508 (6)
N1—H1B	0.8800	C5—H5A	0.9900
N2—C6	1.307 (6)	C5—H5B	0.9900
N2—H2A	0.8800

Cl1—Sn—Cl2	93.44 (4)	Sn—C1—H1D	110.0
Cl1—Sn—Cl3	90.04 (4)	H1C—C1—H1D	108.4
Cl1—Sn—O1	84.52 (8)	C1—C2—C3	113.5 (4)
Cl1—Sn—O2	83.93 (9)	C1—C2—H2C	108.9
Cl1—Sn—C1	162.38 (13)	C3—C2—H2C	108.9
Cl2—Sn—Cl3	93.97 (4)	C1—C2—H2D	108.9
Cl2—Sn—O1	177.51 (8)	C3—C2—H2D	108.9
Cl2—Sn—O2	96.20 (8)	H2C—C2—H2D	107.7
Cl2—Sn—C1	102.37 (12)	O1—C3—N1	120.5 (4)
Cl3—Sn—O1	87.47 (8)	O1—C3—C2	120.3 (4)
Cl3—Sn—O2	168.47 (9)	N1—C3—C2	119.2 (4)
Cl3—Sn—C1	96.48 (13)	C5—C4—Cl4	111.2 (3)
O1—Sn—O2	82.18 (11)	C5—C4—H4A	109.4
O1—Sn—C1	79.47 (14)	Cl4—C4—H4A	109.4
O2—Sn—C1	86.66 (16)	C5—C4—H4B	109.4
Sn—O1—C3	112.5 (3)	Cl4—C4—H4B	109.4
Sn—O2—C6	135.8 (3)	H4A—C4—H4B	108.0
C3—N1—H1A	120.0	C4—C5—C6	113.0 (4)
C3—N1—H1B	120.0	C4—C5—H5A	109.0
H1A—N1—H1B	120.0	C6—C5—H5A	109.0
C6—N2—H2A	120.0	C4—C5—H5B	109.0
C6—N2—H2B	120.0	C6—C5—H5B	109.0
H2A—N2—H2B	120.0	H5A—C5—H5B	107.8
C2—C1—Sn	108.6 (3)	O2—C6—N2	123.7 (4)
C2—C1—H1C	110.0	O2—C6—C5	118.5 (4)
Sn—C1—H1C	110.0	N2—C6—C5	117.8 (4)
C2—C1—H1D	110.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1a···O1ⁱ	0.88	2.06	2.924 (5)	167
N1—H1b···Cl3ⁱⁱ	0.88	2.47	3.326 (4)	166
N2—H2a···Cl2	0.88	2.40	3.227 (4)	156
N2—H2b···Cl3ⁱⁱⁱ	0.88	2.40	3.250 (4)	163
C4—H4a···Cl1^iv	0.99	2.79	3.742 (5)	163
C4—H4b···O2	0.99	2.59	2.923 (6)	100

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

Acknowledgements

The authors thank the EPSRC X-ray Crystallographic Service, University of Southampton for the data collection.

References

Burley, J. W., Hope, O., Hutton, R. E. & Groenenboom, C. J. (1979). J. Organomet. Chem. 170, 21–37. CrossRef CAS Web of Science Google Scholar
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