catena-Poly[[trimethyl­tin(IV)]-μ-2-[(3-oxocyclo­hex-1-enyl)amino]benzoato-κ²O:O′]

The Sn atom in the title compound, [Sn(CH₃)₃(C₁₃H₁₃NO₃)]_n, is five-coordinate in a trigonal–bipyramidal environment. An intra­molecular N—H...O hydrogen bond is present.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.024
• wR factor = 0.087
• Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............      24.98 Deg.

Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.740
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Sn

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           24.98
           From the CIF: _reflns_number_total               2329
           Count of symmetry unique reflns         1557
           Completeness (_total/calc)            149.58%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       772
           Fraction of Friedel pairs measured     0.496
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: This work is part of a wide collaborative project which involves synthesis, sample preparations, activities tests, diffraction data collection and data analysis. Students also participate in the project.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

S1. Comment

The reaction of 2-(3-oxocyclohex-1-enyl)benzoic acid (Vieira et al., 2007) with Sn(CH₃)₃Cl in the presence of triethylamine yielded the title complex. The X-ray crystallographic study revealed that it crystallizes forming an infinity double-polymeric chain structure, where the anionic ligand bridges two tin centre via the monodentate carboxylic moiety and the C?O fragment, Fig. 1. The structure possess one tin atom surrounded by three methyl groups and two oxygen atoms, describing an almost perfect trigonal bypiramid. The equatorial corners are occupied by the methyl groups and the axial positions by the oxygen atoms. The angles C1—Sn—C2 and O1—Sn—O3 are all near 120° and 180° as expected for a trigonal bypiramid.

Related literature

For related literature, see: Vieira et al. (2007).

S2. Experimental

To a round-botton flask charged with 3-[(carboxyphenyl)amino]cyclohexen-2-one (1.0 g, 4.32 mmol) and triethylamine (0.6 ml, 4.32 mmol) dissolved in methanol (20 ml), was added trimethyltin chloride (0.86 g, 4.32 mmol). The X-ray quality crystals were obtained from a methanol/water (3:1) solution. IR (ν/cm^-1): 473 (ν_Sn—O). ¹H NMR (δ, CDCl₃): 8.63 d (C6), 8.0 m (C8, C9), 7.7 m (C7) 6.23 s (C16), 3.0 m (C14), 2.8 m (C12), 2.47 m (C13), 1.58 s (C1, 2, 3). ¹³C-NMR (δ, CDCl₃): 199.5 (C15), 173.4 (C4), 162.5 (C11), 141.8 (C10), 133.9 (C6), 133.6 (C8), 124.3 (C5), 124.2 (C2), 101.58 (C7), 101.56 (C16), 37.5 (C14), 31.2 (C12), 22.8 (C13), 11.7 (C1, 2, 3), ¹¹⁹Sn-NMR (δ, CDCl₃): 97.6, ¹¹⁹Sn Mossbauer (mm.s^-1): δ 1.32, Δ 3.52, Elemental Analysis (%) for C₁₆H₂₁NO₃Sn found (calc.): C 48.41 (48.76), H 5.37 (5.38), N 3.46 (3.55).

S3. Refinement

Fourier difference in the structure determination stage evidenced most of the H atoms in the structure; nevertheless, their positions were subsequently calculated and refined using a riding model approximation. All non-H atoms were refined anisotropically.

Computing details

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS (Siemens, 1991); data reduction: XSCANS (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. Monomeric structure of poly-[trimethyltin-3-{(carboxyphenyl)amino} cyclohexen-2-one]

<it>catena</it>-Poly[[trimethyltin(IV)]-µ-2-[(3-oxocyclohex-1- enyl)amino]benzoato-κ²<it>O</it>:<it>O</it>']

Crystal data

[Sn(CH3)3(C13H13NO3)]	Dx = 1.534 Mg m^−3
Mr = 394.03	Melting point = 440–443 K
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
a = 30.626 (5) Å	Cell parameters from 26 reflections
b = 12.981 (2) Å	θ = 11.8–12.5°
c = 17.164 (2) Å	µ = 1.51 mm^−1
V = 6823.6 (19) Å^3	T = 273 K
Z = 16	Prismatic, colourless
F(000) = 3168	0.2 × 0.2 × 0.2 mm

Data collection

Siemens P4 diffractometer	Rint = 0.039
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.1°
Graphite monochromator	h = −36→36
2θ/ω scans	k = −15→11
7294 measured reflections	l = −19→12
2329 independent reflections	3 standard reflections every 97 reflections
2099 reflections with I > 2σ(I)	intensity decay: 4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.74	(Δ/σ)max < 0.001
2329 reflections	Δρmax = 0.26 e Å^−3
193 parameters	Δρmin = −0.37 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Sn	0.411524 (8)	−0.002008 (19)	0.26150 (5)	0.05087 (14)
C1	0.43775 (19)	0.1345 (4)	0.2137 (4)	0.0718 (15)
H1A	0.4312	0.1915	0.2474	0.108*
H1B	0.4251	0.1466	0.1634	0.108*
H1C	0.4688	0.1276	0.2087	0.108*
C2	0.4509 (2)	−0.0989 (5)	0.3309 (4)	0.0772 (16)
H2A	0.4442	−0.0880	0.3848	0.116*
H2B	0.4811	−0.0832	0.3218	0.116*
H2C	0.4454	−0.1695	0.3175	0.116*
C3	0.3535 (2)	−0.0753 (5)	0.2245 (4)	0.089 (2)
H3A	0.3308	−0.0634	0.2622	0.134*
H3B	0.3585	−0.1480	0.2196	0.134*
H3C	0.3447	−0.0477	0.1751	0.134*
O1	0.38557 (11)	0.0726 (2)	0.3650 (2)	0.0602 (8)
O2	0.33660 (11)	0.1547 (2)	0.2914 (2)	0.0616 (9)
O3	0.44514 (15)	−0.0706 (3)	0.1396 (2)	0.0771 (11)
C4	0.35365 (15)	0.1367 (3)	0.3546 (3)	0.0513 (10)
C5	0.33861 (13)	0.1881 (3)	0.4283 (3)	0.0444 (10)
C6	0.35136 (15)	0.1499 (3)	0.5001 (3)	0.0558 (11)
H6A	0.3703	0.0939	0.5021	0.067*
C7	0.33636 (18)	0.1936 (5)	0.5696 (3)	0.0673 (15)
H7A	0.3450	0.1670	0.6176	0.081*
C8	0.3084 (2)	0.2772 (5)	0.5656 (3)	0.0643 (15)
H8A	0.2977	0.3059	0.6115	0.077*
C9	0.29629 (16)	0.3184 (4)	0.4959 (3)	0.0561 (11)
H9A	0.2778	0.3753	0.4950	0.067*
C10	0.31093 (15)	0.2770 (4)	0.4268 (3)	0.0474 (10)
N	0.29828 (13)	0.3157 (3)	0.3544 (3)	0.0510 (9)
H1N	0.3021 (18)	0.279 (5)	0.310 (3)	0.061*
C11	0.45673 (14)	−0.3331 (3)	0.0821 (3)	0.0449 (10)
C12	0.47411 (17)	−0.3229 (4)	0.0014 (3)	0.0594 (12)
H12A	0.4622	−0.3776	−0.0306	0.071*
H12B	0.5056	−0.3310	0.0026	0.071*
C13	0.4631 (2)	−0.2201 (4)	−0.0352 (3)	0.0703 (15)
H13A	0.4799	−0.2115	−0.0827	0.084*
H13B	0.4323	−0.2187	−0.0488	0.084*
C14	0.47305 (19)	−0.1322 (4)	0.0200 (4)	0.0665 (14)
H14A	0.4616	−0.0688	−0.0018	0.080*
H14B	0.5045	−0.1247	0.0245	0.080*
C15	0.45398 (15)	−0.1476 (3)	0.1002 (3)	0.0528 (11)
C16	0.44788 (16)	−0.2510 (3)	0.1278 (3)	0.0490 (11)
H16A	0.4376	−0.2617	0.1782	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn	0.05684 (19)	0.03705 (18)	0.0587 (2)	0.00106 (12)	−0.00554 (19)	0.00251 (11)
C1	0.098 (4)	0.039 (2)	0.079 (4)	0.003 (2)	0.014 (3)	0.005 (2)
C2	0.094 (4)	0.064 (3)	0.073 (4)	0.011 (3)	0.001 (3)	0.020 (3)
C3	0.084 (4)	0.072 (4)	0.112 (6)	−0.009 (3)	−0.016 (4)	−0.026 (4)
O1	0.071 (2)	0.0529 (19)	0.057 (2)	0.0084 (15)	−0.0044 (17)	0.0016 (15)
O2	0.091 (3)	0.0457 (16)	0.049 (2)	0.0143 (15)	−0.0092 (17)	−0.0075 (14)
O3	0.117 (3)	0.0449 (18)	0.069 (2)	0.0005 (19)	0.007 (2)	−0.0108 (19)
C4	0.068 (3)	0.042 (2)	0.044 (3)	−0.012 (2)	0.001 (2)	0.001 (2)
C5	0.051 (3)	0.038 (2)	0.045 (2)	−0.0123 (16)	−0.0020 (18)	−0.005 (2)
C6	0.059 (2)	0.049 (2)	0.059 (3)	−0.0073 (18)	−0.010 (2)	0.011 (2)
C7	0.087 (4)	0.072 (4)	0.042 (3)	−0.023 (3)	−0.006 (2)	0.016 (3)
C8	0.083 (4)	0.063 (3)	0.047 (3)	−0.020 (3)	0.019 (3)	−0.006 (3)
C9	0.066 (3)	0.048 (2)	0.054 (3)	−0.009 (2)	0.002 (2)	−0.009 (2)
C10	0.049 (2)	0.043 (2)	0.049 (3)	−0.0119 (18)	0.004 (2)	−0.005 (2)
N	0.067 (2)	0.0390 (19)	0.047 (2)	−0.0001 (16)	−0.0032 (18)	−0.0048 (17)
C11	0.047 (2)	0.038 (2)	0.049 (3)	−0.0034 (17)	0.0002 (18)	−0.0043 (19)
C12	0.077 (3)	0.049 (2)	0.053 (3)	0.000 (2)	0.016 (3)	0.003 (3)
C13	0.102 (4)	0.049 (3)	0.061 (4)	−0.003 (3)	0.007 (3)	0.006 (3)
C14	0.089 (4)	0.047 (2)	0.064 (4)	−0.008 (2)	0.009 (3)	0.002 (3)
C15	0.059 (3)	0.038 (2)	0.061 (3)	−0.0014 (18)	0.004 (2)	−0.008 (2)
C16	0.054 (3)	0.043 (2)	0.050 (3)	0.0021 (16)	0.004 (2)	−0.0017 (17)

Geometric parameters (Å, º)

Sn—C1	2.112 (5)	C7—H7A	0.9300
Sn—C2	2.111 (6)	C8—C9	1.362 (8)
Sn—C3	2.113 (6)	C8—H8A	0.9300
Sn—O1	2.174 (4)	C9—C10	1.377 (7)
Sn—O3	2.496 (4)	C9—H9A	0.9300
C1—H1A	0.9600	C10—N	1.396 (7)
C1—H1B	0.9600	N—C11^i	1.376 (6)
C1—H1C	0.9600	N—H1N	0.91 (6)
C2—H2A	0.9600	C11—C16	1.351 (6)
C2—H2B	0.9600	C11—N^ii	1.376 (6)
C2—H2C	0.9600	C11—C12	1.489 (7)
C3—H3A	0.9600	C12—C13	1.513 (8)
C3—H3B	0.9600	C12—H12A	0.9700
C3—H3C	0.9600	C12—H12B	0.9700
O1—C4	1.296 (5)	C13—C14	1.515 (8)
O2—C4	1.227 (6)	C13—H13A	0.9700
O3—C15	1.237 (6)	C13—H13B	0.9700
C4—C5	1.503 (7)	C14—C15	1.508 (8)
C5—C6	1.384 (7)	C14—H14A	0.9700
C5—C10	1.432 (7)	C14—H14B	0.9700
C6—C7	1.400 (8)	C15—C16	1.436 (6)
C6—H6A	0.9300	C16—H16A	0.9300
C7—C8	1.384 (9)
C1—Sn—C2	120.1 (3)	C6—C7—H7A	120.7
C1—Sn—C3	125.5 (3)	C9—C8—C7	121.3 (5)
C2—Sn—C3	112.5 (3)	C9—C8—H8A	119.3
C1—Sn—O1	94.73 (19)	C7—C8—H8A	119.3
C2—Sn—O1	90.8 (2)	C8—C9—C10	121.0 (5)
C3—Sn—O1	97.9 (2)	C8—C9—H9A	119.5
C1—Sn—O3	79.46 (19)	C10—C9—H9A	119.5
C2—Sn—O3	91.4 (2)	C9—C10—N	122.4 (5)
C3—Sn—O3	86.3 (2)	C9—C10—C5	119.5 (5)
O1—Sn—O3	174.13 (13)	N—C10—C5	118.1 (4)
Sn—C1—H1A	109.5	C11^i—N—C10	128.5 (4)
Sn—C1—H1B	109.5	C11^i—N—H1N	106 (4)
H1A—C1—H1B	109.5	C10—N—H1N	122 (4)
Sn—C1—H1C	109.5	C16—C11—N^ii	124.6 (4)
H1A—C1—H1C	109.5	C16—C11—C12	122.8 (4)
H1B—C1—H1C	109.5	N^ii—C11—C12	112.6 (4)
Sn—C2—H2A	109.5	C11—C12—C13	112.7 (4)
Sn—C2—H2B	109.5	C11—C12—H12A	109.1
H2A—C2—H2B	109.5	C13—C12—H12A	109.1
Sn—C2—H2C	109.5	C11—C12—H12B	109.1
H2A—C2—H2C	109.5	C13—C12—H12B	109.1
H2B—C2—H2C	109.5	H12A—C12—H12B	107.8
Sn—C3—H3A	109.5	C14—C13—C12	111.0 (5)
Sn—C3—H3B	109.5	C14—C13—H13A	109.4
H3A—C3—H3B	109.5	C12—C13—H13A	109.4
Sn—C3—H3C	109.5	C14—C13—H13B	109.4
H3A—C3—H3C	109.5	C12—C13—H13B	109.4
H3B—C3—H3C	109.5	H13A—C13—H13B	108.0
C4—O1—Sn	116.7 (3)	C13—C14—C15	113.1 (4)
C15—O3—Sn	146.8 (4)	C13—C14—H14A	109.0
O2—C4—O1	124.4 (4)	C15—C14—H14A	109.0
O2—C4—C5	122.0 (4)	C13—C14—H14B	109.0
O1—C4—C5	113.6 (4)	C15—C14—H14B	109.0
C6—C5—C10	118.1 (4)	H14A—C14—H14B	107.8
C6—C5—C4	120.2 (4)	O3—C15—C16	123.1 (5)
C10—C5—C4	121.6 (4)	O3—C15—C14	118.5 (4)
C5—C6—C7	121.4 (4)	C16—C15—C14	118.4 (4)
C5—C6—H6A	119.3	C11—C16—C15	121.3 (4)
C7—C6—H6A	119.3	C11—C16—H16A	119.4
C8—C7—C6	118.6 (5)	C15—C16—H16A	119.4
C8—C7—H7A	120.7

Symmetry codes: (i) −x+3/4, y+3/4, z+1/4; (ii) −x+3/4, y−3/4, z−1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1N···O2	0.91 (6)	1.96 (6)	2.631 (5)	129 (5)