Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016510/fr1244sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016510/fr1244Isup2.hkl |
CCDC reference: 143240
N-Maleoylglycine was prepared by the literature method (Rich et al., 1975). Solid maleamic acid (8.4 mmol) was suspended in dry toluene and treated with triethylamine (17.0 mmol). The mixture was refluxed under vigorous stirring for 4 h. The water formed was continuously removed via Dean–Stark apparatus. After cooling, toluene was removed from the orange layer, trimethyltin chloride (8.4 mmol) was added in toluene and the mixture was refluxed for 3–4 h. On cooling, triethylammonium chloride was filtered off, toluene removed using a rotary evaporator, and the mass left was crystallized from dichloromethane/n-hexane (1:1) solution to yield thin needles of the title compound.
Most H atoms were visible in difference maps, but were placed in idealized positions (0.95–0.99 Å) for refinement, which utilized a riding model. A torsional parameter was refined for each methyl group. The final difference map was essentially free of any chemically significant features, with the highest electron density 0.9 Å from the Sn atom. There are 51 Å3 voids in the structure at the inversion centres; the final difference map showed no significant electron density in those regions.
Data collection: MSC/AFC Diffractometer Control (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97.
[Sn(CH3)3(C6H4NO4)] | F(000) = 624 |
Mr = 317.89 | Dx = 1.633 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
a = 6.5848 (15) Å | Cell parameters from 20 reflections |
b = 9.991 (4) Å | θ = 10.0–15.0° |
c = 19.688 (6) Å | µ = 1.97 mm−1 |
β = 93.31 (3)° | T = 170 K |
V = 1293.1 (7) Å3 | Block, colourless |
Z = 4 | 0.58 × 0.30 × 0.28 mm |
Rigaku AFC-6S diffractometer | 2205 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.054 |
Graphite monochromator | θmax = 27.5°, θmin = 2.9° |
ω–2θ scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) ψ scan (3 reflections) (North et al., 1968) | k = 0→12 |
Tmin = 0.373, Tmax = 0.576 | l = −25→25 |
3235 measured reflections | 3 standard reflections every 200 reflections |
2985 independent reflections | intensity decay: <0.2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.147 | w = 1/[σ2(Fo2) + (0.0443P)2 + 11.0866P] where P = (Fo2 + 2Fc2)/3 |
S = 1.20 | (Δ/σ)max < 0.001 |
2985 reflections | Δρmax = 1.27 e Å−3 |
140 parameters | Δρmin = −1.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0006 (5) |
[Sn(CH3)3(C6H4NO4)] | V = 1293.1 (7) Å3 |
Mr = 317.89 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.5848 (15) Å | µ = 1.97 mm−1 |
b = 9.991 (4) Å | T = 170 K |
c = 19.688 (6) Å | 0.58 × 0.30 × 0.28 mm |
β = 93.31 (3)° |
Rigaku AFC-6S diffractometer | 2205 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ scan (3 reflections) (North et al., 1968) | Rint = 0.054 |
Tmin = 0.373, Tmax = 0.576 | 3 standard reflections every 200 reflections |
3235 measured reflections | intensity decay: <0.2% |
2985 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0443P)2 + 11.0866P] where P = (Fo2 + 2Fc2)/3 |
2985 reflections | Δρmax = 1.27 e Å−3 |
140 parameters | Δρmin = −1.38 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.43129 (7) | 0.43723 (5) | 0.71962 (2) | 0.02729 (18) | |
O1 | 0.3498 (9) | 0.2800 (5) | 0.6442 (3) | 0.0349 (13) | |
O2 | 0.4945 (9) | 0.1244 (6) | 0.7103 (3) | 0.0390 (13) | |
O3 | 0.4406 (9) | 0.1879 (8) | 0.4785 (3) | 0.0539 (17) | |
O4 | −0.0976 (12) | 0.0980 (9) | 0.6040 (4) | 0.071 (2) | |
N1 | 0.2030 (11) | 0.1115 (7) | 0.5502 (3) | 0.0352 (15) | |
C1 | 0.2687 (15) | 0.5749 (9) | 0.6554 (5) | 0.045 (2) | |
H1A | 0.3637 | 0.6224 | 0.6274 | 0.068* | |
H1B | 0.1984 | 0.6395 | 0.6833 | 0.068* | |
H1C | 0.1688 | 0.5266 | 0.6259 | 0.068* | |
C2 | 0.7494 (14) | 0.4166 (11) | 0.7079 (7) | 0.061 (3) | |
H2A | 0.8215 | 0.4135 | 0.7528 | 0.092* | |
H2B | 0.7981 | 0.4931 | 0.6822 | 0.092* | |
H2C | 0.7749 | 0.3337 | 0.6831 | 0.092* | |
C3 | 0.2775 (13) | 0.3479 (9) | 0.7987 (4) | 0.0392 (19) | |
H3A | 0.3758 | 0.3021 | 0.8299 | 0.059* | |
H3B | 0.1785 | 0.2829 | 0.7795 | 0.059* | |
H3C | 0.2065 | 0.4170 | 0.8235 | 0.059* | |
C4 | 0.3995 (12) | 0.1603 (7) | 0.6567 (4) | 0.0300 (16) | |
C5 | 0.3382 (15) | 0.0570 (9) | 0.6037 (4) | 0.044 (2) | |
H5A | 0.4617 | 0.0215 | 0.5836 | 0.052* | |
H5B | 0.2698 | −0.0184 | 0.6257 | 0.052* | |
C6 | 0.2685 (12) | 0.1827 (9) | 0.4956 (4) | 0.0355 (17) | |
C7 | 0.0836 (13) | 0.2479 (10) | 0.4630 (5) | 0.046 (2) | |
H7 | 0.0791 | 0.2999 | 0.4226 | 0.055* | |
C8 | −0.0712 (13) | 0.2215 (11) | 0.4996 (5) | 0.049 (2) | |
H8 | −0.2068 | 0.2515 | 0.4900 | 0.058* | |
C9 | −0.0020 (14) | 0.1382 (10) | 0.5579 (5) | 0.043 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0307 (3) | 0.0246 (3) | 0.0259 (3) | 0.0004 (2) | −0.00420 (17) | 0.0013 (2) |
O1 | 0.056 (4) | 0.029 (3) | 0.019 (3) | 0.005 (2) | −0.005 (2) | 0.000 (2) |
O2 | 0.054 (4) | 0.031 (3) | 0.031 (3) | 0.008 (3) | −0.006 (3) | 0.003 (2) |
O3 | 0.036 (3) | 0.078 (5) | 0.048 (4) | 0.005 (3) | 0.004 (3) | −0.004 (4) |
O4 | 0.073 (5) | 0.074 (6) | 0.068 (5) | −0.013 (4) | 0.028 (4) | 0.016 (4) |
N1 | 0.040 (4) | 0.034 (3) | 0.031 (3) | 0.002 (3) | −0.004 (3) | −0.003 (3) |
C1 | 0.055 (5) | 0.030 (4) | 0.049 (5) | 0.005 (4) | −0.019 (4) | 0.008 (4) |
C2 | 0.033 (5) | 0.062 (7) | 0.090 (8) | 0.003 (5) | 0.007 (5) | 0.000 (6) |
C3 | 0.042 (5) | 0.034 (4) | 0.043 (5) | −0.005 (4) | 0.008 (4) | 0.002 (4) |
C4 | 0.040 (4) | 0.025 (4) | 0.025 (4) | 0.006 (3) | 0.000 (3) | −0.001 (3) |
C5 | 0.067 (6) | 0.028 (4) | 0.034 (4) | 0.009 (4) | −0.011 (4) | −0.003 (4) |
C6 | 0.032 (4) | 0.044 (5) | 0.029 (4) | 0.002 (4) | −0.003 (3) | −0.008 (4) |
C7 | 0.036 (5) | 0.061 (6) | 0.040 (5) | 0.008 (4) | −0.005 (4) | 0.011 (4) |
C8 | 0.027 (4) | 0.068 (7) | 0.051 (5) | 0.005 (4) | −0.005 (4) | 0.001 (5) |
C9 | 0.041 (5) | 0.045 (5) | 0.044 (5) | −0.007 (4) | 0.005 (4) | −0.006 (4) |
Sn1—C1 | 2.116 (8) | O4—C9 | 1.203 (11) |
Sn1—C2 | 2.131 (9) | N1—C6 | 1.378 (11) |
Sn1—C3 | 2.104 (8) | N1—C9 | 1.393 (11) |
Sn1—O1 | 2.207 (5) | N1—C5 | 1.446 (10) |
Sn1—O2i | 2.358 (6) | C4—C5 | 1.507 (11) |
O1—C4 | 1.260 (9) | C6—C7 | 1.493 (11) |
O2—C4 | 1.248 (9) | C7—C8 | 1.308 (13) |
O2—Sn1ii | 2.358 (6) | C8—C9 | 1.468 (13) |
O3—C6 | 1.202 (10) | ||
C1—Sn1—C2 | 117.7 (4) | C9—N1—C5 | 123.5 (8) |
C1—Sn1—C3 | 118.0 (4) | O2—C4—O1 | 123.4 (7) |
C2—Sn1—C3 | 123.9 (4) | O2—C4—C5 | 119.3 (7) |
C1—Sn1—O1 | 88.0 (3) | O1—C4—C5 | 117.2 (7) |
C2—Sn1—O1 | 93.4 (4) | N1—C5—C4 | 112.1 (7) |
C3—Sn1—O1 | 95.0 (3) | O3—C6—N1 | 125.7 (8) |
C1—Sn1—O2i | 85.1 (3) | O3—C6—C7 | 128.3 (9) |
C2—Sn1—O2i | 88.2 (4) | N1—C6—C7 | 106.0 (7) |
C3—Sn1—O2i | 89.8 (3) | C8—C7—C6 | 108.6 (8) |
O1—Sn1—O2i | 172.90 (19) | C7—C8—C9 | 109.1 (8) |
C4—O1—Sn1 | 119.5 (5) | O4—C9—N1 | 124.8 (9) |
C4—O2—Sn1ii | 143.1 (5) | O4—C9—C8 | 128.8 (9) |
C6—N1—C9 | 109.6 (7) | N1—C9—C8 | 106.4 (7) |
C6—N1—C5 | 123.7 (7) | ||
C3—Sn1—O1—C4 | −57.9 (7) | C5—N1—C6—O3 | 14.5 (14) |
C1—Sn1—O1—C4 | −175.8 (7) | C9—N1—C6—C7 | −5.9 (9) |
C2—Sn1—O1—C4 | 66.5 (7) | C5—N1—C6—C7 | −166.3 (8) |
O2i—Sn1—O1—C4 | 169.8 (16) | O3—C6—C7—C8 | −177.1 (10) |
Sn1ii—O2—C4—O1 | 159.5 (6) | N1—C6—C7—C8 | 3.7 (11) |
Sn1ii—O2—C4—C5 | −20.1 (14) | C6—C7—C8—C9 | −0.1 (12) |
Sn1—O1—C4—O2 | −0.2 (11) | C6—N1—C9—O4 | −174.5 (9) |
Sn1—O1—C4—C5 | 179.4 (6) | C5—N1—C9—O4 | −14.0 (14) |
C6—N1—C5—C4 | 82.1 (10) | C6—N1—C9—C8 | 5.9 (10) |
C9—N1—C5—C4 | −75.6 (11) | C5—N1—C9—C8 | 166.3 (8) |
O2—C4—C5—N1 | 170.9 (8) | C7—C8—C9—O4 | 176.9 (11) |
O1—C4—C5—N1 | −8.7 (12) | C7—C8—C9—N1 | −3.4 (11) |
C9—N1—C6—O3 | 174.9 (9) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Sn(CH3)3(C6H4NO4)] |
Mr | 317.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 170 |
a, b, c (Å) | 6.5848 (15), 9.991 (4), 19.688 (6) |
β (°) | 93.31 (3) |
V (Å3) | 1293.1 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.97 |
Crystal size (mm) | 0.58 × 0.30 × 0.28 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ scan (3 reflections) (North et al., 1968) |
Tmin, Tmax | 0.373, 0.576 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3235, 2985, 2205 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.147, 1.20 |
No. of reflections | 2985 |
No. of parameters | 140 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0443P)2 + 11.0866P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.27, −1.38 |
Computer programs: MSC/AFC Diffractometer Control (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN, SHELXL97.
Sn1—C1 | 2.116 (8) | O2—C4 | 1.248 (9) |
Sn1—C2 | 2.131 (9) | O3—C6 | 1.202 (10) |
Sn1—C3 | 2.104 (8) | O4—C9 | 1.203 (11) |
Sn1—O1 | 2.207 (5) | N1—C6 | 1.378 (11) |
Sn1—O2i | 2.358 (6) | N1—C9 | 1.393 (11) |
O1—C4 | 1.260 (9) | N1—C5 | 1.446 (10) |
C1—Sn1—C2 | 117.7 (4) | C3—Sn1—O2i | 89.8 (3) |
C1—Sn1—C3 | 118.0 (4) | O1—Sn1—O2i | 172.90 (19) |
C2—Sn1—C3 | 123.9 (4) | C4—O1—Sn1 | 119.5 (5) |
C1—Sn1—O1 | 88.0 (3) | C4—O2—Sn1ii | 143.1 (5) |
C2—Sn1—O1 | 93.4 (4) | C6—N1—C9 | 109.6 (7) |
C3—Sn1—O1 | 95.0 (3) | C6—N1—C5 | 123.7 (7) |
C1—Sn1—O2i | 85.1 (3) | C9—N1—C5 | 123.5 (8) |
C2—Sn1—O2i | 88.2 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2. |
In the past two decades, organotin carboxylates have received much attention because of their extensive applications in different fields of life science (Davis et al., 1982; Tagliavini, 1992; Brimah et al., 1994), especially biocidal applications, utilizing the antitumour and anticancer activities of such compounds (Gielen et al., 1994; de Vos et al., 1998). Accordingly and in view of our continuous interest in the synthesis, characterization, biological applications and crystal structures of organotin carboxylates (Danish et al., 1995; Parvez et al., 1997, 1999, 2000), we have prepared a new organotin derivative of 2-maleimidoacetic acid, commonly known as N-maleoylglycine. In this paper we now report the crystal structure of (N-maleoylglycinato)trimethyltin(IV), (I).
The structure of (I) is presented in Fig. 1. The Sn atom is bonded to three methyl groups in the equatorial positions with Sn—C distances [mean 2.117 (11) Å] that are essentially equal within experimental uncertainty and that are in agreement with the values reported for related structures (Allen et al., 1983). The axial positions are occupied by O atoms from the carboxylate residues, with a nearly linear O—Sn—O angle of 172.90 (19)°. The intramolecular distance Sn1—O1 [2.207 (5) Å] is significantly shorter than the intermolecular distance Sn1—O2i [2.358 (6) Å; symmetry code: (i) 1 - x, 1/2 + y, 3/2 - z], indicating that the former is a covalent bond and the latter is a coordinate bond. The Sn atom has distorted trigonal bipyramidal coordination geometry with the Sn atom 0.084 (6) Å out of the equatorial plane formed by the three methyl C atoms, towards the more strongly bound O1 atom. This trend is in line with other similar structures reported by our laboratories, as mentioned above.
The molecular dimensions in the ligand, N-maleoylglycine, are normal, with the five-membered ring essentially planar [maximum deviation: N1 0.035 (5) Å], and slightly pyramidal geometry about N1. The structure is composed of infinite chains of (I) running along the b axis.
A few examples of crystal structures containing triorganotin complexes of protected compounds, forming polymeric chains similar to (I), are: (3-indolylacetato-O,O')tri-n-butyltin (Molloy et al.,1987), (glutamato-O,O')trimethyltin (Huber et al., 1989), [3-(2-thienyl)-2-propenoato)]triethyltin (Danish et al., 1995), 2-[(2,3-dimethylphenyl)aminobenzoato-O,O']trimethyltin (Tahir et al., 1997), (picolinato N-oxide)triphenyltin and (nicotinato N-oxide)triphenyltin (Ng & Kumar Das, 1995), triphenyl(3-ureidopropionato-O,O')tin (Lo et al., 1991) and (N-salicylidene-6-aminohexanoato-O,O')triphenyltin (Toong et al., 1992).