A new linear bismuth coordination polymer based on 1,10-phenanthroline-2,9-di­carb­oxy­lic acid: ionothermal synthesis, crystal structure and fluorescence properties

A new linear bismuth(III) coordination polymer, catena-poly[[chloridobismuth(III)]-μ₃-1,10-phenanthroline-2,9-di­carboxyl­ato-κ⁶O²:O²,N¹,N¹⁰,O⁹:O⁹], [Bi(C₁₄H₆N₂O₄)Cl]_n, has been obtained by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR spectroscopy, thermal stability studies and single-crystal X-ray diffraction. The structure is constructed by Bi(C₁₄H₆N₂O₄)Cl fragments in which each Bi^III centre is seven-coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi^III cation is distorted penta­gonal–bipyramidal (BiO₄N₂Cl), with one bridging carboxyl­ate O atom and one Cl atom located in the axial positions. The Bi(C₁₄H₆N₂O₄)Cl fragments are further extended into a one-dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxyl­ate O atoms). Neighbouring linear chains are assembled via weak C—H...O and C—H...Cl hydrogen bonds, forming a three-dimensional supra­molecular architecture. Inter­molecular π–π stacking inter­actions are observed, with centroid-to-centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid-state fluorescence properties of the title coordination polymer were investigated.

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[chloridobismuth(III)]-µ₃-1,10-phenanthroline-2,9-dicarboxylato-κ⁵O²:N¹,N¹⁰,O⁹:O⁹]

Crystal data

[Bi(C14H6N2O4)Cl]	Z = 2
Mr = 510.64	F(000) = 472
Triclinic, P1	Dx = 2.533 Mg m^−3
a = 8.887 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.118 (5) Å	Cell parameters from 2502 reflections
c = 10.099 (4) Å	θ = 2.5–28.0°
α = 111.034 (13)°	µ = 13.39 mm^−1
β = 115.407 (9)°	T = 296 K
γ = 92.872 (13)°	Block, colourless
V = 669.4 (6) Å^3	0.26 × 0.24 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	2586 independent reflections
Radiation source: fine-focus sealed tube	2387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→6
Tmin = 0.369, Tmax = 0.746	k = −9→11
3659 measured reflections	l = −12→12

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.035P)^2] where P = (Fo^2 + 2Fc^2)/3
2586 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 1.64 e Å^−3
0 restraints	Δρmin = −1.74 e Å^−3

Special details

Experimental. Absorption correction: SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.1239 before and 0.0333 after correction. The Ratio of minimum to maximum transmission is 0.4948. The λ/2 correction factor is Not present.

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
Bi1	0.37660 (2)	0.18971 (2)	0.47993 (2)	0.02700 (10)
C1	0.2339 (8)	−0.2145 (7)	0.2427 (7)	0.0295 (13)
C2	0.0755 (7)	−0.1553 (6)	0.1718 (7)	0.0266 (12)
C3	−0.0805 (8)	−0.2614 (7)	0.0398 (7)	0.0331 (14)
H3	−0.0902	−0.3725	−0.0042	0.040*
C4	−0.2189 (7)	−0.1981 (7)	−0.0232 (7)	0.0350 (14)
H4	−0.3233	−0.2668	−0.1088	0.042*
C5	−0.2012 (7)	−0.0290 (7)	0.0425 (7)	0.0300 (13)
C6	−0.0394 (7)	0.0683 (7)	0.1772 (7)	0.0256 (12)
C7	−0.0135 (7)	0.2434 (7)	0.2483 (7)	0.0265 (12)
C8	−0.1445 (7)	0.3167 (7)	0.1845 (7)	0.0289 (12)
C9	−0.3073 (8)	0.2168 (8)	0.0481 (7)	0.0360 (14)
H9	−0.3952	0.2649	0.0064	0.043*
C10	−0.3346 (8)	0.0491 (8)	−0.0218 (8)	0.0353 (14)
H10	−0.4398	−0.0134	−0.1109	0.042*
C11	−0.1062 (7)	0.4881 (7)	0.2561 (7)	0.0315 (13)
H11	−0.1901	0.5417	0.2188	0.038*
C12	0.0553 (8)	0.5753 (7)	0.3807 (8)	0.0331 (13)
H12	0.0826	0.6879	0.4258	0.040*
C13	0.1807 (8)	0.4902 (7)	0.4401 (8)	0.0304 (13)
C14	0.3633 (8)	0.5742 (7)	0.5774 (7)	0.0323 (13)
Cl1	0.2559 (3)	0.1457 (2)	0.6498 (2)	0.0523 (4)
N1	0.0938 (6)	0.0057 (5)	0.2395 (5)	0.0250 (10)
N2	0.1448 (6)	0.3289 (5)	0.3759 (6)	0.0274 (10)
O1	0.3694 (5)	−0.1018 (5)	0.3640 (5)	0.0352 (10)
O2	0.2340 (6)	−0.3587 (5)	0.1865 (6)	0.0471 (12)
O3	0.4525 (5)	0.4849 (5)	0.6327 (5)	0.0409 (11)
O4	0.4130 (6)	0.7228 (5)	0.6221 (6)	0.0420 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.02535 (13)	0.01731 (13)	0.03377 (15)	0.00634 (8)	0.01205 (10)	0.00850 (9)
C1	0.036 (3)	0.018 (3)	0.030 (3)	0.005 (2)	0.016 (2)	0.005 (2)
C2	0.028 (3)	0.021 (3)	0.027 (3)	0.005 (2)	0.013 (2)	0.007 (2)
C3	0.037 (3)	0.021 (3)	0.030 (3)	0.003 (2)	0.014 (3)	0.002 (2)
C4	0.027 (3)	0.031 (3)	0.035 (3)	0.000 (2)	0.012 (3)	0.006 (3)
C5	0.023 (3)	0.035 (3)	0.027 (3)	0.003 (2)	0.012 (2)	0.009 (2)
C6	0.029 (3)	0.022 (3)	0.029 (3)	0.009 (2)	0.017 (2)	0.009 (2)
C7	0.027 (3)	0.026 (3)	0.029 (3)	0.009 (2)	0.016 (2)	0.011 (2)
C8	0.027 (3)	0.033 (3)	0.034 (3)	0.012 (2)	0.019 (2)	0.015 (3)
C9	0.027 (3)	0.047 (4)	0.036 (3)	0.015 (3)	0.016 (3)	0.018 (3)
C10	0.026 (3)	0.041 (4)	0.034 (3)	0.005 (2)	0.014 (2)	0.011 (3)
C11	0.031 (3)	0.031 (3)	0.043 (4)	0.018 (2)	0.024 (3)	0.018 (3)
C12	0.038 (3)	0.026 (3)	0.047 (4)	0.017 (2)	0.025 (3)	0.020 (3)
C13	0.033 (3)	0.024 (3)	0.041 (3)	0.012 (2)	0.023 (3)	0.015 (3)
C14	0.037 (3)	0.024 (3)	0.034 (3)	0.009 (2)	0.018 (3)	0.009 (3)
Cl1	0.0674 (12)	0.0526 (11)	0.0564 (11)	0.0276 (9)	0.0407 (10)	0.0278 (9)
N1	0.026 (2)	0.018 (2)	0.027 (2)	0.0056 (18)	0.0120 (19)	0.0053 (19)
N2	0.027 (2)	0.021 (2)	0.030 (3)	0.0050 (18)	0.014 (2)	0.0058 (19)
O1	0.028 (2)	0.025 (2)	0.035 (2)	0.0092 (17)	0.0059 (18)	0.0056 (18)
O2	0.048 (3)	0.025 (2)	0.055 (3)	0.014 (2)	0.019 (2)	0.009 (2)
O3	0.039 (2)	0.022 (2)	0.041 (3)	0.0078 (18)	0.006 (2)	0.0071 (19)
O4	0.047 (3)	0.020 (2)	0.048 (3)	0.0037 (18)	0.020 (2)	0.008 (2)

Geometric parameters (Å, º)

Bi1—Cl1	2.508 (2)	C6—N1	1.345 (7)
Bi1—N1	2.538 (5)	C7—C8	1.401 (8)
Bi1—N2	2.514 (5)	C7—N2	1.364 (7)
Bi1—O1^i	2.502 (4)	C8—C9	1.441 (8)
Bi1—O1	2.474 (4)	C8—C11	1.415 (8)
Bi1—O3	2.454 (4)	C9—H9	0.9300
Bi1—O4^ii	2.700 (5)	C9—C10	1.391 (9)
C1—C2	1.508 (8)	C10—H10	0.9300
C1—O1	1.309 (7)	C11—H11	0.9300
C1—O2	1.231 (7)	C11—C12	1.376 (9)
C2—C3	1.410 (8)	C12—H12	0.9300
C2—N1	1.345 (7)	C12—C13	1.432 (8)
C3—H3	0.9300	C13—C14	1.525 (8)
C3—C4	1.384 (9)	C13—N2	1.333 (7)
C4—H4	0.9300	C14—O3	1.271 (7)
C4—C5	1.412 (8)	C14—O4	1.250 (7)
C5—C6	1.426 (8)	O1—Bi1^i	2.502 (4)
C5—C10	1.446 (9)	O4—Bi1^ii	2.700 (5)
C6—C7	1.454 (8)
Cl1—Bi1—N1	85.68 (12)	N1—C6—C5	122.8 (5)
Cl1—Bi1—N2	89.79 (12)	N1—C6—C7	117.9 (5)
Cl1—Bi1—O4^ii	163.92 (11)	C8—C7—C6	120.7 (5)
N1—Bi1—O4^ii	110.21 (15)	N2—C7—C6	116.1 (5)
N2—Bi1—N1	64.18 (15)	N2—C7—C8	123.1 (5)
N2—Bi1—O4^ii	99.23 (15)	C7—C8—C9	119.3 (6)
O1—Bi1—Cl1	90.38 (12)	C7—C8—C11	117.2 (5)
O1^i—Bi1—Cl1	86.41 (13)	C11—C8—C9	123.5 (6)
O1^i—Bi1—N1	126.35 (14)	C8—C9—H9	119.6
O1—Bi1—N1	63.81 (14)	C10—C9—C8	120.8 (6)
O1—Bi1—N2	127.81 (14)	C10—C9—H9	119.6
O1^i—Bi1—N2	168.36 (14)	C5—C10—H10	119.6
O1—Bi1—O1^i	63.29 (15)	C9—C10—C5	120.7 (6)
O1^i—Bi1—O4^ii	82.12 (16)	C9—C10—H10	119.6
O1—Bi1—O4^ii	94.45 (14)	C8—C11—H11	120.0
O3—Bi1—Cl1	92.05 (13)	C12—C11—C8	120.0 (5)
O3—Bi1—N1	129.00 (15)	C12—C11—H11	120.0
O3—Bi1—N2	64.87 (14)	C11—C12—H12	120.5
O3—Bi1—O1	167.12 (14)	C11—C12—C13	119.1 (6)
O3—Bi1—O1^i	104.24 (14)	C13—C12—H12	120.5
O3—Bi1—O4^ii	79.97 (15)	C12—C13—C14	123.6 (5)
O1—C1—C2	115.2 (5)	N2—C13—C12	121.4 (6)
O2—C1—C2	121.4 (5)	N2—C13—C14	115.0 (5)
O2—C1—O1	123.4 (6)	O3—C14—C13	116.5 (5)
C3—C2—C1	122.1 (5)	O4—C14—C13	117.4 (5)
N1—C2—C1	115.7 (5)	O4—C14—O3	126.1 (6)
N1—C2—C3	122.1 (5)	C2—N1—Bi1	120.5 (4)
C2—C3—H3	120.5	C2—N1—C6	119.1 (5)
C4—C3—C2	119.1 (5)	C6—N1—Bi1	120.3 (4)
C4—C3—H3	120.5	C7—N2—Bi1	121.5 (4)
C3—C4—H4	120.1	C13—N2—Bi1	119.2 (4)
C3—C4—C5	119.9 (5)	C13—N2—C7	119.2 (5)
C5—C4—H4	120.1	Bi1—O1—Bi1^i	116.71 (15)
C4—C5—C6	117.0 (5)	C1—O1—Bi1	124.6 (4)
C4—C5—C10	123.9 (5)	C1—O1—Bi1^i	117.8 (4)
C6—C5—C10	119.1 (5)	C14—O3—Bi1	121.9 (4)
C5—C6—C7	119.3 (5)	C14—O4—Bi1^ii	116.4 (4)
C1—C2—C3—C4	−177.5 (6)	N1—Bi1—N2—C7	0.7 (4)
C1—C2—N1—Bi1	−2.8 (7)	N1—Bi1—N2—C13	−175.1 (5)
C1—C2—N1—C6	176.5 (5)	N1—Bi1—O1—Bi1^i	−170.8 (3)
C2—C1—O1—Bi1^i	169.9 (4)	N1—Bi1—O1—C1	−1.7 (4)
C2—C1—O1—Bi1	1.0 (7)	N1—Bi1—O3—C14	−16.8 (6)
C2—C3—C4—C5	1.4 (9)	N1—C2—C3—C4	0.6 (9)
C3—C2—N1—Bi1	179.0 (4)	N1—C6—C7—C8	177.2 (5)
C3—C2—N1—C6	−1.7 (8)	N1—C6—C7—N2	−1.3 (8)
C3—C4—C5—C6	−2.2 (9)	N2—Bi1—N1—C2	177.9 (5)
C3—C4—C5—C10	175.8 (6)	N2—Bi1—N1—C6	−1.4 (4)
C4—C5—C6—C7	179.2 (5)	N2—Bi1—O1—Bi1^i	−175.83 (15)
C4—C5—C6—N1	1.1 (9)	N2—Bi1—O1—C1	−6.7 (6)
C4—C5—C10—C9	−179.2 (6)	N2—Bi1—O3—C14	−14.1 (4)
C5—C6—C7—C8	−1.0 (8)	N2—C7—C8—C9	179.2 (5)
C5—C6—C7—N2	−179.5 (5)	N2—C7—C8—C11	1.3 (8)
C5—C6—N1—Bi1	−179.9 (4)	N2—C13—C14—O3	−10.7 (8)
C5—C6—N1—C2	0.8 (8)	N2—C13—C14—O4	167.5 (5)
C6—C5—C10—C9	−1.3 (9)	O1—Bi1—N1—C2	2.3 (4)
C6—C7—C8—C9	0.8 (8)	O1^i—Bi1—N1—C2	−7.9 (5)
C6—C7—C8—C11	−177.1 (5)	O1^i—Bi1—N1—C6	172.8 (4)
C6—C7—N2—Bi1	0.0 (7)	O1—Bi1—N1—C6	−177.0 (5)
C6—C7—N2—C13	175.8 (5)	O1^i—Bi1—N2—C7	−155.5 (6)
C7—C6—N1—Bi1	2.0 (7)	O1—Bi1—N2—C7	5.7 (5)
C7—C6—N1—C2	−177.3 (5)	O1^i—Bi1—N2—C13	28.7 (9)
C7—C8—C9—C10	−0.9 (9)	O1—Bi1—N2—C13	−170.1 (4)
C7—C8—C11—C12	1.2 (8)	O1^i—Bi1—O1—Bi1^i	0.0
C8—C7—N2—Bi1	−178.5 (4)	O1^i—Bi1—O1—C1	169.1 (6)
C8—C7—N2—C13	−2.7 (8)	O1^i—Bi1—O3—C14	170.3 (4)
C8—C9—C10—C5	1.1 (9)	O1—Bi1—O3—C14	156.3 (6)
C8—C11—C12—C13	−2.3 (9)	O1—C1—C2—C3	179.5 (5)
C9—C8—C11—C12	−176.6 (6)	O1—C1—C2—N1	1.3 (8)
C10—C5—C6—C7	1.2 (8)	O2—C1—C2—C3	0.9 (9)
C10—C5—C6—N1	−176.9 (5)	O2—C1—C2—N1	−177.3 (6)
C11—C8—C9—C10	176.9 (6)	O2—C1—O1—Bi1^i	−11.5 (8)
C11—C12—C13—C14	179.9 (6)	O2—C1—O1—Bi1	179.5 (5)
C11—C12—C13—N2	0.9 (9)	O3—Bi1—N1—C2	−179.4 (4)
C12—C13—C14—O3	170.2 (6)	O3—Bi1—N1—C6	1.3 (5)
C12—C13—C14—O4	−11.6 (9)	O3—Bi1—N2—C7	−177.0 (5)
C12—C13—N2—Bi1	177.4 (4)	O3—Bi1—N2—C13	7.2 (4)
C12—C13—N2—C7	1.5 (8)	O3—Bi1—O1—Bi1^i	15.1 (8)
C13—C14—O3—Bi1	18.7 (7)	O3—Bi1—O1—C1	−175.8 (6)
C13—C14—O4—Bi1^ii	−102.9 (5)	O3—C14—O4—Bi1^ii	75.1 (7)
C14—C13—N2—Bi1	−1.7 (7)	O4^ii—Bi1—N1—C2	87.2 (4)
C14—C13—N2—C7	−177.5 (5)	O4^ii—Bi1—N1—C6	−92.1 (4)
Cl1—Bi1—N1—C2	−90.2 (4)	O4^ii—Bi1—N2—C7	108.7 (4)
Cl1—Bi1—N1—C6	90.5 (4)	O4^ii—Bi1—N2—C13	−67.0 (4)
Cl1—Bi1—N2—C7	−84.6 (4)	O4^ii—Bi1—O1—Bi1^i	78.9 (2)
Cl1—Bi1—N2—C13	99.6 (4)	O4^ii—Bi1—O1—C1	−112.1 (5)
Cl1—Bi1—O1—Bi1^i	−85.79 (19)	O4^ii—Bi1—O3—C14	91.1 (5)
Cl1—Bi1—O1—C1	83.3 (5)	O4—C14—O3—Bi1	−159.4 (5)
Cl1—Bi1—O3—C14	−102.9 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^iii	0.93	2.34	3.201 (7)	155
C4—H4···O3^iv	0.93	2.60	3.492 (7)	161
C11—H11···Cl1^v	0.93	2.89	3.616 (6)	136

Symmetry codes: (iii) −x, −y−1, −z; (iv) x−1, y−1, z−1; (v) −x, −y+1, −z+1.