Dianilinium bis-(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))cuprate(II) hexa-hydrate.

The asymmetric unit of the title complex, (C(6)H(8)N)(2)[Cu(C(7)H(3)NO(4))(2)]·6H(2)O, contains half a copper(II)-dipicolinate complex located on a twofold rotation axis, one protonated aniline mol-ecule and three solvent water mol-ecules. The Cu(II) atom is coordinated by four O atoms and two N atoms from two dipicolinate ligands in a distorted octa-hedral environment. In the crystal, the components are linked into a three-dimensional framework by inter-molecular O-H⋯O and N-H⋯O inter-actions.

Related literature

For metal complexes formed by pyridine­dicarb­oxy­lic acids, see: Crans (2000 ▶); Wang et al. (2004 ▶); Park et al. (2007 ▶); Aghabozorg et al. (2008 ▶, 2011 ▶); Tabatabaee (2010 ▶).

Experimental

Crystal data

(C6H8N)2[Cu(C7H3NO4)2]·6H2O

M = 690.11

Monoclinic,

a = 20.9117 (6) Å

b = 7.9115 (2) Å

c = 19.8842 (5) Å

β = 117.706 (2)°

V = 2912.52 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.83 mm−1

T = 293 K

0.44 × 0.36 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.652, T max = 0.746

48649 measured reflections

5321 independent reflections

4990 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.073

S = 1.06

5321 reflections

213 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.55 e Å−3

Data collection: APEX2 (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: XPW (Siemens, 1996 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028590/vn2037sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028590/vn2037Isup2.hkl

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

(C6H8N)2[Cu(C7H3NO4)2]·6H2O	F(000) = 1436
Mr = 690.11	Dx = 1.574 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9787 reflections
a = 20.9117 (6) Å	θ = 2.3–32.7°
b = 7.9115 (2) Å	µ = 0.83 mm−1
c = 19.8842 (5) Å	T = 293 K
β = 117.706 (2)°	Irregular, green
V = 2912.52 (13) Å3	0.44 × 0.36 × 0.35 mm
Z = 4

Bruker APEXII CCD diffractometer	5321 independent reflections
Radiation source: fine-focus sealed tube	4990 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −31→31
Tmin = 0.652, Tmax = 0.746	k = −12→12
48649 measured reflections	l = −30→30

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0415P)2 + 1.1609P] where P = (Fo2 + 2Fc2)/3
5321 reflections	(Δ/σ)max = 0.001
213 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

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 > 2σ(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	0.5000	0.979382 (19)	0.2500	0.02257 (5)
O1	0.59158 (4)	0.80292 (10)	0.26847 (4)	0.03298 (14)
O2	0.43941 (4)	1.15066 (10)	0.28429 (4)	0.03275 (14)
O3	0.70644 (4)	0.77108 (10)	0.35839 (4)	0.03315 (14)
O4	0.43162 (4)	1.20999 (11)	0.39036 (4)	0.03787 (16)
N1	0.55834 (4)	0.98045 (9)	0.35855 (4)	0.02101 (12)
C1	0.64268 (4)	0.81793 (11)	0.33490 (5)	0.02413 (14)
C2	0.62266 (4)	0.90375 (10)	0.39060 (4)	0.02198 (13)
C3	0.66492 (5)	0.90453 (12)	0.46879 (5)	0.02786 (15)
H3	0.7102	0.8535	0.4911	0.033*
C4	0.63852 (5)	0.98284 (13)	0.51321 (5)	0.03126 (18)
H4	0.6656	0.9822	0.5658	0.038*
C5	0.57176 (5)	1.06210 (12)	0.47912 (5)	0.02811 (16)
H5	0.5534	1.1150	0.5082	0.034*
C6	0.53317 (4)	1.06049 (11)	0.40074 (4)	0.02196 (13)
C7	0.46167 (4)	1.14859 (11)	0.35519 (5)	0.02438 (14)
N2	0.65628 (5)	0.54403 (11)	0.60233 (5)	0.03183 (16)
H2A	0.6328	0.6190	0.6098	0.038*
H2B	0.6526	0.4490	0.6238	0.038*
H2C	0.7012	0.5780	0.6201	0.038*
C8	0.63075 (5)	0.51163 (11)	0.52136 (6)	0.02671 (15)
C9	0.67563 (6)	0.42455 (14)	0.50001 (6)	0.03540 (19)
H9	0.7207	0.3871	0.5364	0.042*
C10	0.65261 (7)	0.39375 (16)	0.42367 (7)	0.0440 (2)
H10	0.6826	0.3359	0.4087	0.053*
C11	0.58577 (8)	0.44806 (16)	0.36981 (7)	0.0442 (3)
H11	0.5706	0.4266	0.3186	0.053*
C12	0.54110 (7)	0.53474 (16)	0.39200 (7)	0.0418 (2)
H12	0.4959	0.5711	0.3556	0.050*
C13	0.56340 (5)	0.56767 (14)	0.46834 (6)	0.03397 (18)
H13	0.5337	0.6262	0.4834	0.041*
O5	0.29295 (4)	0.17557 (11)	0.19901 (5)	0.03988 (17)
H5A	0.3387	0.1722	0.2247	0.060*
H5B	0.2852	0.2755	0.2092	0.060*
O6	0.74953 (5)	0.49186 (10)	0.79362 (5)	0.04002 (17)
H6A	0.7296	0.4169	0.8082	0.060*
H6B	0.7635	0.4372	0.7660	0.060*
O7	0.37393 (5)	0.76400 (11)	0.34828 (4)	0.03909 (16)
H7A	0.3829	0.7562	0.3108	0.059*
H7B	0.3414	0.8380	0.3387	0.059*

	U11	U22	U33	U12	U13	U23
Cu1	0.01931 (7)	0.02986 (8)	0.01981 (7)	0.000	0.01017 (5)	0.000
O1	0.0284 (3)	0.0478 (4)	0.0232 (3)	0.0025 (3)	0.0124 (2)	−0.0029 (3)
O2	0.0236 (3)	0.0484 (4)	0.0236 (3)	0.0075 (3)	0.0088 (2)	0.0010 (3)
O3	0.0245 (3)	0.0373 (4)	0.0392 (3)	0.0072 (3)	0.0161 (3)	−0.0025 (3)
O4	0.0355 (3)	0.0459 (4)	0.0394 (4)	0.0126 (3)	0.0236 (3)	−0.0026 (3)
N1	0.0190 (3)	0.0251 (3)	0.0198 (3)	0.0023 (2)	0.0097 (2)	0.0004 (2)
C1	0.0232 (3)	0.0254 (3)	0.0259 (3)	0.0028 (3)	0.0133 (3)	0.0011 (3)
C2	0.0193 (3)	0.0245 (3)	0.0222 (3)	0.0025 (2)	0.0097 (2)	0.0014 (2)
C3	0.0229 (3)	0.0320 (4)	0.0237 (3)	0.0049 (3)	0.0068 (3)	0.0031 (3)
C4	0.0306 (4)	0.0393 (5)	0.0188 (3)	0.0029 (3)	0.0071 (3)	0.0008 (3)
C5	0.0293 (4)	0.0348 (4)	0.0213 (3)	0.0014 (3)	0.0127 (3)	−0.0027 (3)
C6	0.0204 (3)	0.0261 (3)	0.0209 (3)	0.0009 (3)	0.0109 (3)	−0.0012 (3)
C7	0.0212 (3)	0.0271 (4)	0.0262 (3)	0.0017 (3)	0.0122 (3)	−0.0021 (3)
N2	0.0293 (4)	0.0354 (4)	0.0315 (4)	0.0046 (3)	0.0147 (3)	−0.0007 (3)
C8	0.0267 (4)	0.0248 (3)	0.0313 (4)	−0.0010 (3)	0.0157 (3)	0.0005 (3)
C9	0.0346 (5)	0.0356 (5)	0.0415 (5)	0.0057 (4)	0.0223 (4)	0.0012 (4)
C10	0.0554 (7)	0.0432 (6)	0.0474 (6)	0.0012 (5)	0.0357 (5)	−0.0046 (5)
C11	0.0581 (7)	0.0425 (6)	0.0352 (5)	−0.0113 (5)	0.0244 (5)	−0.0043 (4)
C12	0.0367 (5)	0.0438 (6)	0.0364 (5)	−0.0043 (4)	0.0098 (4)	0.0018 (4)
C13	0.0272 (4)	0.0349 (4)	0.0386 (5)	0.0013 (3)	0.0144 (4)	−0.0004 (4)
O5	0.0276 (3)	0.0430 (4)	0.0443 (4)	0.0022 (3)	0.0128 (3)	0.0012 (3)
O6	0.0493 (5)	0.0317 (4)	0.0429 (4)	−0.0055 (3)	0.0246 (4)	−0.0021 (3)
O7	0.0470 (4)	0.0429 (4)	0.0332 (3)	0.0045 (3)	0.0235 (3)	0.0054 (3)

Cu1—N1	1.9232 (7)	N2—C8	1.4641 (13)
Cu1—N1i	1.9232 (7)	N2—H2A	0.8262
Cu1—O2i	2.1701 (7)	N2—H2B	0.8855
Cu1—O1	2.2577 (7)	N2—H2C	0.8779
Cu1—O2	2.1701 (7)	C8—C9	1.3807 (13)
Cu1—O1i	2.2577 (7)	C8—C13	1.3823 (14)
O1—C1	1.2603 (10)	C9—C10	1.3841 (16)
O2—C7	1.2628 (10)	C9—H9	0.9300
O3—C1	1.2467 (10)	C10—C11	1.376 (2)
O4—C7	1.2364 (10)	C10—H10	0.9300
N1—C2	1.3365 (10)	C11—C12	1.3859 (19)
N1—C6	1.3389 (10)	C11—H11	0.9300
C1—C2	1.5146 (11)	C12—C13	1.3897 (16)
C2—C3	1.3858 (11)	C12—H12	0.9300
C3—C4	1.3865 (13)	C13—H13	0.9300
C3—H3	0.9300	O5—H5A	0.8500
C4—C5	1.3863 (13)	O5—H5B	0.8500
C4—H4	0.9300	O6—H6A	0.8502
C5—C6	1.3823 (11)	O6—H6B	0.8500
C5—H5	0.9300	O7—H7A	0.8499
C6—C7	1.5109 (11)	O7—H7B	0.8500
N1—Cu1—N1i	179.49 (4)	C4—C5—H5	120.8
N1—Cu1—O2i	101.04 (3)	N1—C6—C5	121.15 (8)
N1i—Cu1—O2i	78.64 (3)	N1—C6—C7	114.23 (7)
N1—Cu1—O2	78.64 (3)	C5—C6—C7	124.61 (7)
N1i—Cu1—O2	101.04 (3)	O4—C7—O2	127.31 (8)
O2i—Cu1—O2	102.72 (4)	O4—C7—C6	117.63 (8)
N1—Cu1—O1i	103.46 (3)	O2—C7—C6	115.06 (7)
N1i—Cu1—O1i	76.86 (3)	C8—N2—H2A	112.3
O2i—Cu1—O1i	155.50 (2)	C8—N2—H2B	108.2
O2—Cu1—O1i	82.08 (3)	H2A—N2—H2B	109.3
N1—Cu1—O1	76.86 (3)	C8—N2—H2C	105.7
N1i—Cu1—O1	103.46 (3)	H2A—N2—H2C	108.8
O2i—Cu1—O1	82.08 (3)	H2B—N2—H2C	112.5
O2—Cu1—O1	155.50 (2)	C9—C8—C13	121.51 (10)
O1i—Cu1—O1	103.61 (4)	C9—C8—N2	118.23 (9)
C1—O1—Cu1	110.73 (6)	C13—C8—N2	120.26 (8)
C7—O2—Cu1	112.14 (5)	C8—C9—C10	119.05 (10)
C2—N1—C6	121.17 (7)	C8—C9—H9	120.5
C2—N1—Cu1	120.39 (5)	C10—C9—H9	120.5
C6—N1—Cu1	118.44 (5)	C11—C10—C9	120.53 (11)
O3—C1—O1	127.06 (8)	C11—C10—H10	119.7
O3—C1—C2	118.06 (7)	C9—C10—H10	119.7
O1—C1—C2	114.87 (7)	C10—C11—C12	119.86 (11)
N1—C2—C3	120.56 (7)	C10—C11—H11	120.1
N1—C2—C1	114.45 (7)	C12—C11—H11	120.1
C3—C2—C1	124.99 (7)	C11—C12—C13	120.45 (11)
C2—C3—C4	118.79 (8)	C11—C12—H12	119.8
C2—C3—H3	120.6	C13—C12—H12	119.8
C4—C3—H3	120.6	C8—C13—C12	118.59 (10)
C5—C4—C3	119.95 (8)	C8—C13—H13	120.7
C5—C4—H4	120.0	C12—C13—H13	120.7
C3—C4—H4	120.0	H5A—O5—H5B	99.9
C6—C5—C4	118.33 (8)	H6A—O6—H6B	103.6
C6—C5—H5	120.8	H7A—O7—H7B	109.5
N1—Cu1—O1—C1	−14.29 (6)	O3—C1—C2—C3	−13.90 (13)
N1i—Cu1—O1—C1	165.31 (6)	O1—C1—C2—C3	166.50 (9)
O2i—Cu1—O1—C1	89.06 (6)	N1—C2—C3—C4	1.50 (13)
O2—Cu1—O1—C1	−14.29 (11)	C1—C2—C3—C4	−177.53 (9)
O1i—Cu1—O1—C1	−115.21 (7)	C2—C3—C4—C5	−1.60 (15)
N1—Cu1—O2—C7	−11.16 (6)	C3—C4—C5—C6	−0.05 (15)
N1i—Cu1—O2—C7	169.24 (6)	C2—N1—C6—C5	−2.07 (13)
O2i—Cu1—O2—C7	−110.06 (7)	Cu1—N1—C6—C5	178.37 (7)
O1i—Cu1—O2—C7	94.37 (6)	C2—N1—C6—C7	176.68 (7)
O1—Cu1—O2—C7	−11.16 (11)	Cu1—N1—C6—C7	−2.87 (9)
O2i—Cu1—N1—C2	−71.51 (7)	C4—C5—C6—N1	1.91 (14)
O2—Cu1—N1—C2	−172.44 (7)	C4—C5—C6—C7	−176.72 (9)
O1i—Cu1—N1—C2	108.66 (6)	Cu1—O2—C7—O4	−167.46 (8)
O1—Cu1—N1—C2	7.56 (6)	Cu1—O2—C7—C6	12.58 (9)
O2i—Cu1—N1—C6	108.06 (6)	N1—C6—C7—O4	172.64 (8)
O2—Cu1—N1—C6	7.12 (6)	C5—C6—C7—O4	−8.65 (13)
O1i—Cu1—N1—C6	−71.77 (7)	N1—C6—C7—O2	−7.39 (11)
O1—Cu1—N1—C6	−172.88 (7)	C5—C6—C7—O2	171.32 (9)
Cu1—O1—C1—O3	−162.04 (8)	C13—C8—C9—C10	0.37 (16)
Cu1—O1—C1—C2	17.52 (9)	N2—C8—C9—C10	−179.56 (10)
C6—N1—C2—C3	0.33 (12)	C8—C9—C10—C11	−0.45 (18)
Cu1—N1—C2—C3	179.88 (6)	C9—C10—C11—C12	0.19 (19)
C6—N1—C2—C1	179.46 (7)	C10—C11—C12—C13	0.16 (18)
Cu1—N1—C2—C1	−0.99 (10)	C9—C8—C13—C12	−0.03 (15)
O3—C1—C2—N1	167.02 (8)	N2—C8—C13—C12	179.90 (9)
O1—C1—C2—N1	−12.58 (11)	C11—C12—C13—C8	−0.24 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ii	0.83	1.91	2.7267 (11)	171
N2—H2B···O7iii	0.89	1.93	2.8071 (12)	168
N2—H2C···O3iv	0.88	2.14	2.9842 (12)	162
O5—H5A···O2v	0.85	1.88	2.732	176
O5—H5B···O6iii	0.85	1.97	2.8026 (12)	166
O6—H6A···O3vi	0.85	1.97	2.8066 (11)	167
O6—H6B···O5vii	0.85	1.93	2.7760 (13)	177
O7—H7A···O1i	0.85	1.92	2.750	164
O7—H7B···O6viii	0.85	2.17	3.0083 (12)	170

Table 1

Selected bond lengths (Å)

Cu1—N1	1.9232 (7)
Cu1—O1	2.2577 (7)
Cu1—O2	2.1701 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4i	0.83	1.91	2.7267 (11)	171
N2—H2B⋯O7ii	0.89	1.93	2.8071 (12)	168
N2—H2C⋯O3iii	0.88	2.14	2.9842 (12)	162
O5—H5A⋯O2iv	0.85	1.88	2.732	176
O5—H5B⋯O6ii	0.85	1.97	2.8026 (12)	166
O6—H6A⋯O3v	0.85	1.97	2.8066 (11)	167
O6—H6B⋯O5vi	0.85	1.93	2.7760 (13)	177
O7—H7A⋯O1vii	0.85	1.92	2.750	164
O7—H7B⋯O6viii	0.85	2.17	3.0083 (12)	170

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .