Second-sphere coordination in anion binding: sodium hexa­ammine­cobalt(III) tetra­kis­(4-fluoro­benzoate) monohydrate

In sodium hexa­amminecobalt(III) tetra­kis­(4-fluoro­benzoate) monohydrate, Na[Co(NH₃)₆](C₇H₄FO₂)₄·H₂O, determined at 180 K, [Co(NH₃)₆]³⁺ cations lie on centres of inversion and form layers in which their C₄ axes lie perpendicular to the layer planes. 4-Fluoro­benzoate anions lie on twofold axes and general positions and adopt near-planar geometries. Na⁺ cations and water mol­ecules lie on twofold axes, forming [NaO₅] square pyramids that lie between the [Co(NH₃)₆]³⁺ cations. The second-sphere inter­actions between [Co(NH₃)₆]³⁺ cations and 4-fluorobenzoate anions comprise edge-to-face and vertex-to-face arrangements. The structure is closely comparable with that of the benzoic acid salt, demonstrating that fluorination of the anion in the para position has no significant influence on the second-sphere inter­actions and minimal influence on the gross crystal structure.

S1. Comment

We are currently engaged in studies to explore cobalt(III) complexes as potential anion receptors and have reported previously the crystal structures of some hexaamminecobalt(III) salts with organic sulphonate (Sharma et al., 2004) and benzoate anions (Sharma et al., 2005). The cation [Co(NH₃)₆]³⁺ has also been characterized previously in several structures containing organic carboxylate anions, including [Co(NH₃)₆]₂(Ox)₃·4H₂O (Ox is oxalate; Gorol et al., 2000) and [Co(NH₃)₆][(NpO₂)₂(HMal)(Mal)]·Mal (Mal is malonate; Grigor'ev et al. 2004). In continuation of our interest in this class of compounds, we describe here the crystal structure of sodium hexaamminecobalt(III) para-fluorobenzoate monohydrate, Na[Co(NH₃)₆](FC₆H₄CO₂)₄·H₂O, (I) (Fig. 1).

In compound (I), the [Co(NH₃)₆]³⁺ cations lie on centres of inversion, with an approximately regular octahedral coordination geometry about Co1 (Table 1). There are three crystallographically distinct para-fluorobenzoate anions: one (containing atom F1) lies on a general position, and two (containing atoms F2 and F3) lie on twofold axes. The bond distances and angles in each case are unremarkable. The dihedral angles between the least-squares plane through the six C atoms of the phenyl ring and the plane of the carboxylate group are 8.6 (1), 13.4 (1) and 2.1 (1)° in the three distinct moieties, respectively. Similar near-planar geometry is observed for para-fluorobenzoate or para-fluorobenzoic acid in the relatively small number of crystal structures reported previously. Of 11 examples in the Cambridge Structural Database (November 2004 release plus 2 updates; Allen, 2002), the maximum dihedral angle is ca 18° in the Cu^II complex salt [Cu(NH₂(CH₂)₂NH(CH₂)₂OH)₂](FC₆H₄CO₂)₂ (Qu et al., 2004).

The [Co(NH₃)₆]³⁺ cations in (I) are arranged into layers parallel to the ac plane, lying at y = 1/4 and y = 3/4. The C₄ axes of the cations lie approximately perpendicular to the layer planes (Fig. 2). The Na⁺ cations and water molecules also lie within these layers, so that the hydrophobic and charged portions of the structure are segregated. The FC₆H₄CO₂⁻ anions display essentially two modes of interaction with the [Co(NH₃)₆]³⁺ anions, namely edge-to-face and vertex-to-face (Fig. 3). In the first crystallographically distinct anion (containing atoms O1 and O2), the CO₂⁻ group forms an edge-to-face interaction with a neighbouring [Co(NH₃)₆]³⁺ cation [N1—H11···O1ⁱⁱⁱ, N2—H21···O2ⁱⁱⁱ and N3—H31···O2ⁱⁱⁱ; symmetry code (iii) x, y, z − 1; Table 2]. One O atom of the same CO₂⁻ group (O1) also forms a vertex-to-face interaction with a second [Co(NH₃)₆]³⁺ cation, in which all three N···O contacts are of comparable magnitude [N1—H13···O1ⁱⁱ, N2—H23···O1 and N3—H32···O1ⁱⁱ; symmetry code (ii) 1/2 − x, 1/2 − y, 1 − z]. Atom O2 also forms two opposing corners in the basal plane of the square-pyramidal twofold symmetric coordination environment of Na1 (Table 1). In the other two crystallographically distinct FC₆H₄CO₂⁻ anions, the two O atoms of each CO₂⁻ group form identical interactions (related by twofold rotation axes). In the first anion, atom O3 forms a vertex-to-face interaction comprising one clear non-hydrogen-bonded N···O contact [N2···O3 3.4419 (16) Å], one intermediate N···O contact with a bent N—H···O geometry [N3···O3 3.1548 (16) Å and N3—H33···O3 122 (2)°], and one clear hydrogen bond (N1—H12···O3ⁱⁱ; Table 2). The same O atom also forms the remaining two corners of the basal plane around Na1. In the second anion, atom O4 forms a more symmetrical vertex-to-face interaction with [Co(NH₃)₆]³⁺, comprising two clear hydrogen bonds (N2—H22···O4 and N3—H33···O4ⁱⁱ; Table 2) and one longer bent N—H···O contact [N1···H12 2.9533 (15) Å and N1—H12···O4 103 (1)°].

In projection onto the plane of a single layer (Fig. 4), the [Co(NH₃)₆]³⁺ cations of (I) form an approximate primitive rectangular arrangement of dimensions ca 6.5 × 7.5 Å. The shorter side of the rectangular arrangement is formed by [Co(NH₃)₆]³⁺ cations linked via the anions containing atoms O1 and O2, and the longer sides of the rectangles are linked by anions containing atoms O3 and O4. The centres of these rectangles are occupied by Na⁺ ions. The axial coordination site of Na1 is occupied by a water molecule, which forms O—H···O hydrogen bonds to atom O4 (Table 2). The [NaO₅] square pyramids are situated so that the axial water molecules lie on twofold axes and point into the centres of the layers. Between layers, the phenyl rings of the FC₆H₄CO₂⁻ anions interdigitate in an edge-to-face manner similar to that observed in p-FC₆H₄NH₃⁺X⁻ (X is Br or I), for example (Klebe et al., 1983).

The structure of (I) is closely comparable with that of the benzoate salt Na[Co(NH₃)₆](C₆H₅CO₂)₄·H₂O (Sharma et al., 2005). The layers in the ac plane are essentially identical in both cases, but the structure of (I) expands by ca 1 Å along the b direction to accommodate the fluoro-substituents. This demonstrates that fluorination of the benzoate anion in the para-position has no significant influence on its second-sphere interactions with [Co(NH₃)₆]³⁺, and minimal influence on the gross crystal structure.

S2. Experimental

Hexaamminecobalt(III) chloride (1 g, 0.003 mol) was dissolved in hot water (20 ml) with mechanical stirring. In a second beaker, the sodium salt of para-fluorobenzoic acid (1.825 g, 0.011 mol) was dissolved in hot water (20 ml). These solutions were mixed and allowed to cool slowly to room temperature. After 1 d, orange crystals were formed, which were filtered off and dried in air. The overall yield is quantitative (m.p. 478 K). Elemental analysis is consistent with the composition Na[Co(NH₃)₆](FC₆H₄CO₂)₄·H₂O.

S3. Refinement

H atoms bound to C atoms were placed in calculated positions and allowed to ride during subsequent refinement, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). H atoms of the NH₃ groups were located in difference Fourier maps and refined with isotropic displacement parameters. All nine independent N—H bond lengths were restrained to a common refined value with a standard uncertainty of 0.01 Å. The single unique H atom of the water molecule was also located in a difference Fourier map and refined isotropically without restraint.

Computing details

Data collection: APEX2 (Bruker Nonius, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular units in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (ii) 1/2 − x, 1/2 − y, 1 − z; (iv) −x, y, 1/2 − z; (v) 1 − x, y, 3/2 − z.]
	Fig. 2. A projection of the unit cell of (I) along the c direction, showing layers of [Co(NH3)6]^3+ cations lying parallel to the ac plane at y = 1/4 and y = 3/4. The organic anions are interdigitated between these layers. H atoms have been omitted.
	Fig. 3. The second-sphere coordination of the [Co(NH3)6]^3+ cation in (I). The CO2^− group containing atoms O1 and O2 forms an edge-to-face interaction, while the other three interactions shown are vertex-to-face. Atom Co1 lies on a centre of inversion so that a comparable arrangement is formed on the opposite side of the plane (not shown). H atoms have been omitted. [Symmetry codes: (ii) 1/2 − x, 1/2 − y, 1 − z; (iii) x, y, z − 1.]
	Fig. 4. A projection onto the plane of a single layer, showing the approximate rectangular arrangement of [Co(NH3)6]^3+ cations, with Na^+ cations between them. The [NaO5] square pyramids are viewed in projection along their axial Na1—O1W vectors, which point upwards for [NaO5] lying close to the corners of the unit cell and downwards for [NaO5] lying close to the middle of the unit cell. H atoms have been omitted.

sodium hexaamminecobalt(III) tetrakis(4-fluorobenzoate) monohydrate

Crystal data

Na[Co(NH3)6](C7H4FO2)4·H2O	F(000) = 1568
Mr = 758.55	Dx = 1.543 Mg m^−3
Monoclinic, C2/c	Melting point: 478 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 16.1930 (4) Å	Cell parameters from 6005 reflections
b = 33.4500 (9) Å	θ = 2.3–28.0°
c = 6.5169 (2) Å	µ = 0.62 mm^−1
β = 112.349 (1)°	T = 180 K
V = 3264.77 (16) Å^3	Block, orange
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection

Bruker Nonius X8APEX-II CCD area-detector diffractometer	3531 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
thin–slice ω and ϕ scans	θmax = 28.0°, θmin = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Ratio of minimum to maximum apparent transmission 0.788976	h = −20→18
Tmin = 0.699, Tmax = 0.886	k = −40→44
11474 measured reflections	l = −7→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0506P)^2 + 1.8227P] where P = (Fo^2 + 2Fc^2)/3
3531 reflections	(Δ/σ)max = 0.001
269 parameters	Δρmax = 0.58 e Å^−3
9 restraints	Δρmin = −0.24 e Å^−3

Special details

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

ANION 1 =======

3.4563(0.0121) x − 1.8736(0.0194) y + 5.3499(0.0029) z = 5.4140(0.0084)

* 0.0006 (0.0010) C2 * −0.0049 (0.0011) C3 * 0.0045 (0.0012) C4 * 0.0003 (0.0011) C5 * −0.0046 (0.0012) C6 * 0.0042 (0.0012) C7

Rms deviation of fitted atoms = 0.0037

1.0715(0.0118) x − 1.1486(0.0826) y + 5.8466(0.0019) z = 5.6279(0.0277)

Angle to previous plane (with approximate e.s.d.) = 8.63 (0.08)

* 0.0000 (0.0000) C1 * 0.0000 (0.0000) O1 * 0.0000 (0.0000) O2

Rms deviation of fitted atoms = 0.0000

ANION 2 =======

−15.2312(0.0057) x − 0.0000(0.0002) y + 4.3772(0.0050) z = 1.0943(0.0012)

* 0.0000 (0.0000) C9 * 0.0056 (0.0012) C10 * −0.0055 (0.0012) C11 * 0.0000 (0.0000) C12 * −0.0056 (0.0012) C10 * 0.0055 (0.0012) C11

Rms deviation of fitted atoms = 0.0045

− 16.0890(0.0018) x + 0.0000(0.0003) y + 3.1441(0.0053) z = 0.7860(0.0013)

Angle to previous plane (with approximate e.s.d.) = 13.35 (0.06)

* 0.0000 (0.0000) C8 * 0.0000 (0.0000) O3 * 0.0000 (0.0000) O3

Rms deviation of fitted atoms = 0.0000

ANION 3 ======= 15.6103(0.0047) x − 0.0000(0.0003) y − 3.9912(0.0056) z = 4.8118(0.0065)

* 0.0000 (0.0000) C14 * 0.0030 (0.0013) C15 * −0.0030 (0.0013) C16 * 0.0000 (0.0000) C17 * −0.0030 (0.0013) C15 * 0.0030 (0.0013) C16

Rms deviation of fitted atoms = 0.0025

15.4428(0.0048) x + 0.0000(0.0003) y − 4.1766(0.0049) z = 4.5889(0.0060)

Angle to previous plane (with approximate e.s.d.) = 2.09 (0.07)

* 0.0000 (0.0000) C13 * 0.0000 (0.0000) O4 * 0.0000 (0.0000) O4

Rms deviation of fitted atoms = 0.0000

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.0000	0.30706 (2)	0.7500	0.02469 (19)
Co1	0.2500	0.2500	0.5000	0.01635 (9)
N1	0.32012 (8)	0.24780 (3)	0.3142 (2)	0.0199 (2)
H12	0.3743 (8)	0.2401 (5)	0.395 (3)	0.038 (5)*
H11	0.3206 (14)	0.2701 (4)	0.245 (3)	0.049 (6)*
H13	0.2979 (11)	0.2295 (4)	0.211 (3)	0.031 (5)*
N2	0.25725 (8)	0.30863 (4)	0.50156 (18)	0.0216 (3)
H21	0.2136 (10)	0.3202 (5)	0.393 (3)	0.047 (6)*
H22	0.3084 (9)	0.3156 (5)	0.495 (3)	0.038 (5)*
H23	0.2581 (13)	0.3179 (5)	0.628 (2)	0.041 (5)*
N3	0.14240 (8)	0.25011 (3)	0.2282 (2)	0.0209 (3)
H31	0.1394 (12)	0.2721 (4)	0.152 (3)	0.032 (5)*
H32	0.1425 (12)	0.2301 (4)	0.141 (3)	0.030 (5)*
H33	0.0940 (11)	0.2476 (5)	0.254 (4)	0.054 (7)*
O1	0.27698 (7)	0.31719 (3)	0.97414 (17)	0.0297 (2)
O2	0.14494 (7)	0.32681 (3)	1.00023 (17)	0.0283 (2)
O3	0.03594 (7)	0.30544 (3)	0.43393 (16)	0.0251 (2)
O4	0.45223 (7)	0.30789 (3)	0.57339 (18)	0.0291 (2)
F1	0.27048 (9)	0.50546 (3)	1.01595 (18)	0.0560 (3)
F2	0.0000	0.49109 (4)	0.2500	0.0540 (4)
F3	0.5000	0.49354 (4)	0.7500	0.0590 (5)
C1	0.21670 (10)	0.33954 (4)	0.9896 (2)	0.0229 (3)
C2	0.23177 (10)	0.38393 (4)	0.9968 (2)	0.0234 (3)
C3	0.17330 (11)	0.40959 (5)	1.0425 (3)	0.0299 (3)
H3A	0.1239	0.3989	1.0688	0.036*
C4	0.18627 (12)	0.45061 (5)	1.0503 (3)	0.0367 (4)
H4A	0.1469	0.4681	1.0836	0.044*
C5	0.25735 (11)	0.46525 (5)	1.0087 (2)	0.0369 (4)
C6	0.31642 (12)	0.44119 (5)	0.9612 (3)	0.0399 (4)
H6A	0.3648	0.4523	0.9321	0.048*
C7	0.30349 (11)	0.40006 (5)	0.9568 (3)	0.0322 (3)
H7A	0.3440	0.3828	0.9262	0.039*
C8	0.0000	0.32280 (6)	0.2500	0.0195 (4)
C9	0.0000	0.36805 (6)	0.2500	0.0214 (4)
C10	0.05339 (10)	0.38922 (5)	0.4370 (2)	0.0282 (3)
H10A	0.0897	0.3751	0.5662	0.034*
C11	0.05441 (12)	0.43078 (5)	0.4381 (3)	0.0368 (4)
H11A	0.0916	0.4452	0.5650	0.044*
C12	0.0000	0.45025 (7)	0.2500	0.0353 (5)
C13	0.5000	0.32551 (6)	0.7500	0.0215 (4)
C14	0.5000	0.37072 (6)	0.7500	0.0230 (4)
C15	0.45117 (11)	0.39170 (5)	0.5582 (3)	0.0311 (3)
H15A	0.4178	0.3775	0.4263	0.037*
C16	0.45067 (12)	0.43336 (5)	0.5578 (3)	0.0407 (4)
H16A	0.4169	0.4479	0.4274	0.049*
C17	0.5000	0.45281 (7)	0.7500	0.0384 (5)
O1W	0.0000	0.23282 (5)	0.7500	0.0297 (3)
H1W	0.0088 (14)	0.2167 (6)	0.662 (3)	0.048 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0225 (4)	0.0291 (4)	0.0219 (4)	0.000	0.0079 (3)	0.000
Co1	0.01559 (15)	0.01713 (15)	0.01553 (14)	0.00076 (9)	0.00502 (10)	0.00016 (9)
N1	0.0190 (6)	0.0220 (6)	0.0194 (6)	0.0006 (5)	0.0082 (5)	−0.0007 (4)
N2	0.0234 (6)	0.0215 (6)	0.0194 (6)	0.0007 (5)	0.0078 (5)	0.0004 (4)
N3	0.0188 (6)	0.0231 (6)	0.0196 (6)	−0.0002 (5)	0.0059 (5)	0.0000 (5)
O1	0.0322 (6)	0.0273 (6)	0.0297 (5)	0.0031 (4)	0.0117 (4)	−0.0030 (4)
O2	0.0272 (5)	0.0267 (5)	0.0290 (5)	−0.0044 (4)	0.0084 (4)	0.0023 (4)
O3	0.0281 (5)	0.0249 (5)	0.0220 (5)	0.0054 (4)	0.0093 (4)	0.0035 (4)
O4	0.0285 (5)	0.0273 (5)	0.0305 (6)	−0.0054 (4)	0.0100 (4)	−0.0052 (4)
F1	0.0843 (8)	0.0234 (5)	0.0592 (7)	−0.0134 (5)	0.0259 (6)	−0.0006 (4)
F2	0.0798 (12)	0.0208 (7)	0.0602 (10)	0.000	0.0253 (9)	0.000
F3	0.0843 (13)	0.0208 (7)	0.0733 (11)	0.000	0.0314 (10)	0.000
C1	0.0244 (7)	0.0255 (7)	0.0155 (6)	−0.0013 (6)	0.0039 (5)	−0.0016 (5)
C2	0.0256 (7)	0.0229 (7)	0.0191 (7)	−0.0019 (5)	0.0057 (5)	−0.0006 (5)
C3	0.0307 (8)	0.0267 (8)	0.0343 (8)	−0.0023 (6)	0.0146 (6)	−0.0001 (6)
C4	0.0426 (9)	0.0268 (8)	0.0418 (9)	0.0040 (7)	0.0174 (8)	−0.0022 (7)
C5	0.0507 (11)	0.0216 (8)	0.0344 (9)	−0.0080 (7)	0.0117 (8)	0.0005 (6)
C6	0.0432 (10)	0.0375 (9)	0.0433 (10)	−0.0163 (8)	0.0213 (8)	−0.0014 (8)
C7	0.0313 (8)	0.0342 (8)	0.0340 (8)	−0.0030 (7)	0.0155 (7)	−0.0027 (7)
C8	0.0163 (9)	0.0233 (9)	0.0207 (9)	0.000	0.0089 (7)	0.000
C9	0.0203 (9)	0.0233 (10)	0.0214 (9)	0.000	0.0088 (7)	0.000
C10	0.0290 (8)	0.0281 (8)	0.0233 (7)	0.0000 (6)	0.0052 (6)	−0.0006 (6)
C11	0.0427 (10)	0.0281 (8)	0.0354 (9)	−0.0081 (7)	0.0103 (7)	−0.0070 (7)
C12	0.0467 (13)	0.0210 (11)	0.0420 (13)	0.000	0.0210 (11)	0.000
C13	0.0184 (9)	0.0232 (10)	0.0264 (10)	0.000	0.0125 (8)	0.000
C14	0.0197 (9)	0.0254 (10)	0.0243 (10)	0.000	0.0090 (8)	0.000
C15	0.0326 (8)	0.0277 (8)	0.0285 (8)	0.0004 (6)	0.0063 (6)	0.0025 (6)
C16	0.0483 (11)	0.0309 (9)	0.0398 (10)	0.0056 (7)	0.0131 (8)	0.0103 (7)
C17	0.0459 (14)	0.0212 (11)	0.0527 (15)	0.000	0.0239 (12)	0.000
O1W	0.0314 (8)	0.0305 (9)	0.0288 (8)	0.000	0.0135 (7)	0.000

Geometric parameters (Å, º)

Co1—N1	1.9510 (12)	C2—C7	1.392 (2)
Co1—N1^i	1.9511 (12)	C3—C4	1.386 (2)
Co1—N3^i	1.9562 (12)	C3—H3A	0.950
Co1—N3	1.9562 (12)	C4—C5	1.369 (2)
Co1—N2^i	1.9642 (13)	C4—H4A	0.950
Co1—N2	1.9643 (13)	C5—C6	1.373 (3)
Na1—O3^ii	2.3444 (10)	C6—C7	1.390 (2)
Na1—O3	2.3444 (10)	C6—H6A	0.950
Na1—O2	2.3861 (10)	C7—H7A	0.950
Na1—O2^ii	2.3862 (10)	C8—O3^iii	1.2578 (13)
Na1—O1W	2.4834 (19)	C8—C9	1.514 (3)
N1—H12	0.87 (1)	C9—C10	1.3904 (17)
N1—H11	0.87 (1)	C9—C10^iii	1.3904 (17)
N1—H13	0.88 (1)	C10—C11	1.390 (2)
N2—H21	0.88 (1)	C10—H10A	0.950
N2—H22	0.88 (1)	C11—C12	1.372 (2)
N2—H23	0.88 (1)	C11—H11A	0.950
N3—H31	0.88 (1)	C12—C11^iii	1.372 (2)
N3—H32	0.88 (1)	C13—O4^iv	1.2623 (14)
N3—H33	0.86 (1)	C13—C14	1.512 (3)
O1—C1	1.2635 (19)	C14—C15^iv	1.3885 (18)
O2—C1	1.2640 (18)	C14—C15	1.3886 (18)
O3—C8	1.2578 (13)	C15—C16	1.394 (2)
O4—C13	1.2623 (14)	C15—H15A	0.950
F1—C5	1.3598 (19)	C16—C17	1.367 (2)
F2—C12	1.366 (3)	C16—H16A	0.950
F3—C17	1.363 (3)	C17—C16^iv	1.367 (2)
C1—C2	1.503 (2)	O1W—H1W	0.84 (2)
C2—C3	1.391 (2)
O3—Na1—O3^ii	177.34 (6)	O1—C1—C2	117.78 (13)
O3^ii—Na1—O2	85.08 (4)	O2—C1—C2	118.22 (13)
O3—Na1—O2	95.66 (4)	C3—C2—C7	119.01 (15)
O3^ii—Na1—O2^ii	95.66 (4)	C3—C2—C1	120.04 (13)
O3—Na1—O2^ii	85.08 (4)	C7—C2—C1	120.94 (14)
O2—Na1—O2^ii	147.85 (6)	C4—C3—C2	120.82 (15)
O3^ii—Na1—O1W	88.67 (3)	C4—C3—H3A	119.6
O3—Na1—O1W	88.67 (3)	C2—C3—H3A	119.6
O2—Na1—O1W	106.07 (3)	C5—C4—C3	118.27 (16)
O2^ii—Na1—O1W	106.08 (3)	C5—C4—H4A	120.9
N1—Co1—N2	89.61 (5)	C3—C4—H4A	120.9
N1—Co1—N3	88.06 (5)	F1—C5—C4	118.61 (16)
N2—Co1—N3	91.93 (5)	F1—C5—C6	118.34 (15)
N1—Co1—N1^i	180.0	C4—C5—C6	123.05 (16)
N2—Co1—N2^i	180.0	C5—C6—C7	118.19 (16)
N3—Co1—N3^i	180.0	C5—C6—H6A	120.9
N1—Co1—N2^i	90.39 (5)	C7—C6—H6A	120.9
N1—Co1—N3^i	91.94 (5)	C6—C7—C2	120.64 (15)
N3—Co1—N2^i	88.07 (5)	C6—C7—H7A	119.7
N3^i—Co1—N2	88.06 (5)	C2—C7—H7A	119.7
N1^i—Co1—N2	90.39 (5)	O3^iii—C8—O3	125.01 (18)
N1^i—Co1—N3	91.94 (5)	O3^iii—C8—C9	117.49 (9)
N1^i—Co1—N3^i	88.06 (5)	O3—C8—C9	117.49 (9)
N1^i—Co1—N2^i	89.61 (5)	C10—C9—C10^iii	118.77 (19)
N3^i—Co1—N2^i	91.94 (5)	C10—C9—C8	120.61 (9)
Co1—N1—H12	109.0 (13)	C10^iii—C9—C8	120.61 (9)
Co1—N1—H11	114.2 (15)	C11—C10—C9	121.04 (14)
H12—N1—H11	111.0 (19)	C11—C10—H10A	119.5
Co1—N1—H13	109.6 (12)	C9—C10—H10A	119.5
H12—N1—H13	106.5 (17)	C12—C11—C10	117.91 (15)
H11—N1—H13	106 (2)	C12—C11—H11A	121.0
Co1—N2—O3	84.90 (4)	C10—C11—H11A	121.0
Co1—N2—H21	114.0 (13)	F2—C12—C11^iii	118.35 (11)
O3—N2—H21	55.4 (13)	F2—C12—C11	118.35 (11)
Co1—N2—H22	108.7 (12)	C11^iii—C12—C11	123.3 (2)
O3—N2—H22	163.5 (12)	O4—C13—O4^iv	124.32 (18)
H21—N2—H22	109.1 (18)	O4—C13—C14	117.84 (9)
Co1—N2—H23	109.8 (12)	O4^iv—C13—C14	117.84 (9)
O3—N2—H23	76.9 (13)	C15^iv—C14—C15	119.28 (19)
H21—N2—H23	108.9 (19)	C15^iv—C14—C13	120.36 (10)
H22—N2—H23	106.0 (18)	C15—C14—C13	120.36 (10)
Co1—N3—H31	110.7 (12)	C14—C15—C16	120.54 (15)
Co1—N3—H32	111.4 (12)	C14—C15—H15A	119.7
H31—N3—H32	106.4 (18)	C16—C15—H15A	119.7
Co1—N3—H33	112.7 (17)	C17—C16—C15	118.22 (16)
H31—N3—H33	109.3 (18)	C17—C16—H16A	120.9
H32—N3—H33	106.1 (18)	C15—C16—H16A	120.9
C1—O2—Na1	137.87 (9)	F3—C17—C16^iv	118.40 (11)
C8—O3—Na1	130.32 (7)	F3—C17—C16	118.41 (11)
C8—O3—N2	100.93 (6)	C16^iv—C17—C16	123.2 (2)
Na1—O3—N2	118.75 (4)	Na1—O1W—H1W	129.9 (14)
O1—C1—O2	124.00 (14)
N1—Co1—N2—O3	138.16 (4)	F1—C5—C6—C7	179.17 (14)
N1^i—Co1—N2—O3	−41.84 (4)	C4—C5—C6—C7	−0.4 (2)
N3^i—Co1—N2—O3	−129.89 (4)	C5—C6—C7—C2	0.8 (2)
N3—Co1—N2—O3	50.11 (4)	C3—C2—C7—C6	−0.3 (2)
O3^ii—Na1—O2—C1	−171.04 (14)	C1—C2—C7—C6	179.24 (14)
O3—Na1—O2—C1	11.53 (15)	Na1—O3—C8—O3^iii	−118.43 (11)
O2^ii—Na1—O2—C1	−78.23 (14)	N2—O3—C8—O3^iii	97.82 (5)
O1W—Na1—O2—C1	101.77 (14)	Na1—O3—C8—C9	61.58 (11)
O2—Na1—O3—C8	−125.27 (12)	N2—O3—C8—C9	−82.18 (4)
O2^ii—Na1—O3—C8	22.45 (13)	O3^iii—C8—C9—C10	−166.91 (9)
O1W—Na1—O3—C8	128.71 (12)	O3—C8—C9—C10	13.08 (9)
O2—Na1—O3—N2	13.26 (6)	O3^iii—C8—C9—C10^iii	13.09 (9)
O2^ii—Na1—O3—N2	160.98 (5)	O3—C8—C9—C10^iii	−166.91 (9)
O1W—Na1—O3—N2	−92.76 (4)	C10^iii—C9—C10—C11	−0.54 (12)
Co1—N2—O3—C8	−118.57 (10)	C8—C9—C10—C11	179.46 (12)
Co1—N2—O3—Na1	92.37 (5)	C9—C10—C11—C12	1.0 (2)
Na1—O2—C1—O1	−85.45 (18)	C10—C11—C12—F2	179.49 (11)
Na1—O2—C1—C2	94.87 (15)	C10—C11—C12—C11^iii	−0.51 (11)
O1—C1—C2—C3	−171.65 (13)	O4—C13—C14—C15^iv	177.76 (10)
O2—C1—C2—C3	8.05 (19)	O4^iv—C13—C14—C15^iv	−2.24 (10)
O1—C1—C2—C7	8.78 (19)	O4—C13—C14—C15	−2.24 (10)
O2—C1—C2—C7	−171.53 (13)	O4^iv—C13—C14—C15	177.76 (10)
C7—C2—C3—C4	−0.5 (2)	C15^iv—C14—C15—C16	−0.29 (12)
C1—C2—C3—C4	179.88 (13)	C13—C14—C15—C16	179.71 (12)
C2—C3—C4—C5	0.9 (2)	C14—C15—C16—C17	0.6 (2)
C3—C4—C5—F1	179.98 (14)	C15—C16—C17—F3	179.72 (12)
C3—C4—C5—C6	−0.4 (2)	C15—C16—C17—C16^iv	−0.28 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H12···O3^i	0.87 (1)	2.11 (1)	2.8962 (15)	150 (2)
N1—H11···O1^v	0.87 (1)	2.27 (1)	3.1000 (16)	159 (2)
N1—H13···O1^i	0.88 (1)	2.06 (1)	2.9124 (16)	163 (2)
N2—H21···O2^v	0.88 (1)	2.38 (2)	3.1357 (15)	144 (2)
N2—H22···O4	0.88 (1)	2.20 (1)	3.0108 (16)	153 (2)
N2—H23···O1	0.87 (1)	2.16 (1)	2.9867 (16)	158 (2)
N3—H31···O2^v	0.88 (1)	2.10 (1)	2.9730 (15)	174 (2)
N3—H32···O1^i	0.88 (1)	2.35 (1)	3.1335 (16)	149 (2)
N3—H33···O4^i	0.86 (1)	2.43 (2)	3.0481 (16)	129 (2)
O1W—H1W···O4^i	0.84 (2)	2.04 (2)	2.8519 (14)	163 (2)

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