Diaqua­bis[1-ethyl-6-fluoro-7-(4-methyl­piperazin-4-ium-1-yl)-4-oxo-1,4-dihydro­quinoline-3-carboxyl­ato-κ2O3,O4]manganese(II) benzene-1,4-dicarboxyl­ate tetra­deca­hydrate

An, Z.; Qi, W.; Huang, J.

doi:10.1107/S1600536807032072

Diaquabis[1-ethyl-6-fluoro-7-(4-methylpiperazin-4-ium-1-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylato-κ²O³,O⁴]manganese(II) benzene-1,4-dicarboxylate tetradecahydrate

In the title compound, [Mn(C₁₇H₂₀FN₃O₃)₂(H₂O)₂](C₈H₄O₄).14H₂O, the Mn^II atom (site symmetry $\overline{1}$ ) exhibits a distorted MnO₆ octahedral geometry defined by two neutral bidentate O,O-bonded 1-ethyl-6-fluoro-7-(4-methylpiperazin-4-ium-1-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylate (Hpef) zwitterions and two water molecules. The charge-balancing benzene-1,4-dicarboxylate (1,4-bdc) anion is also centrosymmetric. An extensive network of O—H

O and O—H

N hydrogen bonds helps to establish the crystal packing.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032072/hb2468sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032072/hb2468Isup2.hkl Contains datablock I

CCDC reference: 658943

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.003 Å
R factor = 0.036
wR factor = 0.098
Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        400 Deg.
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   O1      ..       5.39 su
PLAT245_ALERT_2_C U(iso) H1W1    Smaller than U(eq) O1W     by ...       0.02 AngSq
PLAT245_ALERT_2_C U(iso) H1W2    Smaller than U(eq) O1W     by ...       0.02 AngSq
PLAT417_ALERT_2_C Short Inter D-H..H-D       H2O    ..  H6W2    ..       2.11 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            O1  -MN1 -O1  -C1     22.00 19.00   2.556   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O3  -MN1 -O3  -C3     15.00  0.00   2.556   1.555   1.555   1.555
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........         14
PLAT731_ALERT_1_C Bond    Calc     0.84(2), Rep    0.841(9) ......       2.22 su-Ra
              O1W  -H1W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(2), Rep    0.849(9) ......       2.22 su-Ra
              O2W  -H2W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(2), Rep    0.851(9) ......       2.22 su-Ra
              O3W  -H3W1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(2), Rep    0.843(9) ......       2.22 su-Ra
              O3W  -H3W2    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(2), Rep    0.853(9) ......       2.22 su-Ra
              O4   -H2O     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc   0.857(19), Rep    0.857(9) ......       2.11 su-Ra
              O7W  -H7W2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(2), Rep    0.841(9) ......       2.22 su-Ra
              O1W  -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(2), Rep    0.853(9) ......       2.22 su-Ra
              O4   -H2O     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc   0.857(19), Rep    0.857(9) ......       2.11 su-Ra
              O7W  -H12#    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(2), Rep    0.851(9) ......       2.22 su-Ra
              O3W  -H4#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(2), Rep    0.849(9) ......       2.22 su-Ra
              O2W  -H7#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(2), Rep    0.843(9) ......       2.22 su-Ra
              O3W  -H10#    1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.81(2), Rep    1.813(9) ......       2.22 su-Ra
              H1#  -O2      1.555   1.565
PLAT736_ALERT_1_C H...A   Calc     1.96(2), Rep    1.954(9) ......       2.22 su-Ra
              H4#  -O5      1.555   1.555

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.17
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         25

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  23 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

  16 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Pefloxacin (Hpef, C₁₇H₂₀FN₃O₃, 1-ethyl-6-fluoro-7-(4-methylpiperazin-1-yl)-4-oxo-quinoline-3-carboxylic acid) is member of a class of quinolones used to treat infections (Mizuki et al., 1996). The silver(I) derivative of the pefloxacin (pef) anion has been reported (Baenziger et al., 1986). The title manganese(II)-containing complex of Hper, (I), is reported here.

The structure of (I) is built up from Mn²⁺ cations (site symmetry 1) neutral Hpef ligands in their zwittrionic form (i.e. nominal proton transfer from the carboxylic acid group to a piperizine H atom), coordinated water molecules, a centrosymmetric 1,4-bdc anion and uncoordinated water molecules (Fig. 1). The manganese geometry is a slightly distorted octahedron (Table 1).

The components of (I) are linked by O—H···O and O—H···N hydrogen bonds involving all the potential donors, generating a three-dimensional supramolecular network (Table 2).

Related literature top

For the silver and cobalt complexes of the pef anion, see: Baenziger et al. (1986); An et al. (2007). For background literature on the medicinal uses of Hpef, see: Mizuki et al. (1996).

Experimental top

A mixture of Mn(CH₃COO)₂.4H₂O (0.061 g, 0.25 mmol), Hpef (0.17 g, 0.5 mmol), 1,4-benzenedicarboxylic acid (1,4-bdc, 0.04 g, 0.25 mmol) and water (12 ml) was stirred for 30 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Upon cooling, colorless prisms of (I) were obtained from the reaction mixture.

Structure description top

The components of (I) are linked by O—H···O and O—H···N hydrogen bonds involving all the potential donors, generating a three-dimensional supramolecular network (Table 2).

For the silver and cobalt complexes of the pef anion, see: Baenziger et al. (1986); An et al. (2007). For background literature on the medicinal uses of Hpef, see: Mizuki et al. (1996).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. The asymmetric unit of (I), show the Mn coordination, showing 50% displacement ellipsoids.(The uncoordinated water molecules are omitted for clarity). Symmetry code: (i) -x, -y, 1 - z. Yhe unlabelled atoms of the 1,4-bdc dianion are generated by the symmetry operation (1 - x, 1 - y, 2 - z).

Diaquabis[1-ethyl-6-fluoro-7-(4-methylpiperazin-4-ium-1-yl)-4-oxo-1,4- dihydroquinoline-3-carboxylato-κ²O³,O⁴]manganese(II) benzene-1,4-dicarboxylate tetradecahydrate top

Crystal data top

[Mn(C₁₇H₂₀FN₃O₃)₂(H₂O)₂](C₈H₄O₄)·14H₂O	Z = 1
M_r = 1174.03	F(000) = 621
Triclinic, P1	D_x = 1.426 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.147 (3) Å	Cell parameters from 10985 reflections
b = 11.500 (3) Å	θ = 2.5–26.0°
c = 11.832 (3) Å	µ = 0.34 mm⁻¹
α = 111.722 (4)°	T = 295 K
β = 92.011 (4)°	Prism, colorless
γ = 102.066 (4)°	0.34 × 0.26 × 0.18 mm
V = 1367.3 (6) Å³

Data collection top

Bruker SMART CCD diffractometer	5353 independent reflections
Radiation source: fine-focus sealed tube	4645 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.894, T_max = 0.942	k = −13→14
11720 measured reflections	l = −14→14

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)] = 0.036	Hydrogen site location: difmap and geom
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.048P)² + 0.5532P] where P = (F_o² + 2F_c²)/3
5353 reflections	(Δ/σ)_max < 0.001
402 parameters	Δρ_max = 0.38 e Å⁻³
25 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Mn(C₁₇H₂₀FN₃O₃)₂(H₂O)₂](C₈H₄O₄)·14H₂O	γ = 102.066 (4)°
M_r = 1174.03	V = 1367.3 (6) Å³
Triclinic, P1	Z = 1
a = 11.147 (3) Å	Mo Kα radiation
b = 11.500 (3) Å	µ = 0.34 mm⁻¹
c = 11.832 (3) Å	T = 295 K
α = 111.722 (4)°	0.34 × 0.26 × 0.18 mm
β = 92.011 (4)°

Data collection top

Bruker SMART CCD diffractometer	5353 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4645 reflections with I > 2σ(I)
T_min = 0.894, T_max = 0.942	R_int = 0.013
11720 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	25 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.38 e Å⁻³
5353 reflections	Δρ_min = −0.35 e Å⁻³
402 parameters

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

	x	y	z	U_iso*/U_eq
Mn1	0.0000	0.0000	0.5000	0.03248 (11)
F1	0.46666 (10)	0.53125 (9)	0.63639 (11)	0.0466 (3)
O1	0.08828 (11)	−0.14497 (11)	0.51391 (13)	0.0442 (3)
O1W	0.0623 (2)	0.60894 (17)	0.6358 (2)	0.0861 (7)
O2	0.22468 (12)	−0.23558 (13)	0.56627 (17)	0.0632 (5)
O2W	0.14371 (15)	0.64240 (17)	0.92704 (17)	0.0661 (4)
O3	0.18601 (10)	0.10280 (11)	0.51526 (11)	0.0370 (3)
O3W	0.28264 (18)	0.06305 (16)	0.96455 (16)	0.0685 (5)
O4	0.01341 (12)	0.08480 (13)	0.70334 (12)	0.0460 (3)
O4W	0.54654 (17)	0.79875 (16)	0.82458 (17)	0.0690 (5)
O5	0.23622 (11)	0.22196 (11)	0.84581 (12)	0.0427 (3)
O5W	0.30062 (16)	0.81047 (17)	0.83005 (15)	0.0673 (4)
O6	0.18210 (11)	0.39621 (12)	0.84330 (13)	0.0475 (3)
O6W	0.91289 (15)	0.29089 (17)	0.83310 (16)	0.0660 (4)
O7W	0.91049 (14)	0.62388 (13)	0.39048 (14)	0.0551 (4)
N1	0.51219 (12)	0.07432 (13)	0.66259 (13)	0.0324 (3)
N2	0.69176 (12)	0.52516 (14)	0.72389 (13)	0.0353 (3)
N3	0.91188 (13)	0.72584 (14)	0.77586 (14)	0.0364 (3)
C1	0.19619 (15)	−0.14347 (15)	0.55046 (16)	0.0339 (4)
C2	0.29724 (14)	−0.02282 (15)	0.58101 (15)	0.0300 (3)
C3	0.28289 (14)	0.09020 (15)	0.56370 (14)	0.0283 (3)
C4	0.39132 (14)	0.19783 (15)	0.60438 (14)	0.0278 (3)
C5	0.38087 (14)	0.31463 (15)	0.59749 (15)	0.0314 (3)
H5A	0.3063	0.3221	0.5664	0.038*
C6	0.48032 (15)	0.41633 (15)	0.63654 (15)	0.0332 (4)
C7	0.59673 (14)	0.41172 (16)	0.68282 (14)	0.0315 (3)
C8	0.60684 (14)	0.29760 (16)	0.69184 (15)	0.0321 (3)
H8A	0.6819	0.2914	0.7232	0.039*
C9	0.50454 (14)	0.19059 (15)	0.65399 (14)	0.0288 (3)
C10	0.41142 (15)	−0.02378 (16)	0.62819 (15)	0.0329 (4)
H10A	0.4194	−0.0990	0.6370	0.039*
C11	0.62620 (16)	0.05826 (17)	0.71744 (17)	0.0382 (4)
H11A	0.6977	0.1031	0.6929	0.046*
H11B	0.6262	−0.0325	0.6864	0.046*
C12	0.6364 (2)	0.1097 (2)	0.85510 (18)	0.0512 (5)
H12A	0.6413	0.2006	0.8865	0.077*
H12B	0.7095	0.0945	0.8869	0.077*
H12C	0.5650	0.0668	0.8798	0.077*
C13	0.79810 (16)	0.53132 (17)	0.80351 (17)	0.0380 (4)
H13A	0.8515	0.4807	0.7553	0.046*
H13B	0.7705	0.4964	0.8638	0.046*
C14	0.86825 (16)	0.67091 (17)	0.86713 (16)	0.0391 (4)
H14A	0.8149	0.7205	0.9166	0.047*
H14B	0.9386	0.6767	0.9212	0.047*
C15	0.80610 (17)	0.71083 (18)	0.68622 (18)	0.0432 (4)
H15A	0.8371	0.7396	0.6231	0.052*
H15B	0.7515	0.7639	0.7279	0.052*
C16	0.73510 (17)	0.57148 (18)	0.62816 (17)	0.0434 (4)
H16A	0.6648	0.5633	0.5727	0.052*
H16B	0.7879	0.5192	0.5811	0.052*
C17	0.9810 (2)	0.86274 (19)	0.8371 (2)	0.0587 (6)
H17A	0.9272	0.9131	0.8826	0.088*
H17B	1.0105	0.8947	0.7763	0.088*
H17C	1.0498	0.8690	0.8918	0.088*
C18	0.25857 (15)	0.34060 (16)	0.86950 (s15)	0.0335 (4)
C19	0.38438 (14)	0.42305 (15)	0.93586 (14)	0.0311 (3)
C20	0.46415 (16)	0.37370 (17)	0.98691 (18)	0.0426 (4)
H20A	0.4412	0.2880	0.9783	0.051*
C21	0.57784 (16)	0.44940 (17)	1.05081 (19)	0.0434 (4)
H21A	0.6295	0.4141	1.0852	0.052*
H1W1	0.1161 (17)	0.6498 (18)	0.607 (2)	0.065*
H1W2	0.076 (2)	0.5375 (13)	0.629 (2)	0.065*
H2W1	0.161 (2)	0.5696 (12)	0.907 (2)	0.065*
H3W1	0.271 (2)	0.1053 (18)	0.9211 (17)	0.065*
H4W1	0.550 (2)	0.7200 (10)	0.7995 (19)	0.065*
H5W1	0.2664 (17)	0.787 (2)	0.7574 (12)	0.065*
H2W2	0.1932 (19)	0.6898 (17)	0.900 (2)	0.065*
H5W2	0.3756 (10)	0.805 (2)	0.8276 (19)	0.065*
H4W2	0.591 (2)	0.8406 (17)	0.8935 (13)	0.065*
H3W2	0.303 (2)	−0.0048 (15)	0.9206 (18)	0.065*
H1O	0.0850 (10)	0.1230 (19)	0.7420 (19)	0.065*
H3N	0.9643 (18)	0.682 (2)	0.7304 (19)	0.065*
H2O	−0.0366 (15)	0.1318 (19)	0.734 (2)	0.065*
H7W1	0.887 (2)	0.624 (2)	0.3214 (12)	0.065*
H7W2	0.9690 (16)	0.6912 (16)	0.4274 (17)	0.065*
H6W1	0.8902 (18)	0.311 (2)	0.9050 (12)	0.065*
H6W2	0.9887 (11)	0.330 (2)	0.8411 (19)	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.02475 (18)	0.02569 (18)	0.0422 (2)	−0.00318 (13)	−0.00723 (14)	0.01368 (15)
F1	0.0427 (6)	0.0294 (5)	0.0652 (7)	−0.0028 (4)	−0.0135 (5)	0.0234 (5)
O1	0.0340 (6)	0.0271 (6)	0.0653 (9)	−0.0040 (5)	−0.0115 (6)	0.0185 (6)
O1W	0.1294 (17)	0.0606 (11)	0.1088 (15)	0.0548 (11)	0.0819 (13)	0.0552 (11)
O2	0.0359 (7)	0.0407 (8)	0.1243 (14)	0.0035 (6)	0.0029 (8)	0.0481 (9)
O2W	0.0527 (9)	0.0580 (10)	0.0800 (12)	0.0161 (8)	0.0081 (8)	0.0166 (9)
O3	0.0257 (6)	0.0328 (6)	0.0523 (7)	−0.0024 (5)	−0.0070 (5)	0.0225 (6)
O3W	0.0795 (11)	0.0500 (9)	0.0772 (12)	0.0130 (8)	−0.0082 (9)	0.0290 (8)
O4	0.0378 (7)	0.0445 (7)	0.0446 (8)	0.0001 (6)	−0.0074 (6)	0.0110 (6)
O4W	0.0744 (11)	0.0449 (9)	0.0718 (11)	0.0043 (8)	−0.0024 (9)	0.0109 (8)
O5	0.0393 (7)	0.0338 (6)	0.0463 (7)	−0.0006 (5)	−0.0086 (5)	0.0122 (6)
O5W	0.0653 (10)	0.0660 (10)	0.0599 (10)	0.0114 (9)	−0.0115 (8)	0.0163 (8)
O6	0.0359 (7)	0.0423 (7)	0.0594 (8)	0.0026 (5)	−0.0121 (6)	0.0195 (6)
O6W	0.0509 (9)	0.0728 (11)	0.0716 (11)	0.0146 (8)	0.0112 (8)	0.0246 (9)
O7W	0.0614 (9)	0.0354 (7)	0.0620 (9)	−0.0024 (6)	−0.0176 (7)	0.0213 (7)
N1	0.0278 (7)	0.0320 (7)	0.0379 (8)	0.0044 (5)	0.0000 (5)	0.0158 (6)
N2	0.0293 (7)	0.0371 (8)	0.0362 (8)	−0.0074 (6)	−0.0069 (6)	0.0198 (6)
N3	0.0276 (7)	0.0309 (7)	0.0444 (8)	−0.0012 (6)	0.0038 (6)	0.0120 (6)
C1	0.0309 (8)	0.0268 (8)	0.0438 (10)	0.0025 (6)	0.0042 (7)	0.0157 (7)
C2	0.0276 (8)	0.0276 (8)	0.0328 (8)	0.0016 (6)	0.0027 (6)	0.0121 (7)
C3	0.0261 (7)	0.0276 (8)	0.0293 (8)	0.0006 (6)	0.0021 (6)	0.0120 (6)
C4	0.0251 (7)	0.0277 (8)	0.0288 (8)	0.0010 (6)	0.0006 (6)	0.0120 (6)
C5	0.0265 (8)	0.0323 (8)	0.0342 (8)	0.0008 (6)	−0.0040 (6)	0.0157 (7)
C6	0.0357 (9)	0.0270 (8)	0.0363 (9)	0.0003 (7)	−0.0027 (7)	0.0160 (7)
C7	0.0282 (8)	0.0325 (8)	0.0300 (8)	−0.0033 (6)	−0.0011 (6)	0.0138 (7)
C8	0.0240 (7)	0.0366 (9)	0.0342 (8)	0.0009 (6)	−0.0008 (6)	0.0158 (7)
C9	0.0273 (8)	0.0296 (8)	0.0292 (8)	0.0021 (6)	0.0019 (6)	0.0137 (6)
C10	0.0322 (8)	0.0297 (8)	0.0388 (9)	0.0051 (7)	0.0038 (7)	0.0168 (7)
C11	0.0314 (8)	0.0373 (9)	0.0473 (10)	0.0084 (7)	−0.0021 (7)	0.0187 (8)
C12	0.0513 (11)	0.0531 (12)	0.0483 (11)	0.0085 (9)	−0.0065 (9)	0.0220 (10)
C13	0.0311 (8)	0.0408 (9)	0.0410 (10)	−0.0034 (7)	−0.0049 (7)	0.0218 (8)
C14	0.0310 (8)	0.0426 (10)	0.0376 (9)	−0.0021 (7)	−0.0031 (7)	0.0153 (8)
C15	0.0372 (9)	0.0433 (10)	0.0513 (11)	−0.0016 (8)	−0.0008 (8)	0.0272 (9)
C16	0.0411 (10)	0.0461 (10)	0.0386 (10)	−0.0087 (8)	−0.0050 (8)	0.0227 (8)
C17	0.0507 (12)	0.0362 (10)	0.0724 (15)	−0.0085 (9)	−0.0010 (10)	0.0129 (10)
C18	0.0311 (8)	0.0363 (9)	0.0295 (8)	0.0024 (7)	0.0008 (6)	0.0118 (7)
C19	0.0279 (8)	0.0331 (8)	0.0289 (8)	0.0036 (6)	0.0020 (6)	0.0103 (7)
C20	0.0350 (9)	0.0318 (9)	0.0586 (12)	0.0017 (7)	−0.0048 (8)	0.0193 (8)
C21	0.0328 (9)	0.0392 (10)	0.0603 (12)	0.0035 (7)	−0.0081 (8)	0.0253 (9)

Geometric parameters (Å, º) top

Mn1—O3	2.1261 (12)	C2—C10	1.376 (2)
Mn1—O3ⁱ	2.1261 (12)	C2—C3	1.428 (2)
Mn1—O1	2.1569 (13)	C3—C4	1.455 (2)
Mn1—O1ⁱ	2.1569 (13)	C4—C5	1.404 (2)
Mn1—O4ⁱ	2.2223 (15)	C4—C9	1.404 (2)
Mn1—O4	2.2223 (15)	C5—C6	1.354 (2)
F1—C6	1.3621 (19)	C5—H5A	0.9300
O1—C1	1.258 (2)	C6—C7	1.410 (2)
O1W—H1W1	0.841 (9)	C7—C8	1.382 (2)
O1W—H1W2	0.840 (9)	C8—C9	1.409 (2)
O2—C1	1.241 (2)	C8—H8A	0.9300
O2W—H2W1	0.846 (9)	C10—H10A	0.9300
O2W—H2W2	0.849 (9)	C11—C12	1.504 (3)
O3—C3	1.2646 (19)	C11—H11A	0.9700
O3W—H3W1	0.851 (9)	C11—H11B	0.9700
O3W—H3W2	0.843 (9)	C12—H12A	0.9600
O4—H1O	0.848 (9)	C12—H12B	0.9600
O4—H2O	0.853 (9)	C12—H12C	0.9600
O4W—H4W1	0.853 (9)	C13—C14	1.515 (2)
O4W—H4W2	0.849 (9)	C13—H13A	0.9700
O5—C18	1.254 (2)	C13—H13B	0.9700
O5W—H5W1	0.848 (9)	C14—H14A	0.9700
O5W—H5W2	0.852 (9)	C14—H14B	0.9700
O6—C18	1.260 (2)	C15—C16	1.511 (2)
O6W—H6W1	0.857 (9)	C15—H15A	0.9700
O6W—H6W2	0.855 (9)	C15—H15B	0.9700
O7W—H7W1	0.849 (9)	C16—H16A	0.9700
O7W—H7W2	0.857 (9)	C16—H16B	0.9700
N1—C10	1.341 (2)	C17—H17A	0.9600
N1—C9	1.398 (2)	C17—H17B	0.9600
N1—C11	1.483 (2)	C17—H17C	0.9600
N2—C7	1.406 (2)	C18—C19	1.516 (2)
N2—C13	1.461 (2)	C19—C20	1.380 (2)
N2—C16	1.476 (2)	C19—C21ⁱⁱ	1.385 (2)
N3—C17	1.485 (2)	C20—C21	1.386 (2)
N3—C14	1.488 (2)	C20—H20A	0.9300
N3—C15	1.496 (2)	C21—C19ⁱⁱ	1.385 (2)
N3—H3N	0.911 (10)	C21—H21A	0.9300
C1—C2	1.507 (2)

O3—Mn1—O3ⁱ	180.0	C9—C8—H8A	119.7
O3—Mn1—O1	82.48 (5)	N1—C9—C4	117.96 (13)
O3ⁱ—Mn1—O1	97.52 (5)	N1—C9—C8	121.74 (14)
O3—Mn1—O1ⁱ	97.52 (5)	C4—C9—C8	120.29 (14)
O3ⁱ—Mn1—O1ⁱ	82.48 (5)	N1—C10—C2	125.66 (15)
O1—Mn1—O1ⁱ	180.0	N1—C10—H10A	117.2
O3—Mn1—O4ⁱ	91.74 (5)	C2—C10—H10A	117.2
O3ⁱ—Mn1—O4ⁱ	88.26 (5)	N1—C11—C12	111.96 (15)
O1—Mn1—O4ⁱ	91.32 (5)	N1—C11—H11A	109.2
O1ⁱ—Mn1—O4ⁱ	88.68 (5)	C12—C11—H11A	109.2
O3—Mn1—O4	88.26 (5)	N1—C11—H11B	109.2
O3ⁱ—Mn1—O4	91.74 (5)	C12—C11—H11B	109.2
O1—Mn1—O4	88.68 (5)	H11A—C11—H11B	107.9
O1ⁱ—Mn1—O4	91.32 (5)	C11—C12—H12A	109.5
O4ⁱ—Mn1—O4	180.0	C11—C12—H12B	109.5
C1—O1—Mn1	134.01 (10)	H12A—C12—H12B	109.5
H1W1—O1W—H1W2	112.1 (15)	C11—C12—H12C	109.5
H2W1—O2W—H2W2	109.9 (15)	H12A—C12—H12C	109.5
C3—O3—Mn1	128.61 (10)	H12B—C12—H12C	109.5
H3W1—O3W—H3W2	109.5 (15)	N2—C13—C14	108.54 (14)
Mn1—O4—H1O	116.7 (15)	N2—C13—H13A	110.0
Mn1—O4—H2O	116.2 (16)	C14—C13—H13A	110.0
H1O—O4—H2O	108.8 (14)	N2—C13—H13B	110.0
H4W1—O4W—H4W2	109.3 (14)	C14—C13—H13B	110.0
H5W1—O5W—H5W2	108.8 (14)	H13A—C13—H13B	108.4
H6W1—O6W—H6W2	107.5 (14)	N3—C14—C13	110.71 (14)
H7W1—O7W—H7W2	108.5 (14)	N3—C14—H14A	109.5
C10—N1—C9	119.52 (14)	C13—C14—H14A	109.5
C10—N1—C11	118.21 (14)	N3—C14—H14B	109.5
C9—N1—C11	122.10 (13)	C13—C14—H14B	109.5
C7—N2—C13	117.36 (13)	H14A—C14—H14B	108.1
C7—N2—C16	115.44 (13)	N3—C15—C16	110.30 (15)
C13—N2—C16	109.53 (13)	N3—C15—H15A	109.6
C17—N3—C14	111.28 (15)	C16—C15—H15A	109.6
C17—N3—C15	111.36 (15)	N3—C15—H15B	109.6
C14—N3—C15	110.75 (13)	C16—C15—H15B	109.6
C17—N3—H3N	107.0 (15)	H15A—C15—H15B	108.1
C14—N3—H3N	110.6 (15)	N2—C16—C15	110.04 (15)
C15—N3—H3N	105.7 (15)	N2—C16—H16A	109.7
O2—C1—O1	123.65 (15)	C15—C16—H16A	109.7
O2—C1—C2	117.11 (15)	N2—C16—H16B	109.7
O1—C1—C2	119.21 (14)	C15—C16—H16B	109.7
C10—C2—C3	118.45 (14)	H16A—C16—H16B	108.2
C10—C2—C1	116.66 (14)	N3—C17—H17A	109.5
C3—C2—C1	124.89 (14)	N3—C17—H17B	109.5
O3—C3—C2	125.65 (14)	H17A—C17—H17B	109.5
O3—C3—C4	118.56 (14)	N3—C17—H17C	109.5
C2—C3—C4	115.78 (14)	H17A—C17—H17C	109.5
C5—C4—C9	118.85 (14)	H17B—C17—H17C	109.5
C5—C4—C3	118.57 (14)	O5—C18—O6	124.04 (15)
C9—C4—C3	122.54 (14)	O5—C18—C19	118.20 (15)
C6—C5—C4	119.38 (15)	O6—C18—C19	117.75 (15)
C6—C5—H5A	120.3	C20—C19—C21ⁱⁱ	117.87 (15)
C4—C5—H5A	120.3	C20—C19—C18	120.83 (15)
C5—C6—F1	118.66 (15)	C21ⁱⁱ—C19—C18	121.29 (15)
C5—C6—C7	123.54 (15)	C19—C20—C21	121.25 (16)
F1—C6—C7	117.73 (14)	C19—C20—H20A	119.4
C8—C7—N2	124.55 (15)	C21—C20—H20A	119.4
C8—C7—C6	117.26 (14)	C19ⁱⁱ—C21—C20	120.88 (17)
N2—C7—C6	118.06 (15)	C19ⁱⁱ—C21—H21A	119.6
C7—C8—C9	120.62 (15)	C20—C21—H21A	119.6
C7—C8—H8A	119.7

O3—Mn1—O1—C1	17.92 (17)	F1—C6—C7—N2	−1.0 (2)
O3ⁱ—Mn1—O1—C1	−162.08 (17)	N2—C7—C8—C9	176.65 (15)
O1ⁱ—Mn1—O1—C1	22 (19)	C6—C7—C8—C9	1.0 (2)
O4ⁱ—Mn1—O1—C1	109.51 (17)	C10—N1—C9—C4	−2.6 (2)
O4—Mn1—O1—C1	−70.49 (17)	C11—N1—C9—C4	−177.88 (14)
O3ⁱ—Mn1—O3—C3	149 (31)	C10—N1—C9—C8	178.36 (15)
O1—Mn1—O3—C3	−24.78 (14)	C11—N1—C9—C8	3.0 (2)
O1ⁱ—Mn1—O3—C3	155.22 (14)	C5—C4—C9—N1	178.58 (14)
O4ⁱ—Mn1—O3—C3	−115.88 (14)	C3—C4—C9—N1	0.8 (2)
O4—Mn1—O3—C3	64.12 (14)	C5—C4—C9—C8	−2.3 (2)
Mn1—O1—C1—O2	169.97 (15)	C3—C4—C9—C8	179.90 (15)
Mn1—O1—C1—C2	−8.1 (3)	C7—C8—C9—N1	−179.75 (15)
O2—C1—C2—C10	−2.4 (2)	C7—C8—C9—C4	1.2 (2)
O1—C1—C2—C10	175.82 (16)	C9—N1—C10—C2	1.5 (3)
O2—C1—C2—C3	177.16 (17)	C11—N1—C10—C2	177.01 (16)
O1—C1—C2—C3	−4.7 (3)	C3—C2—C10—N1	1.5 (3)
Mn1—O3—C3—C2	23.6 (2)	C1—C2—C10—N1	−178.98 (16)
Mn1—O3—C3—C4	−157.54 (11)	C10—N1—C11—C12	−93.51 (19)
C10—C2—C3—O3	175.89 (16)	C9—N1—C11—C12	81.9 (2)
C1—C2—C3—O3	−3.6 (3)	C7—N2—C13—C14	−162.98 (15)
C10—C2—C3—C4	−3.0 (2)	C16—N2—C13—C14	62.85 (19)
C1—C2—C3—C4	177.45 (15)	C17—N3—C14—C13	−179.95 (16)
O3—C3—C4—C5	5.2 (2)	C15—N3—C14—C13	55.6 (2)
C2—C3—C4—C5	−175.80 (14)	N2—C13—C14—N3	−59.88 (19)
O3—C3—C4—C9	−177.03 (15)	C17—N3—C15—C16	−178.28 (16)
C2—C3—C4—C9	2.0 (2)	C14—N3—C15—C16	−53.9 (2)
C9—C4—C5—C6	1.2 (2)	C7—N2—C16—C15	162.65 (15)
C3—C4—C5—C6	179.08 (15)	C13—N2—C16—C15	−62.2 (2)
C4—C5—C6—F1	−175.97 (14)	N3—C15—C16—N2	57.0 (2)
C4—C5—C6—C7	1.1 (3)	O5—C18—C19—C20	−10.7 (2)
C13—N2—C7—C8	−13.3 (2)	O6—C18—C19—C20	168.18 (17)
C16—N2—C7—C8	118.21 (19)	O5—C18—C19—C21ⁱⁱ	170.47 (17)
C13—N2—C7—C6	162.27 (16)	O6—C18—C19—C21ⁱⁱ	−10.7 (2)
C16—N2—C7—C6	−66.2 (2)	C21ⁱⁱ—C19—C20—C21	0.8 (3)
C5—C6—C7—C8	−2.2 (3)	C18—C19—C20—C21	−178.11 (17)
F1—C6—C7—C8	174.87 (15)	C19—C20—C21—C19ⁱⁱ	−0.8 (3)
C5—C6—C7—N2	−178.13 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O···O5	0.85 (1)	1.91 (1)	2.7565 (18)	173 (2)
N3—H3N···O1Wⁱⁱⁱ	0.91 (1)	1.71 (1)	2.618 (2)	174 (2)
O1W—H1W1···O2^iv	0.84 (1)	1.81 (1)	2.644 (2)	169 (2)
O4—H2O···O6W^v	0.85 (1)	1.98 (1)	2.787 (2)	157 (2)
O7W—H7W1···O6^vi	0.85 (1)	1.98 (1)	2.828 (2)	173 (2)
O7W—H7W2···O1^vii	0.86 (1)	1.95 (1)	2.8013 (18)	174 (2)
O1W—H1W2···O7W^vi	0.84 (1)	1.83 (1)	2.662 (2)	175 (2)
O2W—H2W1···O6	0.85 (1)	1.92 (1)	2.764 (2)	172 (3)
O3W—H3W1···O5	0.85 (1)	1.95 (1)	2.797 (2)	171 (2)
O6W—H6W1···O2Wⁱⁱ	0.86 (1)	1.93 (1)	2.785 (3)	174 (2)
O4W—H4W1···F1	0.85 (1)	2.29 (1)	2.976 (2)	138 (2)
O6W—H6W2···O6ⁱⁱⁱ	0.86 (1)	2.13 (1)	2.972 (2)	170 (2)
O5W—H5W1···O2^iv	0.85 (1)	2.20 (1)	3.023 (3)	164 (2)
O2W—H2W2···O5W	0.85 (1)	2.07 (1)	2.912 (3)	175 (2)
O5W—H5W2···O4W	0.85 (1)	1.92 (1)	2.774 (3)	178 (3)
O4W—H4W2···O3Wⁱⁱ	0.85 (1)	1.96 (1)	2.801 (3)	170 (2)
O3W—H3W2···O5W^viii	0.84 (1)	1.99 (1)	2.802 (3)	162 (2)

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

Experimental details

Crystal data
Chemical formula	[Mn(C₁₇H₂₀FN₃O₃)₂(H₂O)₂](C₈H₄O₄)·14H₂O
M_r	1174.03
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	11.147 (3), 11.500 (3), 11.832 (3)
α, β, γ (°)	111.722 (4), 92.011 (4), 102.066 (4)
V (Å³)	1367.3 (6)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.34 × 0.26 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.894, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	11720, 5353, 4645
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 1.03
No. of reflections	5353
No. of parameters	402
No. of restraints	25
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected bond lengths (Å) top

Mn1—O3	2.1261 (12)	Mn1—O4	2.2223 (15)
Mn1—O1	2.1569 (13)