Diaqua-(6-bromo-picolinato-κN,O)(nitrato-κO,O)copper(II).

In the monomeric title complex, [Cu(C(6)H(3)BrNO(2))(NO(3))(H(2)O)(2)], the Cu(II) ion is coordinated by a bidentate 6-bromo-picolinate ion, one nitrate ion and two water mol-ecules in a geometry inter-mediate between five- and six-coordinate. Conventional O-H⋯O hydrogen bonds link the complex mol-ecules, forming layers parallel to the ab plane.

Related literature

For general background to copper complexes with low-dimensionality synthesized by our group, see: Martins, Ramos Silva et al. (2008 ▶), Martins, Silva et al. (2008 ▶); Ramos Silva et al. (2001a ▶,b ▶,c ▶, 2005a ▶,b ▶). For a magnetic low-dimensional system with picolinic acid, see: Eppley et al. (1997 ▶). For a similar compound with magnetic properties, see: Kukovec et al. (2008 ▶).

Experimental

Crystal data

[Cu(C6H3BrNO2)(NO3)(H2O)2]

M = 362.59

Orthorhombic,

a = 9.0791 (14) Å

b = 14.035 (2) Å

c = 17.165 (2) Å

V = 2187.2 (6) Å3

Z = 8

Mo Kα radiation

μ = 5.68 mm−1

T = 293 K

0.40 × 0.10 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.619, T max = 0.999

35919 measured reflections

3263 independent reflections

1849 reflections with I > 2σ(I)

R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.137

S = 1.03

3263 reflections

167 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.06 e Å−3

Δρmin = −1.19 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100064X/bt5450sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100064X/bt5450Isup2.hkl

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

[Cu(C6H3BrNO2)(NO3)(H2O)2]	F(000) = 1416
Mr = 362.59	Dx = 2.202 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6959 reflections
a = 9.0791 (14) Å	θ = 2.9–26.3°
b = 14.035 (2) Å	µ = 5.68 mm−1
c = 17.165 (2) Å	T = 293 K
V = 2187.2 (6) Å3	Needle, blue
Z = 8	0.40 × 0.10 × 0.08 mm

Bruker APEX CCD area-detector diffractometer	3263 independent reflections
Radiation source: fine-focus sealed tube	1849 reflections with I > 2σ(I)
graphite	Rint = 0.069
φ and ω scans	θmax = 31.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −12→11
Tmin = 0.619, Tmax = 0.999	k = −19→20
35919 measured reflections	l = −24→24

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.137	w = 1/[σ2(Fo2) + (0.0722P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3263 reflections	Δρmax = 1.06 e Å−3
167 parameters	Δρmin = −1.19 e Å−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (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	0.27639 (5)	0.10769 (4)	0.67505 (3)	0.03377 (16)
Br1	−0.01236 (4)	0.12831 (4)	0.52718 (3)	0.04471 (16)
C1	0.5394 (5)	0.1362 (3)	0.6017 (2)	0.0356 (10)
C2	0.4323 (4)	0.1249 (2)	0.5356 (2)	0.0291 (8)
C3	0.4765 (5)	0.1207 (4)	0.4602 (3)	0.0463 (12)
H3	0.5763	0.1214	0.4479	0.056*
C4	0.3723 (6)	0.1155 (4)	0.4020 (3)	0.0542 (14)
H4	0.4004	0.1107	0.3500	0.065*
C5	0.2261 (5)	0.1175 (4)	0.4223 (3)	0.0500 (13)
H5	0.1533	0.1164	0.3843	0.060*
C6	0.1890 (5)	0.1212 (3)	0.5006 (2)	0.0367 (10)
O1	0.4821 (3)	0.1405 (2)	0.66941 (16)	0.0406 (8)
O2	0.6707 (3)	0.1410 (3)	0.58800 (18)	0.0529 (9)
O3	0.1019 (3)	0.0189 (2)	0.67729 (14)	0.0378 (7)
O4	0.2795 (3)	−0.0834 (3)	0.66960 (18)	0.0516 (9)
O5	0.0612 (4)	−0.1309 (2)	0.7005 (2)	0.0572 (9)
O6	0.3112 (3)	0.0737 (3)	0.78475 (15)	0.0505 (9)
H6A	0.3992 (12)	0.074 (3)	0.8019 (8)	0.076*
H6B	0.264 (3)	0.103 (2)	0.8203 (5)	0.076*
O7	0.1350 (4)	0.2239 (2)	0.70395 (19)	0.0494 (8)
H7A	0.156 (5)	0.2826 (10)	0.703 (3)	0.074*
H7B	0.086 (4)	0.222 (4)	0.7459 (14)	0.074*
N1	0.2882 (4)	0.1232 (2)	0.55771 (19)	0.0313 (8)
N2	0.1477 (4)	−0.0683 (3)	0.68317 (17)	0.0356 (8)

	U11	U22	U33	U12	U13	U23
Cu1	0.0240 (3)	0.0461 (4)	0.0312 (2)	0.0008 (2)	0.00166 (17)	0.0011 (2)
Br1	0.0287 (2)	0.0573 (3)	0.0481 (3)	0.00161 (19)	−0.00589 (16)	0.0033 (2)
C1	0.030 (2)	0.040 (3)	0.037 (2)	−0.0019 (18)	−0.0022 (16)	0.0035 (17)
C2	0.028 (2)	0.022 (2)	0.0374 (19)	0.0017 (16)	0.0021 (15)	0.0012 (15)
C3	0.035 (3)	0.063 (3)	0.041 (2)	−0.002 (2)	0.0043 (17)	−0.001 (2)
C4	0.049 (3)	0.079 (4)	0.035 (2)	−0.004 (2)	0.0032 (19)	−0.007 (2)
C5	0.043 (3)	0.070 (4)	0.037 (2)	−0.004 (2)	−0.0053 (18)	0.002 (2)
C6	0.032 (2)	0.045 (3)	0.0328 (19)	0.0002 (17)	−0.0041 (16)	0.0018 (17)
O1	0.0272 (15)	0.064 (2)	0.0312 (14)	−0.0077 (14)	0.0003 (10)	−0.0009 (13)
O2	0.0238 (16)	0.091 (3)	0.0443 (17)	−0.0025 (15)	0.0015 (12)	0.0099 (16)
O3	0.0269 (14)	0.0397 (19)	0.0468 (15)	0.0008 (12)	−0.0003 (11)	0.0047 (12)
O4	0.0397 (19)	0.049 (2)	0.066 (2)	0.0137 (15)	0.0097 (14)	0.0014 (16)
O5	0.055 (2)	0.052 (2)	0.065 (2)	−0.0217 (17)	−0.0069 (17)	0.0160 (16)
O6	0.0313 (16)	0.087 (3)	0.0326 (14)	0.0088 (16)	0.0015 (11)	0.0027 (16)
O7	0.0525 (19)	0.0418 (19)	0.0541 (17)	0.0043 (16)	0.0184 (14)	−0.0001 (16)
N1	0.0277 (17)	0.032 (2)	0.0340 (16)	−0.0022 (14)	0.0002 (13)	0.0037 (13)
N2	0.037 (2)	0.036 (2)	0.0337 (16)	0.0017 (17)	−0.0030 (14)	0.0025 (14)

Cu1—O1	1.926 (3)	C4—C5	1.373 (7)
Cu1—O6	1.968 (3)	C4—H4	0.9300
Cu1—O3	2.016 (3)	C5—C6	1.386 (6)
Cu1—N1	2.029 (3)	C5—H5	0.9300
Cu1—O7	2.134 (3)	C6—N1	1.332 (5)
Br1—C6	1.886 (4)	O3—N2	1.296 (4)
C1—O2	1.218 (5)	O4—N2	1.238 (4)
C1—O1	1.274 (5)	O5—N2	1.215 (5)
C1—C2	1.503 (6)	O6—H6A	0.851 (9)
C2—C3	1.356 (6)	O6—H6B	0.85 (2)
C2—N1	1.363 (5)	O7—H7A	0.845 (10)
C3—C4	1.378 (6)	O7—H7B	0.85 (3)
C3—H3	0.9300
O1—Cu1—O6	87.13 (12)	C3—C4—H4	120.7
O1—Cu1—O3	155.59 (13)	C4—C5—C6	118.9 (4)
O6—Cu1—O3	87.61 (12)	C4—C5—H5	120.6
O1—Cu1—N1	82.72 (12)	C6—C5—H5	120.6
O6—Cu1—N1	165.35 (13)	N1—C6—C5	123.3 (4)
O3—Cu1—N1	97.29 (11)	N1—C6—Br1	118.4 (3)
O1—Cu1—O7	114.35 (14)	C5—C6—Br1	118.2 (3)
O6—Cu1—O7	93.40 (13)	C1—O1—Cu1	115.5 (3)
O3—Cu1—O7	89.74 (13)	N2—O3—Cu1	109.4 (2)
N1—Cu1—O7	100.38 (13)	Cu1—O6—H6A	118.7 (11)
O2—C1—O1	125.0 (4)	Cu1—O6—H6B	118.9 (11)
O2—C1—C2	119.6 (4)	H6A—O6—H6B	103.2 (14)
O1—C1—C2	115.5 (4)	Cu1—O7—H7A	127 (3)
C3—C2—N1	123.3 (4)	Cu1—O7—H7B	119 (3)
C3—C2—C1	122.3 (4)	H7A—O7—H7B	99 (4)
N1—C2—C1	114.3 (3)	C6—N1—C2	116.4 (3)
C2—C3—C4	119.4 (4)	C6—N1—Cu1	133.9 (3)
C2—C3—H3	120.3	C2—N1—Cu1	109.2 (2)
C4—C3—H3	120.3	O5—N2—O4	123.1 (4)
C5—C4—C3	118.6 (4)	O5—N2—O3	119.7 (4)
C5—C4—H4	120.7	O4—N2—O3	117.2 (3)
O2—C1—C2—C3	−0.6 (6)	O7—Cu1—O3—N2	−162.2 (2)
O1—C1—C2—C3	179.0 (4)	C5—C6—N1—C2	2.3 (6)
O2—C1—C2—N1	−178.1 (4)	Br1—C6—N1—C2	−175.4 (3)
O1—C1—C2—N1	1.5 (5)	C5—C6—N1—Cu1	−168.5 (3)
N1—C2—C3—C4	0.7 (7)	Br1—C6—N1—Cu1	13.8 (5)
C1—C2—C3—C4	−176.6 (4)	C3—C2—N1—C6	−2.8 (6)
C2—C3—C4—C5	1.9 (7)	C1—C2—N1—C6	174.7 (3)
C3—C4—C5—C6	−2.3 (7)	C3—C2—N1—Cu1	170.2 (3)
C4—C5—C6—N1	0.2 (7)	C1—C2—N1—Cu1	−12.3 (4)
C4—C5—C6—Br1	177.9 (4)	O1—Cu1—N1—C6	−174.5 (4)
O2—C1—O1—Cu1	−169.1 (4)	O6—Cu1—N1—C6	139.0 (5)
C2—C1—O1—Cu1	11.3 (5)	O3—Cu1—N1—C6	30.1 (4)
O6—Cu1—O1—C1	155.0 (3)	O7—Cu1—N1—C6	−60.9 (4)
O3—Cu1—O1—C1	77.1 (4)	O1—Cu1—N1—C2	14.3 (2)
N1—Cu1—O1—C1	−14.5 (3)	O6—Cu1—N1—C2	−32.2 (6)
O7—Cu1—O1—C1	−112.6 (3)	O3—Cu1—N1—C2	−141.1 (2)
O1—Cu1—O3—N2	8.9 (4)	O7—Cu1—N1—C2	127.8 (2)
O6—Cu1—O3—N2	−68.8 (2)	Cu1—O3—N2—O5	165.8 (3)
N1—Cu1—O3—N2	97.3 (2)	Cu1—O3—N2—O4	−15.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O3i	0.85 (1)	2.03 (2)	2.825 (4)	156 (4)
O6—H6B···O2ii	0.85 (2)	1.86 (1)	2.700 (4)	166 (2)
O7—H7A···O4iii	0.85 (1)	2.06 (2)	2.874 (5)	163 (5)
O7—H7B···O1ii	0.85 (3)	2.08 (3)	2.833 (4)	148 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O3i	0.85 (1)	2.03 (2)	2.825 (4)	156 (4)
O6—H6B⋯O2ii	0.85 (2)	1.86 (1)	2.700 (4)	166 (2)
O7—H7A⋯O4iii	0.85 (1)	2.06 (2)	2.874 (5)	163 (5)
O7—H7B⋯O1ii	0.85 (3)	2.08 (3)	2.833 (4)	148 (5)

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