Bis(2,3-diamino­pyridinium) bis­(μ-pyridine-2,6-dicarboxyl­ato)-κ4O2,N,O6:O6;κ4O2:O2,N,O6-bis­[aqua­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)bis­muthate(III)] tetra­hydrate

Aghabozorg, H.; Kazemi, S.; Agah, A.A.; Mirzaei, M.; Notash, B.

doi:10.1107/S1600536811005629

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Pages m360-m361

doi:10.1107/S1600536811005629

Open

access

Bis(2,3-diaminopyridinium) bis(μ-pyridine-2,6-dicarboxylato)-κ⁴O²,N,O⁶:O⁶;κ⁴O²:O²,N,O⁶-bis[aqua(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)bismuthate(III)] tetrahydrate

Hossein Aghabozorg,^a ^* Shokoofeh Kazemi,^a Ali Akbar Agah,^b Masoud Mirzaei ^c and Behrouz Notash ^d

^aFaculty of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran, ^bFaculty of Chemistry, Tarbiat Moallem University, 15614 Tehran, Iran, ^cDepartment of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad 917791436, Iran, and ^dDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: haghabozorg@yahoo.com

(Received 9 February 2011; accepted 15 February 2011; online 23 February 2011)

In the centrosymmetric dinuclear complex anion of the title compound, (C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O, the Bi^III atom is eight-coordinated in an N₂O₆ environment and has a distorted bicapped trigonal–prismatic coordination environment. Extensive intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds lead to the stability of the crystal structure. Interactions between one C—H group of the 2,3-diaminopyridinium [(2,3-dapyH)⁺] cation and the aromatic ring of the pyridine-2,6-dicarboxylate (pydc) ligand (C—H⋯centroid distance = 2.78 Å) and π–π interactions between the (2,3-dapyH)⁺ cations and between the (2,3-dapyH)⁺ cation and the pydc ligand [centroid–centroid distances = 3.489 (5) and 3.694 (5) Å] are observed.

Related literature

For related structures, see: Aghabozorg et al. (2008 , 2010 ); Sheshmani et al. (2005 ).

Experimental

Crystal data

(C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O
M_r = 1406.76
Triclinic, $[P \overline 1]$
a = 9.3462 (19) Å
b = 10.726 (2) Å
c = 11.098 (2) Å
α = 95.13 (3)°
β = 91.38 (3)°
γ = 90.47 (3)°
V = 1107.7 (4) Å³
Z = 1
Mo Kα radiation
μ = 8.03 mm⁻¹
T = 298 K
0.33 × 0.27 × 0.23 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ) T_min = 0.083, T_max = 0.156
12406 measured reflections
5940 independent reflections
5539 reflections with I > 2σ(I)
R_int = 0.113

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.154
S = 1.05
5940 reflections
347 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.98 e Å⁻³
Δρ_min = −2.93 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O11ⁱ	0.87 (14)	2.02 (14)	2.797 (10)	148 (12)
N4—H4A⋯O2ⁱⁱ	0.86	2.11	2.924 (9)	158
N4—H4B⋯O6ⁱ	0.86	1.97	2.830 (10)	178
N5—H5A⋯O3ⁱⁱⁱ	0.86	2.53	3.216 (10)	138
N5—H5B⋯O6ⁱ	0.86	2.11	2.972 (10)	176
O9—H9A⋯O8^iv	0.81 (7)	2.07 (12)	2.746 (10)	141 (15)
O9—H9B⋯O11^v	0.84 (8)	1.99 (10)	2.771 (11)	155 (15)
O10—H10A⋯O5	0.94 (8)	1.96 (8)	2.862 (9)	160 (11)
O10—H10B⋯O7^vi	0.80 (8)	2.21 (8)	2.972 (10)	160 (13)
O11—H11A⋯O4ⁱⁱⁱ	0.89 (8)	2.01 (13)	2.717 (11)	136 (14)
O11—H11B⋯O10^vii	0.92 (9)	1.96 (9)	2.836 (12)	158 (13)
C11—H11⋯O8^viii	0.93	2.26	3.050 (10)	142
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x, -y, -z+2; (v) x-1, y-1, z; (vi) x+1, y, z; (vii) x, y+1, z; (viii) -x, -y+1, -z+2.

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005629/hy2406sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005629/hy2406Isup2.hkl

checkCIF report

Comment top

Pyridine-2,6-dicarboxylic acid (pydcH₂) can form various complexes containing transition and main metals (Aghabozorg et al., 2008). There are complexes in which pydc acts as a bridging ligand between two metal atoms (Aghabozorg et al., 2010; Sheshmani et al., 2005).

Herein, we report the crystal structure of the title compund as another example of bismuth(III) coordination compound, which bears heterocyclic 2,3-diaminopyridine (2,3-dapy) and pydcH₂ ligands. The molecular structure of the title compound is shown in Fig. 1. The centrosymmetric binuclear unit consists of two Bi^III atoms, four (pydc)^2- ligands, two coordinated water molecules. Two pydc ligands act as tridentate ligands with an N atom of the pyridine ring and two O atoms of the dicarboxylate groups acting as donors. One of the dicarboxylate O atoms for the other two pydc ligands plays a bridging role between two Bi atoms. The structure also contains two (2,3-dapyH)⁺ cations and four uncoordinated water molecules. The Bi^III atom is eight-coordinated in an N₂O₆ environment and has a distorted bicapped trigonal-prismatic geometry, as it is shown in Fig. 2. There are extensive intermolecular O—H···O, N—H···O and weak C—H···O hydrogen bonds, which cause the stability of the crystal structure (Fig. 3, Table 1). There are also π–π interactions between the (2,3-dapyH)⁺ rings and between the (2,3-dapyH)⁺ and pydc rings (Fig. 4), with centroid–centroid distances of 3.489 (5) and 3.694 (5) Å, respectively. Furthermore, there is C—H···π interacton between C—H group of the (2,3-dapyH)⁺ cation and pydc ligand, with an C—H···centroid distance of 2.78 Å (Fig. 5).

Related literature top

For related structures, see: Aghabozorg et al. (2008, 2010); Sheshmani et al. (2005).

Experimental top

An aqueous solution of Bi(NO₃)₃ (1 mmol), pydcH₂ (3 mmol) and 2,3-dapy (1 mmol) was refluxed for about 30 min in a 1:3:1 molar ratio. Brown crystals of the title compound were obtained from the solution by slow evaporation of the solvent within two weeks at room temperature.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. [Symmetry code: (i) -x+1, -y, -z+2.]
	Fig. 2. The coordination environment of the Bi^III atom, showing a distorted bicapped trigonal-prismatic geometry. [Symmetry code: (i) -x+1, -y, -z+2.]
	Fig. 3. A view of the crystal packing, showing O—H···O, N—H···O and weak C—H···O hydrogen bonds (dashed lines) in the title compound.
	Fig. 4. π–π stacking interactions between the aromatic rings of the (2,3-dapyH)⁺ cation and pydc ligand.
	Fig. 5. C—H···π interaction between C—H group of the (2,3-dapyH)⁺ cation and the aromatic ring of the pydc ligand.

Bis(2,3-diaminopyridinium) bis(µ-pyridine-2,6-dicarboxylato)- κ⁴O²,N,O⁶:O⁶; κ⁴O²:O²,N,O⁶-bis[aqua(pyridine-2,6- dicarboxylato-κ³O²,N,O⁶)bismuthate(III)] tetrahydrate top

Crystal data top

(C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O	Z = 1
M_r = 1406.76	F(000) = 680
Triclinic, P1	D_x = 2.109 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3462 (19) Å	Cell parameters from 5940 reflections
b = 10.726 (2) Å	θ = 2.2–29.2°
c = 11.098 (2) Å	µ = 8.03 mm⁻¹
α = 95.13 (3)°	T = 298 K
β = 91.38 (3)°	Prism, brown
γ = 90.47 (3)°	0.33 × 0.27 × 0.23 mm
V = 1107.7 (4) Å³

Data collection top

Stoe IPDS-2 diffractometer	5940 independent reflections
Radiation source: fine-focus sealed tube	5539 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.113
ω scans	θ_max = 29.2°, θ_min = 2.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −12→12
T_min = 0.083, T_max = 0.156	k = −14→14
12406 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.1042P)² + 3.0215P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5940 reflections	Δρ_max = 2.98 e Å⁻³
347 parameters	Δρ_min = −2.93 e Å⁻³
9 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (13)

Crystal data top

(C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O	γ = 90.47 (3)°
M_r = 1406.76	V = 1107.7 (4) Å³
Triclinic, P1	Z = 1
a = 9.3462 (19) Å	Mo Kα radiation
b = 10.726 (2) Å	µ = 8.03 mm⁻¹
c = 11.098 (2) Å	T = 298 K
α = 95.13 (3)°	0.33 × 0.27 × 0.23 mm
β = 91.38 (3)°

Data collection top

Stoe IPDS-2 diffractometer	5940 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	5539 reflections with I > 2σ(I)
T_min = 0.083, T_max = 0.156	R_int = 0.113
12406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	9 restraints
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 2.98 e Å⁻³
5940 reflections	Δρ_min = −2.93 e Å⁻³
347 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O10	0.8002 (8)	0.0220 (8)	0.8803 (9)	0.0534 (19)
O8	−0.0239 (8)	0.3014 (6)	1.0095 (8)	0.056 (2)
O11	0.9124 (8)	0.8479 (8)	0.7003 (7)	0.0502 (17)
O6	0.6729 (7)	0.3001 (6)	0.7953 (8)	0.0494 (17)
Bi1	0.32379 (2)	0.045644 (19)	0.88303 (2)	0.02387 (13)
N1	0.4091 (7)	−0.0927 (6)	0.7035 (5)	0.0265 (11)
C5	0.3481 (8)	−0.0744 (7)	0.5968 (7)	0.0297 (14)
C1	0.5057 (7)	−0.1819 (6)	0.7123 (6)	0.0247 (12)
C3	0.4867 (12)	−0.2374 (10)	0.4998 (8)	0.047 (2)
H3	0.5131	−0.2871	0.4312	0.056*
C7	0.2415 (9)	0.0299 (7)	0.5988 (8)	0.0359 (16)
C2	0.5469 (10)	−0.2566 (9)	0.6098 (8)	0.0426 (19)
H2	0.6147	−0.3188	0.6163	0.051*
C4	0.3855 (10)	−0.1434 (9)	0.4899 (8)	0.0388 (17)
H4	0.3450	−0.1277	0.4155	0.047*
N4	1.1655 (8)	0.4867 (7)	0.2534 (8)	0.0436 (18)
H4A	1.1986	0.4137	0.2319	0.052*
H4B	1.2133	0.5526	0.2398	0.052*
C15	1.0421 (8)	0.4974 (7)	0.3068 (7)	0.0300 (14)
C16	0.9763 (9)	0.6147 (8)	0.3425 (8)	0.0333 (15)
N3	0.9707 (9)	0.3919 (7)	0.3263 (7)	0.0383 (15)
N5	1.0463 (9)	0.7230 (6)	0.3244 (9)	0.0462 (19)
H5A	1.0086	0.7940	0.3469	0.055*
H5B	1.1281	0.7205	0.2904	0.055*
C17	0.8460 (10)	0.6133 (9)	0.3960 (10)	0.043 (2)
H17	0.8021	0.6885	0.4204	0.051*
C19	0.8402 (11)	0.3898 (9)	0.3806 (9)	0.046 (2)
H19	0.7959	0.3144	0.3938	0.055*
C18	0.7782 (10)	0.5004 (11)	0.4144 (10)	0.048 (2)
H18	0.6892	0.5012	0.4502	0.057*
O3	0.2133 (7)	0.0852 (6)	0.7009 (6)	0.0381 (13)
O7	0.0896 (6)	0.1326 (5)	0.9346 (6)	0.0340 (12)
O5	0.5370 (6)	0.1332 (5)	0.8106 (6)	0.0324 (11)
N2	0.3143 (7)	0.2700 (6)	0.8827 (6)	0.0262 (11)
C8	0.4311 (8)	0.3335 (7)	0.8530 (7)	0.0283 (13)
O4	0.1860 (11)	0.0529 (9)	0.5024 (7)	0.066 (2)
C14	0.0788 (9)	0.2486 (7)	0.9591 (8)	0.0331 (15)
C13	0.5562 (8)	0.2518 (7)	0.8158 (7)	0.0290 (14)
C12	0.1996 (8)	0.3318 (7)	0.9215 (7)	0.0294 (14)
C9	0.4360 (8)	0.4623 (7)	0.8582 (8)	0.0321 (15)
H9	0.5173	0.5045	0.8362	0.039*
C11	0.1952 (8)	0.4614 (7)	0.9293 (8)	0.0324 (15)
H11	0.1135	0.5036	0.9554	0.039*
C10	0.3145 (9)	0.5268 (7)	0.8975 (9)	0.0358 (17)
H10	0.3137	0.6138	0.9023	0.043*
O1	0.5240 (6)	−0.1236 (5)	0.9223 (5)	0.0290 (10)
O2	0.6605 (9)	−0.2791 (7)	0.8471 (6)	0.0489 (17)
C6	0.5695 (8)	−0.1989 (7)	0.8366 (7)	0.0276 (13)
O9	0.1606 (8)	−0.1496 (7)	0.8422 (7)	0.0455 (15)
H10B	0.867 (9)	0.064 (12)	0.906 (13)	0.055*
H11A	0.851 (13)	0.845 (14)	0.638 (9)	0.068*
H11B	0.860 (15)	0.908 (13)	0.742 (11)	0.068*
H9A	0.143 (14)	−0.171 (15)	0.909 (8)	0.068*
H9B	0.090 (13)	−0.126 (14)	0.802 (10)	0.068*
H10A	0.717 (9)	0.070 (11)	0.875 (12)	0.055*
H3A	1.007 (14)	0.325 (13)	0.289 (12)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O10	0.036 (3)	0.043 (3)	0.081 (6)	0.007 (3)	−0.001 (3)	0.005 (4)
O8	0.052 (4)	0.029 (3)	0.090 (6)	0.012 (3)	0.045 (4)	0.005 (3)
O11	0.049 (4)	0.054 (4)	0.049 (4)	0.022 (3)	−0.006 (3)	0.011 (3)
O6	0.034 (3)	0.034 (3)	0.080 (5)	−0.004 (2)	0.025 (3)	0.001 (3)
Bi1	0.02420 (17)	0.01863 (16)	0.02853 (18)	0.00371 (9)	0.00376 (9)	−0.00045 (9)
N1	0.030 (3)	0.026 (3)	0.024 (3)	0.004 (2)	0.004 (2)	0.000 (2)
C5	0.032 (3)	0.025 (3)	0.032 (4)	0.000 (3)	0.003 (3)	0.000 (3)
C1	0.025 (3)	0.022 (3)	0.026 (3)	0.002 (2)	0.003 (2)	−0.004 (2)
C3	0.060 (6)	0.049 (5)	0.030 (4)	0.014 (4)	0.012 (4)	−0.010 (4)
C7	0.039 (4)	0.028 (3)	0.042 (4)	0.006 (3)	0.004 (3)	0.006 (3)
C2	0.041 (4)	0.046 (5)	0.037 (4)	0.011 (4)	0.006 (3)	−0.015 (4)
C4	0.045 (4)	0.043 (4)	0.027 (4)	0.004 (3)	0.006 (3)	−0.003 (3)
N4	0.037 (4)	0.030 (3)	0.063 (5)	0.005 (3)	0.019 (3)	−0.004 (3)
C15	0.035 (4)	0.030 (3)	0.025 (3)	0.000 (3)	−0.001 (3)	0.002 (3)
C16	0.032 (4)	0.029 (3)	0.039 (4)	0.000 (3)	0.005 (3)	0.003 (3)
N3	0.045 (4)	0.027 (3)	0.043 (4)	−0.001 (3)	0.010 (3)	−0.002 (3)
N5	0.051 (4)	0.019 (3)	0.069 (5)	0.007 (3)	0.024 (4)	0.002 (3)
C17	0.037 (4)	0.036 (4)	0.055 (6)	0.012 (3)	0.013 (4)	0.002 (4)
C19	0.053 (5)	0.041 (4)	0.044 (5)	−0.009 (4)	0.013 (4)	0.003 (4)
C18	0.033 (4)	0.057 (6)	0.052 (5)	−0.011 (4)	0.015 (4)	−0.008 (4)
O3	0.044 (3)	0.034 (3)	0.036 (3)	0.018 (2)	−0.007 (2)	0.001 (2)
O7	0.029 (2)	0.024 (2)	0.048 (3)	−0.0006 (19)	0.007 (2)	0.004 (2)
O5	0.031 (3)	0.024 (2)	0.042 (3)	0.0096 (19)	0.014 (2)	0.002 (2)
N2	0.027 (3)	0.025 (3)	0.026 (3)	0.005 (2)	0.006 (2)	−0.002 (2)
C8	0.033 (3)	0.022 (3)	0.029 (3)	0.002 (2)	0.006 (3)	0.001 (2)
O4	0.082 (6)	0.073 (5)	0.042 (4)	0.035 (5)	−0.015 (4)	0.003 (4)
C14	0.033 (4)	0.024 (3)	0.043 (4)	0.005 (3)	0.008 (3)	0.008 (3)
C13	0.027 (3)	0.027 (3)	0.032 (3)	0.004 (2)	0.008 (3)	−0.001 (3)
C12	0.028 (3)	0.025 (3)	0.035 (4)	0.002 (2)	0.005 (3)	−0.003 (3)
C9	0.026 (3)	0.025 (3)	0.046 (4)	0.003 (2)	0.008 (3)	0.003 (3)
C11	0.028 (3)	0.026 (3)	0.043 (4)	0.006 (3)	0.007 (3)	−0.001 (3)
C10	0.036 (4)	0.023 (3)	0.048 (5)	0.007 (3)	0.006 (3)	0.000 (3)
O1	0.030 (2)	0.032 (2)	0.023 (2)	0.007 (2)	−0.0015 (19)	−0.0062 (19)
O2	0.067 (4)	0.040 (3)	0.039 (3)	0.029 (3)	−0.002 (3)	−0.002 (3)
C6	0.027 (3)	0.026 (3)	0.029 (3)	0.004 (2)	0.006 (3)	−0.002 (3)
O9	0.045 (3)	0.041 (3)	0.049 (4)	−0.012 (3)	0.010 (3)	−0.005 (3)

Geometric parameters (Å, º) top

O10—H10B	0.80 (8)	C15—C16	1.433 (11)
O10—H10A	0.94 (8)	C16—N5	1.362 (11)
O8—C14	1.239 (10)	C16—C17	1.368 (12)
O11—H11A	0.89 (8)	N3—C19	1.374 (12)
O11—H11B	0.92 (9)	N3—H3A	0.87 (14)
O6—C13	1.238 (9)	N5—H5A	0.8600
Bi1—O3	2.323 (6)	N5—H5B	0.8600
Bi1—O5	2.384 (6)	C17—C18	1.396 (15)
Bi1—N2	2.409 (6)	C17—H17	0.9300
Bi1—O7	2.447 (6)	C19—C18	1.351 (15)
Bi1—N1	2.525 (6)	C19—H19	0.9300
Bi1—O9	2.581 (7)	C18—H18	0.9300
Bi1—O1ⁱ	2.627 (5)	O7—C14	1.255 (9)
Bi1—O1	2.673 (5)	O5—C13	1.279 (9)
N1—C1	1.329 (9)	N2—C12	1.325 (9)
N1—C5	1.333 (10)	N2—C8	1.346 (9)
C5—C4	1.394 (11)	C8—C9	1.377 (10)
C5—C7	1.504 (11)	C8—C13	1.510 (10)
C1—C2	1.395 (10)	C14—C12	1.522 (11)
C1—C6	1.516 (10)	C12—C11	1.386 (10)
C3—C2	1.364 (14)	C9—C10	1.394 (10)
C3—C4	1.398 (14)	C9—H9	0.9300
C3—H3	0.9300	C11—C10	1.381 (12)
C7—O4	1.224 (12)	C11—H11	0.9300
C7—O3	1.266 (11)	C10—H10	0.9300
C2—H2	0.9300	O1—C6	1.275 (9)
C4—H4	0.9300	O1—Bi1ⁱ	2.627 (5)
N4—C15	1.310 (11)	O2—C6	1.225 (10)
N4—H4A	0.8600	O9—H9A	0.81 (7)
N4—H4B	0.8600	O9—H9B	0.84 (8)
C15—N3	1.346 (10)

H10B—O10—H10A	112 (9)	N3—C15—C16	117.8 (7)
H11A—O11—H11B	91 (8)	N5—C16—C17	122.4 (8)
O3—Bi1—O5	87.5 (2)	N5—C16—C15	119.2 (7)
O3—Bi1—N2	73.7 (2)	C17—C16—C15	118.4 (8)
O5—Bi1—N2	67.26 (19)	C15—N3—C19	124.1 (8)
O3—Bi1—O7	74.0 (2)	C15—N3—H3A	113 (9)
O5—Bi1—O7	133.22 (18)	C19—N3—H3A	122 (9)
N2—Bi1—O7	66.40 (19)	C16—N5—H5A	120.0
O3—Bi1—N1	66.3 (2)	C16—N5—H5B	120.0
O5—Bi1—N1	70.7 (2)	H5A—N5—H5B	120.0
N2—Bi1—N1	122.1 (2)	C16—C17—C18	120.9 (8)
O7—Bi1—N1	132.5 (2)	C16—C17—H17	119.6
O3—Bi1—O9	79.0 (3)	C18—C17—H17	119.6
O5—Bi1—O9	140.1 (2)	C18—C19—N3	118.1 (9)
N2—Bi1—O9	140.2 (2)	C18—C19—H19	121.0
O7—Bi1—O9	78.7 (2)	N3—C19—H19	121.0
N1—Bi1—O9	69.4 (2)	C19—C18—C17	120.7 (8)
O3—Bi1—O1ⁱ	150.1 (2)	C19—C18—H18	119.6
O5—Bi1—O1ⁱ	74.6 (2)	C17—C18—H18	119.6
N2—Bi1—O1ⁱ	77.3 (2)	C7—O3—Bi1	124.9 (5)
O7—Bi1—O1ⁱ	100.97 (19)	C14—O7—Bi1	119.0 (5)
N1—Bi1—O1ⁱ	126.40 (18)	C13—O5—Bi1	121.0 (4)
O9—Bi1—O1ⁱ	129.7 (2)	C12—N2—C8	119.8 (6)
O3—Bi1—O1	128.33 (18)	C12—N2—Bi1	120.5 (5)
O5—Bi1—O1	76.04 (18)	C8—N2—Bi1	119.4 (5)
N2—Bi1—O1	136.45 (19)	N2—C8—C9	122.5 (7)
O7—Bi1—O1	147.79 (19)	N2—C8—C13	114.3 (6)
N1—Bi1—O1	61.99 (18)	C9—C8—C13	123.2 (7)
O9—Bi1—O1	83.3 (2)	O8—C14—O7	125.2 (8)
O1ⁱ—Bi1—O1	70.87 (18)	O8—C14—C12	117.1 (7)
C1—N1—C5	120.5 (6)	O7—C14—C12	117.7 (7)
C1—N1—Bi1	123.4 (5)	O6—C13—O5	122.5 (7)
C5—N1—Bi1	116.0 (5)	O6—C13—C8	120.1 (7)
N1—C5—C4	122.3 (7)	O5—C13—C8	117.4 (6)
N1—C5—C7	115.4 (7)	N2—C12—C11	121.4 (7)
C4—C5—C7	122.3 (8)	N2—C12—C14	114.3 (6)
N1—C1—C2	120.7 (7)	C11—C12—C14	124.3 (7)
N1—C1—C6	117.8 (6)	C8—C9—C10	117.5 (7)
C2—C1—C6	121.5 (7)	C8—C9—H9	121.3
C2—C3—C4	120.3 (8)	C10—C9—H9	121.3
C2—C3—H3	119.8	C10—C11—C12	118.8 (7)
C4—C3—H3	119.8	C10—C11—H11	120.6
O4—C7—O3	124.9 (8)	C12—C11—H11	120.6
O4—C7—C5	117.8 (8)	C11—C10—C9	119.9 (7)
O3—C7—C5	117.3 (7)	C11—C10—H10	120.0
C3—C2—C1	119.3 (8)	C9—C10—H10	120.0
C3—C2—H2	120.3	C6—O1—Bi1ⁱ	124.2 (5)
C1—C2—H2	120.3	C6—O1—Bi1	121.5 (5)
C5—C4—C3	116.9 (8)	Bi1ⁱ—O1—Bi1	109.13 (18)
C5—C4—H4	121.6	O2—C6—O1	125.5 (7)
C3—C4—H4	121.6	O2—C6—C1	119.2 (7)
C15—N4—H4A	120.0	O1—C6—C1	115.2 (6)
C15—N4—H4B	120.0	Bi1—O9—H9A	105 (10)
H4A—N4—H4B	120.0	Bi1—O9—H9B	106 (10)
N4—C15—N3	118.1 (8)	H9A—O9—H9B	116 (10)
N4—C15—C16	124.0 (7)

O3—Bi1—N1—C1	−178.5 (6)	O1ⁱ—Bi1—O5—C13	−75.3 (6)
O5—Bi1—N1—C1	85.6 (6)	O1—Bi1—O5—C13	−148.9 (6)
N2—Bi1—N1—C1	131.0 (5)	O3—Bi1—N2—C12	86.6 (6)
O7—Bi1—N1—C1	−142.8 (5)	O5—Bi1—N2—C12	−179.2 (6)
O9—Bi1—N1—C1	−91.8 (6)	O7—Bi1—N2—C12	7.3 (6)
O1ⁱ—Bi1—N1—C1	33.0 (6)	N1—Bi1—N2—C12	134.0 (6)
O1—Bi1—N1—C1	1.6 (5)	O9—Bi1—N2—C12	38.0 (7)
O3—Bi1—N1—C5	−0.5 (5)	O1ⁱ—Bi1—N2—C12	−100.8 (6)
O5—Bi1—N1—C5	−96.4 (5)	O1—Bi1—N2—C12	−144.4 (5)
N2—Bi1—N1—C5	−51.0 (6)	O3—Bi1—N2—C8	−99.3 (6)
O7—Bi1—N1—C5	35.2 (6)	O5—Bi1—N2—C8	−5.1 (5)
O9—Bi1—N1—C5	86.2 (5)	O7—Bi1—N2—C8	−178.5 (6)
O1ⁱ—Bi1—N1—C5	−149.0 (5)	N1—Bi1—N2—C8	−51.9 (6)
O1—Bi1—N1—C5	179.6 (6)	O9—Bi1—N2—C8	−147.8 (5)
C1—N1—C5—C4	−2.4 (11)	O1ⁱ—Bi1—N2—C8	73.3 (5)
Bi1—N1—C5—C4	179.5 (6)	O1—Bi1—N2—C8	29.8 (7)
C1—N1—C5—C7	−179.6 (7)	C12—N2—C8—C9	−1.7 (12)
Bi1—N1—C5—C7	2.4 (8)	Bi1—N2—C8—C9	−175.9 (6)
C5—N1—C1—C2	1.1 (11)	C12—N2—C8—C13	177.3 (7)
Bi1—N1—C1—C2	179.0 (6)	Bi1—N2—C8—C13	3.1 (9)
C5—N1—C1—C6	−179.2 (6)	Bi1—O7—C14—O8	−164.6 (8)
Bi1—N1—C1—C6	−1.3 (9)	Bi1—O7—C14—C12	16.9 (10)
N1—C5—C7—O4	177.7 (9)	Bi1—O5—C13—O6	169.5 (7)
C4—C5—C7—O4	0.5 (13)	Bi1—O5—C13—C8	−8.4 (10)
N1—C5—C7—O3	−4.0 (11)	N2—C8—C13—O6	−174.6 (8)
C4—C5—C7—O3	178.8 (8)	C9—C8—C13—O6	4.4 (13)
C4—C3—C2—C1	0.4 (16)	N2—C8—C13—O5	3.3 (11)
N1—C1—C2—C3	−0.2 (14)	C9—C8—C13—O5	−177.7 (8)
C6—C1—C2—C3	−179.8 (9)	C8—N2—C12—C11	1.8 (12)
N1—C5—C4—C3	2.6 (13)	Bi1—N2—C12—C11	175.9 (6)
C7—C5—C4—C3	179.5 (9)	C8—N2—C12—C14	−176.5 (7)
C2—C3—C4—C5	−1.5 (15)	Bi1—N2—C12—C14	−2.4 (9)
N4—C15—C16—N5	−2.3 (13)	O8—C14—C12—N2	171.6 (9)
N3—C15—C16—N5	179.7 (9)	O7—C14—C12—N2	−9.8 (11)
N4—C15—C16—C17	179.0 (9)	O8—C14—C12—C11	−6.6 (14)
N3—C15—C16—C17	1.0 (12)	O7—C14—C12—C11	172.0 (8)
N4—C15—N3—C19	−179.6 (9)	N2—C8—C9—C10	0.8 (13)
C16—C15—N3—C19	−1.5 (13)	C13—C8—C9—C10	−178.1 (8)
N5—C16—C17—C18	−179.2 (11)	N2—C12—C11—C10	−1.0 (13)
C15—C16—C17—C18	−0.6 (15)	C14—C12—C11—C10	177.1 (8)
C15—N3—C19—C18	1.4 (15)	C12—C11—C10—C9	0.2 (13)
N3—C19—C18—C17	−0.9 (17)	C8—C9—C10—C11	−0.1 (13)
C16—C17—C18—C19	0.6 (17)	O3—Bi1—O1—C6	−2.0 (7)
O4—C7—O3—Bi1	−178.0 (9)	O5—Bi1—O1—C6	−77.3 (6)
C5—C7—O3—Bi1	3.8 (11)	N2—Bi1—O1—C6	−110.2 (6)
O5—Bi1—O3—C7	68.1 (7)	O7—Bi1—O1—C6	124.4 (6)
N2—Bi1—O3—C7	135.2 (8)	N1—Bi1—O1—C6	−1.9 (5)
O7—Bi1—O3—C7	−155.3 (8)	O9—Bi1—O1—C6	68.3 (6)
N1—Bi1—O3—C7	−1.9 (7)	O1ⁱ—Bi1—O1—C6	−155.5 (7)
O9—Bi1—O3—C7	−74.1 (7)	O3—Bi1—O1—Bi1ⁱ	153.5 (2)
O1ⁱ—Bi1—O3—C7	120.6 (7)	O5—Bi1—O1—Bi1ⁱ	78.3 (2)
O1—Bi1—O3—C7	−1.8 (8)	N2—Bi1—O1—Bi1ⁱ	45.4 (4)
O3—Bi1—O7—C14	−91.9 (7)	O7—Bi1—O1—Bi1ⁱ	−80.0 (4)
O5—Bi1—O7—C14	−21.3 (8)	N1—Bi1—O1—Bi1ⁱ	153.6 (3)
N2—Bi1—O7—C14	−13.0 (6)	O9—Bi1—O1—Bi1ⁱ	−136.2 (3)
N1—Bi1—O7—C14	−125.7 (6)	O1ⁱ—Bi1—O1—Bi1ⁱ	0.0
O9—Bi1—O7—C14	−173.6 (7)	Bi1ⁱ—O1—C6—O2	28.4 (11)
O1ⁱ—Bi1—O7—C14	57.8 (7)	Bi1—O1—C6—O2	−179.9 (7)
O1—Bi1—O7—C14	129.2 (6)	Bi1ⁱ—O1—C6—C1	−149.8 (5)
O3—Bi1—O5—C13	80.5 (6)	Bi1—O1—C6—C1	2.0 (8)
N2—Bi1—O5—C13	7.2 (6)	N1—C1—C6—O2	−178.8 (8)
O7—Bi1—O5—C13	15.4 (7)	C2—C1—C6—O2	0.9 (12)
N1—Bi1—O5—C13	146.3 (7)	N1—C1—C6—O1	−0.6 (10)
O9—Bi1—O5—C13	150.0 (6)	C2—C1—C6—O1	179.1 (8)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O11ⁱⁱ	0.87 (14)	2.02 (14)	2.797 (10)	148 (12)
N4—H4A···O2ⁱⁱⁱ	0.86	2.11	2.924 (9)	158
N4—H4B···O6ⁱⁱ	0.86	1.97	2.830 (10)	178
N5—H5A···O3^iv	0.86	2.53	3.216 (10)	138
N5—H5B···O6ⁱⁱ	0.86	2.11	2.972 (10)	176
O9—H9A···O8^v	0.81 (7)	2.07 (12)	2.746 (10)	141 (15)
O9—H9B···O11^vi	0.84 (8)	1.99 (10)	2.771 (11)	155 (15)
O10—H10A···O5	0.94 (8)	1.96 (8)	2.862 (9)	160 (11)
O10—H10B···O7^vii	0.80 (8)	2.21 (8)	2.972 (10)	160 (13)
O11—H11A···O4^iv	0.89 (8)	2.01 (13)	2.717 (11)	136 (14)
O11—H11B···O10^viii	0.92 (9)	1.96 (9)	2.836 (12)	158 (13)
C11—H11···O8^ix	0.93	2.26	3.050 (10)	142

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x, −y, −z+2; (vi) x−1, y−1, z; (vii) x+1, y, z; (viii) x, y+1, z; (ix) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₅H₈N₃)₂[Bi₂(C₇H₃NO₄)₄(H₂O)₂]·4H₂O
M_r	1406.76
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.3462 (19), 10.726 (2), 11.098 (2)
α, β, γ (°)	95.13 (3), 91.38 (3), 90.47 (3)
V (Å³)	1107.7 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	8.03
Crystal size (mm)	0.33 × 0.27 × 0.23

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)
T_min, T_max	0.083, 0.156
No. of measured, independent and observed [I > 2σ(I)] reflections	12406, 5940, 5539
R_int	0.113
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.154, 1.05
No. of reflections	5940
No. of parameters	347
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.98, −2.93

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O11ⁱ	0.87 (14)	2.02 (14)	2.797 (10)	148 (12)
N4—H4A···O2ⁱⁱ	0.86	2.11	2.924 (9)	158
N4—H4B···O6ⁱ	0.86	1.97	2.830 (10)	178
N5—H5A···O3ⁱⁱⁱ	0.86	2.53	3.216 (10)	138
N5—H5B···O6ⁱ	0.86	2.11	2.972 (10)	176
O9—H9A···O8^iv	0.81 (7)	2.07 (12)	2.746 (10)	141 (15)
O9—H9B···O11^v	0.84 (8)	1.99 (10)	2.771 (11)	155 (15)
O10—H10A···O5	0.94 (8)	1.96 (8)	2.862 (9)	160 (11)
O10—H10B···O7^vi	0.80 (8)	2.21 (8)	2.972 (10)	160 (13)
O11—H11A···O4ⁱⁱⁱ	0.89 (8)	2.01 (13)	2.717 (11)	136 (14)
O11—H11B···O10^vii	0.92 (9)	1.96 (9)	2.836 (12)	158 (13)
C11—H11···O8^viii	0.93	2.26	3.050 (10)	142

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y, −z+2; (v) x−1, y−1, z; (vi) x+1, y, z; (vii) x, y+1, z; (viii) −x, −y+1, −z+2.

Acknowledgements

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc. 5, 184–227. CrossRef CAS Google Scholar
Aghabozorg, H., Moteieyan, E., Salimi, A. R., Mirzaei, M., Manteghi, F., Shokrollahi, A., Derki, S., Ghadermazi, M., Sheshmani, S. & Eshtiagh-Hosseini, H. (2010). Polyhedron, 29, 1453–1464. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheshmani, S., Kheirollahi, P. D., Aghabozorg, H., Shokrollahi, A., Kickelbick, G., Shamsipur, M., Ramezanipour, F. & Moghimi, A. (2005). Z. Anorg. Allg. Chem. 631, 3058–3065. Web of Science CSD CrossRef Google Scholar
Stoe & Cie (2005). X-AREA, X-SHAPE and X-RED32. Stoe & Cie, Darmstadt, Germany. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.