Crystal structures and Hirshfeld surface analysis of transition-metal complexes of 1,3-azole­carb­oxy­lic acids

The crystal structures of five new transition-metal complexes synthesized using thia­zole-2-carb­oxy­lic acid (2-Htza), imidazole-2-carb­oxy­lic acid (2-H₂ima) or 1,3-oxazole-4-carb­oxy­lic acid (4-Hoxa), namely di­aqua­bis­(thia­zole-2-carboxyl­ato-κ²N,O)cobalt(II), [Co(C₄H₂NO₂S)₂(H₂O)₂], 1, di­aqua­bis­(thia­zole-2-car­box­yl­ato-κ²N,O)nickel(II), [Ni(C₄H₂NO₂S)₂(H₂O)₂], 2, di­aqua­bis­(thia­zole-2-car­boxyl­ato-κ²N,O)cadmium(II), [Cd(C₄H₂NO₂S)₂(H₂O)₂], 3, di­aqua­bis­(1H-imidazole-2-carboxyl­ato-κ²N³,O)cobalt(II), [Co(C₄H₂N₂O₂)₂(H₂O)₂], 4, and di­aqua­bis­(1,3-oxazole-4-carboxyl­ato-κ²N,O⁴)cobalt(II), [Co(C₄H₂NO₃)₂(H₂O)₂], 5, are reported. The influence of the nature of the heteroatom and the position of the carboxyl group in relation to the heteroatom on the self-assembly process are discussed based upon Hirshfeld surface analysis and used to explain the observed differences in the single-crystal structures and the supra­molecular frameworks and topologies of complexes 1–5.

Computing details

For all structures, data collection: X-AREA (Stoe & Cie, 2016); cell refinement: X-AREA (Stoe & Cie, 2016); data reduction: SORTAV (Blessing, 1987, 1989). Program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a) for Co-2tza, Ni-2tza, Cd-2tza, Co-2Hima; SHELXS86 (Sheldrick, 2008) for Co-4oxa. For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b).

Diaquabis(thiazole-2-carboxylato-κ²N,O)cobalt(II) (Co-2tza)

Crystal data

[Co(C4H2NO2S)2(H2O)2]	F(000) = 354
Mr = 351.21	Dx = 1.948 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.0481 (4) Å	Cell parameters from 4872 reflections
b = 18.633 (2) Å	θ = 2.2–29.6°
c = 6.7533 (6) Å	µ = 1.81 mm^−1
β = 109.517 (7)°	T = 150 K
V = 598.73 (10) Å^3	Block, dark pink
Z = 2	0.50 × 0.17 × 0.17 mm

Data collection

Stoe IPDS2 diffractometer	1606 independent reflections
Radiation source: fine-focus sealed tube	1382 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.025
ω–scans	θmax = 29.2°, θmin = 2.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −4→6
Tmin = 0.677, Tmax = 0.720	k = −25→22
4040 measured reflections	l = −9→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	All H-atom parameters refined
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0344P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
1606 reflections	Δρmax = 0.36 e Å^−3
98 parameters	Δρmin = −0.28 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.

Refinement. X-ray diffraction intensity data of 1</b->-5 were collected in the series of w-scans using Stoe IPDS2 image plate diffractometer operated with Mo Kα radiation at 150 (2) K. The multi-scan absorption corrections were applied for every collected data set (Blessing, 1987; Blessing, 1989). The structures were solved using dual-space methods within SHELXT and full-matrix least squares refinements were carried out within SHELXL-2018/3 via the WinGX program interface (Sheldrick, 2015). All non-hydrogen positions were located in the direct and the difference Fourier maps and refined using anisotropic displacement parameters.

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

	x	y	z	Uiso*/Ueq
Co1	0.500000	0.500000	0.500000	0.01262 (8)
S1	0.68756 (8)	0.71302 (2)	0.82051 (5)	0.01889 (9)
O1	0.3270 (2)	0.52278 (5)	0.73902 (14)	0.0156 (2)
O3	0.1516 (2)	0.54862 (6)	0.27445 (14)	0.0173 (2)
O2	0.3324 (2)	0.60882 (6)	0.97625 (14)	0.0184 (2)
N1	0.6624 (2)	0.60438 (6)	0.58708 (15)	0.0138 (2)
C4	0.3988 (3)	0.58325 (7)	0.82967 (18)	0.0136 (3)
C3	0.5815 (3)	0.62785 (7)	0.74123 (18)	0.0136 (2)
C2	0.8481 (3)	0.71826 (8)	0.6352 (2)	0.0189 (3)
H2	0.946 (2)	0.7588 (9)	0.6121 (5)	0.023*
C1	0.8151 (3)	0.65571 (7)	0.52517 (19)	0.0157 (3)
H1	0.8902 (14)	0.64818 (16)	0.416 (2)	0.019*
H3A	0.188 (5)	0.5618 (11)	0.179 (3)	0.033 (5)*
H3B	−0.008 (5)	0.5279 (13)	0.240 (3)	0.038 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01306 (13)	0.01334 (13)	0.01342 (12)	−0.00155 (10)	0.00703 (9)	−0.00072 (8)
S1	0.02500 (19)	0.01638 (16)	0.02084 (16)	−0.00498 (14)	0.01505 (13)	−0.00464 (11)
O1	0.0160 (5)	0.0157 (4)	0.0179 (4)	−0.0021 (4)	0.0093 (4)	−0.0004 (3)
O3	0.0155 (5)	0.0223 (5)	0.0157 (4)	−0.0021 (4)	0.0075 (4)	0.0024 (4)
O2	0.0233 (5)	0.0184 (5)	0.0185 (4)	0.0001 (4)	0.0136 (4)	0.0005 (4)
N1	0.0131 (5)	0.0152 (5)	0.0144 (5)	−0.0012 (4)	0.0064 (4)	0.0000 (4)
C4	0.0118 (6)	0.0157 (6)	0.0136 (5)	0.0016 (5)	0.0045 (4)	0.0027 (4)
C3	0.0138 (6)	0.0141 (6)	0.0139 (5)	−0.0011 (5)	0.0058 (4)	−0.0002 (4)
C2	0.0213 (7)	0.0178 (7)	0.0222 (6)	−0.0041 (6)	0.0135 (5)	−0.0008 (5)
C1	0.0170 (6)	0.0169 (6)	0.0161 (5)	−0.0009 (5)	0.0095 (5)	0.0012 (5)

Geometric parameters (Å, º)

Co1—O3	2.1082 (10)	O3—H3A	0.77 (2)
Co1—O3^i	2.1082 (10)	O3—H3B	0.85 (3)
Co1—N1^i	2.1161 (12)	O2—C4	1.2412 (16)
Co1—N1	2.1162 (12)	N1—C3	1.3138 (17)
Co1—O1^i	2.1191 (10)	N1—C1	1.3781 (18)
Co1—O1	2.1191 (10)	C4—C3	1.5052 (19)
S1—C3	1.7032 (14)	C2—C1	1.3622 (19)
S1—C2	1.7059 (15)	C2—H2	0.94 (2)
O1—C4	1.2757 (16)	C1—H1	0.945 (17)
O3—Co1—O3^i	180.0	Co1—O3—H3B	119.2 (15)
O3—Co1—N1^i	92.40 (4)	H3A—O3—H3B	112 (2)
O3^i—Co1—N1^i	87.59 (4)	C3—N1—C1	111.28 (11)
O3—Co1—N1	87.60 (4)	C3—N1—Co1	109.39 (9)
O3^i—Co1—N1	92.41 (4)	C1—N1—Co1	139.25 (9)
N1^i—Co1—N1	180.00 (6)	O2—C4—O1	127.78 (13)
O3—Co1—O1^i	89.57 (4)	O2—C4—C3	117.97 (12)
O3^i—Co1—O1^i	90.43 (4)	O1—C4—C3	114.24 (11)
N1^i—Co1—O1^i	79.87 (4)	N1—C3—C4	121.64 (12)
N1—Co1—O1^i	100.13 (4)	N1—C3—S1	114.26 (10)
O3—Co1—O1	90.43 (4)	C4—C3—S1	124.03 (10)
O3^i—Co1—O1	89.57 (4)	C1—C2—S1	110.47 (11)
N1^i—Co1—O1	100.13 (4)	C1—C2—H2	124.8
N1—Co1—O1	79.87 (4)	S1—C2—H2	124.8
O1^i—Co1—O1	180.00 (4)	C2—C1—N1	114.03 (12)
C3—S1—C2	89.96 (7)	C2—C1—H1	123.0
C4—O1—Co1	114.78 (9)	N1—C1—H1	123.0
Co1—O3—H3A	111.7 (16)
Co1—O1—C4—O2	−178.41 (11)	O2—C4—C3—S1	−3.58 (17)
Co1—O1—C4—C3	2.76 (13)	O1—C4—C3—S1	175.38 (9)
C1—N1—C3—C4	176.82 (11)	C2—S1—C3—N1	0.48 (11)
Co1—N1—C3—C4	−0.53 (15)	C2—S1—C3—C4	−176.63 (11)
C1—N1—C3—S1	−0.37 (15)	C3—S1—C2—C1	−0.45 (11)
Co1—N1—C3—S1	−177.73 (6)	S1—C2—C1—N1	0.35 (16)
O2—C4—C3—N1	179.51 (12)	C3—N1—C1—C2	0.01 (17)
O1—C4—C3—N1	−1.54 (18)	Co1—N1—C1—C2	176.18 (10)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···S1^ii	0.94	2.69	3.3950 (15)	132
C2—H2···O2^ii	0.94	2.63	3.3886 (18)	138
C1—H1···O3^iii	0.94	2.63	3.4140 (18)	140
O3—H3A···O2^iv	0.77 (2)	1.96 (2)	2.7158 (14)	168 (2)
O3—H3B···O1^v	0.85 (3)	1.91 (3)	2.7326 (15)	161 (2)

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

Diaquabis(thiazole-2-carboxylato-κ²N,O)nickel(II) (Ni-2tza)

Crystal data

[Ni(C4H2NO2S)2(H2O)2]	F(000) = 356
Mr = 350.99	Dx = 1.959 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.0710 (9) Å	Cell parameters from 4959 reflections
b = 18.239 (3) Å	θ = 2.3–29.6°
c = 6.8383 (17) Å	µ = 2.01 mm^−1
β = 109.780 (16)°	T = 150 K
V = 595.2 (2) Å^3	Block, blue
Z = 2	0.46 × 0.11 × 0.10 mm

Data collection

Stoe IPDS2 diffractometer	1594 independent reflections
Radiation source: fine-focus sealed tube	1367 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.036
ω–scans	θmax = 29.1°, θmin = 2.2°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −6→5
Tmin = 0.817, Tmax = 0.823	k = −21→24
4011 measured reflections	l = −9→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	All H-atom parameters refined
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0372P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.001
1594 reflections	Δρmax = 0.50 e Å^−3
98 parameters	Δρmin = −0.29 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.

Refinement. X-ray diffraction intensity data of 1</b->-5 were collected in the series of w-scans using Stoe IPDS2 image plate diffractometer operated with Mo Kα radiation at 150 (2) K. The multi-scan absorption corrections were applied for every collected data set (Blessing, 1987; Blessing, 1989). The structures were solved using dual-space methods within SHELXT and full-matrix least squares refinements were carried out within SHELXL-2018/3 via the WinGX program interface (Sheldrick, 2015). All non-hydrogen positions were located in the direct and the difference Fourier maps and refined using anisotropic displacement parameters.

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

	x	y	z	Uiso*/Ueq
Ni1	0.500000	0.500000	0.500000	0.01278 (9)
S1	0.31739 (8)	0.71461 (2)	0.18386 (5)	0.01900 (10)
O3	0.8408 (2)	0.54992 (7)	0.72103 (16)	0.0170 (2)
O1	0.6774 (2)	0.52045 (6)	0.26838 (15)	0.0159 (2)
O2	0.6738 (2)	0.60702 (6)	0.03003 (15)	0.0190 (2)
N1	0.3413 (3)	0.60338 (7)	0.41318 (17)	0.0142 (2)
C4	0.6066 (3)	0.58173 (8)	0.1758 (2)	0.0137 (3)
C3	0.4232 (3)	0.62756 (8)	0.2609 (2)	0.0141 (3)
C2	0.1889 (3)	0.65508 (9)	0.4749 (2)	0.0161 (3)
H2	0.1120 (14)	0.64669 (18)	0.584 (2)	0.019*
C1	0.1560 (3)	0.71949 (9)	0.3671 (2)	0.0188 (3)
H1	0.060 (2)	0.7600 (10)	0.3898 (6)	0.023*
H3A	0.811 (5)	0.5601 (13)	0.818 (3)	0.036 (6)*
H3B	0.988 (6)	0.5304 (14)	0.742 (3)	0.037 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01260 (14)	0.01343 (14)	0.01475 (12)	0.00166 (10)	0.00782 (9)	0.00072 (9)
S1	0.0242 (2)	0.0168 (2)	0.02135 (17)	0.00458 (15)	0.01470 (15)	0.00453 (13)
O3	0.0141 (5)	0.0222 (6)	0.0172 (5)	0.0019 (5)	0.0084 (4)	−0.0026 (4)
O1	0.0160 (5)	0.0162 (5)	0.0187 (5)	0.0016 (4)	0.0102 (4)	0.0005 (4)
O2	0.0235 (6)	0.0192 (5)	0.0196 (5)	−0.0005 (5)	0.0143 (4)	−0.0010 (4)
N1	0.0135 (6)	0.0155 (6)	0.0151 (5)	0.0009 (5)	0.0068 (4)	0.0000 (4)
C4	0.0113 (7)	0.0154 (7)	0.0155 (5)	−0.0014 (5)	0.0057 (5)	−0.0032 (5)
C3	0.0129 (7)	0.0151 (7)	0.0150 (5)	0.0000 (5)	0.0057 (5)	0.0000 (5)
C2	0.0161 (7)	0.0175 (7)	0.0175 (6)	0.0011 (6)	0.0095 (5)	−0.0007 (5)
C1	0.0200 (7)	0.0188 (7)	0.0223 (6)	0.0035 (6)	0.0132 (6)	0.0000 (5)

Geometric parameters (Å, º)

Ni1—N1^i	2.0572 (13)	O3—H3B	0.79 (3)
Ni1—N1	2.0573 (13)	O1—C4	1.2748 (18)
Ni1—O3	2.0814 (12)	O2—C4	1.2460 (17)
Ni1—O3^i	2.0814 (12)	N1—C3	1.3207 (18)
Ni1—O1	2.1029 (11)	N1—C2	1.3728 (19)
Ni1—O1^i	2.1029 (11)	C4—C3	1.506 (2)
S1—C3	1.7013 (15)	C2—C1	1.367 (2)
S1—C1	1.7155 (15)	C2—H2	0.967 (18)
O3—H3A	0.75 (2)	C1—H1	0.93 (2)
N1^i—Ni1—N1	180.0	H3A—O3—H3B	114 (2)
N1^i—Ni1—O3	92.51 (5)	C4—O1—Ni1	114.14 (9)
N1—Ni1—O3	87.49 (5)	C3—N1—C2	111.89 (13)
N1^i—Ni1—O3^i	87.49 (5)	C3—N1—Ni1	109.69 (10)
N1—Ni1—O3^i	92.51 (5)	C2—N1—Ni1	138.31 (10)
O3—Ni1—O3^i	180.00 (5)	O2—C4—O1	127.90 (14)
N1^i—Ni1—O1	98.90 (4)	O2—C4—C3	118.40 (13)
N1—Ni1—O1	81.11 (4)	O1—C4—C3	113.69 (12)
O3—Ni1—O1	90.43 (5)	N1—C3—C4	121.29 (13)
O3^i—Ni1—O1	89.57 (5)	N1—C3—S1	113.92 (11)
N1^i—Ni1—O1^i	81.10 (4)	C4—C3—S1	124.72 (11)
N1—Ni1—O1^i	98.89 (4)	C1—C2—N1	113.80 (13)
O3—Ni1—O1^i	89.57 (5)	C1—C2—H2	123.1
O3^i—Ni1—O1^i	90.43 (5)	N1—C2—H2	123.1
O1—Ni1—O1^i	180.00 (6)	C2—C1—S1	110.35 (12)
C3—S1—C1	90.04 (7)	C2—C1—H1	124.8
Ni1—O3—H3A	112.4 (18)	S1—C1—H1	124.8
Ni1—O3—H3B	115.8 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3^ii	0.97	2.60	3.4117 (19)	142
C1—H1···S1^iii	0.93	2.73	3.4060 (16)	131
C1—H1···O2^iii	0.93	2.60	3.346 (2)	138
O3—H3A···O2^iv	0.75 (2)	2.00 (2)	2.7345 (16)	166 (2)
O3—H3B···O1^v	0.79 (3)	1.96 (3)	2.7388 (17)	168 (2)

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

Diaquabis(thiazole-2-carboxylato-κ²N,O)cadmium(II) (Cd-2tza)

Crystal data

[Cd(C4H2NO2S)2(H2O)2]	F(000) = 396
Mr = 404.68	Dx = 2.158 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.0198 (5) Å	Cell parameters from 5602 reflections
b = 19.052 (2) Å	θ = 2.2–29.6°
c = 6.8982 (7) Å	µ = 2.11 mm^−1
β = 109.281 (7)°	T = 150 K
V = 622.71 (11) Å^3	Block, colourless
Z = 2	0.40 × 0.27 × 0.08 mm

Data collection

Stoe IPDS2 diffractometer	1673 independent reflections
Radiation source: fine-focus sealed tube	1458 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.032
ω scans	θmax = 29.2°, θmin = 2.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −6→5
Tmin = 0.850, Tmax = 0.914	k = −25→22
4992 measured reflections	l = −9→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	All H-atom parameters refined
wR(F^2) = 0.047	w = 1/[σ^2(Fo^2) + (0.0313P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
1673 reflections	Δρmax = 0.89 e Å^−3
98 parameters	Δρmin = −0.84 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.

Refinement. X-ray diffraction intensity data of 1</b->-5 were collected in the series of w-scans using Stoe IPDS2 image plate diffractometer operated with Mo Kα radiation at 150 (2) K. The multi-scan absorption corrections were applied for every collected data set (Blessing, 1987; Blessing, 1989). The structures were solved using dual-space methods within SHELXT and full-matrix least squares refinements were carried out within SHELXL-2018/3 via the WinGX program interface (Sheldrick, 2015). All non-hydrogen positions were located in the direct and the difference Fourier maps and refined using anisotropic displacement parameters.

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

	x	y	z	Uiso*/Ueq
Cd1	0.500000	0.500000	0.500000	0.01528 (6)
O3	0.8802 (3)	0.55617 (7)	0.73796 (17)	0.0194 (2)
O1	0.6482 (3)	0.61418 (7)	0.00368 (17)	0.0201 (2)
O2	0.6718 (2)	0.52899 (6)	0.23548 (16)	0.0178 (2)
C1	0.5919 (3)	0.58753 (8)	0.1499 (2)	0.0148 (3)
C2	0.4098 (3)	0.63096 (8)	0.2408 (2)	0.0140 (3)
C3	0.1748 (3)	0.66018 (9)	0.4519 (2)	0.0166 (3)
H3	0.1000 (15)	0.65356 (16)	0.559 (2)	0.020*
C4	0.1409 (3)	0.72058 (9)	0.3421 (2)	0.0191 (3)
H4	0.045 (3)	0.7595 (10)	0.3626 (6)	0.023*
N1	0.3275 (3)	0.60944 (7)	0.39317 (18)	0.0146 (2)
S1	0.30263 (9)	0.71402 (2)	0.16011 (6)	0.01898 (9)
H3B	1.012 (6)	0.5294 (17)	0.779 (4)	0.038 (7)*
H3A	0.839 (5)	0.5707 (14)	0.830 (4)	0.036 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01881 (9)	0.01293 (9)	0.01618 (8)	0.00218 (6)	0.00860 (6)	0.00253 (5)
O3	0.0198 (6)	0.0220 (6)	0.0183 (5)	0.0032 (5)	0.0091 (4)	−0.0017 (4)
O1	0.0282 (6)	0.0172 (6)	0.0211 (5)	0.0008 (5)	0.0167 (5)	0.0002 (4)
O2	0.0209 (6)	0.0164 (6)	0.0197 (5)	0.0038 (5)	0.0115 (4)	0.0016 (4)
C1	0.0147 (7)	0.0152 (7)	0.0160 (6)	−0.0011 (6)	0.0071 (5)	−0.0031 (5)
C2	0.0148 (7)	0.0141 (7)	0.0140 (6)	0.0007 (6)	0.0061 (5)	−0.0003 (5)
C3	0.0192 (7)	0.0166 (8)	0.0172 (6)	0.0007 (6)	0.0103 (6)	−0.0020 (5)
C4	0.0236 (8)	0.0165 (8)	0.0217 (7)	0.0041 (6)	0.0136 (6)	−0.0002 (5)
N1	0.0166 (6)	0.0140 (6)	0.0154 (5)	0.0010 (5)	0.0082 (5)	0.0007 (4)
S1	0.0263 (2)	0.01547 (19)	0.02063 (17)	0.00447 (16)	0.01507 (14)	0.00441 (14)

Geometric parameters (Å, º)

Cd1—N1	2.2845 (14)	O2—C1	1.264 (2)
Cd1—N1^i	2.2845 (14)	C1—C2	1.514 (2)
Cd1—O3	2.3267 (13)	C2—N1	1.3153 (18)
Cd1—O3^i	2.3268 (13)	C2—S1	1.7046 (16)
Cd1—O2	2.3276 (11)	C3—C4	1.357 (2)
Cd1—O2^i	2.3277 (11)	C3—N1	1.375 (2)
O3—H3B	0.81 (3)	C3—H3	0.944 (19)
O3—H3A	0.78 (3)	C4—S1	1.7098 (15)
O1—C1	1.2422 (18)	C4—H4	0.92 (2)
N1—Cd1—N1^i	180.00 (7)	C1—O2—Cd1	115.67 (9)
N1—Cd1—O3	86.74 (5)	O1—C1—O2	128.16 (14)
N1^i—Cd1—O3	93.26 (5)	O1—C1—C2	116.32 (14)
N1—Cd1—O3^i	93.26 (5)	O2—C1—C2	115.51 (12)
N1^i—Cd1—O3^i	86.74 (5)	N1—C2—C1	123.54 (14)
O3—Cd1—O3^i	180.00 (6)	N1—C2—S1	113.69 (11)
N1—Cd1—O2	74.31 (4)	C1—C2—S1	122.73 (11)
N1^i—Cd1—O2	105.69 (4)	C4—C3—N1	114.24 (13)
O3—Cd1—O2	90.80 (4)	C4—C3—H3	122.9
O3^i—Cd1—O2	89.20 (4)	N1—C3—H3	122.9
N1—Cd1—O2^i	105.69 (4)	C3—C4—S1	110.22 (12)
N1^i—Cd1—O2^i	74.31 (4)	C3—C4—H4	124.9
O3—Cd1—O2^i	89.20 (4)	S1—C4—H4	124.9
O3^i—Cd1—O2^i	90.80 (4)	C2—N1—C3	111.66 (13)
O2—Cd1—O2^i	180.0	C2—N1—Cd1	110.90 (10)
Cd1—O3—H3B	110 (2)	C3—N1—Cd1	137.32 (10)
Cd1—O3—H3A	111.1 (19)	C2—S1—C4	90.19 (8)
H3B—O3—H3A	110 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3^ii	0.94	2.66	3.4543 (19)	142
C4—H4···O1^iii	0.92	2.58	3.336 (2)	139
C4—H4···S1^iii	0.92	2.76	3.4218 (16)	130
O3—H3B···O2^iv	0.81 (3)	1.97 (3)	2.7294 (18)	157 (3)
O3—H3A···O1^v	0.78 (3)	1.95 (3)	2.7106 (17)	165 (3)

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

Diaquabis(1H-imidazole-2-carboxylato-κ²N³,O)cobalt(II) (Co-2Hima)

Crystal data

[Co(C4H2N2O2)2(H2O)2]	F(000) = 322
Mr = 317.13	Dx = 1.880 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.1145 (7) Å	Cell parameters from 2611 reflections
b = 10.6123 (12) Å	θ = 2.8–29.5°
c = 10.4179 (13) Å	µ = 1.56 mm^−1
β = 97.858 (10)°	T = 150 K
V = 560.14 (12) Å^3	Block, pale orange
Z = 2	0.20 × 0.11 × 0.11 mm

Data collection

Stoe IPDS2 diffractometer	1495 independent reflections
Radiation source: fine-focus sealed tube	1078 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.027
ω–scans	θmax = 29.2°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −6→7
Tmin = 0.944, Tmax = 0.948	k = −13→14
3303 measured reflections	l = −14→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	All H-atom parameters refined
wR(F^2) = 0.048	w = 1/[σ^2(Fo^2) + (0.0227P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.84	(Δ/σ)max < 0.001
1495 reflections	Δρmax = 0.32 e Å^−3
99 parameters	Δρmin = −0.28 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.

Refinement. X-ray diffraction intensity data of 1</b->-5 were collected in the series of w-scans using Stoe IPDS2 image plate diffractometer operated with Mo Kα radiation at 150 (2) K. The multi-scan absorption corrections were applied for every collected data set (Blessing, 1987; Blessing, 1989). The structures were solved using dual-space methods within SHELXT and full-matrix least squares refinements were carried out within SHELXL-2018/3 via the WinGX program interface (Sheldrick, 2015). All non-hydrogen positions were located in the direct and the difference Fourier maps and refined using anisotropic displacement parameters.

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

	x	y	z	Uiso*/Ueq
Co1	0.500000	0.500000	0.500000	0.01256 (8)
C2	0.2691 (3)	0.89171 (17)	0.42726 (16)	0.0202 (4)
H2	0.1925 (19)	0.9647 (17)	0.43085 (18)	0.024*
O1	0.7373 (2)	0.54766 (10)	0.35744 (11)	0.0154 (2)
O3	0.2152 (2)	0.44396 (13)	0.34702 (12)	0.0171 (2)
O2	0.8152 (2)	0.70089 (11)	0.22067 (12)	0.0210 (3)
N1	0.3895 (3)	0.69131 (12)	0.46601 (13)	0.0149 (3)
C3	0.5145 (3)	0.73694 (15)	0.37229 (15)	0.0152 (3)
C4	0.7044 (3)	0.65913 (15)	0.31028 (15)	0.0143 (3)
C1	0.2359 (3)	0.78838 (15)	0.50138 (17)	0.0181 (3)
H1	0.129 (2)	0.78431 (18)	0.5645 (14)	0.022*
N2	0.4455 (3)	0.85818 (13)	0.34665 (14)	0.0198 (3)
H2A	0.5026 (15)	0.9055 (12)	0.2898 (14)	0.024*
H3A	0.198 (4)	0.368 (2)	0.337 (2)	0.031 (6)*
H3B	0.076 (5)	0.474 (2)	0.343 (2)	0.044 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01397 (13)	0.01072 (13)	0.01381 (14)	0.00019 (14)	0.00483 (9)	0.00071 (15)
C2	0.0227 (8)	0.0161 (8)	0.0230 (9)	0.0064 (6)	0.0079 (7)	−0.0020 (7)
O1	0.0163 (5)	0.0121 (5)	0.0191 (6)	0.0018 (4)	0.0071 (4)	0.0022 (4)
O3	0.0152 (6)	0.0142 (6)	0.0221 (6)	0.0018 (5)	0.0032 (4)	−0.0036 (5)
O2	0.0254 (6)	0.0180 (6)	0.0224 (6)	0.0018 (5)	0.0129 (5)	0.0035 (5)
N1	0.0157 (6)	0.0134 (7)	0.0160 (6)	0.0007 (5)	0.0040 (5)	0.0004 (5)
C3	0.0158 (7)	0.0140 (8)	0.0161 (8)	0.0001 (6)	0.0033 (6)	0.0004 (6)
C4	0.0136 (7)	0.0146 (8)	0.0149 (8)	−0.0017 (6)	0.0025 (6)	−0.0011 (6)
C1	0.0170 (7)	0.0186 (8)	0.0203 (8)	0.0036 (6)	0.0084 (6)	−0.0017 (7)
N2	0.0264 (7)	0.0136 (7)	0.0210 (7)	0.0026 (5)	0.0088 (6)	0.0041 (6)

Geometric parameters (Å, º)

Co1—O3	2.0931 (11)	O3—H3A	0.81 (2)
Co1—O3^i	2.0931 (11)	O3—H3B	0.78 (2)
Co1—O1^i	2.1041 (12)	O2—C4	1.239 (2)
Co1—O1	2.1041 (12)	N1—C3	1.329 (2)
Co1—N1^i	2.1241 (13)	N1—C1	1.376 (2)
Co1—N1	2.1242 (13)	C3—N2	1.351 (2)
C2—N2	1.361 (2)	C3—C4	1.488 (2)
C2—C1	1.365 (2)	C1—H1	0.91 (2)
C2—H2	0.87 (2)	N2—H2A	0.86 (2)
O1—C4	1.2831 (19)
O3—Co1—O3^i	180.0	Co1—O3—H3A	115.5 (14)
O3—Co1—O1^i	93.48 (5)	Co1—O3—H3B	117.2 (18)
O3^i—Co1—O1^i	86.52 (5)	H3A—O3—H3B	109 (2)
O3—Co1—O1	86.52 (5)	C3—N1—C1	105.88 (13)
O3^i—Co1—O1	93.48 (5)	C3—N1—Co1	109.07 (10)
O1^i—Co1—O1	180.0	C1—N1—Co1	145.04 (12)
O3—Co1—N1^i	89.83 (5)	N1—C3—N2	110.67 (14)
O3^i—Co1—N1^i	90.17 (5)	N1—C3—C4	121.65 (14)
O1^i—Co1—N1^i	79.55 (5)	N2—C3—C4	127.67 (15)
O1—Co1—N1^i	100.45 (5)	O2—C4—O1	124.67 (15)
O3—Co1—N1	90.17 (5)	O2—C4—C3	121.46 (15)
O3^i—Co1—N1	89.83 (5)	O1—C4—C3	113.87 (14)
O1^i—Co1—N1	100.45 (5)	C2—C1—N1	109.28 (15)
O1—Co1—N1	79.55 (5)	C2—C1—H1	125.4
N1^i—Co1—N1	180.0	N1—C1—H1	125.4
N2—C2—C1	106.45 (15)	C3—N2—C2	107.71 (15)
N2—C2—H2	126.8	C3—N2—H2A	126.1
C1—C2—H2	126.8	C2—N2—H2A	126.1
C4—O1—Co1	115.71 (10)
C1—N1—C3—N2	−0.31 (16)	N1—C3—C4—O1	−1.3 (2)
Co1—N1—C3—N2	179.03 (10)	N2—C3—C4—O1	177.84 (14)
C1—N1—C3—C4	178.99 (14)	N2—C2—C1—N1	−0.45 (18)
Co1—N1—C3—C4	−1.67 (16)	C3—N1—C1—C2	0.47 (17)
Co1—O1—C4—O2	−175.67 (11)	Co1—N1—C1—C2	−178.44 (14)
Co1—O1—C4—C3	3.72 (15)	N1—C3—N2—C2	0.04 (17)
N1—C3—C4—O2	178.08 (14)	C4—C3—N2—C2	−179.21 (14)
N2—C3—C4—O2	−2.8 (2)	C1—C2—N2—C3	0.25 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2^ii	0.91	2.44	3.347 (2)	172
N2—H2A···O1^iii	0.86	2.37	2.9824 (18)	129
N2—H2A···O3^iii	0.86	2.20	2.978 (2)	151
O3—H3A···O2^iv	0.81 (2)	1.87 (2)	2.6731 (18)	168 (2)
O3—H3B···O1^v	0.78 (2)	1.92 (3)	2.6963 (17)	173 (2)

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

Diaquabis(1,3-oxazole-4-carboxylato-κ²N,O⁴)cobalt(II) (Co-4oxa)

Crystal data

[Co(C4H2NO3)2(H2O)2]	F(000) = 322
Mr = 319.09	Dx = 1.940 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.1664 (7) Å	Cell parameters from 2467 reflections
b = 10.9879 (15) Å	θ = 2.8–29.4°
c = 9.7550 (11) Å	µ = 1.61 mm^−1
β = 99.378 (10)°	T = 150 K
V = 546.37 (12) Å^3	Rod, pink
Z = 2	0.20 × 0.11 × 0.11 mm

Data collection

Stoe IPDS2 diffractometer	1458 independent reflections
Radiation source: fine-focus sealed tube	1104 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	Rint = 0.024
ω–scans	θmax = 29.2°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −7→6
Tmin = 0.942, Tmax = 0.948	k = −13→15
2995 measured reflections	l = −13→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	All H-atom parameters refined
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0281P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max < 0.001
1458 reflections	Δρmax = 0.37 e Å^−3
98 parameters	Δρmin = −0.28 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.

Refinement. X-ray diffraction intensity data of 1</b->-5 were collected in the series of w-scans using Stoe IPDS2 image plate diffractometer operated with Mo Kα radiation at 150 (2) K. The multi-scan absorption corrections were applied for every collected data set (Blessing, 1987; Blessing, 1989). The structures were solved using dual-space methods within SHELXT and full-matrix least squares refinements were carried out within SHELXL-2018/3 via the WinGX program interface (Sheldrick, 2015). All non-hydrogen positions were located in the direct and the difference Fourier maps and refined using anisotropic displacement parameters.

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

	x	y	z	Uiso*/Ueq
Co1	0.500000	0.500000	0.500000	0.01187 (9)
O4	0.2663 (2)	0.88157 (11)	0.48213 (14)	0.0213 (3)
O1	0.7373 (2)	0.56802 (10)	0.36309 (13)	0.0152 (2)
O3	0.2083 (2)	0.46901 (12)	0.32952 (14)	0.0172 (3)
O2	0.8395 (2)	0.73459 (11)	0.25189 (14)	0.0186 (3)
N1	0.3868 (3)	0.68823 (13)	0.49404 (15)	0.0135 (3)
C3	0.5207 (3)	0.74931 (15)	0.40020 (18)	0.0141 (3)
C4	0.7136 (3)	0.68066 (14)	0.33175 (17)	0.0134 (3)
C1	0.2420 (3)	0.77044 (15)	0.53788 (19)	0.0168 (3)
H1	0.132 (2)	0.7548 (4)	0.6016 (14)	0.020*
C2	0.4451 (3)	0.86603 (16)	0.3935 (2)	0.0195 (4)
H2	0.4986 (14)	0.9211 (15)	0.3430 (13)	0.023*
H3A	0.194 (4)	0.398 (3)	0.303 (3)	0.031 (6)*
H3B	0.076 (5)	0.497 (3)	0.334 (3)	0.045 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01175 (13)	0.01075 (13)	0.01405 (16)	−0.00006 (13)	0.00491 (10)	0.00083 (16)
O4	0.0268 (6)	0.0159 (6)	0.0239 (8)	0.0042 (5)	0.0124 (5)	0.0000 (5)
O1	0.0144 (5)	0.0127 (5)	0.0199 (7)	0.0010 (4)	0.0070 (5)	0.0009 (5)
O3	0.0139 (5)	0.0164 (7)	0.0213 (7)	0.0019 (4)	0.0028 (5)	−0.0044 (5)
O2	0.0201 (5)	0.0178 (6)	0.0207 (7)	0.0011 (4)	0.0111 (5)	0.0051 (5)
N1	0.0138 (6)	0.0146 (7)	0.0129 (8)	−0.0009 (5)	0.0043 (5)	0.0002 (5)
C3	0.0147 (7)	0.0152 (7)	0.0131 (9)	−0.0011 (5)	0.0044 (6)	0.0008 (6)
C4	0.0115 (7)	0.0154 (7)	0.0133 (9)	0.0001 (5)	0.0019 (6)	−0.0009 (6)
C1	0.0174 (7)	0.0170 (8)	0.0166 (9)	0.0001 (6)	0.0046 (7)	−0.0004 (7)
C2	0.0241 (8)	0.0162 (8)	0.0209 (10)	0.0005 (6)	0.0113 (7)	0.0021 (7)

Geometric parameters (Å, º)

Co1—O3^i	2.0823 (14)	O3—H3A	0.82 (3)
Co1—O3	2.0823 (14)	O3—H3B	0.76 (3)
Co1—O1^i	2.0928 (11)	O2—C4	1.2434 (19)
Co1—O1	2.0928 (11)	N1—C1	1.289 (2)
Co1—N1	2.1476 (14)	N1—C3	1.405 (2)
Co1—N1^i	2.1476 (14)	C3—C2	1.339 (2)
O4—C1	1.351 (2)	C3—C4	1.492 (2)
O4—C2	1.3753 (19)	C1—H1	0.93 (2)
O1—C4	1.2760 (19)	C2—H2	0.85 (2)
O3^i—Co1—O3	180.0	Co1—O3—H3B	115 (2)
O3^i—Co1—O1^i	88.38 (5)	H3A—O3—H3B	112 (3)
O3—Co1—O1^i	91.62 (5)	C1—N1—C3	104.80 (14)
O3^i—Co1—O1	91.62 (5)	C1—N1—Co1	146.70 (11)
O3—Co1—O1	88.38 (5)	C3—N1—Co1	108.47 (10)
O1^i—Co1—O1	180.00 (4)	C2—C3—N1	108.59 (14)
O3^i—Co1—N1	91.30 (5)	C2—C3—C4	132.31 (15)
O3—Co1—N1	88.71 (5)	N1—C3—C4	119.08 (14)
O1^i—Co1—N1	100.13 (4)	O2—C4—O1	124.94 (13)
O1—Co1—N1	79.87 (4)	O2—C4—C3	119.69 (14)
O3^i—Co1—N1^i	88.70 (5)	O1—C4—C3	115.36 (13)
O3—Co1—N1^i	91.29 (5)	N1—C1—O4	113.76 (14)
O1^i—Co1—N1^i	79.87 (5)	N1—C1—H1	123.1
O1—Co1—N1^i	100.13 (4)	O4—C1—H1	123.1
N1—Co1—N1^i	180.0	C3—C2—O4	107.97 (15)
C1—O4—C2	104.88 (13)	C3—C2—H2	126.0
C4—O1—Co1	117.13 (9)	O4—C2—H2	126.0
Co1—O3—H3A	115.2 (18)
C1—N1—C3—C2	−0.3 (2)	C2—C3—C4—O1	179.7 (2)
Co1—N1—C3—C2	178.36 (13)	N1—C3—C4—O1	1.4 (2)
C1—N1—C3—C4	178.41 (16)	C3—N1—C1—O4	0.0 (2)
Co1—N1—C3—C4	−2.98 (17)	Co1—N1—C1—O4	−177.65 (16)
Co1—O1—C4—O2	−179.81 (13)	C2—O4—C1—N1	0.3 (2)
Co1—O1—C4—C3	1.07 (18)	N1—C3—C2—O4	0.4 (2)
C2—C3—C4—O2	0.6 (3)	C4—C3—C2—O4	−177.97 (17)
N1—C3—C4—O2	−177.72 (16)	C1—O4—C2—C3	−0.5 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O2^ii	0.93	2.27	3.1781 (19)	166
C2—H2···O3^iii	0.85	2.50	3.238 (2)	146
O3—H3A···O2^iv	0.82 (3)	1.88 (3)	2.6949 (18)	178 (2)
O3—H3B···O1^v	0.76 (3)	1.98 (3)	2.7333 (16)	175 (3)

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