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The title compound, [Sb(C11H14NO)3], is monomeric with the Sb atom located on a threefold axis. The complex exhibits distorted trigonal-anti­prismatic geometry around the Sb atom, owing to the presence of intra­molecular N[rightwards arrow]Sb inter­actions. H...phenyl inter­molecular inter­actions lead to the formation of dimers stacked along the c axis. The morpholine rings exhibit almost ideal chair conformations. No inter­molecular inter­actions between the morpholine rings of neighbouring mol­ecules were observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107061896/sf3067sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107061896/sf3067Isup2.hkl
Contains datablock I

CCDC reference: 677096

Comment top

Triorganoantimony compounds have attracted an increased interest in recent years as ligands in transition metal chemistry, owing to the different electronic properties of stibines compared with their lighter analogues (Levason & Reid, 2006). Trialkylantimony derivatives are air sensitive and strong reducing agents, in contrast to the aryl derivatives (Breunig & Wagner, 2007). Optically active {2,2'-bis[di(aryl)stibano]-1,1'-binaphtyl} compounds (aryl is p-tolyl or phenyl) are effective chiral ligands for rhodium-catalyzed asymmetric reduction of prochiral ketones to secondary alcohols (Yasuike et al., 2000, 2003). Recently, an asymmetric stibine, [phenyl(1-phenylethynyl)mesitylstibine], was successfully used as a ligand in order to modify the Co2(CO)8 catalytic system for alkene amidocarbonylation (Wakamatsu reaction) under mild conditions (Gomez et al., 2007).

Symmetric triorganoantimony(III) compounds containing aromatic groups bearing one pendant arm able to establish NSb intramolecular coordination {e.g. 2-(Me2NCH2)C6H4, (II) (Kamepalli et al., 1996; Sharma et al., 2004), 2-(Me2NCHMe)C6H4Me, (III) (Sharma et al., 2004), 2-[(p-tol)CH(CH3)NCH]C6H4, (IV), and 2-[(HOCH2)CH(CH2CH3)NCH]C6H4, (V) (Sharma et al., 2007)} have been reported.

In order to investigate the influence of the pendant arm attached to an aromatic ring on the antimony center, we performed the synthesis and structural characterization of the title compound, (I). Compound (I) is monomeric (Fig. 1). The molecule contains three 2-[O(CH2CH2)2NCH2]C6H4 units bonded to an Sb atom, which lies on a threefold axis of the space group R3, so the primarily monomeric unit is generated by symmetry.

The primary coordination polyhedron consists of a trigonal–pyramidal SbC3 skeleton. Including the three intramolecular NSb interactions, the Sb atom can be described as six-coordinate. The geometry around antimony is a distorted trigonal antiprism; three C atoms describe one triangular base of the antiprism, parallel to the triangular base described by the three N atoms from the pendant arms of the morpholinyl groups (the distance between the C3 and N3 planes is 1.7877 Å). The distortion is the result of the opening on the N3Sb face as evidenced by the large N—Sb—N angles [115.65 (6)°] compared with the C—Sb—C angles [95.54 (11)°]. The bond distances between the Sb and C atoms [2.167 (3) Å] are similar to those in other triorganoantimony derivatives [2.18 (1) Å in (II), 2.17 (1) Å in (III), 2.20 (3) Å in (IV) and 2.18 (1) Å in (V)]. The Sb—N distances in (I) [3.15 (1) Å] lie between the sums of the respective covalent [Σrcov(Sb,N) = 2.11 Å] and van der Waals radii [ΣrvdW(Sb,N) = 3.74 Å] (Emsley, 1994), and are longer than those in related compounds [3.05 (5) Å in (II), 2.95 (5) Å in (III), 2.92 (4) Å in (IV) and 2.87 (2) Å in (V)], owing to the bulkiness of the morpholinyl rings of the pendant arms. The Sb atom deviates from the N3 plane by 0.6639 (3) Å and from the C3 plane by 1.1238 (3) Å. An almost ideal chair conformation was observed for the morpholinyl groups, with torsion angles [C8—N1—C10—C11 = 54.0 (4)° and C11—O1—C9—C8 = -60.3 (4)°] similar to those found in 4-benzylmorpholin-4-ium chloride (Copolovici et al., 2007).

As a result of the intramolecular NSb interactions, nonplanar five-membered rings are formed, with the N atoms lying out of the Sb1/C1/C2/C7 mean plane. The chelate ring exhibits a dihedral angle of 57.67 (1)° between the Sb/N/C and Sb/C/C/C planes. This induces planar chirality (with the aromatic ring and the N atom as chiral plane and pilot atom, respectively; IUPAC, 1979). The compound crystallizes as a racemate, i.e. a mixture of RN,RNi,RNii and SNiii,SNiv,SNv isomers [symmetry codes: (i) 1 - y, 1 + x - y, z; (ii) -x + y, 1 - x, z; (iii) -1/3 + y, 1/3 - x + y, 1/3 - z; (iv) 2/3 + x - y, 1/3 + x, 1/3 - z; (v) 2/3 - x, 4/3 - y, 1/3 - z].

One H atom from the morpholinyl ring is involved in an intramolecular H···Ph interaction (H5···Cg1i; Table 1), while one aromatic H atom forms a weaker intermolecular H···Ph interaction (H11B···Cg2iii), thus resulting in a dimeric unit that contains the two RN,RNi,RNii and SNiii,SNiv,SNv isomers (Fig. 2).

In the crystal structure, the two isomers are arranged alternately and stacked along the c axis, with staggered positions of the different isomers and intercalated position for the same isomers, with no intermolecular interactions between the dimeric units.

Related literature top

(type here to add)

For related literature, see: Breunig & Wagner (2007); Copolovici et al. (2007); Emsley (1994); Gomez et al. (2007); IUPAC (1979); Kamepalli et al. (1996); Levason & Reid (2006); Sharma et al. (2004, 2007); Yasuike et al. (2000, 2003).

Experimental top

A solution of BuLi in hexane (51 ml, 1.6 M, 81.89 mmol) was added dropwise to a stirred solution of {2-[O(CH2CH2)2NCH2]C6H4}Br (20.976 g, 81.89 mmol) in 125 ml of hexane. The reaction mixture was stirred overnight at room temperature, then the solvent was removed with a syringe and the resulting white solid, {2-[O(CH2CH2)2NCH2]C6H4}Li, was washed with hexane and dried under vacuum. Freshly sublimed SbCl3 (4.53 g, 19.85 mmol) dissolved in Et2O (100 ml) was added dropwise to a cooled (195 K) suspension of {2-[O(CH2CH2)2NCH2]C6H4}Li (12.50 g, 68.23 mmol, excess) in Et2O (300 ml). The reaction mixture was stirred at 195 K for 1 h and then overnight while warming to room temperature. The solvent was removed under vacuum and extraction with CH2Cl2 was performed to obtain a yellow solution. Colourless crystals suitable for X-ray diffraction studies were obtained from the concentrated CH2Cl2 solution, maintained at 245 K (yield 8.76 g, 68%; m.p. 523 K. Analysis found: C 60.60, H 6.79, N 6.48%; calculated for C33H42N3O3Sb (650.46): C 60.94, H 6.51, N 6.46%. 1H NMR (300 MHz, CDCl3, 291 K, p.p.m.): δ 2.21 (4H, s, br, N—CH2—CH2—O), 3.06 (4H, s, br, N—CH2—CH2—O), 4.06 (2H, s, br, C6H4—CH2—N), 7.05 (1H, m, C6H4), 7.19 (3H, m, C6H4). 13C NMR (75.4 MHz, CDCl3, 291 K; p.p.m.): δ 52.94 (s, N—CH2—CH2—O), 65.91, 66.28 (s, N—CH2—CH2—O, C6H4—CH2—N), 127.29, 127.33, 129.55 (s, C-3–5), 137.48 (s, C-6), 142.67, 144.58 (s, C-1,2). MS [CIpos, NH3, m/z (%)]: 650 (2) [M+H]+, 473 (100) [M-{2-O(CH2CH2)2NCH2}C6H4]+, 178 (89) [{2-O(CH2CH2)2NCH2}C6H4+2H]+, 88 (34) [2-{O(CH2CH2)2NCH2}C6H4]+.

Refinement top

All H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and treated using a riding model [Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. : A view of (I), showing the atom-numbering scheme (30% probability displacement ellipsoids) for the (RN,RNi,RNii)-(I) isomer. [Symmetry codes: (i) 1 - y, 1 + x - y, z, (ii) -x + y, 1 - x, z.]
[Figure 2] Fig. 2. : The dimer of the title compound. H···Ph interactions are shown as dashed lines. Only H atoms involved in the interactions are shown. [Symmetry codes: (i) 1 - y, 1 + x - y, z, (iii) -1/3 + y, 1/3 - x + y, 1/3 - z.]
Tris[2-(morpholin-4-ylmethyl)phenyl-κ2 C1,N]antimony(III) top
Crystal data top
[Sb(C11H14NO)3]F(000) = 2016
Mr = 650.45Dx = 1.424 Mg m3
Rhombohedral, R3Mo Kα radiation, λ = 0.71073 Å
a = 19.026 (3) ÅCell parameters from 2262 reflections
c = 14.521 (5) Åθ = 2.8–20.9°
α = 90°µ = 0.95 mm1
γ = 120°T = 297 K
V = 4552.4 (17) Å3Block, colourless
Z = 60.20 × 0.13 × 0.10 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2050 independent reflections
Radiation source: fine-focus sealed tube1872 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.062
phi and ω scansθmax = 26.4°, θmin = 1.9°
Absorption correction: multi-scan
(SAINT-Plus; Bruker, 2000)
h = 2323
Tmin = 0.833, Tmax = 0.911k = 2323
12299 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0344P)2 + 3.9169P]
where P = (Fo2 + 2Fc2)/3
1878 reflections(Δ/σ)max < 0.001
121 parametersΔρmax = 1.23 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
[Sb(C11H14NO)3]V = 4552.4 (17) Å3
Mr = 650.45Z = 6
Rhombohedral, R3Mo Kα radiation
a = 19.026 (3) ŵ = 0.95 mm1
c = 14.521 (5) ÅT = 297 K
α = 90°0.20 × 0.13 × 0.10 mm
γ = 120°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2050 independent reflections
Absorption correction: multi-scan
(SAINT-Plus; Bruker, 2000)
1872 reflections with I > 2σ(I)
Tmin = 0.833, Tmax = 0.911Rint = 0.062
12299 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.12Δρmax = 1.23 e Å3
1878 reflectionsΔρmin = 0.39 e Å3
121 parameters
Special details top

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
xyzUiso*/Ueq
C10.22950 (18)0.57739 (18)0.3563 (2)0.0302 (7)
C20.18184 (18)0.49878 (19)0.3919 (2)0.0336 (7)
C30.1139 (2)0.4430 (2)0.3441 (3)0.0435 (8)
H30.08230.39100.36790.052*
C40.0917 (2)0.4626 (2)0.2621 (3)0.0454 (9)
H40.04620.42380.23050.054*
C50.1372 (2)0.5398 (2)0.2268 (2)0.0409 (8)
H50.12210.55400.17210.049*
C60.20585 (19)0.5961 (2)0.2740 (2)0.0354 (7)
H60.23690.64790.24960.042*
C70.2045 (2)0.4755 (2)0.4816 (2)0.0420 (8)
H7A0.20140.50840.53080.050*
H7B0.16570.41920.49510.050*
C80.3106 (3)0.4740 (2)0.5705 (3)0.0542 (10)
H8A0.27080.42080.59340.065*
H8B0.31240.51440.61280.065*
C90.3928 (3)0.4805 (3)0.5667 (3)0.0648 (12)
H9A0.43310.53470.54740.078*
H9B0.40760.47130.62760.078*
C100.2901 (2)0.4301 (2)0.4142 (3)0.0458 (9)
H10A0.27870.44160.35270.055*
H10B0.24920.37500.42980.055*
C110.3731 (2)0.4379 (2)0.4162 (3)0.0545 (10)
H11A0.37430.39950.37320.065*
H11B0.41340.49210.39680.065*
N10.28612 (17)0.48636 (16)0.47941 (18)0.0375 (6)
O10.39276 (17)0.42318 (17)0.5047 (2)0.0638 (8)
Sb10.33330.66670.43369 (2)0.02925 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0277 (16)0.0309 (16)0.0329 (18)0.0153 (14)0.0036 (13)0.0012 (13)
C20.0293 (17)0.0340 (17)0.0400 (19)0.0177 (15)0.0066 (14)0.0034 (14)
C30.0329 (18)0.0321 (18)0.059 (2)0.0117 (16)0.0053 (16)0.0011 (16)
C40.0296 (18)0.045 (2)0.055 (2)0.0136 (16)0.0072 (16)0.0115 (17)
C50.0370 (19)0.051 (2)0.0372 (19)0.0237 (17)0.0047 (15)0.0047 (16)
C60.0331 (17)0.0355 (18)0.0364 (18)0.0164 (15)0.0011 (14)0.0005 (14)
C70.042 (2)0.0359 (18)0.046 (2)0.0171 (16)0.0075 (16)0.0092 (15)
C80.067 (3)0.050 (2)0.048 (2)0.032 (2)0.004 (2)0.0075 (18)
C90.071 (3)0.067 (3)0.064 (3)0.041 (2)0.020 (2)0.005 (2)
C100.048 (2)0.040 (2)0.052 (2)0.0246 (18)0.0021 (17)0.0004 (16)
C110.055 (2)0.047 (2)0.069 (3)0.031 (2)0.003 (2)0.0028 (19)
N10.0423 (16)0.0365 (15)0.0361 (16)0.0216 (13)0.0011 (12)0.0044 (12)
O10.0678 (19)0.0583 (18)0.081 (2)0.0433 (16)0.0081 (16)0.0103 (15)
Sb10.03076 (16)0.03076 (16)0.0262 (2)0.01538 (8)0.0000.000
Geometric parameters (Å, º) top
C1—C61.385 (4)C8—C91.509 (6)
C1—C21.404 (4)C8—H8A0.9700
C1—Sb12.167 (3)C8—H8B0.9700
C2—C31.381 (5)C9—O11.413 (5)
C2—C71.507 (5)C9—H9A0.9700
C3—C41.375 (5)C9—H9B0.9700
C3—H30.9300C10—N11.458 (4)
C4—C51.378 (5)C10—C111.512 (5)
C4—H40.9300C10—H10A0.9700
C5—C61.387 (4)C10—H10B0.9700
C5—H50.9300C11—O11.404 (5)
C6—H60.9300C11—H11A0.9700
C7—N11.461 (4)C11—H11B0.9700
C7—H7A0.9700Sb1—C1i2.167 (3)
C7—H7B0.9700Sb1—C1ii2.167 (3)
C8—N11.460 (4)
C6—C1—C2118.1 (3)C9—C8—H8B109.5
C6—C1—Sb1122.2 (2)H8A—C8—H8B108.1
C2—C1—Sb1119.6 (2)O1—C9—C8111.1 (3)
C3—C2—C1119.4 (3)O1—C9—H9A109.4
C3—C2—C7120.3 (3)C8—C9—H9A109.4
C1—C2—C7120.3 (3)O1—C9—H9B109.4
C4—C3—C2121.6 (3)C8—C9—H9B109.4
C4—C3—H3119.2H9A—C9—H9B108.0
C2—C3—H3119.2N1—C10—C11110.5 (3)
C3—C4—C5119.7 (3)N1—C10—H10A109.5
C3—C4—H4120.1C11—C10—H10A109.5
C5—C4—H4120.1N1—C10—H10B109.5
C4—C5—C6119.2 (3)C11—C10—H10B109.5
C4—C5—H5120.4H10A—C10—H10B108.1
C6—C5—H5120.4O1—C11—C10111.6 (3)
C1—C6—C5122.0 (3)O1—C11—H11A109.3
C1—C6—H6119.0C10—C11—H11A109.3
C5—C6—H6119.0O1—C11—H11B109.3
N1—C7—C2112.3 (3)C10—C11—H11B109.3
N1—C7—H7A109.1H11A—C11—H11B108.0
C2—C7—H7A109.1C10—N1—C8109.4 (3)
N1—C7—H7B109.1C10—N1—C7110.6 (3)
C2—C7—H7B109.1C8—N1—C7111.0 (3)
H7A—C7—H7B107.9C11—O1—C9109.1 (3)
N1—C8—C9110.7 (3)C1—Sb1—C1i95.54 (11)
N1—C8—H8A109.5C1—Sb1—C1ii95.54 (11)
C9—C8—H8A109.5C1i—Sb1—C1ii95.54 (11)
N1—C8—H8B109.5
C6—C1—C2—C30.3 (4)N1—C10—C11—O158.1 (4)
Sb1—C1—C2—C3177.5 (2)C11—C10—N1—C854.0 (4)
C6—C1—C2—C7179.5 (3)C11—C10—N1—C7176.6 (3)
Sb1—C1—C2—C72.4 (4)C9—C8—N1—C1054.3 (4)
C1—C2—C3—C40.2 (5)C9—C8—N1—C7176.7 (3)
C7—C2—C3—C4180.0 (3)C2—C7—N1—C1066.0 (4)
C2—C3—C4—C51.0 (5)C2—C7—N1—C8172.3 (3)
C3—C4—C5—C61.4 (5)C10—C11—O1—C960.4 (4)
C2—C1—C6—C50.1 (5)C8—C9—O1—C1160.3 (4)
Sb1—C1—C6—C5177.0 (2)C6—C1—Sb1—C1i83.9 (2)
C4—C5—C6—C10.9 (5)C2—C1—Sb1—C1i99.1 (3)
C3—C2—C7—N1122.3 (3)C6—C1—Sb1—C1ii12.3 (3)
C1—C2—C7—N157.9 (4)C2—C1—Sb1—C1ii164.7 (2)
N1—C8—C9—O158.3 (4)
Symmetry codes: (i) y+1, xy+1, z; (ii) x+y, x+1, z.

Experimental details

Crystal data
Chemical formula[Sb(C11H14NO)3]
Mr650.45
Crystal system, space groupRhombohedral, R3
Temperature (K)297
a, c (Å)19.026 (3), 14.521 (5)
V3)4552.4 (17)
Z6
Radiation typeMo Kα
µ (mm1)0.95
Crystal size (mm)0.20 × 0.13 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SAINT-Plus; Bruker, 2000)
Tmin, Tmax0.833, 0.911
No. of measured, independent and
observed [I > 2σ(I)] reflections
12299, 2050, 1872
Rint0.062
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.081, 1.12
No. of reflections1878
No. of parameters121
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.23, 0.39

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2000), SHELXTL (Bruker, 2001), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2007).

Y-H···π-ring interactions. top
Y-H···CgY-HH···CgY···CgY-H···Cg
C5-H5···Cg1i0.972.763.68 (1)160
C11-H11B···Cg1iii0.933.143.91 (1)142
Symmetry codes: (i) 1 - y, 1 + x - y, z; (iii) -1/3 + y, 1/3 - x + y, 1/3 - z. Cg1 is the centroid of the C1–C6 benzene ring.
 

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