Di­aqua­bis(1,10-phenanthroline)­cobalt(II) diorotate 2.25-hydrate

In the title compound, [Co(C₁₂H₈N₂)₂(H₂O)₂](C₅H₃N₂O₄)₂·2.25H₂O, the cobalt cation, located on a twofold axis, is coordinated by two symmetry-related aqua ligands together with a pair of symmetry-related bidentate phenanthroline (phen) mol­ecules, and exhibits a distorted octahedral coordination. The unique orotate anion in the asymmetric unit has a single negative charge. The coordin­ated water mol­ecules link the orotate ions to the metal complex via O—H...O hydrogen bonds. Each uncoordinated water mol­ecule is hydrogen bonded to orotate ions through O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• H-atom completeness 99%
• Disorder in solvent or counterion
• R factor = 0.037
• wR factor = 0.100
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .....       0.99
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ..          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ..          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing).          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .......................      12.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ...          <O7
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C13    -   C14    =       1.53 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C34 H30.5 Co1 N8 O12.25
            Atom count from the _atom_site data:  C34 H30 Co1 N8 O12.25
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C34 H30.50 Co N8 O12.25
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        136.00    136.00    0.00
           H        122.00    120.00    2.00
           Co         4.00      4.00    0.00
           N         32.00     32.00    0.00
           O         49.00     49.00    0.00

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Orotic acid (uracil-6-carboxylic acid, vitamin B13) and its metal-ion complexes play a cruical role in the metabolism of pyridine nucleotides and in many living organisms (Lalioti et al., 1998). Its metal-ion complexes are especially found interest in curing syndromes associated with deficiency of various metal ions (Kumberger et al., 1993). Thus, the coordination chemistry of orotic acid has been the subject of many studies (Sabat et al., 1980; Keripides & Thomas, 1986; Castan et al., 1990). Furthermore, DNA interaction of mixed-ligand metal complexes with phenanthroline (phen) was also investigated (Sastri et al., 2003). To study further the effects of metal ions on the complexation of orotic acid and its possible use in pharmocolgy, we have prepared the title compound, (I), and determined its structure.

Fig. 1 shows an ORTEP-3 (Farrugia, 1997) plot of (I). The Co^II atom located at a center of symmetry is octahedrally coordinated by a pair of bidentate phen molecules together with two water molecules. The mean planes through the pair of bidantate phen ligands form a dihedral angle of 75.33 (2)°. The Co—O distance is 2.1089 (13) Å and Co—N distances lie in the range 2.1216 (15)–2.1300 (14) Å (Table 1). The geometry of the phen ligand is comparable to that observed in a phen containing cobalt complex (Hökelek & Necefoğlu, 1997). The two oratate anions in the structure are protonated and included as counter-anions in the first coordination sphere. The orotate moeities are essentially planar. Nevertheless, there is a slight deviation from planarity arising from the torsion angle N3—C14—C13—O5 of 5.0 (2)°. The mean plane through the orotate molecule in the asymmetric unit is almost parallel [dihedral angle 2.74 (5)°] to that through the phen moiety.

The crystal structure of (I) is shown in Fig. 2. The coordinated water molecules link the oratate ions to the metal complex via O1—H1A···O2ⁱ and O1—H1B···O5ⁱⁱ hydrogen bonds (symmetry codes as in Table 2). Each lattice water molecule (O6) is hydrogen bonded to orotate ions through O6—H6B···O4 and O6—H6A···O3^v hydrogen bonds. Furthermore, the symmetry-related orotate ions are linked by N3—H3···O3ⁱⁱⁱ and N4—H4···O2^iv hydrogen bonds to form chains (see Table 2 for symmetry codes).

S2. Experimental

[Co(HOra)(H₂O)₄]·H₂O precursor was prepared as previously described in İçbudak et al. (2003). A solution of phenanthroline (0.748 g, 4 mmol) in ethanol (15 ml) was added dropwise into a stirred solution of [Co(HOra)(H₂O)₄]·H₂O (0.61 g, 2 mmol) in water (50 ml). The resulting solution was heated to 333 K in a temperature-controlled bath and then refluxed and stirred for 12 h at 333 K. The orange crystals of the title compound that formed after cooling to room temparature, filtered off and washed with 10 ml portions of cold distilled water and acetone and dried in vacuo. Yield: 0.92 g (79.3%). Found: C 29.5, H 5.3, N 19.7%; calculated for C₃₄H_30.5CoN₈O_12.25: C 29.1, H 5.4, N 19.4%.

S3. Refinement

H atoms attached to the water atoms O1 and O6 were located from a difference Fourier map and their x, y, z and U_iso parameters were refined [O—H = 0.82 (5)–0.88 (4) Å]. The remaining H atoms were placed geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq(C or N). At this stage, the maximum difference density of 1.61 e Å⁻³ (the ratio of maximum /minimum residual density is 3.22) indicated the presence of a possible atom site. Also a check for the solvent-accessible volume using PLATON (Spek, 1997) showed total potential solvent area volume of 74 ų. Attempts to refine this peak as a water O atom (O7) resulted in a partial occupancy of 0.131 (5). The occupancy was later fixed at 0.125 to result in one water O7 per unit cell. H atoms attached to O7 were not located.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title compound, showing the atom-numbering scheme and 50% probability displacement ellipsoids. H atoms have been omitted for clearity. Atoms with an asterix are at the symmetry position (1 − x, y, 1/2 − z). Water oxygen O7 is disordered with an occupancy of one per unit cell.
	Fig. 2. The crystal structure of (I).

(I)

Crystal data

[Co(C12H8N2)2(H2O)2](C5H3N2O4)2·2.25H2O	F(000) = 1662
Mr = 806.09	Dx = 1.595 Mg m^−3 Dm = 1.59 Mg m^−3 Dm measured by not measured
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4607 reflections
a = 16.1401 (11) Å	θ = 2.1–29.7°
b = 12.5692 (10) Å	µ = 0.59 mm^−1
c = 16.5650 (11) Å	T = 293 K
β = 92.435 (5)°	Prism, orange
V = 3357.5 (4) Å^3	0.35 × 0.23 × 0.15 mm
Z = 4

Data collection

Stoe IPDS-2 diffractometer	3086 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 29.4°, θmin = 2.1°
Detector resolution: 6.67 pixels mm^-1	h = −22→22
ϕ scans	k = 0→17
4607 measured reflections	l = 0→22
4607 independent reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0648P)^2] where P = (Fo^2 + 2Fc^2)/3
4607 reflections	(Δ/σ)max < 0.001
267 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.51 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.

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	Occ. (<1)
Co1	0.5000	0.74187 (3)	0.2500	0.03888 (10)
O1	0.58166 (8)	0.86648 (11)	0.28418 (8)	0.0466 (3)
O2	0.49164 (8)	0.00566 (12)	0.10797 (8)	0.0570 (4)
O3	0.68053 (8)	0.16286 (12)	−0.04585 (8)	0.0556 (4)
O4	0.67869 (11)	0.22904 (13)	0.30089 (9)	0.0696 (4)
O5	0.75468 (9)	0.30950 (14)	0.20987 (9)	0.0625 (4)
O6	0.73922 (14)	0.0553 (2)	0.39015 (14)	0.0868 (6)
N1	0.55141 (9)	0.73772 (12)	0.13373 (9)	0.0431 (3)
N2	0.42321 (9)	0.62817 (12)	0.18875 (9)	0.0437 (3)
N3	0.68639 (8)	0.19895 (11)	0.08901 (8)	0.0386 (3)
H3	0.7273	0.2420	0.0841	0.046*
N4	0.58923 (9)	0.08267 (12)	0.03426 (9)	0.0442 (3)
H4	0.5688	0.0491	−0.0072	0.053*
C1	0.61693 (13)	0.78915 (17)	0.10804 (13)	0.0556 (5)
H1	0.6514	0.8247	0.1455	0.067*
C2	0.63616 (14)	0.79193 (19)	0.02662 (14)	0.0623 (5)
H2	0.6823	0.8297	0.0107	0.075*
C3	0.58763 (14)	0.73963 (16)	−0.02909 (13)	0.0580 (5)
H3A	0.6000	0.7417	−0.0834	0.070*
C4	0.51834 (12)	0.68201 (15)	−0.00417 (11)	0.0484 (4)
C5	0.50334 (10)	0.68386 (13)	0.07881 (10)	0.0409 (4)
C6	0.43525 (10)	0.62364 (13)	0.10819 (11)	0.0421 (4)
C7	0.36385 (12)	0.56786 (16)	0.21761 (14)	0.0544 (5)
H7	0.3551	0.5701	0.2727	0.065*
C8	0.31401 (12)	0.50121 (16)	0.16868 (17)	0.0633 (6)
H8	0.2742	0.4582	0.1913	0.076*
C9	0.32410 (13)	0.49981 (17)	0.08840 (16)	0.0627 (6)
H9	0.2900	0.4573	0.0552	0.075*
C10	0.38590 (11)	0.56230 (15)	0.05476 (13)	0.0505 (4)
C11	0.40186 (14)	0.56483 (19)	−0.03010 (14)	0.0620 (6)
H11	0.3679	0.5265	−0.0664	0.074*
C12	0.46503 (14)	0.62174 (18)	−0.05741 (13)	0.0585 (5)
H12	0.4743	0.6219	−0.1124	0.070*
C13	0.70097 (11)	0.24621 (15)	0.23176 (11)	0.0463 (4)
C14	0.65663 (10)	0.18347 (13)	0.16392 (10)	0.0395 (3)
C15	0.59223 (10)	0.11708 (15)	0.17480 (11)	0.0448 (4)
H15	0.5732	0.1058	0.2263	0.054*
C16	0.55352 (10)	0.06420 (15)	0.10672 (11)	0.0448 (4)
C17	0.65450 (10)	0.14971 (14)	0.02185 (10)	0.0406 (4)
H1A	0.5636 (14)	0.9110 (19)	0.3175 (14)	0.058 (6)*
H1B	0.631 (2)	0.856 (3)	0.300 (2)	0.108 (11)*
H6A	0.712 (3)	0.000 (4)	0.385 (3)	0.15 (2)*
H6B	0.713 (2)	0.098 (3)	0.356 (2)	0.110 (12)*
O7	0.5000	0.3473 (9)	0.2500	0.084 (3)*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03765 (16)	0.04209 (19)	0.03728 (17)	0.000	0.00592 (12)	0.000
O1	0.0378 (6)	0.0506 (7)	0.0513 (8)	0.0040 (6)	0.0009 (5)	−0.0108 (6)
O2	0.0474 (7)	0.0663 (9)	0.0575 (8)	−0.0235 (6)	0.0047 (6)	0.0124 (7)
O3	0.0552 (7)	0.0727 (9)	0.0396 (7)	−0.0269 (7)	0.0103 (6)	−0.0026 (6)
O4	0.0967 (12)	0.0718 (10)	0.0414 (7)	−0.0113 (9)	0.0165 (8)	−0.0027 (7)
O5	0.0500 (7)	0.0855 (11)	0.0526 (8)	−0.0230 (7)	0.0086 (6)	−0.0146 (7)
O6	0.0884 (13)	0.0853 (14)	0.0854 (14)	0.0102 (12)	−0.0099 (11)	0.0119 (11)
N1	0.0433 (7)	0.0454 (8)	0.0412 (7)	−0.0059 (6)	0.0101 (6)	−0.0039 (6)
N2	0.0405 (7)	0.0419 (8)	0.0491 (8)	−0.0033 (6)	0.0068 (6)	0.0013 (6)
N3	0.0348 (6)	0.0417 (7)	0.0397 (7)	−0.0072 (5)	0.0061 (5)	0.0006 (6)
N4	0.0420 (7)	0.0477 (8)	0.0431 (8)	−0.0137 (6)	0.0051 (6)	0.0030 (6)
C1	0.0522 (10)	0.0598 (11)	0.0559 (11)	−0.0136 (9)	0.0163 (9)	−0.0065 (9)
C2	0.0621 (12)	0.0649 (13)	0.0621 (13)	−0.0112 (10)	0.0271 (10)	−0.0011 (10)
C3	0.0698 (12)	0.0591 (12)	0.0468 (10)	0.0099 (10)	0.0203 (9)	0.0043 (9)
C4	0.0556 (10)	0.0466 (10)	0.0431 (9)	0.0119 (8)	0.0039 (8)	−0.0019 (7)
C5	0.0428 (8)	0.0391 (8)	0.0412 (9)	0.0050 (7)	0.0045 (7)	−0.0028 (7)
C6	0.0402 (8)	0.0359 (8)	0.0501 (10)	0.0040 (7)	0.0013 (7)	−0.0014 (7)
C7	0.0468 (9)	0.0471 (10)	0.0699 (13)	−0.0036 (8)	0.0113 (9)	0.0089 (9)
C8	0.0453 (10)	0.0429 (10)	0.1019 (19)	−0.0070 (8)	0.0070 (11)	0.0050 (11)
C9	0.0472 (10)	0.0462 (11)	0.0940 (17)	−0.0024 (8)	−0.0059 (10)	−0.0124 (11)
C10	0.0447 (9)	0.0419 (9)	0.0643 (12)	0.0053 (7)	−0.0070 (8)	−0.0110 (8)
C11	0.0599 (12)	0.0623 (13)	0.0623 (13)	0.0121 (10)	−0.0157 (10)	−0.0199 (10)
C12	0.0699 (13)	0.0618 (12)	0.0429 (10)	0.0185 (10)	−0.0063 (9)	−0.0092 (9)
C13	0.0445 (8)	0.0514 (10)	0.0433 (9)	0.0021 (8)	0.0058 (7)	−0.0029 (8)
C14	0.0363 (7)	0.0415 (8)	0.0410 (9)	0.0027 (6)	0.0066 (6)	0.0044 (7)
C15	0.0410 (8)	0.0512 (10)	0.0428 (9)	−0.0040 (7)	0.0087 (7)	0.0056 (7)
C16	0.0375 (8)	0.0466 (9)	0.0507 (10)	−0.0059 (7)	0.0066 (7)	0.0100 (7)
C17	0.0369 (7)	0.0429 (9)	0.0423 (9)	−0.0067 (7)	0.0055 (6)	0.0024 (7)

Geometric parameters (Å, º)

Co1—O1	2.1089 (13)	C1—C2	1.397 (3)
Co1—O1^i	2.1089 (13)	C1—H1	0.93
Co1—N2	2.1216 (15)	C2—C3	1.355 (3)
Co1—N2^i	2.1216 (15)	C2—H2	0.93
Co1—N1^i	2.1300 (14)	C3—C4	1.409 (3)
Co1—N1	2.1300 (14)	C3—H3A	0.93
O1—H1A	0.85 (3)	C4—C5	1.406 (2)
O1—H1B	0.85 (3)	C4—C12	1.424 (3)
O2—C16	1.241 (2)	C5—C6	1.436 (2)
O3—C17	1.225 (2)	C6—C10	1.397 (2)
O4—C13	1.234 (2)	C7—C8	1.397 (3)
O5—C13	1.242 (2)	C7—H7	0.93
O6—H6A	0.82 (5)	C8—C9	1.347 (3)
O6—H6B	0.88 (4)	C8—H8	0.93
N1—C1	1.325 (2)	C9—C10	1.403 (3)
N1—C5	1.352 (2)	C9—H9	0.93
N2—C7	1.327 (2)	C10—C11	1.440 (3)
N2—C6	1.358 (2)	C11—C12	1.340 (3)
N3—C17	1.355 (2)	C11—H11	0.93
N3—C14	1.363 (2)	C12—H12	0.93
N3—H3	0.86	C13—C14	1.526 (2)
N4—C17	1.371 (2)	C14—C15	1.351 (2)
N4—C16	1.373 (2)	C15—C16	1.430 (3)
N4—H4	0.86	C15—H15	0.93
O1—Co1—O1^i	84.08 (8)	C5—C4—C12	119.33 (18)
O1—Co1—N2	167.01 (5)	C3—C4—C12	123.94 (19)
O1^i—Co1—N2	91.50 (6)	N1—C5—C4	123.26 (16)
O1—Co1—N2^i	91.50 (6)	N1—C5—C6	117.48 (15)
O1^i—Co1—N2^i	167.01 (5)	C4—C5—C6	119.24 (16)
N2—Co1—N2^i	95.31 (8)	N2—C6—C10	122.97 (17)
O1—Co1—N1^i	92.20 (6)	N2—C6—C5	117.02 (15)
O1^i—Co1—N1^i	89.88 (5)	C10—C6—C5	120.00 (17)
N2—Co1—N1^i	100.01 (6)	N2—C7—C8	122.7 (2)
N2^i—Co1—N1^i	78.06 (5)	N2—C7—H7	118.6
O1—Co1—N1	89.88 (5)	C8—C7—H7	118.6
O1^i—Co1—N1	92.20 (6)	C9—C8—C7	119.3 (2)
N2—Co1—N1	78.06 (5)	C9—C8—H8	120.3
N2^i—Co1—N1	100.01 (6)	C7—C8—H8	120.3
N1^i—Co1—N1	177.19 (8)	C8—C9—C10	120.2 (2)
Co1—O1—H1A	115.9 (15)	C8—C9—H9	119.9
Co1—O1—H1B	122 (2)	C10—C9—H9	119.9
H1A—O1—H1B	105 (3)	C6—C10—C9	116.9 (2)
H6A—O6—H6B	103 (4)	C6—C10—C11	119.03 (19)
C1—N1—C5	118.12 (16)	C9—C10—C11	124.02 (19)
C1—N1—Co1	128.71 (13)	C12—C11—C10	120.77 (19)
C5—N1—Co1	112.72 (11)	C12—C11—H11	119.6
C7—N2—C6	117.77 (17)	C10—C11—H11	119.6
C7—N2—Co1	128.95 (14)	C11—C12—C4	121.6 (2)
C6—N2—Co1	113.15 (11)	C11—C12—H12	119.2
C17—N3—C14	123.08 (14)	C4—C12—H12	119.2
C17—N3—H3	118.5	O4—C13—O5	128.15 (18)
C14—N3—H3	118.5	O4—C13—C14	116.55 (16)
C17—N4—C16	126.05 (15)	O5—C13—C14	115.30 (16)
C17—N4—H4	117.0	C15—C14—N3	120.81 (16)
C16—N4—H4	117.0	C15—C14—C13	124.09 (16)
N1—C1—C2	122.4 (2)	N3—C14—C13	115.10 (14)
N1—C1—H1	118.8	C14—C15—C16	119.66 (16)
C2—C1—H1	118.8	C14—C15—H15	120.2
C3—C2—C1	119.98 (19)	C16—C15—H15	120.2
C3—C2—H2	120.0	O2—C16—N4	118.86 (17)
C1—C2—H2	120.0	O2—C16—C15	125.97 (16)
C2—C3—C4	119.54 (18)	N4—C16—C15	115.17 (14)
C2—C3—H3A	120.2	O3—C17—N3	123.81 (15)
C4—C3—H3A	120.2	O3—C17—N4	121.04 (16)
C5—C4—C3	116.72 (17)	N3—C17—N4	115.15 (14)
O1—Co1—N1—C1	7.80 (18)	N1—C5—C6—N2	1.8 (2)
O1^i—Co1—N1—C1	91.87 (18)	C4—C5—C6—N2	−179.87 (15)
N2—Co1—N1—C1	−177.06 (18)	N1—C5—C6—C10	−176.91 (15)
N2^i—Co1—N1—C1	−83.69 (18)	C4—C5—C6—C10	1.4 (2)
O1—Co1—N1—C5	−164.20 (12)	C6—N2—C7—C8	−0.2 (3)
O1^i—Co1—N1—C5	−80.13 (12)	Co1—N2—C7—C8	175.41 (14)
N2—Co1—N1—C5	10.93 (12)	N2—C7—C8—C9	−2.2 (3)
N2^i—Co1—N1—C5	104.30 (12)	C7—C8—C9—C10	2.0 (3)
O1—Co1—N2—C7	−163.6 (2)	N2—C6—C10—C9	−3.0 (3)
O1^i—Co1—N2—C7	−93.84 (16)	C5—C6—C10—C9	175.73 (17)
N2^i—Co1—N2—C7	75.09 (16)	N2—C6—C10—C11	178.24 (17)
N1^i—Co1—N2—C7	−3.69 (17)	C5—C6—C10—C11	−3.1 (3)
N1—Co1—N2—C7	174.23 (17)	C8—C9—C10—C6	0.4 (3)
O1—Co1—N2—C6	12.2 (3)	C8—C9—C10—C11	179.2 (2)
O1^i—Co1—N2—C6	81.92 (12)	C6—C10—C11—C12	2.6 (3)
N2^i—Co1—N2—C6	−109.15 (13)	C9—C10—C11—C12	−176.1 (2)
N1^i—Co1—N2—C6	172.07 (11)	C10—C11—C12—C4	−0.3 (3)
N1—Co1—N2—C6	−10.01 (12)	C5—C4—C12—C11	−1.4 (3)
C5—N1—C1—C2	1.9 (3)	C3—C4—C12—C11	177.3 (2)
Co1—N1—C1—C2	−169.74 (16)	C17—N3—C14—C15	−0.3 (3)
N1—C1—C2—C3	−0.9 (4)	C17—N3—C14—C13	179.98 (15)
C1—C2—C3—C4	−0.5 (3)	O4—C13—C14—C15	4.5 (3)
C2—C3—C4—C5	0.8 (3)	O5—C13—C14—C15	−174.72 (18)
C2—C3—C4—C12	−178.0 (2)	O4—C13—C14—N3	−175.81 (17)
C1—N1—C5—C4	−1.6 (3)	O5—C13—C14—N3	5.0 (2)
Co1—N1—C5—C4	171.33 (13)	N3—C14—C15—C16	−1.4 (3)
C1—N1—C5—C6	176.61 (17)	C13—C14—C15—C16	178.29 (16)
Co1—N1—C5—C6	−10.46 (19)	C17—N4—C16—O2	176.05 (17)
C3—C4—C5—N1	0.3 (3)	C17—N4—C16—C15	−3.3 (3)
C12—C4—C5—N1	179.07 (16)	C14—C15—C16—O2	−176.25 (18)
C3—C4—C5—C6	−177.90 (16)	C14—C15—C16—N4	3.0 (3)
C12—C4—C5—C6	0.9 (3)	C14—N3—C17—O3	179.95 (17)
C7—N2—C6—C10	2.8 (3)	C14—N3—C17—N4	0.2 (2)
Co1—N2—C6—C10	−173.46 (13)	C16—N4—C17—O3	−178.03 (18)
C7—N2—C6—C5	−175.90 (16)	C16—N4—C17—N3	1.7 (3)
Co1—N2—C6—C5	7.83 (19)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O5	0.86	2.27	2.639 (2)	106
O6—H6B···O4	0.88 (4)	1.95 (4)	2.790 (3)	160 (3)
O1—H1A···O2^ii	0.85 (3)	1.96 (3)	2.798 (2)	173 (2)
O1—H1B···O5^iii	0.85 (3)	1.94 (4)	2.735 (2)	156 (3)
N3—H3···O3^iv	0.86	2.03	2.876 (2)	167
N4—H4···O2^v	0.86	2.02	2.868 (2)	170
O6—H6A···O3^vi	0.82 (5)	2.41 (5)	3.103 (3)	143 (4)

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