Bis(μ²-2-(dimethylamino)ethoxo-N,O,O)-di(phenolato-O)ditin(II): a high-resolution single-crystal X-ray diffraction and quantum chemical study

Experimental and calculated electron density functions ρ(r) of the title compound in the crystal were obtained. These were compared with ρ(r) for an isolated dimer. Application of the `Atoms in Molecules' theory allowed the visualization of the electron lone pair (Lp) of tin(II) and the calculation of some bond energies and all atomic charges. The stereochemical activity of the Lp was demonstrated and its volume was estimated to be approximately 10 ų. The energies of N→Sn and Sn—O bonds were found to be 13–18 and 25–52 kJ mol⁻¹. According to the experimental, AM05-PW and PBE0/6-311G(d,p) calculation data, µ²-2-(dimethylamino)ethoxoate accepts 0.68, 0.45 and 0.40 e from the Sn atom. Using the example of µ²-2-(dimethylamino)ethoxoates and complexes of bis(n-butyl)tin(IV) it was demonstrated that the more screened the Sn atom, the better the catalytic activity of its complex in polyurethane synthesis.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL ver. 5.1 (Sheldrick, 2008); program(s) used to refine structure: SHELXTL ver. 5.1 (Sheldrick, 2008); molecular graphics: SHELXTL ver. 5.1 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL ver. 5.1 (Sheldrick, 2008).

bis(mu₂-2-(dimethylamino)ethoxo-N,O,O)-di(phenolyato-O)-di-tin(II)

Crystal data

C20H30N2O4Sn2	F(000) = 1184
Mr = 599.84	Dx = 1.718 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 876 reflections
a = 13.0745 (2) Å	θ = 3.5–32.1°
b = 12.9669 (2) Å	µ = 2.18 mm^−1
c = 13.6824 (3) Å	T = 100 K
V = 2319.66 (7) Å^3	Prism, colorless
Z = 4	0.19 × 0.12 × 0.07 mm

Data collection

Bruker Apex II CCD area detector diffractometer	12165 independent reflections
Radiation source: fine-focus sealed tube	7690 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 50.0°, θmin = 3.1°
Absorption correction: multi-scan SADABS (Sheldrick, 1998)	h = −28→28
Tmin = 0.796, Tmax = 0.914	k = −27→27
203973 measured reflections	l = −29→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Hydrogen site location: difference Fourier map
wR(F^2) = 0.092	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 7.5P] where P = (Fo^2 + 2Fc^2)/3
12165 reflections	(Δ/σ)max = 0.002
187 parameters	Δρmax = 1.45 e Å^−3
0 restraints	Δρmin = −1.17 e Å^−3

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
Sn1	−0.000277 (7)	0.866394 (6)	0.034612 (6)	0.01288 (2)
O1	−0.05745 (9)	1.01436 (9)	0.07082 (8)	0.01607 (16)
O2	0.13330 (9)	0.88734 (11)	0.11603 (10)	0.0202 (2)
N1	−0.07542 (11)	0.85290 (12)	0.19989 (10)	0.0190 (2)
C1	−0.10681 (13)	1.03406 (13)	0.16113 (12)	0.0186 (2)
C2	−0.06864 (13)	0.95904 (14)	0.23803 (11)	0.0194 (2)
C3	−0.01892 (19)	0.78054 (19)	0.26234 (17)	0.0306 (4)
C4	−0.18256 (16)	0.81897 (17)	0.18982 (15)	0.0257 (3)
C5	0.20782 (11)	0.95116 (13)	0.08605 (12)	0.0175 (2)
C6	0.28425 (13)	0.91667 (15)	0.02220 (13)	0.0210 (3)
C7	0.36081 (15)	0.98312 (19)	−0.00974 (15)	0.0269 (3)
C8	0.36356 (16)	1.08508 (18)	0.02221 (18)	0.0298 (4)
C9	0.28982 (18)	1.11932 (15)	0.08716 (19)	0.0294 (4)
C10	0.21252 (14)	1.05352 (14)	0.11898 (15)	0.0234 (3)
H1B	−0.180 (2)	1.029 (2)	0.153 (2)	0.021 (7)*
H1A	−0.093 (2)	1.105 (2)	0.184 (2)	0.024 (7)*
H2A	0.001 (2)	0.971 (2)	0.250 (3)	0.025 (7)*
H2B	−0.108 (2)	0.970 (2)	0.300 (2)	0.025 (7)*
H3C	0.048 (3)	0.806 (3)	0.271 (3)	0.045 (10)*
H3B	−0.047 (3)	0.782 (3)	0.329 (3)	0.034 (9)*
H3A	−0.021 (2)	0.710 (3)	0.233 (2)	0.028 (8)*
H4C	−0.181 (2)	0.748 (2)	0.167 (2)	0.027 (7)*
H4B	−0.219 (2)	0.859 (2)	0.143 (2)	0.025 (7)*
H4A	−0.215 (3)	0.820 (3)	0.249 (2)	0.031 (8)*
H6	0.281 (2)	0.848 (2)	0.001 (2)	0.027 (8)*
H7	0.416 (3)	0.960 (3)	−0.056 (2)	0.037 (9)*
H8	0.411 (3)	1.129 (2)	−0.002 (2)	0.031 (8)*
H9	0.293 (2)	1.187 (3)	0.111 (2)	0.034 (8)*
H10	0.164 (3)	1.077 (3)	0.164 (2)	0.034 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.01450 (3)	0.01133 (3)	0.01280 (3)	−0.00020 (3)	0.00049 (3)	0.00016 (2)
O1	0.0186 (4)	0.0162 (4)	0.0134 (3)	0.0013 (3)	0.0029 (3)	0.0005 (3)
O2	0.0149 (4)	0.0248 (5)	0.0210 (5)	−0.0010 (4)	−0.0015 (4)	0.0057 (4)
N1	0.0192 (5)	0.0219 (5)	0.0159 (4)	−0.0003 (4)	0.0013 (4)	0.0037 (4)
C1	0.0194 (5)	0.0207 (6)	0.0159 (5)	0.0005 (5)	0.0038 (4)	−0.0011 (4)
C2	0.0198 (6)	0.0255 (6)	0.0129 (5)	−0.0019 (5)	0.0012 (4)	0.0002 (4)
C3	0.0336 (10)	0.0323 (9)	0.0258 (8)	0.0036 (8)	−0.0012 (7)	0.0131 (7)
C4	0.0235 (7)	0.0292 (8)	0.0244 (7)	−0.0073 (6)	0.0035 (6)	0.0004 (6)
C5	0.0144 (4)	0.0198 (5)	0.0184 (5)	0.0007 (4)	−0.0022 (4)	0.0016 (4)
C6	0.0168 (5)	0.0252 (7)	0.0209 (6)	−0.0003 (5)	−0.0004 (5)	−0.0024 (5)
C7	0.0177 (6)	0.0394 (10)	0.0237 (7)	−0.0045 (6)	0.0001 (5)	0.0042 (7)
C8	0.0233 (7)	0.0307 (9)	0.0355 (10)	−0.0097 (7)	−0.0081 (7)	0.0113 (8)
C9	0.0288 (8)	0.0188 (6)	0.0406 (11)	−0.0018 (6)	−0.0117 (8)	0.0025 (7)
C10	0.0214 (6)	0.0205 (6)	0.0284 (8)	0.0034 (5)	−0.0044 (6)	−0.0019 (6)

Geometric parameters (Å, º)

Sn1—O2	2.0893 (13)	C3—H3B	0.99 (3)
Sn1—O1	2.1179 (11)	C3—H3A	1.00 (3)
Sn1—O1^i	2.2453 (11)	C4—H4C	0.97 (3)
Sn1—N1	2.4718 (14)	C4—H4B	0.95 (3)
O1—C1	1.4172 (19)	C4—H4A	0.91 (3)
O1—Sn1^i	2.2453 (11)	C5—C6	1.401 (2)
O2—C5	1.343 (2)	C5—C10	1.403 (2)
N1—C3	1.468 (2)	C6—C7	1.391 (3)
N1—C2	1.474 (2)	C6—H6	0.94 (3)
N1—C4	1.475 (2)	C7—C8	1.393 (3)
C1—C2	1.517 (2)	C7—H7	1.00 (3)
C1—H1B	0.97 (3)	C8—C9	1.384 (4)
C1—H1A	0.99 (3)	C8—H8	0.90 (3)
C2—H2A	0.93 (3)	C9—C10	1.392 (3)
C2—H2B	1.00 (3)	C9—H9	0.94 (3)
C3—H3C	0.94 (4)	C10—H10	0.94 (3)
O2—Sn1—O1	93.01 (5)	N1—C3—H3B	110 (2)
O2—Sn1—O1^i	88.40 (5)	H3C—C3—H3B	103 (3)
O1—Sn1—O1^i	69.21 (5)	N1—C3—H3A	109.8 (19)
O2—Sn1—N1	81.58 (5)	H3C—C3—H3A	113 (3)
O1—Sn1—N1	73.13 (5)	H3B—C3—H3A	112 (3)
O1^i—Sn1—N1	140.37 (5)	N1—C4—H4C	106.9 (18)
C1—O1—Sn1	121.87 (10)	N1—C4—H4B	111.9 (18)
C1—O1—Sn1^i	126.09 (10)	H4C—C4—H4B	108 (3)
Sn1—O1—Sn1^i	110.79 (5)	N1—C4—H4A	111 (2)
C5—O2—Sn1	121.59 (10)	H4C—C4—H4A	108 (3)
C3—N1—C2	111.11 (16)	H4B—C4—H4A	111 (3)
C3—N1—C4	109.97 (16)	O2—C5—C6	120.77 (16)
C2—N1—C4	111.64 (15)	O2—C5—C10	121.11 (16)
C3—N1—Sn1	112.19 (13)	C6—C5—C10	118.11 (16)
C2—N1—Sn1	103.52 (9)	C7—C6—C5	120.76 (18)
C4—N1—Sn1	108.25 (11)	C7—C6—H6	121 (2)
O1—C1—C2	109.83 (13)	C5—C6—H6	118 (2)
O1—C1—H1B	110.0 (17)	C6—C7—C8	120.5 (2)
C2—C1—H1B	111.3 (17)	C6—C7—H7	122 (2)
O1—C1—H1A	111.3 (17)	C8—C7—H7	117 (2)
C2—C1—H1A	108.5 (17)	C9—C8—C7	119.20 (18)
H1B—C1—H1A	106 (2)	C9—C8—H8	121 (2)
N1—C2—C1	109.47 (13)	C7—C8—H8	120 (2)
N1—C2—H2A	106 (2)	C8—C9—C10	120.64 (19)
C1—C2—H2A	109 (2)	C8—C9—H9	119 (2)
N1—C2—H2B	113.9 (17)	C10—C9—H9	120 (2)
C1—C2—H2B	109.1 (17)	C9—C10—C5	120.73 (19)
H2A—C2—H2B	109 (3)	C9—C10—H10	120 (2)
N1—C3—H3C	109 (2)	C5—C10—H10	119 (2)
O2—Sn1—O1—C1	−80.81 (12)	O1^i—Sn1—N1—C4	111.65 (13)
O1^i—Sn1—O1—C1	−167.95 (15)	Sn1—O1—C1—C2	26.69 (18)
N1—Sn1—O1—C1	−0.55 (11)	Sn1^i—O1—C1—C2	−139.33 (11)
O2—Sn1—O1—Sn1^i	87.14 (6)	C3—N1—C2—C1	167.46 (15)
O1^i—Sn1—O1—Sn1^i	0.0	C4—N1—C2—C1	−69.37 (17)
N1—Sn1—O1—Sn1^i	167.40 (7)	Sn1—N1—C2—C1	46.85 (14)
O1—Sn1—O2—C5	−72.32 (13)	O1—C1—C2—N1	−50.65 (18)
O1^i—Sn1—O2—C5	−3.24 (13)	Sn1—O2—C5—C6	−86.42 (17)
N1—Sn1—O2—C5	−144.77 (13)	Sn1—O2—C5—C10	94.74 (17)
O2—Sn1—N1—C3	−49.70 (14)	O2—C5—C6—C7	179.27 (16)
O1—Sn1—N1—C3	−145.46 (15)	C10—C5—C6—C7	−1.9 (3)
O1^i—Sn1—N1—C3	−126.82 (14)	C5—C6—C7—C8	0.8 (3)
O2—Sn1—N1—C2	70.18 (10)	C6—C7—C8—C9	0.8 (3)
O1—Sn1—N1—C2	−25.58 (10)	C7—C8—C9—C10	−1.2 (3)
O1^i—Sn1—N1—C2	−6.94 (14)	C8—C9—C10—C5	0.1 (3)
O2—Sn1—N1—C4	−171.23 (13)	O2—C5—C10—C9	−179.71 (17)
O1—Sn1—N1—C4	93.01 (13)	C6—C5—C10—C9	1.4 (3)

Symmetry code: (i) −x, −y+2, −z.