Polymorphism of di­nitro­[tris­(2-amino­eth­yl)amine]­cobalt(III) chloride

Three polymorphs of bis­(nitrito-κN)[tris­(2-amino­eth­yl)amine-κ⁴N,N′,N′′,N′′′]cobalt(III) chloride, [Co(NO₂)₂(C₆H₁₈N₄)]Cl, have been structurally characterized in the 100–300 K temperature range. Two ortho­rhom­bic polymorphs are related by a solid-state enanti­otropic order–disorder k2 phase transition at ca 152 K. The third, monoclinic, polymorph crystallizes as a nonmerohedral twin. In the structure of the high-temperature (300 K) ortho­rhom­bic polymorph, the Co^III complex cation resides on a crystallographic mirror plane, whereas the Cl⁻ anion occupies a crystallographic twofold axis. In the unit cell of the monoclinic polymorph, the cationic Co^III complex is in a general position, whose charge is balanced by two halves of two Cl⁻ anions, each residing on a crystallographic twofold axis.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT-Plus (Bruker, 2014); data reduction: SAINT-Plus (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and PLATON (Spek, 2009).

(pbcm) Bis(nitrito-κN)[tris(2-aminoethyl)amine-κ⁴N,N',N'',N''']cobalt(III) chloride

Crystal data

[Co(NO2)2(C6H18N4)]Cl	Dx = 1.775 Mg m^−3
Mr = 332.64	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcm	Cell parameters from 9933 reflections
a = 8.4892 (1) Å	θ = 2.4–26.4°
b = 12.1555 (2) Å	µ = 1.61 mm^−1
c = 12.0631 (2) Å	T = 300 K
V = 1244.80 (3) Å^3	Block, orange
Z = 4	0.22 × 0.2 × 0.12 mm
F(000) = 688

Data collection

Bruker SMART APEXII area-detector diffractometer	1339 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	1293 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.022
Detector resolution: 7.9 pixels mm^-1	θmax = 26.4°, θmin = 2.4°
0.5° ω and 0.5° φ scans	h = −10→10
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015)	k = −15→15
Tmin = 0.341, Tmax = 0.430	l = −15→15
25379 measured reflections

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)] = 0.019	H-atom parameters constrained
wR(F^2) = 0.053	w = 1/[σ^2(Fo^2) + (0.0277P)^2 + 0.5979P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
1339 reflections	Δρmax = 0.47 e Å^−3
96 parameters	Δρmin = −0.22 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.72722 (3)	0.63251 (2)	0.7500	0.01735 (9)
Cl1	1.03578 (6)	0.7500	0.5000	0.03053 (13)
N2	0.95694 (19)	0.64590 (13)	0.7500	0.0223 (3)
H2A	0.9857	0.6983	0.7026	0.027*	0.5
H2B	0.9896	0.6654	0.8173	0.027*	0.5
N3	0.72223 (14)	0.62018 (10)	0.58872 (10)	0.0258 (3)
H3A	0.6327	0.6488	0.5633	0.031*
H3B	0.8017	0.6584	0.5600	0.031*
N1	0.75791 (18)	0.47226 (13)	0.7500	0.0222 (3)
O1	0.70138 (18)	0.84023 (10)	0.66206 (10)	0.0469 (3)
N4	0.70746 (19)	0.78937 (13)	0.7500	0.0244 (4)
N5	0.4950 (2)	0.63174 (13)	0.7500	0.0286 (4)
O2	0.42082 (15)	0.63656 (12)	0.66216 (11)	0.0514 (4)
C1	0.9312 (2)	0.44485 (17)	0.7500	0.0285 (4)
H1A	0.9613	0.4199	0.8234	0.034*	0.5
H1B	0.9500	0.3850	0.6985	0.034*	0.5
C3	0.68122 (19)	0.43054 (12)	0.64690 (13)	0.0309 (3)
H3C	0.5675	0.4333	0.6542	0.037*
H3D	0.7122	0.3549	0.6332	0.037*
C4	0.73445 (19)	0.50344 (13)	0.55273 (13)	0.0335 (3)
H4A	0.8425	0.4864	0.5331	0.040*
H4B	0.6687	0.4911	0.4882	0.040*
C2	1.0323 (3)	0.5411 (2)	0.7182 (2)	0.0301 (7)	0.5
H2C	1.1338	0.5350	0.7546	0.036*	0.5
H2D	1.0499	0.5402	0.6387	0.036*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01923 (14)	0.01594 (14)	0.01689 (15)	0.00010 (9)	0.000	0.000
Cl1	0.0317 (3)	0.0340 (3)	0.0259 (2)	0.000	0.000	0.00322 (19)
N2	0.0237 (8)	0.0216 (8)	0.0217 (8)	−0.0016 (6)	0.000	0.000
N3	0.0310 (6)	0.0267 (6)	0.0196 (6)	−0.0015 (5)	−0.0018 (5)	0.0004 (5)
N1	0.0237 (8)	0.0172 (7)	0.0257 (9)	−0.0006 (6)	0.000	0.000
O1	0.0777 (9)	0.0267 (6)	0.0364 (7)	0.0099 (6)	0.0069 (6)	0.0104 (5)
N4	0.0228 (8)	0.0207 (8)	0.0295 (9)	0.0023 (6)	0.000	0.000
N5	0.0242 (8)	0.0252 (8)	0.0364 (10)	−0.0012 (7)	0.000	0.000
O2	0.0297 (6)	0.0766 (10)	0.0479 (8)	0.0036 (6)	−0.0131 (6)	−0.0065 (6)
C1	0.0270 (10)	0.0225 (9)	0.0360 (11)	0.0056 (8)	0.000	0.000
C3	0.0338 (7)	0.0229 (7)	0.0359 (8)	−0.0034 (6)	−0.0057 (7)	−0.0081 (6)
C4	0.0433 (9)	0.0326 (8)	0.0245 (8)	0.0005 (6)	−0.0031 (6)	−0.0097 (6)
C2	0.0238 (12)	0.0277 (13)	0.039 (2)	0.0044 (10)	0.0068 (10)	0.0003 (10)

Geometric parameters (Å, º)

Co1—N2	1.9570 (16)	O1—N4	1.2289 (14)
Co1—N3^i	1.9517 (12)	N4—O1^i	1.2289 (14)
Co1—N3	1.9517 (12)	N5—O2^i	1.2339 (15)
Co1—N1	1.9653 (17)	N5—O2	1.2339 (15)
Co1—N4	1.9141 (16)	C1—H1A	0.9700
Co1—N5	1.9716 (18)	C1—H1B	0.9700
N2—H2A	0.8900	C1—C2	1.500 (3)
N2—H2B	0.8900	C3—H3C	0.9700
N2—C2	1.477 (3)	C3—H3D	0.9700
N3—H3A	0.8900	C3—C4	1.510 (2)
N3—H3B	0.8900	C4—H4A	0.9700
N3—C4	1.4876 (19)	C4—H4B	0.9700
N1—C1	1.508 (2)	C2—H2C	0.9700
N1—C3^i	1.4926 (17)	C2—H2D	0.9700
N1—C3	1.4926 (17)
N2—Co1—N1	87.15 (7)	C3—N1—C3^i	112.87 (16)
N2—Co1—N5	175.50 (7)	O1^i—N4—Co1	120.32 (9)
N3^i—Co1—N2	91.60 (4)	O1—N4—Co1	120.32 (9)
N3—Co1—N2	91.60 (4)	O1^i—N4—O1	119.36 (18)
N3^i—Co1—N3	170.84 (7)	O2^i—N5—Co1	120.66 (9)
N3—Co1—N1	85.80 (4)	O2—N5—Co1	120.66 (9)
N3^i—Co1—N1	85.80 (4)	O2^i—N5—O2	118.35 (19)
N3^i—Co1—N5	88.74 (4)	N1—C1—H1A	109.1
N3—Co1—N5	88.74 (4)	N1—C1—H1B	109.1
N1—Co1—N5	97.35 (7)	H1A—C1—H1B	107.8
N4—Co1—N2	90.25 (7)	C2—C1—N1	112.68 (17)
N4—Co1—N3	94.28 (4)	C2—C1—H1A	109.1
N4—Co1—N3^i	94.28 (4)	C2—C1—H1B	109.1
N4—Co1—N1	177.41 (7)	N1—C3—H3C	110.3
N4—Co1—N5	85.24 (7)	N1—C3—H3D	110.3
Co1—N2—H2A	109.4	N1—C3—C4	107.28 (12)
Co1—N2—H2B	109.4	H3C—C3—H3D	108.5
H2A—N2—H2B	108.0	C4—C3—H3C	110.3
C2—N2—Co1	111.08 (14)	C4—C3—H3D	110.3
C2—N2—H2A	109.4	N3—C4—C3	108.63 (12)
C2—N2—H2B	109.4	N3—C4—H4A	110.0
Co1—N3—H3A	109.4	N3—C4—H4B	110.0
Co1—N3—H3B	109.4	C3—C4—H4A	110.0
H3A—N3—H3B	108.0	C3—C4—H4B	110.0
C4—N3—Co1	111.27 (9)	H4A—C4—H4B	108.3
C4—N3—H3A	109.4	N2—C2—C1	111.01 (19)
C4—N3—H3B	109.4	N2—C2—H2C	109.4
C1—N1—Co1	110.38 (12)	N2—C2—H2D	109.4
C3—N1—Co1	106.20 (9)	C1—C2—H2C	109.4
C3^i—N1—Co1	106.20 (9)	C1—C2—H2D	109.4
C3^i—N1—C1	110.51 (10)	H2C—C2—H2D	108.0
C3—N1—C1	110.51 (10)
Co1—N2—C2—C1	−28.8 (2)	N1—C3—C4—N3	−45.72 (16)
Co1—N3—C4—C3	22.78 (15)	C1—N1—C3—C4	−72.68 (16)
Co1—N1—C1—C2	−16.11 (12)	C3—N1—C1—C2	101.07 (17)
Co1—N1—C3—C4	47.04 (14)	C3^i—N1—C1—C2	−133.28 (15)
N1—C1—C2—N2	29.3 (2)	C3^i—N1—C3—C4	163.01 (10)

Symmetry code: (i) x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.89	2.56	3.3382 (7)	147
N2—H2B···Cl1^i	0.89	2.46	3.3382 (7)	168
N3—H3A···O2	0.89	2.16	2.7151 (18)	120
N3—H3B···Cl1	0.89	2.39	3.2742 (13)	173

Symmetry code: (i) x, y, −z+3/2.

(pbca) Bis(nitrito-κN)[tris(2-aminoethyl)amine-κ⁴N,N',N'',N''']cobalt(III) chloride

Crystal data

[Co(NO2)2(C6H18N4)]Cl	Dx = 1.822 Mg m^−3
Mr = 332.64	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9947 reflections
a = 16.7032 (6) Å	θ = 3.0–26.4°
b = 12.0743 (4) Å	µ = 1.65 mm^−1
c = 12.0288 (4) Å	T = 100 K
V = 2425.96 (14) Å^3	Block, orange
Z = 8	0.27 × 0.2 × 0.12 mm
F(000) = 1376

Data collection

Bruker SMART APEXII area-detector diffractometer	2277 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.021
0.5° ω and 0.5° φ scans	θmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015)	h = −20→20
Tmin = 0.322, Tmax = 0.430	k = −15→15
49052 measured reflections	l = −15→15
2475 independent reflections

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)] = 0.018	H-atom parameters constrained
wR(F^2) = 0.056	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 0.7351P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
2475 reflections	Δρmax = 0.44 e Å^−3
163 parameters	Δρmin = −0.22 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
Co1	0.63574 (2)	0.36734 (2)	0.25510 (2)	0.00590 (7)
O1	0.64362 (5)	0.15880 (7)	0.16448 (7)	0.01557 (18)
O2	0.79136 (5)	0.36189 (7)	0.16599 (7)	0.01750 (19)
O3	0.65149 (5)	0.15776 (7)	0.34258 (7)	0.01518 (18)
O4	0.79157 (5)	0.35893 (7)	0.34358 (7)	0.01741 (19)
N1	0.62188 (6)	0.52908 (9)	0.25711 (6)	0.0082 (2)
N2	0.51891 (6)	0.35622 (8)	0.25260 (6)	0.0088 (2)
H2A	0.5039	0.3012	0.2053	0.011*
H2B	0.5008	0.3387	0.3217	0.011*
N3	0.63816 (5)	0.38214 (8)	0.09294 (8)	0.00964 (19)
H3A	0.6834	0.3498	0.0661	0.012*
H3B	0.5954	0.3461	0.0632	0.012*
N4	0.64472 (6)	0.20922 (9)	0.25413 (6)	0.0091 (2)
N5	0.75374 (7)	0.36565 (8)	0.25509 (6)	0.0104 (2)
N6	0.63834 (5)	0.37710 (7)	0.41703 (8)	0.00917 (19)
H6A	0.5976	0.3361	0.4459	0.011*
H6B	0.6853	0.3485	0.4425	0.011*
C1	0.53413 (7)	0.55850 (9)	0.25567 (8)	0.0101 (2)
H1A	0.5258	0.6228	0.2060	0.012*
H1B	0.5172	0.5803	0.3315	0.012*
C2	0.48252 (6)	0.46250 (9)	0.21619 (9)	0.0122 (2)
H2C	0.4279	0.4695	0.2475	0.015*
H2D	0.4783	0.4640	0.1341	0.015*
C3	0.66379 (6)	0.57144 (9)	0.15573 (8)	0.0111 (2)
H3C	0.7225	0.5655	0.1650	0.013*
H3D	0.6500	0.6501	0.1428	0.013*
C4	0.63614 (6)	0.50079 (9)	0.05839 (9)	0.0123 (2)
H4A	0.5811	0.5219	0.0366	0.015*
H4B	0.6719	0.5125	−0.0062	0.015*
C5	0.65963 (6)	0.56942 (9)	0.36251 (9)	0.0104 (2)
H5A	0.6436	0.6469	0.3775	0.012*
H5B	0.7187	0.5663	0.3567	0.012*
C6	0.63052 (6)	0.49387 (9)	0.45511 (9)	0.0115 (2)
H6C	0.6630	0.5057	0.5230	0.014*
H6D	0.5739	0.5105	0.4729	0.014*
Cl1	0.47975 (2)	0.25197 (2)	−0.00029 (2)	0.01040 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.00676 (11)	0.00528 (11)	0.00567 (11)	0.00004 (5)	−0.00015 (4)	0.00014 (4)
O1	0.0236 (4)	0.0114 (4)	0.0117 (4)	0.0018 (3)	−0.0020 (3)	−0.0041 (3)
O2	0.0124 (4)	0.0241 (5)	0.0159 (4)	0.0012 (3)	0.0053 (3)	0.0023 (3)
O3	0.0221 (4)	0.0111 (4)	0.0123 (4)	0.0020 (3)	−0.0001 (3)	0.0037 (3)
O4	0.0116 (4)	0.0246 (5)	0.0160 (4)	0.0005 (3)	−0.0052 (3)	−0.0017 (3)
N1	0.0082 (4)	0.0077 (5)	0.0086 (5)	−0.0003 (3)	−0.0001 (3)	−0.0002 (3)
N2	0.0100 (5)	0.0079 (5)	0.0086 (5)	−0.0001 (4)	−0.0005 (3)	−0.0001 (3)
N3	0.0114 (5)	0.0097 (4)	0.0078 (5)	0.0001 (3)	0.0001 (3)	0.0001 (3)
N4	0.0072 (5)	0.0094 (5)	0.0106 (5)	0.0000 (4)	−0.0001 (3)	0.0005 (3)
N5	0.0108 (5)	0.0075 (5)	0.0129 (5)	−0.0009 (3)	−0.0001 (3)	0.0003 (3)
N6	0.0105 (5)	0.0087 (4)	0.0082 (5)	−0.0006 (3)	−0.0003 (3)	0.0001 (3)
C1	0.0093 (5)	0.0079 (5)	0.0130 (5)	0.0024 (4)	−0.0004 (3)	−0.0002 (3)
C2	0.0108 (5)	0.0104 (5)	0.0154 (5)	0.0015 (4)	−0.0025 (4)	0.0004 (4)
C3	0.0127 (5)	0.0094 (5)	0.0111 (5)	−0.0024 (4)	0.0026 (4)	0.0029 (4)
C4	0.0178 (5)	0.0103 (5)	0.0087 (5)	0.0005 (4)	0.0011 (4)	0.0024 (4)
C5	0.0117 (5)	0.0089 (5)	0.0106 (5)	−0.0024 (4)	−0.0018 (4)	−0.0016 (4)
C6	0.0158 (5)	0.0106 (5)	0.0082 (5)	0.0003 (4)	−0.0009 (4)	−0.0027 (4)
Cl1	0.01074 (15)	0.01112 (15)	0.00934 (15)	0.00040 (8)	0.00013 (8)	−0.00088 (9)

Geometric parameters (Å, º)

Co1—N1	1.9667 (11)	N6—H6A	0.9100
Co1—N2	1.9563 (11)	N6—H6B	0.9100
Co1—N3	1.9591 (10)	N6—C6	1.4881 (14)
Co1—N4	1.9151 (11)	C1—H1A	0.9900
Co1—N5	1.9712 (11)	C1—H1B	0.9900
Co1—N6	1.9519 (10)	C1—C2	1.5207 (15)
O1—N4	1.2386 (12)	C2—H2C	0.9900
O2—N5	1.2432 (12)	C2—H2D	0.9900
O3—N4	1.2373 (12)	C3—H3C	0.9900
O4—N5	1.2405 (12)	C3—H3D	0.9900
N1—C1	1.5082 (14)	C3—C4	1.5205 (15)
N1—C3	1.4962 (13)	C4—H4A	0.9900
N1—C5	1.4974 (13)	C4—H4B	0.9900
N2—H2A	0.9100	C5—H5A	0.9900
N2—H2B	0.9100	C5—H5B	0.9900
N2—C2	1.4860 (14)	C5—C6	1.5197 (15)
N3—H3A	0.9100	C6—H6C	0.9900
N3—H3B	0.9100	C6—H6D	0.9900
N3—C4	1.4921 (14)
N1—Co1—N5	97.35 (4)	H6A—N6—H6B	108.0
N2—Co1—N1	87.19 (4)	C6—N6—Co1	111.25 (7)
N2—Co1—N3	90.67 (3)	C6—N6—H6A	109.4
N2—Co1—N5	175.39 (4)	C6—N6—H6B	109.4
N3—Co1—N1	85.65 (4)	N1—C1—H1A	109.2
N3—Co1—N5	88.87 (3)	N1—C1—H1B	109.2
N4—Co1—N1	177.71 (4)	N1—C1—C2	112.03 (9)
N4—Co1—N2	90.55 (4)	H1A—C1—H1B	107.9
N4—Co1—N3	94.78 (4)	C2—C1—H1A	109.2
N4—Co1—N5	84.91 (4)	C2—C1—H1B	109.2
N4—Co1—N6	93.70 (3)	N2—C2—C1	109.53 (8)
N6—Co1—N1	86.01 (3)	N2—C2—H2C	109.8
N6—Co1—N2	92.39 (3)	N2—C2—H2D	109.8
N6—Co1—N3	170.96 (5)	C1—C2—H2C	109.8
N6—Co1—N5	88.76 (3)	C1—C2—H2D	109.8
C1—N1—Co1	110.37 (7)	H2C—C2—H2D	108.2
C3—N1—Co1	105.92 (7)	N1—C3—H3C	110.3
C3—N1—C1	111.39 (8)	N1—C3—H3D	110.3
C3—N1—C5	112.45 (9)	N1—C3—C4	107.09 (8)
C5—N1—Co1	106.49 (7)	H3C—C3—H3D	108.6
C5—N1—C1	110.02 (8)	C4—C3—H3C	110.3
Co1—N2—H2A	109.5	C4—C3—H3D	110.3
Co1—N2—H2B	109.5	N3—C4—C3	108.50 (9)
H2A—N2—H2B	108.1	N3—C4—H4A	110.0
C2—N2—Co1	110.69 (7)	N3—C4—H4B	110.0
C2—N2—H2A	109.5	C3—C4—H4A	110.0
C2—N2—H2B	109.5	C3—C4—H4B	110.0
Co1—N3—H3A	109.4	H4A—C4—H4B	108.4
Co1—N3—H3B	109.4	N1—C5—H5A	110.3
H3A—N3—H3B	108.0	N1—C5—H5B	110.3
C4—N3—Co1	111.37 (7)	N1—C5—C6	106.89 (8)
C4—N3—H3A	109.4	H5A—C5—H5B	108.6
C4—N3—H3B	109.4	C6—C5—H5A	110.3
O1—N4—Co1	119.62 (7)	C6—C5—H5B	110.3
O3—N4—Co1	120.18 (7)	N6—C6—C5	108.36 (9)
O3—N4—O1	120.21 (11)	N6—C6—H6C	110.0
O2—N5—Co1	120.38 (7)	N6—C6—H6D	110.0
O4—N5—Co1	120.66 (7)	C5—C6—H6C	110.0
O4—N5—O2	118.68 (11)	C5—C6—H6D	110.0
Co1—N6—H6A	109.4	H6C—C6—H6D	108.4
Co1—N6—H6B	109.4
Co1—N1—C1—C2	−18.41 (9)	N1—C5—C6—N6	46.66 (11)
Co1—N1—C3—C4	48.30 (9)	C1—N1—C3—C4	−71.73 (11)
Co1—N1—C5—C6	−46.48 (9)	C1—N1—C5—C6	73.14 (11)
Co1—N2—C2—C1	−32.84 (10)	C3—N1—C1—C2	98.96 (10)
Co1—N3—C4—C3	20.92 (10)	C3—N1—C5—C6	−162.06 (8)
Co1—N6—C6—C5	−24.92 (10)	C5—N1—C1—C2	−135.64 (9)
N1—C1—C2—N2	33.37 (11)	C5—N1—C3—C4	164.23 (8)
N1—C3—C4—N3	−45.28 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.91	2.58	3.3564 (8)	144
N2—H2B···Cl1^i	0.91	2.43	3.3121 (8)	163
N3—H3A···O2	0.91	2.17	2.7165 (12)	118
N3—H3B···Cl1	0.91	2.37	3.2756 (9)	176
N6—H6A···Cl1^i	0.91	2.33	3.2305 (9)	170
N6—H6B···O4	0.91	2.14	2.7165 (12)	120

Symmetry code: (i) x, −y+1/2, z+1/2.

(a2) Bis(nitrito-κN)[tris(2-aminoethyl)amine-κ⁴N,N',N'',N''']cobalt(III) chloride

Crystal data

[Co(NO2)2(C6H18N4)]Cl	F(000) = 688
Mr = 332.64	Dx = 1.777 Mg m^−3
Monoclinic, A2	Mo Kα radiation, λ = 0.71073 Å
a = 8.856 (4) Å	Cell parameters from 4064 reflections
b = 11.950 (5) Å	θ = 3.4–26.2°
c = 11.750 (4) Å	µ = 1.61 mm^−1
β = 90.000 (13)°	T = 100 K
V = 1243.5 (8) Å^3	Block, orange
Z = 4	0.4 × 0.3 × 0.2 mm

Data collection

Bruker SMART APEXII area-detector diffractometer	2533 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2418 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.053
Detector resolution: 7.9 pixels mm^-1	θmax = 26.3°, θmin = 2.3°
0.5\ ω and 0.5\ φ scans	h = −10→11
Absorption correction: multi-scan (SADABS2014; Krause et al., 2015)	k = −14→14
Tmin = 0.671, Tmax = 0.745	l = −14→14
10969 measured reflections

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)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0366P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2533 reflections	Δρmax = 0.45 e Å^−3
165 parameters	Δρmin = −0.72 e Å^−3
1 restraint	Absolute structure: Twinning involves inversion, so Flack parameter cannot be determined

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. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Co1	0.28312 (9)	0.62203 (5)	0.25609 (10)	0.00941 (18)
O1	0.2855 (7)	0.4024 (5)	0.1906 (5)	0.0273 (15)
O2	0.5810 (8)	0.6161 (5)	0.1684 (4)	0.0203 (14)
O3	0.3526 (7)	0.4253 (4)	0.3640 (5)	0.0215 (14)
O4	0.5745 (7)	0.6384 (5)	0.3492 (4)	0.0202 (14)
N1	0.2418 (6)	0.7837 (4)	0.2434 (6)	0.0120 (10)
N2	0.0638 (5)	0.6011 (3)	0.2563 (7)	0.0096 (12)
H2A	0.0324	0.5812	0.1854	0.011*
H2B	0.0389	0.5450	0.3052	0.011*
N3	0.2935 (10)	0.6210 (6)	0.0915 (4)	0.0129 (14)
H3A	0.3874	0.5993	0.0692	0.016*
H3B	0.2259	0.5706	0.0637	0.016*
N4	0.3107 (6)	0.4635 (5)	0.2721 (5)	0.0125 (14)
N5	0.5059 (5)	0.6297 (4)	0.2587 (7)	0.0128 (11)
N6	0.2800 (10)	0.6479 (5)	0.4204 (4)	0.0107 (14)
H6A	0.1989	0.6124	0.4513	0.013*
H6B	0.3649	0.6185	0.4521	0.013*
C1	0.0740 (6)	0.8054 (5)	0.2453 (8)	0.0137 (12)
H1A	0.0390	0.8219	0.1671	0.016*
H1B	0.0532	0.8719	0.2930	0.016*
C2	−0.0139 (8)	0.7062 (6)	0.2916 (6)	0.0136 (15)
H2C	−0.0189	0.7104	0.3757	0.016*
H2D	−0.1182	0.7072	0.2615	0.016*
C3	0.3066 (11)	0.8199 (6)	0.1312 (7)	0.0144 (19)
H3C	0.4180	0.8245	0.1360	0.017*
H3D	0.2669	0.8944	0.1098	0.017*
C4	0.2602 (11)	0.7331 (6)	0.0438 (6)	0.0156 (19)
H4A	0.1510	0.7398	0.0269	0.019*
H4B	0.3171	0.7444	−0.0278	0.019*
C5	0.3176 (11)	0.8366 (7)	0.3423 (6)	0.017 (2)
H5A	0.2857	0.9157	0.3497	0.020*
H5B	0.4286	0.8345	0.3325	0.020*
C6	0.2716 (12)	0.7707 (6)	0.4475 (5)	0.0131 (17)
H6C	0.3402	0.7886	0.5115	0.016*
H6D	0.1675	0.7910	0.4702	0.016*
Cl1	0.0000	0.4971 (2)	0.0000	0.0158 (7)
Cl2	0.0000	0.4871 (2)	0.5000	0.0128 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0102 (3)	0.0061 (3)	0.0119 (4)	0.0005 (4)	0.0004 (6)	0.0001 (6)
O1	0.041 (4)	0.012 (2)	0.029 (3)	0.007 (3)	−0.010 (3)	−0.004 (3)
O2	0.017 (3)	0.025 (3)	0.019 (3)	0.004 (3)	0.007 (2)	0.001 (3)
O3	0.035 (4)	0.011 (3)	0.018 (3)	0.008 (3)	0.001 (3)	0.004 (2)
O4	0.015 (3)	0.026 (3)	0.019 (3)	−0.004 (3)	−0.005 (2)	−0.001 (2)
N1	0.015 (2)	0.011 (2)	0.010 (3)	−0.001 (2)	0.002 (3)	−0.004 (3)
N2	0.014 (2)	0.006 (3)	0.009 (3)	0.0013 (17)	0.005 (4)	−0.003 (3)
N3	0.012 (3)	0.010 (3)	0.017 (3)	−0.002 (3)	0.002 (3)	0.000 (3)
N4	0.012 (3)	0.010 (3)	0.016 (4)	−0.001 (2)	0.003 (3)	−0.002 (3)
N5	0.016 (2)	0.007 (2)	0.015 (3)	−0.001 (3)	0.005 (3)	0.003 (3)
N6	0.011 (3)	0.008 (3)	0.012 (3)	−0.001 (3)	−0.002 (3)	−0.002 (2)
C1	0.016 (3)	0.012 (3)	0.013 (3)	0.005 (2)	0.002 (5)	0.000 (4)
C2	0.013 (3)	0.010 (3)	0.018 (4)	0.003 (3)	0.002 (3)	−0.002 (2)
C3	0.013 (5)	0.011 (3)	0.019 (4)	−0.002 (3)	0.003 (4)	0.005 (3)
C4	0.020 (5)	0.013 (4)	0.014 (4)	0.004 (4)	0.002 (3)	−0.002 (3)
C5	0.024 (6)	0.014 (4)	0.011 (4)	−0.003 (4)	0.004 (4)	−0.005 (3)
C6	0.019 (4)	0.006 (3)	0.015 (4)	0.000 (3)	−0.004 (3)	−0.004 (3)
Cl1	0.0193 (18)	0.0139 (13)	0.0143 (13)	0.000	−0.0017 (14)	0.000
Cl2	0.0144 (17)	0.0118 (13)	0.0121 (12)	0.000	0.0018 (13)	0.000

Geometric parameters (Å, º)

Co1—N1	1.972 (5)	N6—H6A	0.9100
Co1—N2	1.959 (5)	N6—H6B	0.9100
Co1—N3	1.936 (5)	N6—C6	1.503 (8)
Co1—N4	1.919 (6)	C1—H1A	0.9900
Co1—N5	1.975 (5)	C1—H1B	0.9900
Co1—N6	1.956 (5)	C1—C2	1.518 (9)
O1—N4	1.225 (8)	C2—H2C	0.9900
O2—N5	1.263 (9)	C2—H2D	0.9900
O3—N4	1.230 (8)	C3—H3C	0.9900
O4—N5	1.229 (9)	C3—H3D	0.9900
N1—C1	1.509 (7)	C3—C4	1.517 (10)
N1—C3	1.502 (10)	C4—H4A	0.9900
N1—C5	1.484 (10)	C4—H4B	0.9900
N2—H2A	0.9100	C5—H5A	0.9900
N2—H2B	0.9100	C5—H5B	0.9900
N2—C2	1.490 (8)	C5—C6	1.521 (10)
N3—H3A	0.9100	C6—H6C	0.9900
N3—H3B	0.9100	C6—H6D	0.9900
N3—C4	1.481 (10)
N1—Co1—N5	98.1 (2)	H6A—N6—H6B	108.0
N2—Co1—N1	86.60 (19)	C6—N6—Co1	111.4 (4)
N2—Co1—N5	175.2 (2)	C6—N6—H6A	109.4
N3—Co1—N1	86.5 (3)	C6—N6—H6B	109.4
N3—Co1—N2	92.7 (4)	N1—C1—H1A	109.2
N3—Co1—N5	88.2 (4)	N1—C1—H1B	109.2
N3—Co1—N6	171.1 (3)	N1—C1—C2	112.1 (5)
N4—Co1—N1	176.4 (3)	H1A—C1—H1B	107.9
N4—Co1—N2	90.0 (2)	C2—C1—H1A	109.2
N4—Co1—N3	94.9 (3)	C2—C1—H1B	109.2
N4—Co1—N5	85.2 (2)	N2—C2—C1	108.7 (5)
N4—Co1—N6	93.5 (3)	N2—C2—H2C	109.9
N6—Co1—N1	85.2 (3)	N2—C2—H2D	109.9
N6—Co1—N2	90.3 (4)	C1—C2—H2C	109.9
N6—Co1—N5	89.5 (4)	C1—C2—H2D	109.9
C1—N1—Co1	110.5 (4)	H2C—C2—H2D	108.3
C3—N1—Co1	106.1 (4)	N1—C3—H3C	110.3
C3—N1—C1	109.9 (7)	N1—C3—H3D	110.3
C5—N1—Co1	105.9 (5)	N1—C3—C4	107.1 (6)
C5—N1—C1	111.2 (7)	H3C—C3—H3D	108.6
C5—N1—C3	113.1 (6)	C4—C3—H3C	110.3
Co1—N2—H2A	109.5	C4—C3—H3D	110.3
Co1—N2—H2B	109.5	N3—C4—C3	107.9 (6)
H2A—N2—H2B	108.1	N3—C4—H4A	110.1
C2—N2—Co1	110.5 (4)	N3—C4—H4B	110.1
C2—N2—H2A	109.5	C3—C4—H4A	110.1
C2—N2—H2B	109.5	C3—C4—H4B	110.1
Co1—N3—H3A	109.4	H4A—C4—H4B	108.4
Co1—N3—H3B	109.4	N1—C5—H5A	110.3
H3A—N3—H3B	108.0	N1—C5—H5B	110.3
C4—N3—Co1	111.3 (5)	N1—C5—C6	107.1 (7)
C4—N3—H3A	109.4	H5A—C5—H5B	108.5
C4—N3—H3B	109.4	C6—C5—H5A	110.3
O1—N4—Co1	119.2 (5)	C6—C5—H5B	110.3
O1—N4—O3	121.3 (6)	N6—C6—C5	108.7 (6)
O3—N4—Co1	119.5 (5)	N6—C6—H6C	110.0
O2—N5—Co1	120.5 (5)	N6—C6—H6D	110.0
O4—N5—Co1	120.8 (6)	C5—C6—H6C	110.0
O4—N5—O2	118.5 (5)	C5—C6—H6D	110.0
Co1—N6—H6A	109.4	H6C—C6—H6D	108.3
Co1—N6—H6B	109.4
Co1—N1—C1—C2	17.5 (9)	N1—C5—C6—N6	43.7 (10)
Co1—N1—C3—C4	44.9 (7)	C1—N1—C3—C4	−74.6 (7)
Co1—N1—C5—C6	−49.3 (7)	C1—N1—C5—C6	70.8 (8)
Co1—N2—C2—C1	35.6 (8)	C3—N1—C1—C2	134.2 (7)
Co1—N3—C4—C3	28.4 (9)	C3—N1—C5—C6	−165.1 (7)
Co1—N6—C6—C5	−17.7 (10)	C5—N1—C1—C2	−99.9 (7)
N1—C1—C2—N2	−34.4 (9)	C5—N1—C3—C4	160.6 (7)
N1—C3—C4—N3	−48.1 (9)