Modified photoreactivity due to mixed crystal formation. I. Three mixed crystals between isostructural cobaloxime complexes

Three crystals of 2-cyanoethyl cobaloxime complexes with 3-chloropyridine, 3-bromopyridine and 3-methylpyridine as axial base ligands are isostructural to one another. Three mixed crystals were formed between the pairs: (3-bromo­pyridine)(2-cyano­ethyl)cobaloxime-(2-cyan­oethyl)(3-methyl­pyridine)cobaloxime(0.45/0.55);(3-chloro­pyridine)(2-cyano­ethyl)cobaloxime-(2-cyano­ethyl)(3bromo­pyridine)­cobalox­ime (0.61/0.39); (3-chloro­pyridine)(2-cyano­ethyl)cobaloxime-(2-cyano­ethyl)(3-methyl­pyridine)cobaloxime (0.44/0.56). The X-ray crystal structure analysis revealed that the mixed compounds are also isostructural to the component crystals. It was found from the change in IR spectra that the 2-cyanoethyl groups in the three mixed crystals isomerized to 1-cyanoethyl groups on exposure to a xenon lamp, as observed for the 2-cyanoethyl groups in the component crystals. Rate constants for the three mixed and three component crystals, measured under the same conditions, are approximately the same, as the reaction cavities for the 2-cyanoethyl groups in the six crystals have almost the same size. For the mixed crystal between 3-chloropyridine and 3-methylpyridine complexes, the isomerization proceeded with retention of the single-crystal form. The conformation and configuration of the 1-cyanoethyl group that was produced were well explained by the shape of the reaction cavity before irradiation.

Computing details

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

(Mix-I) [(3-chloropyridine) (2-cyanoethyl) cobaloxime] [(2-cyanoethyl)(3-bromopyridine) cobaloxime]

Crystal data

C16H22Br0.39Cl0.61CoN6O4	F(000) = 1136
Mr = 474.55	Dx = 1.59 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 23.818 (3) Å	Cell parameters from 20 reflections
b = 9.4510 (3) Å	θ = 12.5–15°
c = 8.8553 (18) Å	µ = 1.77 mm^−1
β = 94.842 (13)°	T = 293 K
V = 1986.3 (5) Å^3	Prismatic, orange
Z = 4	0.5 × 0.4 × 0.2 mm

Data collection

AFC7R-RIGAKU diffractometer	3812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ω–2θ scan	h = −30→30
Absorption correction: psi-scan (North, Phillips & Mathews, 1968)	k = 0→12
Tmin = 0.502, Tmax = 0.702	l = −11→0
4852 measured reflections	3 standard reflections every 150 reflections
4563 independent reflections	intensity decay: −0.7%

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0956P)^2 + 0.7262P] where P = (Fo^2 + 2Fc^2)/3
4563 reflections	(Δ/σ)max = 0.002
279 parameters	Δρmax = 1.62 e Å^−3
2 restraints	Δρmin = −0.94 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	0.140920 (14)	0.16243 (3)	0.79376 (4)	0.03166 (14)
O3	0.12826 (9)	−0.1154 (2)	0.6743 (2)	0.0445 (5)
O4	0.17078 (9)	0.0615 (2)	0.5052 (2)	0.0465 (5)
H4	0.1567	−0.0184	0.5684	0.056*
O1	0.11449 (10)	0.2648 (2)	1.0809 (2)	0.0528 (5)
H1	0.1338	0.3602	1.0048	0.063*
O2	0.15775 (10)	0.4391 (2)	0.9193 (2)	0.0499 (5)
N3	0.11977 (10)	−0.0300 (2)	0.7907 (3)	0.0371 (5)
N4	0.16920 (9)	0.1744 (2)	0.6013 (3)	0.0364 (5)
N1	0.11313 (10)	0.1532 (2)	0.9864 (3)	0.0388 (5)
N2	0.16274 (10)	0.3541 (2)	0.7973 (3)	0.0375 (5)
N5	0.31878 (17)	0.2679 (5)	0.6945 (5)	0.0908 (12)
N6	0.06264 (9)	0.2239 (2)	0.6968 (2)	0.0358 (5)
C4	0.18376 (11)	0.2973 (3)	0.5564 (3)	0.0381 (5)
C2	0.18076 (11)	0.4049 (3)	0.6748 (3)	0.0398 (6)
C8	0.20339 (15)	0.3298 (4)	0.4050 (4)	0.0531 (8)
H3A	0.1956	0.2507	0.3384	0.080*
H3B	0.2432	0.3477	0.4153	0.080*
H3C	0.1840	0.4119	0.3635	0.080*
C6	0.19903 (17)	0.5550 (4)	0.6584 (5)	0.0603 (9)
H4A	0.1923	0.6069	0.7483	0.090*
H4B	0.1781	0.5970	0.5725	0.090*
H4C	0.2385	0.5575	0.6439	0.090*
C3	0.09712 (11)	−0.0766 (3)	0.9100 (3)	0.0405 (6)
C1	0.09317 (13)	0.0325 (3)	1.0254 (3)	0.0432 (6)
C7	0.07835 (15)	−0.2268 (4)	0.9271 (4)	0.0556 (8)
H7A	0.0912	−0.2831	0.8466	0.083*
H7B	0.0380	−0.2301	0.9226	0.083*
H7C	0.0938	−0.2633	1.0228	0.083*
C5	0.06915 (17)	0.0083 (4)	1.1747 (4)	0.0600 (9)
H8A	0.0715	0.0942	1.2327	0.090*
H8B	0.0902	−0.0647	1.2295	0.090*
H8C	0.0305	−0.0202	1.1573	0.090*
C12	0.03379 (12)	0.3305 (3)	0.7556 (3)	0.0420 (6)
H12	0.0510	0.3735	0.8438	0.050*
C13	−0.01723 (12)	0.3764 (2)	0.6868 (4)	0.0471 (7)
C14	−0.04024 (14)	0.3125 (4)	0.5569 (4)	0.0557 (8)
H14	−0.0758	0.3289	0.5169	0.067*
C15	−0.01043 (14)	0.2048 (4)	0.4974 (4)	0.0543 (8)
H15	−0.0248	0.1600	0.4120	0.065*
C16	0.04056 (13)	0.1641 (3)	0.5682 (3)	0.0440 (6)
H16	0.0630	0.0852	0.5249	0.053*
C11	0.29437 (14)	0.2375 (4)	0.7910 (5)	0.0629 (9)
C9	0.21603 (12)	0.0934 (3)	0.8852 (4)	0.0441 (6)
H9A	0.2100 (15)	0.044 (4)	0.981 (4)	0.053*
H9B	0.2289 (15)	0.032 (4)	0.816 (4)	0.053*
C10	0.26403 (14)	0.1982 (4)	0.9223 (4)	0.0538 (7)
H10A	0.2893 (17)	0.148 (4)	1.000 (5)	0.065*
H10B	0.2474 (16)	0.282 (5)	0.970 (5)	0.065*
Br	−0.05315 (15)	0.5260 (3)	0.7753 (5)	0.0540 (6)	0.390 (4)
Cl	−0.0526 (3)	0.5176 (6)	0.7618 (10)	0.080 (2)	0.610 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0369 (2)	0.0257 (2)	0.0332 (2)	0.00002 (12)	0.00776 (14)	−0.00330 (12)
O3	0.0577 (12)	0.0282 (9)	0.0488 (11)	−0.0013 (8)	0.0107 (9)	−0.0105 (8)
O4	0.0599 (12)	0.0376 (11)	0.0443 (11)	0.0009 (9)	0.0178 (9)	−0.0117 (8)
O1	0.0781 (15)	0.0433 (12)	0.0390 (10)	0.0026 (11)	0.0160 (10)	−0.0116 (9)
O2	0.0695 (14)	0.0330 (10)	0.0484 (11)	−0.0053 (9)	0.0113 (10)	−0.0141 (9)
N3	0.0397 (11)	0.0298 (11)	0.0423 (11)	0.0012 (8)	0.0067 (9)	−0.0046 (9)
N4	0.0371 (11)	0.0324 (11)	0.0406 (12)	0.0018 (8)	0.0089 (9)	−0.0063 (9)
N1	0.0453 (12)	0.0372 (12)	0.0346 (11)	0.0023 (9)	0.0077 (9)	−0.0052 (9)
N2	0.0415 (12)	0.0297 (11)	0.0420 (12)	−0.0006 (9)	0.0084 (9)	−0.0053 (9)
N5	0.073 (2)	0.107 (3)	0.093 (3)	−0.015 (2)	0.012 (2)	0.019 (3)
N6	0.0364 (10)	0.0352 (11)	0.0368 (11)	0.0003 (9)	0.0089 (8)	−0.0028 (9)
C4	0.0375 (12)	0.0364 (13)	0.0411 (13)	0.0032 (10)	0.0081 (10)	0.0013 (11)
C2	0.0391 (13)	0.0324 (13)	0.0487 (15)	0.0009 (10)	0.0086 (11)	−0.0012 (11)
C8	0.0608 (19)	0.0504 (18)	0.0503 (17)	0.0022 (14)	0.0176 (14)	0.0078 (14)
C6	0.071 (2)	0.0347 (15)	0.077 (2)	−0.0060 (14)	0.0178 (18)	0.0043 (15)
C3	0.0410 (13)	0.0343 (13)	0.0464 (14)	−0.0021 (11)	0.0056 (11)	0.0046 (11)
C1	0.0475 (14)	0.0429 (15)	0.0405 (14)	0.0023 (12)	0.0124 (11)	0.0039 (12)
C7	0.0635 (19)	0.0389 (16)	0.065 (2)	−0.0090 (14)	0.0089 (15)	0.0064 (14)
C5	0.070 (2)	0.065 (2)	0.0486 (17)	0.0024 (17)	0.0252 (15)	0.0088 (16)
C12	0.0433 (14)	0.0365 (14)	0.0470 (15)	0.0023 (11)	0.0089 (11)	−0.0069 (11)
C13	0.0456 (15)	0.0370 (14)	0.0603 (18)	0.0068 (12)	0.0141 (13)	0.0039 (13)
C14	0.0435 (15)	0.059 (2)	0.063 (2)	0.0045 (14)	−0.0029 (14)	0.0074 (16)
C15	0.0523 (17)	0.0584 (19)	0.0509 (17)	0.0025 (15)	−0.0027 (13)	−0.0084 (15)
C16	0.0458 (15)	0.0428 (15)	0.0438 (15)	0.0002 (11)	0.0061 (11)	−0.0071 (12)
C11	0.0452 (16)	0.064 (2)	0.078 (2)	−0.0039 (15)	−0.0031 (16)	0.0159 (18)
C9	0.0414 (14)	0.0412 (15)	0.0495 (16)	0.0030 (11)	0.0023 (12)	0.0035 (13)
C10	0.0497 (16)	0.0512 (18)	0.0593 (19)	0.0006 (14)	−0.0032 (14)	0.0032 (15)
Br	0.0493 (12)	0.0447 (12)	0.0696 (10)	0.0125 (8)	0.0142 (8)	−0.0049 (8)
Cl	0.076 (3)	0.055 (2)	0.112 (4)	0.0229 (18)	0.027 (3)	−0.018 (2)

Geometric parameters (Å, º)

Co—N1	1.883 (2)	C6—H4B	0.9600
Co—N2	1.884 (2)	C6—H4C	0.9600
Co—N3	1.887 (2)	C3—C1	1.460 (4)
Co—N4	1.888 (2)	C3—C7	1.500 (4)
Co—C9	2.009 (3)	C1—C5	1.502 (4)
Co—N6	2.069 (2)	C7—H7A	0.9600
O3—N3	1.338 (3)	C7—H7B	0.9600
O4—N4	1.367 (3)	C7—H7C	0.9600
O4—H4	1.014 (2)	C5—H8A	0.9600
O1—N1	1.345 (3)	C5—H8B	0.9600
O1—H1	1.237 (2)	C5—H8C	0.9600
O2—N2	1.360 (3)	C12—C13	1.382 (4)
O2—H1	1.236 (2)	C12—H12	0.943 (3)
N3—C3	1.302 (4)	C13—C14	1.372 (5)
N4—C4	1.285 (4)	C13—Cl	1.7399 (10)
N1—C1	1.294 (4)	C13—Br	1.8597 (10)
N2—C2	1.292 (4)	C14—C15	1.372 (5)
N5—C11	1.111 (6)	C14—H14	0.903 (3)
N6—C16	1.339 (4)	C15—C16	1.374 (4)
N6—C12	1.349 (3)	C15—H15	0.908 (3)
C4—C2	1.467 (4)	C16—H16	1.011 (3)
C4—C8	1.489 (4)	C11—C10	1.468 (6)
C2—C6	1.494 (4)	C9—C10	1.527 (5)
C8—H3A	0.9600	C9—H9A	0.99 (4)
C8—H3B	0.9600	C9—H9B	0.91 (4)
C8—H3C	0.9600	C10—H10A	0.99 (4)
C6—H4A	0.9600	C10—H10B	1.00 (4)
N1—Co—N2	98.45 (10)	H4B—C6—H4C	109.5
N1—Co—N3	81.63 (10)	N3—C3—C1	112.6 (2)
N2—Co—N3	179.47 (10)	N3—C3—C7	123.3 (3)
N1—Co—N4	179.15 (10)	C1—C3—C7	124.1 (3)
N2—Co—N4	80.71 (10)	N1—C1—C3	112.9 (2)
N3—Co—N4	99.21 (10)	N1—C1—C5	123.0 (3)
N1—Co—C9	89.36 (12)	C3—C1—C5	124.1 (3)
N2—Co—C9	94.03 (12)	C3—C7—H7A	109.5
N3—Co—C9	85.44 (12)	C3—C7—H7B	109.5
N4—Co—C9	90.57 (12)	H7A—C7—H7B	109.5
N1—Co—N6	90.90 (10)	C3—C7—H7C	109.5
N2—Co—N6	88.56 (10)	H7A—C7—H7C	109.5
N3—Co—N6	91.97 (10)	H7B—C7—H7C	109.5
N4—Co—N6	89.21 (9)	C1—C5—H8A	109.5
C9—Co—N6	177.34 (11)	C1—C5—H8B	109.5
N4—O4—H4	102.10 (18)	H8A—C5—H8B	109.5
N1—O1—H1	102.87 (18)	C1—C5—H8C	109.5
N2—O2—H1	101.86 (17)	H8A—C5—H8C	109.5
C3—N3—O3	121.4 (2)	H8B—C5—H8C	109.5
C3—N3—Co	116.27 (19)	N6—C12—C13	121.5 (3)
O3—N3—Co	122.32 (18)	N6—C12—H12	116.2 (3)
C4—N4—O4	119.4 (2)	C13—C12—H12	122.3 (3)
C4—N4—Co	117.36 (18)	C14—C13—C12	120.4 (2)
O4—N4—Co	123.10 (17)	C14—C13—Cl	119.0 (4)
C1—N1—O1	121.0 (2)	C12—C13—Cl	120.6 (4)
C1—N1—Co	116.59 (19)	C14—C13—Br	121.5 (3)
O1—N1—Co	122.40 (18)	C12—C13—Br	118.1 (2)
C2—N2—O2	120.3 (2)	Cl—C13—Br	2.6 (4)
C2—N2—Co	117.03 (19)	C15—C14—C13	117.7 (3)
O2—N2—Co	122.62 (18)	C15—C14—H14	118.4 (4)
C16—N6—C12	117.9 (2)	C13—C14—H14	123.2 (4)
C16—N6—Co	120.69 (19)	C14—C15—C16	119.9 (3)
C12—N6—Co	121.34 (19)	C14—C15—H15	119.7 (3)
N4—C4—C2	112.0 (2)	C16—C15—H15	120.4 (3)
N4—C4—C8	125.4 (3)	N6—C16—C15	122.6 (3)
C2—C4—C8	122.6 (3)	N6—C16—H16	116.8 (3)
N2—C2—C4	112.4 (2)	C15—C16—H16	120.6 (3)
N2—C2—C6	123.7 (3)	N5—C11—C10	177.9 (4)
C4—C2—C6	123.8 (3)	C10—C9—Co	120.1 (2)
C4—C8—H3A	109.5	C10—C9—H9A	106 (2)
C4—C8—H3B	109.5	Co—C9—H9A	108 (2)
H3A—C8—H3B	109.5	C10—C9—H9B	106 (2)
C4—C8—H3C	109.5	Co—C9—H9B	106 (2)
H3A—C8—H3C	109.5	H9A—C9—H9B	111 (3)
H3B—C8—H3C	109.5	C11—C10—C9	113.8 (3)
C2—C6—H4A	109.5	C11—C10—H10A	111 (2)
C2—C6—H4B	109.5	C9—C10—H10A	104 (2)
H4A—C6—H4B	109.5	C11—C10—H10B	112 (2)
C2—C6—H4C	109.5	C9—C10—H10B	107 (2)
H4A—C6—H4C	109.5	H10A—C10—H10B	109 (3)

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

Crystal data

C16.565H23.695Cl0.435CoN6O4	F(000) = 996
Mr = 445.34	Dx = 1.492 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 23.751 (4) Å	Cell parameters from 20 reflections
b = 9.4680 (12) Å	θ = 12.5–15°
c = 8.8453 (14) Å	µ = 0.96 mm^−1
β = 94.672 (13)°	T = 293 K
V = 1982.5 (5) Å^3	Prismatic, orange
Z = 4	0.5 × 0.4 × 0.2 mm

Data collection

AFC7R-RIGAKU diffractometer	3860 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ω–2 θ scan	h = 0→30
Absorption correction: ψ scan (North, Phillips & Mathews, 1968)	k = 0→12
Tmin = 0.673, Tmax = 0.812	l = −11→11
4656 measured reflections	3 standard reflections every 150 reflections
4547 independent reflections	intensity decay: 0.2%

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.6457P] where P = (Fo^2 + 2Fc^2)/3
4547 reflections	(Δ/σ)max = 0.002
280 parameters	Δρmax = 0.41 e Å^−3
2 restraints	Δρmin = −0.36 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	0.359724 (9)	0.16511 (2)	0.20391 (2)	0.02960 (8)
O1	0.38766 (7)	0.26646 (15)	−0.08388 (16)	0.0519 (4)
H1	0.3676	0.3574	−0.0312	0.062*
O2	0.34360 (6)	0.44082 (14)	0.07775 (16)	0.0480 (3)
O3	0.37133 (6)	−0.11253 (13)	0.32352 (15)	0.0428 (3)
O4	0.32852 (6)	0.06483 (14)	0.49202 (15)	0.0442 (3)
H4	0.3468	−0.0141	0.4236	0.053*
N1	0.38787 (7)	0.15496 (16)	0.01214 (17)	0.0375 (3)
N2	0.33826 (6)	0.35694 (15)	0.19918 (17)	0.0353 (3)
N3	0.38041 (6)	−0.02761 (15)	0.20720 (17)	0.0343 (3)
N4	0.33074 (6)	0.17692 (15)	0.39556 (17)	0.0336 (3)
N5	0.18063 (10)	0.2667 (3)	0.3058 (3)	0.0909 (8)
N6	0.43801 (6)	0.22546 (15)	0.30245 (16)	0.0333 (3)
C1	0.40806 (8)	0.0344 (2)	−0.0272 (2)	0.0402 (4)
C3	0.40372 (7)	−0.07450 (19)	0.0885 (2)	0.0380 (4)
C2	0.31948 (7)	0.40795 (19)	0.3220 (2)	0.0379 (4)
C4	0.31592 (7)	0.3007 (2)	0.4403 (2)	0.0367 (4)
C5	0.43176 (10)	0.0093 (3)	−0.1763 (2)	0.0584 (6)
H5A	0.4347	0.0976	−0.2284	0.088*
H5B	0.4072	−0.0530	−0.2366	0.088*
H5C	0.4685	−0.0327	−0.1596	0.088*
C7	0.42236 (9)	−0.2236 (2)	0.0710 (3)	0.0528 (5)
H6A	0.4086	−0.2804	0.1500	0.079*
H6B	0.4629	−0.2274	0.0776	0.079*
H6C	0.4076	−0.2590	−0.0260	0.079*
C6	0.30094 (10)	0.5570 (2)	0.3376 (3)	0.0566 (5)
H7A	0.3223	0.6169	0.2759	0.085*
H7B	0.3071	0.5856	0.4418	0.085*
H7C	0.2615	0.5647	0.3052	0.085*
C8	0.29628 (10)	0.3329 (2)	0.5919 (2)	0.0502 (5)
H8A	0.3074	0.2579	0.6611	0.075*
H8B	0.2559	0.3416	0.5836	0.075*
H8C	0.3129	0.4199	0.6290	0.075*
C9	0.28420 (8)	0.0972 (2)	0.1113 (2)	0.0429 (4)
H9A	0.2937 (11)	0.053 (3)	0.017 (3)	0.064*
H9B	0.2706 (11)	0.025 (3)	0.181 (3)	0.064*
C10	0.23643 (9)	0.2018 (3)	0.0753 (3)	0.0515 (5)
H10A	0.2045 (12)	0.160 (3)	−0.014 (3)	0.077*
H10B	0.2501 (12)	0.292 (3)	0.029 (3)	0.077*
C11	0.20589 (9)	0.2396 (3)	0.2073 (3)	0.0599 (6)
C16	0.45967 (8)	0.1646 (2)	0.4311 (2)	0.0408 (4)
H16	0.4359	0.0914	0.4665	0.061*
C15	0.51075 (9)	0.2035 (3)	0.5030 (3)	0.0515 (5)
H15	0.5285	0.1586	0.6038	0.077*
C14	0.54118 (9)	0.3110 (3)	0.4433 (3)	0.0536 (5)
H14	0.5797	0.3412	0.5084	0.080*
C12	0.46755 (8)	0.33079 (19)	0.2447 (2)	0.0403 (4)
H12	0.4519	0.3752	0.1546	0.060*
C13	0.51882 (8)	0.3771 (2)	0.3118 (2)	0.0460 (4)
Cl	0.5507 (2)	0.5164 (5)	0.2277 (6)	0.0666 (8)	0.435 (5)
C17	0.5532 (8)	0.4973 (15)	0.250 (2)	0.078 (4)	0.565 (5)
H17A	0.5911	0.4654	0.2394	0.117*	0.565 (5)
H17B	0.5541	0.5758	0.3186	0.117*	0.565 (5)
H17C	0.5362	0.5260	0.1525	0.117*	0.565 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02966 (13)	0.02710 (13)	0.03220 (13)	−0.00025 (8)	0.00350 (9)	0.00277 (8)
O1	0.0732 (10)	0.0447 (8)	0.0389 (7)	−0.0027 (7)	0.0116 (7)	0.0121 (6)
O2	0.0623 (9)	0.0351 (7)	0.0469 (7)	0.0043 (6)	0.0060 (6)	0.0138 (6)
O3	0.0504 (7)	0.0316 (6)	0.0469 (7)	0.0016 (5)	0.0072 (6)	0.0103 (5)
O4	0.0509 (7)	0.0387 (7)	0.0447 (7)	−0.0007 (6)	0.0144 (6)	0.0118 (6)
N1	0.0410 (8)	0.0377 (8)	0.0338 (7)	−0.0034 (6)	0.0037 (6)	0.0040 (6)
N2	0.0352 (7)	0.0295 (7)	0.0409 (8)	0.0002 (6)	0.0013 (6)	0.0054 (6)
N3	0.0319 (7)	0.0306 (7)	0.0403 (8)	−0.0012 (6)	0.0030 (6)	0.0035 (6)
N4	0.0308 (7)	0.0327 (7)	0.0376 (7)	−0.0021 (5)	0.0058 (6)	0.0053 (6)
N5	0.0574 (13)	0.120 (2)	0.0954 (19)	0.0170 (15)	0.0082 (13)	−0.0242 (17)
N6	0.0301 (6)	0.0333 (7)	0.0368 (7)	−0.0005 (6)	0.0044 (5)	0.0019 (6)
C1	0.0370 (8)	0.0450 (10)	0.0389 (9)	−0.0034 (8)	0.0057 (7)	−0.0034 (8)
C3	0.0342 (8)	0.0353 (9)	0.0445 (9)	0.0009 (7)	0.0024 (7)	−0.0044 (7)
C2	0.0353 (8)	0.0317 (8)	0.0465 (10)	0.0002 (7)	0.0027 (7)	−0.0003 (7)
C4	0.0306 (8)	0.0379 (8)	0.0421 (9)	−0.0033 (7)	0.0055 (7)	−0.0023 (7)
C5	0.0643 (14)	0.0669 (14)	0.0466 (11)	−0.0025 (11)	0.0199 (10)	−0.0095 (10)
C7	0.0544 (12)	0.0409 (10)	0.0634 (13)	0.0085 (9)	0.0060 (10)	−0.0085 (9)
C6	0.0641 (13)	0.0361 (10)	0.0707 (14)	0.0088 (10)	0.0121 (11)	−0.0039 (10)
C8	0.0542 (12)	0.0496 (12)	0.0481 (11)	−0.0031 (9)	0.0128 (9)	−0.0074 (9)
C9	0.0338 (9)	0.0436 (10)	0.0505 (11)	−0.0034 (8)	−0.0016 (8)	−0.0052 (9)
C10	0.0411 (10)	0.0532 (12)	0.0582 (13)	0.0002 (9)	−0.0085 (9)	−0.0019 (10)
C11	0.0370 (10)	0.0646 (14)	0.0762 (16)	0.0046 (10)	−0.0057 (10)	−0.0135 (12)
C16	0.0374 (9)	0.0425 (10)	0.0424 (10)	−0.0021 (7)	0.0018 (7)	0.0065 (8)
C15	0.0433 (11)	0.0607 (12)	0.0488 (11)	−0.0011 (9)	−0.0066 (9)	0.0040 (10)
C14	0.0366 (10)	0.0585 (13)	0.0643 (14)	−0.0058 (9)	−0.0043 (9)	−0.0086 (10)
C12	0.0371 (9)	0.0386 (9)	0.0457 (10)	−0.0041 (7)	0.0064 (7)	0.0043 (7)
C13	0.0375 (9)	0.0403 (10)	0.0614 (12)	−0.0068 (8)	0.0106 (8)	−0.0040 (9)
Cl	0.0513 (13)	0.0595 (13)	0.0904 (17)	−0.0223 (11)	0.0141 (12)	0.0078 (13)
C17	0.062 (6)	0.067 (6)	0.105 (9)	−0.015 (4)	0.011 (5)	0.020 (5)

Geometric parameters (Å, º)

Co—N1	1.8758 (15)	C5—H5C	0.9600
Co—N4	1.8842 (15)	C7—H6A	0.9600
Co—N2	1.8860 (15)	C7—H6B	0.9600
Co—N3	1.8893 (15)	C7—H6C	0.9600
Co—C9	2.0155 (18)	C6—H7A	0.9600
Co—N6	2.0688 (14)	C6—H7B	0.9600
O1—N1	1.3547 (19)	C6—H7C	0.9600
O1—H1	1.1053 (15)	C8—H8A	0.9600
O2—N2	1.3501 (19)	C8—H8B	0.9600
O2—H1	1.4025 (15)	C8—H8C	0.9600
O3—N3	1.3371 (19)	C9—C10	1.520 (3)
O3—H4	1.4407 (14)	C9—H9A	0.98 (3)
O4—N4	1.3654 (18)	C9—H9B	0.99 (3)
O4—H4	1.0752 (14)	C10—C11	1.469 (3)
N1—C1	1.297 (2)	C10—H10A	1.12 (3)
N2—C2	1.300 (2)	C10—H10B	1.01 (3)
N3—C3	1.304 (2)	C16—C15	1.373 (3)
N4—C4	1.295 (2)	C16—H16	0.9627 (18)
N5—C11	1.126 (4)	C15—C14	1.378 (3)
N6—C16	1.340 (2)	C15—H15	1.045 (2)
N6—C12	1.344 (2)	C14—C13	1.388 (3)
C1—C3	1.463 (3)	C14—H14	1.078 (2)
C1—C5	1.494 (3)	C12—C13	1.382 (3)
C3—C7	1.492 (3)	C12—H12	0.9499 (19)
C2—C4	1.465 (3)	C13—C17	1.528 (7)
C2—C6	1.488 (3)	C13—Cl	1.7200 (10)
C4—C8	1.488 (3)	C17—H17A	0.9600
C5—H5A	0.9600	C17—H17B	0.9600
C5—H5B	0.9600	C17—H17C	0.9600
N1—Co—N4	179.27 (6)	H6A—C7—H6B	109.5
N1—Co—N2	98.33 (7)	C3—C7—H6C	109.5
N4—Co—N2	81.07 (6)	H6A—C7—H6C	109.5
N1—Co—N3	81.55 (6)	H6B—C7—H6C	109.5
N4—Co—N3	99.04 (6)	C2—C6—H7A	109.5
N2—Co—N3	179.30 (6)	C2—C6—H7B	109.5
N1—Co—C9	89.27 (8)	H7A—C6—H7B	109.5
N4—Co—C9	90.35 (8)	C2—C6—H7C	109.5
N2—Co—C9	93.91 (8)	H7A—C6—H7C	109.5
N3—Co—C9	85.41 (7)	H7B—C6—H7C	109.5
N1—Co—N6	91.19 (6)	C4—C8—H8A	109.5
N4—Co—N6	89.21 (6)	C4—C8—H8B	109.5
N2—Co—N6	88.59 (6)	H8A—C8—H8B	109.5
N3—Co—N6	92.10 (6)	C4—C8—H8C	109.5
C9—Co—N6	177.37 (7)	H8A—C8—H8C	109.5
N1—O1—H1	108.82 (12)	H8B—C8—H8C	109.5
N2—O2—H1	106.57 (11)	C10—C9—Co	120.11 (15)
N3—O3—H4	100.52 (10)	C10—C9—H9A	108.8 (15)
N4—O4—H4	98.66 (11)	Co—C9—H9A	103.0 (15)
C1—N1—O1	120.01 (16)	C10—C9—H9B	107.7 (15)
C1—N1—Co	117.06 (13)	Co—C9—H9B	106.9 (15)
O1—N1—Co	122.93 (12)	H9A—C9—H9B	110 (2)
C2—N2—O2	120.46 (15)	C11—C10—C9	113.6 (2)
C2—N2—Co	116.72 (12)	C11—C10—H10A	107.1 (15)
O2—N2—Co	122.78 (12)	C9—C10—H10A	111.6 (14)
C3—N3—O3	121.36 (15)	C11—C10—H10B	108.2 (17)
C3—N3—Co	116.32 (12)	C9—C10—H10B	112.2 (17)
O3—N3—Co	122.31 (11)	H10A—C10—H9B	103 (2)
C4—N4—O4	119.17 (15)	N5—C11—C10	177.4 (3)
C4—N4—Co	117.18 (12)	N6—C16—C15	122.79 (18)
O4—N4—Co	123.48 (11)	N6—C16—H16	113.03 (17)
C16—N6—C12	117.73 (15)	C15—C16—H16	124.2 (2)
C16—N6—Co	120.58 (12)	C16—C15—C14	119.4 (2)
C12—N6—Co	121.61 (12)	C16—C15—H15	124.5 (2)
N1—C1—C3	112.57 (16)	C14—C15—H15	116.05 (19)
N1—C1—C5	123.44 (18)	C15—C14—C13	118.51 (18)
C3—C1—C5	123.97 (18)	C15—C14—H14	116.0 (2)
N3—C3—C1	112.48 (16)	C13—C14—H14	125.3 (2)
N3—C3—C7	123.72 (18)	N6—C12—C13	122.79 (18)
C1—C3—C7	123.78 (17)	N6—C12—H12	117.81 (18)
N2—C2—C4	112.50 (15)	C13—C12—H12	119.39 (18)
N2—C2—C6	123.65 (18)	C12—C13—C14	118.70 (17)
C4—C2—C6	123.78 (18)	C12—C13—C17	124.1 (8)
N4—C4—C2	112.11 (16)	C14—C13—C17	117.2 (8)
N4—C4—C8	125.02 (17)	C12—C13—Cl	117.5 (2)
C2—C4—C8	122.87 (17)	C14—C13—Cl	123.8 (3)
C1—C5—H5A	109.5	C17—C13—Cl	6.7 (10)
C1—C5—H5B	109.5	C13—C17—H17A	109.5
H5A—C5—H5B	109.5	C13—C17—H17B	109.5
C1—C5—H5C	109.5	H17A—C17—H17B	109.5
H5A—C5—H5C	109.5	C13—C17—H17C	109.5
H5B—C5—H5C	109.5	H17A—C17—H17C	109.5
C3—C7—H6A	109.5	H17B—C17—H17C	109.5
C3—C7—H6B	109.5

(Mix-IIprime) [(3-chloropyridine) (2-cyanoethyl) cobaloxime] [(2-cyanoethyl)(3-methylpyridine) cobaloxime]

Crystal data

C16.518H19.572Cl0.476CoN6O4	Z = 4
Mr = 442.12	F(000) = 968
Monoclinic, P21/a	Dx = 1.472 Mg m^−3
a = 23.7797 (11) Å	Mo Kα radiation, λ = 0.71069 Å
b = 9.5032 (5) Å	µ = 0.96 mm^−1
c = 8.8569 (4) Å	T = 293 K
β = 94.479 (1)°	Prismatic, brown
V = 1995.40 (17) Å^3	0.5 × 0.4 × 0.2 mm

Data collection

SMART CCD diffractometer	4580 independent reflections
Radiation source: fine-focus sealed tube	3677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan SADABS( (Sheldrick, 1996)	h = −30→30
Tmin = 0.635, Tmax = 0.825	k = −12→9
13847 measured reflections	l = −11→11

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0684P)^2 + 2.1437P] where P = (Fo^2 + 2Fc^2)/3
4580 reflections	(Δ/σ)max = 0.050
295 parameters	Δρmax = 0.70 e Å^−3
12 restraints	Δρmin = −0.41 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	0.639575 (7)	0.167188 (19)	0.793731 (19)	0.03431 (4)
O4	0.67131 (4)	0.06659 (11)	0.50619 (11)	0.0483 (3)
H4	0.6549	−0.0189	0.5774	0.058*
O3	0.62914 (4)	−0.10958 (11)	0.67499 (12)	0.0467 (3)
O2	0.65418 (5)	0.44213 (11)	0.91846 (13)	0.0565 (3)
O1	0.61077 (5)	0.26776 (12)	1.08057 (12)	0.0585 (3)
H1	0.6207	0.3461	1.0206	0.070*
N4	0.66880 (5)	0.17856 (12)	0.60180 (13)	0.0378 (3)
N3	0.61973 (5)	−0.02496 (12)	0.79101 (13)	0.0380 (3)
N2	0.66026 (5)	0.35846 (12)	0.79769 (13)	0.0411 (3)
N1	0.61151 (5)	0.15682 (13)	0.98578 (13)	0.0424 (3)
N6	0.56130 (4)	0.22542 (12)	0.69608 (12)	0.0353 (3)
C4	0.68374 (6)	0.30173 (16)	0.55757 (17)	0.0426 (4)
C2	0.67957 (6)	0.40924 (15)	0.67539 (17)	0.0432 (4)
C8	0.70328 (7)	0.33377 (19)	0.40511 (19)	0.0583 (5)
H3A	0.6902	0.2618	0.3348	0.087*
H3B	0.7437	0.3369	0.4116	0.087*
H3C	0.6884	0.4232	0.3709	0.087*
C6	0.69739 (8)	0.55759 (18)	0.6574 (2)	0.0660 (6)
H4A	0.6816	0.6149	0.7327	0.099*
H4B	0.6843	0.5906	0.5584	0.099*
H4C	0.7378	0.5633	0.6695	0.099*
C3	0.59669 (6)	−0.07229 (16)	0.91004 (16)	0.0421 (4)
C1	0.59193 (6)	0.03629 (17)	1.02623 (16)	0.0450 (4)
C7	0.57903 (8)	−0.22182 (18)	0.9287 (2)	0.0591 (5)
H7A	0.5943	−0.2788	0.8524	0.089*
H7B	0.5386	−0.2277	0.9187	0.089*
H7C	0.5928	−0.2549	1.0271	0.089*
C5	0.56828 (8)	0.0098 (2)	1.17481 (19)	0.0642 (5)
H8A	0.5742	0.0911	1.2384	0.096*
H8B	0.5869	−0.0699	1.2230	0.096*
H8C	0.5286	−0.0089	1.1586	0.096*
C9	0.715575 (18)	0.10106 (4)	0.88785 (4)	0.0573 (5)
C12	0.53180 (6)	0.32880 (16)	0.75444 (17)	0.0444 (4)
H12	0.5461	0.3715	0.8438	0.053*
C13	0.48031 (3)	0.37510 (5)	0.68624 (9)	0.0510 (4)
C14	0.45857 (7)	0.30890 (19)	0.5563 (2)	0.0599 (5)
H14	0.4236	0.3351	0.5104	0.072*
C15	0.48911 (7)	0.2042 (2)	0.4957 (2)	0.0565 (5)
H15	0.4756	0.1600	0.4065	0.068*
C16	0.54001 (6)	0.16441 (16)	0.56748 (16)	0.0435 (4)
H16	0.5604	0.0928	0.5254	0.052*
C10	0.76274 (2)	0.20196 (14)	0.92838 (5)	0.0569 (6)	0.798 (2)
C11	0.79507 (3)	0.24082 (15)	0.79594 (6)	0.0647 (7)	0.798 (2)
N5	0.81909 (3)	0.26933 (16)	0.69706 (6)	0.0932 (9)	0.798 (2)
C11B	0.758938 (19)	0.17305 (5)	0.80421 (5)	0.153 (5)	0.202 (2)
N5B	0.78976 (2)	0.22618 (9)	0.74309 (9)	0.101 (3)	0.202 (2)
C17	0.44754 (4)	0.49023 (8)	0.75036 (17)	0.0942 (15)	0.524 (2)
H17A	0.4699	0.5340	0.8324	0.141*	0.524 (2)
H17B	0.4137	0.4525	0.7871	0.141*	0.524 (2)
H17C	0.4378	0.5588	0.6732	0.141*	0.524 (2)
Cl	0.44787 (3)	0.51486 (7)	0.77001 (11)	0.0767 (3)	0.476 (2)
C9A	0.72663 (5)	0.1251 (2)	1.05316 (4)	0.122 (8)*	0.121 (2)
C9B	0.73578 (5)	−0.04058 (4)	0.93771 (11)	0.119 (12)*	0.081 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.03318 (8)	0.03421 (8)	0.03570 (8)	0.00027 (7)	0.00373 (6)	−0.00519 (7)
O4	0.0519 (5)	0.0481 (5)	0.0468 (5)	0.0018 (5)	0.0153 (4)	−0.0129 (4)
O3	0.0536 (5)	0.0379 (5)	0.0488 (5)	0.0001 (4)	0.0058 (4)	−0.0113 (4)
O2	0.0709 (7)	0.0437 (5)	0.0552 (6)	−0.0062 (5)	0.0079 (5)	−0.0193 (5)
O1	0.0826 (7)	0.0523 (6)	0.0417 (5)	0.0039 (6)	0.0121 (5)	−0.0138 (5)
N4	0.0339 (5)	0.0391 (6)	0.0409 (5)	0.0010 (5)	0.0069 (4)	−0.0056 (5)
N3	0.0352 (5)	0.0372 (6)	0.0414 (5)	0.0029 (5)	0.0013 (4)	−0.0054 (5)
N2	0.0406 (5)	0.0376 (6)	0.0445 (6)	−0.0008 (5)	0.0000 (5)	−0.0082 (5)
N1	0.0456 (6)	0.0453 (6)	0.0362 (5)	0.0045 (5)	0.0030 (5)	−0.0069 (5)
N6	0.0319 (5)	0.0380 (5)	0.0364 (5)	0.0009 (4)	0.0051 (4)	−0.0022 (5)
C4	0.0331 (6)	0.0472 (7)	0.0480 (7)	0.0028 (6)	0.0064 (6)	0.0054 (6)
C2	0.0370 (6)	0.0377 (7)	0.0553 (8)	−0.0010 (6)	0.0058 (6)	0.0006 (6)
C8	0.0603 (9)	0.0614 (10)	0.0553 (8)	0.0037 (8)	0.0182 (7)	0.0120 (8)
C6	0.0713 (10)	0.0440 (8)	0.0848 (12)	−0.0101 (8)	0.0190 (9)	0.0043 (9)
C3	0.0374 (6)	0.0427 (7)	0.0459 (7)	−0.0002 (6)	0.0019 (6)	0.0053 (6)
C1	0.0431 (7)	0.0518 (8)	0.0402 (7)	0.0043 (6)	0.0043 (6)	0.0048 (6)
C7	0.0626 (9)	0.0500 (8)	0.0642 (10)	−0.0081 (8)	0.0019 (8)	0.0091 (8)
C5	0.0706 (10)	0.0746 (11)	0.0496 (8)	0.0031 (9)	0.0191 (7)	0.0071 (9)
C9	0.0373 (7)	0.0702 (10)	0.0626 (9)	0.0015 (7)	−0.0079 (7)	0.0083 (9)
C12	0.0415 (6)	0.0458 (7)	0.0462 (7)	0.0023 (6)	0.0054 (6)	−0.0072 (6)
C13	0.0418 (7)	0.0465 (8)	0.0658 (9)	0.0099 (6)	0.0116 (7)	0.0038 (7)
C14	0.0388 (7)	0.0654 (10)	0.0739 (11)	0.0079 (7)	−0.0050 (7)	0.0113 (9)
C15	0.0468 (8)	0.0702 (10)	0.0504 (8)	0.0014 (8)	−0.0090 (7)	−0.0051 (8)
C16	0.0387 (6)	0.0469 (7)	0.0444 (7)	0.0026 (6)	0.0013 (6)	−0.0064 (6)
C10	0.0438 (9)	0.0598 (12)	0.0648 (12)	−0.0038 (9)	−0.0109 (9)	0.0042 (10)
C11	0.0391 (9)	0.0752 (14)	0.0760 (14)	−0.0067 (10)	−0.0206 (9)	0.0100 (12)
N5	0.0589 (11)	0.125 (2)	0.0953 (16)	−0.0134 (13)	0.0035 (11)	0.0292 (15)
C11B	0.065 (5)	0.289 (12)	0.096 (6)	0.093 (6)	−0.042 (4)	−0.114 (6)
N5B	0.066 (3)	0.115 (7)	0.110 (5)	0.036 (4)	−0.077 (3)	−0.037 (5)
C17	0.085 (2)	0.076 (2)	0.126 (3)	0.026 (2)	0.035 (2)	−0.019 (2)
Cl	0.0583 (5)	0.0681 (5)	0.1048 (8)	0.0273 (4)	0.0149 (5)	−0.0104 (5)

Geometric parameters (Å, º)

Co—N1	1.8777 (12)	C3—C7	1.495 (2)
Co—N2	1.8826 (12)	C1—C5	1.492 (2)
Co—N3	1.8856 (12)	C7—H7A	0.9600
Co—N4	1.8891 (11)	C7—H7B	0.9600
Co—C9	2.0299 (5)	C7—H7C	0.9600
Co—N6	2.0656 (10)	C5—H8A	0.9600
O4—N4	1.3643 (15)	C5—H8B	0.9600
O4—H4	1.1172 (11)	C5—H8C	0.9600
O3—N3	1.3375 (15)	C9—C11B	1.4830 (5)
O3—H4	1.3957 (10)	C9—C9B	1.4848 (7)
O2—N2	1.3497 (16)	C9—C9A	1.4849 (6)
O1—N1	1.3486 (16)	C9—C10	1.4979 (10)
O1—H1	0.9549 (12)	C12—C13	1.3936 (15)
N4—C4	1.2929 (19)	C12—H12	0.9300
N3—C3	1.3055 (19)	C13—C14	1.376 (2)
N2—C2	1.3017 (19)	C13—C17	1.4820 (8)
N1—C1	1.297 (2)	C13—Cl	1.7318 (7)
N6—C12	1.3347 (18)	C14—C15	1.366 (3)
N6—C16	1.3415 (18)	C14—H14	0.9300
C4—C2	1.469 (2)	C15—C16	1.375 (2)
C4—C8	1.493 (2)	C15—H15	0.9300
C2—C6	1.484 (2)	C16—H16	0.9300
C8—H3A	0.9600	C10—C11	1.4981 (7)
C8—H3B	0.9600	C11—N5	1.1157 (7)
C8—H3C	0.9600	C11B—N5B	1.0710 (6)
C6—H4A	0.9600	C17—H17A	0.9600
C6—H4B	0.9600	C17—H17B	0.9600
C6—H4C	0.9600	C17—H17C	0.9600
C3—C1	1.468 (2)
N1—Co—N2	98.32 (5)	N3—C3—C7	123.80 (14)
N1—Co—N3	81.63 (5)	C1—C3—C7	123.58 (14)
N2—Co—N3	179.29 (5)	N1—C1—C3	112.21 (13)
N1—Co—N4	179.18 (5)	N1—C1—C5	124.10 (14)
N2—Co—N4	81.23 (5)	C3—C1—C5	123.67 (14)
N3—Co—N4	98.81 (5)	C3—C7—H7A	109.5
N1—Co—C9	88.84 (4)	C3—C7—H7B	109.5
N2—Co—C9	93.92 (4)	H7A—C7—H7B	109.5
N3—Co—C9	85.38 (4)	C3—C7—H7C	109.5
N4—Co—C9	90.51 (3)	H7A—C7—H7C	109.5
N1—Co—N6	91.20 (5)	H7B—C7—H7C	109.5
N2—Co—N6	88.55 (5)	C1—C5—H8A	109.5
N3—Co—N6	92.15 (5)	C1—C5—H8B	109.5
N4—Co—N6	89.47 (4)	H8A—C5—H8B	109.5
C9—Co—N6	177.50 (4)	C1—C5—H8C	109.5
N4—O4—H4	100.52 (9)	H8A—C5—H8C	109.5
N3—O3—H4	102.25 (8)	H8B—C5—H8C	109.5
N1—O1—H1	104.33 (10)	C11B—C9—C9B	110.20 (5)
C4—N4—O4	119.46 (12)	C11B—C9—C9A	110.18 (6)
C4—N4—Co	116.97 (10)	C9B—C9—C9A	79.51 (10)
O4—N4—Co	123.43 (8)	C11B—C9—C10	44.56 (3)
C3—N3—O3	121.28 (12)	C9B—C9—C10	106.88 (6)
C3—N3—Co	116.34 (10)	C9A—C9—C10	66.02 (6)
O3—N3—Co	122.38 (9)	C11B—C9—Co	106.47 (3)
C2—N2—O2	120.50 (12)	C9B—C9—Co	131.29 (5)
C2—N2—Co	116.81 (10)	C9A—C9—Co	116.15 (7)
O2—N2—Co	122.66 (9)	C10—C9—Co	121.75 (5)
C1—N1—O1	119.73 (12)	N6—C12—C13	122.36 (12)
C1—N1—Co	117.20 (10)	N6—C12—H12	118.8
O1—N1—Co	123.07 (9)	C13—C12—H12	118.8
C12—N6—C16	118.15 (11)	C14—C13—C12	118.56 (10)
C12—N6—Co	121.25 (9)	C14—C13—C17	118.90 (10)
C16—N6—Co	120.53 (9)	C12—C13—C17	122.52 (9)
N4—C4—C2	112.27 (13)	C14—C13—Cl	123.91 (9)
N4—C4—C8	124.80 (14)	C12—C13—Cl	117.53 (8)
C2—C4—C8	122.94 (14)	C17—C13—Cl	5.36 (5)
N2—C2—C4	112.39 (13)	C15—C14—C13	119.00 (14)
N2—C2—C6	124.33 (15)	C15—C14—H14	120.5
C4—C2—C6	123.24 (14)	C13—C14—H14	120.5
C4—C8—H3A	109.5	C14—C15—C16	119.63 (16)
C4—C8—H3B	109.5	C14—C15—H15	120.2
H3A—C8—H3B	109.5	C16—C15—H15	120.2
C4—C8—H3C	109.5	N6—C16—C15	122.27 (14)
H3A—C8—H3C	109.5	N6—C16—H16	118.9
H3B—C8—H3C	109.5	C15—C16—H16	118.9
C2—C6—H4A	109.5	C9—C10—C11	113.01 (6)
C2—C6—H4B	109.5	N5—C11—C10	179.74 (14)
H4A—C6—H4B	109.5	N5B—C11B—C9	179.09 (6)
C2—C6—H4C	109.5	C13—C17—H17A	109.5
H4A—C6—H4C	109.5	C13—C17—H17B	109.5
H4B—C6—H4C	109.5	C13—C17—H17C	109.5
N3—C3—C1	112.59 (13)

(Mix-III) [(3-bromopyridine) (2-cyanoethyl) cobaloxime] [(2-cyanoethyl)(3-methylpyridine) cobaloxime]

Crystal data

C16.55H23.64Br0.45CoN6O4	F(000) = 1084
Mr = 465.54	Dx = 1.551 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71069 Å
a = 23.82 (2) Å	Cell parameters from 20 reflections
b = 9.52 (1) Å	θ = 12.5–15°
c = 8.822 (5) Å	µ = 1.80 mm^−1
β = 94.73 (6)°	T = 293 K
V = 1994 (3) Å^3	Diamond, orange
Z = 4	0.7 × 0.2 × 0.2 mm

Data collection

AFC7R-RIGAKU diffractometer	3638 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.103
Graphite monochromator	θmax = 27.6°, θmin = 2.7°
ω–2 θ scan	h = −30→31
Absorption correction: psi-scan (North, Phillips & Mathews, 1968)	k = −12→0
Tmin = 0.451, Tmax = 0.698	l = −11→0
4886 measured reflections	3 standard reflections every 150 reflections
4591 independent reflections	intensity decay: −0.3%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.177	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0954P)^2 + 3.0983P] where P = (Fo^2 + 2Fc^2)/3
4591 reflections	(Δ/σ)max = 0.008
268 parameters	Δρmax = 0.77 e Å^−3
2 restraints	Δρmin = −0.99 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	0.35920 (2)	0.16419 (5)	0.70504 (5)	0.02951 (17)
O1	0.38674 (15)	0.2650 (3)	0.4169 (3)	0.0508 (8)
H1	0.3687	0.3409	0.4853	0.061*
O2	0.34342 (14)	0.4399 (3)	0.5795 (3)	0.0476 (7)
O3	0.37062 (13)	−0.1126 (3)	0.8242 (3)	0.0415 (6)
O4	0.32826 (13)	0.0636 (3)	0.9930 (3)	0.0440 (7)
H4	0.3454	−0.0106	0.9260	0.053*
N1	0.38758 (14)	0.1540 (3)	0.5126 (3)	0.0373 (7)
N2	0.33763 (14)	0.3553 (3)	0.7009 (4)	0.0357 (7)
N3	0.38008 (13)	−0.0275 (3)	0.7092 (4)	0.0331 (6)
N4	0.32997 (13)	0.1761 (3)	0.8974 (4)	0.0340 (6)
N5	0.1802 (3)	0.2690 (8)	0.8047 (7)	0.0926 (18)
N6	0.43726 (13)	0.2238 (3)	0.8044 (3)	0.0339 (6)
C1	0.40754 (17)	0.0346 (4)	0.4737 (4)	0.0393 (8)
C3	0.40298 (17)	−0.0743 (4)	0.5899 (4)	0.0380 (8)
C5	0.4316 (2)	0.0085 (6)	0.3250 (5)	0.0584 (12)
H3A	0.4374	0.0966	0.2756	0.088*
H3B	0.4060	−0.0481	0.2614	0.088*
H3C	0.4670	−0.0397	0.3425	0.088*
C7	0.4214 (2)	−0.2227 (5)	0.5716 (6)	0.0511 (11)
H4A	0.4087	−0.2789	0.6524	0.077*
H4B	0.4618	−0.2263	0.5752	0.077*
H4C	0.4057	−0.2584	0.4756	0.077*
C2	0.31933 (16)	0.4059 (4)	0.8232 (5)	0.0377 (8)
C4	0.31581 (16)	0.2989 (4)	0.9417 (4)	0.0349 (7)
C6	0.3016 (2)	0.5548 (5)	0.8404 (6)	0.0576 (12)
H7A	0.3187	0.6123	0.7677	0.086*
H7B	0.3132	0.5867	0.9413	0.086*
H7C	0.2613	0.5613	0.8232	0.086*
C8	0.2958 (2)	0.3314 (5)	1.0941 (5)	0.0500 (10)
H8A	0.3085	0.2594	1.1651	0.075*
H8B	0.2554	0.3352	1.0861	0.075*
H8C	0.3108	0.4204	1.1289	0.075*
C9	0.28419 (17)	0.0961 (5)	0.6123 (5)	0.0426 (9)
H9A	0.2908	0.0481	0.5185	0.051*
H9B	0.2707	0.0262	0.6805	0.051*
C10	0.23623 (19)	0.2013 (5)	0.5758 (5)	0.0507 (10)
H10A	0.2517	0.2857	0.5340	0.061*
H10B	0.2098	0.1611	0.4981	0.061*
C11	0.20619 (19)	0.2394 (6)	0.7046 (6)	0.0581 (13)
C16	0.45884 (17)	0.1633 (4)	0.9335 (4)	0.0396 (8)
H16	0.4384	0.0927	0.9766	0.047*
C15	0.5103 (2)	0.2019 (5)	1.0047 (5)	0.0497 (10)
H15	0.5244	0.1566	1.0932	0.060*
C14	0.54027 (19)	0.3071 (5)	0.9441 (6)	0.0506 (11)
H14	0.5753	0.3332	0.9897	0.061*
C13	0.51813 (17)	0.3739 (3)	0.8150 (5)	0.0435 (9)
C12	0.46690 (17)	0.3287 (4)	0.7465 (5)	0.0388 (8)
H12	0.4524	0.3723	0.6574	0.047*
Br	0.55385 (9)	0.5245 (3)	0.7292 (3)	0.0548 (5)	0.454 (4)
C17	0.5510 (10)	0.492 (2)	0.755 (3)	0.084 (10)	0.546 (4)
H17A	0.5318	0.5271	0.6632	0.126*	0.546 (4)
H17B	0.5877	0.4593	0.7353	0.126*	0.546 (4)
H17C	0.5546	0.5661	0.8296	0.126*	0.546 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.0325 (3)	0.0246 (3)	0.0314 (3)	−0.00018 (18)	0.00282 (18)	0.00325 (18)
O1	0.076 (2)	0.0402 (16)	0.0365 (14)	−0.0020 (15)	0.0091 (14)	0.0114 (12)
O2	0.067 (2)	0.0307 (13)	0.0456 (15)	0.0043 (13)	0.0062 (14)	0.0147 (12)
O3	0.0510 (17)	0.0281 (13)	0.0461 (15)	−0.0001 (12)	0.0085 (12)	0.0099 (11)
O4	0.0531 (17)	0.0373 (15)	0.0432 (15)	−0.0044 (13)	0.0139 (12)	0.0101 (12)
N1	0.0392 (17)	0.0388 (17)	0.0340 (15)	−0.0043 (14)	0.0048 (13)	0.0066 (13)
N2	0.0350 (16)	0.0304 (15)	0.0411 (16)	0.0015 (12)	−0.0002 (13)	0.0054 (13)
N3	0.0312 (15)	0.0285 (15)	0.0392 (15)	0.0005 (12)	0.0007 (12)	0.0030 (12)
N4	0.0295 (15)	0.0350 (16)	0.0377 (16)	−0.0002 (12)	0.0032 (12)	0.0055 (12)
N5	0.072 (3)	0.111 (5)	0.096 (4)	0.022 (3)	0.009 (3)	−0.016 (4)
N6	0.0347 (16)	0.0305 (15)	0.0369 (15)	0.0000 (12)	0.0046 (12)	0.0017 (12)
C1	0.040 (2)	0.041 (2)	0.0368 (18)	−0.0022 (16)	0.0061 (15)	−0.0028 (16)
C3	0.0364 (19)	0.0343 (19)	0.043 (2)	0.0039 (15)	0.0040 (15)	−0.0050 (16)
C5	0.070 (3)	0.061 (3)	0.047 (2)	−0.006 (2)	0.022 (2)	−0.010 (2)
C7	0.058 (3)	0.037 (2)	0.059 (3)	0.0075 (19)	0.009 (2)	−0.0060 (19)
C2	0.0348 (19)	0.0305 (18)	0.048 (2)	0.0018 (14)	0.0023 (16)	−0.0038 (16)
C4	0.0317 (17)	0.0347 (18)	0.0386 (18)	−0.0034 (14)	0.0043 (14)	−0.0038 (15)
C6	0.072 (3)	0.032 (2)	0.071 (3)	0.011 (2)	0.018 (2)	−0.005 (2)
C8	0.061 (3)	0.047 (2)	0.044 (2)	0.001 (2)	0.016 (2)	−0.0082 (19)
C9	0.039 (2)	0.042 (2)	0.046 (2)	−0.0001 (16)	−0.0035 (16)	−0.0077 (17)
C10	0.042 (2)	0.050 (2)	0.059 (3)	0.0009 (19)	−0.0089 (19)	−0.003 (2)
C11	0.035 (2)	0.061 (3)	0.076 (3)	0.009 (2)	−0.009 (2)	−0.015 (3)
C16	0.038 (2)	0.040 (2)	0.0410 (19)	−0.0018 (16)	0.0042 (15)	0.0049 (16)
C15	0.049 (3)	0.052 (2)	0.046 (2)	0.001 (2)	−0.0060 (19)	0.0049 (19)
C14	0.036 (2)	0.054 (3)	0.061 (3)	−0.0038 (19)	−0.0026 (19)	−0.006 (2)
C13	0.043 (2)	0.0321 (19)	0.056 (2)	−0.0067 (16)	0.0100 (18)	−0.0036 (17)
C12	0.0380 (19)	0.0353 (19)	0.043 (2)	−0.0013 (15)	0.0057 (15)	0.0049 (16)
Br	0.0473 (7)	0.0448 (10)	0.0736 (11)	−0.0136 (6)	0.0121 (6)	0.0072 (8)
C17	0.088 (14)	0.061 (13)	0.107 (15)	−0.007 (8)	0.031 (9)	0.036 (8)

Geometric parameters (Å, º)

Co—N1	1.881 (3)	C2—C4	1.467 (6)
Co—N2	1.890 (4)	C2—C6	1.490 (6)
Co—N4	1.890 (3)	C4—C8	1.495 (5)
Co—N3	1.891 (4)	C6—H7A	0.9600
Co—C9	2.010 (4)	C6—H7B	0.9600
Co—N6	2.069 (4)	C6—H7C	0.9600
O1—N1	1.352 (4)	C8—H8A	0.9600
O1—H1	1.055 (3)	C8—H8B	0.9600
O2—N2	1.356 (4)	C8—H8C	0.9600
O2—H1	1.423 (3)	C9—C10	1.533 (6)
O3—N3	1.332 (4)	C9—H9A	0.9700
O4—N4	1.366 (4)	C9—H9B	0.9700
O4—H4	1.027 (3)	C10—C11	1.438 (7)
N1—C1	1.289 (5)	C10—H10A	0.9700
N2—C2	1.290 (5)	C10—H10B	0.9700
N3—C3	1.304 (5)	C16—C15	1.381 (6)
N4—C4	1.286 (5)	C16—H16	0.9300
N5—C11	1.155 (8)	C15—C14	1.365 (7)
N6—C16	1.340 (5)	C15—H15	0.9300
N6—C12	1.347 (5)	C14—C13	1.371 (6)
C1—C3	1.469 (6)	C14—H14	0.9300
C1—C5	1.496 (6)	C13—C12	1.385 (6)
C3—C7	1.493 (6)	C13—C17	1.4903 (14)
C5—H3A	0.9600	C13—Br	1.8592 (16)
C5—H3B	0.9600	C12—H12	0.9300
C5—H3C	0.9600	C17—H17A	0.9600
C7—H4A	0.9600	C17—H17B	0.9600
C7—H4B	0.9600	C17—H17C	0.9600
C7—H4C	0.9600
N1—Co—N2	98.61 (14)	C4—C2—C6	123.7 (4)
N1—Co—N4	179.26 (14)	N4—C4—C2	112.5 (3)
N2—Co—N4	80.79 (14)	N4—C4—C8	124.9 (4)
N1—Co—N3	81.61 (14)	C2—C4—C8	122.6 (4)
N2—Co—N3	179.47 (13)	C2—C6—H7A	109.5
N4—Co—N3	98.98 (14)	C2—C6—H7B	109.5
N1—Co—C9	89.40 (17)	H7A—C6—H7B	109.5
N2—Co—C9	94.07 (16)	C2—C6—H7C	109.5
N4—Co—C9	90.21 (17)	H7A—C6—H7C	109.5
N3—Co—C9	85.45 (16)	H7B—C6—H7C	109.5
N1—Co—N6	91.11 (15)	C4—C8—H8A	109.5
N2—Co—N6	88.71 (14)	C4—C8—H8B	109.5
N4—Co—N6	89.31 (14)	H8A—C8—H8B	109.5
N3—Co—N6	91.77 (13)	C4—C8—H8C	109.5
C9—Co—N6	177.06 (15)	H8A—C8—H8C	109.5
N1—O1—H1	99.5 (3)	H8B—C8—H8C	109.5
N2—O2—H1	98.2 (2)	C10—C9—Co	119.8 (3)
N4—O4—H4	98.7 (2)	C10—C9—H9A	107.4
C1—N1—O1	120.7 (3)	Co—C9—H9A	107.4
C1—N1—Co	117.0 (3)	C10—C9—H9B	107.4
O1—N1—Co	122.4 (3)	Co—C9—H9B	107.4
C2—N2—O2	120.1 (3)	H9A—C9—H9B	106.9
C2—N2—Co	117.0 (3)	C11—C10—C9	114.2 (4)
O2—N2—Co	122.8 (3)	C11—C10—H10A	108.7
C3—N3—O3	121.0 (3)	C9—C10—H10A	108.7
C3—N3—Co	116.2 (3)	C11—C10—H10B	108.7
O3—N3—Co	122.8 (2)	C9—C10—H10B	108.7
C4—N4—O4	120.2 (3)	H10A—C10—H10B	107.6
C4—N4—Co	116.9 (3)	N5—C11—C10	177.4 (6)
O4—N4—Co	122.6 (2)	N6—C16—C15	122.4 (4)
C16—N6—C12	117.7 (3)	N6—C16—H16	118.8
C16—N6—Co	120.7 (3)	C15—C16—H16	118.8
C12—N6—Co	121.6 (3)	C14—C15—C16	119.3 (4)
N1—C1—C3	112.7 (3)	C14—C15—H15	120.3
N1—C1—C5	123.8 (4)	C16—C15—H15	120.3
C3—C1—C5	123.4 (4)	C15—C14—C13	119.2 (4)
N3—C3—C1	112.5 (3)	C15—C14—H14	120.4
N3—C3—C7	123.9 (4)	C13—C14—H14	120.4
C1—C3—C7	123.6 (4)	C14—C13—C12	118.8 (3)
C1—C5—H3A	109.5	C14—C13—C17	117.7 (11)
C1—C5—H3B	109.5	C12—C13—C17	123.4 (11)
H3A—C5—H3B	109.5	C14—C13—Br	122.6 (3)
C1—C5—H3C	109.5	C12—C13—Br	118.6 (3)
H3A—C5—H3C	109.5	C17—C13—Br	4.9 (11)
H3B—C5—H3C	109.5	N6—C12—C13	122.4 (4)
C3—C7—H4A	109.5	N6—C12—H12	118.8
C3—C7—H4B	109.5	C13—C12—H12	118.8
H4A—C7—H4B	109.5	C13—C17—H17A	109.5
C3—C7—H4C	109.5	C13—C17—H17B	109.5
H4A—C7—H4C	109.5	H17A—C17—H17B	109.5
H4B—C7—H4C	109.5	C13—C17—H17C	109.5
N2—C2—C4	112.3 (3)	H17A—C17—H17C	109.5
N2—C2—C6	124.0 (4)	H17B—C17—H17C	109.5