catena-Poly[[trimethyl­tin(IV)]-μ-2,5-difluoro­benzoato-κ²O:O′]

In the title polymeric coordination compound, [Sn(CH₃)₃(C₇H₃F₂O₂)]_n, the Sn atom exhibits a distorted trigonal-bipyramidal coordination geometry with the carboxyl­ate O atoms in the axial positions and the equatorial positions occupied by the methyl groups. The two Sn—O bond lengths are 2.225 (5) and 2.410 (6) Å.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.036
• wR factor = 0.107
• Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Sn1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C6
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         14
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C1     -   C2     ...       1.54 Ang.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.94
PLAT234_ALERT_4_C Large Hirshfeld Difference Sn1    --  C9      ..       0.12  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C1     --  C2      ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C2     --  C3      ..       0.16  Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  F1      ..       2.63 Ang.

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      0.944
            Tmax scaled      0.566 Tmin scaled      0.474
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           24.99
           From the CIF: _reflns_number_total               2152
           Count of symmetry unique reflns         1322
           Completeness (_total/calc)            162.78%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       830
           Fraction of Friedel pairs measured     0.628
           Are heavy atom types Z>Si present        yes

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

   0 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
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In recent years the organotin derivatives have attracted considerable attention due to a significant antimicrobial properties as well as antitumor activities. Studies on organotin complexes containing carboxylate ligands with an additional donor atom (e.g N, S or F) that is available for coordinating to Sn atom have revealed that new structural types may lead to different activities. We have therefore synthesized the title compound, and present its crystal structure here. The molecular structure of the compound is shown in Fig.1 The Sn atom, assumes a distorted trigonal bipyramidal coordination geometry, provided by three methyl groups at the equatorial positions and two carboxylate groups at the axial positions. The Sn—O bond lengths in the compound (Table 1), are similar to those found in related organotin carboxylates (Wang et al., 2007). In the crystal packing, molecules are linked by intermolecular C—H···F hydrogen bonds (Fig.2, Table 1,)

Related literature

For a related structure, see: Wang et al. (2007).

S2. Experimental

The reaction was carried out under nitrogen atmosphere. 2,5-Difluorobenzoic acid (1 mmol) and sodium ethoxide (1.2 mmol) were added to a stirred solution of benzene (30 ml) in a Schlenk flask and stirred for 0.5 h. Trimethyltin chloride (1 mmol) was then added to the reactor and the reaction mixture was stirred for 12 h at room temperature. The resulting clear solution was evaporated under vacuum. The product was crystallized from dichloromethane/methanol (1:1) to yield colourless block crystals (yield 83%. m.p.393K). Anal. Calcd (%) for C₁₀H₁₂F₂O₂Sn(Mr = 320.91): C, 37.43; H, 3.77; F, 11.84; Sn, 36.99. Found (%): C, 37.39; H, 3.86; F, 11.78; Sn, 36.89.

S3. Refinement

The H atoms were positioned geometrically, with methyl C—H distances of 0.96 Å and aromatic C—H distances of 0.93 Å, and refined as riding on their parent atoms, with U_iso(H) = 1.2 U_eq(C, O) or 1.5 U_eq(C) for the methyl group.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. Symmetry codes: (A) = x - 1/2,-y + 3/2,-z + 1/4, (B) = x + 1/2,-y + 3/2,-z + 1/4

catena-Poly[[trimethyltin(IV)]-µ-2,5-difluorobenzoato-κ²O:O']

Crystal data

[Sn(CH3)3(C7H3F2O2)]	Dx = 1.752 Mg m^−3
Mr = 320.91	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 5675 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–26.4°
a = 9.8857 (9) Å	µ = 2.11 mm^−1
c = 24.896 (2) Å	T = 298 K
V = 2433.0 (4) Å^3	Block, colourless
Z = 8	0.38 × 0.29 × 0.27 mm
F(000) = 1248

Data collection

Siemens SMART CCD diffractometer	2152 independent reflections
Radiation source: fine-focus sealed tube	1996 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.502, Tmax = 0.600	k = −11→7
10078 measured reflections	l = −16→29

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.066P)^2 + 4.861P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2152 reflections	Δρmax = 0.54 e Å^−3
136 parameters	Δρmin = −0.46 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (8)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.79786 (5)	0.82634 (5)	0.11522 (2)	0.05163 (18)
F1	1.1717 (7)	1.1333 (7)	0.1597 (3)	0.111 (2)
F2	1.4123 (8)	1.0943 (8)	−0.0335 (3)	0.131 (3)
O1	0.9583 (5)	0.9696 (5)	0.0890 (2)	0.0632 (14)
O2	1.1085 (6)	0.8095 (6)	0.1065 (3)	0.0786 (18)
C1	1.0763 (7)	0.9249 (7)	0.0922 (3)	0.0552 (19)
C2	1.1900 (8)	1.0242 (7)	0.0773 (3)	0.0561 (18)
C3	1.2313 (10)	1.1239 (11)	0.1101 (4)	0.080 (3)
C4	1.3367 (11)	1.2144 (9)	0.0992 (5)	0.089 (3)
H4	1.3649	1.2787	0.1240	0.107*
C5	1.3953 (9)	1.2021 (11)	0.0498 (5)	0.082 (3)
H5	1.4635	1.2615	0.0395	0.098*
C6	1.3539 (10)	1.1028 (11)	0.0153 (4)	0.081 (3)
C7	1.2516 (10)	1.0141 (11)	0.0269 (4)	0.078 (3)
H7	1.2240	0.9495	0.0020	0.093*
C8	0.6502 (9)	0.9694 (8)	0.0912 (3)	0.067 (2)
H8A	0.6849	1.0227	0.0621	0.100*
H8B	0.6287	1.0274	0.1210	0.100*
H8C	0.5700	0.9229	0.0797	0.100*
C9	0.8458 (10)	0.6721 (11)	0.0603 (4)	0.081 (3)
H9A	0.7645	0.6261	0.0497	0.122*
H9B	0.9065	0.6088	0.0769	0.122*
H9C	0.8882	0.7108	0.0292	0.122*
C10	0.8626 (9)	0.8328 (10)	0.1959 (3)	0.070 (2)
H10A	0.9112	0.7514	0.2043	0.105*
H10B	0.7854	0.8405	0.2191	0.105*
H10C	0.9207	0.9095	0.2011	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0368 (3)	0.0477 (3)	0.0704 (3)	0.0054 (2)	−0.0009 (2)	0.0029 (2)
F1	0.121 (6)	0.108 (5)	0.103 (4)	−0.027 (4)	0.039 (4)	−0.022 (4)
F2	0.138 (6)	0.136 (6)	0.120 (5)	0.010 (5)	0.067 (5)	0.039 (4)
O1	0.040 (3)	0.047 (3)	0.102 (4)	0.009 (2)	0.009 (3)	0.020 (3)
O2	0.054 (3)	0.054 (3)	0.128 (5)	0.005 (3)	−0.001 (3)	0.029 (4)
C1	0.031 (3)	0.047 (4)	0.087 (5)	−0.004 (3)	0.012 (3)	0.014 (4)
C2	0.033 (3)	0.046 (4)	0.089 (5)	0.005 (3)	0.003 (4)	0.015 (4)
C3	0.063 (6)	0.083 (7)	0.094 (7)	0.012 (5)	0.020 (5)	0.004 (6)
C4	0.100 (8)	0.048 (5)	0.119 (8)	−0.007 (5)	0.014 (6)	0.007 (5)
C5	0.046 (5)	0.067 (6)	0.133 (9)	0.001 (5)	0.013 (5)	0.035 (6)
C6	0.058 (5)	0.087 (7)	0.099 (7)	0.012 (5)	0.025 (5)	0.039 (6)
C7	0.067 (6)	0.089 (7)	0.077 (6)	0.006 (5)	0.011 (5)	0.026 (5)
C8	0.062 (5)	0.050 (5)	0.088 (5)	0.013 (4)	−0.004 (4)	0.007 (4)
C9	0.074 (6)	0.092 (7)	0.078 (6)	0.025 (6)	−0.012 (5)	−0.009 (5)
C10	0.068 (5)	0.074 (6)	0.068 (5)	0.008 (4)	−0.003 (4)	−0.004 (4)

Geometric parameters (Å, º)

Sn1—C9	2.103 (9)	C4—H4	0.9300
Sn1—C10	2.110 (8)	C5—C6	1.366 (15)
Sn1—C8	2.118 (7)	C5—H5	0.9300
Sn1—O1	2.225 (5)	C6—C7	1.369 (14)
Sn1—O2^i	2.410 (6)	C7—H7	0.9300
F1—C3	1.373 (11)	C8—H8A	0.9600
F2—C6	1.349 (11)	C8—H8B	0.9600
O1—C1	1.250 (9)	C8—H8C	0.9600
O2—C1	1.237 (9)	C9—H9A	0.9600
O2—Sn1^ii	2.410 (6)	C9—H9B	0.9600
C1—C2	1.537 (10)	C9—H9C	0.9600
C2—C3	1.344 (13)	C10—H10A	0.9600
C2—C7	1.399 (12)	C10—H10B	0.9600
C3—C4	1.399 (14)	C10—H10C	0.9600
C4—C5	1.365 (14)
C9—Sn1—C10	125.0 (4)	C6—C5—H5	119.9
C9—Sn1—C8	117.1 (4)	F2—C6—C5	118.8 (10)
C10—Sn1—C8	117.2 (3)	F2—C6—C7	117.7 (11)
C9—Sn1—O1	96.3 (3)	C5—C6—C7	123.4 (10)
C10—Sn1—O1	92.5 (3)	C6—C7—C2	117.7 (11)
C8—Sn1—O1	89.1 (3)	C6—C7—H7	121.2
C9—Sn1—O2^i	87.8 (3)	C2—C7—H7	121.2
C10—Sn1—O2^i	88.5 (3)	Sn1—C8—H8A	109.5
C8—Sn1—O2^i	85.4 (3)	Sn1—C8—H8B	109.5
O1—Sn1—O2^i	174.15 (19)	H8A—C8—H8B	109.5
C1—O1—Sn1	114.9 (4)	Sn1—C8—H8C	109.5
C1—O2—Sn1^ii	142.9 (5)	H8A—C8—H8C	109.5
O2—C1—O1	125.8 (6)	H8B—C8—H8C	109.5
O2—C1—C2	118.1 (6)	Sn1—C9—H9A	109.5
O1—C1—C2	116.2 (6)	Sn1—C9—H9B	109.5
C3—C2—C7	117.7 (8)	H9A—C9—H9B	109.5
C3—C2—C1	123.0 (8)	Sn1—C9—H9C	109.5
C7—C2—C1	119.3 (8)	H9A—C9—H9C	109.5
C2—C3—F1	117.8 (9)	H9B—C9—H9C	109.5
C2—C3—C4	125.3 (9)	Sn1—C10—H10A	109.5
F1—C3—C4	116.8 (10)	Sn1—C10—H10B	109.5
C5—C4—C3	115.7 (10)	H10A—C10—H10B	109.5
C5—C4—H4	122.1	Sn1—C10—H10C	109.5
C3—C4—H4	122.1	H10A—C10—H10C	109.5
C4—C5—C6	120.1 (9)	H10B—C10—H10C	109.5
C4—C5—H5	119.9
C9—Sn1—O1—C1	−58.5 (6)	C1—C2—C3—F1	2.4 (13)
C10—Sn1—O1—C1	67.1 (6)	C7—C2—C3—C4	−3.8 (15)
C8—Sn1—O1—C1	−175.6 (7)	C1—C2—C3—C4	178.1 (9)
Sn1^ii—O2—C1—O1	−166.0 (7)	C2—C3—C4—C5	3.6 (16)
Sn1^ii—O2—C1—C2	13.5 (15)	F1—C3—C4—C5	179.3 (8)
Sn1—O1—C1—O2	2.8 (12)	C3—C4—C5—C6	−2.5 (15)
Sn1—O1—C1—C2	−176.8 (5)	C4—C5—C6—F2	179.0 (9)
O2—C1—C2—C3	−103.1 (10)	C4—C5—C6—C7	2.0 (16)
O1—C1—C2—C3	76.4 (11)	F2—C6—C7—C2	−179.2 (8)
O2—C1—C2—C7	78.8 (11)	C5—C6—C7—C2	−2.1 (15)
O1—C1—C2—C7	−101.7 (9)	C3—C2—C7—C6	2.9 (13)
C7—C2—C3—F1	−179.5 (8)	C1—C2—C7—C6	−178.9 (8)

Symmetry codes: (i) x−1/2, −y+3/2, −z+1/4; (ii) x+1/2, −y+3/2, −z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1^iii	0.93	2.63	3.336 (13)	133

Symmetry code: (iii) x+1/2, −y+5/2, −z+1/4.