3D semicon­ducting Co–MOFs based on 5-(hy­droxy­meth­yl)isophthalic acid and imidazole derivatives: syntheses and crystal structures

Two three-dimensional cobalt-based metal–organic frameworks with 5-(hy­­droxy­meth­yl)isophthalic acid (H₂HIPA), namely poly[[μ₂-1,4-bis­(2-methyl-1H-imidazol-1-yl)benzene-κ²N³:N^3′][μ₂-5-(hy­droxy­meth­yl)isophthalato-κ²O¹:O³]cobalt(II)], [Co(C₉H₆O₅)(C₁₄H₁₄N₄)]_n (1), and poly[tris­[μ₂-1,4-bis­(1H-imidazol-1-yl)benzene-κ²N³:N^3′]bis­[μ₃-5-(hy­droxy­meth­yl)isophthalato-κ²O¹:O³:O⁵]dicobalt(II)], [Co₂(C₉H₆O₅)₂(C₁₂H₁₀N₄)₃]_n (2), were synthesized under similar hydro­thermal con­ditions. Single-crystal X-ray diffraction analyses revealed that 5-(hy­droxy­meth­yl)isophthalate (HIPA²⁻) and 1,4-bis­(2-methyl-1H-imidazol-1-yl)benzene (1,4-BMIB) are simple linkers con­necting cobalt centres to build a fourfold inter­penetration dia framework in com­plex 1. However, com­plex 2 is a pillared-layer framework with a (3,6)-con­nected network con­structed by 1,4-bis­(1H-imidazol-1-yl)benzene (1,4-DIB) linkers, 3-con­nected HIPA²⁻ ligands and 6-con­­nected Co^II centres. The above significant structural differences can be ascribed to the introduction of the different auxiliary N-donor ligands. Moreover, UV–Vis spectroscopy and Mott–Schottky measurements con­firmed that com­plexes 1 and 2 are typical n-type semicon­ductors.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[µ₂-1,4-bis(2-methyl-1H-imidazol-1-yl)benzene-κ²N³:N^3'][µ₂-5-(hydroxymethyl)isophthalato-κ²O¹:O³]cobalt(II)] (1)

Crystal data

[Co(C9H6O5)(C14H14N4)]	Dx = 1.388 Mg m^−3
Mr = 491.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Ibca	Cell parameters from 6718 reflections
a = 17.1976 (10) Å	θ = 4.5–30.2°
b = 16.7629 (9) Å	µ = 0.77 mm^−1
c = 16.3162 (10) Å	T = 295 K
V = 4703.7 (5) Å^3	Block, clear light colourless
Z = 8	0.2 × 0.2 × 0.15 mm
F(000) = 2024

Data collection

Rigaku 003 diffractometer	3198 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2615 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ω scans	θmax = 30.3°, θmin = 4.2°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −24→19
Tmin = 0.611, Tmax = 1.000	k = −23→21
14797 measured reflections	l = −21→20

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0577P)^2 + 1.7017P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3198 reflections	Δρmax = 0.39 e Å^−3
158 parameters	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.56110 (2)	0.500000	0.250000	0.02278 (10)
O1	0.61338 (7)	0.56154 (7)	0.33544 (7)	0.0447 (3)
O2	0.65793 (9)	0.44750 (8)	0.38295 (11)	0.0676 (5)
O3	0.66849 (10)	0.80932 (13)	0.5103 (2)	0.0508 (6)	0.5
H3	0.666855	0.848525	0.540322	0.076*	0.5
N1	0.48553 (7)	0.41496 (7)	0.29050 (8)	0.0321 (3)
N2	0.38453 (7)	0.33508 (7)	0.29418 (8)	0.0331 (3)
C1	0.65544 (8)	0.52094 (10)	0.38427 (10)	0.0346 (3)
C2	0.70364 (8)	0.56757 (8)	0.44451 (9)	0.0287 (3)
C3	0.750000	0.52628 (12)	0.500000	0.0319 (4)
H3A	0.750002	0.470798	0.500000	0.038*
C4	0.70389 (8)	0.65096 (8)	0.44477 (8)	0.0290 (3)
H4	0.672902	0.678537	0.407624	0.035*
C5	0.750000	0.69337 (11)	0.500000	0.0291 (4)
C6	0.750000	0.78376 (12)	0.500000	0.0439 (5)
H6B	0.781715	0.803884	0.544605	0.053*	0.5
H6A	0.770794	0.803883	0.448749	0.053*	0.5
C7	0.48053 (9)	0.38138 (10)	0.36757 (10)	0.0413 (4)
H7	0.514461	0.391300	0.410762	0.050*
C8	0.41858 (10)	0.33181 (11)	0.37043 (11)	0.0461 (4)
H8	0.402243	0.301558	0.414996	0.055*
C9	0.42686 (9)	0.38562 (11)	0.24724 (9)	0.0350 (3)
C10	0.41145 (14)	0.40255 (17)	0.15932 (12)	0.0743 (8)
H10A	0.373266	0.444102	0.154886	0.111*
H10B	0.392413	0.355167	0.133075	0.111*
H10C	0.458728	0.419333	0.133213	0.111*
C11	0.31592 (8)	0.29163 (9)	0.27027 (10)	0.0310 (3)
C12	0.31432 (8)	0.20970 (9)	0.28126 (11)	0.0351 (3)
H12	0.357445	0.183224	0.302300	0.042*
C13	0.25234 (9)	0.33247 (9)	0.23946 (10)	0.0361 (3)
H13	0.254263	0.387527	0.232705	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01881 (14)	0.02342 (14)	0.02609 (15)	0.000	0.000	−0.00293 (9)
O1	0.0483 (7)	0.0464 (6)	0.0392 (6)	−0.0140 (5)	−0.0172 (5)	0.0001 (5)
O2	0.0612 (8)	0.0378 (6)	0.1040 (13)	0.0067 (6)	−0.0362 (8)	−0.0303 (7)
O3	0.0517 (13)	0.0258 (11)	0.0751 (19)	0.0070 (10)	−0.0080 (13)	−0.0052 (11)
N1	0.0283 (6)	0.0363 (6)	0.0315 (6)	−0.0097 (5)	0.0010 (4)	−0.0011 (5)
N2	0.0263 (6)	0.0355 (6)	0.0376 (7)	−0.0094 (5)	−0.0001 (5)	0.0020 (5)
C1	0.0274 (7)	0.0392 (7)	0.0371 (8)	−0.0026 (6)	−0.0040 (6)	−0.0127 (6)
C2	0.0278 (6)	0.0280 (6)	0.0303 (6)	−0.0005 (5)	−0.0059 (5)	−0.0059 (5)
C3	0.0320 (9)	0.0225 (8)	0.0410 (11)	0.000	−0.0058 (8)	0.000
C4	0.0317 (6)	0.0289 (6)	0.0265 (6)	0.0027 (5)	−0.0076 (5)	0.0017 (5)
C5	0.0344 (9)	0.0227 (8)	0.0303 (9)	0.000	−0.0051 (8)	0.000
C6	0.0534 (13)	0.0224 (9)	0.0559 (14)	0.000	−0.0123 (11)	0.000
C7	0.0334 (8)	0.0552 (10)	0.0354 (8)	−0.0125 (7)	−0.0050 (6)	0.0080 (7)
C8	0.0368 (8)	0.0595 (11)	0.0420 (9)	−0.0156 (8)	−0.0043 (7)	0.0165 (8)
C9	0.0326 (7)	0.0400 (8)	0.0325 (7)	−0.0145 (6)	0.0009 (5)	−0.0008 (6)
C10	0.0784 (14)	0.1073 (19)	0.0373 (10)	−0.0612 (14)	−0.0117 (10)	0.0091 (11)
C11	0.0241 (6)	0.0319 (7)	0.0369 (7)	−0.0079 (5)	0.0016 (5)	0.0010 (6)
C12	0.0264 (7)	0.0314 (7)	0.0474 (9)	−0.0014 (5)	−0.0026 (6)	0.0040 (6)
C13	0.0319 (7)	0.0255 (7)	0.0508 (9)	−0.0044 (6)	−0.0012 (6)	0.0031 (6)

Geometric parameters (Å, º)

Co1—O1	1.9534 (11)	C4—H4	0.9300
Co1—O1^i	1.9534 (11)	C4—C5	1.3951 (16)
Co1—N1	2.0391 (11)	C5—C6	1.515 (3)
Co1—N1^i	2.0391 (11)	C6—H6B	0.9700
O1—C1	1.273 (2)	C6—H6A	0.9700
O2—C1	1.232 (2)	C7—H7	0.9300
O3—H3	0.8200	C7—C8	1.352 (2)
O3—C6	1.4755 (16)	C8—H8	0.9300
N1—C7	1.380 (2)	C9—C10	1.486 (2)
N1—C9	1.3259 (18)	C10—H10A	0.9600
N2—C8	1.376 (2)	C10—H10B	0.9600
N2—C9	1.3543 (19)	C10—H10C	0.9600
N2—C11	1.4405 (17)	C11—C12	1.385 (2)
C1—C2	1.5048 (18)	C11—C13	1.384 (2)
C2—C3	1.3909 (17)	C12—H12	0.9300
C2—C4	1.3978 (19)	C12—C13^ii	1.389 (2)
C3—H3A	0.9300	C13—H13	0.9300
O1—Co1—O1^i	125.19 (8)	O3—C6—H6B	110.3
O1—Co1—N1^i	98.94 (5)	O3—C6—H6A	110.3
O1—Co1—N1	115.55 (5)	C5—C6—H6B	110.3
O1^i—Co1—N1^i	115.55 (5)	C5—C6—H6A	110.3
O1^i—Co1—N1	98.94 (5)	H6B—C6—H6A	108.6
N1^i—Co1—N1	100.80 (7)	N1—C7—H7	125.3
C1—O1—Co1	115.20 (10)	C8—C7—N1	109.34 (14)
C6—O3—H3	109.5	C8—C7—H7	125.3
C7—N1—Co1	128.31 (10)	N2—C8—H8	126.9
C9—N1—Co1	124.88 (10)	C7—C8—N2	106.24 (14)
C9—N1—C7	106.63 (12)	C7—C8—H8	126.9
C8—N2—C11	124.97 (13)	N1—C9—N2	109.88 (13)
C9—N2—C8	107.91 (12)	N1—C9—C10	125.35 (14)
C9—N2—C11	127.12 (13)	N2—C9—C10	124.72 (14)
O1—C1—C2	116.36 (13)	C9—C10—H10A	109.5
O2—C1—O1	122.89 (14)	C9—C10—H10B	109.5
O2—C1—C2	120.75 (14)	C9—C10—H10C	109.5
C3—C2—C1	118.84 (13)	H10A—C10—H10B	109.5
C3—C2—C4	119.60 (13)	H10A—C10—H10C	109.5
C4—C2—C1	121.54 (13)	H10B—C10—H10C	109.5
C2^iii—C3—C2	120.30 (18)	C12—C11—N2	118.84 (13)
C2—C3—H3A	119.8	C13—C11—N2	119.69 (14)
C2^iii—C3—H3A	119.8	C13—C11—C12	121.44 (13)
C2—C4—H4	119.6	C11—C12—H12	120.3
C5—C4—C2	120.88 (13)	C11—C12—C13^ii	119.32 (14)
C5—C4—H4	119.6	C13^ii—C12—H12	120.3
C4^iii—C5—C4	118.73 (17)	C11—C13—C12^ii	119.25 (14)
C4—C5—C6	120.63 (9)	C11—C13—H13	120.4
C4^iii—C5—C6	120.63 (9)	C12^ii—C13—H13	120.4
O3—C6—C5	106.88 (12)
Co1—O1—C1—O2	−6.3 (2)	C4^iii—C5—C6—O3	−124.50 (14)
Co1—O1—C1—C2	173.17 (10)	C4—C5—C6—O3	55.50 (14)
Co1—N1—C7—C8	175.30 (13)	C7—N1—C9—N2	0.40 (19)
Co1—N1—C9—N2	−175.15 (10)	C7—N1—C9—C10	−177.1 (2)
Co1—N1—C9—C10	7.3 (3)	C8—N2—C9—N1	−0.6 (2)
O1—C1—C2—C3	179.24 (12)	C8—N2—C9—C10	176.9 (2)
O1—C1—C2—C4	−2.0 (2)	C8—N2—C11—C12	−53.7 (2)
O2—C1—C2—C3	−1.3 (2)	C8—N2—C11—C13	124.20 (19)
O2—C1—C2—C4	177.44 (16)	C9—N1—C7—C8	−0.1 (2)
N1—C7—C8—N2	−0.3 (2)	C9—N2—C8—C7	0.5 (2)
N2—C11—C12—C13^ii	178.22 (15)	C9—N2—C11—C12	126.24 (18)
N2—C11—C13—C12^ii	−178.21 (15)	C9—N2—C11—C13	−55.8 (2)
C1—C2—C3—C2^iii	178.80 (14)	C11—N2—C8—C7	−179.48 (15)
C1—C2—C4—C5	−178.79 (12)	C11—N2—C9—N1	179.42 (14)
C2—C4—C5—C4^iii	0.02 (10)	C11—N2—C9—C10	−3.1 (3)
C2—C4—C5—C6	−179.98 (10)	C12—C11—C13—C12^ii	−0.3 (3)
C3—C2—C4—C5	−0.05 (19)	C13—C11—C12—C13^ii	0.3 (3)
C4—C2—C3—C2^iii	0.02 (10)

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

Poly[tris[µ₂-1,4-bis(1H-imidazol-1-yl)benzene-κ²N³:N^3']bis[µ₃-5-(hydroxymethyl)isophthalato-κ²O¹:O³:O⁵]dicobalt(II)] (2)

Crystal data

[Co2(C9H6O5)2(C12H10N4)3]	F(000) = 1168
Mr = 1136.86	Dx = 1.528 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.0331 (4) Å	Cell parameters from 3691 reflections
b = 17.6045 (11) Å	θ = 2.6–27.8°
c = 17.6523 (9) Å	µ = 0.75 mm^−1
β = 98.077 (4)°	T = 295 K
V = 2471.6 (2) Å^3	Block, clear light colourless
Z = 2	0.3 × 0.3 × 0.3 mm

Data collection

Rigaku Oxford Diffraction four-circle diffractometer	5127 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3727 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 16.2083 pixels mm^-1	θmax = 28.5°, θmin = 2.3°
ω scans	h = −10→7
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	k = −23→14
Tmin = 0.691, Tmax = 1.000	l = −23→21
11072 measured reflections

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0389P)^2 + 0.444P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5127 reflections	Δρmax = 0.34 e Å^−3
353 parameters	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
Co1	0.77941 (3)	0.74899 (2)	0.75481 (2)	0.01846 (10)
O4	−0.06834 (18)	0.76592 (10)	0.35833 (9)	0.0280 (4)
O5	−0.00473 (18)	0.79399 (11)	0.70503 (9)	0.0318 (4)
H5	0.061163	0.807427	0.742362	0.048*
O3	0.15764 (19)	0.69704 (11)	0.34424 (9)	0.0345 (5)
O1	0.6208 (2)	0.76690 (11)	0.65661 (9)	0.0388 (5)
O2	0.67104 (19)	0.74757 (10)	0.53708 (9)	0.0321 (4)
N3	0.5871 (2)	0.69188 (12)	0.80706 (11)	0.0276 (5)
N1	0.7021 (2)	0.85640 (12)	0.79070 (11)	0.0275 (5)
N2	0.5951 (2)	0.93655 (12)	0.86666 (11)	0.0301 (5)
N5	0.8597 (2)	0.64134 (13)	0.72094 (11)	0.0303 (5)
N4	0.4924 (2)	0.60671 (13)	0.88200 (12)	0.0311 (5)
N6	0.9377 (3)	0.55818 (12)	0.64039 (12)	0.0323 (5)
C8	0.0755 (3)	0.73935 (14)	0.38136 (12)	0.0207 (5)
C7	0.2895 (3)	0.80249 (14)	0.60943 (12)	0.0224 (5)
H7	0.336547	0.815761	0.658825	0.027*
C6	0.1179 (3)	0.81217 (14)	0.58683 (12)	0.0213 (5)
C2	0.3917 (3)	0.77319 (14)	0.55905 (12)	0.0210 (5)
C4	0.1507 (3)	0.76232 (13)	0.46154 (12)	0.0197 (5)
C5	0.0499 (3)	0.79172 (14)	0.51309 (12)	0.0230 (5)
H5A	−0.064901	0.797654	0.497602	0.028*
C3	0.3220 (3)	0.75341 (13)	0.48505 (12)	0.0200 (5)
H3	0.390283	0.734150	0.451212	0.024*
C18	0.6214 (3)	0.65161 (16)	0.86930 (14)	0.0321 (6)
H18	0.723622	0.653666	0.901348	0.039*
C1	0.5782 (3)	0.76154 (14)	0.58532 (13)	0.0222 (5)
C9	0.0084 (3)	0.84402 (15)	0.64257 (12)	0.0276 (6)
H9A	0.055087	0.892055	0.662378	0.033*
H9B	−0.103132	0.853814	0.615515	0.033*
C24	0.8896 (3)	0.62984 (15)	0.65083 (14)	0.0296 (6)
H24	0.878681	0.666884	0.612903	0.036*
C12	0.6777 (3)	0.87091 (15)	0.86120 (14)	0.0314 (6)
H12	0.713535	0.839412	0.902586	0.038*
C13	0.5463 (3)	0.96915 (15)	0.93411 (13)	0.0282 (6)
C25	0.9716 (3)	0.52739 (15)	0.56917 (14)	0.0300 (6)
C15	0.5490 (3)	0.92528 (15)	0.99926 (14)	0.0338 (6)
H15	0.581586	0.874619	0.998628	0.041*
C27	1.0491 (3)	0.57265 (16)	0.52123 (15)	0.0371 (7)
H27	1.082007	0.621709	0.536053	0.044*
C19	0.4951 (3)	0.55267 (15)	0.94203 (15)	0.0334 (6)
C26	0.9221 (3)	0.45481 (15)	0.54903 (15)	0.0372 (7)
H26	0.870154	0.424624	0.582048	0.045*
C16	0.4246 (3)	0.67273 (16)	0.77809 (15)	0.0376 (7)
H16	0.364760	0.692540	0.733537	0.045*
C17	0.3650 (3)	0.62138 (17)	0.82342 (16)	0.0423 (7)
H17	0.258214	0.599857	0.816573	0.051*
C10	0.6297 (4)	0.91499 (17)	0.74806 (16)	0.0464 (8)
H10	0.626816	0.920009	0.695449	0.056*
C23	0.9395 (4)	0.52144 (18)	0.70851 (16)	0.0488 (8)
H23	0.967695	0.470941	0.719140	0.059*
C14	0.4965 (3)	1.04378 (15)	0.93477 (14)	0.0339 (6)
H14	0.493361	1.073338	0.890931	0.041*
C22	0.8918 (4)	0.57350 (18)	0.75732 (16)	0.0464 (8)
H22	0.882198	0.564400	0.808420	0.056*
C11	0.5626 (4)	0.96484 (18)	0.79337 (15)	0.0523 (9)
H11	0.505677	1.009488	0.778094	0.063*
C20	0.3556 (4)	0.54086 (19)	0.97643 (18)	0.0534 (9)
H20	0.257538	0.568031	0.960793	0.064*
C21	0.6386 (4)	0.51194 (19)	0.96518 (18)	0.0553 (9)
H21	0.733335	0.519868	0.941355	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01510 (16)	0.0282 (2)	0.01141 (16)	0.00229 (13)	−0.00033 (11)	−0.00315 (13)
O4	0.0202 (8)	0.0459 (12)	0.0156 (8)	0.0054 (8)	−0.0058 (6)	−0.0035 (8)
O5	0.0227 (8)	0.0586 (13)	0.0138 (8)	−0.0056 (9)	0.0013 (6)	0.0030 (8)
O3	0.0307 (9)	0.0510 (13)	0.0198 (9)	0.0108 (9)	−0.0035 (7)	−0.0105 (9)
O1	0.0267 (9)	0.0664 (15)	0.0198 (9)	0.0133 (9)	−0.0091 (7)	−0.0087 (9)
O2	0.0185 (8)	0.0516 (13)	0.0264 (9)	0.0025 (8)	0.0041 (7)	−0.0023 (9)
N3	0.0252 (10)	0.0333 (13)	0.0248 (11)	−0.0023 (10)	0.0054 (8)	0.0008 (10)
N1	0.0299 (10)	0.0295 (13)	0.0236 (11)	0.0050 (10)	0.0053 (8)	−0.0050 (10)
N2	0.0381 (12)	0.0280 (13)	0.0254 (11)	0.0067 (10)	0.0091 (9)	−0.0024 (10)
N5	0.0354 (11)	0.0337 (14)	0.0224 (11)	0.0070 (10)	0.0061 (9)	−0.0048 (10)
N4	0.0304 (11)	0.0325 (14)	0.0321 (12)	−0.0047 (10)	0.0109 (9)	0.0002 (10)
N6	0.0432 (12)	0.0278 (13)	0.0277 (12)	0.0086 (11)	0.0108 (9)	−0.0013 (10)
C8	0.0190 (11)	0.0293 (15)	0.0128 (11)	−0.0040 (10)	−0.0011 (9)	−0.0001 (10)
C7	0.0243 (11)	0.0307 (15)	0.0108 (11)	−0.0033 (11)	−0.0019 (9)	−0.0019 (10)
C6	0.0210 (11)	0.0282 (14)	0.0150 (11)	0.0015 (10)	0.0042 (9)	0.0013 (10)
C2	0.0160 (10)	0.0284 (14)	0.0171 (11)	−0.0004 (10)	−0.0024 (9)	0.0011 (10)
C4	0.0196 (11)	0.0276 (14)	0.0111 (10)	−0.0023 (10)	−0.0014 (9)	0.0017 (10)
C5	0.0157 (10)	0.0349 (15)	0.0178 (12)	−0.0009 (11)	0.0000 (9)	0.0037 (11)
C3	0.0178 (10)	0.0270 (14)	0.0152 (11)	0.0025 (10)	0.0025 (8)	−0.0006 (10)
C18	0.0283 (13)	0.0406 (17)	0.0279 (14)	−0.0084 (12)	0.0057 (10)	−0.0014 (13)
C1	0.0176 (11)	0.0265 (15)	0.0211 (12)	−0.0007 (10)	−0.0023 (9)	−0.0033 (10)
C9	0.0272 (12)	0.0391 (17)	0.0169 (12)	0.0039 (12)	0.0040 (9)	−0.0009 (11)
C24	0.0381 (14)	0.0245 (15)	0.0266 (14)	0.0058 (12)	0.0058 (11)	−0.0015 (11)
C12	0.0373 (14)	0.0329 (16)	0.0232 (13)	0.0113 (13)	0.0012 (11)	−0.0058 (12)
C13	0.0343 (13)	0.0274 (15)	0.0241 (13)	0.0055 (12)	0.0082 (10)	−0.0046 (11)
C25	0.0376 (14)	0.0254 (14)	0.0287 (14)	0.0083 (12)	0.0111 (11)	−0.0025 (12)
C15	0.0496 (16)	0.0214 (14)	0.0318 (15)	0.0091 (13)	0.0107 (12)	−0.0015 (12)
C27	0.0499 (16)	0.0213 (14)	0.0436 (17)	−0.0006 (13)	0.0192 (13)	−0.0084 (13)
C19	0.0371 (14)	0.0307 (16)	0.0350 (15)	−0.0054 (13)	0.0142 (11)	0.0008 (12)
C26	0.0515 (16)	0.0269 (16)	0.0382 (16)	0.0018 (14)	0.0242 (13)	0.0003 (13)
C16	0.0292 (13)	0.0438 (19)	0.0384 (16)	−0.0028 (13)	−0.0002 (11)	0.0054 (14)
C17	0.0263 (13)	0.0446 (19)	0.0546 (19)	−0.0094 (13)	0.0007 (13)	0.0032 (15)
C10	0.076 (2)	0.0399 (19)	0.0275 (15)	0.0160 (16)	0.0213 (14)	0.0060 (14)
C23	0.079 (2)	0.0323 (18)	0.0396 (17)	0.0203 (16)	0.0245 (15)	0.0105 (14)
C14	0.0483 (15)	0.0277 (15)	0.0272 (14)	0.0071 (13)	0.0104 (11)	0.0025 (12)
C22	0.069 (2)	0.045 (2)	0.0275 (15)	0.0161 (17)	0.0172 (14)	0.0067 (14)
C11	0.090 (2)	0.0389 (19)	0.0306 (16)	0.0296 (18)	0.0189 (15)	0.0082 (14)
C20	0.0372 (15)	0.059 (2)	0.067 (2)	0.0041 (15)	0.0199 (15)	0.0236 (18)
C21	0.0393 (16)	0.064 (2)	0.069 (2)	0.0029 (16)	0.0290 (15)	0.0251 (18)

Geometric parameters (Å, º)

Co1—O4^i	2.0678 (14)	C2—C1	1.519 (3)
Co1—O5^ii	2.1988 (16)	C4—C5	1.400 (3)
Co1—O1	2.0267 (16)	C4—C3	1.389 (3)
Co1—N3	2.1562 (19)	C5—H5A	0.9300
Co1—N1	2.115 (2)	C3—H3	0.9300
Co1—N5	2.115 (2)	C18—H18	0.9300
O4—C8	1.260 (3)	C9—H9A	0.9700
O5—H5	0.8200	C9—H9B	0.9700
O5—C9	1.427 (3)	C24—H24	0.9300
O3—C8	1.241 (3)	C12—H12	0.9300
O1—C1	1.260 (3)	C13—C15	1.383 (3)
O2—C1	1.233 (3)	C13—C14	1.374 (3)
N3—C18	1.304 (3)	C25—C27	1.373 (3)
N3—C16	1.375 (3)	C25—C26	1.370 (3)
N1—C12	1.312 (3)	C15—H15	0.9300
N1—C10	1.359 (3)	C15—C14^iii	1.380 (3)
N2—C12	1.343 (3)	C27—H27	0.9300
N2—C13	1.425 (3)	C27—C26^iv	1.381 (3)
N2—C11	1.377 (3)	C19—C20	1.363 (4)
N5—C24	1.309 (3)	C19—C21	1.370 (4)
N5—C22	1.363 (3)	C26—H26	0.9300
N4—C18	1.347 (3)	C16—H16	0.9300
N4—C19	1.422 (3)	C16—C17	1.339 (4)
N4—C17	1.373 (3)	C17—H17	0.9300
N6—C24	1.340 (3)	C10—H10	0.9300
N6—C25	1.430 (3)	C10—C11	1.350 (4)
N6—C23	1.364 (3)	C23—H23	0.9300
C8—C4	1.514 (3)	C23—C22	1.350 (4)
C7—H7	0.9300	C14—H14	0.9300
C7—C6	1.391 (3)	C22—H22	0.9300
C7—C2	1.392 (3)	C11—H11	0.9300
C6—C5	1.387 (3)	C20—H20	0.9300
C6—C9	1.516 (3)	C20—C21^v	1.384 (4)
C2—C3	1.391 (3)	C21—H21	0.9300
O4^i—Co1—O5^ii	89.84 (6)	N4—C18—H18	123.8
O4^i—Co1—N3	86.17 (7)	O1—C1—C2	114.4 (2)
O4^i—Co1—N1	90.62 (7)	O2—C1—O1	126.8 (2)
O4^i—Co1—N5	88.28 (7)	O2—C1—C2	118.8 (2)
O1—Co1—O4^i	176.71 (7)	O5—C9—C6	112.7 (2)
O1—Co1—O5^ii	92.20 (7)	O5—C9—H9A	109.1
O1—Co1—N3	92.08 (8)	O5—C9—H9B	109.1
O1—Co1—N1	86.64 (7)	C6—C9—H9A	109.1
O1—Co1—N5	94.46 (7)	C6—C9—H9B	109.1
N3—Co1—O5^ii	172.60 (7)	H9A—C9—H9B	107.8
N1—Co1—O5^ii	94.52 (8)	N5—C24—N6	111.7 (2)
N1—Co1—N3	91.75 (8)	N5—C24—H24	124.1
N1—Co1—N5	178.90 (8)	N6—C24—H24	124.1
N5—Co1—O5^ii	85.46 (8)	N1—C12—N2	112.1 (2)
N5—Co1—N3	88.20 (8)	N1—C12—H12	123.9
C8—O4—Co1^vi	129.77 (15)	N2—C12—H12	123.9
Co1^vii—O5—H5	103.8	C15—C13—N2	119.7 (2)
C9—O5—Co1^vii	132.81 (13)	C14—C13—N2	120.4 (2)
C9—O5—H5	109.5	C14—C13—C15	119.8 (2)
C1—O1—Co1	153.14 (16)	C27—C25—N6	118.7 (2)
C18—N3—Co1	122.30 (15)	C26—C25—N6	119.8 (2)
C18—N3—C16	104.9 (2)	C26—C25—C27	121.4 (2)
C16—N3—Co1	130.92 (17)	C13—C15—H15	119.8
C12—N1—Co1	123.20 (18)	C14^iii—C15—C13	120.4 (2)
C12—N1—C10	105.6 (2)	C14^iii—C15—H15	119.8
C10—N1—Co1	129.33 (17)	C25—C27—H27	120.1
C12—N2—C13	127.1 (2)	C25—C27—C26^iv	119.9 (2)
C12—N2—C11	105.9 (2)	C26^iv—C27—H27	120.1
C11—N2—C13	127.0 (2)	C20—C19—N4	120.4 (2)
C24—N5—Co1	120.63 (18)	C20—C19—C21	119.8 (3)
C24—N5—C22	105.2 (2)	C21—C19—N4	119.7 (2)
C22—N5—Co1	134.16 (17)	C25—C26—C27^iv	118.7 (2)
C18—N4—C19	125.8 (2)	C25—C26—H26	120.6
C18—N4—C17	105.9 (2)	C27^iv—C26—H26	120.6
C17—N4—C19	128.2 (2)	N3—C16—H16	125.0
C24—N6—C25	124.9 (2)	C17—C16—N3	110.1 (2)
C24—N6—C23	107.0 (2)	C17—C16—H16	125.0
C23—N6—C25	128.0 (2)	N4—C17—H17	126.7
O4—C8—C4	115.5 (2)	C16—C17—N4	106.6 (2)
O3—C8—O4	125.7 (2)	C16—C17—H17	126.7
O3—C8—C4	118.81 (19)	N1—C10—H10	125.0
C6—C7—H7	119.6	C11—C10—N1	109.9 (2)
C6—C7—C2	120.8 (2)	C11—C10—H10	125.0
C2—C7—H7	119.6	N6—C23—H23	127.1
C7—C6—C9	120.08 (19)	C22—C23—N6	105.8 (3)
C5—C6—C7	118.8 (2)	C22—C23—H23	127.1
C5—C6—C9	121.13 (19)	C13—C14—C15^iii	119.8 (2)
C7—C2—C1	120.02 (19)	C13—C14—H14	120.1
C3—C2—C7	119.79 (19)	C15^iii—C14—H14	120.1
C3—C2—C1	120.2 (2)	N5—C22—H22	124.9
C5—C4—C8	121.02 (19)	C23—C22—N5	110.2 (2)
C3—C4—C8	119.8 (2)	C23—C22—H22	124.9
C3—C4—C5	119.14 (19)	N2—C11—H11	126.8
C6—C5—C4	121.23 (19)	C10—C11—N2	106.4 (3)
C6—C5—H5A	119.4	C10—C11—H11	126.8
C4—C5—H5A	119.4	C19—C20—H20	120.3
C2—C3—H3	119.9	C19—C20—C21^v	119.4 (3)
C4—C3—C2	120.2 (2)	C21^v—C20—H20	120.3
C4—C3—H3	119.9	C19—C21—C20^v	120.8 (3)
N3—C18—N4	112.5 (2)	C19—C21—H21	119.6
N3—C18—H18	123.8	C20^v—C21—H21	119.6

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