Modified photoreactivity due to mixed crystal formation. II. Enhanced reactivity upon conformational mimicry and cavity enlargement

The 2-cyanopropyl (β-cyanopropyl) group in the cobaloxime complex of (2-cyanopropyl)(3-methylpyridine)bis(dimethylglyoximato)cobalt(III) takes a trans conformation around the Co—C—C—CN bond in the crystal and undergoes isomerization to the 1-cyanopropyl (α-cyanopropyl) group with a low reaction rate when the powdered crystals are irradiated with a xenon lamp. When the complex was mixed with (2-cyanoethyl)(3-methylpyridine)bis(dimethylglyoximato)cobalt(III) or (2-cyanoethyl)(3-ethylpyridine)bis(dimethylgly­oximato)cobalt(III), a mixed crystal, Mix-I or Mix-II, was obtained. The cell parameters of Mix-I and Mix-II were considerably different. When the crystals of Mix-I and Mix-II were irradiated with the xenon lamp, the 2-cyanopropyl group and the 2-cyanoethyl group isomerized to the 1-cyanopropyl and 1-cyanoethyl groups, respectively, in the crystalline state as well as in the solid state. The isomerization rates of the 2-cyanopropyl and 2-cyanoethyl groups of the mixed crystals became significantly higher than the corresponding rates in the component crystals. For the 2-cyanopropyl group, the conformational change from trans to cis in the mixed crystals caused reaction rates to be enhanced, and the expanded volume of the reaction cavity in the mixed crystals increased the reactivity for the 2-cyanoethyl group, when compared with the reactivity of each component crystal. A quantitative discussion of the increased rate constants is presented, which is based on the crystal structures. The shapes of the reaction cavities for the reactive groups undergoing isomerization control the conformation and configuration of the produced1-cyanoethyl and 1-cyanopropyl groups.

Computing details

Data collection: SMART ( Siemens, 1995) for 2cp3mpy; SMART( Siemens, 1995) for mix-I, mix-Iprime, Mix-II, mix-IIprime. Cell refinement: SAINT (Siemens,1995) for 2cp3mpy; SAINT(Siemens,1995) for mix-I, mix-Iprime, Mix-II, mix-IIprime. Data reduction: SAINT (Siemens,1995) for 2cp3mpy; SAINT(Siemens,1995) for mix-I, mix-Iprime, Mix-II, mix-IIprime. Program(s) used to solve structure: SIR92 (Altomare et al., 1994) for 2cp3mpy; SIR92(Altomare et al., 1994) for mix-I, mix-Iprime, Mix-II, mix-IIprime. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for 2cp3mpy, mix-Iprime, Mix-II, mix-IIprime; SHELXS97(Sheldrick, 1997) for mix-I. For all compounds, molecular graphics: ORTEP-III(Burnet & Johnson, 1996).

Figures

(2cp3mpy) (2-cyanopropyl)(3-methylpyridine) cobaloxime

Crystal data

C18H26.712CoN6O4	Z = 4
Mr = 450.08	F(000) = 936
Monoclinic, P21/n	Dx = 1.41 Mg m^−3
a = 15.5525 (1) Å	Mo Kα radiation, λ = 0.71069 Å
b = 7.5711 (1) Å	µ = 0.85 mm^−1
c = 18.1578 (1) Å	T = 293 K
β = 98.42°	Plates, orange
V = 2115.01 (3) Å^3	0.5 × 0.35 × 0.05 mm

Data collection

SMART CCD diffractometer	4814 independent reflections
Radiation source: fine-focus sealed tube	4163 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan SADABS( (Sheldrick, 1996)	h = −18→20
Tmin = 0.709, Tmax = 1.000	k = −9→9
14434 measured reflections	l = −23→14

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0534P)^2 + 0.674P] where P = (Fo^2 + 2Fc^2)/3
4814 reflections	(Δ/σ)max = 0.001
281 parameters	Δρmax = 0.46 e Å^−3
1 restraint	Δρmin = −0.43 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.498962 (15)	0.22389 (3)	0.742033 (13)	0.02077 (9)
O1	0.49476 (10)	−0.12723 (17)	0.79915 (8)	0.0346 (3)
H1	0.5550 (17)	−0.104 (3)	0.7769 (13)	0.042*
O2	0.37644 (10)	0.50167 (18)	0.74680 (9)	0.0353 (3)
O3	0.62477 (10)	−0.05286 (17)	0.74020 (8)	0.0331 (3)
O4	0.50621 (11)	0.57613 (17)	0.68554 (9)	0.0370 (4)
H4	0.4482 (18)	0.558 (3)	0.7099 (14)	0.044*
N1	0.45386 (11)	0.0308 (2)	0.78947 (8)	0.0253 (3)
N2	0.39629 (10)	0.3326 (2)	0.76396 (9)	0.0258 (3)
N3	0.60224 (10)	0.1159 (2)	0.72036 (9)	0.0254 (3)
N4	0.54573 (11)	0.41549 (19)	0.69486 (9)	0.0259 (3)
N5	0.56365 (10)	0.3097 (2)	0.84498 (8)	0.0257 (3)
N6	0.3556 (2)	−0.1865 (4)	0.51300 (15)	0.0756 (8)
C1	0.38167 (13)	0.0576 (3)	0.81565 (10)	0.0289 (4)
C2	0.34767 (13)	0.2368 (3)	0.80121 (11)	0.0284 (4)
C3	0.65426 (13)	0.2122 (3)	0.68700 (10)	0.0277 (4)
C4	0.61963 (13)	0.3916 (3)	0.67117 (10)	0.0288 (4)
C5	0.33867 (17)	−0.0798 (3)	0.85758 (13)	0.0445 (6)
H5A	0.3560	−0.1953	0.8436	0.067*
H5B	0.2767	−0.0685	0.8459	0.067*
H5C	0.3559	−0.0633	0.9101	0.067*
C6	0.26726 (14)	0.3047 (3)	0.82804 (13)	0.0399 (5)
H6A	0.2641	0.4306	0.8218	0.060*
H6B	0.2691	0.2761	0.8798	0.060*
H6C	0.2170	0.2510	0.7998	0.060*
C7	0.73865 (14)	0.1479 (3)	0.66682 (13)	0.0396 (5)
H7A	0.7445	0.0238	0.6771	0.059*
H7B	0.7857	0.2104	0.6956	0.059*
H7C	0.7399	0.1683	0.6148	0.059*
C8	0.66446 (17)	0.5295 (3)	0.63173 (14)	0.0461 (6)
H8A	0.6413	0.6436	0.6408	0.069*
H8B	0.6553	0.5058	0.5792	0.069*
H8C	0.7256	0.5275	0.6498	0.069*
C9	0.55270 (13)	0.4724 (2)	0.87261 (11)	0.0292 (4)
H9	0.5144	0.5493	0.8445	0.035*
C10	0.59572 (14)	0.5312 (3)	0.94107 (11)	0.0325 (4)
C11	0.65391 (15)	0.4147 (3)	0.98188 (11)	0.0381 (5)
H11	0.6846	0.4492	1.0274	0.046*
C12	0.66551 (15)	0.2483 (3)	0.95412 (12)	0.0383 (5)
H12	0.7041	0.1695	0.9808	0.046*
C13	0.61914 (13)	0.1995 (3)	0.88604 (11)	0.0310 (4)
H13	0.6267	0.0863	0.8681	0.037*
C14	0.5808 (2)	0.7155 (3)	0.96855 (13)	0.0499 (6)
H14A	0.5398	0.7759	0.9325	0.075*
H14B	0.6348	0.7790	0.9756	0.075*
H14C	0.5584	0.7086	1.0150	0.075*
C16	0.42907 (15)	0.1378 (3)	0.64306 (11)	0.0329 (5)
H16	0.3653 (16)	0.103 (3)	0.6624 (13)	0.040*
C17	0.46372 (17)	−0.0325 (3)	0.61564 (14)	0.0463 (6)
H17A	0.5175	−0.0079	0.5965	0.056*
H17B	0.4770	−0.1127	0.6574	0.056*
C18	0.40346 (17)	−0.1200 (3)	0.55734 (12)	0.0428 (5)
C15B	0.3494 (15)	0.228 (4)	0.6050 (17)	0.060*	0.096 (6)
C15	0.4075 (2)	0.2751 (3)	0.58352 (15)	0.0499 (9)	0.904 (6)
H15A	0.3819	0.3759	0.6040	0.075*	0.904 (6)
H15B	0.3672	0.2269	0.5435	0.075*	0.904 (6)
H15C	0.4597	0.3104	0.5650	0.075*	0.904 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02110 (14)	0.01653 (13)	0.02494 (14)	0.00087 (9)	0.00428 (9)	0.00165 (8)
O1	0.0441 (9)	0.0198 (6)	0.0409 (8)	0.0044 (6)	0.0095 (7)	0.0080 (6)
O2	0.0317 (8)	0.0227 (7)	0.0515 (9)	0.0087 (6)	0.0063 (6)	0.0010 (6)
O3	0.0338 (8)	0.0232 (6)	0.0418 (8)	0.0102 (6)	0.0044 (6)	0.0024 (6)
O4	0.0420 (9)	0.0192 (7)	0.0505 (9)	0.0034 (6)	0.0088 (7)	0.0097 (6)
N1	0.0295 (9)	0.0203 (7)	0.0257 (8)	0.0006 (6)	0.0033 (6)	0.0008 (6)
N2	0.0234 (8)	0.0216 (7)	0.0321 (8)	0.0025 (6)	0.0026 (6)	−0.0010 (6)
N3	0.0255 (8)	0.0217 (7)	0.0285 (8)	0.0030 (6)	0.0026 (6)	−0.0002 (6)
N4	0.0282 (9)	0.0186 (7)	0.0305 (8)	−0.0005 (6)	0.0031 (6)	0.0023 (6)
N5	0.0254 (8)	0.0253 (8)	0.0266 (8)	−0.0008 (6)	0.0047 (6)	0.0006 (6)
N6	0.088 (2)	0.0745 (17)	0.0563 (15)	−0.0032 (15)	−0.0162 (14)	−0.0278 (13)
C1	0.0321 (11)	0.0289 (9)	0.0258 (9)	−0.0071 (8)	0.0042 (8)	0.0007 (7)
C2	0.0252 (10)	0.0325 (10)	0.0272 (9)	−0.0014 (8)	0.0032 (7)	−0.0049 (7)
C3	0.0242 (10)	0.0324 (10)	0.0264 (9)	−0.0014 (7)	0.0034 (7)	−0.0050 (7)
C4	0.0298 (10)	0.0299 (9)	0.0267 (9)	−0.0071 (8)	0.0046 (7)	0.0004 (7)
C5	0.0481 (14)	0.0470 (13)	0.0408 (12)	−0.0110 (11)	0.0140 (10)	0.0116 (10)
C6	0.0279 (11)	0.0504 (13)	0.0430 (12)	0.0012 (9)	0.0104 (9)	−0.0100 (10)
C7	0.0266 (11)	0.0529 (14)	0.0407 (12)	0.0024 (9)	0.0097 (9)	−0.0084 (10)
C8	0.0473 (14)	0.0437 (13)	0.0505 (14)	−0.0145 (11)	0.0178 (11)	0.0075 (10)
C9	0.0316 (11)	0.0246 (9)	0.0311 (10)	−0.0021 (8)	0.0035 (8)	0.0005 (7)
C10	0.0387 (12)	0.0316 (10)	0.0281 (10)	−0.0071 (8)	0.0082 (8)	−0.0017 (8)
C11	0.0398 (12)	0.0468 (12)	0.0263 (10)	−0.0046 (10)	0.0001 (8)	−0.0024 (9)
C12	0.0371 (12)	0.0467 (12)	0.0297 (10)	0.0073 (9)	0.0003 (8)	0.0051 (9)
C13	0.0291 (10)	0.0323 (10)	0.0316 (10)	0.0049 (8)	0.0040 (8)	0.0012 (8)
C14	0.0744 (19)	0.0361 (12)	0.0372 (12)	−0.0039 (11)	0.0021 (12)	−0.0095 (9)
C16	0.0415 (12)	0.0269 (10)	0.0279 (10)	0.0008 (8)	−0.0034 (8)	−0.0001 (7)
C17	0.0517 (15)	0.0380 (12)	0.0440 (13)	0.0126 (10)	−0.0104 (11)	−0.0125 (10)
C18	0.0515 (14)	0.0418 (12)	0.0347 (11)	0.0008 (10)	0.0047 (10)	−0.0090 (9)
C15	0.063 (2)	0.0373 (14)	0.0419 (15)	0.0029 (12)	−0.0185 (13)	0.0055 (11)

Geometric parameters (Å, º)

Co—N1	1.8836 (16)	C6—H6B	0.9600
Co—N4	1.8841 (16)	C6—H6C	0.9600
Co—N2	1.8901 (16)	C7—H7A	0.9600
Co—N3	1.8944 (16)	C7—H7B	0.9600
Co—C16	2.0649 (19)	C7—H7C	0.9600
Co—N5	2.0922 (15)	C8—H8A	0.9600
O1—N1	1.354 (2)	C8—H8B	0.9600
O1—H1	1.09 (3)	C8—H8C	0.9600
O2—N2	1.342 (2)	C9—C10	1.396 (3)
O2—H4	1.45 (3)	C9—H9	0.9300
O3—N3	1.3594 (19)	C10—C11	1.396 (3)
O3—H1	1.41 (3)	C10—C14	1.511 (3)
O4—N4	1.362 (2)	C11—C12	1.379 (3)
O4—H4	1.07 (3)	C11—H11	0.9300
N1—C1	1.298 (3)	C12—C13	1.387 (3)
N2—C2	1.306 (3)	C12—H12	0.9300
N3—C3	1.303 (3)	C13—H13	0.9300
N4—C4	1.297 (3)	C14—H14A	0.9600
N5—C13	1.345 (2)	C14—H14B	0.9600
N5—C9	1.350 (2)	C14—H14C	0.9600
N6—C18	1.131 (3)	C16—C15B	1.495 (10)
C1—C2	1.466 (3)	C16—C15	1.502 (3)
C1—C5	1.502 (3)	C16—C17	1.509 (3)
C2—C6	1.498 (3)	C16—H16	1.13 (3)
C3—C4	1.474 (3)	C17—C18	1.465 (3)
C3—C7	1.495 (3)	C17—H17A	0.9700
C4—C8	1.495 (3)	C17—H17B	0.9700
C5—H5A	0.9600	C15B—H16	1.40 (3)
C5—H5B	0.9600	C15—H15A	0.9600
C5—H5C	0.9600	C15—H15B	0.9600
C6—H6A	0.9600	C15—H15C	0.9600
N1—Co—N4	179.15 (7)	C3—C7—H7A	109.5
N1—Co—N2	81.90 (7)	C3—C7—H7B	109.5
N4—Co—N2	98.90 (7)	H7A—C7—H7B	109.5
N1—Co—N3	98.28 (7)	C3—C7—H7C	109.5
N4—Co—N3	80.93 (7)	H7A—C7—H7C	109.5
N2—Co—N3	179.68 (7)	H7B—C7—H7C	109.5
N1—Co—C16	88.23 (8)	C4—C8—H8A	109.5
N4—Co—C16	92.09 (8)	C4—C8—H8B	109.5
N2—Co—C16	88.14 (8)	H8A—C8—H8B	109.5
N3—Co—C16	92.13 (8)	C4—C8—H8C	109.5
N1—Co—N5	89.71 (6)	H8A—C8—H8C	109.5
N4—Co—N5	90.00 (6)	H8B—C8—H8C	109.5
N2—Co—N5	89.26 (7)	N5—C9—C10	123.51 (18)
N3—Co—N5	90.47 (6)	N5—C9—H9	118.2
C16—Co—N5	176.89 (8)	C10—C9—H9	118.2
N1—O1—H1	102.7 (13)	C9—C10—C11	117.38 (19)
N2—O2—H4	102.9 (10)	C9—C10—C14	120.82 (19)
N3—O3—H1	101.2 (10)	C11—C10—C14	121.79 (19)
N4—O4—H4	103.2 (14)	C12—C11—C10	119.52 (19)
C1—N1—O1	120.36 (16)	C12—C11—H11	120.2
C1—N1—Co	116.52 (13)	C10—C11—H11	120.2
O1—N1—Co	123.07 (13)	C11—C12—C13	119.4 (2)
C2—N2—O2	121.26 (17)	C11—C12—H12	120.3
C2—N2—Co	115.99 (13)	C13—C12—H12	120.3
O2—N2—Co	122.62 (13)	N5—C13—C12	122.45 (19)
C3—N3—O3	119.73 (16)	N5—C13—H13	118.8
C3—N3—Co	117.27 (13)	C12—C13—H13	118.8
O3—N3—Co	122.96 (13)	C10—C14—H14A	109.5
C4—N4—O4	119.27 (16)	C10—C14—H14B	109.5
C4—N4—Co	117.58 (13)	H14A—C14—H14B	109.5
O4—N4—Co	123.15 (13)	C10—C14—H14C	109.5
C13—N5—C9	117.75 (16)	H14A—C14—H14C	109.5
C13—N5—Co	119.23 (13)	H14B—C14—H14C	109.5
C9—N5—Co	123.02 (13)	C15B—C16—C15	42.8 (14)
N1—C1—C2	112.81 (17)	C15B—C16—C17	123.5 (13)
N1—C1—C5	123.43 (19)	C15—C16—C17	114.0 (2)
C2—C1—C5	123.8 (2)	C15B—C16—Co	123.5 (13)
N2—C2—C1	112.70 (18)	C15—C16—Co	116.19 (15)
N2—C2—C6	123.51 (19)	C17—C16—Co	112.88 (14)
C1—C2—C6	123.77 (19)	C15B—C16—H16	62.9 (18)
N3—C3—C4	111.87 (17)	C15—C16—H16	105.7 (12)
N3—C3—C7	124.00 (19)	C17—C16—H16	106.0 (12)
C4—C3—C7	124.13 (19)	Co—C16—H16	100.2 (12)
N4—C4—C3	112.34 (17)	C18—C17—C16	113.75 (19)
N4—C4—C8	124.00 (19)	C18—C17—H17A	108.8
C3—C4—C8	123.7 (2)	C16—C17—H17A	108.8
C1—C5—H5A	109.5	C18—C17—H17B	108.8
C1—C5—H5B	109.5	C16—C17—H17B	108.8
H5A—C5—H5B	109.5	H17A—C17—H17B	107.7
C1—C5—H5C	109.5	N6—C18—C17	178.6 (3)
H5A—C5—H5C	109.5	C16—C15B—H16	45.8 (11)
H5B—C5—H5C	109.5	C16—C15—H15A	109.5
C2—C6—H6A	109.5	C16—C15—H15B	109.5
C2—C6—H6B	109.5	H15A—C15—H15B	109.5
H6A—C6—H6B	109.5	C16—C15—H15C	109.5
C2—C6—H6C	109.5	H15A—C15—H15C	109.5
H6A—C6—H6C	109.5	H15B—C15—H15C	109.5
H6B—C6—H6C	109.5

(mix-I) [(2-cyanoethyl)(3-methylpyridine)cobaloxime] [(2-cyanopropyl)(3-methylpyridine)cobaloxime]

Crystal data

C17.48H21CoN6O4	Z = 4
Mr = 438.09	F(000) = 932
Monoclinic, P21/n	Dx = 1.40 Mg m^−3
a = 11.5388 (2) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.3751 (2) Å	µ = 0.86 mm^−1
c = 19.2929 (4) Å	T = 293 K
β = 92.204 (1)°	Plates, yellow
V = 2085.51 (7) Å^3	0.4 × 0.3 × 0.04 mm

Data collection

SMART CCD diffractometer	4761 independent reflections
Radiation source: fine-focus sealed tube	3427 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ω scan	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan SADABS(Sheldrick, 1996)	h = −14→14
Tmin = 0.726, Tmax = 1.000	k = −12→12
14242 measured reflections	l = −22→25

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0795P)^2 + 1.695P] where P = (Fo^2 + 2Fc^2)/3
4761 reflections	(Δ/σ)max = 0.036
280 parameters	Δρmax = 0.87 e Å^−3
16 restraints	Δρmin = −0.52 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.76152 (2)	0.22288 (3)	0.909091 (13)	0.03753 (7)
O1	0.97888 (13)	0.08910 (19)	0.93895 (9)	0.0607 (5)
H1	0.916 (2)	0.019 (3)	0.9372 (12)	0.073*
O2	0.71846 (15)	0.51623 (16)	0.87737 (9)	0.0654 (5)
H2	0.645 (2)	0.462 (3)	0.8779 (13)	0.079*
O3	0.80576 (14)	−0.06928 (15)	0.94044 (9)	0.0591 (5)
O4	0.54551 (14)	0.35741 (18)	0.87413 (11)	0.0736 (6)
N1	0.92351 (14)	0.21162 (18)	0.92395 (8)	0.0428 (4)
N2	0.79874 (15)	0.41612 (18)	0.89463 (9)	0.0470 (5)
N3	0.72473 (15)	0.02952 (17)	0.92246 (9)	0.0433 (4)
N4	0.59986 (14)	0.23374 (19)	0.89186 (10)	0.0480 (5)
N5	0.74173 (14)	0.26276 (17)	1.01389 (9)	0.0438 (4)
C1	0.98131 (17)	0.3296 (3)	0.92018 (11)	0.0512 (6)
C2	0.9065 (2)	0.4516 (2)	0.90216 (11)	0.0526 (6)
C3	0.61593 (18)	−0.0061 (2)	0.91497 (11)	0.0486 (6)
C4	0.54193 (18)	0.1164 (2)	0.89567 (12)	0.0516 (6)
C5	1.1104 (2)	0.3380 (4)	0.92964 (15)	0.0823 (9)
H5A	1.1389	0.2524	0.9516	0.123*
H5B	1.1308	0.4187	0.9582	0.123*
H5C	1.1442	0.3483	0.8852	0.123*
C6	0.9517 (2)	0.5992 (3)	0.89047 (15)	0.0801 (8)
H6A	0.8914	0.6674	0.8981	0.120*
H6B	0.9763	0.6075	0.8437	0.120*
H6C	1.0162	0.6173	0.9221	0.120*
C7	0.5721 (2)	−0.1542 (2)	0.92451 (14)	0.0696 (7)
H7A	0.6366	−0.2184	0.9301	0.104*
H7B	0.5252	−0.1816	0.8845	0.104*
H7C	0.5263	−0.1578	0.9650	0.104*
C8	0.4137 (2)	0.1047 (4)	0.88088 (16)	0.0838 (10)
H8A	0.3804	0.1984	0.8782	0.126*
H8B	0.3791	0.0519	0.9174	0.126*
H8C	0.3996	0.0562	0.8375	0.126*
C9	0.79389 (18)	0.1830 (2)	1.06326 (11)	0.0474 (5)
H9	0.8390	0.1067	1.0494	0.057*
C10	0.78504 (11)	0.20689 (12)	1.13452 (6)	0.0589 (7)
C11	0.7179 (2)	0.3222 (3)	1.15303 (13)	0.0701 (7)
H11	0.7097	0.3430	1.1997	0.084*
C12	0.6639 (2)	0.4052 (3)	1.10403 (13)	0.0668 (7)
H12	0.6189	0.4824	1.1168	0.080*
C13	0.67692 (19)	0.3734 (2)	1.03476 (13)	0.0543 (6)
H13	0.6396	0.4303	1.0013	0.065*
C14	0.84750 (17)	0.10864 (18)	1.18711 (8)	0.0886 (11)
C16	0.77448 (4)	0.17463 (6)	0.80667 (3)	0.0593 (7)
H16	0.717 (2)	0.117 (3)	0.7977 (12)	0.071*
C17	0.803395 (4)	0.284060 (17)	0.75116 (4)	0.0608 (14)*	0.451 (4)
H17A	0.7856	0.2421	0.7061	0.073*	0.451 (4)
H17B	0.7525	0.3656	0.7560	0.073*	0.451 (4)
C18	0.921993 (5)	0.335377 (18)	0.75196 (10)	0.060*	0.451 (4)
C15	0.86384 (8)	0.05483 (7)	0.80163 (9)	0.055*	0.129 (5)
C17B	0.887615 (6)	0.126171 (9)	0.783213 (17)	0.0729 (18)*	0.404 (3)
H17C	0.9204	0.0613	0.8179	0.088*	0.404 (3)
H17D	0.8744	0.0718	0.7409	0.088*	0.404 (3)
C18B	0.972411 (7)	0.233213 (10)	0.770302 (19)	0.078 (2)*	0.404 (3)
N6B	1.037793 (9)	0.310629 (13)	0.76021 (2)	0.080*	0.404 (3)
C15B	0.72616 (7)	0.28983 (9)	0.75735 (7)	0.055*	0.351 (5)
C18A	0.959120 (7)	0.288775 (8)	0.761436 (19)	0.030*	0.145 (3)
C17A	0.888075 (8)	0.166598 (8)	0.77271 (2)	0.030*	0.145 (3)
N6	1.013393 (5)	0.378681 (9)	0.75193 (2)	0.084*	0.596 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.03446 (12)	0.02820 (11)	0.05005 (14)	−0.00607 (10)	0.00322 (10)	−0.00062 (11)
O1	0.0405 (7)	0.0625 (10)	0.0792 (10)	0.0065 (7)	0.0021 (7)	0.0079 (8)
O2	0.0702 (10)	0.0327 (7)	0.0933 (12)	0.0011 (7)	0.0015 (9)	0.0102 (8)
O3	0.0634 (9)	0.0310 (7)	0.0821 (10)	0.0037 (7)	−0.0060 (8)	0.0040 (7)
O4	0.0471 (8)	0.0513 (9)	0.1212 (14)	0.0099 (7)	−0.0096 (9)	0.0092 (10)
N1	0.0373 (8)	0.0475 (9)	0.0438 (8)	−0.0041 (7)	0.0046 (7)	0.0006 (7)
N2	0.0539 (9)	0.0341 (8)	0.0534 (9)	−0.0080 (8)	0.0051 (8)	0.0023 (8)
N3	0.0467 (8)	0.0303 (8)	0.0529 (9)	−0.0043 (7)	0.0024 (7)	−0.0007 (7)
N4	0.0381 (8)	0.0429 (9)	0.0628 (10)	0.0000 (7)	−0.0001 (8)	0.0026 (8)
N5	0.0392 (8)	0.0364 (8)	0.0565 (9)	−0.0124 (7)	0.0099 (7)	−0.0057 (7)
C1	0.0422 (10)	0.0674 (13)	0.0445 (11)	−0.0195 (10)	0.0065 (8)	−0.0002 (10)
C2	0.0645 (12)	0.0466 (11)	0.0473 (11)	−0.0263 (10)	0.0093 (9)	−0.0028 (9)
C3	0.0533 (11)	0.0419 (10)	0.0508 (11)	−0.0185 (9)	0.0060 (9)	−0.0023 (9)
C4	0.0395 (10)	0.0528 (12)	0.0626 (13)	−0.0133 (9)	0.0037 (9)	−0.0059 (10)
C5	0.0468 (12)	0.118 (2)	0.0824 (17)	−0.0326 (14)	0.0031 (12)	0.0014 (17)
C6	0.0987 (17)	0.0555 (13)	0.0872 (18)	−0.0450 (12)	0.0161 (14)	−0.0012 (13)
C7	0.0853 (15)	0.0470 (12)	0.0767 (16)	−0.0334 (11)	0.0078 (13)	0.0008 (12)
C8	0.0361 (11)	0.103 (2)	0.112 (2)	−0.0195 (13)	0.0005 (13)	−0.0098 (19)
C9	0.0450 (10)	0.0444 (10)	0.0531 (11)	−0.0112 (9)	0.0078 (9)	−0.0047 (9)
C10	0.0581 (12)	0.0630 (14)	0.0561 (12)	−0.0248 (10)	0.0116 (10)	−0.0078 (11)
C11	0.0724 (14)	0.0744 (15)	0.0654 (13)	−0.0294 (12)	0.0272 (11)	−0.0236 (12)
C12	0.0587 (12)	0.0554 (13)	0.0884 (15)	−0.0148 (11)	0.0303 (11)	−0.0230 (12)
C13	0.0477 (11)	0.0403 (10)	0.0759 (14)	−0.0084 (9)	0.0162 (10)	−0.0096 (10)
C14	0.106 (2)	0.104 (2)	0.0549 (15)	−0.0053 (19)	−0.0046 (15)	0.0158 (15)
C16	0.0625 (13)	0.0640 (13)	0.0514 (12)	−0.0225 (11)	0.0013 (10)	−0.0058 (11)

Geometric parameters (Å, º)

Co—N3	1.8818 (16)	C7—H7C	0.9600
Co—N1	1.8831 (16)	C8—H8A	0.9600
Co—N4	1.8849 (17)	C8—H8B	0.9600
Co—N2	1.8851 (17)	C8—H8C	0.9600
Co—C16	2.0381 (7)	C9—C10	1.401 (2)
Co—N5	2.0774 (17)	C9—H9	0.9300
O1—N1	1.341 (2)	C10—C11	1.384 (3)
O1—H1	0.98 (3)	C10—C14	1.5300 (9)
O2—N2	1.351 (2)	C11—C12	1.358 (4)
O2—H2	0.98 (3)	C11—H11	0.9300
O3—N3	1.352 (2)	C12—C13	1.383 (3)
O4—N4	1.356 (2)	C12—H12	0.9300
N1—C1	1.295 (3)	C13—H13	0.9300
N2—C2	1.290 (3)	C16—C17B	1.4700 (5)
N3—C3	1.302 (3)	C16—C17A	1.4897 (5)
N4—C4	1.291 (3)	C16—C17	1.5292 (7)
N5—C9	1.336 (3)	C16—C15	1.5303 (7)
N5—C13	1.349 (3)	C16—C15B	1.5304 (8)
C1—C2	1.466 (3)	C16—H16	0.87 (2)
C1—C5	1.495 (3)	C17—C18	1.4501
C2—C6	1.499 (3)	C17—H17A	0.9700
C3—C4	1.470 (3)	C17—H17B	0.9700
C3—C7	1.492 (3)	C18—N6	1.1301
C4—C8	1.500 (3)	C17B—C18B	1.4301
C5—H5A	0.9600	C17B—H17C	0.9700
C5—H5B	0.9600	C17B—H17D	0.9700
C5—H5C	0.9600	C18B—N6B	1.0701
C6—H6A	0.9600	C18B—N6	1.4906 (2)
C6—H6B	0.9600	N6B—N6	0.7130 (2)
C6—H6C	0.9600	C18A—N6	1.0701
C7—H7A	0.9600	C18A—C17A	1.4301
C7—H7B	0.9600
N3—Co—N1	98.80 (7)	C4—C8—H8C	109.5
N3—Co—N4	81.33 (8)	H8A—C8—H8C	109.5
N1—Co—N4	178.60 (8)	H8B—C8—H8C	109.5
N3—Co—N2	179.34 (8)	N5—C9—C10	124.23 (18)
N1—Co—N2	81.14 (8)	N5—C9—H9	117.9
N4—Co—N2	98.72 (8)	C10—C9—H9	117.9
N3—Co—C16	86.81 (5)	C11—C10—C9	116.15 (16)
N1—Co—C16	91.47 (5)	C11—C10—C14	123.56 (15)
N4—Co—C16	87.14 (6)	C9—C10—C14	120.29 (14)
N2—Co—C16	92.53 (5)	C12—C11—C10	121.0 (2)
N3—Co—N5	90.35 (7)	C12—C11—H11	119.5
N1—Co—N5	90.43 (7)	C10—C11—H11	119.5
N4—Co—N5	90.96 (7)	C11—C12—C13	119.0 (2)
N2—Co—N5	90.30 (7)	C11—C12—H12	120.5
C16—Co—N5	176.80 (5)	C13—C12—H12	120.5
N1—O1—H1	102.5 (15)	N5—C13—C12	122.4 (2)
N2—O2—H2	102.7 (16)	N5—C13—H13	118.8
C1—N1—O1	120.11 (17)	C12—C13—H13	118.8
C1—N1—Co	116.99 (15)	C17B—C16—C17A	16.685 (11)
O1—N1—Co	122.88 (13)	C17B—C16—C17	76.79 (3)
C2—N2—O2	119.83 (17)	C17A—C16—C17	60.43 (2)
C2—N2—Co	117.08 (15)	C17B—C16—C15	31.25 (4)
O2—N2—Co	123.09 (13)	C17A—C16—C15	47.82 (4)
C3—N3—O3	120.50 (17)	C17—C16—C15	106.39 (6)
C3—N3—Co	116.96 (14)	C17B—C16—C15B	109.47 (5)
O3—N3—Co	122.54 (13)	C17A—C16—C15B	93.89 (5)
C4—N4—O4	120.51 (17)	C17—C16—C15B	34.42 (4)
C4—N4—Co	117.07 (15)	C15—C16—C15B	135.13 (8)
O4—N4—Co	122.39 (13)	C17B—C16—Co	117.79 (4)
C9—N5—C13	117.21 (19)	C17A—C16—Co	122.43 (4)
C9—N5—Co	121.99 (14)	C17—C16—Co	123.79 (4)
C13—N5—Co	120.78 (15)	C15—C16—Co	107.41 (7)
N1—C1—C2	112.32 (18)	C15B—C16—Co	114.06 (6)
N1—C1—C5	123.4 (2)	C17B—C16—H16	115.4 (16)
C2—C1—C5	124.2 (2)	C17A—C16—H16	124.1 (16)
N2—C2—C1	112.42 (19)	C17—C16—H16	117.7 (15)
N2—C2—C6	124.1 (2)	C15—C16—H16	92.5 (16)
C1—C2—C6	123.4 (2)	C15B—C16—H16	93.4 (16)
N3—C3—C4	112.10 (18)	Co—C16—H16	104.2 (15)
N3—C3—C7	123.7 (2)	C18—C17—C16	116.51 (7)
C4—C3—C7	124.2 (2)	C18—C17—H17A	108.2
N4—C4—C3	112.52 (18)	C16—C17—H17A	108.2
N4—C4—C8	124.1 (2)	C18—C17—H17B	108.2
C3—C4—C8	123.4 (2)	C16—C17—H17B	108.2
C1—C5—H5A	109.5	H17A—C17—H17B	107.3
C1—C5—H5B	109.5	N6—C18—C17	178.21 (8)
H5A—C5—H5B	109.5	C18B—C17B—C16	117.28 (2)
C1—C5—H5C	109.5	C18B—C17B—H17C	108.0
H5A—C5—H5C	109.5	C16—C17B—H17C	108.0
H5B—C5—H5C	109.5	C18B—C17B—H17D	108.0
C2—C6—H6A	109.5	C16—C17B—H17D	108.0
C2—C6—H6B	109.5	H17C—C17B—H17D	107.2
H6A—C6—H6B	109.5	N6B—C18B—C17B	178.135 (19)
C2—C6—H6C	109.5	N6B—C18B—N6	26.351 (8)
H6A—C6—H6C	109.5	C17B—C18B—N6	155.345 (9)
H6B—C6—H6C	109.5	N6—N6B—C18B	111.874 (14)
C3—C7—H7A	109.5	N6—C18A—C17A	178.48 (3)
C3—C7—H7B	109.5	C18A—C17A—C16	123.07 (2)
H7A—C7—H7B	109.5	N6B—N6—C18A	59.033 (10)
C3—C7—H7C	109.5	N6B—N6—C18	92.23 (2)
H7A—C7—H7C	109.5	C18A—N6—C18	33.35 (3)
H7B—C7—H7C	109.5	N6B—N6—C18B	41.775 (9)
C4—C8—H8A	109.5	C18A—N6—C18B	17.355 (8)
C4—C8—H8B	109.5	C18—N6—C18B	50.70 (3)
H8A—C8—H8B	109.5

(mix-Iprime) [(2-cyanoethyl)(3-methylpyridine)cobaloxime] [(2-cyanopropyl)(3-methylpyridine)cobaloxime]

Crystal data

C17.50H19CoN6O4	Z = 4
Mr = 436.31	F(000) = 888
Monoclinic, P21/n	Dx = 1.37 Mg m^−3
a = 11.5432 (9) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.3978 (4) Å	µ = 0.85 mm^−1
c = 19.5033 (16) Å	T = 293 K
β = 90.992 (4)°	Plate, orange
V = 2115.4 (3) Å^3	0.4 × 0.3 × 0.04 mm

Data collection

SMART CCD diffractometer	4856 independent reflections
Radiation source: fine-focus sealed tube	2223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scan	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan SADABS(Sheldrick, 1996)	h = −12→14
Tmin = 0.503, Tmax = 1.000	k = −12→12
14831 measured reflections	l = −25→21

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)] = 0.110	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.317	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1163P)^2 + 7.8125P] where P = (Fo^2 + 2Fc^2)/3
4856 reflections	(Δ/σ)max = 0.048
294 parameters	Δρmax = 0.71 e Å^−3
20 restraints	Δρmin = −0.58 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.76785 (7)	−0.22686 (8)	0.58618 (4)	0.0621 (2)
O1	0.7255 (5)	−0.5213 (4)	0.6136 (3)	0.106 (2)
O2	0.9820 (3)	−0.0889 (5)	0.5637 (2)	0.0803 (16)
H1	0.895 (5)	0.004 (7)	0.560 (3)	0.096*
O3	0.5522 (3)	−0.3630 (5)	0.6138 (3)	0.0909 (18)	0.980 (9)
H2	0.664 (6)	−0.447 (7)	0.604 (3)	0.109*
O4	0.8090 (4)	0.0671 (4)	0.5608 (2)	0.0826 (16)
N1	0.8067 (4)	−0.4215 (5)	0.5972 (3)	0.0646 (16)
N2	0.9296 (4)	−0.2127 (5)	0.5749 (2)	0.0648 (15)
N3	0.6063 (4)	−0.2388 (5)	0.6007 (3)	0.0697 (17)	0.984 (10)
N4	0.7292 (3)	−0.0325 (4)	0.5765 (2)	0.0541 (14)
N5	0.7421 (4)	−0.2596 (4)	0.4830 (3)	0.0612 (15)
C1	0.9170 (5)	−0.4504 (7)	0.5927 (3)	0.0702 (19)
C2	0.9901 (6)	−0.3270 (8)	0.5794 (3)	0.074 (2)	0.982 (13)
C3	0.5487 (7)	−0.1210 (7)	0.5985 (4)	0.088 (3)
C4	0.6176 (5)	−0.0001 (6)	0.5839 (3)	0.0646 (19)	0.971 (12)
C5	0.9613 (7)	−0.6015 (7)	0.6038 (4)	0.108 (3)
H5A	0.9034	−0.6681	0.5885	0.162*
H5B	0.9778	−0.6163	0.6517	0.162*
H5C	1.0307	−0.6153	0.5782	0.162*
C6	1.1187 (6)	−0.3355 (9)	0.5726 (4)	0.104 (3)	0.984 (14)
H6A	1.1462	−0.2515	0.5501	0.156*
H6B	1.1383	−0.4178	0.5461	0.156*
H6C	1.1542	−0.3425	0.6174	0.156*
C7	0.4235 (6)	−0.1120 (10)	0.6118 (5)	0.116 (4)
H7A	0.3929	−0.2061	0.6179	0.174*
H7B	0.3848	−0.0673	0.5735	0.174*
H7C	0.4114	−0.0570	0.6525	0.174*
C8	0.5767 (7)	0.1509 (7)	0.5772 (4)	0.099 (3)	0.976 (14)
H8A	0.6424	0.2136	0.5774	0.148*
H8B	0.5278	0.1738	0.6149	0.148*
H8C	0.5339	0.1619	0.5349	0.148*
C9	0.7899 (5)	−0.1776 (6)	0.4354 (3)	0.0622 (18)
H9	0.8355	−0.1023	0.4510	0.075*
C10	0.7786 (5)	−0.1934 (7)	0.3649 (3)	0.077 (2)
C11	0.7100 (6)	−0.3073 (8)	0.3436 (4)	0.076 (2)	0.881 (13)
H11	0.6981	−0.3245	0.2971	0.091*
C12	0.6607 (5)	−0.3925 (7)	0.3902 (4)	0.085 (2)	0.978 (13)
H12	0.6156	−0.4689	0.3754	0.102*
C13	0.6759 (5)	−0.3685 (6)	0.4601 (4)	0.072 (2)
H13	0.6401	−0.4281	0.4914	0.087*
C14	0.8366 (8)	−0.0944 (10)	0.3137 (4)	0.110 (3)
C16	0.793415 (7)	−0.184702 (12)	0.687746 (8)	0.096 (3)
H16	0.724 (6)	−0.146 (8)	0.705 (3)	0.115*
C18B	0.967797 (9)	−0.274764 (8)	0.73207 (2)	0.100*	0.299 (8)
N6B	1.026741 (9)	−0.365418 (9)	0.74019 (2)	0.120*	0.299 (8)
C17B	0.888994 (10)	−0.155962 (9)	0.72255 (3)	0.100*	0.299 (8)
C17	0.806969 (5)	−0.287870 (15)	0.74804 (5)	0.100*	0.343 (8)
N6	1.010856 (6)	−0.392393 (16)	0.7498 (8)	0.130*	0.343 (8)
C18	0.923336 (6)	−0.346041 (17)	0.7491 (8)	0.100*	0.343 (8)
C15	0.87146 (13)	−0.05744 (11)	0.70470 (19)	0.075*	0.16 (1)
C16A	0.7037 (5)	−0.1669 (8)	0.7408 (5)	0.070*	0.25 (1)
C15A	0.6562 (17)	−0.3083 (10)	0.7598 (11)	0.070*	0.20 (1)
C18A	0.892792 (7)	−0.265617 (12)	0.712248 (9)	0.125*	0.358 (9)
N6A	0.965977 (8)	−0.327541 (14)	0.733405 (9)	0.135*	0.358 (9)
C15B	0.73961 (13)	−0.30584 (8)	0.72882 (5)	0.075*	0.14 (1)
C16C	0.7648 (11)	−0.0629 (8)	0.7331 (6)	0.075*	0.11 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0927 (5)	0.0403 (3)	0.0528 (4)	0.0008 (4)	−0.0107 (4)	−0.0087 (4)
O1	0.168 (4)	0.041 (2)	0.107 (4)	−0.017 (3)	−0.021 (3)	0.003 (2)
O2	0.132 (4)	0.081 (3)	0.0283 (19)	−0.001 (3)	−0.006 (2)	0.008 (2)
O3	0.175 (5)	0.070 (3)	0.028 (2)	−0.012 (3)	0.001 (3)	0.0104 (19)
O4	0.117 (3)	0.044 (2)	0.087 (3)	0.002 (2)	0.015 (3)	0.006 (2)
N1	0.101 (4)	0.049 (2)	0.044 (2)	−0.005 (2)	−0.008 (2)	−0.009 (2)
N2	0.078 (3)	0.059 (2)	0.057 (3)	0.005 (2)	−0.014 (2)	−0.028 (2)
N3	0.113 (4)	0.056 (3)	0.040 (2)	0.001 (3)	−0.013 (3)	−0.006 (2)
N4	0.090 (3)	0.045 (2)	0.028 (2)	0.002 (2)	−0.002 (2)	−0.0011 (18)
N5	0.102 (3)	0.041 (2)	0.041 (2)	0.002 (2)	−0.005 (2)	−0.0158 (19)
C1	0.093 (4)	0.077 (3)	0.040 (3)	0.010 (3)	−0.023 (3)	−0.034 (3)
C2	0.073 (4)	0.088 (4)	0.061 (4)	0.013 (3)	−0.020 (3)	−0.018 (3)
C3	0.090 (5)	0.060 (3)	0.114 (6)	0.012 (3)	−0.016 (4)	−0.031 (4)
C4	0.080 (4)	0.059 (3)	0.054 (3)	0.011 (3)	−0.015 (3)	−0.028 (3)
C5	0.147 (6)	0.073 (4)	0.102 (5)	0.007 (4)	−0.034 (5)	−0.052 (3)
C6	0.117 (6)	0.146 (6)	0.049 (4)	0.006 (5)	−0.003 (4)	−0.045 (4)
C7	0.158 (8)	0.133 (7)	0.056 (4)	−0.008 (6)	0.001 (5)	−0.028 (5)
C8	0.126 (6)	0.059 (4)	0.111 (6)	0.010 (4)	−0.015 (5)	−0.040 (4)
C9	0.090 (4)	0.055 (3)	0.042 (3)	0.008 (3)	−0.012 (3)	−0.018 (2)
C10	0.097 (4)	0.073 (4)	0.060 (3)	0.008 (3)	−0.027 (3)	−0.025 (3)
C11	0.087 (5)	0.083 (5)	0.058 (4)	0.015 (4)	−0.032 (3)	−0.031 (3)
C12	0.132 (5)	0.071 (4)	0.052 (3)	0.030 (4)	−0.036 (3)	−0.030 (3)
C13	0.114 (5)	0.053 (3)	0.048 (3)	0.020 (3)	−0.016 (3)	−0.013 (3)
C14	0.093 (5)	0.121 (6)	0.115 (7)	−0.013 (5)	0.003 (5)	−0.001 (6)
C16	0.121 (6)	0.105 (5)	0.061 (4)	−0.006 (5)	−0.007 (4)	−0.017 (4)

Geometric parameters (Å, º)

Co—N4	1.889 (4)	C7—H7B	0.9600
Co—N2	1.889 (5)	C7—H7C	0.9600
Co—N1	1.894 (5)	C8—H8A	0.9600
Co—N3	1.895 (5)	C8—H8B	0.9600
Co—C16	2.0367 (9)	C8—H8C	0.9600
Co—N5	2.051 (5)	C9—C10	1.386 (9)
O1—N1	1.368 (7)	C9—H9	0.9300
O1—H2	1.01 (7)	C10—C11	1.391 (10)
O2—N2	1.331 (6)	C10—C14	1.528 (11)
O2—H1	1.33 (6)	C11—C12	1.345 (10)
O3—N3	1.350 (6)	C11—H11	0.9300
O4—N4	1.352 (6)	C12—C13	1.389 (10)
O4—H1	1.16 (6)	C12—H12	0.9300
N1—C1	1.307 (7)	C13—H13	0.9300
N2—C2	1.283 (8)	C16—C17B	1.3134 (3)
N3—C3	1.291 (8)	C16—C18A	1.4504 (1)
N4—C4	1.334 (7)	C16—C16A	1.486 (7)
N5—C9	1.334 (7)	C16—C16C	1.488 (8)
N5—C13	1.349 (7)	C16—C15B	1.5300 (8)
C1—C2	1.460 (9)	C16—C17	1.5301 (8)
C1—C5	1.523 (9)	C16—C15	1.5301 (12)
C2—C6	1.495 (9)	C16—H16	0.95 (7)
C3—C4	1.420 (9)	C18B—N6B	1.1000 (1)
C3—C7	1.474 (11)	C18B—C17B	1.4500 (1)
C4—C8	1.500 (9)	C17—C18	1.4501 (2)
C5—H5A	0.9600	N6—C18	1.1000 (2)
C5—H5B	0.9600	C16A—C15A	1.487 (12)
C5—H5C	0.9600	C16A—H16	0.76 (7)
C6—H6A	0.9600	C18A—N6A	1.1002 (1)
C6—H6B	0.9600	C15B—H16	1.58 (7)
C6—H6C	0.9600	C16C—H16	1.06 (7)
C7—H7A	0.9600
N4—Co—N2	98.76 (19)	H8A—C8—H8B	109.5
N4—Co—N1	179.2 (2)	C4—C8—H8C	109.5
N2—Co—N1	81.3 (2)	H8A—C8—H8C	109.5
N4—Co—N3	80.84 (19)	H8B—C8—H8C	109.5
N2—Co—N3	178.0 (2)	N5—C9—C10	126.6 (5)
N1—Co—N3	99.1 (2)	N5—C9—H9	116.7
N4—Co—C16	86.51 (14)	C10—C9—H9	116.7
N2—Co—C16	88.43 (15)	C9—C10—C11	115.0 (6)
N1—Co—C16	92.71 (16)	C9—C10—C14	123.2 (6)
N3—Co—C16	89.59 (17)	C11—C10—C14	121.8 (7)
N4—Co—N5	90.98 (18)	C12—C11—C10	120.1 (7)
N2—Co—N5	91.33 (19)	C12—C11—H11	120.0
N1—Co—N5	89.8 (2)	C10—C11—H11	120.0
N3—Co—N5	90.6 (2)	C11—C12—C13	121.3 (6)
C16—Co—N5	177.41 (12)	C11—C12—H12	119.4
N1—O1—H2	88 (4)	C13—C12—H12	119.4
N2—O2—H1	104 (3)	N5—C13—C12	120.6 (6)
N4—O4—H1	103 (3)	N5—C13—H13	119.7
C1—N1—O1	123.0 (5)	C12—C13—H13	119.7
C1—N1—Co	115.0 (4)	C17B—C16—C18A	44.357 (8)
O1—N1—Co	121.8 (4)	C17B—C16—C16A	101.9 (3)
C2—N2—O2	119.7 (5)	C18A—C16—C16A	112.7 (3)
C2—N2—Co	118.1 (4)	C17B—C16—C16C	74.2 (5)
O2—N2—Co	122.2 (3)	C18A—C16—C16C	113.0 (5)
C3—N3—O3	120.5 (5)	C16A—C16—C16C	48.3 (5)
C3—N3—Co	116.9 (5)	C17B—C16—C15B	103.14 (6)
O3—N3—Co	122.6 (3)	C18A—C16—C15B	76.30 (6)
C4—N4—O4	121.9 (4)	C16A—C16—C15B	54.9 (3)
C4—N4—Co	115.9 (4)	C16C—C16—C15B	99.5 (4)
O4—N4—Co	122.1 (3)	C17B—C16—C17	70.080 (19)
C9—N5—C13	116.5 (5)	C18A—C16—C17	49.062 (12)
C9—N5—Co	122.8 (4)	C16A—C16—C17	66.4 (3)
C13—N5—Co	120.7 (4)	C16C—C16—C17	92.9 (4)
N1—C1—C2	114.4 (5)	C15B—C16—C17	33.18 (5)
N1—C1—C5	120.7 (6)	C17B—C16—C15	40.65 (8)
C2—C1—C5	124.9 (5)	C18A—C16—C15	83.06 (6)
N2—C2—C1	111.2 (5)	C16A—C16—C15	100.2 (3)
N2—C2—C6	125.3 (7)	C16C—C16—C15	53.6 (5)
C1—C2—C6	123.4 (6)	C15B—C16—C15	135.34 (14)
N3—C3—C4	113.7 (7)	C17—C16—C15	106.09 (12)
N3—C3—C7	123.3 (7)	C17B—C16—Co	130.46 (3)
C4—C3—C7	122.9 (6)	C18A—C16—Co	108.60 (2)
N4—C4—C3	112.6 (5)	C16A—C16—Co	127.5 (3)
N4—C4—C8	120.6 (6)	C16C—C16—Co	134.3 (4)
C3—C4—C8	126.8 (6)	C15B—C16—Co	108.13 (5)
C1—C5—H5A	109.5	C17—C16—Co	129.45 (3)
C1—C5—H5B	109.5	C15—C16—Co	115.92 (14)
H5A—C5—H5B	109.5	C17B—C16—H16	116 (4)
C1—C5—H5C	109.5	C18A—C16—H16	139 (4)
H5A—C5—H5C	109.5	C16A—C16—H16	26 (4)
H5B—C5—H5C	109.5	C16C—C16—H16	45 (4)
C2—C6—H6A	109.5	C15B—C16—H16	75 (4)
C2—C6—H6B	109.5	C17—C16—H16	93 (4)
H6A—C6—H6B	109.5	C15—C16—H16	97 (4)
C2—C6—H6C	109.5	Co—C16—H16	108 (4)
H6A—C6—H6C	109.5	N6B—C18B—C17B	178.93 (4)
H6B—C6—H6C	109.5	C16—C17B—C18B	115.301 (18)
C3—C7—H7A	109.5	C18—C17—C16	109.4 (5)
C3—C7—H7B	109.5	N6—C18—C17	178.8 (4)
H7A—C7—H7B	109.5	C16—C16A—C15A	109.7 (9)
C3—C7—H7C	109.5	C16—C16A—H16	34 (5)
H7A—C7—H7C	109.5	C15A—C16A—H16	125 (5)
H7B—C7—H7C	109.5	N6A—C18A—C16	177.040 (18)
C4—C8—H8A	109.5	C16—C15B—H16	36 (3)
C4—C8—H8B	109.5	C16—C16C—H16	40 (4)

(Mix-II) [(2-cyanoethyl)(3-ethylpyridine)cobaloxime] [(2-cyanopropyl)(3-methylpyridine)cobaloxime]

Crystal data

C18H21CoN6O4	Z = 4
Mr = 444.33	F(000) = 932
Monoclinic, P21/n	Dx = 1.37 Mg m^−3
a = 11.7299 (4) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.2358 (3) Å	µ = 0.83 mm^−1
c = 19.8561 (6) Å	T = 293 K
β = 91.082 (1)°	Plate, yellow
V = 2150.73 (12) Å^3	0.5 × 0.45 × 0.05 mm

Data collection

SMART CCD diffractometer	4876 independent reflections
Radiation source: fine-focus sealed tube	3259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
ω scan	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan SADABS(Sheldrick,1996)	h = −15→15
Tmin = 0.380, Tmax = 1.000	k = −11→10
14428 measured reflections	l = −25→22

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.217	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0832P)^2 + 2.7552P] where P = (Fo^2 + 2Fc^2)/3
4876 reflections	(Δ/σ)max = 0.005
280 parameters	Δρmax = 0.61 e Å^−3
10 restraints	Δρmin = −0.95 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.73067 (5)	0.21853 (7)	0.90971 (3)	0.0435 (2)
O1	0.5185 (3)	0.0866 (5)	0.9397 (2)	0.0673 (11)
O2	0.7732 (4)	0.5144 (4)	0.8758 (2)	0.0732 (12)
H2	0.836 (6)	0.444 (8)	0.879 (3)	0.088*
O3	0.6889 (4)	−0.0754 (4)	0.9429 (2)	0.0677 (11)
H3	0.593 (6)	0.002 (7)	0.941 (3)	0.081*
O4	0.9412 (3)	0.3527 (5)	0.8766 (2)	0.0752 (12)
N1	0.5725 (3)	0.2096 (5)	0.9237 (2)	0.0483 (10)
N2	0.6937 (4)	0.4145 (5)	0.8935 (2)	0.0522 (10)
N3	0.7669 (4)	0.0236 (4)	0.9254 (2)	0.0482 (10)
N4	0.8881 (4)	0.2288 (5)	0.8939 (2)	0.0530 (10)
N5	0.7588 (3)	0.2654 (4)	1.0109 (2)	0.0478 (10)
C1	0.5155 (5)	0.3286 (7)	0.9189 (3)	0.0571 (14)
C2	0.5890 (5)	0.4516 (6)	0.9007 (3)	0.0586 (14)
C3	0.8732 (5)	−0.0133 (6)	0.9188 (3)	0.0529 (12)
C4	0.9455 (5)	0.1096 (6)	0.9006 (3)	0.0583 (14)
C5	0.3903 (5)	0.3406 (10)	0.9272 (4)	0.094 (2)
H5A	0.3622	0.2535	0.9474	0.142*
H5B	0.3540	0.3542	0.8839	0.142*
H5C	0.3739	0.4217	0.9556	0.142*
C6	0.5462 (7)	0.6034 (7)	0.8902 (4)	0.091 (2)
H6A	0.6086	0.6701	0.8951	0.136*
H6B	0.4895	0.6249	0.9229	0.136*
H6C	0.5133	0.6120	0.8457	0.136*
C7	0.9176 (6)	−0.1640 (7)	0.9281 (3)	0.0783 (19)
H7A	0.8548	−0.2300	0.9318	0.117*
H7B	0.9640	−0.1685	0.9684	0.117*
H7C	0.9626	−0.1903	0.8901	0.117*
C8	1.0697 (5)	0.0953 (9)	0.8892 (4)	0.089 (2)
H8A	1.1048	0.1891	0.8916	0.134*
H8B	1.0817	0.0540	0.8455	0.134*
H8C	1.1030	0.0336	0.9231	0.134*
C9	0.7140 (4)	0.1855 (6)	1.0597 (3)	0.0553 (13)
H9	0.6685	0.1073	1.0469	0.066*
C10	0.7301 (5)	0.2103 (7)	1.1280 (3)	0.0654 (16)
C11	0.7996 (6)	0.3266 (8)	1.1450 (3)	0.0738 (18)
H11	0.8139	0.3478	1.1902	0.089*
C12	0.8472 (5)	0.4103 (7)	1.0965 (3)	0.0707 (17)
H12	0.8930	0.4889	1.1082	0.085*
C13	0.8264 (5)	0.3768 (6)	1.0299 (3)	0.0597 (14)
H13	0.8601	0.4328	0.9969	0.072*
C14	0.6769 (7)	0.1072 (10)	1.1792 (3)	0.095 (2)
C15	0.6545 (14)	0.1889 (16)	1.2428 (7)	0.048*	0.339 (12)
C17	0.7066 (5)	0.1610 (7)	0.8109 (3)	0.0609 (15)
H17	0.765 (5)	0.130 (7)	0.803 (3)	0.073*
C16	0.6077 (8)	0.0563 (11)	0.7973 (6)	0.033*	0.358 (11)
C18	0.6964 (7)	0.2764 (9)	0.7585 (4)	0.063 (2)*	0.680 (10)
H18A	0.7516	0.3517	0.7688	0.076*	0.680 (10)
H18B	0.7157	0.2352	0.7152	0.076*	0.680 (10)
C19	0.5841 (7)	0.3416 (11)	0.7529 (5)	0.081 (3)*	0.680 (10)
N6	0.5007 (8)	0.4001 (14)	0.7478 (6)	0.120 (4)*	0.680 (10)
C19B	0.5249 (13)	0.248 (2)	0.7682 (14)	0.101 (9)*	0.320 (10)
C18B	0.5903 (10)	0.1173 (19)	0.7812 (14)	0.101 (9)*	0.320 (10)
H18C	0.6001	0.0639	0.7396	0.121*	0.320 (10)
H18D	0.5505	0.0558	0.8126	0.121*	0.320 (10)
C16B	0.762 (2)	0.272 (2)	0.7649 (12)	0.035*	0.142 (11)
C15B	0.589 (2)	0.161 (3)	1.2291 (13)	0.048*	0.161 (12)
N6B	0.4658 (16)	0.341 (2)	0.7583 (10)	0.076 (5)*	0.320 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0419 (4)	0.0373 (4)	0.0513 (4)	0.0058 (3)	−0.0001 (3)	−0.0015 (3)
O1	0.046 (2)	0.071 (3)	0.084 (3)	−0.009 (2)	0.0024 (19)	0.006 (2)
O2	0.080 (3)	0.041 (2)	0.098 (3)	−0.002 (2)	0.002 (2)	0.009 (2)
O3	0.077 (3)	0.0377 (19)	0.088 (3)	−0.0032 (19)	0.008 (2)	0.0016 (19)
O4	0.051 (2)	0.069 (3)	0.106 (3)	−0.014 (2)	0.015 (2)	0.005 (2)
N1	0.040 (2)	0.054 (3)	0.051 (2)	0.006 (2)	−0.0021 (17)	−0.0024 (19)
N2	0.054 (3)	0.041 (2)	0.061 (3)	0.010 (2)	−0.004 (2)	0.004 (2)
N3	0.047 (2)	0.040 (2)	0.058 (2)	0.0031 (18)	0.0045 (19)	−0.0032 (19)
N4	0.043 (2)	0.051 (2)	0.065 (3)	0.005 (2)	0.0055 (19)	−0.002 (2)
N5	0.042 (2)	0.043 (2)	0.058 (2)	0.0119 (18)	−0.0055 (18)	−0.0075 (19)
C1	0.050 (3)	0.073 (4)	0.048 (3)	0.022 (3)	−0.004 (2)	−0.003 (3)
C2	0.062 (3)	0.058 (3)	0.055 (3)	0.025 (3)	−0.011 (3)	−0.005 (3)
C3	0.051 (3)	0.049 (3)	0.058 (3)	0.016 (2)	−0.005 (2)	−0.006 (2)
C4	0.048 (3)	0.068 (4)	0.059 (3)	0.016 (3)	−0.002 (2)	−0.015 (3)
C5	0.047 (3)	0.143 (7)	0.093 (5)	0.037 (4)	0.004 (3)	−0.009 (5)
C6	0.104 (6)	0.065 (4)	0.102 (5)	0.041 (4)	−0.017 (4)	−0.001 (4)
C7	0.094 (5)	0.062 (4)	0.079 (4)	0.036 (4)	−0.004 (4)	−0.002 (3)
C8	0.041 (3)	0.123 (6)	0.104 (5)	0.022 (4)	0.004 (3)	−0.014 (5)
C9	0.047 (3)	0.062 (3)	0.057 (3)	0.012 (2)	−0.002 (2)	−0.008 (3)
C10	0.060 (3)	0.076 (4)	0.059 (3)	0.024 (3)	−0.002 (3)	−0.007 (3)
C11	0.073 (4)	0.084 (4)	0.064 (4)	0.022 (4)	−0.018 (3)	−0.023 (3)
C12	0.059 (4)	0.069 (4)	0.083 (4)	0.014 (3)	−0.017 (3)	−0.023 (4)
C13	0.049 (3)	0.054 (3)	0.076 (4)	0.006 (2)	−0.010 (3)	−0.011 (3)
C14	0.105 (6)	0.124 (7)	0.058 (4)	0.004 (5)	0.018 (4)	0.004 (4)
C17	0.054 (3)	0.069 (4)	0.059 (3)	0.014 (3)	0.003 (3)	−0.006 (3)

Geometric parameters (Å, º)

Co—N3	1.875 (4)	C7—H7B	0.9600
Co—N4	1.882 (4)	C7—H7C	0.9600
Co—N1	1.883 (4)	C8—H8A	0.9600
Co—N2	1.887 (4)	C8—H8B	0.9600
Co—C17	2.048 (6)	C8—H8C	0.9600
Co—N5	2.076 (4)	C9—C10	1.384 (8)
O1—N1	1.342 (6)	C9—H9	0.9300
O1—H3	1.17 (7)	C10—C11	1.386 (9)
O2—N2	1.363 (6)	C10—C14	1.534 (10)
O2—H2	0.99 (7)	C11—C12	1.364 (9)
O3—N3	1.344 (5)	C11—H11	0.9300
O3—H3	1.34 (7)	C12—C13	1.374 (8)
O4—N4	1.350 (6)	C12—H12	0.9300
N1—C1	1.289 (7)	C13—H13	0.9300
N2—C2	1.285 (7)	C14—C15	1.499 (16)
N3—C3	1.301 (6)	C14—C15B	1.5299 (10)
N4—C4	1.295 (7)	C15—C15B	0.85 (3)
N5—C9	1.334 (7)	C17—C18	1.492 (10)
N5—C13	1.348 (7)	C17—C18B	1.5298 (10)
C1—C2	1.475 (9)	C17—C16B	1.5301 (10)
C1—C5	1.484 (8)	C17—C16	1.5303 (10)
C2—C6	1.502 (8)	C17—H17	0.77 (6)
C3—C4	1.467 (8)	C18—C19	1.4506 (9)
C3—C7	1.496 (8)	C18—H18A	0.9700
C4—C8	1.485 (8)	C18—H18B	0.9700
C5—H5A	0.9600	C19—N6	1.1206 (9)
C5—H5B	0.9600	C19B—N6B	1.1212 (10)
C5—H5C	0.9600	C19B—C18B	1.4513 (10)
C6—H6A	0.9600	C18B—H18C	0.9700
C6—H6B	0.9600	C18B—H18D	0.9700
C6—H6C	0.9600	C16B—H17	1.52 (7)
C7—H7A	0.9600
N3—Co—N4	81.69 (19)	C3—C7—H7C	109.5
N3—Co—N1	98.90 (19)	H7A—C7—H7C	109.5
N4—Co—N1	178.83 (19)	H7B—C7—H7C	109.5
N3—Co—N2	179.7 (2)	C4—C8—H8A	109.5
N4—Co—N2	98.4 (2)	C4—C8—H8B	109.5
N1—Co—N2	80.96 (19)	H8A—C8—H8B	109.5
N3—Co—C17	86.4 (2)	C4—C8—H8C	109.5
N4—Co—C17	88.4 (2)	H8A—C8—H8C	109.5
N1—Co—C17	90.66 (19)	H8B—C8—H8C	109.5
N2—Co—C17	93.3 (2)	N5—C9—C10	124.8 (6)
N3—Co—N5	90.43 (17)	N5—C9—H9	117.6
N4—Co—N5	90.68 (18)	C10—C9—H9	117.6
N1—Co—N5	90.32 (17)	C9—C10—C11	115.9 (6)
N2—Co—N5	89.80 (18)	C9—C10—C14	119.7 (6)
C17—Co—N5	176.8 (2)	C11—C10—C14	124.3 (6)
N1—O1—H3	102 (3)	C12—C11—C10	120.9 (6)
N2—O2—H2	93 (4)	C12—C11—H11	119.6
N3—O3—H3	102 (3)	C10—C11—H11	119.6
C1—N1—O1	119.5 (5)	C11—C12—C13	119.0 (6)
C1—N1—Co	117.6 (4)	C11—C12—H12	120.5
O1—N1—Co	122.9 (3)	C13—C12—H12	120.5
C2—N2—O2	120.5 (5)	N5—C13—C12	122.3 (6)
C2—N2—Co	117.0 (4)	N5—C13—H13	118.8
O2—N2—Co	122.5 (3)	C12—C13—H13	118.8
C3—N3—O3	120.4 (4)	C15—C14—C15B	32.7 (12)
C3—N3—Co	116.7 (4)	C15—C14—C10	109.0 (9)
O3—N3—Co	122.9 (3)	C15B—C14—C10	121.0 (14)
C4—N4—O4	120.3 (5)	C15B—C15—C14	75.6 (12)
C4—N4—Co	116.7 (4)	C18—C17—C18B	82.0 (10)
O4—N4—Co	122.9 (3)	C18—C17—C16B	29.9 (11)
C9—N5—C13	117.1 (5)	C18B—C17—C16B	109.6 (15)
C9—N5—Co	122.0 (4)	C18—C17—C16	106.2 (7)
C13—N5—Co	120.8 (4)	C18B—C17—C16	25.6 (8)
N1—C1—C2	111.6 (5)	C16B—C17—C16	130.6 (12)
N1—C1—C5	124.6 (6)	C18—C17—Co	119.4 (5)
C2—C1—C5	123.7 (6)	C18B—C17—Co	122.9 (11)
N2—C2—C1	112.7 (5)	C16B—C17—Co	110.2 (11)
N2—C2—C6	123.4 (6)	C16—C17—Co	115.0 (5)
C1—C2—C6	123.8 (6)	C18—C17—H17	100 (5)
N3—C3—C4	112.4 (4)	C18B—C17—H17	128 (5)
N3—C3—C7	124.3 (6)	C16B—C17—H17	74 (5)
C4—C3—C7	123.3 (5)	C16—C17—H17	114 (5)
N4—C4—C3	112.4 (5)	Co—C17—H17	101 (5)
N4—C4—C8	124.7 (6)	C19—C18—C17	114.2 (7)
C3—C4—C8	122.8 (5)	C19—C18—H18A	108.7
C1—C5—H5A	109.5	C17—C18—H18A	108.7
C1—C5—H5B	109.5	C19—C18—H18B	108.7
H5A—C5—H5B	109.5	C17—C18—H18B	108.7
C1—C5—H5C	109.5	H18A—C18—H18B	107.6
H5A—C5—H5C	109.5	N6—C19—C18	175.6 (12)
H5B—C5—H5C	109.5	N6B—C19B—C18B	173.7 (13)
C2—C6—H6A	109.5	C19B—C18B—C17	108.2 (11)
C2—C6—H6B	109.5	C19B—C18B—H18C	110.1
H6A—C6—H6B	109.5	C17—C18B—H18C	110.1
C2—C6—H6C	109.5	C19B—C18B—H18D	110.0
H6A—C6—H6C	109.5	C17—C18B—H18D	110.1
H6B—C6—H6C	109.5	H18C—C18B—H18D	108.4
C3—C7—H7A	109.5	C17—C16B—H17	29 (2)
C3—C7—H7B	109.5	C15—C15B—C14	71.7 (12)
H7A—C7—H7B	109.5

(mix-IIprime) [(2-cyanoethyl)(3-ethylpyridine)cobaloxime] [(2-cyanopropyl)(3-methylpyridine)cobaloxime]

Crystal data

C18H18CoN6O4	Z = 4
Mr = 441.31	F(000) = 936
Monoclinic, P21/n	Dx = 1.35 Mg m^−3
a = 11.5090 (4) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.4410 (3) Å	µ = 0.83 mm^−1
c = 20.0330 (7) Å	T = 293 K
β = 95.875 (2)°	Plate, orange
V = 2165.28 (13) Å^3	0.45 × 0.4 × 0.05 mm

Data collection

SMART CCD diffractometer	4998 independent reflections
Radiation source: fine-focus sealed tube	2565 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
ω scan	θmax = 27.6°, θmin = 2.0°
Absorption correction: multi-scan SADABS(Sheldrick,1996)	h = −14→14
Tmin = 0.793, Tmax = 1.000	k = −12→11
15233 measured reflections	l = −16→26

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.210	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
4998 reflections	(Δ/σ)max = 0.011
281 parameters	Δρmax = 0.50 e Å^−3
9 restraints	Δρmin = −0.67 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.22037 (5)	0.23109 (7)	0.41758 (4)	0.0453 (3)
O1	0.0079 (3)	0.0914 (5)	0.4367 (2)	0.0760 (12)
O2	0.2569 (4)	0.5263 (4)	0.3969 (2)	0.0787 (13)
H1	0.326 (6)	0.482 (8)	0.391 (3)	0.094*
O3	0.1817 (4)	−0.0643 (4)	0.4362 (2)	0.0720 (12)
H2	0.098 (6)	0.001 (7)	0.426 (3)	0.086*
O4	0.4317 (3)	0.3697 (5)	0.3944 (2)	0.0753 (12)
N1	0.0602 (3)	0.2155 (5)	0.4274 (2)	0.0537 (11)
N2	0.1800 (4)	0.4225 (5)	0.4088 (2)	0.0538 (11)
N3	0.2598 (4)	0.0382 (5)	0.4252 (2)	0.0538 (11)
N4	0.3810 (3)	0.2452 (5)	0.4044 (2)	0.0545 (11)
N5	0.2595 (3)	0.2573 (4)	0.5186 (2)	0.0453 (10)
N6	0.0125 (6)	0.3624 (8)	0.2634 (3)	0.110 (2)
C1	0.0007 (5)	0.3304 (7)	0.4237 (3)	0.0613 (15)
C2	0.0704 (5)	0.4552 (7)	0.4122 (3)	0.0648 (16)
C3	0.3671 (5)	0.0040 (6)	0.4177 (3)	0.0615 (15)
C4	0.4386 (4)	0.1276 (7)	0.4056 (3)	0.0590 (15)
C5	−0.1298 (5)	0.3355 (10)	0.4271 (4)	0.106 (3)
H5A	−0.1505	0.2724	0.4615	0.160*
H5B	−0.1692	0.3072	0.3846	0.160*
H5C	−0.1526	0.4303	0.4372	0.160*
C6	0.0244 (7)	0.6027 (7)	0.4016 (4)	0.098 (2)
H6A	0.0882	0.6686	0.4058	0.147*
H6B	−0.0280	0.6238	0.4346	0.147*
H6C	−0.0167	0.6103	0.3576	0.147*
C7	0.4115 (6)	−0.1449 (7)	0.4184 (4)	0.089 (2)
H7A	0.3522	−0.2078	0.4315	0.134*
H7B	0.4799	−0.1526	0.4499	0.134*
H7C	0.4307	−0.1701	0.3744	0.134*
C8	0.5641 (5)	0.1186 (9)	0.3928 (4)	0.100 (3)
H8A	0.5966	0.2122	0.3923	0.149*
H8B	0.5698	0.0738	0.3502	0.149*
H8C	0.6064	0.0639	0.4276	0.149*
C9	0.2168 (4)	0.1719 (6)	0.5637 (3)	0.0499 (13)
H9	0.1679	0.0984	0.5477	0.060*
C10	0.2404 (5)	0.1856 (6)	0.6318 (3)	0.0593 (15)
C11	0.3125 (5)	0.2973 (7)	0.6544 (3)	0.0655 (16)
H11	0.3301	0.3120	0.7002	0.079*
C12	0.3575 (5)	0.3857 (6)	0.6096 (4)	0.0619 (15)
H12	0.4063	0.4602	0.6245	0.074*
C13	0.3293 (4)	0.3627 (5)	0.5423 (3)	0.0532 (14)
H13	0.3601	0.4230	0.5119	0.064*
C14	0.1911 (6)	0.0798 (8)	0.6808 (3)	0.090 (2)
C18	0.1773 (6)	0.1981 (8)	0.3172 (3)	0.094 (2)
C19	0.0848 (6)	0.2896 (8)	0.2873 (3)	0.0784 (19)
C15B	0.0901 (11)	0.1262 (16)	0.7190 (8)	0.033*	0.264 (10)
C17B	0.2708 (15)	0.201 (2)	0.2682 (9)	0.080*	0.348 (17)
C15	0.1516 (14)	0.1601 (15)	0.7403 (6)	0.033*	0.273 (10)
C16	0.102 (2)	−0.022 (2)	0.2642 (19)	0.077*	0.163 (12)
C17	0.2027 (15)	0.0830 (15)	0.2670 (8)	0.065*	0.299 (13)
C16A	0.3174 (13)	0.2784 (18)	0.2411 (8)	0.077*	0.353 (12)
C17A	0.2599 (15)	0.1472 (12)	0.2671 (9)	0.070*	0.353 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0355 (3)	0.0409 (4)	0.0596 (5)	0.0083 (3)	0.0059 (3)	−0.0007 (3)
O1	0.043 (2)	0.079 (3)	0.106 (4)	−0.012 (2)	0.008 (2)	−0.006 (2)
O2	0.089 (3)	0.047 (3)	0.099 (4)	0.001 (2)	0.007 (3)	0.012 (2)
O3	0.079 (3)	0.045 (2)	0.094 (4)	−0.003 (2)	0.018 (2)	0.004 (2)
O4	0.057 (2)	0.073 (3)	0.098 (4)	−0.017 (2)	0.019 (2)	0.003 (2)
N1	0.035 (2)	0.063 (3)	0.062 (3)	0.006 (2)	0.0022 (19)	−0.003 (2)
N2	0.057 (3)	0.046 (3)	0.058 (3)	0.009 (2)	0.005 (2)	0.002 (2)
N3	0.053 (3)	0.048 (3)	0.061 (3)	0.006 (2)	0.009 (2)	−0.006 (2)
N4	0.040 (2)	0.064 (3)	0.061 (3)	0.003 (2)	0.0093 (19)	0.001 (2)
N5	0.0349 (18)	0.041 (2)	0.060 (3)	0.0094 (17)	0.0046 (18)	0.000 (2)
N6	0.111 (5)	0.124 (6)	0.085 (5)	0.035 (4)	−0.033 (4)	−0.012 (4)
C1	0.049 (3)	0.079 (4)	0.055 (4)	0.022 (3)	0.002 (3)	−0.005 (3)
C2	0.066 (4)	0.067 (4)	0.059 (4)	0.035 (3)	−0.003 (3)	−0.005 (3)
C3	0.063 (4)	0.057 (4)	0.063 (4)	0.025 (3)	0.003 (3)	−0.007 (3)
C4	0.042 (3)	0.080 (4)	0.056 (4)	0.024 (3)	0.006 (2)	−0.003 (3)
C5	0.044 (3)	0.152 (8)	0.120 (7)	0.036 (4)	−0.004 (4)	−0.021 (5)
C6	0.123 (6)	0.078 (5)	0.090 (6)	0.063 (4)	−0.005 (4)	0.007 (4)
C7	0.104 (5)	0.070 (5)	0.092 (6)	0.051 (4)	0.004 (4)	−0.001 (4)
C8	0.049 (4)	0.147 (8)	0.105 (7)	0.028 (4)	0.022 (4)	0.003 (5)
C9	0.037 (2)	0.050 (3)	0.063 (4)	0.006 (2)	0.009 (2)	−0.008 (3)
C10	0.052 (3)	0.061 (4)	0.066 (5)	0.014 (3)	0.007 (3)	0.002 (3)
C11	0.060 (3)	0.080 (5)	0.054 (4)	0.017 (3)	−0.005 (3)	−0.015 (3)
C12	0.048 (3)	0.056 (4)	0.080 (5)	0.005 (3)	−0.001 (3)	−0.008 (3)
C13	0.046 (3)	0.046 (3)	0.066 (4)	0.008 (2)	0.003 (3)	−0.002 (3)
C14	0.107 (5)	0.093 (5)	0.073 (5)	−0.009 (4)	0.024 (4)	0.014 (4)
C18	0.091 (5)	0.135 (7)	0.053 (4)	0.052 (5)	−0.009 (3)	−0.017 (4)
C19	0.074 (4)	0.097 (5)	0.061 (4)	0.009 (4)	−0.010 (3)	−0.011 (4)

Geometric parameters (Å, º)

Co—N2	1.869 (4)	C5—H5C	0.9600
Co—N1	1.879 (4)	C6—H6A	0.9600
Co—N3	1.880 (4)	C6—H6B	0.9600
Co—N4	1.898 (4)	C6—H6C	0.9600
Co—N5	2.042 (4)	C7—H7A	0.9600
Co—C18	2.045 (6)	C7—H7B	0.9600
O1—N1	1.339 (6)	C7—H7C	0.9600
O1—H2	1.37 (7)	C8—H8A	0.9600
O2—N2	1.358 (6)	C8—H8B	0.9600
O2—H1	0.92 (7)	C8—H8C	0.9600
O3—N3	1.354 (6)	C9—C10	1.368 (7)
O3—H2	1.15 (7)	C9—H9	0.9300
O4—N4	1.337 (5)	C10—C11	1.389 (8)
N1—C1	1.281 (7)	C10—C14	1.549 (9)
N2—C2	1.307 (7)	C11—C12	1.366 (8)
N3—C3	1.300 (6)	C11—H11	0.9300
N4—C4	1.292 (6)	C12—C13	1.371 (8)
N5—C13	1.335 (6)	C12—H12	0.9300
N5—C9	1.342 (7)	C13—H13	0.9300
N6—C19	1.145 (8)	C14—C15B	1.5196 (10)
C1—C2	1.457 (9)	C14—C15	1.5198 (10)
C1—C5	1.511 (8)	C18—C19	1.452 (9)
C2—C6	1.497 (8)	C18—C17	1.5297 (10)
C3—C4	1.462 (8)	C18—C17A	1.5299 (10)
C3—C7	1.496 (8)	C18—C17B	1.5301 (10)
C4—C8	1.495 (7)	C16—C17	1.5201 (10)
C5—H5A	0.9600	C16A—C17A	1.5202 (10)
C5—H5B	0.9600
N2—Co—N1	81.3 (2)	H5B—C5—H5C	109.5
N2—Co—N3	179.2 (2)	C2—C6—H6A	109.5
N1—Co—N3	98.4 (2)	C2—C6—H6B	109.5
N2—Co—N4	98.9 (2)	H6A—C6—H6B	109.5
N1—Co—N4	177.99 (19)	C2—C6—H6C	109.5
N3—Co—N4	81.30 (19)	H6A—C6—H6C	109.5
N2—Co—N5	90.21 (18)	H6B—C6—H6C	109.5
N1—Co—N5	91.42 (17)	C3—C7—H7A	109.5
N3—Co—N5	90.57 (17)	C3—C7—H7B	109.5
N4—Co—N5	90.58 (17)	H7A—C7—H7B	109.5
N2—Co—C18	91.2 (2)	C3—C7—H7C	109.5
N1—Co—C18	87.1 (2)	H7A—C7—H7C	109.5
N3—Co—C18	88.0 (2)	H7B—C7—H7C	109.5
N4—Co—C18	90.9 (2)	C4—C8—H8A	109.5
N5—Co—C18	177.8 (3)	C4—C8—H8B	109.5
N1—O1—H2	100 (3)	H8A—C8—H8B	109.5
N2—O2—H1	106 (5)	C4—C8—H8C	109.5
N3—O3—H2	99 (3)	H8A—C8—H8C	109.5
C1—N1—O1	120.2 (4)	H8B—C8—H8C	109.5
C1—N1—Co	116.9 (4)	N5—C9—C10	124.5 (5)
O1—N1—Co	122.9 (3)	N5—C9—H9	117.8
C2—N2—O2	119.2 (5)	C10—C9—H9	117.8
C2—N2—Co	117.1 (4)	C9—C10—C11	116.6 (5)
O2—N2—Co	123.6 (3)	C9—C10—C14	121.5 (6)
C3—N3—O3	119.8 (5)	C11—C10—C14	121.9 (6)
C3—N3—Co	117.1 (4)	C12—C11—C10	120.2 (6)
O3—N3—Co	123.1 (3)	C12—C11—H11	119.9
C4—N4—O4	121.8 (4)	C10—C11—H11	119.9
C4—N4—Co	116.3 (4)	C11—C12—C13	118.8 (6)
O4—N4—Co	121.9 (3)	C11—C12—H12	120.6
C13—N5—C9	117.2 (5)	C13—C12—H12	120.6
C13—N5—Co	120.4 (4)	N5—C13—C12	122.8 (5)
C9—N5—Co	122.4 (4)	N5—C13—H13	118.6
N1—C1—C2	113.2 (5)	C12—C13—H13	118.6
N1—C1—C5	123.6 (6)	C15B—C14—C15	32.5 (7)
C2—C1—C5	123.2 (6)	C15B—C14—C10	118.9 (8)
N2—C2—C1	111.5 (5)	C15—C14—C10	109.5 (8)
N2—C2—C6	122.8 (6)	C19—C18—C17	109.4 (9)
C1—C2—C6	125.6 (6)	C19—C18—C17A	113.2 (9)
N3—C3—C4	112.3 (5)	C17—C18—C17A	34.0 (7)
N3—C3—C7	124.0 (6)	C19—C18—C17B	105.0 (10)
C4—C3—C7	123.7 (5)	C17—C18—C17B	52.8 (11)
N4—C4—C3	113.1 (4)	C17A—C18—C17B	19.7 (9)
N4—C4—C8	123.3 (6)	C19—C18—Co	114.1 (4)
C3—C4—C8	123.6 (5)	C17—C18—Co	135.4 (9)
C1—C5—H5A	109.5	C17A—C18—Co	126.1 (9)
C1—C5—H5B	109.5	C17B—C18—Co	120.9 (10)
H5A—C5—H5B	109.5	N6—C19—C18	179.5 (9)
C1—C5—H5C	109.5	C16—C17—C18	106.88 (10)
H5A—C5—H5C	109.5	C16A—C17A—C18	106.86 (10)