Aqua-(3-formyl-2-oxidobenzoato-κO,O)(1,10-phenanthroline-κN,N')copper(II) methanol solvate.

In the structure of the title complex, [Cu(C(8)H(4)O(4))(C(12)H(8)N(2))(H(2)O)]·CH(4)O, the Cu(II) ion is penta-coordinated in a tetra-gonal-pyramidal geometry, with two O atoms of the 3-formyl-2-oxidobenzoate (3-formyl-salicylate) anion and two N atoms of 1,10-phenanthroline occupying the basal plane, and a water O atom located at the apical site. The structure displays O-H⋯O hydrogen bonding.

Related literature

For related literature, see: Erxleben & Schumacher (2001 ▶); Ma et al. (2007 ▶); Akitsu & Einaga (2006 ▶); Yu, Cui et al. (2007 ▶); Yu, Hao et al. (2006 ▶); Costes et al. (2004 ▶); Karmakar et al. (2005 ▶).

Experimental

Crystal data

[Cu(C8H4O4)(C12H8N2)(H2O)]·CH4O

M = 457.91

Triclinic,

a = 8.6714 (11) Å

b = 10.3895 (13) Å

c = 11.7617 (14) Å

α = 115.125 (2)°

β = 95.859 (2)°

γ = 93.589 (2)°

V = 947.7 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.20 mm−1

T = 296 (2) K

0.21 × 0.16 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: none

4953 measured reflections

3336 independent reflections

2336 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.100

S = 0.94

3336 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.56 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 2005 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067967/kj2080sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067967/kj2080Isup2.hkl

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

[Cu(C8H4O4)(C12H8N2)(H2O)]·CH4O	Z = 2
Mr = 457.91	F000 = 470
Triclinic, P1	Dx = 1.605 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 8.6714 (11) Å	Cell parameters from 1476 reflections
b = 10.3895 (13) Å	θ = 2.4–23.1º
c = 11.7617 (14) Å	µ = 1.20 mm−1
α = 115.125 (2)º	T = 296 (2) K
β = 95.859 (2)º	Block, green
γ = 93.589 (2)º	0.21 × 0.16 × 0.15 mm
V = 947.7 (2) Å3

Bruker APEXII CCD area-detector diffractometer	2336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.061
Monochromator: graphite	θmax = 25.0º
T = 296(2) K	θmin = 1.9º
φ and ω scans	h = −10→8
Absorption correction: none	k = −11→12
4953 measured reflections	l = −13→11
3336 independent reflections

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.100	w = 1/[σ2(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94	(Δ/σ)max < 0.001
3336 reflections	Δρmax = 0.56 e Å−3
273 parameters	Δρmin = −0.40 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Cu1	0.04891 (5)	0.15042 (5)	0.43931 (4)	0.04238 (18)
O1W	0.2655 (3)	0.2918 (3)	0.4306 (3)	0.0690 (8)
H1WA	0.3370	0.2382	0.4054	0.083*
H1WB	0.2452	0.3275	0.3785	0.083*
N1	−0.1078 (3)	0.2009 (3)	0.3305 (3)	0.0395 (7)
N2	0.0517 (3)	−0.0202 (3)	0.2729 (3)	0.0366 (7)
O1	0.0334 (3)	0.4719 (2)	0.7766 (2)	0.0541 (7)
O2	−0.0072 (3)	0.3010 (3)	0.5848 (2)	0.0518 (7)
O3	0.1798 (3)	0.0801 (2)	0.5341 (2)	0.0433 (6)
O4	0.5232 (3)	−0.0845 (3)	0.6619 (3)	0.0694 (9)
C1	0.2080 (4)	0.2978 (3)	0.7301 (3)	0.0344 (8)
C2	0.2507 (4)	0.1602 (3)	0.6484 (3)	0.0347 (8)
C3	0.3754 (4)	0.1093 (4)	0.6985 (3)	0.0364 (8)
C4	0.4531 (4)	0.1902 (4)	0.8211 (4)	0.0455 (9)
H4A	0.5349	0.1545	0.8517	0.055*
C5	0.4121 (5)	0.3205 (4)	0.8972 (4)	0.0517 (10)
H5A	0.4649	0.3738	0.9788	0.062*
C6	0.2905 (4)	0.3714 (4)	0.8503 (3)	0.0433 (9)
H6A	0.2624	0.4601	0.9025	0.052*
C7	0.0722 (4)	0.3618 (4)	0.6951 (3)	0.0377 (8)
C8	0.4236 (4)	−0.0293 (4)	0.6237 (4)	0.0480 (10)
H8A	0.3748	−0.0798	0.5404	0.058*
C9	−0.1828 (4)	0.3141 (4)	0.3596 (4)	0.0511 (10)
H9A	−0.1596	0.3876	0.4413	0.061*
C10	−0.2942 (5)	0.3298 (4)	0.2752 (4)	0.0560 (11)
H10A	−0.3451	0.4116	0.3005	0.067*
C11	−0.3287 (5)	0.2251 (4)	0.1550 (4)	0.0554 (11)
H11A	−0.4043	0.2347	0.0979	0.066*
C12	−0.2512 (4)	0.1027 (4)	0.1166 (3)	0.0429 (9)
C13	−0.2754 (5)	−0.0140 (4)	−0.0074 (4)	0.0534 (11)
H13A	−0.3494	−0.0119	−0.0695	0.064*
C14	−0.1935 (5)	−0.1267 (4)	−0.0360 (4)	0.0546 (11)
H14A	−0.2120	−0.2007	−0.1177	0.066*
C15	−0.0787 (4)	−0.1356 (4)	0.0558 (3)	0.0421 (9)
C16	0.0130 (5)	−0.2480 (4)	0.0336 (3)	0.0505 (10)
H16A	0.0007	−0.3254	−0.0461	0.061*
C17	0.1192 (5)	−0.2437 (4)	0.1277 (4)	0.0493 (10)
H17A	0.1810	−0.3178	0.1126	0.059*
C18	0.1366 (4)	−0.1285 (4)	0.2479 (3)	0.0429 (9)
H18A	0.2095	−0.1276	0.3120	0.051*
C19	−0.0538 (4)	−0.0235 (4)	0.1789 (3)	0.0362 (8)
C20	−0.1402 (4)	0.0960 (4)	0.2081 (3)	0.0373 (8)
C21	0.6449 (6)	0.4308 (6)	0.6735 (6)	0.108 (2)
H21A	0.6025	0.4468	0.7501	0.162*
H21B	0.6887	0.3416	0.6434	0.162*
H21C	0.5635	0.4275	0.6103	0.162*
O5	0.7606 (4)	0.5414 (3)	0.6979 (3)	0.0751 (9)
H5	0.8459	0.5183	0.7138	0.113*

	U11	U22	U33	U12	U13	U23
Cu1	0.0434 (3)	0.0424 (3)	0.0300 (3)	0.0188 (2)	0.00278 (19)	0.0037 (2)
O1W	0.0605 (19)	0.0671 (19)	0.092 (2)	0.0250 (16)	0.0175 (17)	0.0422 (18)
N1	0.0402 (18)	0.0358 (17)	0.0363 (17)	0.0096 (15)	0.0087 (14)	0.0085 (14)
N2	0.0324 (17)	0.0363 (17)	0.0342 (17)	0.0068 (14)	0.0089 (14)	0.0074 (14)
O1	0.0666 (19)	0.0384 (15)	0.0413 (15)	0.0236 (14)	0.0049 (14)	0.0001 (13)
O2	0.0540 (17)	0.0520 (16)	0.0321 (14)	0.0283 (14)	0.0016 (12)	0.0000 (12)
O3	0.0487 (16)	0.0346 (13)	0.0327 (14)	0.0154 (12)	−0.0007 (12)	0.0014 (11)
O4	0.0579 (19)	0.0649 (19)	0.092 (2)	0.0275 (16)	0.0107 (17)	0.0382 (18)
C1	0.036 (2)	0.0324 (19)	0.0313 (19)	0.0047 (16)	0.0042 (16)	0.0100 (16)
C2	0.034 (2)	0.036 (2)	0.034 (2)	0.0034 (17)	0.0070 (16)	0.0144 (17)
C3	0.032 (2)	0.037 (2)	0.042 (2)	0.0041 (17)	0.0067 (17)	0.0188 (18)
C4	0.036 (2)	0.051 (2)	0.055 (3)	0.0044 (19)	0.0007 (19)	0.030 (2)
C5	0.054 (3)	0.049 (2)	0.042 (2)	−0.003 (2)	−0.012 (2)	0.015 (2)
C6	0.050 (2)	0.033 (2)	0.037 (2)	0.0011 (18)	0.0020 (18)	0.0064 (17)
C7	0.041 (2)	0.034 (2)	0.032 (2)	0.0050 (17)	0.0070 (17)	0.0079 (17)
C8	0.041 (2)	0.049 (2)	0.057 (3)	0.011 (2)	0.012 (2)	0.024 (2)
C9	0.049 (2)	0.046 (2)	0.055 (3)	0.014 (2)	0.009 (2)	0.018 (2)
C10	0.050 (3)	0.054 (3)	0.068 (3)	0.019 (2)	0.008 (2)	0.029 (2)
C11	0.051 (3)	0.064 (3)	0.060 (3)	0.006 (2)	−0.003 (2)	0.038 (3)
C12	0.039 (2)	0.050 (2)	0.042 (2)	−0.0015 (19)	0.0021 (18)	0.025 (2)
C13	0.057 (3)	0.062 (3)	0.041 (2)	−0.011 (2)	−0.009 (2)	0.029 (2)
C14	0.066 (3)	0.053 (3)	0.033 (2)	−0.012 (2)	−0.001 (2)	0.010 (2)
C15	0.044 (2)	0.042 (2)	0.033 (2)	−0.0061 (19)	0.0078 (18)	0.0098 (17)
C16	0.058 (3)	0.042 (2)	0.034 (2)	−0.003 (2)	0.016 (2)	−0.0004 (19)
C17	0.054 (3)	0.036 (2)	0.048 (2)	0.0128 (19)	0.022 (2)	0.0048 (19)
C18	0.037 (2)	0.043 (2)	0.044 (2)	0.0078 (18)	0.0091 (18)	0.0141 (18)
C19	0.037 (2)	0.038 (2)	0.0274 (19)	−0.0022 (17)	0.0053 (16)	0.0089 (16)
C20	0.035 (2)	0.043 (2)	0.032 (2)	−0.0003 (18)	0.0048 (17)	0.0157 (18)
C21	0.068 (4)	0.116 (5)	0.173 (6)	0.040 (4)	0.040 (4)	0.085 (5)
O5	0.078 (2)	0.0586 (19)	0.085 (2)	0.0297 (18)	0.001 (2)	0.0276 (18)

Cu1—O1W	2.348 (3)	C8—H8A	0.9300
Cu1—O2	1.898 (2)	C9—C10	1.381 (5)
Cu1—O3	1.898 (2)	C9—H9A	0.9300
Cu1—N1	2.016 (3)	C10—C11	1.356 (5)
Cu1—N2	2.011 (3)	C10—H10A	0.9300
O1W—H1WA	0.8500	C11—C12	1.399 (5)
O1W—H1WB	0.8499	C11—H11A	0.9300
N1—C9	1.312 (4)	C12—C20	1.396 (5)
N1—C20	1.373 (4)	C12—C13	1.430 (5)
N2—C18	1.327 (4)	C13—C14	1.344 (5)
N2—C19	1.348 (4)	C13—H13A	0.9300
O1—C7	1.234 (4)	C14—C15	1.430 (5)
O2—C7	1.273 (4)	C14—H14A	0.9300
O3—C2	1.301 (4)	C15—C16	1.401 (5)
O4—C8	1.216 (4)	C15—C19	1.403 (4)
C1—C6	1.380 (5)	C16—C17	1.350 (5)
C1—C2	1.441 (4)	C16—H16A	0.9300
C1—C7	1.494 (5)	C17—C18	1.397 (5)
C2—C3	1.415 (5)	C17—H17A	0.9300
C3—C4	1.394 (5)	C18—H18A	0.9300
C3—C8	1.448 (5)	C19—C20	1.424 (5)
C4—C5	1.363 (5)	C21—O5	1.388 (5)
C4—H4A	0.9300	C21—H21A	0.9600
C5—C6	1.375 (5)	C21—H21B	0.9600
C5—H5A	0.9300	C21—H21C	0.9600
C6—H6A	0.9300	O5—H5	0.8200
O1W—Cu1—O2	93.40 (11)	C3—C8—H8A	117.6
O1W—Cu1—O3	90.04 (10)	N1—C9—C10	123.4 (4)
O1W—Cu1—N1	96.50 (11)	N1—C9—H9A	118.3
O1W—Cu1—N2	97.69 (10)	C10—C9—H9A	118.3
O2—Cu1—O3	94.32 (10)	C11—C10—C9	119.5 (4)
O2—Cu1—N1	88.77 (11)	C11—C10—H10A	120.2
O2—Cu1—N2	166.01 (11)	C9—C10—H10A	120.2
O3—Cu1—N1	172.59 (11)	C10—C11—C12	120.2 (4)
O3—Cu1—N2	94.17 (11)	C10—C11—H11A	119.9
N1—Cu1—N2	81.55 (11)	C12—C11—H11A	119.9
Cu1—O1W—H1WA	107.8	C20—C12—C11	116.4 (4)
Cu1—O1W—H1WB	112.5	C20—C12—C13	118.0 (4)
H1WA—O1W—H1WB	107.7	C11—C12—C13	125.6 (4)
C9—N1—C20	117.2 (3)	C14—C13—C12	121.4 (4)
C9—N1—Cu1	130.2 (3)	C14—C13—H13A	119.3
C20—N1—Cu1	112.5 (2)	C12—C13—H13A	119.3
C18—N2—C19	118.4 (3)	C13—C14—C15	121.6 (4)
C18—N2—Cu1	128.5 (3)	C13—C14—H14A	119.2
C19—N2—Cu1	113.0 (2)	C15—C14—H14A	119.2
C7—O2—Cu1	126.8 (2)	C16—C15—C19	116.4 (4)
C2—O3—Cu1	123.3 (2)	C16—C15—C14	125.3 (4)
C6—C1—C2	118.7 (3)	C19—C15—C14	118.3 (4)
C6—C1—C7	117.6 (3)	C17—C16—C15	120.0 (3)
C2—C1—C7	123.6 (3)	C17—C16—H16A	120.0
O3—C2—C3	118.8 (3)	C15—C16—H16A	120.0
O3—C2—C1	124.2 (3)	C16—C17—C18	120.2 (4)
C3—C2—C1	117.0 (3)	C16—C17—H17A	119.9
C4—C3—C2	120.9 (3)	C18—C17—H17A	119.9
C4—C3—C8	118.5 (3)	N2—C18—C17	121.7 (4)
C2—C3—C8	120.6 (3)	N2—C18—H18A	119.2
C5—C4—C3	121.6 (3)	C17—C18—H18A	119.2
C5—C4—H4A	119.2	N2—C19—C15	123.5 (3)
C3—C4—H4A	119.2	N2—C19—C20	116.9 (3)
C4—C5—C6	118.3 (4)	C15—C19—C20	119.6 (3)
C4—C5—H5A	120.8	N1—C20—C12	123.3 (3)
C6—C5—H5A	120.8	N1—C20—C19	115.7 (3)
C5—C6—C1	123.6 (3)	C12—C20—C19	121.0 (3)
C5—C6—H6A	118.2	O5—C21—H21A	109.5
C1—C6—H6A	118.2	O5—C21—H21B	109.5
O1—C7—O2	120.1 (3)	H21A—C21—H21B	109.5
O1—C7—C1	118.9 (3)	O5—C21—H21C	109.5
O2—C7—C1	120.9 (3)	H21A—C21—H21C	109.5
O4—C8—C3	124.8 (4)	H21B—C21—H21C	109.5
O4—C8—H8A	117.6	C21—O5—H5	109.5
O2—Cu1—N1—C9	12.7 (3)	C6—C1—C7—O2	178.7 (3)
N2—Cu1—N1—C9	−177.4 (3)	C2—C1—C7—O2	−5.4 (5)
O1W—Cu1—N1—C9	−80.5 (3)	C4—C3—C8—O4	3.6 (5)
O2—Cu1—N1—C20	−165.8 (2)	C2—C3—C8—O4	−175.6 (3)
N2—Cu1—N1—C20	4.1 (2)	C20—N1—C9—C10	2.1 (5)
O1W—Cu1—N1—C20	100.9 (2)	Cu1—N1—C9—C10	−176.3 (3)
O2—Cu1—N2—C18	−134.6 (4)	N1—C9—C10—C11	−0.8 (6)
O3—Cu1—N2—C18	−7.3 (3)	C9—C10—C11—C12	−0.5 (6)
N1—Cu1—N2—C18	178.7 (3)	C10—C11—C12—C20	0.4 (5)
O1W—Cu1—N2—C18	83.3 (3)	C10—C11—C12—C13	−179.2 (4)
O2—Cu1—N2—C19	42.0 (6)	C20—C12—C13—C14	−0.5 (5)
O3—Cu1—N2—C19	169.2 (2)	C11—C12—C13—C14	179.1 (4)
N1—Cu1—N2—C19	−4.7 (2)	C12—C13—C14—C15	0.2 (6)
O1W—Cu1—N2—C19	−100.2 (2)	C13—C14—C15—C16	−179.2 (3)
O3—Cu1—O2—C7	25.9 (3)	C13—C14—C15—C19	0.7 (5)
N2—Cu1—O2—C7	153.2 (4)	C19—C15—C16—C17	−0.6 (5)
N1—Cu1—O2—C7	−160.8 (3)	C14—C15—C16—C17	179.3 (3)
O1W—Cu1—O2—C7	−64.4 (3)	C15—C16—C17—C18	0.8 (6)
O2—Cu1—O3—C2	−27.2 (3)	C19—N2—C18—C17	0.2 (5)
N2—Cu1—O3—C2	163.9 (3)	Cu1—N2—C18—C17	176.6 (2)
O1W—Cu1—O3—C2	66.2 (3)	C16—C17—C18—N2	−0.7 (5)
Cu1—O3—C2—C3	−163.8 (2)	C18—N2—C19—C15	0.0 (5)
Cu1—O3—C2—C1	17.9 (4)	Cu1—N2—C19—C15	−176.9 (2)
C6—C1—C2—O3	178.8 (3)	C18—N2—C19—C20	−178.5 (3)
C7—C1—C2—O3	2.8 (5)	Cu1—N2—C19—C20	4.6 (4)
C6—C1—C2—C3	0.4 (5)	C16—C15—C19—N2	0.2 (5)
C7—C1—C2—C3	−175.5 (3)	C14—C15—C19—N2	−179.7 (3)
O3—C2—C3—C4	−178.9 (3)	C16—C15—C19—C20	178.6 (3)
C1—C2—C3—C4	−0.5 (5)	C14—C15—C19—C20	−1.2 (5)
O3—C2—C3—C8	0.3 (5)	C9—N1—C20—C12	−2.3 (5)
C1—C2—C3—C8	178.7 (3)	Cu1—N1—C20—C12	176.5 (3)
C2—C3—C4—C5	0.2 (5)	C9—N1—C20—C19	178.4 (3)
C8—C3—C4—C5	−179.0 (3)	Cu1—N1—C20—C19	−2.9 (4)
C3—C4—C5—C6	0.2 (5)	C11—C12—C20—N1	1.1 (5)
C4—C5—C6—C1	−0.3 (6)	C13—C12—C20—N1	−179.4 (3)
C2—C1—C6—C5	−0.1 (5)	C11—C12—C20—C19	−179.7 (3)
C7—C1—C6—C5	176.1 (3)	C13—C12—C20—C19	−0.1 (5)
Cu1—O2—C7—O1	169.4 (2)	N2—C19—C20—N1	−1.1 (4)
Cu1—O2—C7—C1	−13.8 (5)	C15—C19—C20—N1	−179.7 (3)
C6—C1—C7—O1	−4.5 (5)	N2—C19—C20—C12	179.5 (3)
C2—C1—C7—O1	171.4 (3)	C15—C19—C20—C12	0.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1i	0.82	1.89	2.703 (4)	171
O1W—H1WB···O5ii	0.85	1.93	2.747 (4)	162
O1W—H1WA···O4iii	0.85	2.00	2.844 (4)	170

Cu1—O1W	2.348 (3)
Cu1—O2	1.898 (2)
Cu1—O3	1.898 (2)
Cu1—N1	2.016 (3)
Cu1—N2	2.011 (3)

O1W—Cu1—O2	93.40 (11)
O1W—Cu1—O3	90.04 (10)
O1W—Cu1—N1	96.50 (11)
O1W—Cu1—N2	97.69 (10)
O2—Cu1—O3	94.32 (10)
O2—Cu1—N1	88.77 (11)
O2—Cu1—N2	166.01 (11)
O3—Cu1—N1	172.59 (11)
O3—Cu1—N2	94.17 (11)
N1—Cu1—N2	81.55 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1i	0.82	1.89	2.703 (4)	171
O1W—H1WB⋯O5ii	0.85	1.93	2.747 (4)	162
O1W—H1WA⋯O4iii	0.85	2.00	2.844 (4)	170

Symmetry codes: (i) ; (ii) ; (iii) .