[N-(3-Meth-oxy-2-oxidobenzyl-idene-κO)threoninato-κO,N](1,10-phenanthroline-κN,N')copper(II) hemihydrate.

In the title complex, [Cu(C(12)H(13)NO(5))(C(12)H(8)N(2))]·0.5H(2)O, the Cu(II) ion is five-coordinated by one N atom and two O atoms from a tridentate Schiff base ligand, derived from the condensation of l-threonine and o-vanillin, and two N atoms from a 1,10-phenanthroline ligand in a distorted square-pyramidal geometry. In the crystal, inter-molecular O-H⋯O hydrogen bonds form a one-dimensional left-handed helical structureextending parallel to [001]. The water molecule of crystallization shows half-occupancy.

Related literature

For general background to Schiff bases and their metal complexes, see: Chohan et al. (1998 ▶); Nath et al. (2001 ▶); Yamada (1966 ▶). For structures of related complexes with five-coordinate copper(II) derived from amino acid Schiff base ligands, see: Huang et al. (2010 ▶); Qiu et al. (2008 ▶).

Experimental

Crystal data

[Cu(C12H13NO5)(C12H8N2)]·0.5H2O

M = 503.99

Tetragonal,

a = 22.527 (6) Å

c = 10.290 (4) Å

V = 5222 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.87 mm−1

T = 293 K

0.50 × 0.15 × 0.11 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.669, T max = 0.910

13788 measured reflections

4560 independent reflections

2419 reflections with I > 2σ(I)

R int = 0.084

Refinement

R[F 2 > 2σ(F 2)] = 0.076

wR(F 2) = 0.267

S = 0.90

4560 reflections

307 parameters

511 restraints

H-atom parameters constrained

Δρmax = 0.83 e Å−3

Δρmin = −0.40 e Å−3

Absolute structure: Flack (1983 ▶), 2126 Friedel pairs

Flack parameter: −0.13 (5)

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012049/hy2419sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012049/hy2419Isup2.hkl

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

[Cu(C12H13NO5)(C12H8N2)]·0.5H2O	Dx = 1.282 Mg m−3
Mr = 503.99	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1876 reflections
Hall symbol: I 4	θ = 2.2–18.4°
a = 22.527 (6) Å	µ = 0.87 mm−1
c = 10.290 (4) Å	T = 293 K
V = 5222 (3) Å3	Block, green
Z = 8	0.50 × 0.15 × 0.11 mm
F(000) = 2080

Bruker SMART 1000 CCD diffractometer	4560 independent reflections
Radiation source: fine-focus sealed tube	2419 reflections with I > 2σ(I)
graphite	Rint = 0.084
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→20
Tmin = 0.669, Tmax = 0.910	k = −26→26
13788 measured reflections	l = −12→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.076	H-atom parameters constrained
wR(F2) = 0.267	w = 1/[σ2(Fo2) + (0.182P)2] where P = (Fo2 + 2Fc2)/3
S = 0.90	(Δ/σ)max < 0.001
4560 reflections	Δρmax = 0.83 e Å−3
307 parameters	Δρmin = −0.40 e Å−3
511 restraints	Absolute structure: Flack (1983), 2126 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.13 (5)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.87663 (4)	0.35499 (4)	0.6986 (2)	0.0480 (4)
N1	0.9319 (3)	0.3654 (4)	0.5559 (8)	0.0497 (19)
N2	0.7903 (4)	0.3312 (4)	0.5991 (9)	0.061 (2)
N3	0.8201 (4)	0.3524 (4)	0.8489 (8)	0.055 (2)
O1	0.8764 (3)	0.4423 (3)	0.7022 (10)	0.0605 (15)
O2	0.9201 (4)	0.5211 (3)	0.6114 (8)	0.082 (2)
O3	0.8996 (3)	0.3845 (3)	0.3014 (7)	0.0669 (19)
H3	0.9057	0.3985	0.2291	0.100*
O4	0.8993 (3)	0.2736 (3)	0.7261 (7)	0.061 (2)
O5	0.9025 (4)	0.1616 (3)	0.7772 (10)	0.089 (3)
O6	0.0168 (13)	0.2227 (13)	0.067 (3)	0.177 (12)	0.50
H25	0.0133	0.2266	−0.0149	0.265*	0.50
H26	0.0155	0.1854	0.0797	0.265*	0.50
C1	0.9087 (5)	0.4666 (5)	0.6146 (11)	0.063 (2)
C2	0.9336 (5)	0.4259 (5)	0.5068 (10)	0.063 (2)
H2	0.9739	0.4376	0.4815	0.075*
C3	0.8892 (5)	0.4301 (5)	0.3891 (10)	0.065 (2)
H3A	0.8493	0.4239	0.4244	0.077*
C4	0.8898 (6)	0.4907 (5)	0.3298 (12)	0.079 (3)
H4A	0.8622	0.4920	0.2588	0.118*
H4B	0.9290	0.4995	0.2984	0.118*
H4C	0.8786	0.5195	0.3940	0.118*
C5	0.9646 (5)	0.3267 (5)	0.5069 (11)	0.058 (2)
H5	0.9904	0.3385	0.4414	0.069*
C6	0.9653 (4)	0.2659 (5)	0.5439 (9)	0.059 (2)
C7	0.9331 (5)	0.2421 (4)	0.6499 (10)	0.063 (2)
C8	0.9367 (5)	0.1805 (4)	0.6756 (13)	0.070 (2)
C9	0.9703 (5)	0.1430 (5)	0.5961 (12)	0.076 (3)
H9	0.9695	0.1022	0.6104	0.091*
C10	1.0053 (5)	0.1662 (4)	0.4943 (11)	0.081 (3)
H10	1.0306	0.1420	0.4465	0.097*
C11	1.0007 (4)	0.2271 (4)	0.4679 (12)	0.070 (3)
H11	1.0216	0.2427	0.3979	0.084*
C12	0.9017 (6)	0.1000 (5)	0.8092 (16)	0.091 (3)
H12A	0.8767	0.0938	0.8835	0.137*
H12B	0.9413	0.0870	0.8288	0.137*
H12C	0.8866	0.0778	0.7368	0.137*
C13	0.7756 (5)	0.3181 (5)	0.4748 (11)	0.067 (3)
H13	0.8050	0.3210	0.4116	0.081*
C14	0.7194 (4)	0.3008 (5)	0.4365 (13)	0.078 (3)
H14	0.7113	0.2919	0.3500	0.093*
C15	0.6757 (5)	0.2969 (6)	0.5295 (13)	0.075 (3)
H15	0.6369	0.2877	0.5055	0.091*
C16	0.6892 (4)	0.3066 (5)	0.6563 (11)	0.067 (2)
C17	0.7462 (4)	0.3256 (4)	0.6924 (11)	0.0588 (18)
C18	0.7628 (5)	0.3374 (5)	0.8214 (8)	0.061 (2)
C19	0.7194 (5)	0.3332 (5)	0.9200 (8)	0.070 (2)
C20	0.7350 (5)	0.3438 (5)	1.0495 (10)	0.074 (3)
H20	0.7076	0.3398	1.1166	0.089*
C21	0.7923 (5)	0.3605 (6)	1.0725 (11)	0.079 (3)
H21	0.8035	0.3704	1.1567	0.095*
C22	0.8342 (5)	0.3630 (5)	0.9741 (10)	0.068 (3)
H22	0.8733	0.3722	0.9951	0.082*
C23	0.6463 (6)	0.3046 (6)	0.7582 (11)	0.081 (3)
H23	0.6072	0.2952	0.7375	0.097*
C24	0.6605 (5)	0.3161 (6)	0.8868 (11)	0.081 (3)
H24	0.6317	0.3127	0.9512	0.098*

	U11	U22	U33	U12	U13	U23
Cu1	0.0526 (6)	0.0562 (7)	0.0354 (5)	−0.0025 (5)	0.0009 (7)	0.0008 (7)
N1	0.052 (5)	0.059 (5)	0.038 (4)	0.007 (4)	−0.007 (4)	0.001 (4)
N2	0.069 (5)	0.069 (6)	0.046 (5)	0.002 (4)	0.000 (4)	0.009 (4)
N3	0.060 (5)	0.063 (5)	0.041 (5)	−0.003 (4)	0.002 (3)	0.006 (4)
O1	0.071 (4)	0.067 (4)	0.044 (3)	−0.002 (3)	0.004 (5)	0.002 (5)
O2	0.123 (7)	0.055 (4)	0.068 (5)	−0.028 (4)	0.019 (5)	−0.005 (4)
O3	0.093 (5)	0.071 (5)	0.036 (4)	−0.008 (4)	−0.004 (4)	0.000 (3)
O4	0.071 (4)	0.056 (4)	0.055 (6)	−0.002 (3)	0.007 (4)	−0.001 (3)
O5	0.107 (7)	0.051 (4)	0.109 (7)	−0.011 (4)	0.007 (5)	−0.002 (4)
O6	0.155 (13)	0.187 (14)	0.188 (15)	−0.014 (9)	0.013 (9)	−0.002 (9)
C1	0.073 (5)	0.067 (5)	0.050 (5)	−0.002 (5)	−0.005 (5)	0.009 (5)
C2	0.075 (5)	0.069 (5)	0.044 (5)	−0.006 (5)	−0.001 (4)	0.004 (4)
C3	0.075 (5)	0.077 (5)	0.042 (5)	−0.004 (5)	−0.001 (4)	0.010 (5)
C4	0.100 (5)	0.083 (5)	0.054 (5)	−0.001 (5)	0.003 (5)	0.010 (4)
C5	0.053 (5)	0.074 (5)	0.046 (5)	−0.005 (4)	−0.004 (4)	−0.007 (4)
C6	0.053 (5)	0.066 (5)	0.059 (5)	0.004 (4)	−0.010 (4)	−0.006 (4)
C7	0.061 (5)	0.060 (5)	0.068 (5)	0.004 (4)	−0.009 (4)	−0.003 (4)
C8	0.066 (5)	0.065 (5)	0.077 (6)	−0.001 (4)	−0.008 (4)	−0.007 (5)
C9	0.079 (5)	0.062 (5)	0.086 (6)	0.012 (4)	−0.002 (5)	−0.011 (5)
C10	0.080 (6)	0.075 (5)	0.086 (7)	0.007 (5)	−0.006 (5)	−0.014 (5)
C11	0.056 (5)	0.081 (5)	0.073 (6)	0.008 (5)	0.003 (5)	−0.011 (5)
C12	0.099 (5)	0.072 (5)	0.102 (6)	0.001 (5)	−0.002 (5)	0.003 (5)
C13	0.072 (6)	0.076 (6)	0.053 (6)	−0.001 (5)	−0.006 (5)	0.000 (5)
C14	0.085 (6)	0.082 (6)	0.065 (6)	0.000 (5)	−0.026 (5)	0.011 (5)
C15	0.072 (6)	0.081 (6)	0.073 (6)	−0.017 (5)	−0.021 (5)	0.005 (5)
C16	0.058 (4)	0.076 (5)	0.066 (5)	−0.009 (4)	−0.005 (4)	0.001 (4)
C17	0.058 (4)	0.066 (4)	0.052 (4)	−0.008 (3)	−0.002 (4)	0.005 (5)
C18	0.066 (4)	0.070 (5)	0.048 (4)	−0.007 (4)	0.004 (4)	0.010 (4)
C19	0.070 (5)	0.088 (5)	0.052 (5)	−0.001 (5)	0.013 (5)	0.005 (5)
C20	0.080 (6)	0.086 (6)	0.055 (5)	−0.004 (5)	0.016 (5)	0.007 (5)
C21	0.092 (6)	0.096 (6)	0.049 (6)	0.003 (6)	0.002 (5)	0.004 (5)
C22	0.077 (6)	0.071 (6)	0.056 (6)	−0.004 (5)	−0.004 (5)	0.007 (5)
C23	0.067 (5)	0.095 (6)	0.081 (6)	−0.009 (5)	−0.005 (4)	0.010 (5)
C24	0.073 (5)	0.098 (6)	0.073 (6)	−0.006 (5)	0.019 (5)	0.012 (5)

Cu1—N1	1.940 (8)	C6—C11	1.417 (8)
Cu1—N2	2.263 (9)	C7—C8	1.417 (8)
Cu1—N3	2.004 (8)	C8—C9	1.397 (16)
Cu1—O1	1.966 (6)	C9—C10	1.413 (9)
Cu1—O4	1.924 (7)	C9—H9	0.9300
N1—C5	1.246 (13)	C10—C11	1.403 (8)
N1—C2	1.456 (12)	C10—H10	0.9300
N2—C17	1.387 (13)	C11—H11	0.9300
N2—C13	1.354 (14)	C12—H12A	0.9600
N3—C22	1.348 (13)	C12—H12B	0.9600
N3—C18	1.364 (13)	C12—H12C	0.9600
O1—C1	1.282 (13)	C13—C14	1.383 (10)
O2—C1	1.255 (12)	C13—H13	0.9300
O3—C3	1.388 (13)	C14—C15	1.376 (11)
O3—H3	0.8200	C14—H14	0.9300
O4—C7	1.302 (12)	C15—C16	1.358 (17)
O5—C8	1.367 (15)	C15—H15	0.9300
O5—C12	1.426 (13)	C16—C17	1.403 (8)
O6—H25	0.8500	C16—C23	1.427 (16)
O6—H26	0.8501	C17—C18	1.404 (8)
C1—C2	1.544 (15)	C18—C19	1.412 (8)
C2—C3	1.573 (14)	C19—C20	1.398 (8)
C2—H2	0.9800	C19—C24	1.424 (15)
C3—C4	1.494 (15)	C20—C21	1.365 (15)
C3—H3A	0.9800	C20—H20	0.9300
C4—H4A	0.9600	C21—C22	1.386 (10)
C4—H4B	0.9600	C21—H21	0.9300
C4—H4C	0.9600	C22—H22	0.9300
C5—C6	1.422 (15)	C23—C24	1.386 (9)
C5—H5	0.9300	C23—H23	0.9300
C6—C7	1.414 (8)	C24—H24	0.9300
N1—Cu1—O4	93.2 (3)	C9—C8—O5	124.4 (9)
N1—Cu1—O1	84.0 (3)	C9—C8—C7	121.0 (11)
O4—Cu1—O1	161.9 (3)	O5—C8—C7	114.5 (10)
N1—Cu1—N3	174.7 (3)	C8—C9—C10	120.8 (11)
O4—Cu1—N3	91.6 (3)	C8—C9—H9	119.6
O1—Cu1—N3	90.8 (3)	C10—C9—H9	119.6
N1—Cu1—N2	103.8 (3)	C11—C10—C9	117.7 (11)
O4—Cu1—N2	94.0 (3)	C11—C10—H10	121.2
O1—Cu1—N2	104.1 (3)	C9—C10—H10	121.2
N3—Cu1—N2	78.2 (4)	C10—C11—C6	122.5 (10)
C5—N1—C2	119.9 (9)	C10—C11—H11	118.8
C5—N1—Cu1	126.9 (8)	C6—C11—H11	118.8
C2—N1—Cu1	113.1 (6)	O5—C12—H12A	109.5
C17—N2—C13	117.4 (9)	O5—C12—H12B	109.5
C17—N2—Cu1	108.9 (6)	H12A—C12—H12B	109.5
C13—N2—Cu1	133.5 (7)	O5—C12—H12C	109.5
C22—N3—C18	117.7 (9)	H12A—C12—H12C	109.5
C22—N3—Cu1	125.6 (7)	H12B—C12—H12C	109.5
C18—N3—Cu1	116.6 (6)	N2—C13—C14	123.6 (11)
C1—O1—Cu1	114.4 (7)	N2—C13—H13	118.2
C3—O3—H3	109.5	C14—C13—H13	118.2
C7—O4—Cu1	125.9 (6)	C15—C14—C13	118.4 (12)
C8—O5—C12	119.1 (10)	C15—C14—H14	120.8
H25—O6—H26	104.6	C13—C14—H14	120.8
O1—C1—O2	123.5 (11)	C14—C15—C16	119.8 (11)
O1—C1—C2	117.2 (9)	C14—C15—H15	120.1
O2—C1—C2	119.2 (10)	C16—C15—H15	120.1
N1—C2—C1	107.3 (8)	C15—C16—C17	120.6 (11)
N1—C2—C3	107.9 (8)	C15—C16—C23	123.3 (9)
C1—C2—C3	106.7 (9)	C17—C16—C23	115.8 (10)
N1—C2—H2	111.6	N2—C17—C16	119.9 (10)
C1—C2—H2	111.6	N2—C17—C18	116.5 (7)
C3—C2—H2	111.6	C16—C17—C18	123.5 (10)
O3—C3—C4	114.2 (9)	N3—C18—C17	119.7 (7)
O3—C3—C2	110.4 (9)	N3—C18—C19	121.4 (9)
C4—C3—C2	111.3 (9)	C17—C18—C19	118.9 (10)
O3—C3—H3A	106.8	C20—C19—C24	120.6 (9)
C4—C3—H3A	106.8	C20—C19—C18	120.0 (10)
C2—C3—H3A	106.8	C24—C19—C18	119.4 (10)
C3—C4—H4A	109.5	C19—C20—C21	116.7 (11)
C3—C4—H4B	109.5	C19—C20—H20	121.6
H4A—C4—H4B	109.5	C21—C20—H20	121.6
C3—C4—H4C	109.5	C22—C21—C20	121.9 (11)
H4A—C4—H4C	109.5	C22—C21—H21	119.1
H4B—C4—H4C	109.5	C20—C21—H21	119.1
N1—C5—C6	124.9 (10)	N3—C22—C21	122.0 (11)
N1—C5—H5	117.6	N3—C22—H22	119.0
C6—C5—H5	117.6	C21—C22—H22	119.0
C7—C6—C11	118.8 (9)	C24—C23—C16	122.6 (11)
C7—C6—C5	124.4 (8)	C24—C23—H23	118.7
C11—C6—C5	116.9 (9)	C16—C23—H23	118.7
O4—C7—C6	123.9 (8)	C23—C24—C19	119.7 (11)
O4—C7—C8	117.1 (9)	C23—C24—H24	120.1
C6—C7—C8	119.0 (10)	C19—C24—H24	120.1

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2i	0.82	2.10	2.767 (11)	138

Table 1

Selected bond lengths (Å)

Cu1—N1	1.940 (8)
Cu1—N2	2.263 (9)
Cu1—N3	2.004 (8)
Cu1—O1	1.966 (6)
Cu1—O4	1.924 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2i	0.82	2.10	2.767 (11)	138

Symmetry code: (i) .