Tetra­kis(dihydrogen pefloxacinium) di-μ2-chlorido-bis­[tetra­chloridobismuthate(III)] tetra­chloride octa­hydrate

Polishchuk, A.V.; Gerasimenko, A.V.; Gayvoronskaya, K.A.; Karaseva, E.T.

doi:10.1107/S1600536808017674

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m931-m932

doi:10.1107/S1600536808017674

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Tetrakis(dihydrogen pefloxacinium) di-μ₂-chlorido-bis[tetrachloridobismuthate(III)] tetrachloride octahydrate

A. V. Polishchuk,^a A. V. Gerasimenko,^a ^* K. A. Gayvoronskaya ^a and E. T. Karaseva ^a

^aInstitute of Chemistry, FEB RAS, Prospekt 100-letiya Vladivostoka 159, Vladivostok 690022, Russian Federation
^*Correspondence e-mail: gerasimenko@ich.dvo.ru

(Received 2 June 2008; accepted 11 June 2008; online 19 June 2008)

The title compound {systematic name: tetrakis[4-(3-carboxy-1-ethyl-6-fluoro-4-hydroxonio-1,4-dihydro-7-quinolyl)-1-methylpiperazin-1-ium] di-μ₂-chlorido-bis[tetrachloridobismuthate(III)] tetrachloride octahydrate}, (C₁₇H₂₂FN₃O₃)₄[Bi₂Cl₁₀]Cl₄·8H₂O, is composed of edge-shared centrosymmetric dinuclear [Bi₂Cl₁₀]⁴⁻ anions, Cl⁻ anions, dihydrogen pefloxacinium cations and water molecules. The Bi^III coordination polyhedron is a distorted octahedron. There are four short terminal Bi—Cl bonds [2.5037 (10)–2.6911 (7) Å] and two longer bridging bonds [2.8834 (8) and 3.0687 (9) Å] in each octahedron. Two sets of chloride ions and water molecules are disordered over the same sites with site occupancies of 1/3 and 2/3, respectively. Anions, cations and water molecules are linked by O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming a three-dimensional framework. There are also π–π stacking interactions between quinoline ring systems [centroid–centroid distance = 3.575 (1) Å].

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

(C₁₇H₂₂FN₃O₃)₄[Bi₂Cl₁₀]Cl₄·8H₂O
M_r = 2399.89
Monoclinic, C 2/m
a = 14.4201 (14) Å
b = 25.305 (3) Å
c = 12.6359 (12) Å
β = 99.028 (2)°
V = 4553.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 4.35 mm⁻¹
T = 173 (2) K
0.30 × 0.05 × 0.01 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: Gaussian (XPREP, SADABS; Bruker, 2003 ) T_min = 0.606, T_max = 0.958
16488 measured reflections
6329 independent reflections
5310 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.077
S = 1.08
6329 reflections
303 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.17 e Å⁻³

Table 1
Selected interatomic distances and short contacts to water molecules (Å)

Bi—Cl2	2.5037 (10)
Bi—Cl4	2.5737 (11)
Bi—Cl3	2.6910 (7)
Bi—Cl3ⁱ	2.6911 (7)
Bi—Cl1	2.8834 (8)
Bi—Cl1ⁱⁱ	3.0687 (9)

O6⋯O6ⁱ	2.822 (6)
O6⋯Cl6ⁱⁱⁱ	2.863 (5)
O6⋯O5^iv	2.961 (4)
O6⋯O6ⁱⁱⁱ	3.074 (6)
O6⋯O3^v	3.091 (4)
O7⋯Cl7^vi	2.888 (7)
O7⋯O7^vi	3.146 (14)
Symmetry codes: (i) x, -y+1, z; (ii) -x+1, -y+1, -z+2; (iii) -x+2, y, -z+1; (iv) x+1, -y+1, z; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+1]$ ; (vi) -x, -y+1, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H4⋯Cl5^vii	0.84	2.18	3.014 (2)	174
O3—H3⋯O1	0.84	1.96	2.675 (3)	143
O3—H3⋯Cl6^viii	0.84	2.06	2.559 (5)	118
O5—H5B⋯O1^ix	0.83 (1)	2.009 (18)	2.790 (3)	157 (4)
O5—H5C⋯O7^x	0.83 (1)	2.029 (13)	2.851 (5)	173 (3)
O5—H5C⋯Cl7^x	0.83 (1)	2.238 (13)	3.056 (4)	170 (3)
N2—H2⋯Cl1^xi	0.93	2.52	3.262 (2)	137
N2—H2⋯Cl3^xii	0.93	2.77	3.423 (2)	128
Symmetry codes: (vii) x, y, z+1; (viii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+1]$ ; (ix) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (x) -x, -y+1, -z+1; (xi) -x+1, -y+1, -z+1; (xii) -x+1, y, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT ; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL ; molecular graphics: XP in SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017674/ci2612sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017674/ci2612Isup2.hkl

checkCIF report

Comment top

Pefloxacin (pfH) belongs to the second-generation quinolone antimicrobial agents. According to a search of the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002), well determined structures are those where pefloxacin acts as an anion or as a single protonated cation. The present research deals with the synthesis and structure of a chlorido-bismuth complex with the doubly protonated cation of pefloxacin (pfH₃)²⁺.

The asymmetric unit of the title compound, (I), contains one Bi atom, seven chlorine atoms (two of them are disordered), one pfH₃ cation and three H₂O molecules (from them a two are disordered). The Bi atoms are coordinated by six Cl atoms in a distorted octahedral geometry. Two Bi-centred octahedra are linked by double Cl bridges to form a centrosymmetric dinuclear [Bi₂F₁₀]^4- complex (Fig. 1), with a Bi···Biⁱ distance of 4.4596 (5) Å. In the Bi-octahedra there are four short terminal Bi—Cl bonds [2.5037 (10)-2.6911 (7) Å] and two longer bridging bonds [2.8834 (8) and 3.0687 (9) Å]. These Bi-anions pack up in columns parallel to the [0 0 1] direction (Fig. 2).

The protonation of pfH₃²⁺ is realised on the carbonyl atom O3 and N2 of the piperazine ring (Fig. 3). The hydrogen atom H3 is linked by an intramolecular hydrogen bond with O1 atom of the carboxyl group. Atoms O2 and N2 in the cation act as hydrogen-bond donors, via H4 and H2

There are three uncoordinated chlorine atoms (Cl5, Cl6 and Cl7) of which Cl6 and Cl7 are disordered and statistically replaced by atoms O6 and O7 of water molecules, respectively [Wyckoff positions 8j and 4i for Cl6/O6 and Cl7/O7, respectively]. Site occupation factors of these chloride ions were assigned equal to 1/3, and water molecule to 2/3 from the crystal chemistry considerations. The refinement of the Cl6/O6 and Cl7/O7 site occupation factors resulted in the same values with accuracy within 0.04. As the hydrogen atoms were not located for disordered water molecules, probable hydrogen bonds involving these atoms are given in Table 3.

In the crystal structure, the cations are packed along the aaxis. There exist π–π stacking interactions between quinoline ring systems (Fig.4), with nearest C···C contacts are in the range 3.292 (5)-3.365 (3) Å. Anions, cations and H₂O-molecules are linked by a network of O—H···O, O—H···Cl and N—H···Cl hydrogen bonds into a three-dimensional framework.

Related literature top

For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Bi(OH)₃ (1.00 g, 3.85 mmol) was reacted with pfH (1.50 g, 5.77 mmol) in a solution of HCl (35%, 15 ml). Yellow crystals were obtained after evaporation for 72 h at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. A view of the dinuclear [Bi₂F₁₀]^4- complex, with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: x, 1-y, z; (ii) 1-x, 1-y, 2-z.]
	Fig. 2. The crystal structure of the title compound, viewed along the c axis. Dashed lines represent hydrogen bonds.
	Fig. 3. A view of the pfH₃²⁺ canion, with displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 4. The crystal structure of the title compound, viewed along the a axis. Dashed lines represent hydrogen bonds.

Tetrakis[4-(3-carboxy-1-ethyl-6-fluoro-4-hydroxonio-1,4-dihydro-7-quinolyl)- 1-methylpiperazin-1-ium] di-µ₂-chlorido-bis[tetrachloridobismuthate(III)] tetrachloride octahydrate top

Crystal data top

(C₁₇H₂₂FN₃O₃)₄[Bi₂Cl₁₀]Cl₄·8H₂O	F(000) = 2392
M_r = 2399.89	D_x = 1.750 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 897 reflections
a = 14.4201 (14) Å	θ = 2.8–27.5°
b = 25.305 (3) Å	µ = 4.35 mm⁻¹
c = 12.6359 (12) Å	T = 173 K
β = 99.028 (2)°	Prism, yellow
V = 4553.7 (8) Å³	0.30 × 0.05 × 0.01 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6329 independent reflections
Radiation source: fine-focus sealed tube	5310 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 8.33 pixels mm^-1	θ_max = 29.5°, θ_min = 1.6°
ω scans	h = −16→19
Absorption correction: gaussian (SADABS; Bruker, 2003)	k = −34→30
T_min = 0.606, T_max = 0.958	l = −17→8
16488 measured reflections

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0241P)² + 5.6647P] where P = (F_o² + 2F_c²)/3
6329 reflections	(Δ/σ)_max = 0.010
303 parameters	Δρ_max = 1.23 e Å⁻³
3 restraints	Δρ_min = −1.17 e Å⁻³

Crystal data top

(C₁₇H₂₂FN₃O₃)₄[Bi₂Cl₁₀]Cl₄·8H₂O	V = 4553.7 (8) Å³
M_r = 2399.89	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 14.4201 (14) Å	µ = 4.35 mm⁻¹
b = 25.305 (3) Å	T = 173 K
c = 12.6359 (12) Å	0.30 × 0.05 × 0.01 mm
β = 99.028 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6329 independent reflections
Absorption correction: gaussian (SADABS; Bruker, 2003)	5310 reflections with I > 2σ(I)
T_min = 0.606, T_max = 0.958	R_int = 0.048
16488 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	3 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.23 e Å⁻³
6329 reflections	Δρ_min = −1.17 e Å⁻³
303 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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Bi	0.478467 (9)	0.5000	1.170934 (10)	0.01789 (3)
Cl1	0.36184 (6)	0.5000	0.96352 (7)	0.02166 (18)
Cl2	0.32976 (7)	0.5000	1.24998 (8)	0.0332 (2)
Cl3	0.46439 (4)	0.39397 (2)	1.16382 (5)	0.02578 (14)
Cl4	0.58921 (10)	0.5000	1.35173 (9)	0.0501 (3)
Cl5	0.5000	0.19810 (4)	0.0000	0.0277 (2)
Cl6	0.9645 (3)	0.58510 (18)	0.4025 (3)	0.0829 (12)	0.33333
O6	0.9296 (2)	0.55576 (12)	0.3952 (3)	0.0376 (8)	0.66667
Cl7	0.0257 (3)	0.5000	0.9040 (4)	0.0483 (12)	0.33333
O7	0.0152 (4)	0.5000	0.8794 (5)	0.0447 (17)	0.66667
F2	0.69789 (11)	0.22163 (6)	0.19969 (11)	0.0286 (4)
O1	0.55734 (13)	0.17802 (7)	0.73845 (15)	0.0286 (5)
O2	0.56440 (14)	0.25726 (7)	0.81762 (14)	0.0302 (5)
H4	0.5504	0.2396	0.8692	0.045*
O3	0.60949 (13)	0.17118 (7)	0.54491 (15)	0.0283 (5)
H3	0.5969	0.1586	0.6025	0.042*
O5	0.05523 (17)	0.41020 (10)	0.2439 (2)	0.0570 (7)
H5B	0.0279 (12)	0.3815 (5)	0.234 (3)	0.085*
H5C	0.0302 (18)	0.4357 (6)	0.210 (2)	0.085*
N1	0.70541 (15)	0.33043 (8)	0.19082 (16)	0.0218 (5)
N2	0.74434 (15)	0.38831 (9)	0.00739 (17)	0.0235 (5)
H2	0.6895	0.4083	−0.0053	0.028*
N3	0.62148 (14)	0.33321 (8)	0.55077 (16)	0.0198 (5)
C1	0.60166 (16)	0.30659 (10)	0.6364 (2)	0.0215 (6)
H1A	0.5905	0.3263	0.6972	0.026*
C2	0.59658 (16)	0.25233 (10)	0.6410 (2)	0.0203 (6)
C3	0.61226 (17)	0.22153 (11)	0.5512 (2)	0.0227 (6)
C4	0.63379 (16)	0.25024 (10)	0.45924 (19)	0.0187 (5)
C5	0.65146 (16)	0.22261 (10)	0.36745 (19)	0.0209 (6)
H5	0.6481	0.1851	0.3656	0.025*
C6	0.67306 (17)	0.24941 (10)	0.28238 (19)	0.0212 (6)
C7	0.67653 (16)	0.30550 (10)	0.27776 (19)	0.0206 (6)
C8	0.65728 (17)	0.33298 (10)	0.36801 (19)	0.0209 (6)
H8	0.6572	0.3705	0.3677	0.025*
C9	0.63802 (16)	0.30572 (10)	0.45928 (19)	0.0191 (5)
C10	0.65575 (17)	0.31800 (11)	0.08222 (19)	0.0220 (6)
H10A	0.5970	0.3388	0.0675	0.026*
H10B	0.6391	0.2800	0.0778	0.026*
C11	0.71759 (18)	0.33095 (11)	0.0000 (2)	0.0249 (6)
H11A	0.7749	0.3088	0.0126	0.030*
H11B	0.6838	0.3231	−0.0726	0.030*
C12	0.79311 (18)	0.40046 (11)	0.1187 (2)	0.0253 (6)
H12A	0.8084	0.4386	0.1245	0.030*
H12B	0.8527	0.3804	0.1333	0.030*
C13	0.73148 (19)	0.38594 (11)	0.2011 (2)	0.0250 (6)
H13A	0.7657	0.3928	0.2740	0.030*
H13B	0.6742	0.4081	0.1904	0.030*
C14	0.57179 (17)	0.22525 (10)	0.73660 (19)	0.0214 (6)
C15	0.62925 (18)	0.39181 (10)	0.5556 (2)	0.0248 (6)
H15A	0.5993	0.4049	0.6159	0.030*
H15B	0.5948	0.4070	0.4886	0.030*
C16	0.72972 (19)	0.41048 (11)	0.5703 (2)	0.0293 (7)
H16A	0.7600	0.4031	0.6438	0.044*
H16B	0.7312	0.4486	0.5569	0.044*
H16C	0.7633	0.3919	0.5198	0.044*
C17	0.8038 (2)	0.40306 (12)	−0.0740 (2)	0.0336 (7)
H17A	0.8594	0.3802	−0.0661	0.050*
H17B	0.8235	0.4400	−0.0635	0.050*
H17C	0.7678	0.3987	−0.1459	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi	0.02397 (6)	0.01417 (5)	0.01620 (5)	0.000	0.00521 (4)	0.000
Cl1	0.0236 (4)	0.0201 (4)	0.0211 (4)	0.000	0.0032 (3)	0.000
Cl2	0.0413 (4)	0.0254 (4)	0.0391 (5)	0.000	0.0257 (4)	0.000
Cl3	0.0324 (3)	0.0162 (3)	0.0304 (3)	0.0004 (2)	0.0101 (3)	0.0003 (2)
Cl4	0.0714 (8)	0.0404 (6)	0.0299 (5)	0.000	−0.0188 (5)	0.000
Cl5	0.0309 (4)	0.0253 (4)	0.0282 (4)	0.000	0.0085 (4)	0.000
Cl6	0.079 (2)	0.088 (3)	0.084 (2)	−0.014 (2)	0.0203 (19)	−0.022 (2)
O6	0.058 (2)	0.0163 (14)	0.0394 (17)	0.0067 (14)	0.0099 (15)	0.0009 (13)
Cl7	0.050 (2)	0.0267 (17)	0.058 (2)	0.000	−0.0206 (18)	0.000
O7	0.042 (3)	0.038 (3)	0.050 (3)	0.000	−0.004 (3)	0.000
F2	0.0418 (8)	0.0238 (8)	0.0208 (7)	0.0034 (7)	0.0070 (6)	−0.0058 (6)
O1	0.0358 (10)	0.0205 (9)	0.0294 (10)	0.0011 (8)	0.0042 (8)	0.0024 (7)
O2	0.0472 (10)	0.0221 (9)	0.0239 (9)	−0.0025 (8)	0.0138 (8)	−0.0013 (7)
O3	0.0393 (10)	0.0200 (9)	0.0267 (9)	−0.0044 (8)	0.0087 (8)	0.0007 (7)
O5	0.0548 (14)	0.0491 (15)	0.0700 (17)	−0.0072 (12)	0.0190 (13)	0.0058 (13)
N1	0.0286 (10)	0.0186 (10)	0.0177 (10)	−0.0028 (9)	0.0020 (8)	−0.0021 (8)
N2	0.0248 (10)	0.0225 (11)	0.0235 (10)	0.0054 (9)	0.0047 (8)	0.0037 (8)
N3	0.0231 (9)	0.0181 (10)	0.0188 (9)	0.0037 (8)	0.0052 (8)	−0.0024 (8)
C1	0.0185 (10)	0.0255 (13)	0.0210 (11)	−0.0011 (10)	0.0048 (9)	−0.0041 (10)
C2	0.0162 (10)	0.0235 (12)	0.0212 (11)	−0.0002 (9)	0.0026 (9)	−0.0001 (9)
C3	0.0188 (11)	0.0258 (13)	0.0226 (12)	−0.0009 (10)	0.0005 (10)	−0.0026 (10)
C4	0.0143 (10)	0.0214 (12)	0.0197 (11)	0.0022 (9)	0.0004 (9)	−0.0020 (9)
C5	0.0188 (11)	0.0200 (12)	0.0233 (12)	−0.0019 (9)	0.0016 (9)	−0.0038 (9)
C6	0.0203 (11)	0.0239 (12)	0.0190 (11)	0.0043 (10)	0.0021 (9)	−0.0060 (9)
C7	0.0173 (10)	0.0238 (12)	0.0198 (11)	0.0006 (9)	0.0007 (9)	−0.0009 (9)
C8	0.0233 (11)	0.0156 (11)	0.0223 (12)	0.0027 (9)	−0.0010 (10)	−0.0024 (9)
C9	0.0180 (10)	0.0224 (12)	0.0159 (11)	0.0007 (9)	0.0001 (9)	−0.0029 (9)
C10	0.0236 (11)	0.0260 (13)	0.0157 (11)	0.0008 (10)	0.0009 (9)	−0.0016 (9)
C11	0.0291 (12)	0.0244 (13)	0.0221 (12)	0.0028 (11)	0.0062 (10)	−0.0022 (10)
C12	0.0259 (12)	0.0226 (13)	0.0264 (13)	−0.0001 (10)	0.0012 (10)	0.0034 (10)
C13	0.0306 (13)	0.0228 (13)	0.0204 (12)	−0.0016 (11)	0.0006 (10)	−0.0047 (10)
C14	0.0184 (11)	0.0261 (13)	0.0199 (11)	0.0009 (10)	0.0030 (9)	0.0011 (10)
C15	0.0318 (12)	0.0199 (12)	0.0238 (12)	0.0043 (10)	0.0078 (10)	−0.0025 (10)
C16	0.0367 (14)	0.0227 (13)	0.0297 (13)	−0.0025 (11)	0.0085 (11)	−0.0062 (11)
C17	0.0360 (14)	0.0361 (16)	0.0314 (14)	0.0074 (12)	0.0140 (12)	0.0112 (12)

Geometric parameters (Å, º) top

Bi—Cl2	2.5037 (10)	C2—C14	1.480 (4)
Bi—Cl4	2.5737 (11)	C3—C4	1.445 (4)
Bi—Cl3	2.6910 (7)	C4—C9	1.405 (3)
Bi—Cl3ⁱ	2.6911 (7)	C4—C5	1.411 (3)
Bi—Cl1	2.8834 (8)	C5—C6	1.348 (4)
Bi—Cl1ⁱⁱ	3.0687 (9)	C5—H5	0.95
Bi—Biⁱⁱ	4.4596 (5)	C6—C7	1.422 (4)
Cl1—Biⁱⁱ	3.0687 (9)	C7—C8	1.400 (4)
F2—C6	1.353 (3)	C8—C9	1.408 (4)
O1—C14	1.214 (3)	C8—H8	0.95
O2—C14	1.323 (3)	C10—C11	1.507 (4)
O2—H4	0.84	C10—H10A	0.99
O3—C3	1.277 (3)	C10—H10B	0.99
O3—H3	0.84	C11—H11A	0.99
O5—H5B	0.828 (10)	C11—H11B	0.99
O5—H5C	0.826 (11)	C12—C13	1.516 (4)
N1—C7	1.386 (3)	C12—H12A	0.99
N1—C13	1.455 (3)	C12—H12B	0.99
N1—C10	1.479 (3)	C13—H13A	0.99
N2—C17	1.486 (4)	C13—H13B	0.99
N2—C11	1.501 (3)	C15—C16	1.507 (4)
N2—C12	1.503 (3)	C15—H15A	0.99
N2—H2	0.93	C15—H15B	0.99
N3—C1	1.343 (3)	C16—H16A	0.98
N3—C9	1.401 (3)	C16—H16B	0.98
N3—C15	1.488 (3)	C16—H16C	0.98
C1—C2	1.377 (4)	C17—H17A	0.98
C1—H1A	0.95	C17—H17B	0.98
C2—C3	1.424 (4)	C17—H17C	0.98

O6···O6ⁱ	2.822 (6)	O6···O3^v	3.091 (4)
O6···Cl6ⁱⁱⁱ	2.863 (5)	O7···Cl7^vi	2.888 (7)
O6···O5^iv	2.961 (4)	O7···O7^vi	3.146 (14)
O6···O6ⁱⁱⁱ	3.074 (6)

Cl2—Bi—Cl4	95.56 (4)	N1—C7—C8	122.8 (2)
Cl2—Bi—Cl3	87.046 (14)	N1—C7—C6	120.2 (2)
Cl4—Bi—Cl3	93.594 (14)	C8—C7—C6	116.7 (2)
Cl2—Bi—Cl3ⁱ	87.046 (14)	C7—C8—C9	120.9 (2)
Cl4—Bi—Cl3ⁱ	93.594 (14)	C7—C8—H8	119.6
Cl3—Bi—Cl3ⁱ	171.10 (3)	C9—C8—H8	119.6
Cl2—Bi—Cl1	87.06 (3)	N3—C9—C4	118.9 (2)
Cl4—Bi—Cl1	177.38 (4)	N3—C9—C8	120.9 (2)
Cl3—Bi—Cl1	86.529 (14)	C4—C9—C8	120.2 (2)
Cl3ⁱ—Bi—Cl1	86.529 (14)	N1—C10—C11	109.9 (2)
Cl2—Bi—Cl1ⁱⁱ	170.06 (3)	N1—C10—H10A	109.7
Cl4—Bi—Cl1ⁱⁱ	94.38 (4)	C11—C10—H10A	109.7
Cl3—Bi—Cl1ⁱⁱ	92.335 (14)	N1—C10—H10B	109.7
Cl3ⁱ—Bi—Cl1ⁱⁱ	92.335 (14)	C11—C10—H10B	109.7
Cl1—Bi—Cl1ⁱⁱ	83.00 (3)	H10A—C10—H10B	108.2
Cl2—Bi—Biⁱⁱ	130.14 (2)	N2—C11—C10	110.0 (2)
Cl4—Bi—Biⁱⁱ	134.31 (3)	N2—C11—H11A	109.7
Cl3—Bi—Biⁱⁱ	89.364 (14)	C10—C11—H11A	109.7
Cl3ⁱ—Bi—Biⁱⁱ	89.364 (14)	N2—C11—H11B	109.7
Cl1—Bi—Biⁱⁱ	43.076 (18)	C10—C11—H11B	109.7
Cl1ⁱⁱ—Bi—Biⁱⁱ	39.921 (15)	H11A—C11—H11B	108.2
Bi—Cl1—Biⁱⁱ	97.00 (2)	N2—C12—C13	110.8 (2)
C14—O2—H4	109.5	N2—C12—H12A	109.5
C3—O3—H3	109.5	C13—C12—H12A	109.5
H5B—O5—H5C	117 (3)	N2—C12—H12B	109.5
C7—N1—C13	118.3 (2)	C13—C12—H12B	109.5
C7—N1—C10	118.5 (2)	H12A—C12—H12B	108.1
C13—N1—C10	111.7 (2)	N1—C13—C12	110.1 (2)
C17—N2—C11	111.8 (2)	N1—C13—H13A	109.6
C17—N2—C12	111.1 (2)	C12—C13—H13A	109.6
C11—N2—C12	109.50 (19)	N1—C13—H13B	109.6
C17—N2—H2	108.1	C12—C13—H13B	109.6
C11—N2—H2	108.1	H13A—C13—H13B	108.2
C12—N2—H2	108.1	O1—C14—O2	123.6 (2)
C1—N3—C9	120.1 (2)	O1—C14—C2	122.4 (2)
C1—N3—C15	119.4 (2)	O2—C14—C2	114.0 (2)
C9—N3—C15	120.5 (2)	N3—C15—C16	112.5 (2)
N3—C1—C2	123.6 (2)	N3—C15—H15A	109.1
N3—C1—H1A	118.2	C16—C15—H15A	109.1
C2—C1—H1A	118.2	N3—C15—H15B	109.1
C1—C2—C3	119.7 (2)	C16—C15—H15B	109.1
C1—C2—C14	121.2 (2)	H15A—C15—H15B	107.8
C3—C2—C14	119.1 (2)	C15—C16—H16A	109.5
O3—C3—C2	126.0 (2)	C15—C16—H16B	109.5
O3—C3—C4	117.4 (2)	H16A—C16—H16B	109.5
C2—C3—C4	116.5 (2)	C15—C16—H16C	109.5
C9—C4—C5	118.8 (2)	H16A—C16—H16C	109.5
C9—C4—C3	121.1 (2)	H16B—C16—H16C	109.5
C5—C4—C3	120.1 (2)	N2—C17—H17A	109.5
C6—C5—C4	120.0 (2)	N2—C17—H17B	109.5
C6—C5—H5	120.0	H17A—C17—H17B	109.5
C4—C5—H5	120.0	N2—C17—H17C	109.5
C5—C6—F2	118.5 (2)	H17A—C17—H17C	109.5
C5—C6—C7	123.3 (2)	H17B—C17—H17C	109.5
F2—C6—C7	118.1 (2)

Symmetry codes: (i) x, −y+1, z; (ii) −x+1, −y+1, −z+2; (iii) −x+2, y, −z+1; (iv) x+1, −y+1, z; (v) −x+3/2, y+1/2, −z+1; (vi) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H4···Cl5^vii	0.84	2.18	3.014 (2)	174
O3—H3···O1	0.84	1.96	2.675 (3)	143
O3—H3···Cl6^viii	0.84	2.06	2.559 (5)	118
O5—H5B···O1^ix	0.83 (1)	2.01 (2)	2.790 (3)	157 (4)
O5—H5C···O7^x	0.83 (1)	2.03 (1)	2.851 (5)	173 (3)
O5—H5C···Cl7^x	0.83 (1)	2.24 (1)	3.056 (4)	170 (3)
N2—H2···Cl1^xi	0.93	2.52	3.262 (2)	137
N2—H2···Cl3^xii	0.93	2.77	3.423 (2)	128

Symmetry codes: (vii) x, y, z+1; (viii) −x+3/2, y−1/2, −z+1; (ix) −x+1/2, −y+1/2, −z+1; (x) −x, −y+1, −z+1; (xi) −x+1, −y+1, −z+1; (xii) −x+1, y, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₇H₂₂FN₃O₃)₄[Bi₂Cl₁₀]Cl₄·8H₂O
M_r	2399.89
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	173
a, b, c (Å)	14.4201 (14), 25.305 (3), 12.6359 (12)
β (°)	99.028 (2)
V (Å³)	4553.7 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.35
Crystal size (mm)	0.30 × 0.05 × 0.01

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Gaussian (SADABS; Bruker, 2003)
T_min, T_max	0.606, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	16488, 6329, 5310
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.693

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.077, 1.08
No. of reflections	6329
No. of parameters	303
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.23, −1.17

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2008).

Selected interatomic distances (Å) top

Bi—Cl2	2.5037 (10)	Bi—Cl3ⁱ	2.6911 (7)
Bi—Cl4	2.5737 (11)	Bi—Cl1	2.8834 (8)
Bi—Cl3	2.6910 (7)	Bi—Cl1ⁱⁱ	3.0687 (9)

O6···O6ⁱ	2.822 (6)	O6···O3^v	3.091 (4)
O6···Cl6ⁱⁱⁱ	2.863 (5)	O7···Cl7^vi	2.888 (7)
O6···O5^iv	2.961 (4)	O7···O7^vi	3.146 (14)
O6···O6ⁱⁱⁱ	3.074 (6)

Symmetry codes: (i) x, −y+1, z; (ii) −x+1, −y+1, −z+2; (iii) −x+2, y, −z+1; (iv) x+1, −y+1, z; (v) −x+3/2, y+1/2, −z+1; (vi) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H4···Cl5^vii	0.84	2.18	3.014 (2)	174
O3—H3···O1	0.84	1.96	2.675 (3)	143
O3—H3···Cl6^viii	0.84	2.06	2.559 (5)	118
O5—H5B···O1^ix	0.83 (1)	2.009 (18)	2.790 (3)	157 (4)
O5—H5C···O7^x	0.83 (1)	2.029 (13)	2.851 (5)	173 (3)
O5—H5C···Cl7^x	0.83 (1)	2.238 (13)	3.056 (4)	170 (3)
N2—H2···Cl1^xi	0.93	2.52	3.262 (2)	137
N2—H2···Cl3^xii	0.93	2.77	3.423 (2)	128

Symmetry codes: (vii) x, y, z+1; (viii) −x+3/2, y−1/2, −z+1; (ix) −x+1/2, −y+1/2, −z+1; (x) −x, −y+1, −z+1; (xi) −x+1, −y+1, −z+1; (xii) −x+1, y, −z+1.

Acknowledgements

The authors thank the Russian Foundation for Basic Research (project No. 08–03–91750) for financial support.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar

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