A second polymorph of aqua-{4-chloro-2-[(pyridin-2-ylmeth-yl)imino-meth-yl]-phenolato}copper(II) nitrate mono-hydrate.

The title complex, [Cu(C(13)H(10)ClN(2)O)(H(2)O)]NO(3)·H(2)O, was obtained by the reaction of 5-chloro-salicyl-aldehyde, 2-(amino-meth-yl)pyridine and copper nitrate in methanol. The first reported polymorph of this complex was triclinic [Liang et al. (2010 ▶). Acta Cryst. E66, m40]. The present polymorph crystallized in the monoclinic space group P2(1)/c. The Cu(II) ion is in a square planar environment and is coordinated by one phenolate O, one imine N and one pyridine N atom of the tridentate Schiff base ligand and by one water O atom. In the crystal, mol-ecules are linked through inter-molecular O-H⋯O hydrogen bonds to form chains along the a axis.

Related literature

For the structures and properties of Schiff base copper(II) complexes, see: Patel et al. (2011 ▶); Creaven et al. (2010 ▶); Osowole et al. (2008 ▶). For the complex with triclinic space group P , see: Liang et al. (2010 ▶).

Experimental

Crystal data

[Cu(C13H10ClN2O)(H2O)]NO3·H2O

M = 407.26

Monoclinic,

a = 7.840 (2) Å

b = 8.815 (3) Å

c = 23.079 (3) Å

β = 99.680 (2)°

V = 1572.4 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.60 mm−1

T = 298 K

0.22 × 0.20 × 0.19 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.720, T max = 0.752

12290 measured reflections

3410 independent reflections

2647 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.089

S = 1.06

3410 reflections

233 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.48 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 and local programs.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812004564/qm2051sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812004564/qm2051Isup2.hkl

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

[Cu(C13H10ClN2O)(H2O)]NO3·H2O	F(000) = 828
Mr = 407.26	Dx = 1.720 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.840 (2) Å	Cell parameters from 3984 reflections
b = 8.815 (3) Å	θ = 2.5–26.9°
c = 23.079 (3) Å	µ = 1.60 mm−1
β = 99.680 (2)°	T = 298 K
V = 1572.4 (7) Å3	Block, blue
Z = 4	0.22 × 0.20 × 0.19 mm

Bruker SMART 1K CCD area-detector diffractometer	3410 independent reflections
Radiation source: fine-focus sealed tube	2647 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ω scans	θmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
Tmin = 0.720, Tmax = 0.752	k = −11→10
12290 measured reflections	l = −29→29

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0362P)2 + 0.669P] where P = (Fo2 + 2Fc2)/3
3410 reflections	(Δ/σ)max < 0.001
233 parameters	Δρmax = 0.39 e Å−3
3 restraints	Δρmin = −0.48 e Å−3

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	0.31780 (4)	0.86046 (4)	0.441029 (14)	0.03273 (12)
Cl1	0.30943 (12)	1.01565 (10)	0.74737 (3)	0.0561 (2)
N1	0.2244 (3)	1.0428 (2)	0.46999 (9)	0.0311 (5)
N2	0.2433 (3)	0.9578 (2)	0.36353 (9)	0.0341 (5)
N3	0.0449 (3)	0.5644 (3)	0.39668 (10)	0.0427 (6)
O1	0.3889 (3)	0.7778 (2)	0.51693 (8)	0.0387 (5)
O2	0.4383 (4)	0.6939 (3)	0.40783 (11)	0.0392 (5)
O3	0.1648 (3)	0.5200 (3)	0.37200 (10)	0.0539 (6)
O4	−0.0834 (3)	0.4839 (3)	0.39510 (12)	0.0764 (8)
O5	0.0556 (3)	0.6892 (3)	0.42285 (11)	0.0595 (6)
O6	0.6908 (3)	0.5408 (3)	0.47630 (10)	0.0499 (5)
C1	0.2878 (3)	0.9799 (3)	0.57295 (12)	0.0315 (6)
C2	0.3686 (3)	0.8378 (3)	0.56748 (11)	0.0317 (6)
C3	0.4316 (4)	0.7585 (3)	0.61943 (12)	0.0388 (7)
H3	0.4867	0.6658	0.6170	0.047*
C4	0.4142 (4)	0.8134 (3)	0.67321 (12)	0.0397 (7)
H4	0.4573	0.7583	0.7069	0.048*
C5	0.3323 (4)	0.9515 (3)	0.67803 (12)	0.0383 (7)
C6	0.2709 (4)	1.0331 (3)	0.62901 (12)	0.0380 (7)
H6	0.2169	1.1257	0.6327	0.046*
C7	0.2211 (3)	1.0744 (3)	0.52380 (12)	0.0339 (6)
H7	0.1715	1.1663	0.5317	0.041*
C8	0.1576 (4)	1.1552 (3)	0.42524 (12)	0.0383 (7)
H8A	0.2252	1.2476	0.4318	0.046*
H8B	0.0385	1.1793	0.4279	0.046*
C9	0.1674 (3)	1.0935 (3)	0.36544 (12)	0.0323 (6)
C10	0.1044 (4)	1.1749 (3)	0.31527 (13)	0.0443 (7)
H10	0.0529	1.2693	0.3177	0.053*
C11	0.1198 (4)	1.1132 (4)	0.26167 (13)	0.0486 (8)
H11	0.0773	1.1651	0.2272	0.058*
C12	0.1979 (4)	0.9748 (4)	0.25938 (13)	0.0470 (8)
H12	0.2096	0.9321	0.2234	0.056*
C13	0.2586 (4)	0.9002 (3)	0.31071 (13)	0.0420 (7)
H13	0.3122	0.8066	0.3090	0.050*
H6A	0.773 (3)	0.535 (3)	0.4574 (12)	0.045 (10)*
H2A	0.362 (5)	0.633 (4)	0.3958 (16)	0.067 (14)*
H2B	0.502 (5)	0.656 (4)	0.4284 (15)	0.047 (12)*
H6B	0.657 (5)	0.452 (2)	0.4820 (18)	0.100 (16)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0389 (2)	0.02223 (18)	0.03751 (19)	0.00418 (15)	0.00787 (14)	−0.00095 (14)
Cl1	0.0715 (6)	0.0575 (5)	0.0400 (4)	−0.0038 (4)	0.0120 (4)	−0.0117 (4)
N1	0.0343 (12)	0.0188 (11)	0.0396 (12)	0.0034 (9)	0.0045 (10)	0.0015 (9)
N2	0.0384 (13)	0.0257 (12)	0.0381 (12)	−0.0011 (10)	0.0063 (10)	0.0001 (10)
N3	0.0444 (16)	0.0418 (16)	0.0400 (13)	−0.0038 (13)	0.0014 (11)	0.0011 (12)
O1	0.0533 (12)	0.0250 (10)	0.0385 (10)	0.0094 (9)	0.0100 (9)	−0.0021 (8)
O2	0.0399 (14)	0.0312 (12)	0.0468 (13)	0.0071 (11)	0.0079 (11)	−0.0014 (11)
O3	0.0568 (14)	0.0522 (14)	0.0567 (13)	−0.0071 (11)	0.0214 (11)	−0.0186 (11)
O4	0.0560 (16)	0.082 (2)	0.095 (2)	−0.0297 (15)	0.0250 (14)	−0.0259 (16)
O5	0.0533 (14)	0.0371 (13)	0.0913 (17)	0.0026 (11)	0.0211 (13)	−0.0148 (13)
O6	0.0554 (15)	0.0354 (13)	0.0579 (14)	0.0075 (11)	0.0067 (12)	−0.0017 (11)
C1	0.0319 (15)	0.0227 (13)	0.0401 (14)	−0.0018 (11)	0.0063 (12)	−0.0035 (11)
C2	0.0319 (15)	0.0252 (14)	0.0382 (14)	−0.0022 (11)	0.0064 (11)	−0.0022 (11)
C3	0.0438 (17)	0.0255 (15)	0.0464 (16)	0.0020 (13)	0.0057 (13)	0.0011 (12)
C4	0.0437 (18)	0.0359 (16)	0.0385 (15)	−0.0040 (13)	0.0042 (13)	0.0042 (13)
C5	0.0402 (17)	0.0370 (17)	0.0390 (15)	−0.0085 (13)	0.0099 (12)	−0.0094 (13)
C6	0.0402 (17)	0.0297 (15)	0.0451 (16)	0.0001 (13)	0.0099 (13)	−0.0076 (13)
C7	0.0329 (15)	0.0230 (13)	0.0460 (16)	0.0026 (12)	0.0073 (12)	−0.0037 (12)
C8	0.0460 (17)	0.0240 (14)	0.0438 (15)	0.0078 (13)	0.0040 (13)	0.0021 (12)
C9	0.0283 (14)	0.0245 (13)	0.0429 (15)	−0.0029 (11)	0.0021 (12)	−0.0002 (12)
C10	0.0478 (19)	0.0321 (16)	0.0468 (17)	0.0032 (14)	−0.0100 (14)	0.0017 (13)
C11	0.056 (2)	0.0434 (19)	0.0400 (16)	−0.0029 (16)	−0.0088 (14)	0.0048 (14)
C12	0.053 (2)	0.0446 (19)	0.0403 (16)	−0.0076 (16)	−0.0013 (14)	−0.0066 (14)
C13	0.0471 (18)	0.0327 (16)	0.0459 (17)	0.0002 (13)	0.0074 (14)	−0.0042 (13)

Cu1—O1	1.8925 (18)	C2—C3	1.404 (4)
Cu1—N1	1.932 (2)	C3—C4	1.360 (4)
Cu1—O2	1.970 (2)	C3—H3	0.9300
Cu1—N2	1.981 (2)	C4—C5	1.389 (4)
Cl1—C5	1.735 (3)	C4—H4	0.9300
N1—C7	1.277 (3)	C5—C6	1.359 (4)
N1—C8	1.463 (3)	C6—H6	0.9300
N2—C9	1.340 (3)	C7—H7	0.9300
N2—C13	1.345 (3)	C8—C9	1.497 (4)
N3—O4	1.227 (3)	C8—H8A	0.9700
N3—O3	1.241 (3)	C8—H8B	0.9700
N3—O5	1.251 (3)	C9—C10	1.381 (4)
O1—C2	1.314 (3)	C10—C11	1.375 (4)
O2—H2A	0.81 (4)	C10—H10	0.9300
O2—H2B	0.71 (4)	C11—C12	1.371 (4)
O6—H6A	0.839 (10)	C11—H11	0.9300
O6—H6B	0.845 (10)	C12—C13	1.368 (4)
C1—C6	1.403 (4)	C12—H12	0.9300
C1—C2	1.419 (3)	C13—H13	0.9300
C1—C7	1.434 (4)
O1—Cu1—N1	94.00 (8)	C5—C4—H4	119.9
O1—Cu1—O2	89.27 (9)	C6—C5—C4	120.1 (3)
N1—Cu1—O2	171.71 (10)	C6—C5—Cl1	121.2 (2)
O1—Cu1—N2	176.94 (8)	C4—C5—Cl1	118.7 (2)
N1—Cu1—N2	83.13 (9)	C5—C6—C1	121.0 (3)
O2—Cu1—N2	93.43 (10)	C5—C6—H6	119.5
C7—N1—C8	118.4 (2)	C1—C6—H6	119.5
C7—N1—Cu1	126.06 (19)	N1—C7—C1	125.3 (2)
C8—N1—Cu1	115.50 (16)	N1—C7—H7	117.3
C9—N2—C13	118.3 (2)	C1—C7—H7	117.3
C9—N2—Cu1	114.98 (18)	N1—C8—C9	109.7 (2)
C13—N2—Cu1	126.67 (19)	N1—C8—H8A	109.7
O4—N3—O3	118.9 (3)	C9—C8—H8A	109.7
O4—N3—O5	120.7 (3)	N1—C8—H8B	109.7
O3—N3—O5	120.3 (3)	C9—C8—H8B	109.7
C2—O1—Cu1	127.32 (17)	H8A—C8—H8B	108.2
Cu1—O2—H2A	105 (3)	N2—C9—C10	122.3 (3)
Cu1—O2—H2B	115 (3)	N2—C9—C8	116.5 (2)
H2A—O2—H2B	108 (4)	C10—C9—C8	121.2 (2)
H6A—O6—H6B	109 (2)	C11—C10—C9	118.4 (3)
C6—C1—C2	119.3 (2)	C11—C10—H10	120.8
C6—C1—C7	117.2 (2)	C9—C10—H10	120.8
C2—C1—C7	123.5 (2)	C12—C11—C10	119.6 (3)
O1—C2—C3	118.7 (2)	C12—C11—H11	120.2
O1—C2—C1	123.8 (2)	C10—C11—H11	120.2
C3—C2—C1	117.5 (2)	C13—C12—C11	119.1 (3)
C4—C3—C2	121.8 (3)	C13—C12—H12	120.4
C4—C3—H3	119.1	C11—C12—H12	120.4
C2—C3—H3	119.1	N2—C13—C12	122.2 (3)
C3—C4—C5	120.2 (3)	N2—C13—H13	118.9
C3—C4—H4	119.9	C12—C13—H13	118.9

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6B···O1i	0.85 (1)	2.06 (1)	2.887 (3)	167 (3)
O2—H2B···O6	0.71 (4)	1.98 (4)	2.681 (4)	172 (4)
O2—H2A···O5	0.81 (4)	2.63 (4)	3.078 (3)	116 (3)
O2—H2A···O3	0.81 (4)	1.85 (4)	2.652 (4)	170 (4)
O6—H6A···O4ii	0.84 (1)	2.02 (1)	2.831 (3)	162 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6B⋯O1i	0.85 (1)	2.06 (1)	2.887 (3)	167 (3)
O2—H2B⋯O6	0.71 (4)	1.98 (4)	2.681 (4)	172 (4)
O2—H2A⋯O5	0.81 (4)	2.63 (4)	3.078 (3)	116 (3)
O2—H2A⋯O3	0.81 (4)	1.85 (4)	2.652 (4)	170 (4)
O6—H6A⋯O4ii	0.84 (1)	2.02 (1)	2.831 (3)	162 (3)

Symmetry codes: (i) ; (ii) .