Aqua-cyanido{6,6'-dimeth-oxy-2,2'-[1,2-phenyl-enebis(nitrilo-methanylyl-idene)]diphenolato}cobalt(III) acetonitrile hemisolvate.

In the title complex, [Co(C(22)H(18)N(2)O(4))(CN)(H(2)O)]·0.5CH(3)CN, the Co(III) cation is N,N',O,O'-chelated by a 6,6'-dimeth-oxy-2,2'-[1,2-phenyl-enebis(nitrilo-methanylyl-idene)]diphenolate dianion, and is further coordinated by a cyanide anion and a water mol-ecule in the axial sites, completing a distorted octa-hedral coordination geometry. In the crystal, pairs of bifurcated O-H⋯(O,O) hydrogen bonds link adjacent mol-ecules, forming centrosymmetric dimers. The acetonitrile solvent mol-ecule shows 0.5 occupancy.

Related literature

For the synthesis, see: Costes et al. (2000 ▶). For related complexes with a similar ligand, see: Lin et al. (2011 ▶). For bond-valence calculations, see: Spek (2009 ▶).

Experimental

Crystal data

[Co(C22H18N2O4)(CN)(H2O)]·0.5C2H3N

M = 497.95

Triclinic,

a = 8.6487 (17) Å

b = 11.689 (2) Å

c = 12.229 (2) Å

α = 112.10 (3)°

β = 102.30 (3)°

γ = 97.85 (3)°

V = 1086.6 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.83 mm−1

T = 293 K

0.23 × 0.21 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.831, T max = 0.878

10646 measured reflections

4911 independent reflections

3570 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.158

S = 1.05

4911 reflections

319 parameters

16 restraints

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.89 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681105330X/xu5401sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681105330X/xu5401Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co(C22H18N2O4)(CN)(H2O)]·0.5C2H3N	Z = 2
Mr = 497.95	F(000) = 514
Triclinic, P1	Dx = 1.522 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6487 (17) Å	Cell parameters from 8343 reflections
b = 11.689 (2) Å	θ = 3.2–27.5°
c = 12.229 (2) Å	µ = 0.83 mm−1
α = 112.10 (3)°	T = 293 K
β = 102.30 (3)°	Block, red-brown
γ = 97.85 (3)°	0.23 × 0.21 × 0.16 mm
V = 1086.6 (5) Å3

Rigaku R-AXIS RAPID diffractometer	4911 independent reflections
Radiation source: fine-focus sealed tube	3570 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω scan	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
Tmin = 0.831, Tmax = 0.878	k = −15→15
10646 measured reflections	l = −15→15

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.1004P)2] where P = (Fo2 + 2Fc2)/3
4911 reflections	(Δ/σ)max < 0.001
319 parameters	Δρmax = 0.52 e Å−3
16 restraints	Δρmin = −0.89 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. dfix 1.15 0.001 n4 c24 dfix 1.47 0.001 c24 c25 dfix 2.62 0.001 n4 c25 isor 0.01 c24 n4 dfix 1.50 0.01 c24 c25 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.5411 (4)	0.7915 (3)	0.5742 (3)	0.0327 (6)
C2	0.6334 (4)	0.8623 (3)	0.6996 (3)	0.0366 (7)
C3	0.6087 (4)	0.9779 (3)	0.7700 (3)	0.0438 (8)
H3	0.6712	1.0227	0.8518	0.053*
C4	0.4896 (4)	1.0283 (3)	0.7190 (3)	0.0474 (8)
H4	0.4720	1.1057	0.7673	0.057*
C5	0.4008 (4)	0.9649 (3)	0.6001 (3)	0.0421 (7)
H5	0.3222	0.9992	0.5671	0.051*
C6	0.4253 (4)	0.8455 (3)	0.5234 (3)	0.0364 (6)
C7	0.3364 (4)	0.7893 (3)	0.3972 (3)	0.0400 (7)
H7	0.2612	0.8304	0.3715	0.048*
C8	0.2706 (4)	0.6445 (3)	0.1871 (3)	0.0416 (7)
C9	0.1671 (4)	0.7046 (4)	0.1359 (4)	0.0521 (9)
H9	0.1397	0.7759	0.1870	0.063*
C10	0.1057 (5)	0.6584 (5)	0.0103 (4)	0.0650 (12)
H10	0.0359	0.6981	−0.0235	0.078*
C11	0.1465 (5)	0.5535 (5)	−0.0663 (4)	0.0615 (11)
H11	0.1054	0.5240	−0.1513	0.074*
C12	0.2471 (4)	0.4922 (4)	−0.0186 (3)	0.0537 (9)
H12	0.2745	0.4217	−0.0708	0.064*
C13	0.3082 (4)	0.5363 (3)	0.1093 (3)	0.0419 (7)
C14	0.4470 (4)	0.3753 (3)	0.1133 (3)	0.0427 (7)
H14	0.3935	0.3316	0.0295	0.051*
C15	0.5590 (4)	0.3186 (3)	0.1660 (3)	0.0423 (7)
C16	0.5876 (5)	0.2028 (3)	0.0879 (3)	0.0520 (9)
H16	0.5282	0.1638	0.0051	0.062*
C17	0.6983 (5)	0.1489 (4)	0.1313 (4)	0.0605 (10)
H17	0.7137	0.0726	0.0786	0.073*
C18	0.7910 (5)	0.2064 (3)	0.2554 (4)	0.0504 (9)
H18	0.8702	0.1698	0.2839	0.061*
C19	0.7655 (4)	0.3164 (3)	0.3349 (3)	0.0392 (7)
C20	0.6478 (4)	0.3764 (3)	0.2929 (3)	0.0358 (7)
C21	0.9775 (4)	0.3347 (4)	0.5076 (4)	0.0573 (10)
H21A	0.9401	0.2479	0.4942	0.086*
H21B	1.0214	0.3869	0.5944	0.086*
H21C	1.0605	0.3403	0.4675	0.086*
C22	0.8491 (5)	0.8702 (4)	0.8620 (3)	0.0602 (10)
H22A	0.9104	0.9501	0.8719	0.090*
H22B	0.9226	0.8202	0.8785	0.090*
H22C	0.7845	0.8849	0.9186	0.090*
C23	0.6571 (4)	0.6832 (3)	0.3194 (3)	0.0396 (7)
C25	0.8598 (12)	0.8846 (9)	0.1678 (9)	0.082 (3)	0.50
H25A	0.7929	0.8049	0.1538	0.123*	0.50
H25B	0.9149	0.8713	0.1053	0.123*	0.50
H25C	0.7926	0.9429	0.1647	0.123*	0.50
C24	0.9809 (11)	0.9376 (14)	0.2899 (9)	0.140 (6)	0.50
N4	1.0569 (11)	0.9860 (13)	0.3921 (9)	0.132 (4)	0.50
Co1	0.49216 (5)	0.58348 (4)	0.34297 (4)	0.03236 (16)
N1	0.3503 (3)	0.6849 (2)	0.3133 (2)	0.0349 (5)
N2	0.4128 (3)	0.4825 (3)	0.1717 (2)	0.0366 (6)
N3	0.7556 (4)	0.7451 (3)	0.3036 (3)	0.0600 (9)
O1	0.5684 (3)	0.68069 (19)	0.51481 (19)	0.0362 (5)
O2	0.7461 (3)	0.8045 (2)	0.7402 (2)	0.0476 (6)
O3	0.6284 (3)	0.4801 (2)	0.37473 (19)	0.0367 (5)
O4	0.8432 (3)	0.3779 (2)	0.4577 (2)	0.0461 (6)
O5	0.3077 (2)	0.4757 (2)	0.36607 (19)	0.0371 (5)
H51	0.3288	0.4073	0.3676	0.056*
H52	0.2908	0.5179	0.4343	0.056*

	U11	U22	U33	U12	U13	U23
C1	0.0382 (15)	0.0286 (14)	0.0302 (15)	0.0068 (12)	0.0109 (12)	0.0111 (12)
C2	0.0422 (16)	0.0335 (15)	0.0345 (16)	0.0119 (13)	0.0108 (13)	0.0138 (13)
C3	0.058 (2)	0.0314 (16)	0.0363 (18)	0.0084 (15)	0.0156 (15)	0.0079 (14)
C4	0.065 (2)	0.0344 (17)	0.048 (2)	0.0193 (16)	0.0244 (18)	0.0155 (15)
C5	0.0518 (19)	0.0372 (17)	0.049 (2)	0.0205 (15)	0.0229 (16)	0.0230 (16)
C6	0.0430 (16)	0.0322 (15)	0.0361 (17)	0.0079 (13)	0.0135 (13)	0.0159 (13)
C7	0.0390 (16)	0.0454 (18)	0.0448 (19)	0.0130 (14)	0.0130 (14)	0.0270 (16)
C8	0.0410 (16)	0.0450 (18)	0.0380 (18)	0.0022 (14)	0.0037 (14)	0.0235 (15)
C9	0.050 (2)	0.053 (2)	0.054 (2)	0.0070 (17)	0.0022 (17)	0.0319 (19)
C10	0.060 (2)	0.080 (3)	0.061 (3)	0.003 (2)	−0.003 (2)	0.052 (3)
C11	0.056 (2)	0.085 (3)	0.039 (2)	−0.005 (2)	−0.0026 (17)	0.038 (2)
C12	0.055 (2)	0.068 (2)	0.0322 (18)	−0.0007 (19)	0.0066 (15)	0.0227 (18)
C13	0.0401 (16)	0.0505 (19)	0.0326 (17)	−0.0005 (14)	0.0066 (13)	0.0208 (15)
C14	0.0464 (17)	0.0461 (18)	0.0222 (15)	−0.0018 (15)	0.0074 (13)	0.0058 (13)
C15	0.0538 (19)	0.0385 (17)	0.0315 (16)	0.0066 (15)	0.0183 (14)	0.0096 (14)
C16	0.075 (2)	0.0423 (18)	0.0342 (18)	0.0136 (18)	0.0233 (17)	0.0074 (15)
C17	0.088 (3)	0.048 (2)	0.050 (2)	0.027 (2)	0.038 (2)	0.0122 (18)
C18	0.061 (2)	0.0440 (19)	0.053 (2)	0.0235 (17)	0.0267 (18)	0.0189 (17)
C19	0.0439 (17)	0.0349 (16)	0.0412 (18)	0.0097 (14)	0.0190 (14)	0.0149 (14)
C20	0.0418 (16)	0.0329 (15)	0.0320 (16)	0.0058 (13)	0.0171 (13)	0.0104 (13)
C21	0.049 (2)	0.057 (2)	0.071 (3)	0.0225 (18)	0.0124 (19)	0.031 (2)
C22	0.065 (2)	0.063 (2)	0.0345 (19)	0.016 (2)	−0.0011 (17)	0.0092 (18)
C23	0.0424 (17)	0.0412 (17)	0.0363 (17)	0.0123 (14)	0.0093 (14)	0.0177 (14)
C25	0.113 (8)	0.082 (7)	0.094 (8)	0.041 (6)	0.059 (7)	0.059 (6)
C24	0.129 (9)	0.133 (9)	0.168 (10)	0.012 (7)	0.086 (8)	0.058 (7)
N4	0.077 (5)	0.179 (9)	0.147 (8)	0.043 (6)	0.033 (5)	0.070 (7)
Co1	0.0380 (2)	0.0324 (2)	0.0258 (2)	0.00821 (17)	0.00750 (16)	0.01238 (17)
N1	0.0318 (12)	0.0416 (14)	0.0325 (14)	0.0070 (11)	0.0047 (10)	0.0198 (12)
N2	0.0401 (13)	0.0410 (14)	0.0260 (13)	0.0049 (11)	0.0074 (10)	0.0140 (11)
N3	0.0559 (19)	0.062 (2)	0.073 (2)	0.0101 (16)	0.0259 (17)	0.0368 (19)
O1	0.0474 (12)	0.0295 (10)	0.0286 (11)	0.0133 (9)	0.0070 (9)	0.0097 (9)
O2	0.0571 (14)	0.0414 (13)	0.0326 (12)	0.0172 (11)	0.0017 (11)	0.0073 (10)
O3	0.0421 (11)	0.0367 (11)	0.0274 (11)	0.0148 (9)	0.0073 (9)	0.0087 (9)
O4	0.0451 (12)	0.0452 (13)	0.0476 (14)	0.0200 (11)	0.0099 (11)	0.0178 (11)
O5	0.0461 (12)	0.0337 (11)	0.0325 (11)	0.0097 (9)	0.0121 (9)	0.0144 (9)

C1—O1	1.308 (3)	C16—C17	1.340 (6)
C1—C6	1.411 (4)	C16—H16	0.9300
C1—C2	1.420 (4)	C17—C18	1.402 (6)
C2—O2	1.371 (4)	C17—H17	0.9300
C2—C3	1.377 (4)	C18—C19	1.369 (4)
C3—C4	1.403 (5)	C18—H18	0.9300
C3—H3	0.9300	C19—O4	1.360 (4)
C4—C5	1.346 (5)	C19—C20	1.426 (5)
C4—H4	0.9300	C20—O3	1.308 (4)
C5—C6	1.433 (4)	C21—O4	1.438 (4)
C5—H5	0.9300	C21—H21A	0.9600
C6—C7	1.414 (5)	C21—H21B	0.9600
C7—N1	1.307 (4)	C21—H21C	0.9600
C7—H7	0.9300	C22—O2	1.410 (4)
C8—C13	1.396 (5)	C22—H22A	0.9600
C8—C9	1.396 (4)	C22—H22B	0.9600
C8—N1	1.411 (4)	C22—H22C	0.9600
C9—C10	1.373 (6)	C23—N3	1.137 (4)
C9—H9	0.9300	C25—C24	1.4738 (12)
C10—C11	1.378 (7)	C25—H25A	0.9600
C10—H10	0.9300	C25—H25B	0.9600
C11—C12	1.372 (5)	C25—H25C	0.9600
C11—H11	0.9300	C24—N4	1.1532 (11)
C12—C13	1.399 (5)	Co1—O1	1.884 (2)
C12—H12	0.9300	Co1—O3	1.884 (2)
C13—N2	1.420 (4)	Co1—O5	2.030 (2)
C14—N2	1.299 (4)	Co1—N1	1.890 (2)
C14—C15	1.422 (5)	Co1—N2	1.885 (3)
C14—H14	0.9300	Co1—C23	1.858 (3)
C15—C20	1.420 (5)	O5—H51	0.8500
C15—C16	1.423 (5)	O5—H52	0.8500
O1—C1—C6	124.8 (3)	O4—C19—C18	125.5 (3)
O1—C1—C2	117.7 (3)	O4—C19—C20	113.5 (3)
C6—C1—C2	117.5 (3)	C18—C19—C20	121.0 (3)
O2—C2—C3	125.0 (3)	O3—C20—C15	124.8 (3)
O2—C2—C1	113.5 (3)	O3—C20—C19	117.5 (3)
C3—C2—C1	121.5 (3)	C15—C20—C19	117.7 (3)
C2—C3—C4	120.3 (3)	O4—C21—H21A	109.5
C2—C3—H3	119.9	O4—C21—H21B	109.5
C4—C3—H3	119.9	H21A—C21—H21B	109.5
C5—C4—C3	120.1 (3)	O4—C21—H21C	109.5
C5—C4—H4	120.0	H21A—C21—H21C	109.5
C3—C4—H4	120.0	H21B—C21—H21C	109.5
C4—C5—C6	121.2 (3)	O2—C22—H22A	109.5
C4—C5—H5	119.4	O2—C22—H22B	109.5
C6—C5—H5	119.4	H22A—C22—H22B	109.5
C1—C6—C7	122.6 (3)	O2—C22—H22C	109.5
C1—C6—C5	119.5 (3)	H22A—C22—H22C	109.5
C7—C6—C5	117.9 (3)	H22B—C22—H22C	109.5
N1—C7—C6	126.0 (3)	N3—C23—Co1	178.5 (3)
N1—C7—H7	117.0	C24—C25—H25A	109.5
C6—C7—H7	117.0	C24—C25—H25B	109.5
C13—C8—C9	119.4 (3)	H25A—C25—H25B	109.5
C13—C8—N1	114.1 (3)	C24—C25—H25C	109.5
C9—C8—N1	126.4 (3)	H25A—C25—H25C	109.5
C10—C9—C8	119.9 (4)	H25B—C25—H25C	109.5
C10—C9—H9	120.0	N4—C24—C25	169.6 (8)
C8—C9—H9	120.0	C23—Co1—O3	92.27 (12)
C9—C10—C11	120.6 (4)	C23—Co1—O1	91.05 (13)
C9—C10—H10	119.7	O3—Co1—O1	84.29 (9)
C11—C10—H10	119.7	C23—Co1—N2	90.44 (13)
C12—C11—C10	120.7 (4)	O3—Co1—N2	95.12 (11)
C12—C11—H11	119.6	O1—Co1—N2	178.41 (10)
C10—C11—H11	119.6	C23—Co1—N1	89.65 (12)
C11—C12—C13	119.5 (4)	O3—Co1—N1	178.03 (10)
C11—C12—H12	120.2	O1—Co1—N1	95.21 (10)
C13—C12—H12	120.2	N2—Co1—N1	85.34 (12)
C8—C13—C12	119.8 (3)	C23—Co1—O5	178.58 (11)
C8—C13—N2	114.3 (3)	O3—Co1—O5	89.01 (9)
C12—C13—N2	125.8 (3)	O1—Co1—O5	89.68 (10)
N2—C14—C15	125.9 (3)	N2—Co1—O5	88.83 (11)
N2—C14—H14	117.1	N1—Co1—O5	89.08 (10)
C15—C14—H14	117.1	C7—N1—C8	121.7 (3)
C20—C15—C14	122.1 (3)	C7—N1—Co1	124.9 (2)
C20—C15—C16	119.0 (3)	C8—N1—Co1	113.1 (2)
C14—C15—C16	118.8 (3)	C14—N2—C13	121.8 (3)
C17—C16—C15	121.4 (4)	C14—N2—Co1	125.6 (2)
C17—C16—H16	119.3	C13—N2—Co1	112.7 (2)
C15—C16—H16	119.3	C1—O1—Co1	125.53 (19)
C16—C17—C18	120.6 (3)	C2—O2—C22	117.8 (3)
C16—C17—H17	119.7	C20—O3—Co1	126.2 (2)
C18—C17—H17	119.7	C19—O4—C21	118.4 (3)
C19—C18—C17	120.3 (3)	Co1—O5—H51	112.8
C19—C18—H18	119.9	Co1—O5—H52	109.2
C17—C18—H18	119.9	H51—O5—H52	107.5

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O1i	0.85	2.18	2.913 (3)	145.
O5—H51···O2i	0.85	2.24	2.959 (3)	142.
O5—H52···O3i	0.85	2.28	2.926 (3)	133.
O5—H52···O4i	0.85	2.10	2.883 (3)	153.

Table 1

Selected bond lengths (Å)

Co1—O1	1.884 (2)
Co1—O3	1.884 (2)
Co1—O5	2.030 (2)
Co1—N1	1.890 (2)
Co1—N2	1.885 (3)
Co1—C23	1.858 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O1i	0.85	2.18	2.913 (3)	145
O5—H51⋯O2i	0.85	2.24	2.959 (3)	142
O5—H52⋯O3i	0.85	2.28	2.926 (3)	133
O5—H52⋯O4i	0.85	2.10	2.883 (3)	153

Symmetry code: (i) .