Bis(dihydrogen norfloxacinium) tri-μ2-chlorido-bis­[trichloridobismuthate(III)] chloride dihydrate

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

doi:10.1107/S1600536808001244

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m378

doi:10.1107/S1600536808001244

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Bis(dihydrogen norfloxacinium) tri-μ₂-chlorido-bis[trichloridobismuthate(III)] chloride dihydrate

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

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

(Received 25 December 2007; accepted 12 January 2008; online 23 January 2008)

The title compound, {systematic name: (3-carboxy-1-ethyl-6-fluoro-7-piperazin-4-ium-1-yl-1H-quinolin-4-ylidene)oxonium tri-μ₂-chlorido-bis[trichloridobismuthate(III)] chloride dihydrate], (C₁₆H₂₀FN₃O₃)₂[Bi₂Cl₉]Cl·2H₂O, is composed of [Bi₂Cl₉]³⁻ anions lying on crystallographic twofold rotation axes, Cl⁻ anions also on twofold axes, C₁₆H₂₀FN₃O₃²⁺ cations, and water molecules. The Bi^III coordination polyhedron is a distorted octahedron and two such octahedra share a triangular face to form the complex anion. There are three short terminal Bi—Cl bonds [2.5471 (6)–2.5781(5 Å] and three longer bridging bonds [2.8599 (5)–2.9984 (6) Å] in each octahedron. Anions, cations and water molecules are linked by hydrogen bonds to form a three-dimensional network. There are also π–π stacking interactions between quinoline ring systems, with an interplanar distance of 3.27 (1) Å.

Related literature

For the Cambridge Structural Database (Version 5.28) used to identify related structures, see: Allen (2002 ).

Experimental

Crystal data

(C₁₆H₂₀FN₃O₃)₂[Bi₂Cl₉]Cl·2H₂O
M_r = 1451.19
Monoclinic, C 2/c
a = 13.9109 (12) Å
b = 22.7104 (19) Å
c = 14.5964 (12) Å
β = 92.798 (2)°
V = 4605.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 8.27 mm⁻¹
T = 203 (2) K
0.27 × 0.22 × 0.17 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: Gaussian (SADABS; Bruker, 2003 ) T_min = 0.180, T_max = 0.334
16736 measured reflections
6987 independent reflections
6081 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.061
S = 1.06
6987 reflections
282 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.58 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Selected bond lengths (Å)

Bi1⋯Bi1ⁱ	3.7851 (3)
Bi1—Cl4	2.5471 (6)
Bi1—Cl3	2.5497 (5)
Bi1—Cl5	2.5781 (5)
Bi1—Cl1	2.8599 (5)
Bi1—Cl2	2.9194 (6)
Bi1—Cl2ⁱ	2.9984 (6)
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1	0.83	1.85	2.583 (2)	146
O2—H2⋯Cl6ⁱⁱ	0.83	2.19	3.0150 (15)	173
O4—H4A⋯Cl5	0.715 (18)	2.563 (18)	3.270 (2)	170 (4)
O4—H4B⋯Cl6	0.717 (19)	2.47 (2)	3.146 (2)	157 (4)
N3—H3A⋯Cl2ⁱⁱⁱ	0.91	2.51	3.3961 (19)	165
N3—H3B⋯O4^iv	0.91	1.82	2.693 (3)	160
Symmetry codes: (ii) x+1, y, z; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iv) $[x, -y+1, z+{\script{1\over 2}}]$ .

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 (Version 1.9.0; Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001244/cf2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001244/cf2178Isup2.hkl

checkCIF report

Comment top

Norfloxacin (nfH) 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 relevant structures are those where norfloxacin acts as an anion, a singly protonated cation or a zwitterion. The present research deals with the synthesis and structure of a chlorido-bismuth complex with the doubly protonated cation of norfloxacin (nfH₃)²⁺.

The asymmetric unit of the title compound, (I), contains one Bi atom, five chlorine atoms, one nfH₃ cation and one H₂O molecule. The Bi atoms are coordinated by six Cl atoms in a distorted octahedral geometry. Two Bi-centred octahedra are linked by triple Cl bridges to form a dinuclear [Bi₂Cl₉]^3- complex (Fig. 1), which lies on a twofold rotation axis, with a Bi···Bi distance of 3.7851 (3) Å. In the Bi-centred octahedra there are three short terminal Bi—Cl bonds [2.5471 (6)–2.5781 (5) Å] and three longer bridging bonds [2.8599 (5)–2.9984(6] Å). These anions pack in columns parallel to the [101] direction.

The protonation of nfH₃²⁺ is realised on the carbonyl atom O3 and N3 of the piperazine ring (Fig. 2). The hydrogen atom H3 is linked by an intramolecular hydrogen bond with O1 of the carboxyl group. O2 and N3 in the cation act as hydrogen-bond donors, via H2, H3A and H3B.

Water molecules, uncoordinated chloride anions (Cl6) and nfH₃²⁺ cations are linked in zigzag chains by hydrogen bonds parallel to the [102] direction (Fig. 3). In the chain, the nfH₃²⁺ cations are pairwise parallel (as a result of inversion symmetry), and there exist also π–π interactions between quinoline ring systems, with an interplanar distance of 3.27 (1) Å.

The combination of the hydrogen bonds and π–π stacking generates a three-dimensional network (Fig. 4).

Related literature top

For the Cambridge Structural Database (Version 5.28) used to identify related structures, see: Allen (2002).

Experimental top

Bi(OH)₃ (0.052 g, 0.2 mmol) was reacted with nfH (0.066 g, 0.2 mmol) in an aqueous solution of HCl (21%, 20 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 (Version 1.9.0; Westrip, 2008).

Figures top

	Fig. 1. A view of the dinuclear [Bi₂Cl₉]^3- complex, with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) -x, y, 1/2 - z.]
	Fig. 2. A view of the nfH₃²⁺ canion, with displacement ellipsoids drawn at the 50% probability level. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 3. Fragment of the zigzag chain formed from water molecules, chloride anions and nfH₃²⁺ canions, with hydrogen bonds shown as dashed lines.
	Fig. 4. The crystal structure of the title compound viewed along the c axis. Dashed lines represent hydrogen bonds.

(3-carboxy-1-ethyl-6-fluoro-7-piperazin-4-ium-1-yl-1H-quinolin-4- ylidene)oxonium tri-µ₂-chlorido-bis[trichloridobismuthate(III)] chloride dihydrate] top

Crystal data top

(C₁₆H₂₀FN₃O₃)₂[Bi₂Cl₉]Cl·2H₂O	F(000) = 2784
M_r = 1451.19	D_x = 2.093 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9109 (12) Å	Cell parameters from 951 reflections
b = 22.7104 (19) Å	θ = 3.9–30.6°
c = 14.5964 (12) Å	µ = 8.27 mm⁻¹
β = 92.798 (2)°	T = 203 K
V = 4605.8 (7) Å³	Prism, yellow
Z = 4	0.27 × 0.22 × 0.17 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6987 independent reflections
Radiation source: fine-focus sealed tube	6081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8.33 pixels mm^-1	θ_max = 31.5°, θ_min = 3.6°
ϕ and ω scans	h = −20→15
Absorption correction: gaussian (SADABS; Bruker, 2003)	k = −31→32
T_min = 0.180, T_max = 0.334	l = −20→14
16736 measured reflections

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0269P)² + 1.9407P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.012
6987 reflections	Δρ_max = 1.58 e Å⁻³
282 parameters	Δρ_min = −0.84 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000362 (17)

Crystal data top

(C₁₆H₂₀FN₃O₃)₂[Bi₂Cl₉]Cl·2H₂O	V = 4605.8 (7) Å³
M_r = 1451.19	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.9109 (12) Å	µ = 8.27 mm⁻¹
b = 22.7104 (19) Å	T = 203 K
c = 14.5964 (12) Å	0.27 × 0.22 × 0.17 mm
β = 92.798 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	6987 independent reflections
Absorption correction: gaussian (SADABS; Bruker, 2003)	6081 reflections with I > 2σ(I)
T_min = 0.180, T_max = 0.334	R_int = 0.031
16736 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	1 restraint
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 1.58 e Å⁻³
6987 reflections	Δρ_min = −0.84 e Å⁻³
282 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
Bi1	0.125399 (5)	0.231497 (3)	0.205209 (5)	0.01711 (2)
Cl1	0.0000	0.13708 (3)	0.2500	0.02433 (15)
Cl2	0.06458 (4)	0.26380 (2)	0.38711 (4)	0.02637 (11)
Cl3	0.16112 (4)	0.18802 (2)	0.04945 (3)	0.02670 (11)
Cl4	0.27484 (4)	0.18468 (3)	0.28222 (4)	0.03193 (13)
Cl5	0.20122 (4)	0.33350 (2)	0.18044 (4)	0.03441 (13)
Cl6	0.5000	0.48180 (3)	0.2500	0.0356 (2)
F1	0.75259 (8)	0.46603 (5)	0.43340 (9)	0.0275 (3)
O1	1.25735 (10)	0.45323 (6)	0.28600 (10)	0.0262 (3)
O2	1.32428 (11)	0.54074 (6)	0.32107 (12)	0.0317 (4)
H2	1.3714	0.5259	0.2970	0.048*
O3	1.08058 (10)	0.43447 (6)	0.32403 (10)	0.0225 (3)
H3	1.1348	0.4259	0.3067	0.034*
O4	0.42564 (14)	0.36716 (10)	0.14845 (15)	0.0632 (6)
H4A	0.3777 (12)	0.3561 (14)	0.152 (3)	0.076*
H4B	0.429 (3)	0.3968 (8)	0.165 (2)	0.076*
N1	1.07419 (11)	0.60588 (7)	0.41452 (11)	0.0167 (3)
N2	0.73624 (11)	0.58287 (7)	0.48464 (11)	0.0200 (4)
N3	0.56019 (12)	0.64241 (8)	0.52271 (13)	0.0275 (4)
H3A	0.5558	0.6702	0.4778	0.033*
H3B	0.5084	0.6464	0.5579	0.033*
C1	1.15439 (13)	0.58404 (8)	0.38258 (13)	0.0184 (4)
H1	1.2091	0.6083	0.3820	0.022*
C2	1.16090 (13)	0.52665 (8)	0.34983 (13)	0.0179 (4)
C3	1.08010 (13)	0.48980 (8)	0.35148 (13)	0.0172 (4)
C4	0.99316 (13)	0.51308 (8)	0.38424 (13)	0.0167 (4)
C5	0.91002 (14)	0.47809 (8)	0.38934 (13)	0.0192 (4)
H5	0.9105	0.4386	0.3700	0.023*
C6	0.82924 (13)	0.50185 (8)	0.42245 (13)	0.0193 (4)
C7	0.82172 (13)	0.56183 (8)	0.45095 (13)	0.0180 (4)
C8	0.90503 (13)	0.59551 (8)	0.44819 (13)	0.0176 (4)
H8	0.9043	0.6348	0.4684	0.021*
C9	0.99058 (13)	0.57178 (8)	0.41560 (13)	0.0170 (4)
C10	1.07597 (14)	0.66786 (8)	0.44871 (14)	0.0211 (4)
H10A	1.1427	0.6794	0.4639	0.025*
H10B	1.0406	0.6701	0.5050	0.025*
C11	1.03232 (16)	0.71041 (9)	0.37950 (16)	0.0282 (5)
H11A	1.0642	0.7065	0.3222	0.042*
H11B	1.0403	0.7503	0.4023	0.042*
H11C	0.9643	0.7019	0.3694	0.042*
C12	1.25206 (14)	0.50349 (9)	0.31606 (14)	0.0213 (4)
C13	0.73860 (14)	0.64186 (9)	0.52505 (14)	0.0228 (4)
H13A	0.7405	0.6714	0.4763	0.027*
H13B	0.7969	0.6463	0.5650	0.027*
C14	0.65017 (15)	0.65186 (10)	0.58046 (16)	0.0270 (5)
H14A	0.6516	0.6247	0.6327	0.032*
H14B	0.6511	0.6921	0.6045	0.032*
C15	0.55900 (15)	0.58264 (10)	0.48029 (16)	0.0284 (5)
H15A	0.5012	0.5782	0.4397	0.034*
H15B	0.5572	0.5526	0.5284	0.034*
C16	0.64805 (14)	0.57405 (10)	0.42577 (14)	0.0254 (5)
H16A	0.6480	0.5342	0.4001	0.031*
H16B	0.6471	0.6021	0.3748	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.01352 (3)	0.01870 (3)	0.01912 (3)	−0.00108 (2)	0.00093 (2)	−0.00093 (2)
Cl1	0.0228 (3)	0.0167 (3)	0.0330 (4)	0.000	−0.0039 (3)	0.000
Cl2	0.0241 (2)	0.0284 (2)	0.0269 (2)	−0.00434 (18)	0.00425 (19)	−0.00849 (19)
Cl3	0.0214 (2)	0.0372 (2)	0.0214 (2)	0.00634 (19)	−0.00045 (18)	−0.0049 (2)
Cl4	0.0214 (2)	0.0466 (3)	0.0275 (3)	0.0063 (2)	−0.00225 (19)	0.0042 (2)
Cl5	0.0332 (3)	0.0226 (2)	0.0480 (3)	−0.0083 (2)	0.0071 (2)	−0.0018 (2)
Cl6	0.0209 (3)	0.0200 (3)	0.0671 (5)	0.000	0.0154 (3)	0.000
F1	0.0198 (5)	0.0281 (6)	0.0351 (7)	−0.0095 (5)	0.0049 (5)	−0.0042 (5)
O1	0.0213 (7)	0.0252 (7)	0.0324 (8)	0.0038 (6)	0.0036 (6)	−0.0085 (6)
O2	0.0182 (7)	0.0258 (7)	0.0523 (10)	−0.0008 (6)	0.0126 (6)	−0.0086 (7)
O3	0.0206 (6)	0.0201 (6)	0.0267 (7)	0.0011 (5)	0.0017 (6)	−0.0056 (5)
O4	0.0324 (9)	0.0866 (13)	0.0726 (13)	−0.0253 (9)	0.0216 (9)	−0.0498 (11)
N1	0.0134 (6)	0.0167 (6)	0.0199 (7)	−0.0018 (5)	0.0008 (6)	−0.0012 (6)
N2	0.0109 (7)	0.0268 (7)	0.0223 (8)	0.0003 (6)	−0.0003 (6)	−0.0025 (7)
N3	0.0158 (7)	0.0310 (8)	0.0360 (10)	0.0057 (7)	0.0045 (7)	0.0098 (8)
C1	0.0142 (8)	0.0213 (8)	0.0196 (9)	−0.0020 (6)	0.0008 (7)	0.0016 (7)
C2	0.0151 (8)	0.0208 (8)	0.0178 (8)	0.0006 (7)	0.0013 (7)	−0.0004 (7)
C3	0.0183 (8)	0.0163 (7)	0.0167 (8)	0.0006 (6)	−0.0004 (7)	0.0005 (7)
C4	0.0157 (8)	0.0186 (8)	0.0159 (8)	−0.0006 (6)	−0.0002 (6)	−0.0002 (7)
C5	0.0194 (8)	0.0209 (8)	0.0171 (8)	−0.0032 (7)	−0.0002 (7)	−0.0016 (7)
C6	0.0148 (8)	0.0240 (8)	0.0189 (9)	−0.0045 (7)	−0.0002 (7)	−0.0007 (7)
C7	0.0159 (8)	0.0211 (8)	0.0168 (8)	−0.0015 (7)	−0.0016 (7)	0.0003 (7)
C8	0.0165 (8)	0.0183 (8)	0.0180 (8)	0.0006 (6)	0.0001 (7)	−0.0016 (7)
C9	0.0141 (8)	0.0200 (8)	0.0168 (8)	−0.0002 (6)	−0.0004 (6)	0.0006 (7)
C10	0.0171 (8)	0.0192 (8)	0.0273 (10)	−0.0027 (7)	0.0027 (7)	−0.0087 (7)
C11	0.0277 (10)	0.0224 (9)	0.0348 (12)	0.0019 (8)	0.0045 (9)	0.0004 (9)
C12	0.0200 (9)	0.0248 (9)	0.0191 (9)	0.0019 (7)	0.0008 (7)	0.0007 (7)
C13	0.0175 (8)	0.0232 (9)	0.0277 (10)	0.0006 (7)	0.0029 (7)	−0.0024 (8)
C14	0.0199 (9)	0.0276 (9)	0.0338 (11)	0.0043 (8)	0.0048 (8)	0.0006 (9)
C15	0.0157 (9)	0.0325 (10)	0.0367 (12)	0.0009 (8)	−0.0014 (8)	0.0053 (9)
C16	0.0169 (9)	0.0361 (10)	0.0229 (10)	−0.0016 (8)	−0.0028 (7)	0.0020 (8)

Geometric parameters (Å, º) top

Bi1—Bi1ⁱ	3.7851 (3)	C1—H1	0.940
Bi1—Cl4	2.5471 (6)	C2—C3	1.402 (3)
Bi1—Cl3	2.5497 (5)	C2—C12	1.479 (3)
Bi1—Cl5	2.5781 (5)	C3—C4	1.424 (3)
Bi1—Cl1	2.8599 (5)	C4—C5	1.408 (3)
Bi1—Cl2	2.9194 (6)	C4—C9	1.411 (3)
Bi1—Cl2ⁱ	2.9984 (6)	C5—C6	1.357 (3)
Cl1—Bi1ⁱ	2.8599 (5)	C5—H5	0.940
Cl2—Bi1ⁱ	2.9984 (6)	C6—C7	1.430 (3)
F1—C6	1.357 (2)	C7—C8	1.391 (3)
O1—C12	1.226 (2)	C8—C9	1.410 (3)
O2—C12	1.313 (2)	C8—H8	0.940
O2—H2	0.830	C10—C11	1.504 (3)
O3—C3	1.319 (2)	C10—H10A	0.980
O3—H3	0.830	C10—H10B	0.980
O4—H4A	0.715 (18)	C11—H11A	0.970
O4—H4B	0.717 (19)	C11—H11B	0.970
N1—C1	1.326 (2)	C11—H11C	0.970
N1—C9	1.398 (2)	C13—C14	1.522 (3)
N1—C10	1.493 (2)	C13—H13A	0.980
N2—C7	1.393 (2)	C13—H13B	0.980
N2—C13	1.464 (3)	C14—H14A	0.980
N2—C16	1.477 (3)	C14—H14B	0.980
N3—C14	1.490 (3)	C15—C16	1.517 (3)
N3—C15	1.492 (3)	C15—H15A	0.980
N3—H3A	0.910	C15—H15B	0.980
N3—H3B	0.910	C16—H16A	0.980
C1—C2	1.393 (3)	C16—H16B	0.980

Cl4—Bi1—Cl3	92.375 (18)	F1—C6—C7	117.90 (16)
Cl4—Bi1—Cl5	96.10 (2)	C8—C7—N2	123.26 (17)
Cl3—Bi1—Cl5	97.124 (19)	C8—C7—C6	116.27 (17)
Cl4—Bi1—Cl1	94.585 (16)	N2—C7—C6	120.35 (16)
Cl3—Bi1—Cl1	93.506 (14)	C7—C8—C9	121.19 (17)
Cl5—Bi1—Cl1	164.578 (16)	C7—C8—H8	119.4
Cl4—Bi1—Cl2	88.285 (17)	C9—C8—H8	119.4
Cl3—Bi1—Cl2	170.408 (16)	N1—C9—C8	120.56 (16)
Cl5—Bi1—Cl2	92.318 (17)	N1—C9—C4	119.04 (16)
Cl1—Bi1—Cl2	76.903 (12)	C8—C9—C4	120.39 (16)
Cl4—Bi1—Cl2ⁱ	169.401 (17)	N1—C10—C11	112.43 (16)
Cl3—Bi1—Cl2ⁱ	84.255 (16)	N1—C10—H10A	109.1
Cl5—Bi1—Cl2ⁱ	94.291 (17)	C11—C10—H10A	109.1
Cl1—Bi1—Cl2ⁱ	75.647 (12)	N1—C10—H10B	109.1
Cl2—Bi1—Cl2ⁱ	93.385 (16)	C11—C10—H10B	109.1
Bi1—Cl1—Bi1ⁱ	82.867 (18)	H10A—C10—H10B	107.9
Bi1—Cl2—Bi1ⁱ	79.513 (14)	C10—C11—H11A	109.5
C12—O2—H2	109.5	C10—C11—H11B	109.5
C3—O3—H3	109.5	H11A—C11—H11B	109.5
H4A—O4—H4B	110 (4)	C10—C11—H11C	109.5
C1—N1—C9	120.76 (15)	H11A—C11—H11C	109.5
C1—N1—C10	118.00 (15)	H11B—C11—H11C	109.5
C9—N1—C10	121.24 (15)	O1—C12—O2	124.09 (19)
C7—N2—C13	116.96 (15)	O1—C12—C2	121.17 (18)
C7—N2—C16	116.57 (16)	O2—C12—C2	114.74 (17)
C13—N2—C16	111.13 (16)	N2—C13—C14	110.36 (16)
C14—N3—C15	110.96 (16)	N2—C13—H13A	109.6
C14—N3—H3A	109.4	C14—C13—H13A	109.6
C15—N3—H3A	109.4	N2—C13—H13B	109.6
C14—N3—H3B	109.4	C14—C13—H13B	109.6
C15—N3—H3B	109.4	H13A—C13—H13B	108.1
H3A—N3—H3B	108.0	N3—C14—C13	110.88 (18)
N1—C1—C2	122.72 (17)	N3—C14—H14A	109.5
N1—C1—H1	118.6	C13—C14—H14A	109.5
C2—C1—H1	118.6	N3—C14—H14B	109.5
C1—C2—C3	119.14 (17)	C13—C14—H14B	109.5
C1—C2—C12	121.21 (17)	H14A—C14—H14B	108.1
C3—C2—C12	119.62 (16)	N3—C15—C16	110.00 (17)
O3—C3—C2	123.19 (17)	N3—C15—H15A	109.7
O3—C3—C4	118.21 (16)	C16—C15—H15A	109.7
C2—C3—C4	118.61 (16)	N3—C15—H15B	109.7
C5—C4—C9	118.83 (17)	C16—C15—H15B	109.7
C5—C4—C3	121.43 (17)	H15A—C15—H15B	108.2
C9—C4—C3	119.70 (16)	N2—C16—C15	110.71 (17)
C6—C5—C4	119.41 (17)	N2—C16—H16A	109.5
C6—C5—H5	120.3	C15—C16—H16A	109.5
C4—C5—H5	120.3	N2—C16—H16B	109.5
C5—C6—F1	118.21 (17)	C15—C16—H16B	109.5
C5—C6—C7	123.80 (17)	H16A—C16—H16B	108.1

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.83	1.85	2.583 (2)	146
O2—H2···Cl6ⁱⁱ	0.83	2.19	3.0150 (15)	173
O4—H4A···Cl5	0.72 (2)	2.56 (2)	3.270 (2)	170 (4)
O4—H4B···Cl6	0.72 (2)	2.47 (2)	3.146 (2)	157 (4)
N3—H3A···Cl2ⁱⁱⁱ	0.91	2.51	3.3961 (19)	165
N3—H3B···O4^iv	0.91	1.82	2.693 (3)	160

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

Experimental details

Crystal data
Chemical formula	(C₁₆H₂₀FN₃O₃)₂[Bi₂Cl₉]Cl·2H₂O
M_r	1451.19
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	203
a, b, c (Å)	13.9109 (12), 22.7104 (19), 14.5964 (12)
β (°)	92.798 (2)
V (Å³)	4605.8 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.27
Crystal size (mm)	0.27 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Gaussian (SADABS; Bruker, 2003)
T_min, T_max	0.180, 0.334
No. of measured, independent and observed [I > 2σ(I)] reflections	16736, 6987, 6081
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.061, 1.06
No. of reflections	6987
No. of parameters	282
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.58, −0.84

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2003), XP in SHELXTL (Sheldrick, 2008), publCIF (Version 1.9.0; Westrip, 2008).

Selected bond lengths (Å) top

Bi1—Bi1ⁱ	3.7851 (3)	Bi1—Cl1	2.8599 (5)
Bi1—Cl4	2.5471 (6)	Bi1—Cl2	2.9194 (6)
Bi1—Cl3	2.5497 (5)	Bi1—Cl2ⁱ	2.9984 (6)
Bi1—Cl5	2.5781 (5)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1	0.83	1.85	2.583 (2)	146
O2—H2···Cl6ⁱⁱ	0.83	2.19	3.0150 (15)	173
O4—H4A···Cl5	0.715 (18)	2.563 (18)	3.270 (2)	170 (4)
O4—H4B···Cl6	0.717 (19)	2.47 (2)	3.146 (2)	157 (4)
N3—H3A···Cl2ⁱⁱⁱ	0.91	2.51	3.3961 (19)	165
N3—H3B···O4^iv	0.91	1.82	2.693 (3)	160

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

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (1998). SMART. Version 5.054. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT (Version 6.45) and SADABS (Version 2.10). 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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