(N,N-Dimethyl-formamide-κO)bis-(3-hy-droxy-picolinato-κN,O)phenyl-bis-muth(III).

The title organometallic complex, [Bi(C(6)H(5))(C(6)H(4)NO(3))(2)(C(3)H(7)NO)], features a Bi(III) atom in a distorted pentagonal-pyramidal coordination by two N,O-donating bidentate 3-hy-droxy-picolinate (3-hpic) ligands, one monodentate dimethyl-formamide (dmf) mol-ecule and one phenyl ring. The C atom of the aryl ligand occupies the apical position of the BiCN(2)O(3) coordination polyhedron, while the equatorial plane is formed by one O atom of the dmf ligand and two sets of N and O atoms from the chelating 3-hpic ligands. Inter-molecular secondary Bi⋯O [3.485 (3) Å] and O-H⋯O hydrogen-bonding inter-actions connect the complexes into a three-dimensional network. Intramolecular O-H⋯O hydrogen bonds are also observed.

Related literature

For a review on the structural chemistry of organobismuth derivatives, see Silvestru et al. (1999 ▶). For the crystal structures of related aryl­bis­muth(III) compounds, see: Stavila et al. (2007 ▶, 2009 ▶); Stavila & Dikarev (2009 ▶); Andrews et al. (2006 ▶); Yu et al. (2004 ▶). For bis­muth(III) picolinate complexes, see: Callens et al. (2008 ▶). For a review on biomedical applications of bis­muth(III) compounds, see: Briand & Burford (1999 ▶).

Experimental

Crystal data

[Bi(C6H5)(C6H4NO3)2(C3H7NO)]

M = 635.38

Monoclinic,

a = 8.2377 (16) Å

b = 21.989 (4) Å

c = 12.380 (3) Å

β = 104.24 (3)°

V = 2173.6 (7) Å3

Z = 4

Mo Kα radiation

μ = 8.16 mm−1

T = 294 K

0.14 × 0.11 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.356, T max = 0.450

15126 measured reflections

3669 independent reflections

3314 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.048

S = 1.11

3669 reflections

299 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.72 e Å−3

Δρmin = −0.94 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810044235/sj5046sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044235/sj5046Isup2.hkl

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

[Bi(C6H5)(C6H4NO3)2(C3H7NO)]	F(000) = 1224
Mr = 635.38	Dx = 1.942 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7774 reflections
a = 8.2377 (16) Å	θ = 2.5–24.7°
b = 21.989 (4) Å	µ = 8.16 mm−1
c = 12.380 (3) Å	T = 294 K
β = 104.24 (3)°	Block, light-yellow
V = 2173.6 (7) Å3	0.14 × 0.11 × 0.10 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3669 independent reflections
Radiation source: fine-focus sealed tube	3314 reflections with I > 2σ(I)
graphite	Rint = 0.031
ω scans	θmax = 24.8°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.356, Tmax = 0.450	k = −25→25
15126 measured reflections	l = −14→13

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.048	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0202P)2 + 1.6444P] where P = (Fo2 + 2Fc2)/3
3669 reflections	(Δ/σ)max < 0.001
299 parameters	Δρmax = 0.72 e Å−3
4 restraints	Δρmin = −0.94 e Å−3

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.

	x	y	z	Uiso*/Ueq
Bi1	0.163597 (16)	0.410112 (6)	0.270490 (11)	0.02944 (6)
N1	−0.0947 (4)	0.39564 (14)	0.0950 (3)	0.0350 (7)
N2	0.4598 (3)	0.44505 (13)	0.3132 (2)	0.0296 (7)
N3	−0.1613 (4)	0.30791 (16)	0.4752 (3)	0.0484 (9)
O11	0.2210 (3)	0.43021 (14)	0.0973 (2)	0.0460 (7)
O12	0.1580 (4)	0.43682 (17)	−0.0856 (2)	0.0616 (9)
O13	−0.1422 (4)	0.42463 (17)	−0.1993 (3)	0.0700 (10)
H13A	−0.047 (2)	0.4405 (17)	−0.179 (3)	0.084*
O21	0.3075 (3)	0.39088 (11)	0.4591 (2)	0.0345 (6)
O22	0.5381 (3)	0.40081 (12)	0.5967 (2)	0.0431 (7)
O23	0.7918 (3)	0.45888 (13)	0.5663 (2)	0.0424 (7)
H23A	0.721 (3)	0.4455 (17)	0.599 (2)	0.051*
O31	−0.0596 (3)	0.35957 (13)	0.3485 (2)	0.0463 (7)
C11	0.1176 (5)	0.42747 (18)	0.0033 (3)	0.0384 (9)
C12	−0.0582 (5)	0.41051 (16)	−0.0012 (3)	0.0342 (8)
C13	−0.1795 (6)	0.41097 (19)	−0.1030 (4)	0.0483 (11)
C14	−0.3443 (6)	0.3973 (2)	−0.1012 (4)	0.0602 (13)
H14A	−0.4287	0.3973	−0.1668	0.072*
C15	−0.3797 (5)	0.3840 (2)	−0.0021 (4)	0.0568 (12)
H15A	−0.4893	0.3757	0.0007	0.068*
C16	−0.2524 (5)	0.3828 (2)	0.0945 (4)	0.0446 (10)
H16A	−0.2781	0.3727	0.1614	0.053*
C21	0.4577 (5)	0.40784 (15)	0.4986 (3)	0.0311 (8)
C22	0.5437 (4)	0.43992 (15)	0.4213 (3)	0.0279 (8)
C23	0.7050 (4)	0.46376 (16)	0.4596 (3)	0.0310 (8)
C24	0.7768 (4)	0.49391 (17)	0.3847 (3)	0.0372 (9)
H24A	0.8836	0.5105	0.4082	0.045*
C25	0.6894 (5)	0.49916 (19)	0.2758 (3)	0.0405 (10)
H25A	0.7360	0.5194	0.2247	0.049*
C26	0.5304 (5)	0.47394 (18)	0.2424 (3)	0.0381 (9)
H26A	0.4716	0.4774	0.1682	0.046*
C31	−0.0559 (5)	0.34549 (19)	0.4457 (4)	0.0421 (10)
H31A	0.024 (5)	0.3600 (19)	0.512 (4)	0.056 (13)*
C32	−0.1501 (7)	0.2935 (3)	0.5913 (4)	0.0744 (16)
H32A	−0.0565	0.3146	0.6378	0.112*
H32B	−0.1352	0.2505	0.6026	0.112*
H32C	−0.2513	0.3060	0.6104	0.112*
C33	−0.2927 (7)	0.2800 (3)	0.3906 (5)	0.0903 (19)
H33A	−0.2842	0.2932	0.3183	0.135*
H33B	−0.3997	0.2916	0.4017	0.135*
H33C	−0.2814	0.2365	0.3955	0.135*
C41	0.2374 (4)	0.31401 (17)	0.2439 (3)	0.0341 (8)
C42	0.2978 (6)	0.2968 (2)	0.1537 (4)	0.0550 (12)
H42A	0.3107	0.3258	0.1019	0.066*
C43	0.3391 (6)	0.2369 (3)	0.1397 (4)	0.0666 (14)
H43A	0.3812	0.2263	0.0791	0.080*
C44	0.3194 (6)	0.1938 (3)	0.2124 (4)	0.0676 (16)
H44A	0.3451	0.1535	0.2011	0.081*
C45	0.2610 (6)	0.2096 (2)	0.3034 (4)	0.0602 (13)
H45A	0.2486	0.1800	0.3545	0.072*
C46	0.2204 (5)	0.26970 (18)	0.3191 (4)	0.0453 (10)
H46A	0.1814	0.2802	0.3810	0.054*

	U11	U22	U33	U12	U13	U23
Bi1	0.03053 (9)	0.03335 (9)	0.02336 (9)	−0.00432 (6)	0.00457 (6)	0.00018 (6)
N1	0.0321 (17)	0.0393 (18)	0.0307 (19)	0.0017 (13)	0.0023 (14)	0.0009 (14)
N2	0.0325 (16)	0.0342 (16)	0.0216 (16)	−0.0069 (13)	0.0061 (13)	0.0022 (13)
N3	0.0418 (19)	0.053 (2)	0.052 (2)	−0.0026 (16)	0.0139 (17)	0.0137 (18)
O11	0.0412 (15)	0.0690 (19)	0.0247 (15)	−0.0184 (14)	0.0023 (12)	0.0043 (13)
O12	0.062 (2)	0.095 (2)	0.0273 (17)	−0.0225 (18)	0.0102 (15)	0.0074 (16)
O13	0.071 (2)	0.105 (3)	0.0252 (18)	−0.019 (2)	−0.0061 (16)	0.0155 (17)
O21	0.0361 (14)	0.0410 (14)	0.0254 (14)	−0.0129 (11)	0.0057 (11)	0.0031 (11)
O22	0.0423 (16)	0.0582 (18)	0.0249 (16)	−0.0082 (12)	0.0006 (12)	0.0097 (12)
O23	0.0358 (15)	0.0568 (18)	0.0301 (16)	−0.0098 (13)	−0.0005 (12)	0.0040 (13)
O31	0.0390 (15)	0.0590 (18)	0.0429 (18)	−0.0015 (13)	0.0141 (13)	0.0088 (14)
C11	0.048 (2)	0.040 (2)	0.026 (2)	−0.0058 (17)	0.0056 (18)	0.0034 (17)
C12	0.040 (2)	0.033 (2)	0.025 (2)	−0.0022 (16)	−0.0009 (16)	0.0041 (15)
C13	0.056 (3)	0.049 (3)	0.032 (3)	−0.005 (2)	−0.002 (2)	0.0060 (19)
C14	0.043 (3)	0.070 (3)	0.052 (3)	−0.005 (2)	−0.018 (2)	0.005 (2)
C15	0.036 (2)	0.072 (3)	0.056 (3)	−0.005 (2)	−0.001 (2)	0.004 (3)
C16	0.038 (2)	0.054 (3)	0.041 (3)	−0.0027 (19)	0.0094 (19)	0.000 (2)
C21	0.036 (2)	0.0296 (19)	0.027 (2)	−0.0038 (15)	0.0065 (17)	−0.0030 (15)
C22	0.0313 (18)	0.0269 (18)	0.025 (2)	0.0009 (14)	0.0069 (15)	−0.0014 (15)
C23	0.0310 (18)	0.0309 (19)	0.030 (2)	0.0008 (15)	0.0058 (16)	−0.0020 (16)
C24	0.0295 (19)	0.043 (2)	0.039 (2)	−0.0086 (16)	0.0087 (17)	−0.0041 (18)
C25	0.041 (2)	0.049 (2)	0.035 (2)	−0.0106 (18)	0.0179 (19)	0.0022 (18)
C26	0.041 (2)	0.048 (2)	0.025 (2)	−0.0090 (18)	0.0059 (17)	0.0032 (17)
C31	0.033 (2)	0.045 (2)	0.048 (3)	0.0026 (18)	0.008 (2)	0.003 (2)
C32	0.068 (3)	0.095 (4)	0.064 (4)	0.007 (3)	0.022 (3)	0.037 (3)
C33	0.082 (4)	0.092 (4)	0.093 (5)	−0.042 (3)	0.014 (3)	0.005 (4)
C41	0.0299 (19)	0.040 (2)	0.029 (2)	0.0004 (16)	0.0014 (16)	−0.0051 (17)
C42	0.059 (3)	0.066 (3)	0.042 (3)	0.012 (2)	0.015 (2)	−0.002 (2)
C43	0.074 (3)	0.078 (4)	0.048 (3)	0.027 (3)	0.014 (3)	−0.018 (3)
C44	0.071 (3)	0.059 (3)	0.060 (4)	0.027 (3)	−0.007 (3)	−0.021 (3)
C45	0.069 (3)	0.046 (3)	0.061 (3)	0.009 (2)	0.005 (3)	0.005 (2)
C46	0.054 (2)	0.040 (2)	0.041 (2)	0.0068 (19)	0.011 (2)	−0.002 (2)

Bi1—C41	2.245 (4)	O31—C31	1.235 (5)
Bi1—O11	2.348 (3)	C11—C12	1.483 (5)
Bi1—O21	2.382 (3)	C12—C13	1.403 (6)
Bi1—N2	2.488 (3)	C13—C14	1.396 (7)
Bi1—O31	2.534 (3)	C14—C15	1.360 (7)
Bi1—N1	2.660 (3)	C15—C16	1.384 (6)
N1—C16	1.328 (5)	C21—C22	1.499 (5)
N1—C12	1.338 (5)	C22—C23	1.398 (5)
N2—C26	1.327 (4)	C23—C24	1.386 (5)
N2—C22	1.352 (4)	C24—C25	1.368 (5)
N3—C31	1.313 (5)	C25—C26	1.388 (5)
N3—C33	1.445 (6)	C41—C46	1.378 (6)
N3—C32	1.453 (6)	C41—C42	1.382 (5)
O11—C11	1.264 (5)	C42—C43	1.381 (7)
O12—C11	1.243 (5)	C43—C44	1.345 (7)
O13—C13	1.336 (5)	C44—C45	1.374 (7)
O21—C21	1.269 (4)	C45—C46	1.389 (6)
O22—C21	1.242 (5)	O13—H13A	0.84 (3)
O23—C23	1.342 (4)	O23—H23A	0.84 (3)
C41—Bi1—O11	85.44 (12)	N1—C12—C11	117.3 (3)
C41—Bi1—O21	83.65 (11)	C13—C12—C11	120.3 (4)
O11—Bi1—O21	139.90 (9)	O13—C13—C14	120.1 (4)
C41—Bi1—N2	92.01 (11)	O13—C13—C12	122.3 (4)
O11—Bi1—N2	74.25 (9)	C14—C13—C12	117.7 (4)
O21—Bi1—N2	67.72 (9)	C15—C14—C13	119.1 (4)
C41—Bi1—O31	83.76 (12)	C14—C15—C16	119.9 (4)
O11—Bi1—O31	139.33 (9)	N1—C16—C15	122.1 (4)
O21—Bi1—O31	77.37 (9)	O22—C21—O21	125.1 (3)
N2—Bi1—O31	145.09 (9)	O22—C21—C22	117.4 (3)
C41—Bi1—N1	87.62 (11)	O21—C21—C22	117.5 (3)
O11—Bi1—N1	64.98 (10)	N2—C22—C23	121.1 (3)
O21—Bi1—N1	152.21 (9)	N2—C22—C21	117.7 (3)
N2—Bi1—N1	139.13 (10)	C23—C22—C21	121.3 (3)
O31—Bi1—N1	75.49 (10)	O23—C23—C24	119.0 (3)
C16—N1—C12	118.8 (3)	O23—C23—C22	122.4 (3)
C16—N1—Bi1	127.9 (3)	C24—C23—C22	118.6 (3)
C12—N1—Bi1	112.8 (2)	C25—C24—C23	119.5 (3)
C26—N2—C22	119.6 (3)	C24—C25—C26	119.3 (3)
C26—N2—Bi1	125.0 (2)	N2—C26—C25	121.9 (3)
C22—N2—Bi1	114.9 (2)	O31—C31—N3	124.7 (4)
C31—N3—C33	119.6 (4)	C46—C41—C42	117.9 (4)
C31—N3—C32	121.8 (4)	C46—C41—Bi1	119.3 (3)
C33—N3—C32	118.6 (4)	C42—C41—Bi1	122.7 (3)
C11—O11—Bi1	126.2 (2)	C43—C42—C41	120.8 (5)
C21—O21—Bi1	121.9 (2)	C44—C43—C42	120.9 (5)
C31—O31—Bi1	129.4 (3)	C43—C44—C45	119.7 (5)
O12—C11—O11	122.8 (4)	C44—C45—C46	120.0 (5)
O12—C11—C12	118.7 (3)	C41—C46—C45	120.7 (4)
O11—C11—C12	118.5 (3)	O13—H13A—O12	147 (4)
N1—C12—C13	122.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O12	0.84 (3)	1.80 (3)	2.541 (5)	147 (4)
O23—H23A···O22	0.84 (3)	1.79 (3)	2.555 (5)	150 (3)
O23—H23A···O13i	0.84 (3)	2.52 (2)	2.917 (6)	110 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O12	0.84 (3)	1.80 (3)	2.541 (5)	147 (4)
O23—H23A⋯O22	0.84 (3)	1.79 (3)	2.555 (5)	150 (3)
O23—H23A⋯O13i	0.84 (3)	2.52 (2)	2.917 (6)	110 (2)

Symmetry code: (i) .