μ-Carbonato-bis-(bis-{2-[(diethyl-amino)-meth-yl]phen-yl}bis-muth(III)).

The mol-ecular structure of the title compound, [Bi(2)(C(11)H(16)N)(4)(CO(3))], consists of a symmetrically bridging carbonato group which binds two [2-Et(2)NCH(2)C(6)H(4)](2)Bi units that are crystallographically related via a twofold rotation axis bis-ecting the carbonate group. The two Bi atoms and two of the C atoms directly bonded to bis-muth are quasi-planar [deviations of 0.323 (1) and 0.330 (9)Å for the Bi and C atoms, respectively] with the carbonate group. The remaining two ligands are in a trans arrangement relative to the quasi-planar (CBi)(2)CO(3) system. The metal atom is strongly coordinated by the N atom of one pendant arm [Bi-N = 2.739 (6) Å], almost trans to the O atom, while the N atom of the other pendant arm exhibits a weaker intra-molecular inter-action [Bi⋯N = 3.659 (7) Å] almost trans to a C atom. If both these intra-molecular N→Bi inter-actions per metal atom are considered, the overall coordination geometry at bis-muth becomes distorted square-pyramidal [(C,N)(2)BiO cores] and the compound can be described as a hypervalent 12-Bi-5 species. Additional quite short intra-molecular Bi⋯O inter-actions are also present [3.796 (8)-4.020 (9) Å]. Inter-molecular associations through weak η(6)⋯Bi inter-actions [Bi⋯centroid of benzene ring = 3.659 (1) Å] lead to a ribbon-like supra-molecular association.

Related literature

For structures of related carbonates and similar η6⋯n class="Chemical">Bi inter­actions, see: Breunig et al. (2008 ▶, 2010 ▶); Yin et al. (2008 ▶). For the chirality induced by the coordination of the N atom, see: IUPAC (1979 ▶). For Bi—N, Bi—O and Bi—C bond lengths, see: Emsley, (1994 ▶). For CO2 absorption by bis(diorganobismuth)oxides, see: Suzuki et al. (1994 ▶).

Experimental

Crystal data

[Bi2(C11H16N)4(CO3)]

M = 1126.96

Monoclinic,

a = 12.263 (3) Å

b = 12.785 (2) Å

c = 15.286 (2) Å

β = 105.94 (1)°

V = 2304.4 (7) Å3

Z = 2

Mo Kα radiation

μ = 7.67 mm−1

T = 173 K

0.60 × 0.30 × 0.20 mm

Data collection

Siemens P4 diffractometer

Absorption correction: refined from ΔF (Walker & Stuart, 1983 ▶) T min = 0.076, T max = 0.526

9290 measured reflections

4065 independent reflections

3351 reflections with I > 2σ(I)

R int = 0.047

3 standard reflections every 197 reflections intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.104

S = 1.01

4065 reflections

243 parameters

H-atom parameters constrained

Δρmax = 1.83 e Å−3

Δρmin = −2.12 e Å−3

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCAn class="Chemical">NS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681005453X/rk2252sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681005453X/rk2252Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Bi2(C11H16N)4(CO3)]	F(000) = 1104
Mr = 1126.96	Dx = 1.624 Mg m−3
Monoclinic, P2/c	Melting point: 393 K
Hall symbol: -P 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.263 (3) Å	Cell parameters from 37 reflections
b = 12.785 (2) Å	θ = 4.9–25.0°
c = 15.286 (2) Å	µ = 7.67 mm−1
β = 105.94 (1)°	T = 173 K
V = 2304.4 (7) Å3	Block, colourless
Z = 2	0.60 × 0.30 × 0.20 mm

Siemens P4 diffractometer	3351 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.047
graphite	θmax = 25.0°, θmin = 2.5°
2θ/ω scans	h = −14→7
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −15→15
Tmin = 0.076, Tmax = 0.526	l = −17→18
9290 measured reflections	3 standard reflections every 197 reflections
4065 independent reflections	intensity decay: 2%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0659P)2] where P = (Fo2 + 2Fc2)/3
4065 reflections	(Δ/σ)max = 0.001
243 parameters	Δρmax = 1.83 e Å−3
0 restraints	Δρmin = −2.12 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

	x	y	z	Uiso*/Ueq
Bi1	0.88618 (2)	0.358681 (18)	0.053526 (14)	0.01998 (12)
C1	0.7204 (6)	0.3360 (5)	0.0910 (4)	0.0204 (14)
C2	0.6990 (7)	0.2406 (6)	0.1311 (4)	0.0282 (17)
C3	0.5970 (8)	0.2327 (7)	0.1543 (5)	0.039 (2)
H3	0.5803	0.1709	0.1800	0.047*
C4	0.5218 (8)	0.3126 (9)	0.1405 (6)	0.051 (3)
H4	0.4550	0.3051	0.1576	0.062*
C5	0.5425 (9)	0.4052 (8)	0.1013 (6)	0.050 (2)
H5	0.4898	0.4594	0.0911	0.060*
C6	0.6429 (7)	0.4161 (7)	0.0775 (5)	0.0332 (18)
H6	0.6582	0.4786	0.0521	0.040*
C7	0.7840 (8)	0.1526 (5)	0.1513 (5)	0.0313 (18)
H7A	0.8586	0.1815	0.1792	0.038*
H7B	0.7655	0.1059	0.1952	0.038*
C8	0.6832 (10)	0.0306 (7)	0.0375 (6)	0.051 (3)
H8A	0.6195	0.0766	0.0348	0.062*
H8B	0.6821	−0.0241	0.0812	0.062*
C9	0.6676 (11)	−0.0192 (8)	−0.0557 (6)	0.066 (3)
H9A	0.6701	0.0340	−0.0994	0.099*
H9B	0.5957	−0.0543	−0.0738	0.099*
H9C	0.7273	−0.0689	−0.0527	0.099*
C10	0.8872 (10)	0.0226 (7)	0.0953 (6)	0.051 (3)
H10A	0.8787	−0.0314	0.0494	0.061*
H10B	0.8892	−0.0114	0.1524	0.061*
C11	0.9977 (9)	0.0769 (7)	0.1053 (6)	0.049 (2)
H11A	1.0003	0.1041	0.0474	0.074*
H11B	1.0587	0.0281	0.1270	0.074*
H11C	1.0052	0.1333	0.1480	0.074*
C12	0.8403 (7)	0.5173 (5)	−0.0111 (4)	0.0248 (16)
C13	0.8200 (7)	0.5211 (5)	−0.1059 (4)	0.0248 (16)
C14	0.7937 (7)	0.6172 (6)	−0.1503 (5)	0.0277 (16)
H14	0.7774	0.6202	−0.2134	0.033*
C15	0.7918 (7)	0.7076 (6)	−0.1014 (4)	0.0280 (16)
H15	0.7761	0.7715	−0.1314	0.034*
C16	0.8130 (7)	0.7034 (6)	−0.0077 (5)	0.0316 (18)
H16	0.8110	0.7642	0.0251	0.038*
C17	0.8372 (7)	0.6090 (6)	0.0367 (5)	0.0284 (17)
H17	0.8516	0.6067	0.0997	0.034*
C18	0.8293 (8)	0.4243 (6)	−0.1593 (5)	0.0310 (17)
H18A	0.7928	0.4363	−0.2233	0.037*
H18B	0.9086	0.4088	−0.1526	0.037*
C19	0.6523 (8)	0.3465 (6)	−0.1538 (5)	0.037 (2)
H19A	0.6271	0.3559	−0.2192	0.044*
H19B	0.6338	0.4098	−0.1260	0.044*
C20	0.5867 (8)	0.2568 (7)	−0.1285 (5)	0.044 (2)
H20A	0.5886	0.1980	−0.1671	0.066*
H20B	0.5095	0.2778	−0.1362	0.066*
H20C	0.6204	0.2377	−0.0662	0.066*
C21	0.8230 (14)	0.2316 (8)	−0.1560 (7)	0.087 (3)
H21A	0.9051	0.2348	−0.1353	0.105*
H21B	0.7991	0.1733	−0.1251	0.105*
C22	0.7903 (14)	0.2099 (9)	−0.2524 (7)	0.087 (3)
H22A	0.7095	0.2023	−0.2735	0.131*
H22B	0.8260	0.1464	−0.2637	0.131*
H22C	0.8138	0.2666	−0.2842	0.131*
C23	1.0000	0.4009 (8)	0.2500	0.022 (2)
N1	0.7887 (6)	0.0909 (5)	0.0702 (4)	0.0340 (15)
N2	0.7747 (6)	0.3336 (5)	−0.1268 (4)	0.0302 (15)
O1	0.9491 (5)	0.4556 (4)	0.1793 (3)	0.0277 (12)
O2	1.0000	0.3026 (5)	0.2500	0.0249 (15)

	U11	U22	U33	U12	U13	U23
Bi1	0.02017 (17)	0.01928 (16)	0.02040 (16)	0.00227 (12)	0.00542 (11)	−0.00038 (9)
C1	0.008 (3)	0.030 (4)	0.023 (3)	0.000 (3)	0.003 (3)	0.000 (3)
C2	0.027 (4)	0.037 (4)	0.021 (3)	−0.007 (4)	0.008 (3)	−0.006 (3)
C3	0.036 (5)	0.049 (5)	0.036 (4)	−0.011 (4)	0.015 (4)	−0.004 (4)
C4	0.022 (5)	0.090 (8)	0.047 (5)	−0.001 (5)	0.017 (4)	−0.003 (5)
C5	0.039 (6)	0.068 (7)	0.044 (5)	0.018 (5)	0.015 (4)	−0.002 (5)
C6	0.031 (5)	0.042 (4)	0.029 (4)	0.009 (4)	0.011 (3)	0.002 (3)
C7	0.033 (5)	0.031 (4)	0.031 (4)	−0.008 (4)	0.009 (3)	0.001 (3)
C8	0.060 (7)	0.041 (5)	0.052 (5)	−0.016 (5)	0.014 (5)	−0.013 (4)
C9	0.081 (9)	0.037 (5)	0.078 (7)	−0.019 (6)	0.017 (7)	−0.020 (5)
C10	0.066 (8)	0.032 (5)	0.057 (5)	0.001 (5)	0.022 (5)	0.000 (4)
C11	0.053 (7)	0.039 (5)	0.056 (5)	0.009 (5)	0.015 (5)	−0.003 (4)
C12	0.028 (4)	0.022 (4)	0.020 (3)	0.006 (3)	−0.001 (3)	0.000 (3)
C13	0.031 (5)	0.022 (4)	0.023 (3)	0.003 (3)	0.009 (3)	0.000 (3)
C14	0.030 (4)	0.030 (4)	0.024 (3)	0.000 (4)	0.009 (3)	0.002 (3)
C15	0.021 (4)	0.027 (4)	0.036 (4)	0.003 (3)	0.008 (3)	0.008 (3)
C16	0.032 (5)	0.022 (4)	0.044 (4)	0.003 (4)	0.016 (4)	−0.005 (3)
C17	0.030 (5)	0.027 (4)	0.026 (3)	0.010 (4)	0.003 (3)	0.000 (3)
C18	0.042 (5)	0.028 (4)	0.027 (3)	−0.006 (4)	0.016 (3)	−0.007 (3)
C19	0.035 (5)	0.043 (5)	0.026 (4)	−0.003 (4)	−0.003 (4)	−0.003 (3)
C20	0.034 (5)	0.058 (6)	0.033 (4)	−0.018 (5)	−0.002 (4)	0.001 (4)
C21	0.154 (11)	0.043 (4)	0.078 (5)	0.002 (6)	0.051 (6)	−0.019 (4)
C22	0.154 (11)	0.043 (4)	0.078 (5)	0.002 (6)	0.051 (6)	−0.019 (4)
C23	0.016 (5)	0.025 (5)	0.023 (5)	0.000	0.003 (4)	0.000
N1	0.038 (4)	0.025 (3)	0.038 (3)	−0.009 (3)	0.010 (3)	−0.004 (3)
N2	0.030 (4)	0.031 (3)	0.029 (3)	−0.007 (3)	0.005 (3)	−0.008 (3)
O1	0.036 (3)	0.025 (3)	0.018 (2)	−0.001 (2)	−0.001 (2)	−0.0007 (18)
O2	0.023 (4)	0.026 (4)	0.024 (3)	0.000	0.003 (3)	0.000

Bi1—O1	2.238 (4)	C12—C17	1.387 (10)
Bi1—C12	2.259 (7)	C12—C13	1.402 (9)
Bi1—C1	2.277 (7)	C13—C14	1.398 (9)
Bi1—N2	2.739 (6)	C13—C18	1.504 (9)
C1—C6	1.373 (10)	C14—C15	1.381 (10)
C1—C2	1.422 (10)	C14—H14	0.9300
C2—C3	1.393 (11)	C15—C16	1.384 (9)
C2—C7	1.508 (11)	C15—H15	0.9300
C3—C4	1.354 (13)	C16—C17	1.377 (10)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.382 (15)	C17—H17	0.9300
C4—H4	0.9300	C18—N2	1.491 (10)
C5—C6	1.383 (13)	C18—H18A	0.9700
C5—H5	0.9300	C18—H18B	0.9700
C6—H6	0.9300	C19—N2	1.453 (11)
C7—N1	1.484 (9)	C19—C20	1.510 (11)
C7—H7A	0.9700	C19—H19A	0.9700
C7—H7B	0.9700	C19—H19B	0.9700
C8—N1	1.470 (12)	C20—H20A	0.9600
C8—C9	1.525 (11)	C20—H20B	0.9600
C8—H8A	0.9700	C20—H20C	0.9600
C8—H8B	0.9700	C21—C22	1.444 (13)
C9—H9A	0.9600	C21—N2	1.548 (12)
C9—H9B	0.9600	C21—H21A	0.9700
C9—H9C	0.9600	C21—H21B	0.9700
C10—N1	1.454 (12)	C22—H22A	0.9600
C10—C11	1.492 (14)	C22—H22B	0.9600
C10—H10A	0.9700	C22—H22C	0.9600
C10—H10B	0.9700	C23—O2	1.257 (13)
C11—H11A	0.9600	C23—O1i	1.295 (7)
C11—H11B	0.9600	C23—O1	1.295 (7)
C11—H11C	0.9600
O1—Bi1—C12	82.2 (2)	C14—C13—C18	120.1 (6)
O1—Bi1—C1	88.6 (2)	C12—C13—C18	121.0 (6)
C12—Bi1—C1	95.3 (3)	C15—C14—C13	120.6 (6)
O1—Bi1—N2	152.65 (18)	C15—C14—H14	119.7
C12—Bi1—N2	70.7 (2)	C13—C14—H14	119.7
C1—Bi1—N2	90.3 (2)	C14—C15—C16	120.1 (6)
C6—C1—C2	120.1 (7)	C14—C15—H15	120.0
C6—C1—Bi1	119.7 (5)	C16—C15—H15	120.0
C2—C1—Bi1	120.1 (5)	C17—C16—C15	119.9 (7)
C3—C2—C1	117.2 (8)	C17—C16—H16	120.0
C3—C2—C7	120.8 (7)	C15—C16—H16	120.0
C1—C2—C7	122.0 (7)	C16—C17—C12	120.9 (6)
C4—C3—C2	121.8 (8)	C16—C17—H17	119.5
C4—C3—H3	119.1	C12—C17—H17	119.5
C2—C3—H3	119.1	N2—C18—C13	110.6 (6)
C3—C4—C5	121.0 (9)	N2—C18—H18A	109.5
C3—C4—H4	119.5	C13—C18—H18A	109.5
C5—C4—H4	119.5	N2—C18—H18B	109.5
C4—C5—C6	118.9 (9)	C13—C18—H18B	109.5
C4—C5—H5	120.6	H18A—C18—H18B	108.1
C6—C5—H5	120.6	N2—C19—C20	115.0 (7)
C1—C6—C5	121.0 (8)	N2—C19—H19A	108.5
C1—C6—H6	119.5	C20—C19—H19A	108.5
C5—C6—H6	119.5	N2—C19—H19B	108.5
N1—C7—C2	114.2 (6)	C20—C19—H19B	108.5
N1—C7—H7A	108.7	H19A—C19—H19B	107.5
C2—C7—H7A	108.7	C19—C20—H20A	109.5
N1—C7—H7B	108.7	C19—C20—H20B	109.5
C2—C7—H7B	108.7	H20A—C20—H20B	109.5
H7A—C7—H7B	107.6	C19—C20—H20C	109.5
N1—C8—C9	114.2 (8)	H20A—C20—H20C	109.5
N1—C8—H8A	108.7	H20B—C20—H20C	109.5
C9—C8—H8A	108.7	C22—C21—N2	115.8 (10)
N1—C8—H8B	108.7	C22—C21—H21A	108.3
C9—C8—H8B	108.7	N2—C21—H21A	108.3
H8A—C8—H8B	107.6	C22—C21—H21B	108.3
C8—C9—H9A	109.5	N2—C21—H21B	108.3
C8—C9—H9B	109.5	H21A—C21—H21B	107.4
H9A—C9—H9B	109.5	C21—C22—H22A	109.5
C8—C9—H9C	109.5	C21—C22—H22B	109.5
H9A—C9—H9C	109.5	H22A—C22—H22B	109.5
H9B—C9—H9C	109.5	C21—C22—H22C	109.5
N1—C10—C11	114.4 (7)	H22A—C22—H22C	109.5
N1—C10—H10A	108.7	H22B—C22—H22C	109.5
C11—C10—H10A	108.7	O2—C23—O1i	122.7 (4)
N1—C10—H10B	108.7	O2—C23—O1	122.7 (4)
C11—C10—H10B	108.7	O1i—C23—O1	114.7 (9)
H10A—C10—H10B	107.6	C10—N1—C8	111.4 (7)
C10—C11—H11A	109.5	C10—N1—C7	108.6 (6)
C10—C11—H11B	109.5	C8—N1—C7	109.3 (7)
H11A—C11—H11B	109.5	C19—N2—C18	109.9 (6)
C10—C11—H11C	109.5	C19—N2—C21	117.5 (8)
H11A—C11—H11C	109.5	C18—N2—C21	108.5 (7)
H11B—C11—H11C	109.5	C19—N2—Bi1	117.6 (5)
C17—C12—C13	119.5 (6)	C18—N2—Bi1	95.6 (4)
C17—C12—Bi1	124.6 (5)	C21—N2—Bi1	105.3 (6)
C13—C12—Bi1	115.8 (5)	C23—O1—Bi1	113.1 (5)
C14—C13—C12	118.9 (6)
O1—Bi1—C1—C6	75.9 (5)	C13—C12—C17—C16	0.9 (13)
C12—Bi1—C1—C6	−6.1 (6)	Bi1—C12—C17—C16	177.2 (6)
N2—Bi1—C1—C6	−76.7 (5)	C14—C13—C18—N2	−138.3 (8)
O1—Bi1—C1—C2	−101.8 (5)	C12—C13—C18—N2	43.4 (11)
C12—Bi1—C1—C2	176.1 (5)	C11—C10—N1—C8	164.4 (7)
N2—Bi1—C1—C2	105.5 (5)	C11—C10—N1—C7	−75.1 (9)
C6—C1—C2—C3	0.8 (10)	C9—C8—N1—C10	−71.3 (10)
Bi1—C1—C2—C3	178.6 (5)	C9—C8—N1—C7	168.7 (8)
C6—C1—C2—C7	−177.0 (6)	C2—C7—N1—C10	169.2 (7)
Bi1—C1—C2—C7	0.8 (9)	C2—C7—N1—C8	−69.0 (8)
C1—C2—C3—C4	−0.8 (12)	C20—C19—N2—C18	177.3 (6)
C7—C2—C3—C4	177.0 (7)	C20—C19—N2—C21	52.6 (9)
C2—C3—C4—C5	1.0 (14)	C20—C19—N2—Bi1	−74.8 (7)
C3—C4—C5—C6	−1.1 (14)	C13—C18—N2—C19	71.0 (8)
C2—C1—C6—C5	−1.0 (11)	C13—C18—N2—C21	−159.3 (8)
Bi1—C1—C6—C5	−178.8 (6)	C13—C18—N2—Bi1	−51.0 (7)
C4—C5—C6—C1	1.1 (13)	C22—C21—N2—C19	56.3 (14)
C3—C2—C7—N1	105.3 (8)	C22—C21—N2—C18	−69.1 (13)
C1—C2—C7—N1	−76.9 (9)	C22—C21—N2—Bi1	−170.6 (10)
O1—Bi1—C12—C17	−14.3 (7)	O1—Bi1—N2—C19	−69.1 (7)
C1—Bi1—C12—C17	73.5 (7)	C12—Bi1—N2—C19	−77.1 (6)
N2—Bi1—C12—C17	162.0 (8)	C1—Bi1—N2—C19	18.4 (6)
O1—Bi1—C12—C13	162.1 (6)	O1—Bi1—N2—C18	46.9 (7)
C1—Bi1—C12—C13	−110.0 (6)	C12—Bi1—N2—C18	38.9 (5)
N2—Bi1—C12—C13	−21.6 (5)	C1—Bi1—N2—C18	134.4 (5)
C17—C12—C13—C14	−1.9 (12)	O1—Bi1—N2—C21	157.8 (6)
Bi1—C12—C13—C14	−178.5 (6)	C12—Bi1—N2—C21	149.8 (7)
C17—C12—C13—C18	176.4 (8)	C1—Bi1—N2—C21	−114.7 (6)
Bi1—C12—C13—C18	−0.2 (10)	O2—C23—O1—Bi1	−9.0 (4)
C12—C13—C14—C15	2.4 (13)	O1i—C23—O1—Bi1	171.0 (4)
C18—C13—C14—C15	−176.0 (8)	C12—Bi1—O1—C23	−175.1 (4)
C13—C14—C15—C16	−1.7 (13)	C1—Bi1—O1—C23	89.3 (4)
C14—C15—C16—C17	0.6 (12)	N2—Bi1—O1—C23	177.3 (3)
C15—C16—C17—C12	−0.2 (13)