Synthesis, crystal structures and characterizations of two homochiral coordination polymers based on a chiral reduced Schiff base ligand

Two homochiral coordination polymers based on a chiral reduced Schiff base ligand, namely poly[([mu]₅-4-{[(NR,1S)-(1-carboxyl­ato-2-phenyl­ethyl)amino]­methyl}benzoato)zinc(II)], [Zn(C₁₇H₁₅NO₄)]_n, (1), and poly[([mu]₅-4-{[(NR,1S)-(1-car­boxyl­­ato-2-phenyl­ethyl)amino]­methyl}benzoato)cobalt(II)], [Co(C₁₇H₁₅NO₄)]_n, (2), have been obtained by hydro­thermal methods and studied by single-crystal X-ray diffraction, elemental analyses, powder X-ray diffraction, thermogravimetric analysis, IR spectroscopy and fluorescence spectroscopy. Compounds (1) and (2) are isostructural and crystallize in the P2₁2₁2₁ space group. Both display a three-dimensional network structure with a one-dimensional channel, with the benzyl group of the ligand directed towards the channel. An investigation of photoluminescence properties shows that compound (1) displays a strong emission in the purple region.

S1. Introduction

In the past few decades, functional coordination compounds have attracted much attention due to their potential applications in the fields of catalysis, ion exchange, proton conductivity, inter­calation chemistry, photochemistry, gas sorption, selective separation, magnetism, electronics, nonlinear optics and materials chemistry (Yaghi et al., 2003; Kitagawa et al., 2004; Zhao et al., 2001). According to their space group, we can divide coordination compounds into two categories, viz. centrosymmetric or noncentrosymmetric (NCS) compounds. NCS compounds are of great inter­est because of their potential applications in many areas, such as pyroelectricity, ferroelectricity, and especially second-order nonlinear optics (NLO) (Evans & Lin, 2002; Jayanty et al., 2002; Prakash & Radhakrishnan, 2006). A search of the Cambridge Structural Database (Version 5.34; Allen, 2002) shows that the proportion of NCS compounds is very small [Please check rephrasing. How small is the proportion, e.g. as a percentage?]. NCS structures are difficult to obtain because inorganic–organic hybrid systems tend to arrange in opposing directions, thus forming a centrosymmetric structure. Chiral or asymmetric ligands are a good choice to obtain NCS structures (Li et al., 2010; Du et al., 2010). Thus, we have focused on reduced Schiff base ligands which have a chiral C atom. We can obtain reduced Schiff base ligands of this type by reacting amino acids, having a chiral C atom, with 4-carb­oxy­benzaldehyde to obtain the Schiff bases and then reducing the C═N bond. Up to now, to the best of our knowledge, there are still only a few NCS compounds based on reduced Schiff base ligands of this type (Yang et al., 2011; Ying, 2012; Ying & Huang, 2013). In order to study the form of the NCS compounds which are induced by reduced Schiff base ligands of this type, we have synthesized a chiral reduced Schiff base ligand formed by 4-carb­oxy­benzaldehyde with L-phenyl­alanine, namely 4-{[(1-carb­oxy-2-phenyl­ethyl)­amino]­methyl}­benzoic acid (H₂L), and two NCS compounds have been obtained, namely poly[(µ₅-4-{[(1-carboxyl­ato-2-phenyl­ethyl)­amino]­methyl}­benzoato)zinc(II)], (1), and poly[(µ₅-4-{[(1-carboxyl­ato-2-phenyl­ethyl)­amino]­methyl}­benzoato)cobalt(II)], (2). Herein, we report their syntheses, characterization and crystal structures.

S2. Experimental

S2.1. Synthesis and crystallization

H₂L was synthesized according to the previously described procedure (Das & Bharadwaj, 2009, 2010). A mixture of KOH (50 mmol, 2.80 g) and L-phenyl­alanine (50 mmol, 8.25 g) in CH₃OH (50 ml) was stirred for 30 min at room temperature. A mixture of 4-carb­oxy­benzaldehyde (50 mmol, 7.50 g) and KOH (50 mmol, 2.80 g) in CH₃OH (50 ml) was also stirred for 30 min at room temperature, and then the latter was added slowly to the former. The resulting solution was refluxed for 6 h then cooled in an ice bath, and excess NaBH₄ was added. After 30 min, the solution was acidified with concentrated HCl to a pH of 5.0. The resulting solid was filtered off, washed with water and ethanol, and recrystallized from water–ethanol (1:1 v/v) (yield 80%). ESI–MS (methanol) m/z: 299.9 [M + H]⁺.

A mixture of Zn(NO₃)₂.6H₂O (0.060 g, 0.2 mmol), H₂L (0.060 g, 0.1 mmol), di­methyl­formamide (1 ml), EtOH (4 ml) and deionized water (4 ml) was sealed in a steel bomb equipped with a Teflon liner (15 ml) and then heated at 383 K for 3 d. White [Colourless in CIF tables - please clarify] block-shaped crystals of compound (1) were recovered in ca 30% yield based on the H2L ligand. Elemental analysis found for (1), C₁₇H₁₅NO₄Zn: C 56.15, H 4.04, N 3.83%; calculated: C 56.25, H 4.14, N 3.86%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3314 (m), 2939 (m), 1630 (s), 1606 (s), 1556 (s), 1398 (s), 1323 (m), 1251 (m), 1207 (m), 1175 (m), 1107 (m), 1083 (m), 1017 (m), 950(m), 891 (m), 858 (s), 828 (m), 799 (m).

The synthesis of (2) was similar to (1), but using Co(NO₃)₂.6H₂O (0.059 g, 0.2 mmol) in place of Zn(NO₃)₂.6H₂O. Pink block-shaped crystals of compound (2) were recovered in ca 25% yield based on the H2L ligand. Elemental analysis found for (2), C₁₇H₁₅CoNO₄: C 57.19, H 4.25, N 3.88%; calculated: C 57.27, H 4.21, N 3.93%. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3308 (m), 2939 (m), 1627 (s), 1601 (s), 1555 (s), 1401 (s), 1324 (m), 1252 (m), 1208 (m), 1176 (m), 1105 (m), 1083 (m), 1018 (m), 950 (m), 894 (m), 859 (s), 828 (m), 799 (m).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were generated geometrically, with C—H = 0.93–0.98 Å, O—H = 0.82 Å and N—H = 0.91 Å, and refined in the riding-model approximation, with U_iso(H) = 1.2U_eq(C), 1.5U_eq(O) and 1.2 U_eq(N).

S3. Results and discussion

Compounds (1) and (2) are isostructural. The structure of (1) will be discussed in detail as an example. As shown in Fig. 1, (1) contains one Zn^II cation and an L anion in its asymmetric unit. The Zn^II cations are six-coordinated by five O atoms and one N atom from five L anions in a distorted o­cta­hedral geometry. The Zn—O distances range from 2.052 (3) to 2.229 (4) Å and the Zn—N distance is 2.208 (4) Å (Table 2). The reduced Schiff base ligand is penta­dentate. The four O atoms in the two COO^- groups of the reduced Schiff base ligand bridge five Zn^II anions, while one of these COO^- O atoms and an N atom chelate a Zn^II cation. By the bridging of the Schiff base ligands, a three-dimensional framework structure with a one-dimensional channel is formed (Fig. 2). There are two kinds of one-dimensional channel in the three-dimensional framework and these are occupied by the benzyl groups.

The simulated and experimental powder X-ray diffraction (PXRD) patterns of (1) and (2) are in good agreement with each other (Fig. 3), indicating the phase purity of the products. The thermal behaviour of (1) and (2) was studied to reveal their thermal stability. The thermogravimetric analysis (TGA) curves of (1) and (2) are similar (Fig. 4). Both compounds are stable to 673 K. The solid-state photoluminescent spectra of compound (1) at room temperature are depicted in Fig. 5. Compound (1) exhibits an emission peak at 415 nm upon excitation at 313 nm. These bands are probably generated from intra-ligand luminescent transitions (Yam & Lo, 1999), and suggest that these types of compound would be good candidates as potential photoactive materials.

Related literature

For related literature, see: Das & Bharadwaj (2009, 2010); Du et al. (2010); Evans & Lin (2002); Jayanty et al. (2002); Kitagawa et al. (2004); Li et al. (2010); Prakash & Radhakrishnan (2006); Yaghi et al. (2003); Yam & Lo (1999); Yang et al. (2011); Ying (2012); Ying & Huang (2013); Zhao et al. (2001).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of compound (1), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The structure of (2) is analogous. [Symmetry codes: (A) x - 1/2, -y + 3/2, -z + 2; (B) x - 1, y, z; (C) -x + 5/2, -y + 2, z + 1/2; (D) -x + 2, y - 1/2, -z + 3/2; (E) x + 1/2, -y + 3/2, -z + 2; (F) x + 1, y, z; (G) -x + 5/2, -y + 2, z - 1/2; (H) -x + 2, y + 1/2, -z + 3/2.]
	Fig. 2. A view of the structure of (1), down the a axis. The structure of (2) is analogous. H atoms and solvent water molecules [There are none?] have been omitted for clarity.
	Fig. 3. Simulated and experimental PXRD patterns of compounds (1) and (2).
	Fig. 4. The TGA curves of compounds (1) and (2).
	Fig. 5. The solid-state photoluminescent spectra of compound (1).

(1) poly[(µ₅-4-{[(1-carboxylato-2-phenylethyl)amino]methyl}benzoato)zinc(II)]

Crystal data

[Zn(C17H15NO4)]	Z = 4
Mr = 362.67	F(000) = 744
Orthorhombic, P212121	Dx = 1.564 Mg m^−3
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 5.6649 (11) Å	µ = 1.61 mm^−1
b = 14.196 (3) Å	T = 123 K
c = 19.148 (4) Å	Prism, colourless
V = 1539.9 (5) Å^3	0.10 × 0.09 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer	2901 independent reflections
Radiation source: fine-focus sealed tube	2069 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −6→6
Tmin = 0.855, Tmax = 0.882	k = −16→17
5970 measured reflections	l = −23→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0124P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.84	(Δ/σ)max = 0.019
2901 reflections	Δρmax = 0.87 e Å^−3
208 parameters	Δρmin = −0.69 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1184 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

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
Zn1	0.93840 (11)	0.81450 (4)	0.97733 (3)	0.01628 (16)
O4	1.1600 (6)	1.2257 (2)	0.6025 (2)	0.0198 (10)
O3	1.4335 (7)	1.1202 (2)	0.56522 (18)	0.0192 (9)
O2	1.6289 (6)	0.8897 (2)	0.9778 (2)	0.0199 (9)
O1	1.3224 (6)	0.7936 (2)	0.95729 (19)	0.0173 (10)
N1	1.0484 (8)	0.9269 (2)	0.9046 (2)	0.0152 (10)
H1AA	0.9506	0.9772	0.9101	0.018*
C14	1.2162 (9)	1.0872 (3)	0.6676 (3)	0.0162 (13)
C5	1.0150 (9)	1.1805 (3)	0.9464 (3)	0.0286 (15)
H5A	0.9099	1.1581	0.9799	0.034*
C13	1.3652 (10)	1.0127 (3)	0.6847 (3)	0.0206 (15)
H13A	1.5043	1.0035	0.6599	0.025*
C7	1.2846 (9)	1.0430 (3)	0.9722 (3)	0.0224 (14)
H7A	1.1683	1.0329	1.0086	0.027*
H7B	1.4372	1.0507	0.9944	0.027*
C9	1.4238 (11)	0.8738 (3)	0.9563 (3)	0.0169 (13)
C4	1.2241 (10)	1.1320 (3)	0.9331 (3)	0.0205 (14)
C15	1.0134 (9)	1.0996 (3)	0.7055 (3)	0.0210 (15)
H15A	0.9134	1.1495	0.6949	0.025*
C12	1.3064 (10)	0.9525 (4)	0.7386 (3)	0.0220 (14)
H12A	1.4084	0.9036	0.7501	0.026*
C10	1.0321 (10)	0.8937 (3)	0.8318 (3)	0.0219 (14)
H10A	0.8714	0.8731	0.8234	0.026*
H10B	1.1335	0.8391	0.8268	0.026*
C16	0.9548 (11)	1.0382 (3)	0.7598 (3)	0.0227 (13)
H16A	0.8170	1.0482	0.7851	0.027*
C17	1.2740 (10)	1.1505 (4)	0.6065 (3)	0.0194 (14)
C11	1.0973 (11)	0.9636 (3)	0.7762 (3)	0.0183 (13)
C8	1.2920 (9)	0.9553 (3)	0.9244 (3)	0.0167 (13)
H8A	1.3749	0.9732	0.8815	0.020*
C6	0.9639 (12)	1.2631 (4)	0.9092 (3)	0.0367 (17)
H6A	0.8237	1.2951	0.9178	0.044*
C2	1.3243 (12)	1.2491 (4)	0.8479 (4)	0.046 (2)
H2A	1.4302	1.2718	0.8149	0.056*
C3	1.3751 (10)	1.1679 (3)	0.8838 (3)	0.0339 (17)
H3A	1.5156	1.1365	0.8745	0.041*
C1	1.1186 (12)	1.2968 (4)	0.8605 (4)	0.046 (2)
H1A	1.0844	1.3517	0.8360	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0173 (3)	0.0173 (3)	0.0142 (3)	−0.0011 (3)	0.0001 (4)	0.0005 (3)
O4	0.030 (2)	0.0121 (18)	0.017 (3)	0.0023 (17)	0.004 (2)	−0.0006 (17)
O3	0.017 (2)	0.0186 (17)	0.022 (2)	0.003 (2)	0.002 (2)	0.0034 (16)
O2	0.019 (2)	0.0233 (18)	0.018 (2)	−0.0038 (15)	−0.002 (2)	0.001 (2)
O1	0.020 (2)	0.0134 (19)	0.018 (3)	−0.0028 (16)	0.0000 (18)	−0.0004 (15)
N1	0.020 (3)	0.014 (2)	0.012 (3)	0.003 (2)	−0.002 (2)	0.0010 (18)
C14	0.015 (3)	0.017 (3)	0.016 (4)	0.001 (2)	0.000 (3)	0.001 (3)
C5	0.027 (4)	0.026 (3)	0.032 (4)	0.000 (3)	−0.001 (3)	−0.006 (3)
C13	0.027 (4)	0.022 (3)	0.013 (4)	−0.001 (3)	0.009 (3)	0.003 (3)
C7	0.025 (3)	0.016 (3)	0.026 (4)	0.001 (2)	−0.008 (3)	−0.001 (3)
C9	0.022 (3)	0.021 (3)	0.007 (3)	0.007 (3)	0.009 (3)	0.003 (2)
C4	0.023 (4)	0.012 (3)	0.026 (4)	−0.003 (3)	0.000 (3)	0.001 (3)
C15	0.017 (4)	0.019 (3)	0.026 (4)	0.006 (2)	−0.001 (3)	0.007 (3)
C12	0.024 (3)	0.021 (3)	0.021 (4)	0.002 (3)	−0.001 (3)	0.004 (3)
C10	0.027 (4)	0.022 (3)	0.017 (3)	−0.005 (3)	−0.001 (3)	−0.003 (2)
C16	0.017 (3)	0.027 (3)	0.023 (4)	0.002 (3)	0.001 (3)	0.004 (3)
C17	0.028 (4)	0.014 (3)	0.016 (4)	−0.009 (3)	0.000 (3)	0.000 (3)
C11	0.022 (4)	0.017 (3)	0.016 (3)	−0.005 (3)	0.000 (3)	0.003 (2)
C8	0.021 (3)	0.015 (3)	0.015 (4)	−0.005 (2)	−0.001 (3)	0.001 (3)
C6	0.036 (4)	0.027 (3)	0.046 (5)	0.016 (3)	−0.010 (4)	−0.007 (3)
C2	0.047 (5)	0.034 (4)	0.058 (6)	0.001 (4)	0.012 (4)	0.018 (4)
C3	0.026 (4)	0.025 (3)	0.050 (5)	−0.005 (3)	0.000 (3)	0.003 (3)
C1	0.060 (5)	0.035 (4)	0.042 (5)	−0.004 (4)	−0.017 (4)	0.013 (3)

Geometric parameters (Å, º)

Zn1—O3^i	2.054 (3)	C13—H13A	0.9300
Zn1—O4^ii	2.058 (4)	C7—C4	1.508 (7)
Zn1—O2^iii	2.053 (3)	C7—C8	1.545 (7)
Zn1—O1^iv	2.086 (3)	C7—H7A	0.9700
Zn1—N1	2.208 (4)	C7—H7B	0.9700
Zn1—O1	2.229 (4)	C9—C8	1.506 (6)
O4—C17	1.251 (6)	C4—C3	1.372 (7)
O4—Zn1^v	2.058 (4)	C15—C16	1.396 (6)
O3—C17	1.275 (6)	C15—H15A	0.9300
O3—Zn1^vi	2.054 (3)	C12—C11	1.395 (7)
O2—C9	1.253 (6)	C12—H12A	0.9300
O2—Zn1^vii	2.053 (3)	C10—C11	1.501 (7)
O1—C9	1.275 (6)	C10—H10A	0.9700
O1—Zn1^viii	2.086 (3)	C10—H10B	0.9700
N1—C10	1.474 (6)	C16—C11	1.369 (6)
N1—C8	1.487 (6)	C16—H16A	0.9300
N1—H1AA	0.9100	C8—H8A	0.9800
C14—C15	1.370 (7)	C6—C1	1.367 (8)
C14—C13	1.392 (6)	C6—H6A	0.9300
C14—C17	1.511 (7)	C2—C1	1.369 (8)
C5—C4	1.393 (6)	C2—C3	1.372 (7)
C5—C6	1.402 (7)	C2—H2A	0.9300
C5—H5A	0.9300	C3—H3A	0.9300
C13—C12	1.380 (7)	C1—H1A	0.9300
O3^i—Zn1—O4^ii	168.70 (13)	O1—C9—C8	118.0 (5)
O3^i—Zn1—O2^iii	93.64 (15)	C3—C4—C5	118.2 (5)
O4^ii—Zn1—O2^iii	95.20 (15)	C3—C4—C7	120.8 (5)
O3^i—Zn1—O1^iv	87.21 (14)	C5—C4—C7	121.0 (5)
O4^ii—Zn1—O1^iv	84.83 (13)	C14—C15—C16	120.9 (5)
O2^iii—Zn1—O1^iv	96.34 (14)	C14—C15—H15A	119.6
O3^i—Zn1—N1	95.23 (14)	C16—C15—H15A	119.6
O4^ii—Zn1—N1	92.91 (15)	C13—C12—C11	121.4 (5)
O2^iii—Zn1—N1	82.44 (15)	C13—C12—H12A	119.3
O1^iv—Zn1—N1	177.33 (16)	C11—C12—H12A	119.3
O3^i—Zn1—O1	81.74 (14)	N1—C10—C11	116.3 (4)
O4^ii—Zn1—O1	93.14 (15)	N1—C10—H10A	108.2
O2^iii—Zn1—O1	154.67 (13)	C11—C10—H10A	108.2
O1^iv—Zn1—O1	108.22 (11)	N1—C10—H10B	108.2
N1—Zn1—O1	73.28 (15)	C11—C10—H10B	108.2
C17—O4—Zn1^v	135.1 (4)	H10A—C10—H10B	107.4
C17—O3—Zn1^vi	127.4 (3)	C11—C16—C15	120.9 (5)
C9—O2—Zn1^vii	134.1 (3)	C11—C16—H16A	119.5
C9—O1—Zn1^viii	121.6 (4)	C15—C16—H16A	119.5
C9—O1—Zn1	108.9 (3)	O4—C17—O3	128.0 (5)
Zn1^viii—O1—Zn1	107.59 (15)	O4—C17—C14	116.3 (5)
C10—N1—C8	112.7 (4)	O3—C17—C14	115.7 (5)
C10—N1—Zn1	110.3 (3)	C16—C11—C12	118.0 (5)
C8—N1—Zn1	107.3 (3)	C16—C11—C10	122.0 (5)
C10—N1—H1AA	108.8	C12—C11—C10	120.0 (5)
C8—N1—H1AA	108.8	N1—C8—C9	110.8 (4)
Zn1—N1—H1AA	108.8	N1—C8—C7	110.1 (4)
C15—C14—C13	118.8 (5)	C9—C8—C7	113.1 (4)
C15—C14—C17	121.0 (5)	N1—C8—H8A	107.5
C13—C14—C17	120.2 (5)	C9—C8—H8A	107.5
C4—C5—C6	119.7 (6)	C7—C8—H8A	107.5
C4—C5—H5A	120.1	C1—C6—C5	120.5 (6)
C6—C5—H5A	120.2	C1—C6—H6A	119.8
C12—C13—C14	120.0 (5)	C5—C6—H6A	119.8
C12—C13—H13A	120.0	C1—C2—C3	120.4 (7)
C14—C13—H13A	120.0	C1—C2—H2A	119.8
C4—C7—C8	112.8 (5)	C3—C2—H2A	119.8
C4—C7—H7A	109.0	C4—C3—C2	121.7 (6)
C8—C7—H7A	109.0	C4—C3—H3A	119.1
C4—C7—H7B	109.0	C2—C3—H3A	119.1
C8—C7—H7B	109.0	C6—C1—C2	119.5 (6)
H7A—C7—H7B	107.8	C6—C1—H1A	120.2
O2—C9—O1	125.0 (5)	C2—C1—H1A	120.2
O2—C9—C8	117.0 (4)

Symmetry codes: (i) −x+5/2, −y+2, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) x−1, y, z; (iv) x−1/2, −y+3/2, −z+2; (v) −x+2, y+1/2, −z+3/2; (vi) −x+5/2, −y+2, z−1/2; (vii) x+1, y, z; (viii) x+1/2, −y+3/2, −z+2.

(2) Poly[(µ₅-4-{[(1-carboxylato-2-phenylethyl)amino]methyl}benzoato)cobalt(II)]

Crystal data

[Co(C17H15NO4)]	Z = 4
Mr = 356.23	F(000) = 732
Orthorhombic, P212121	Dx = 1.535 Mg m^−3
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 5.6619 (15) Å	µ = 1.13 mm^−1
b = 14.198 (4) Å	T = 123 K
c = 19.180 (5) Å	Prism, pink
V = 1541.8 (7) Å^3	0.07 × 0.06 × 0.05 mm

Data collection

Bruker APEX CCD area-detector diffractometer	3211 independent reflections
Radiation source: fine-focus sealed tube	2678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.093
ω scans	θmax = 27.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −5→7
Tmin = 0.925, Tmax = 0.946	k = −18→17
7783 measured reflections	l = −24→22

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.077	H-atom parameters constrained
wR(F^2) = 0.174	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 7.5189P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3211 reflections	Δρmax = 0.64 e Å^−3
208 parameters	Δρmin = −1.13 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 1294 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (5)

Special details

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. 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.

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

	x	y	z	Uiso*/Ueq
Co1	0.94051 (19)	0.81432 (7)	0.97654 (5)	0.0124 (2)
O4	1.1627 (11)	1.2274 (4)	0.6035 (3)	0.0183 (13)
O3	1.4322 (12)	1.1209 (3)	0.5653 (2)	0.0189 (12)
O2	1.6246 (9)	0.8885 (4)	0.9791 (3)	0.0205 (12)
O1	1.3182 (10)	0.7941 (3)	0.9578 (2)	0.0127 (12)
N1	1.0482 (14)	0.9270 (4)	0.9047 (3)	0.0178 (14)
H1AA	0.9505	0.9773	0.9103	0.021*
C14	1.2189 (14)	1.0874 (5)	0.6690 (4)	0.0130 (16)
C5	1.0161 (15)	1.1799 (6)	0.9469 (4)	0.0246 (19)
H5A	0.9107	1.1574	0.9801	0.029*
C13	1.3724 (16)	1.0125 (5)	0.6851 (4)	0.0203 (19)
H13A	1.5118	1.0037	0.6603	0.024*
C7	1.2852 (15)	1.0425 (5)	0.9722 (4)	0.0214 (17)
H7A	1.1713	1.0320	1.0092	0.026*
H7B	1.4391	1.0505	0.9936	0.026*
C9	1.4232 (15)	0.8735 (5)	0.9570 (3)	0.0135 (16)
C4	1.2212 (15)	1.1313 (5)	0.9340 (4)	0.0183 (17)
C15	1.0147 (15)	1.1005 (6)	0.7066 (4)	0.0194 (19)
H15A	0.9153	1.1507	0.6961	0.023*
C12	1.3103 (16)	0.9522 (6)	0.7388 (4)	0.0198 (18)
H12A	1.4108	0.9026	0.7499	0.024*
C10	1.0310 (16)	0.8931 (5)	0.8319 (4)	0.0186 (17)
H10A	0.8684	0.8752	0.8229	0.022*
H10B	1.1267	0.8367	0.8275	0.022*
C16	0.9566 (17)	1.0392 (5)	0.7600 (4)	0.0218 (17)
H16A	0.8184	1.0482	0.7854	0.026*
C17	1.2791 (14)	1.1512 (5)	0.6076 (4)	0.0150 (16)
C11	1.1080 (15)	0.9630 (6)	0.7757 (4)	0.0155 (17)
C8	1.2915 (14)	0.9546 (5)	0.9243 (4)	0.0133 (15)
H8A	1.3751	0.9721	0.8815	0.016*
C6	0.9636 (19)	1.2630 (6)	0.9105 (5)	0.030 (2)
H6A	0.8240	1.2952	0.9196	0.037*
C2	1.324 (2)	1.2500 (7)	0.8476 (6)	0.041 (3)
H2A	1.4278	1.2733	0.8142	0.050*
C3	1.3786 (15)	1.1671 (6)	0.8837 (5)	0.027 (2)
H3A	1.5191	1.1356	0.8744	0.032*
C1	1.1190 (19)	1.2964 (6)	0.8616 (5)	0.038 (3)
H1A	1.0837	1.3515	0.8375	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0142 (5)	0.0110 (4)	0.0120 (4)	−0.0006 (5)	−0.0003 (4)	0.0008 (4)
O4	0.027 (4)	0.011 (3)	0.018 (3)	0.007 (2)	0.000 (2)	−0.007 (2)
O3	0.024 (3)	0.013 (2)	0.020 (3)	0.004 (3)	0.004 (3)	0.001 (2)
O2	0.016 (3)	0.019 (3)	0.026 (3)	−0.002 (2)	−0.003 (3)	−0.002 (3)
O1	0.014 (3)	0.013 (3)	0.011 (2)	−0.004 (2)	−0.0016 (19)	−0.0016 (18)
N1	0.020 (4)	0.013 (3)	0.021 (3)	−0.001 (3)	−0.006 (3)	0.004 (2)
C14	0.015 (4)	0.009 (3)	0.015 (4)	−0.004 (3)	0.000 (3)	0.003 (3)
C5	0.021 (5)	0.026 (4)	0.027 (4)	0.002 (4)	0.002 (3)	0.001 (4)
C13	0.023 (5)	0.014 (4)	0.024 (4)	−0.004 (3)	0.001 (3)	0.001 (3)
C7	0.029 (5)	0.016 (4)	0.019 (4)	−0.003 (3)	−0.002 (4)	0.004 (4)
C9	0.016 (4)	0.012 (3)	0.013 (3)	−0.007 (3)	−0.005 (3)	−0.005 (3)
C4	0.022 (5)	0.007 (4)	0.026 (4)	−0.005 (3)	−0.008 (3)	0.003 (3)
C15	0.016 (5)	0.023 (4)	0.020 (4)	0.003 (3)	0.000 (3)	0.006 (3)
C12	0.025 (5)	0.015 (4)	0.019 (4)	0.003 (4)	−0.003 (3)	0.002 (3)
C10	0.019 (5)	0.015 (4)	0.022 (4)	−0.003 (3)	0.002 (3)	0.000 (3)
C16	0.020 (5)	0.024 (4)	0.022 (4)	0.003 (4)	0.005 (4)	0.004 (3)
C17	0.013 (4)	0.014 (4)	0.018 (4)	0.005 (3)	−0.004 (3)	−0.001 (3)
C11	0.012 (5)	0.022 (4)	0.012 (3)	−0.005 (3)	−0.001 (3)	0.003 (3)
C8	0.012 (4)	0.012 (4)	0.016 (3)	0.003 (3)	−0.001 (3)	0.003 (3)
C6	0.026 (5)	0.026 (4)	0.039 (5)	0.012 (4)	−0.006 (4)	0.002 (4)
C2	0.039 (7)	0.032 (5)	0.054 (6)	−0.005 (5)	0.000 (5)	0.020 (5)
C3	0.012 (5)	0.027 (5)	0.042 (5)	−0.007 (4)	0.003 (3)	0.012 (4)
C1	0.045 (7)	0.021 (5)	0.047 (6)	0.001 (4)	−0.012 (5)	0.009 (4)

Geometric parameters (Å, º)

Co1—O3^i	2.065 (5)	C13—H13A	0.9300
Co1—O2^ii	2.076 (5)	C7—C4	1.502 (10)
Co1—O4^iii	2.055 (5)	C7—C8	1.550 (10)
Co1—O1^iv	2.106 (5)	C7—H7A	0.9700
Co1—N1	2.198 (6)	C7—H7B	0.9700
Co1—O1	2.187 (6)	C9—C8	1.509 (10)
O4—C17	1.269 (9)	C4—C3	1.408 (11)
O4—Co1^v	2.055 (5)	C15—C16	1.383 (10)
O3—C17	1.262 (9)	C15—H15A	0.9300
O3—Co1^vi	2.065 (5)	C12—C11	1.356 (12)
O2—C9	1.235 (9)	C12—H12A	0.9300
O2—Co1^vii	2.076 (5)	C10—C11	1.529 (10)
O1—C9	1.274 (8)	C10—H10A	0.9700
O1—Co1^viii	2.106 (5)	C10—H10B	0.9700
N1—C10	1.480 (9)	C16—C11	1.413 (11)
N1—C8	1.481 (11)	C16—H16A	0.9300
N1—H1AA	0.9100	C8—H8A	0.9800
C14—C15	1.376 (11)	C6—C1	1.372 (14)
C14—C13	1.408 (11)	C6—H6A	0.9300
C14—C17	1.524 (10)	C2—C1	1.362 (15)
C5—C4	1.373 (11)	C2—C3	1.399 (12)
C5—C6	1.402 (11)	C2—H2A	0.9300
C5—H5A	0.9300	C3—H3A	0.9300
C13—C12	1.384 (11)	C1—H1A	0.9300
O3^i—Co1—O2^ii	93.2 (2)	O1—C9—C8	116.7 (7)
O3^i—Co1—O4^iii	169.4 (2)	C3—C4—C5	118.5 (7)
O2^ii—Co1—O4^iii	94.4 (2)	C3—C4—C7	118.9 (8)
O3^i—Co1—O1^iv	87.0 (2)	C5—C4—C7	122.6 (8)
O2^ii—Co1—O1^iv	94.2 (2)	C14—C15—C16	120.2 (8)
O4^iii—Co1—O1^iv	85.1 (2)	C14—C15—H15A	119.9
O3^i—Co1—N1	95.5 (2)	C16—C15—H15A	119.9
O2^ii—Co1—N1	83.4 (3)	C13—C12—C11	122.2 (8)
O4^iii—Co1—N1	92.7 (2)	C13—C12—H12A	118.9
O1^iv—Co1—N1	176.6 (3)	C11—C12—H12A	118.9
O3^i—Co1—O1	81.5 (2)	N1—C10—C11	115.7 (6)
O2^ii—Co1—O1	155.9 (2)	N1—C10—H10A	108.3
O4^iii—Co1—O1	94.4 (2)	C11—C10—H10A	108.3
O1^iv—Co1—O1	108.89 (17)	N1—C10—H10B	108.3
N1—Co1—O1	73.8 (2)	C11—C10—H10B	108.3
C17—O4—Co1^v	134.8 (5)	H10A—C10—H10B	107.4
C17—O3—Co1^vi	128.1 (5)	C11—C16—C15	119.7 (8)
C9—O2—Co1^vii	134.4 (5)	C11—C16—H16A	120.1
C9—O1—Co1^viii	120.0 (5)	C15—C16—H16A	120.1
C9—O1—Co1	110.0 (5)	O4—C17—O3	127.4 (7)
Co1^viii—O1—Co1	108.6 (2)	O4—C17—C14	115.9 (7)
C10—N1—C8	112.8 (7)	O3—C17—C14	116.6 (6)
C10—N1—Co1	109.6 (4)	C16—C11—C12	119.2 (7)
C8—N1—Co1	106.9 (4)	C16—C11—C10	118.4 (7)
C10—N1—H1AA	109.1	C12—C11—C10	122.4 (7)
C8—N1—H1AA	109.1	N1—C8—C9	111.3 (6)
Co1—N1—H1AA	109.1	N1—C8—C7	110.0 (6)
C15—C14—C13	120.4 (7)	C9—C8—C7	112.3 (6)
C15—C14—C17	120.9 (7)	N1—C8—H8A	107.7
C13—C14—C17	118.7 (7)	C9—C8—H8A	107.7
C4—C5—C6	120.9 (8)	C7—C8—H8A	107.7
C4—C5—H5A	119.6	C1—C6—C5	119.7 (9)
C6—C5—H5A	119.6	C1—C6—H6A	120.2
C12—C13—C14	118.3 (8)	C5—C6—H6A	120.2
C12—C13—H13A	120.9	C1—C2—C3	119.8 (9)
C14—C13—H13A	120.9	C1—C2—H2A	120.1
C4—C7—C8	113.1 (7)	C3—C2—H2A	120.1
C4—C7—H7A	109.0	C4—C3—C2	120.2 (8)
C8—C7—H7A	109.0	C4—C3—H3A	119.9
C4—C7—H7B	109.0	C2—C3—H3A	119.9
C8—C7—H7B	109.0	C6—C1—C2	120.9 (9)
H7A—C7—H7B	107.8	C6—C1—H1A	119.5
O2—C9—O1	125.4 (7)	C2—C1—H1A	119.5
O2—C9—C8	117.8 (6)

Symmetry codes: (i) −x+5/2, −y+2, z+1/2; (ii) x−1, y, z; (iii) −x+2, y−1/2, −z+3/2; (iv) x−1/2, −y+3/2, −z+2; (v) −x+2, y+1/2, −z+3/2; (vi) −x+5/2, −y+2, z−1/2; (vii) x+1, y, z; (viii) x+1/2, −y+3/2, −z+2.