A new polymorph of a cobalt(III) Schiff base complex exhibits a one-dimensional C—H...O hydrogen-bonded extended structure with helical 2₁ symmetry

In a new polymorph of acetato(2,2′-{imino­bis[(E)-propane-3,1-diylnitrilo­methyl­idyne]}diphenol­ato)­cobalt(III), [Co(C₂₀H₂₃N₃O₂)(C₂H₃O₂)], in the space group P2₁/c, the Co^III ion is six-coordinate, with unequal Co—O_phenolate distances that average 1.908 (12) Å and more similar Co—N_imine distances averaging 1.937 (4) Å. The acetate ion occupies the sixth coordination site and forms an intra­molecular hydrogen bond (H...O = 1.95 Å) with the Co-bound NH group of the penta­dentate chelate. The extended structure is a one-dimensional (aryl)C—H...O(carbonyl) hydrogen-bonded polymer with 2₁ (helical) symmetry and is thus distinct from the simple hydrogen-bonded stack of the P2₁/n polymorph [Matsumoto, Imaizumi & Ohyoshi (1983). Polyhedron, 2, 137–139].

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX.

acetato(2,2'-{iminobis[(E)-propane-3,1- diylnitrilomethylylidyne]}diphenolato)cobalt(III)

Crystal data

[Co(C2H3O2)(C20H23N3O2)]	F(000) = 952
Mr = 455.39	Dx = 1.482 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1765 reflections
a = 7.730 (2) Å	θ = 4.7–31.8°
b = 20.439 (3) Å	µ = 0.88 mm^−1
c = 13.321 (2) Å	T = 100 K
β = 104.169 (18)°	Rectangular plate, black
V = 2040.6 (7) Å^3	0.27 × 0.17 × 0.06 mm
Z = 4

Data collection

Oxford Xcalibur2 CCD area-detector diffractometer	5817 reflections with I > 2σ(I)
ω scans	Rint = 0.019
Absorption correction: numerical [CrysAlis RED (Oxford Diffraction, 2003); analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	θmax = 31.9°, θmin = 4.8°
Tmin = 0.688, Tmax = 0.904	h = −9→11
18148 measured reflections	k = −29→29
6468 independent reflections	l = −19→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0339P)^2 + 1.8518P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max = 0.002
S = 1.05	Δρmax = 0.50 e Å^−3
6468 reflections	Δρmin = −0.63 e Å^−3
276 parameters

Special details

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

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

	x	y	z	Uiso*/Ueq
C1	0.30106 (17)	0.85246 (6)	−0.05702 (10)	0.0118 (2)
C2	0.12905 (17)	0.83640 (7)	−0.11897 (10)	0.0145 (2)
H2	0.0673	0.7996	−0.1014	0.017*
C3	0.05040 (18)	0.87398 (7)	−0.20491 (11)	0.0184 (3)
H3	−0.0652	0.8627	−0.2449	0.022*
C4	0.13801 (19)	0.92822 (7)	−0.23381 (11)	0.0192 (3)
H4	0.0835	0.9531	−0.2934	0.023*
C5	0.30559 (18)	0.94498 (7)	−0.17408 (11)	0.0171 (2)
H5	0.3662	0.9815	−0.1934	0.02*
C6	0.38729 (17)	0.90865 (6)	−0.08520 (10)	0.0132 (2)
C7	0.56812 (17)	0.92566 (7)	−0.03000 (10)	0.0150 (2)
H7	0.6273	0.958	−0.0604	0.018*
C8	0.84835 (17)	0.91538 (7)	0.09177 (11)	0.0168 (2)
H8A	0.8704	0.9429	0.1548	0.02*
H8B	0.887	0.9402	0.0373	0.02*
C9	0.95766 (18)	0.85171 (7)	0.11537 (11)	0.0176 (2)
H9A	1.0639	0.8554	0.0866	0.021*
H9B	1.0002	0.8468	0.1914	0.021*
C10	0.85370 (18)	0.79060 (7)	0.07136 (11)	0.0177 (3)
H10A	0.7931	0.7981	−0.0023	0.021*
H10B	0.9375	0.7536	0.0747	0.021*
C11	0.63930 (19)	0.70850 (7)	0.09726 (11)	0.0162 (2)
H11A	0.7342	0.6781	0.0886	0.019*
H11B	0.5516	0.7126	0.0296	0.019*
C12	0.54728 (19)	0.68075 (6)	0.17684 (11)	0.0173 (2)
H12A	0.5118	0.635	0.158	0.021*
H12B	0.6335	0.6801	0.2454	0.021*
C13	0.38296 (18)	0.71920 (6)	0.18554 (11)	0.0155 (2)
H13A	0.2947	0.7187	0.1177	0.019*
H13B	0.3281	0.6975	0.2366	0.019*
C14	0.36132 (17)	0.80937 (6)	0.29216 (10)	0.0132 (2)
H14	0.3164	0.7783	0.3323	0.016*
C15	0.35400 (16)	0.87762 (6)	0.31908 (10)	0.0119 (2)
C16	0.31713 (18)	0.89341 (7)	0.41473 (10)	0.0149 (2)
H16	0.3085	0.8593	0.4617	0.018*
C17	0.29326 (19)	0.95746 (7)	0.44161 (11)	0.0173 (2)
H17	0.2761	0.968	0.508	0.021*
C18	0.29511 (19)	1.00650 (7)	0.36832 (11)	0.0169 (2)
H18	0.2754	1.0507	0.3848	0.02*
C19	0.32500 (18)	0.99196 (6)	0.27252 (10)	0.0152 (2)
H19	0.3212	1.0262	0.2238	0.018*
C20	0.36109 (16)	0.92728 (6)	0.24532 (9)	0.0112 (2)
Co	0.54484 (2)	0.844060 (8)	0.138864 (13)	0.01007 (5)
N1	0.65555 (14)	0.90075 (5)	0.05668 (9)	0.01279 (19)
N2	0.71844 (15)	0.77340 (6)	0.12983 (9)	0.0133 (2)
N3	0.42453 (14)	0.78765 (5)	0.21748 (8)	0.01164 (19)
O3	0.70453 (12)	0.87880 (5)	0.26124 (7)	0.01269 (17)
O1	0.37569 (12)	0.81359 (5)	0.02018 (7)	0.01335 (17)
O2	0.39145 (12)	0.91547 (4)	0.15406 (7)	0.01207 (17)
O4	0.84012 (16)	0.78999 (5)	0.34637 (8)	0.0225 (2)
C21	0.79996 (17)	0.84872 (6)	0.34102 (10)	0.0134 (2)
C22	0.8632 (2)	0.89399 (7)	0.43335 (11)	0.0188 (3)
H22A	0.7603	0.9089	0.458	0.028*
H22B	0.9239	0.9319	0.4126	0.028*
H22C	0.9461	0.8704	0.489	0.028*
H100	0.776 (3)	0.7712 (10)	0.1983 (17)	0.024 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0123 (5)	0.0121 (5)	0.0116 (5)	−0.0001 (4)	0.0044 (4)	−0.0019 (4)
C2	0.0123 (5)	0.0157 (6)	0.0153 (6)	−0.0017 (4)	0.0032 (4)	−0.0025 (4)
C3	0.0135 (6)	0.0206 (6)	0.0193 (6)	0.0010 (5)	0.0005 (5)	−0.0012 (5)
C4	0.0169 (6)	0.0199 (6)	0.0189 (6)	0.0028 (5)	0.0006 (5)	0.0041 (5)
C5	0.0168 (6)	0.0159 (6)	0.0181 (6)	0.0014 (5)	0.0033 (5)	0.0034 (5)
C6	0.0133 (5)	0.0137 (5)	0.0126 (5)	−0.0009 (4)	0.0030 (4)	0.0001 (4)
C7	0.0150 (5)	0.0159 (6)	0.0150 (6)	−0.0036 (4)	0.0055 (4)	0.0000 (4)
C8	0.0122 (5)	0.0207 (6)	0.0170 (6)	−0.0053 (5)	0.0025 (4)	0.0000 (5)
C9	0.0112 (5)	0.0239 (7)	0.0184 (6)	−0.0015 (5)	0.0048 (5)	−0.0040 (5)
C10	0.0147 (6)	0.0217 (6)	0.0187 (6)	−0.0019 (5)	0.0082 (5)	−0.0064 (5)
C11	0.0183 (6)	0.0132 (6)	0.0182 (6)	0.0006 (4)	0.0064 (5)	−0.0034 (4)
C12	0.0216 (6)	0.0105 (5)	0.0209 (6)	0.0027 (5)	0.0076 (5)	−0.0001 (4)
C13	0.0185 (6)	0.0107 (5)	0.0186 (6)	−0.0018 (4)	0.0071 (5)	0.0002 (4)
C14	0.0137 (5)	0.0111 (5)	0.0154 (5)	0.0007 (4)	0.0048 (4)	0.0023 (4)
C15	0.0120 (5)	0.0106 (5)	0.0140 (5)	0.0009 (4)	0.0048 (4)	0.0007 (4)
C16	0.0166 (6)	0.0156 (6)	0.0138 (5)	0.0018 (4)	0.0061 (4)	0.0016 (4)
C17	0.0199 (6)	0.0184 (6)	0.0147 (6)	0.0012 (5)	0.0065 (5)	−0.0025 (5)
C18	0.0190 (6)	0.0131 (6)	0.0198 (6)	0.0004 (5)	0.0072 (5)	−0.0026 (5)
C19	0.0183 (6)	0.0113 (5)	0.0173 (6)	0.0006 (4)	0.0067 (5)	0.0005 (4)
C20	0.0108 (5)	0.0113 (5)	0.0118 (5)	−0.0004 (4)	0.0032 (4)	0.0002 (4)
Co	0.01011 (8)	0.01022 (8)	0.01027 (8)	−0.00054 (5)	0.00321 (6)	−0.00034 (5)
N1	0.0113 (4)	0.0144 (5)	0.0129 (5)	−0.0031 (4)	0.0035 (4)	−0.0004 (4)
N2	0.0132 (5)	0.0140 (5)	0.0135 (5)	0.0008 (4)	0.0046 (4)	−0.0029 (4)
N3	0.0127 (5)	0.0091 (4)	0.0135 (5)	−0.0003 (4)	0.0040 (4)	0.0013 (3)
O3	0.0128 (4)	0.0129 (4)	0.0117 (4)	−0.0003 (3)	0.0018 (3)	−0.0007 (3)
O1	0.0141 (4)	0.0130 (4)	0.0119 (4)	−0.0027 (3)	0.0010 (3)	−0.0001 (3)
O2	0.0140 (4)	0.0113 (4)	0.0116 (4)	0.0018 (3)	0.0045 (3)	0.0006 (3)
O4	0.0305 (6)	0.0177 (5)	0.0172 (5)	0.0084 (4)	0.0017 (4)	0.0003 (4)
C21	0.0117 (5)	0.0168 (6)	0.0125 (5)	0.0012 (4)	0.0047 (4)	−0.0001 (4)
C22	0.0207 (6)	0.0215 (6)	0.0135 (6)	−0.0026 (5)	0.0029 (5)	−0.0021 (5)

Geometric parameters (Å, º)

C1—O1	1.3157 (15)	C13—N3	1.4747 (16)
C1—C2	1.4211 (18)	C13—H13A	0.99
C1—C6	1.4236 (18)	C13—H13B	0.99
C2—C3	1.3890 (19)	C14—N3	1.2897 (16)
C2—H2	0.95	C14—C15	1.4448 (18)
C3—C4	1.401 (2)	C14—H14	0.95
C3—H3	0.95	C15—C16	1.4095 (18)
C4—C5	1.387 (2)	C15—C20	1.4230 (17)
C4—H4	0.95	C16—C17	1.3813 (19)
C5—C6	1.4093 (18)	C16—H16	0.95
C5—H5	0.95	C17—C18	1.402 (2)
C6—C7	1.4534 (18)	C17—H17	0.95
C7—N1	1.2913 (17)	C18—C19	1.3837 (18)
C7—H7	0.95	C18—H18	0.95
C8—N1	1.4792 (17)	C19—C20	1.4165 (17)
C8—C9	1.542 (2)	C19—H19	0.95
C8—H8A	0.99	C20—O2	1.3157 (15)
C8—H8B	0.99	Co—O1	1.8934 (10)
C9—C10	1.523 (2)	Co—O2	1.9222 (9)
C9—H9A	0.99	Co—O3	1.9236 (10)
C9—H9B	0.99	Co—N1	1.9318 (11)
C10—N2	1.4907 (17)	Co—N3	1.9410 (11)
C10—H10A	0.99	Co—N2	1.9950 (11)
C10—H10B	0.99	N2—H100	0.91 (2)
C11—N2	1.4806 (17)	O3—C21	1.2914 (16)
C11—C12	1.5234 (19)	O4—C21	1.2375 (17)
C11—H11A	0.99	C21—C22	1.5210 (19)
C11—H11B	0.99	C22—H22A	0.98
C12—C13	1.5220 (19)	C22—H22B	0.98
C12—H12A	0.99	C22—H22C	0.98
C12—H12B	0.99
O1—C1—C2	118.90 (11)	C15—C14—H14	117.7
O1—C1—C6	123.31 (12)	C16—C15—C20	120.75 (11)
C2—C1—C6	117.72 (12)	C16—C15—C14	118.32 (11)
C3—C2—C1	120.63 (12)	C20—C15—C14	120.44 (11)
C3—C2—H2	119.7	C17—C16—C15	121.38 (12)
C1—C2—H2	119.7	C17—C16—H16	119.3
C2—C3—C4	121.36 (13)	C15—C16—H16	119.3
C2—C3—H3	119.3	C16—C17—C18	118.18 (12)
C4—C3—H3	119.3	C16—C17—H17	120.9
C5—C4—C3	118.95 (13)	C18—C17—H17	120.9
C5—C4—H4	120.5	C19—C18—C17	121.42 (12)
C3—C4—H4	120.5	C19—C18—H18	119.3
C4—C5—C6	121.02 (13)	C17—C18—H18	119.3
C4—C5—H5	119.5	C18—C19—C20	121.62 (12)
C6—C5—H5	119.5	C18—C19—H19	119.2
C5—C6—C1	120.28 (12)	C20—C19—H19	119.2
C5—C6—C7	118.47 (12)	O2—C20—C19	119.89 (11)
C1—C6—C7	120.93 (12)	O2—C20—C15	123.57 (11)
N1—C7—C6	125.88 (12)	C19—C20—C15	116.47 (11)
N1—C7—H7	117.1	O1—Co—O2	91.14 (4)
C6—C7—H7	117.1	O1—Co—O3	176.17 (4)
N1—C8—C9	110.69 (11)	O2—Co—O3	85.12 (4)
N1—C8—H8A	109.5	O1—Co—N1	92.02 (5)
C9—C8—H8A	109.5	O2—Co—N1	88.54 (5)
N1—C8—H8B	109.5	O3—Co—N1	88.71 (5)
C9—C8—H8B	109.5	O1—Co—N3	86.04 (5)
H8A—C8—H8B	108.1	O2—Co—N3	90.28 (4)
C10—C9—C8	113.75 (11)	O3—Co—N3	93.14 (4)
C10—C9—H9A	108.8	N1—Co—N3	177.71 (5)
C8—C9—H9A	108.8	O1—Co—N2	92.80 (5)
C10—C9—H9B	108.8	O2—Co—N2	175.88 (4)
C8—C9—H9B	108.8	O3—Co—N2	90.96 (5)
H9A—C9—H9B	107.7	N1—Co—N2	90.13 (5)
N2—C10—C9	111.33 (11)	N3—Co—N2	91.19 (5)
N2—C10—H10A	109.4	C7—N1—C8	117.98 (11)
C9—C10—H10A	109.4	C7—N1—Co	122.40 (9)
N2—C10—H10B	109.4	C8—N1—Co	119.60 (9)
C9—C10—H10B	109.4	C11—N2—C10	110.51 (10)
H10A—C10—H10B	108	C11—N2—Co	115.50 (8)
N2—C11—C12	111.06 (11)	C10—N2—Co	115.41 (9)
N2—C11—H11A	109.4	C11—N2—H100	108.3 (13)
C12—C11—H11A	109.4	C10—N2—H100	107.6 (13)
N2—C11—H11B	109.4	Co—N2—H100	98.3 (13)
C12—C11—H11B	109.4	C14—N3—C13	116.89 (11)
H11A—C11—H11B	108	C14—N3—Co	122.26 (9)
C13—C12—C11	113.66 (11)	C13—N3—Co	120.47 (8)
C13—C12—H12A	108.8	C21—O3—Co	129.83 (9)
C11—C12—H12A	108.8	C1—O1—Co	122.36 (8)
C13—C12—H12B	108.8	C20—O2—Co	119.39 (8)
C11—C12—H12B	108.8	O4—C21—O3	126.42 (13)
H12A—C12—H12B	107.7	O4—C21—C22	121.13 (12)
N3—C13—C12	112.64 (11)	O3—C21—C22	112.44 (11)
N3—C13—H13A	109.1	C21—C22—H22A	109.5
C12—C13—H13A	109.1	C21—C22—H22B	109.5
N3—C13—H13B	109.1	H22A—C22—H22B	109.5
C12—C13—H13B	109.1	C21—C22—H22C	109.5
H13A—C13—H13B	107.8	H22A—C22—H22C	109.5
N3—C14—C15	124.69 (12)	H22B—C22—H22C	109.5
N3—C14—H14	117.7
O1—C1—C2—C3	−176.09 (12)	C12—C11—N2—C10	162.20 (11)
C6—C1—C2—C3	1.06 (19)	C12—C11—N2—Co	−64.49 (13)
C1—C2—C3—C4	0.6 (2)	C9—C10—N2—C11	−170.90 (11)
C2—C3—C4—C5	−1.0 (2)	C9—C10—N2—Co	55.74 (14)
C3—C4—C5—C6	−0.4 (2)	O1—Co—N2—C11	−37.87 (9)
C4—C5—C6—C1	2.1 (2)	O3—Co—N2—C11	141.39 (9)
C4—C5—C6—C7	175.64 (13)	N1—Co—N2—C11	−129.90 (10)
O1—C1—C6—C5	174.63 (12)	N3—Co—N2—C11	48.23 (10)
C2—C1—C6—C5	−2.39 (18)	O1—Co—N2—C10	93.16 (9)
O1—C1—C6—C7	1.26 (19)	O3—Co—N2—C10	−87.59 (9)
C2—C1—C6—C7	−175.77 (12)	N1—Co—N2—C10	1.13 (9)
C5—C6—C7—N1	174.13 (13)	N3—Co—N2—C10	179.25 (9)
C1—C6—C7—N1	−12.4 (2)	C15—C14—N3—C13	−165.87 (12)
N1—C8—C9—C10	15.37 (16)	C15—C14—N3—Co	7.04 (18)
C8—C9—C10—N2	−72.21 (15)	C12—C13—N3—C14	−131.29 (13)
N2—C11—C12—C13	66.81 (15)	C12—C13—N3—Co	55.67 (14)
C11—C12—C13—N3	−60.78 (15)	O1—Co—N3—C14	−124.64 (11)
N3—C14—C15—C16	−166.80 (13)	O2—Co—N3—C14	−33.51 (11)
N3—C14—C15—C20	21.1 (2)	O3—Co—N3—C14	51.61 (11)
C20—C15—C16—C17	−2.4 (2)	N2—Co—N3—C14	142.64 (11)
C14—C15—C16—C17	−174.47 (13)	O1—Co—N3—C13	48.02 (10)
C15—C16—C17—C18	4.1 (2)	O2—Co—N3—C13	139.15 (10)
C16—C17—C18—C19	−1.8 (2)	O3—Co—N3—C13	−135.73 (10)
C17—C18—C19—C20	−2.2 (2)	N2—Co—N3—C13	−44.70 (10)
C18—C19—C20—O2	−179.00 (12)	O2—Co—O3—C21	138.39 (11)
C18—C19—C20—C15	3.77 (19)	N1—Co—O3—C21	−132.97 (11)
C16—C15—C20—O2	−178.65 (12)	N3—Co—O3—C21	48.38 (11)
C14—C15—C20—O2	−6.75 (19)	N2—Co—O3—C21	−42.86 (11)
C16—C15—C20—C19	−1.53 (18)	C2—C1—O1—Co	−153.00 (9)
C14—C15—C20—C19	170.37 (12)	C6—C1—O1—Co	30.01 (16)
C6—C7—N1—C8	169.31 (13)	O2—Co—O1—C1	49.32 (10)
C6—C7—N1—Co	−9.14 (19)	N1—Co—O1—C1	−39.25 (10)
C9—C8—N1—C7	−126.40 (13)	N3—Co—O1—C1	139.52 (10)
C9—C8—N1—Co	52.10 (14)	N2—Co—O1—C1	−129.48 (10)
O1—Co—N1—C7	28.83 (11)	C19—C20—O2—Co	150.32 (10)
O2—Co—N1—C7	−62.26 (11)	C15—C20—O2—Co	−32.66 (16)
O3—Co—N1—C7	−147.41 (11)	O1—Co—O2—C20	131.67 (9)
N2—Co—N1—C7	121.64 (11)	O3—Co—O2—C20	−47.51 (9)
O1—Co—N1—C8	−149.59 (10)	N1—Co—O2—C20	−136.34 (9)
O2—Co—N1—C8	119.32 (10)	N3—Co—O2—C20	45.62 (9)
O3—Co—N1—C8	34.17 (10)	Co—O3—C21—O4	17.4 (2)
N2—Co—N1—C8	−56.79 (10)	Co—O3—C21—C22	−162.75 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H100···O4	0.91 (2)	1.95 (2)	2.8270 (17)	160.3 (19)
C2—H2···O4^i	0.95	2.51	3.372 (2)	150
C8—H8A···O3	0.99	2.50	2.8496 (18)	100
C11—H11B···O1	0.99	2.46	2.9658 (19)	111
C13—H13A···O1	0.99	2.50	2.9183 (18)	105

Symmetry code: (i) x−1, −y+3/2, z−1/2.