Solvent exchange in a metal–organic framework single crystal monitored by dynamic in situ X-ray diffraction

Understanding the processes by which porous solid-state materials adsorb and release guest molecules would represent a significant step towards developing rational design principles for functional porous materials. To elucidate the process of liquid exchange in these materials, dynamic in situ X-ray diffraction techniques have been developed which utilize liquid-phase chemical stimuli. Using these time-resolved diffraction techniques, the ethanol solvation process in a flexible metal–organic framework [Co(AIP)(bpy)_0.5(H₂O)]·2H₂O was examined. The measurements provide important insight into the nature of the chemical transformation in this system including the presence of a previously unreported neat ethanol solvate structure.

Computing details

Cell refinement: SAINT v8.34A (Bruker, 2013) for structure1. Data reduction: SAINT v8.34A (Bruker, 2013) for structure1. For all structures, program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(structure1)

Crystal data

C13H11CoN2O5·2(H2O)	F(000) = 760
Mr = 370.20	Dx = 1.660 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.40651 Å
a = 12.655 (3) Å	Cell parameters from 1379 reflections
b = 7.6693 (19) Å	θ = 2.5–13.0°
c = 15.934 (4) Å	µ = 0.63 mm^−1
β = 106.636 (5)°	T = 296 K
V = 1481.7 (6) Å^3	Prism, violet
Z = 4	0.4 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX2 area detector diffractometer	2948 independent reflections
Silicon 111 monochromator	1801 reflections with I > 2σ(I)
Detector resolution: 7.9 pixels mm^-1	Rint = 0.118
ω and φ scans	θmax = 14.8°, θmin = 1.5°
Absorption correction: multi-scan SADABS-2014/2 (Bruker,2014/2) was used for absorption correction. wR2(int) was 0.1112 before and 0.0704 after correction. The Ratio of minimum to maximum transmission is 0.8584. The λ/2 correction factor is 0.00150.	h = −14→15
Tmin = 0.639, Tmax = 0.744	k = −8→9
13840 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 2.0543P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
2948 reflections	Δρmax = 0.63 e Å^−3
215 parameters	Δρmin = −0.56 e Å^−3
2 restraints

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	0.80404 (6)	0.50847 (11)	0.17795 (3)	0.0189 (2)
O1	0.8304 (3)	0.4437 (5)	0.30343 (19)	0.0283 (10)
O2	0.8734 (3)	0.1640 (6)	0.3301 (2)	0.0321 (10)
O3	0.7954 (3)	0.8376 (5)	0.5472 (2)	0.0317 (10)
O4	0.8707 (3)	0.7466 (5)	0.68121 (19)	0.0260 (9)
O5	0.6656 (3)	0.6589 (6)	0.2042 (2)	0.0389 (11)
H5A	0.6900	0.7289	0.2489	0.058*
H5B	0.6178	0.5878	0.2162	0.058*
N1	0.9516 (3)	0.1114 (6)	0.6621 (2)	0.0192 (10)
H1A	0.9915	0.1537	0.7134	0.023*
H1B	0.9919	0.0309	0.6451	0.023*
N2	0.6853 (4)	0.3284 (7)	0.1105 (2)	0.0250 (11)
C1	0.8598 (4)	0.3143 (8)	0.3537 (3)	0.0199 (12)
C2	0.8755 (4)	0.3517 (7)	0.4502 (3)	0.0157 (11)
C3	0.8537 (4)	0.5157 (8)	0.4772 (3)	0.0207 (11)
H3	0.8285	0.6038	0.4362	0.025*
C4	0.8695 (4)	0.5491 (7)	0.5665 (3)	0.0185 (12)
C5	0.8439 (4)	0.7189 (7)	0.5985 (3)	0.0193 (12)
C6	0.9072 (4)	0.4138 (7)	0.6266 (3)	0.0163 (11)
H6	0.9192	0.4349	0.6861	0.020*
C7	0.9267 (4)	0.2494 (7)	0.5989 (3)	0.0164 (11)
C8	0.9113 (4)	0.2176 (7)	0.5105 (3)	0.0172 (11)
H8	0.9249	0.1073	0.4916	0.021*
C9	0.6266 (7)	0.3461 (11)	0.0282 (4)	0.072 (3)
H9	0.6346	0.4474	−0.0015	0.086*
C10	0.5541 (7)	0.2206 (12)	−0.0155 (4)	0.086 (4)
H10	0.5149	0.2400	−0.0737	0.104*
C11	0.5374 (5)	0.0686 (8)	0.0233 (3)	0.0309 (14)
C12	0.6024 (6)	0.0475 (10)	0.1072 (4)	0.054 (2)
H12	0.5998	−0.0560	0.1370	0.064*
C13	0.6729 (6)	0.1817 (10)	0.1483 (3)	0.049 (2)
H13	0.7138	0.1657	0.2064	0.059*
O6	0.7325 (4)	−0.1012 (7)	0.3607 (3)	0.0505 (13)
H6A	0.7806	−0.0301	0.3532	0.076*
H6B	0.7474	−0.1272	0.4147	0.076*
O7	0.4876 (7)	0.4655 (19)	0.2131 (5)	0.209 (7)
H7A	0.4179	0.4648	0.1917	0.313*
H7B	0.5064	0.3909	0.2542	0.313*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0303 (4)	0.0147 (4)	0.0104 (3)	−0.0050 (4)	0.0037 (2)	0.0002 (3)
O1	0.048 (2)	0.024 (3)	0.0116 (15)	0.0060 (18)	0.0068 (15)	0.0049 (14)
O2	0.055 (3)	0.027 (3)	0.0134 (16)	0.009 (2)	0.0088 (16)	−0.0033 (16)
O3	0.049 (2)	0.017 (2)	0.0243 (17)	0.0082 (19)	0.0039 (17)	−0.0002 (16)
O4	0.043 (2)	0.021 (3)	0.0148 (16)	0.0041 (19)	0.0091 (15)	−0.0046 (14)
O5	0.041 (3)	0.033 (3)	0.039 (2)	0.004 (2)	0.0053 (19)	−0.0006 (19)
N1	0.033 (3)	0.015 (3)	0.0082 (17)	0.007 (2)	0.0028 (16)	0.0037 (16)
N2	0.029 (3)	0.026 (3)	0.0172 (19)	−0.005 (2)	0.0026 (17)	−0.0013 (19)
C1	0.024 (3)	0.028 (4)	0.008 (2)	0.001 (2)	0.0045 (18)	0.000 (2)
C2	0.024 (3)	0.013 (3)	0.012 (2)	0.000 (2)	0.0077 (18)	−0.0001 (18)
C3	0.027 (3)	0.019 (3)	0.016 (2)	0.003 (3)	0.0061 (18)	0.003 (2)
C4	0.024 (3)	0.013 (3)	0.018 (2)	0.000 (2)	0.0063 (19)	−0.0042 (18)
C5	0.027 (3)	0.012 (3)	0.019 (2)	0.000 (2)	0.008 (2)	−0.002 (2)
C6	0.029 (3)	0.012 (3)	0.0081 (19)	0.000 (2)	0.0057 (18)	−0.0003 (18)
C7	0.022 (3)	0.015 (3)	0.012 (2)	0.001 (2)	0.0044 (18)	0.0002 (19)
C8	0.031 (3)	0.009 (3)	0.014 (2)	0.003 (2)	0.011 (2)	−0.0012 (19)
C9	0.104 (7)	0.054 (6)	0.031 (3)	−0.052 (5)	−0.023 (4)	0.016 (3)
C10	0.123 (7)	0.066 (7)	0.031 (3)	−0.064 (6)	−0.040 (4)	0.020 (4)
C11	0.036 (3)	0.021 (4)	0.030 (3)	−0.008 (3)	−0.001 (2)	0.004 (2)
C12	0.069 (5)	0.047 (6)	0.029 (3)	−0.032 (4)	−0.012 (3)	0.011 (3)
C13	0.067 (5)	0.046 (5)	0.020 (3)	−0.023 (4)	−0.011 (3)	0.011 (3)
O6	0.061 (3)	0.046 (4)	0.037 (2)	−0.011 (3)	0.003 (2)	0.006 (2)
O7	0.107 (6)	0.42 (2)	0.107 (6)	−0.133 (10)	0.048 (5)	−0.013 (8)

Geometric parameters (Å, º)

Co1—O1	1.993 (3)	C2—C8	1.392 (7)
Co1—O3^i	2.370 (4)	C3—H3	0.9300
Co1—O4^i	2.054 (4)	C3—C4	1.403 (6)
Co1—O5	2.234 (4)	C4—C5	1.467 (7)
Co1—N1^ii	2.160 (4)	C4—C6	1.400 (7)
Co1—N2	2.097 (4)	C6—H6	0.9300
O1—C1	1.263 (6)	C6—C7	1.381 (7)
O2—C1	1.239 (7)	C7—C8	1.388 (6)
O3—Co1^iii	2.370 (4)	C8—H8	0.9300
O3—C5	1.259 (6)	C9—H9	0.9300
O4—Co1^iii	2.054 (4)	C9—C10	1.374 (9)
O4—C5	1.282 (5)	C10—H10	0.9300
O5—H5A	0.8747	C10—C11	1.364 (9)
O5—H5B	0.8752	C11—C11^v	1.468 (11)
N1—Co1^iv	2.161 (4)	C11—C12	1.364 (7)
N1—H1A	0.8900	C12—H12	0.9300
N1—H1B	0.8900	C12—C13	1.396 (9)
N1—C7	1.432 (6)	C13—H13	0.9300
N2—C9	1.315 (7)	O6—H6A	0.8507
N2—C13	1.307 (8)	O6—H6B	0.8496
C1—C2	1.521 (6)	O7—H7A	0.8499
C2—C3	1.383 (7)	O7—H7B	0.8499
O1—Co1—O3^i	163.39 (15)	C2—C3—H3	120.0
O1—Co1—O4^i	104.65 (14)	C2—C3—C4	119.9 (5)
O1—Co1—O5	81.71 (15)	C4—C3—H3	120.0
O1—Co1—N1^ii	96.28 (15)	C3—C4—C5	122.2 (5)
O1—Co1—N2	103.88 (17)	C6—C4—C3	118.7 (5)
O4^i—Co1—O3^i	58.79 (13)	C6—C4—C5	119.1 (4)
O4^i—Co1—O5	82.02 (17)	O3—C5—O4	118.9 (5)
O4^i—Co1—N1^ii	91.71 (16)	O3—C5—C4	122.1 (4)
O4^i—Co1—N2	147.59 (15)	O4—C5—C4	119.0 (4)
O5—Co1—O3^i	93.80 (15)	C4—C6—H6	119.5
N1^ii—Co1—O3^i	86.15 (15)	C7—C6—C4	121.0 (4)
N1^ii—Co1—O5	172.66 (16)	C7—C6—H6	119.5
N2—Co1—O3^i	91.80 (14)	C6—C7—N1	118.2 (4)
N2—Co1—O5	87.19 (18)	C6—C7—C8	120.0 (4)
N2—Co1—N1^ii	100.15 (17)	C8—C7—N1	121.5 (5)
C1—O1—Co1	140.0 (3)	C2—C8—H8	120.2
C5—O3—Co1^iii	84.2 (3)	C7—C8—C2	119.6 (5)
C5—O4—Co1^iii	98.0 (3)	C7—C8—H8	120.2
Co1—O5—H5A	110.9	N2—C9—H9	118.8
Co1—O5—H5B	110.4	N2—C9—C10	122.5 (7)
H5A—O5—H5B	108.0	C10—C9—H9	118.8
Co1^iv—N1—H1A	109.2	C9—C10—H10	118.8
Co1^iv—N1—H1B	109.2	C11—C10—C9	122.4 (6)
H1A—N1—H1B	107.9	C11—C10—H10	118.8
C7—N1—Co1^iv	111.9 (3)	C10—C11—C11^v	123.0 (6)
C7—N1—H1A	109.2	C12—C11—C10	114.7 (6)
C7—N1—H1B	109.2	C12—C11—C11^v	122.1 (7)
C9—N2—Co1	124.0 (4)	C11—C12—H12	120.1
C13—N2—Co1	119.5 (3)	C11—C12—C13	119.8 (6)
C13—N2—C9	116.2 (5)	C13—C12—H12	120.1
O1—C1—C2	115.0 (5)	N2—C13—C12	124.3 (5)
O2—C1—O1	125.4 (4)	N2—C13—H13	117.9
O2—C1—C2	119.5 (4)	C12—C13—H13	117.9
C3—C2—C1	120.4 (4)	H6A—O6—H6B	109.5
C3—C2—C8	120.8 (4)	H7A—O7—H7B	109.5
C8—C2—C1	118.7 (5)
Co1—O1—C1—O2	−7.4 (10)	C2—C3—C4—C6	−0.2 (7)
Co1—O1—C1—C2	174.4 (4)	C3—C2—C8—C7	−0.9 (8)
Co1^iii—O3—C5—O4	−2.2 (5)	C3—C4—C5—O3	7.8 (8)
Co1^iii—O3—C5—C4	177.0 (5)	C3—C4—C5—O4	−173.0 (5)
Co1^iii—O4—C5—O3	2.6 (5)	C3—C4—C6—C7	−1.1 (7)
Co1^iii—O4—C5—C4	−176.7 (4)	C4—C6—C7—N1	−172.2 (4)
Co1^iv—N1—C7—C6	85.4 (5)	C4—C6—C7—C8	1.4 (8)
Co1^iv—N1—C7—C8	−88.2 (5)	C5—C4—C6—C7	176.6 (5)
Co1—N2—C9—C10	176.1 (8)	C6—C4—C5—O3	−169.8 (5)
Co1—N2—C13—C12	−175.0 (6)	C6—C4—C5—O4	9.4 (7)
O1—C1—C2—C3	2.6 (7)	C6—C7—C8—C2	−0.4 (8)
O1—C1—C2—C8	−177.9 (5)	C8—C2—C3—C4	1.2 (7)
O2—C1—C2—C3	−175.7 (5)	C9—N2—C13—C12	−0.4 (12)
O2—C1—C2—C8	3.7 (7)	C9—C10—C11—C11^v	−178.2 (9)
N1—C7—C8—C2	173.0 (5)	C9—C10—C11—C12	−3.2 (14)
N2—C9—C10—C11	0.2 (17)	C10—C11—C12—C13	4.4 (12)
C1—C2—C3—C4	−179.4 (4)	C11^v—C11—C12—C13	179.4 (8)
C1—C2—C8—C7	179.7 (5)	C11—C12—C13—N2	−2.8 (12)
C2—C3—C4—C5	−177.8 (5)	C13—N2—C9—C10	1.7 (13)

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

(structure2)

Crystal data

C15H15CoN2O5·H2O	F(000) = 784
Mr = 380.23	Dx = 1.679 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.40651 Å
a = 12.899 (9) Å	Cell parameters from 540 reflections
b = 7.638 (7) Å	θ = 1.5–15.0°
c = 16.085 (11) Å	µ = 0.62 mm^−1
β = 108.337 (11)°	T = 296 K
V = 1504 (2) Å^3	Prism, violet
Z = 4	0.4 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX2 area detector diffractometer	3213 independent reflections
Silicon 111 monochromator	2091 reflections with I > 2σ(I)
Detector resolution: 7.9 pixels mm^-1	Rint = 0.136
ω and φ scans	θmax = 15.0°, θmin = 1.5°
Absorption correction: multi-scan SADABS-2014/2 (Bruker,2014/2) was used for absorption correction. wR2(int) was 0.1195 before and 0.0743 after correction. The Ratio of minimum to maximum transmission is 0.8560. The λ/2 correction factor is 0.00150.	h = −16→14
Tmin = 0.637, Tmax = 0.744	k = −8→9
21276 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.086	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.198	w = 1/[σ^2(Fo^2) + (0.0593P)^2 + 10.1986P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
3213 reflections	Δρmax = 0.77 e Å^−3
224 parameters	Δρmin = −0.73 e Å^−3
6 restraints

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	0.19089 (8)	0.49578 (13)	0.81978 (5)	0.0196 (3)
O1	0.1616 (5)	0.5436 (7)	0.6947 (3)	0.0428 (16)
O2	0.1067 (5)	0.8176 (8)	0.6675 (3)	0.0362 (14)
O3	0.2059 (5)	0.1580 (8)	0.4536 (4)	0.0507 (17)
O4	0.1431 (5)	0.2584 (7)	0.3192 (3)	0.0354 (13)
O5	0.3331 (7)	0.3481 (9)	0.7796 (5)	0.072 (2)
H5	0.326 (2)	0.243 (2)	0.7567 (19)	0.107*
N1	0.0481 (5)	0.8901 (8)	0.3385 (3)	0.0222 (13)
H1A	0.0119	0.9718	0.3576	0.027*
H1B	0.0045	0.8503	0.2875	0.027*
N2	0.3125 (5)	0.6720 (8)	0.8872 (3)	0.0255 (14)
C1	0.1285 (6)	0.6731 (10)	0.6438 (4)	0.0242 (16)
C2	0.1205 (6)	0.6412 (9)	0.5492 (4)	0.0211 (15)
C3	0.1469 (6)	0.4774 (9)	0.5217 (4)	0.0216 (14)
H3	0.1720	0.3875	0.5621	0.026*
C4	0.1352 (6)	0.4504 (8)	0.4329 (4)	0.0205 (15)
C5	0.1633 (6)	0.2801 (9)	0.4015 (5)	0.0270 (16)
C6	0.0980 (6)	0.5861 (9)	0.3738 (4)	0.0200 (14)
H6	0.0875	0.5665	0.3146	0.024*
C7	0.0762 (5)	0.7487 (8)	0.4006 (3)	0.0162 (13)
C8	0.0866 (6)	0.7777 (9)	0.4885 (4)	0.0204 (14)
H8	0.0710	0.8873	0.5067	0.025*
C9	0.3712 (8)	0.6543 (12)	0.9708 (5)	0.054 (3)
H9	0.3620	0.5543	1.0008	0.065*
C10	0.4453 (9)	0.7787 (14)	1.0148 (5)	0.070 (4)
H10	0.4860	0.7583	1.0729	0.084*
C11	0.4613 (6)	0.9317 (10)	0.9760 (4)	0.0275 (16)
C12	0.3951 (7)	0.9544 (11)	0.8914 (5)	0.041 (2)
H12	0.3983	1.0583	0.8621	0.050*
C13	0.3231 (7)	0.8228 (12)	0.8491 (4)	0.044 (2)
H13	0.2804	0.8410	0.7913	0.052*
C14	0.3931 (9)	0.443 (2)	0.7305 (8)	0.107 (6)
H14A	0.3520	0.5458	0.7031	0.129*
H14B	0.4032	0.3689	0.6847	0.129*
C15	0.5030 (11)	0.498 (2)	0.7923 (9)	0.109 (5)
H15A	0.5288	0.5989	0.7691	0.164*
H15B	0.5541	0.4038	0.7988	0.164*
H15C	0.4958	0.5264	0.8484	0.164*
O6	0.7570 (9)	0.8930 (11)	0.3522 (5)	0.098 (3)
H6A	0.7565	0.8953	0.4048	0.146*
H6B	0.7801	0.9905	0.3395	0.146*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0344 (5)	0.0140 (4)	0.0085 (4)	−0.0085 (5)	0.0040 (3)	0.0002 (4)
O1	0.091 (5)	0.027 (3)	0.013 (2)	−0.011 (3)	0.019 (3)	0.002 (2)
O2	0.057 (4)	0.041 (4)	0.013 (2)	0.003 (3)	0.015 (2)	−0.010 (2)
O3	0.061 (4)	0.022 (3)	0.048 (3)	0.016 (3)	−0.013 (3)	−0.010 (3)
O4	0.072 (4)	0.018 (3)	0.027 (3)	−0.002 (3)	0.031 (3)	−0.009 (2)
O5	0.093 (6)	0.045 (5)	0.073 (5)	−0.009 (4)	0.020 (4)	0.002 (4)
N1	0.038 (4)	0.018 (3)	0.012 (2)	0.003 (3)	0.010 (2)	0.003 (2)
N2	0.035 (4)	0.023 (3)	0.015 (2)	−0.011 (3)	0.003 (2)	−0.001 (2)
C1	0.036 (4)	0.030 (4)	0.009 (3)	−0.017 (3)	0.010 (3)	−0.003 (3)
C2	0.035 (4)	0.019 (4)	0.010 (3)	−0.004 (3)	0.007 (3)	−0.002 (2)
C3	0.037 (4)	0.011 (4)	0.016 (3)	−0.001 (3)	0.007 (3)	0.004 (3)
C4	0.038 (4)	0.009 (3)	0.017 (3)	−0.001 (3)	0.013 (3)	−0.003 (2)
C5	0.037 (4)	0.009 (4)	0.035 (4)	0.002 (3)	0.012 (3)	−0.008 (3)
C6	0.042 (4)	0.012 (3)	0.008 (3)	−0.002 (3)	0.011 (3)	−0.002 (2)
C7	0.029 (4)	0.015 (3)	0.007 (2)	0.001 (3)	0.008 (2)	0.003 (2)
C8	0.035 (4)	0.013 (4)	0.016 (3)	0.003 (3)	0.013 (3)	0.001 (3)
C9	0.074 (7)	0.041 (6)	0.029 (4)	−0.039 (5)	−0.011 (4)	0.012 (4)
C10	0.095 (8)	0.066 (7)	0.018 (4)	−0.048 (6)	−0.028 (4)	0.013 (4)
C11	0.034 (4)	0.024 (4)	0.022 (3)	−0.014 (3)	0.004 (3)	−0.005 (3)
C12	0.055 (5)	0.038 (6)	0.023 (3)	−0.025 (4)	0.001 (3)	0.006 (3)
C13	0.061 (6)	0.044 (5)	0.016 (3)	−0.026 (5)	−0.003 (3)	0.003 (3)
C14	0.052 (7)	0.187 (19)	0.085 (9)	−0.018 (9)	0.024 (6)	0.035 (10)
C15	0.087 (10)	0.135 (15)	0.114 (11)	−0.023 (11)	0.043 (9)	−0.029 (11)
O6	0.170 (9)	0.053 (6)	0.072 (5)	−0.026 (6)	0.041 (6)	0.000 (4)

Geometric parameters (Å, º)

Co1—O1	1.962 (5)	C3—C4	1.404 (8)
Co1—O3^i	2.406 (6)	C4—C5	1.482 (9)
Co1—O4^i	2.036 (6)	C4—C6	1.386 (9)
Co1—O5	2.409 (8)	C6—H6	0.9300
Co1—N1^ii	2.142 (6)	C6—C7	1.373 (9)
Co1—N2	2.093 (6)	C7—C8	1.395 (8)
O1—C1	1.269 (9)	C8—H8	0.9300
O2—C1	1.229 (9)	C9—H9	0.9300
O3—Co1^iii	2.406 (6)	C9—C10	1.375 (11)
O3—C5	1.259 (9)	C10—H10	0.9300
O4—Co1^iii	2.036 (5)	C10—C11	1.370 (12)
O4—C5	1.276 (8)	C11—C11^v	1.483 (13)
O5—H5	0.876 (9)	C11—C12	1.372 (10)
O5—C14	1.462 (13)	C12—H12	0.9300
N1—Co1^iv	2.142 (6)	C12—C13	1.392 (11)
N1—H1A	0.8900	C13—H13	0.9300
N1—H1B	0.8900	C14—H14A	0.9700
N1—C7	1.439 (8)	C14—H14B	0.9700
N2—C9	1.326 (9)	C14—C15	1.512 (17)
N2—C13	1.332 (10)	C15—H15A	0.9600
C1—C2	1.513 (8)	C15—H15B	0.9600
C2—C3	1.404 (9)	C15—H15C	0.9600
C2—C8	1.401 (9)	O6—H6A	0.8483
C3—H3	0.9300	O6—H6B	0.8506
O1—Co1—O3^i	160.7 (2)	C6—C4—C5	119.4 (6)
O1—Co1—O4^i	102.3 (2)	O3—C5—O4	119.9 (6)
O1—Co1—O5	74.3 (3)	O3—C5—C4	121.7 (6)
O1—Co1—N1^ii	99.9 (2)	O4—C5—C4	118.4 (6)
O1—Co1—N2	106.5 (2)	C4—C6—H6	119.3
O3^i—Co1—O5	99.1 (2)	C7—C6—C4	121.4 (5)
O4^i—Co1—O3^i	58.50 (19)	C7—C6—H6	119.3
O4^i—Co1—O5	78.9 (2)	C6—C7—N1	119.5 (5)
O4^i—Co1—N1^ii	96.7 (2)	C6—C7—C8	119.9 (6)
O4^i—Co1—N2	142.4 (2)	C8—C7—N1	120.5 (6)
N1^ii—Co1—O3^i	84.5 (2)	C2—C8—H8	120.1
N1^ii—Co1—O5	171.5 (2)	C7—C8—C2	119.8 (6)
N2—Co1—O3^i	90.8 (2)	C7—C8—H8	120.1
N2—Co1—O5	86.0 (3)	N2—C9—H9	118.9
N2—Co1—N1^ii	101.7 (2)	N2—C9—C10	122.2 (8)
C1—O1—Co1	136.3 (5)	C10—C9—H9	118.9
C5—O3—Co1^iii	82.5 (4)	C9—C10—H10	118.8
C5—O4—Co1^iii	99.0 (4)	C11—C10—C9	122.4 (7)
Co1—O5—H5	124.0 (18)	C11—C10—H10	118.8
C14—O5—Co1	119.3 (8)	C10—C11—C11^v	122.5 (8)
C14—O5—H5	103.1 (17)	C10—C11—C12	115.1 (7)
Co1^iv—N1—H1A	109.4	C12—C11—C11^v	122.3 (9)
Co1^iv—N1—H1B	109.4	C11—C12—H12	119.9
H1A—N1—H1B	108.0	C11—C12—C13	120.3 (7)
C7—N1—Co1^iv	111.3 (4)	C13—C12—H12	119.9
C7—N1—H1A	109.4	N2—C13—C12	123.3 (6)
C7—N1—H1B	109.4	N2—C13—H13	118.4
C9—N2—Co1	123.8 (5)	C12—C13—H13	118.4
C9—N2—C13	116.5 (6)	O5—C14—H14A	109.9
C13—N2—Co1	119.1 (5)	O5—C14—H14B	109.9
O1—C1—C2	115.2 (6)	O5—C14—C15	109.1 (11)
O2—C1—O1	124.3 (6)	H14A—C14—H14B	108.3
O2—C1—C2	120.5 (6)	C15—C14—H14A	109.9
C3—C2—C1	120.9 (6)	C15—C14—H14B	109.9
C8—C2—C1	119.3 (6)	C14—C15—H15A	109.5
C8—C2—C3	119.8 (5)	C14—C15—H15B	109.5
C2—C3—H3	120.3	C14—C15—H15C	109.5
C4—C3—C2	119.5 (6)	H15A—C15—H15B	109.5
C4—C3—H3	120.3	H15A—C15—H15C	109.5
C3—C4—C5	121.1 (6)	H15B—C15—H15C	109.5
C6—C4—C3	119.5 (6)	H6A—O6—H6B	109.6
Co1—O1—C1—O2	1.5 (13)	C2—C3—C4—C6	0.2 (10)
Co1—O1—C1—C2	179.5 (5)	C3—C2—C8—C7	1.8 (10)
Co1^iii—O3—C5—O4	−2.3 (7)	C3—C4—C5—O3	−5.1 (12)
Co1^iii—O3—C5—C4	177.4 (7)	C3—C4—C5—O4	174.6 (7)
Co1^iii—O4—C5—O3	2.8 (8)	C3—C4—C6—C7	2.5 (11)
Co1^iii—O4—C5—C4	−177.0 (6)	C4—C6—C7—N1	173.9 (6)
Co1—O5—C14—C15	101.8 (12)	C4—C6—C7—C8	−3.0 (11)
Co1^iv—N1—C7—C6	−81.1 (7)	C5—C4—C6—C7	−176.7 (7)
Co1^iv—N1—C7—C8	95.7 (6)	C6—C4—C5—O3	174.0 (7)
Co1—N2—C9—C10	−175.4 (9)	C6—C4—C5—O4	−6.2 (11)
Co1—N2—C13—C12	174.3 (7)	C6—C7—C8—C2	0.8 (10)
O1—C1—C2—C3	0.9 (10)	C8—C2—C3—C4	−2.3 (10)
O1—C1—C2—C8	−178.9 (7)	C9—N2—C13—C12	3.0 (14)
O2—C1—C2—C3	179.0 (7)	C9—C10—C11—C11^v	178.2 (11)
O2—C1—C2—C8	−0.8 (10)	C9—C10—C11—C12	2.4 (17)
N1—C7—C8—C2	−176.0 (6)	C10—C11—C12—C13	−3.9 (14)
N2—C9—C10—C11	1.9 (19)	C11^v—C11—C12—C13	−179.6 (10)
C1—C2—C3—C4	177.9 (6)	C11—C12—C13—N2	1.3 (15)
C1—C2—C8—C7	−178.4 (6)	C13—N2—C9—C10	−4.6 (15)
C2—C3—C4—C5	179.3 (7)

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

(structure3)

Crystal data

C13H9CoN2O4·C2H6O	F(000) = 744
Mr = 362.22	Dx = 1.648 Mg m^−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.40651 Å
a = 12.631 (2) Å	Cell parameters from 533 reflections
b = 7.5996 (14) Å	θ = 1.5–14.7°
c = 16.109 (3) Å	µ = 0.63 mm^−1
β = 109.223 (3)°	T = 296 K
V = 1460.1 (5) Å^3	Prism, violet
Z = 4	0.4 × 0.16 × 0.16 mm

Data collection

Bruker SMART APEX2 area detector diffractometer	2988 independent reflections
Silicon 111 monochromator	2104 reflections with I > 2σ(I)
Detector resolution: 7.9 pixels mm^-1	Rint = 0.109
ω and φ scans	θmax = 14.7°, θmin = 1.5°
Absorption correction: multi-scan SADABS-2014/2 (Bruker,2014/2) was used for absorption correction. wR2(int) was 0.1162 before and 0.0725 after correction. The Ratio of minimum to maximum transmission is 0.8766. The λ/2 correction factor is 0.00150.	h = −14→15
Tmin = 0.652, Tmax = 0.744	k = −8→9
23515 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.072	H-atom parameters constrained
wR(F^2) = 0.179	w = 1/[σ^2(Fo^2) + (0.0661P)^2 + 7.9649P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
2988 reflections	Δρmax = 1.57 e Å^−3
195 parameters	Δρmin = −0.69 e Å^−3
1 restraint

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	0.18043 (7)	0.50291 (11)	0.32019 (4)	0.0196 (2)
O1	0.1766 (3)	0.5318 (5)	0.1982 (2)	0.0239 (10)
O2	0.0979 (4)	−0.2951 (6)	0.6689 (2)	0.0291 (10)
O3	0.1950 (4)	0.3535 (6)	0.4518 (3)	0.0331 (11)
O4	0.1535 (4)	0.2424 (5)	0.3200 (2)	0.0255 (10)
N1	0.0388 (4)	−0.3851 (6)	0.3403 (3)	0.0183 (10)
H1A	−0.0075	−0.3440	0.2896	0.022*
H1B	0.0025	−0.4669	0.3600	0.022*
N2	0.3131 (4)	0.6630 (7)	0.3885 (3)	0.0264 (12)
C1	0.1328 (5)	−0.1577 (7)	0.6462 (3)	0.0167 (12)
C2	0.1237 (4)	−0.1319 (7)	0.5510 (3)	0.0150 (11)
C3	0.1506 (5)	0.0291 (7)	0.5220 (3)	0.0174 (12)
H3	0.1773	0.1207	0.5617	0.021*
C4	0.1377 (5)	0.0529 (7)	0.4337 (3)	0.0166 (11)
C5	0.1641 (5)	0.2259 (8)	0.4011 (3)	0.0189 (12)
C6	0.0979 (5)	−0.0833 (8)	0.3742 (3)	0.0171 (11)
H6	0.0884	−0.0662	0.3150	0.021*
C7	0.0723 (5)	−0.2450 (7)	0.4028 (3)	0.0172 (12)
C8	0.0850 (5)	−0.2701 (7)	0.4912 (3)	0.0158 (11)
H8	0.0679	−0.3784	0.5104	0.019*
C9	0.3631 (8)	0.6596 (11)	0.4751 (4)	0.062 (3)
H9	0.3468	0.5674	0.5069	0.075*
C10	0.4375 (9)	0.7860 (13)	0.5196 (4)	0.074 (3)
H10	0.4724	0.7752	0.5800	0.089*
C11	0.4613 (5)	0.9278 (9)	0.4766 (4)	0.0288 (14)
C12	0.4058 (7)	0.9343 (11)	0.3893 (4)	0.053 (2)
H12	0.4160	1.0302	0.3569	0.063*
C13	0.3346 (7)	0.8009 (12)	0.3477 (4)	0.054 (2)
H13	0.2996	0.8088	0.2872	0.065*
O5	0.3948 (15)	0.167 (2)	0.7339 (11)	0.241 (8)*
H5	0.3338	0.1178	0.7168	0.361*
C14	0.3948 (13)	0.312 (2)	0.6763 (10)	0.126 (5)*
H14A	0.4621	0.3818	0.7006	0.151*
H14B	0.3928	0.2679	0.6193	0.151*
C15	0.3002 (12)	0.413 (2)	0.6679 (9)	0.122 (5)*
H15A	0.2416	0.3814	0.6148	0.183*
H15B	0.3183	0.5354	0.6656	0.183*
H15C	0.2755	0.3929	0.7174	0.183*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0366 (4)	0.0136 (4)	0.0085 (3)	−0.0072 (4)	0.0073 (3)	−0.0011 (3)
O1	0.043 (2)	0.020 (2)	0.0117 (17)	0.0031 (19)	0.0117 (16)	0.0035 (15)
O2	0.053 (3)	0.024 (2)	0.0116 (18)	−0.010 (2)	0.0134 (18)	0.0011 (16)
O3	0.058 (3)	0.015 (2)	0.020 (2)	−0.012 (2)	0.0039 (19)	0.0019 (17)
O4	0.052 (3)	0.013 (2)	0.0150 (18)	−0.0039 (19)	0.0157 (18)	0.0027 (16)
N1	0.034 (3)	0.013 (2)	0.0072 (19)	−0.006 (2)	0.0062 (18)	−0.0030 (17)
N2	0.034 (3)	0.029 (3)	0.015 (2)	−0.007 (2)	0.007 (2)	−0.003 (2)
C1	0.025 (3)	0.018 (3)	0.008 (2)	0.002 (2)	0.006 (2)	0.001 (2)
C2	0.021 (3)	0.013 (3)	0.010 (2)	−0.002 (2)	0.004 (2)	0.001 (2)
C3	0.027 (3)	0.013 (3)	0.011 (2)	0.002 (2)	0.006 (2)	−0.003 (2)
C4	0.028 (3)	0.009 (3)	0.014 (2)	−0.002 (2)	0.007 (2)	0.0023 (19)
C5	0.028 (3)	0.013 (3)	0.015 (2)	−0.001 (2)	0.006 (2)	0.002 (2)
C6	0.029 (3)	0.016 (3)	0.006 (2)	0.002 (2)	0.006 (2)	0.001 (2)
C7	0.025 (3)	0.016 (3)	0.010 (2)	−0.001 (2)	0.006 (2)	−0.001 (2)
C8	0.027 (3)	0.009 (3)	0.012 (2)	−0.001 (2)	0.008 (2)	−0.001 (2)
C9	0.096 (7)	0.051 (6)	0.022 (3)	−0.047 (5)	−0.004 (4)	0.009 (3)
C10	0.114 (8)	0.066 (6)	0.015 (3)	−0.056 (6)	−0.017 (4)	0.009 (4)
C11	0.034 (3)	0.031 (4)	0.021 (3)	−0.012 (3)	0.007 (2)	0.000 (3)
C12	0.075 (6)	0.053 (5)	0.024 (3)	−0.043 (4)	0.007 (3)	0.005 (3)
C13	0.073 (6)	0.063 (6)	0.019 (3)	−0.045 (5)	0.007 (3)	0.000 (3)

Geometric parameters (Å, º)

Co1—O1	1.963 (3)	C4—C6	1.387 (8)
Co1—O3	2.359 (4)	C6—H6	0.9300
Co1—O4	2.009 (4)	C6—C7	1.387 (8)
Co1—N1^i	2.101 (5)	C7—C8	1.392 (7)
Co1—N2	2.070 (5)	C8—H8	0.9300
Co1—C5	2.520 (6)	C9—H9	0.9300
O1—C1^ii	1.272 (6)	C9—C10	1.370 (10)
O2—C1	1.235 (7)	C10—H10	0.9300
O3—C5	1.245 (7)	C10—C11	1.366 (10)
O4—C5	1.274 (6)	C11—C11^v	1.498 (12)
N1—Co1^iii	2.100 (5)	C11—C12	1.350 (9)
N1—H1A	0.8900	C12—H12	0.9300
N1—H1B	0.8900	C12—C13	1.375 (10)
N1—C7	1.431 (7)	C13—H13	0.9300
N2—C9	1.328 (8)	O5—H5	0.8200
N2—C13	1.312 (9)	O5—C14	1.436 (19)
C1—O1^iv	1.272 (7)	C14—H14A	0.9700
C1—C2	1.512 (6)	C14—H14B	0.9700
C2—C3	1.391 (7)	C14—C15	1.390 (18)
C2—C8	1.400 (7)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C3—C4	1.390 (7)	C15—H15C	0.9600
C4—C5	1.493 (7)
O1—Co1—O3	157.41 (16)	O3—C5—C4	120.9 (5)
O1—Co1—O4	99.25 (16)	O4—C5—Co1	52.2 (3)
O1—Co1—N1^i	111.60 (17)	O4—C5—C4	119.1 (5)
O1—Co1—N2	102.44 (18)	C4—C5—Co1	169.4 (4)
O1—Co1—C5	129.23 (17)	C4—C6—H6	119.9
O3—Co1—C5	29.33 (15)	C4—C6—C7	120.2 (4)
O4—Co1—O3	59.32 (15)	C7—C6—H6	119.9
O4—Co1—N1^i	104.28 (18)	C6—C7—N1	118.2 (4)
O4—Co1—N2	133.4 (2)	C6—C7—C8	120.0 (5)
O4—Co1—C5	30.08 (16)	C8—C7—N1	121.7 (5)
N1^i—Co1—O3	82.78 (17)	C2—C8—H8	120.1
N1^i—Co1—C5	92.26 (18)	C7—C8—C2	119.8 (5)
N2—Co1—O3	89.71 (17)	C7—C8—H8	120.1
N2—Co1—N1^i	105.16 (19)	N2—C9—H9	118.6
N2—Co1—C5	113.94 (19)	N2—C9—C10	122.9 (7)
C1^ii—O1—Co1	127.2 (4)	C10—C9—H9	118.6
C5—O3—Co1	82.5 (3)	C9—C10—H10	119.5
C5—O4—Co1	97.7 (3)	C11—C10—C9	121.0 (6)
Co1^iii—N1—H1A	109.7	C11—C10—H10	119.5
Co1^iii—N1—H1B	109.7	C10—C11—C11^v	122.6 (7)
H1A—N1—H1B	108.2	C12—C11—C10	115.6 (6)
C7—N1—Co1^iii	109.9 (3)	C12—C11—C11^v	121.7 (7)
C7—N1—H1A	109.7	C11—C12—H12	119.6
C7—N1—H1B	109.7	C11—C12—C13	120.9 (7)
C9—N2—Co1	124.7 (5)	C13—C12—H12	119.6
C13—N2—Co1	117.9 (4)	N2—C13—C12	123.7 (6)
C13—N2—C9	115.9 (6)	N2—C13—H13	118.2
O1^iv—C1—C2	116.2 (5)	C12—C13—H13	118.2
O2—C1—O1^iv	124.1 (5)	C14—O5—H5	109.5
O2—C1—C2	119.7 (5)	O5—C14—H14A	110.2
C3—C2—C1	120.6 (5)	O5—C14—H14B	110.2
C3—C2—C8	119.8 (4)	H14A—C14—H14B	108.5
C8—C2—C1	119.5 (5)	C15—C14—O5	107.7 (15)
C2—C3—H3	120.0	C15—C14—H14A	110.2
C4—C3—C2	119.9 (5)	C15—C14—H14B	110.2
C4—C3—H3	120.0	C14—C15—H15A	109.5
C3—C4—C5	120.7 (5)	C14—C15—H15B	109.5
C6—C4—C3	120.2 (5)	C14—C15—H15C	109.5
C6—C4—C5	119.1 (4)	H15A—C15—H15B	109.5
O3—C5—Co1	68.1 (3)	H15A—C15—H15C	109.5
O3—C5—O4	120.1 (5)	H15B—C15—H15C	109.5
Co1—O3—C5—O4	5.5 (5)	C3—C4—C5—Co1	−149 (2)
Co1—O3—C5—C4	−173.8 (5)	C3—C4—C5—O3	−2.0 (9)
Co1—O4—C5—O3	−6.5 (6)	C3—C4—C5—O4	178.6 (5)
Co1—O4—C5—C4	172.8 (4)	C3—C4—C6—C7	−0.9 (9)
Co1^iii—N1—C7—C6	79.0 (5)	C4—C6—C7—N1	−175.8 (5)
Co1^iii—N1—C7—C8	−97.6 (5)	C4—C6—C7—C8	0.9 (8)
Co1—N2—C9—C10	−168.8 (9)	C5—C4—C6—C7	−179.6 (5)
Co1—N2—C13—C12	167.8 (8)	C6—C4—C5—Co1	30 (3)
O1^iv—C1—C2—C3	−6.9 (8)	C6—C4—C5—O3	176.7 (6)
O1^iv—C1—C2—C8	174.7 (5)	C6—C4—C5—O4	−2.7 (8)
O2—C1—C2—C3	172.7 (5)	C6—C7—C8—C2	0.0 (8)
O2—C1—C2—C8	−5.7 (8)	C8—C2—C3—C4	0.8 (8)
N1—C7—C8—C2	176.6 (5)	C9—N2—C13—C12	1.5 (14)
N2—C9—C10—C11	2.4 (18)	C9—C10—C11—C11^v	177.6 (10)
C1—C2—C3—C4	−177.6 (5)	C9—C10—C11—C12	0.9 (15)
C1—C2—C8—C7	177.5 (5)	C10—C11—C12—C13	−2.8 (14)
C2—C3—C4—C5	178.7 (5)	C11^v—C11—C12—C13	−179.6 (9)
C2—C3—C4—C6	0.1 (8)	C11—C12—C13—N2	1.8 (16)
C3—C2—C8—C7	−0.9 (8)	C13—N2—C9—C10	−3.5 (15)

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