Crystal structure and spectroscopic characterization of a cobalt(II) tetra­aza­macrocycle: completing a series of first-row transition-metal complexes

The tetra­aza­macrocyclic ligand 1,4,8,11-tetra­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane (TMC) has been used to bind a variety of first-row transition metals but to date the crystal structure of the cobalt(II) complex has been missing from this series. The missing cobalt complex chlorido­(1,4,8,11-tetra­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ⁴N)cobalt(II) chloride dihydrate, [CoCl(C₁₄H₃₂N₄)]Cl·2H₂O or [Co^IICl(TMC)]Cl·2H₂O, crystallizes as a purple crystal. This species adopts a distorted square-pyramidal geometry in which the TMC ligand assumes the trans-I configuration and the chloride ion binds in the syn-methyl pocket of the ligand. The Co^II ion adopts an S = spin state, as measured by the Evans NMR method, and UV–visible spectroscopic studies indicate that the title hydrated salt is stable in solution. Density functional theory (DFT) studies reveal that the geometric parameters of [Co^IICl(TMC)]Cl·2H₂O are sensitive to the cobalt spin state and correctly predict a change in spin state upon a minor perturbation to the ligand environment.

Computing details

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Chlorido(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)cobalt(II) chloride dihydrate

Crystal data

[CoCl(C14H32N4)]Cl·2H2O	F(000) = 900
Mr = 422.30	Dx = 1.419 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.2864 (8) Å	Cell parameters from 9870 reflections
b = 17.0679 (16) Å	θ = 2.5–35.8°
c = 13.9733 (14) Å	µ = 1.15 mm^−1
β = 90.735 (4)°	T = 100 K
V = 1976.1 (3) Å^3	Block, purple
Z = 4	0.40 × 0.30 × 0.25 mm

Data collection

Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS diffractometer	9577 independent reflections
Radiation source: IµS HB micro-focus sealed tube	7769 reflections with I > 2σ(I)
Detector resolution: 10.24 pixels mm^-1	Rint = 0.043
φ and ω scans	θmax = 36.4°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −13→13
Tmin = 0.691, Tmax = 0.747	k = −28→28
72258 measured reflections	l = −23→23

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)] = 0.032	Hydrogen site location: mixed
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0244P)^2 + 0.7824P] where P = (Fo^2 + 2Fc^2)/3
9577 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.56 e Å^−3
4 restraints	Δρmin = −0.56 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.

Low-temperature diffraction data (φ and ω scans) were collected on a Bruker AXS D8 VENTURE KAPPA diffractometer coupled to a PHOTON 100 CMOS detector with Mo Kα radiation (λ = 0.71073 Å) from an IµS micro-source for the structure of compound (1). The structure was solved by direct methods using SHELXS (Sheldrick, 1990) and refined against F² on all data by full-matrix least-squares with SHELXL2014 (Sheldrick, 2008) using established refinement techniques (Müller, 2009). All non-H atoms were refined anisotropically.

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

	x	y	z	Uiso*/Ueq
Cl1	0.51121 (3)	0.66061 (2)	0.60021 (2)	0.01723 (5)
Cl2	0.06423 (3)	0.86258 (2)	0.50039 (2)	0.01387 (4)
Co1	0.70186 (2)	0.62697 (2)	0.71424 (2)	0.00774 (3)
N1	0.92925 (9)	0.61319 (5)	0.64915 (6)	0.01016 (14)
C1	1.06802 (11)	0.64827 (6)	0.70353 (7)	0.01284 (16)
H1A	1.168131	0.638070	0.667682	0.015*
H1B	1.078240	0.621100	0.765913	0.015*
C2	1.05589 (11)	0.73585 (6)	0.72198 (7)	0.01317 (17)
H2A	1.031204	0.762659	0.660694	0.016*
H2B	1.162105	0.755086	0.745178	0.016*
C3	0.92830 (11)	0.75832 (6)	0.79439 (7)	0.01311 (17)
H3A	0.944496	0.726034	0.852584	0.016*
H3B	0.945020	0.813761	0.812835	0.016*
C11	0.92116 (12)	0.64801 (6)	0.55156 (7)	0.01463 (17)
H11A	0.892834	0.703609	0.556246	0.022*
H11B	0.838966	0.620606	0.513205	0.022*
H11C	1.026354	0.642729	0.520950	0.022*
N2	0.75794 (9)	0.74860 (5)	0.76028 (6)	0.01052 (14)
C4	0.64897 (12)	0.75884 (6)	0.84295 (7)	0.01296 (17)
H4A	0.537548	0.768126	0.819173	0.016*
H4B	0.683263	0.805357	0.880333	0.016*
C5	0.65108 (11)	0.68738 (6)	0.90727 (7)	0.01222 (16)
H5A	0.760621	0.680253	0.935032	0.015*
H5B	0.575100	0.695196	0.960533	0.015*
C12	0.72070 (13)	0.81142 (6)	0.69011 (8)	0.01583 (18)
H12A	0.608937	0.805911	0.667317	0.024*
H12B	0.793923	0.807228	0.635831	0.024*
H12C	0.734623	0.862643	0.720811	0.024*
N3	0.60402 (9)	0.61598 (5)	0.85200 (6)	0.00892 (13)
C6	0.65983 (11)	0.54640 (6)	0.90793 (7)	0.01222 (16)
H6A	0.610241	0.548372	0.971971	0.015*
H6B	0.778208	0.550192	0.917275	0.015*
C7	0.62092 (12)	0.46739 (6)	0.86275 (7)	0.01314 (17)
H7A	0.639592	0.425825	0.911057	0.016*
H7B	0.505031	0.466325	0.844684	0.016*
C8	0.72004 (12)	0.44890 (6)	0.77465 (7)	0.01401 (17)
H8A	0.835687	0.456146	0.790969	0.017*
H8B	0.703973	0.393054	0.757900	0.017*
C13	0.42510 (11)	0.61438 (6)	0.84195 (7)	0.01385 (17)
H13A	0.392948	0.570952	0.799971	0.021*
H13B	0.387433	0.663945	0.814205	0.021*
H13C	0.377045	0.607174	0.905065	0.021*
N4	0.68022 (10)	0.49764 (5)	0.68876 (6)	0.01139 (14)
C9	0.80575 (12)	0.48387 (6)	0.61544 (7)	0.01512 (18)
H9A	0.765011	0.501631	0.552162	0.018*
H9B	0.828800	0.427073	0.611178	0.018*
C10	0.95983 (12)	0.52758 (6)	0.64065 (7)	0.01353 (17)
H10A	1.004203	0.507481	0.702014	0.016*
H10B	1.040874	0.518220	0.590476	0.016*
C14	0.52429 (13)	0.47017 (6)	0.64767 (8)	0.01698 (19)
H14A	0.494482	0.502896	0.592598	0.025*
H14B	0.440415	0.473888	0.696270	0.025*
H14C	0.534960	0.415567	0.626997	0.025*
O2W	0.12364 (11)	1.01349 (5)	0.36822 (6)	0.02094 (16)
H2W2	0.0802 (19)	1.0482 (9)	0.3992 (11)	0.031*
H2W1	0.114 (2)	0.9743 (9)	0.4022 (11)	0.031*
O1W	0.26421 (10)	0.71355 (5)	0.42894 (6)	0.01797 (15)
H1W1	0.3258 (18)	0.7025 (9)	0.4779 (10)	0.027*
H1W2	0.2118 (18)	0.7541 (8)	0.4498 (11)	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.01406 (10)	0.02120 (12)	0.01628 (11)	−0.00094 (8)	−0.00644 (8)	0.00522 (9)
Cl2	0.01321 (9)	0.01239 (10)	0.01603 (10)	−0.00032 (7)	0.00103 (7)	−0.00044 (8)
Co1	0.00643 (5)	0.00968 (6)	0.00711 (5)	0.00036 (4)	0.00040 (4)	0.00065 (4)
N1	0.0095 (3)	0.0107 (3)	0.0102 (3)	0.0001 (3)	0.0018 (3)	0.0013 (3)
C1	0.0078 (3)	0.0153 (4)	0.0154 (4)	−0.0008 (3)	0.0001 (3)	0.0024 (3)
C2	0.0099 (4)	0.0147 (4)	0.0149 (4)	−0.0036 (3)	−0.0002 (3)	0.0019 (3)
C3	0.0114 (4)	0.0140 (4)	0.0138 (4)	−0.0026 (3)	−0.0018 (3)	−0.0008 (3)
C11	0.0164 (4)	0.0170 (4)	0.0106 (4)	−0.0008 (3)	0.0033 (3)	0.0027 (3)
N2	0.0101 (3)	0.0100 (3)	0.0114 (3)	0.0007 (3)	−0.0003 (3)	0.0010 (3)
C4	0.0131 (4)	0.0113 (4)	0.0145 (4)	0.0018 (3)	0.0023 (3)	−0.0025 (3)
C5	0.0127 (4)	0.0139 (4)	0.0101 (4)	−0.0006 (3)	0.0017 (3)	−0.0022 (3)
C12	0.0186 (4)	0.0106 (4)	0.0182 (5)	0.0024 (3)	−0.0003 (4)	0.0041 (3)
N3	0.0072 (3)	0.0104 (3)	0.0092 (3)	0.0001 (2)	0.0004 (2)	0.0002 (3)
C6	0.0120 (4)	0.0146 (4)	0.0101 (4)	0.0003 (3)	−0.0003 (3)	0.0035 (3)
C7	0.0135 (4)	0.0125 (4)	0.0135 (4)	−0.0008 (3)	0.0019 (3)	0.0039 (3)
C8	0.0159 (4)	0.0110 (4)	0.0151 (4)	0.0016 (3)	0.0023 (3)	0.0027 (3)
C13	0.0075 (3)	0.0181 (5)	0.0159 (4)	0.0004 (3)	0.0010 (3)	0.0004 (3)
N4	0.0121 (3)	0.0110 (3)	0.0111 (3)	−0.0012 (3)	0.0011 (3)	−0.0005 (3)
C9	0.0186 (4)	0.0125 (4)	0.0144 (4)	−0.0015 (3)	0.0055 (3)	−0.0031 (3)
C10	0.0135 (4)	0.0114 (4)	0.0159 (4)	0.0022 (3)	0.0060 (3)	−0.0007 (3)
C14	0.0177 (4)	0.0166 (5)	0.0165 (4)	−0.0069 (4)	−0.0014 (4)	−0.0022 (4)
O2W	0.0299 (4)	0.0149 (4)	0.0182 (4)	0.0042 (3)	0.0049 (3)	0.0003 (3)
O1W	0.0172 (3)	0.0177 (4)	0.0189 (4)	0.0032 (3)	−0.0026 (3)	0.0005 (3)

Geometric parameters (Å, º)

Cl1—Co1	2.3022 (3)	C12—H12C	0.9800
Co1—N3	2.1066 (8)	N3—C13	1.4877 (12)
Co1—N1	2.1158 (8)	N3—C6	1.4920 (12)
Co1—N2	2.2208 (9)	C6—C7	1.5218 (14)
Co1—N4	2.2427 (9)	C6—H6A	0.9900
N1—C10	1.4880 (13)	C6—H6B	0.9900
N1—C11	1.4883 (13)	C7—C8	1.5217 (14)
N1—C1	1.4953 (13)	C7—H7A	0.9900
C1—C2	1.5204 (14)	C7—H7B	0.9900
C1—H1A	0.9900	C8—N4	1.4937 (13)
C1—H1B	0.9900	C8—H8A	0.9900
C2—C3	1.5218 (14)	C8—H8B	0.9900
C2—H2A	0.9900	C13—H13A	0.9800
C2—H2B	0.9900	C13—H13B	0.9800
C3—N2	1.4934 (12)	C13—H13C	0.9800
C3—H3A	0.9900	N4—C14	1.4832 (13)
C3—H3B	0.9900	N4—C9	1.4880 (12)
C11—H11A	0.9800	C9—C10	1.5164 (14)
C11—H11B	0.9800	C9—H9A	0.9900
C11—H11C	0.9800	C9—H9B	0.9900
N2—C12	1.4828 (13)	C10—H10A	0.9900
N2—C4	1.4856 (12)	C10—H10B	0.9900
C4—C5	1.5152 (14)	C14—H14A	0.9800
C4—H4A	0.9900	C14—H14B	0.9800
C4—H4B	0.9900	C14—H14C	0.9800
C5—N3	1.4919 (12)	O2W—H2W2	0.820 (13)
C5—H5A	0.9900	O2W—H2W1	0.825 (13)
C5—H5B	0.9900	O1W—H1W1	0.869 (13)
C12—H12A	0.9800	O1W—H1W2	0.869 (12)
C12—H12B	0.9800
N3—Co1—N1	137.57 (3)	H12A—C12—H12B	109.5
N3—Co1—N2	84.26 (3)	N2—C12—H12C	109.5
N1—Co1—N2	92.53 (3)	H12A—C12—H12C	109.5
N3—Co1—N4	91.52 (3)	H12B—C12—H12C	109.5
N1—Co1—N4	83.81 (3)	C13—N3—C5	108.51 (7)
N2—Co1—N4	169.13 (3)	C13—N3—C6	109.67 (7)
N3—Co1—Cl1	112.70 (2)	C5—N3—C6	107.56 (7)
N1—Co1—Cl1	109.71 (2)	C13—N3—Co1	108.07 (6)
N2—Co1—Cl1	96.12 (2)	C5—N3—Co1	107.42 (5)
N4—Co1—Cl1	94.75 (2)	C6—N3—Co1	115.42 (6)
C10—N1—C11	108.94 (8)	N3—C6—C7	115.18 (8)
C10—N1—C1	107.64 (7)	N3—C6—H6A	108.5
C11—N1—C1	109.33 (7)	C7—C6—H6A	108.5
C10—N1—Co1	107.28 (5)	N3—C6—H6B	108.5
C11—N1—Co1	108.64 (6)	C7—C6—H6B	108.5
C1—N1—Co1	114.86 (6)	H6A—C6—H6B	107.5
N1—C1—C2	115.32 (8)	C8—C7—C6	113.94 (8)
N1—C1—H1A	108.4	C8—C7—H7A	108.8
C2—C1—H1A	108.4	C6—C7—H7A	108.8
N1—C1—H1B	108.4	C8—C7—H7B	108.8
C2—C1—H1B	108.4	C6—C7—H7B	108.8
H1A—C1—H1B	107.5	H7A—C7—H7B	107.7
C1—C2—C3	114.11 (8)	N4—C8—C7	114.74 (8)
C1—C2—H2A	108.7	N4—C8—H8A	108.6
C3—C2—H2A	108.7	C7—C8—H8A	108.6
C1—C2—H2B	108.7	N4—C8—H8B	108.6
C3—C2—H2B	108.7	C7—C8—H8B	108.6
H2A—C2—H2B	107.6	H8A—C8—H8B	107.6
N2—C3—C2	114.95 (8)	N3—C13—H13A	109.5
N2—C3—H3A	108.5	N3—C13—H13B	109.5
C2—C3—H3A	108.5	H13A—C13—H13B	109.5
N2—C3—H3B	108.5	N3—C13—H13C	109.5
C2—C3—H3B	108.5	H13A—C13—H13C	109.5
H3A—C3—H3B	107.5	H13B—C13—H13C	109.5
N1—C11—H11A	109.5	C14—N4—C9	107.26 (8)
N1—C11—H11B	109.5	C14—N4—C8	108.50 (8)
H11A—C11—H11B	109.5	C9—N4—C8	108.42 (8)
N1—C11—H11C	109.5	C14—N4—Co1	116.11 (6)
H11A—C11—H11C	109.5	C9—N4—Co1	102.10 (6)
H11B—C11—H11C	109.5	C8—N4—Co1	113.85 (6)
C12—N2—C4	107.79 (8)	N4—C9—C10	110.88 (8)
C12—N2—C3	108.57 (8)	N4—C9—H9A	109.5
C4—N2—C3	108.68 (8)	C10—C9—H9A	109.5
C12—N2—Co1	116.32 (6)	N4—C9—H9B	109.5
C4—N2—Co1	102.02 (6)	C10—C9—H9B	109.5
C3—N2—Co1	112.94 (6)	H9A—C9—H9B	108.1
N2—C4—C5	111.35 (8)	N1—C10—C9	110.97 (8)
N2—C4—H4A	109.4	N1—C10—H10A	109.4
C5—C4—H4A	109.4	C9—C10—H10A	109.4
N2—C4—H4B	109.4	N1—C10—H10B	109.4
C5—C4—H4B	109.4	C9—C10—H10B	109.4
H4A—C4—H4B	108.0	H10A—C10—H10B	108.0
N3—C5—C4	110.45 (8)	N4—C14—H14A	109.5
N3—C5—H5A	109.6	N4—C14—H14B	109.5
C4—C5—H5A	109.6	H14A—C14—H14B	109.5
N3—C5—H5B	109.6	N4—C14—H14C	109.5
C4—C5—H5B	109.6	H14A—C14—H14C	109.5
H5A—C5—H5B	108.1	H14B—C14—H14C	109.5
N2—C12—H12A	109.5	H2W2—O2W—H2W1	103.8 (16)
N2—C12—H12B	109.5	H1W1—O1W—H1W2	101.5 (14)
C10—N1—C1—C2	−178.34 (8)	C13—N3—C6—C7	61.68 (10)
C11—N1—C1—C2	63.46 (10)	C5—N3—C6—C7	179.50 (8)
Co1—N1—C1—C2	−58.94 (9)	Co1—N3—C6—C7	−60.63 (9)
N1—C1—C2—C3	70.73 (11)	N3—C6—C7—C8	71.35 (11)
C1—C2—C3—N2	−70.86 (11)	C6—C7—C8—N4	−69.80 (11)
C2—C3—N2—C12	−73.00 (10)	C7—C8—N4—C14	−74.47 (10)
C2—C3—N2—C4	170.00 (8)	C7—C8—N4—C9	169.34 (8)
C2—C3—N2—Co1	57.55 (9)	C7—C8—N4—Co1	56.47 (10)
C12—N2—C4—C5	166.95 (8)	C14—N4—C9—C10	166.18 (8)
C3—N2—C4—C5	−75.56 (10)	C8—N4—C9—C10	−76.84 (10)
Co1—N2—C4—C5	43.96 (8)	Co1—N4—C9—C10	43.64 (9)
N2—C4—C5—N3	−57.53 (10)	C11—N1—C10—C9	−79.54 (9)
C4—C5—N3—C13	−79.89 (9)	C1—N1—C10—C9	162.01 (8)
C4—C5—N3—C6	161.54 (7)	Co1—N1—C10—C9	37.89 (9)
C4—C5—N3—Co1	36.71 (8)	N4—C9—C10—N1	−58.26 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Cl2^i	0.99	2.83	3.7784 (11)	160
C3—H3A···Cl2^ii	0.99	2.74	3.7054 (11)	166
C11—H11C···O1W^i	0.98	2.66	3.5203 (13)	147
C5—H5A···Cl2^ii	0.99	2.76	3.7452 (10)	171
C12—H12A···Cl1	0.98	2.77	3.3409 (11)	118
C7—H7A···Cl2^iii	0.99	2.94	3.6790 (10)	132
C8—H8A···O2W^ii	0.99	2.66	3.6324 (14)	168
C13—H13C···Cl2^iv	0.98	2.97	3.7640 (10)	138
C9—H9B···O1W^v	0.99	2.58	3.4736 (13)	150
C10—H10A···O2W^ii	0.99	2.54	3.5121 (14)	168
C14—H14A···Cl1	0.98	2.70	3.3189 (12)	122
O2W—H2W2···Cl2^vi	0.82 (1)	2.40 (1)	3.2158 (9)	173 (2)
O2W—H2W1···Cl2	0.83 (1)	2.39 (1)	3.2110 (9)	175 (2)
O1W—H1W1···Cl1	0.87 (1)	2.39 (1)	3.2568 (9)	173 (1)
O1W—H1W2···Cl2	0.87 (1)	2.33 (1)	3.2024 (9)	178 (1)

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