[μ-N,N,N',N'-Tetra-kis(2-pyridyl-meth-yl)butane-1,4-diamine]-bis-[dichlorido-copper(II)] trihydrate.

The title dinuclear copper complex, [Cu(2)Cl(4)(C(28)H(32)N(6))]·3H(2)O, is located on a crystallographic inversion center. The unique Cu(II) ion is coordinated in a slightly distorted square-pyramidal environment in which the N atoms of the dipicolyl-amine group and a chloride ligand form the basal plane. The apical position is occupied by a second chloride atom. While the Cu-N distances of the pyridine N atoms are the same within expermental error, the Cu-N distance to the tertiary N atom is slightly elongated. The apical Cu-Cl distance is elongated due to typical Jahn-Teller distortion. One of the water O atoms was refined as disordered over two sites with occupancies 0.734 (17):0.266 (17) and another with half occupancy. H atoms for the disordered solvent atoms were not included in the refinement.

Related literature

For crystallographic data of tetra­kis­(pyridin-2-yl-meth­yl)alkyl-diamines, see: Fujihara et al. (2004 ▶); Mambanda et al. (2007 ▶). For the superoxide dismutase activity of iron complexes, see: Tamura et al. (2000 ▶). For dinuclear Pt complexes of similar ligands, see: Ertürk et al. (2007 ▶). For the use of the dipicolyl­amine moiety for binding of the M(CO)3 core (M = Re, 99Tc), see: Bartholomä et al. (2009 ▶). For crystal structures closely related to the title compound, see: Bartholomä et al. (2010a ▶,b ▶,c ▶,d ▶).

Experimental

Crystal data

[Cu2Cl4(C28H32N6)]·3H2O

M = 775.52

Monoclinic,

a = 11.4403 (5) Å

b = 10.0230 (5) Å

c = 14.2943 (7) Å

β = 106.143 (1)°

V = 1574.44 (13) Å3

Z = 2

Mo Kα radiation

μ = 1.73 mm−1

T = 90 K

0.26 × 0.18 × 0.14 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.662, T max = 0.794

15464 measured reflections

3906 independent reflections

3746 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.125

S = 1.25

3906 reflections

209 parameters

H-atom parameters constrained

Δρmax = 0.76 e Å−3

Δρmin = −0.49 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034501/lh5107sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034501/lh5107Isup2.hkl

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

[Cu2Cl4(C28H32N6)]·3H2O	F(000) = 796
Mr = 775.52	Dx = 1.636 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5514 reflections
a = 11.4403 (5) Å	θ = 2.5–28.2°
b = 10.0230 (5) Å	µ = 1.73 mm−1
c = 14.2943 (7) Å	T = 90 K
β = 106.143 (1)°	Block, blue
V = 1574.44 (13) Å3	0.26 × 0.18 × 0.14 mm
Z = 2

Bruker APEX CCD diffractometer	3906 independent reflections
Radiation source: fine-focus sealed tube	3746 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 512 pixels mm-1	θmax = 28.3°, θmin = 1.9°
φ and ω scans	h = −15→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→12
Tmin = 0.662, Tmax = 0.794	l = −19→19
15464 measured reflections

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.25	w = 1/[σ2(Fo2) + (0.0448P)2 + 3.8247P] where P = (Fo2 + 2Fc2)/3
3906 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.76 e Å−3
0 restraints	Δρmin = −0.49 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	Occ. (<1)
Cu1	0.66753 (3)	0.34837 (4)	0.83401 (3)	0.01782 (12)
Cl1	0.75297 (10)	0.11459 (9)	0.88332 (8)	0.0361 (2)
Cl2	0.68782 (7)	0.45176 (8)	0.97763 (5)	0.01982 (17)
O1A	0.0560 (9)	0.1843 (9)	0.0017 (4)	0.077 (3)	0.734 (17)
O1B	−0.0110 (12)	0.2423 (13)	0.0088 (8)	0.034 (4)	0.266 (17)
O2	0.1966 (10)	0.1197 (11)	0.9798 (7)	0.091 (3)	0.50
N1	0.6228 (2)	0.3205 (3)	0.68520 (19)	0.0180 (5)
N2	0.8238 (2)	0.4118 (3)	0.81070 (19)	0.0191 (5)
N3	0.4893 (2)	0.3059 (3)	0.80922 (19)	0.0173 (5)
C1	0.7378 (3)	0.2849 (3)	0.6642 (2)	0.0226 (7)
H1A	0.7299	0.2968	0.5940	0.027*
H1B	0.7581	0.1903	0.6813	0.027*
C2	0.8365 (3)	0.3741 (3)	0.7235 (2)	0.0205 (6)
C3	0.9347 (3)	0.4152 (4)	0.6916 (3)	0.0281 (7)
H3	0.9411	0.3895	0.6292	0.034*
C4	1.0234 (3)	0.4943 (4)	0.7523 (3)	0.0296 (8)
H4	1.0916	0.5235	0.7321	0.036*
C5	1.0118 (3)	0.5302 (4)	0.8424 (3)	0.0259 (7)
H5	1.0723	0.5833	0.8853	0.031*
C6	0.9106 (3)	0.4878 (4)	0.8695 (2)	0.0227 (7)
H6	0.9023	0.5131	0.9314	0.027*
C7	0.5324 (3)	0.2111 (3)	0.6684 (2)	0.0216 (7)
H7A	0.5728	0.1257	0.6930	0.026*
H7B	0.4918	0.2014	0.5979	0.026*
C8	0.4408 (3)	0.2469 (3)	0.7223 (2)	0.0187 (6)
C9	0.3169 (3)	0.2237 (3)	0.6863 (2)	0.0220 (6)
H9	0.2841	0.1849	0.6239	0.026*
C10	0.2420 (3)	0.2587 (4)	0.7439 (3)	0.0269 (7)
H10	0.1569	0.2427	0.7216	0.032*
C11	0.2915 (3)	0.3166 (3)	0.8337 (3)	0.0237 (7)
H11	0.2415	0.3400	0.8742	0.028*
C12	0.4152 (3)	0.3399 (3)	0.8636 (2)	0.0192 (6)
H12	0.4492	0.3815	0.9248	0.023*
C13	0.5697 (3)	0.4462 (3)	0.6335 (2)	0.0188 (6)
H13A	0.6345	0.5146	0.6450	0.023*
H13B	0.5062	0.4793	0.6626	0.023*
C14	0.5139 (3)	0.4315 (3)	0.5237 (2)	0.0208 (7)
H14A	0.5712	0.3832	0.4951	0.025*
H14B	0.4379	0.3787	0.5110	0.025*

	U11	U22	U33	U12	U13	U23
Cu1	0.0181 (2)	0.0213 (2)	0.0155 (2)	−0.00268 (15)	0.00696 (14)	−0.00284 (14)
Cl1	0.0447 (6)	0.0233 (4)	0.0501 (6)	0.0064 (4)	0.0293 (5)	0.0045 (4)
Cl2	0.0218 (4)	0.0235 (4)	0.0137 (3)	−0.0005 (3)	0.0042 (3)	−0.0016 (3)
O1A	0.085 (6)	0.085 (6)	0.059 (4)	−0.025 (5)	0.017 (3)	−0.014 (3)
O1B	0.035 (7)	0.039 (7)	0.026 (5)	0.015 (5)	0.003 (4)	0.010 (4)
O2	0.100 (8)	0.088 (7)	0.079 (7)	0.005 (6)	0.016 (6)	0.005 (5)
N1	0.0201 (13)	0.0188 (13)	0.0173 (12)	−0.0048 (10)	0.0086 (10)	−0.0066 (10)
N2	0.0183 (13)	0.0212 (13)	0.0196 (12)	0.0002 (10)	0.0081 (10)	0.0003 (11)
N3	0.0184 (12)	0.0184 (13)	0.0155 (12)	−0.0006 (10)	0.0051 (10)	0.0001 (10)
C1	0.0272 (17)	0.0220 (16)	0.0229 (15)	−0.0014 (13)	0.0141 (13)	−0.0046 (13)
C2	0.0197 (15)	0.0228 (16)	0.0207 (15)	0.0024 (12)	0.0084 (12)	0.0004 (12)
C3	0.0267 (18)	0.0318 (19)	0.0307 (18)	0.0006 (15)	0.0162 (14)	−0.0020 (15)
C4	0.0191 (17)	0.033 (2)	0.040 (2)	0.0004 (14)	0.0135 (15)	0.0052 (16)
C5	0.0160 (15)	0.0293 (18)	0.0290 (17)	−0.0005 (13)	0.0005 (13)	0.0060 (14)
C6	0.0205 (16)	0.0254 (17)	0.0204 (15)	−0.0004 (13)	0.0026 (12)	0.0019 (13)
C7	0.0270 (17)	0.0206 (16)	0.0197 (15)	−0.0077 (13)	0.0108 (12)	−0.0062 (12)
C8	0.0236 (16)	0.0159 (14)	0.0179 (14)	−0.0023 (12)	0.0076 (12)	0.0007 (11)
C9	0.0236 (16)	0.0202 (16)	0.0202 (14)	−0.0041 (12)	0.0031 (12)	−0.0040 (12)
C10	0.0175 (15)	0.0249 (17)	0.0376 (19)	−0.0023 (13)	0.0063 (14)	−0.0069 (15)
C11	0.0232 (16)	0.0215 (16)	0.0287 (17)	0.0008 (13)	0.0109 (13)	−0.0030 (13)
C12	0.0228 (16)	0.0177 (15)	0.0175 (14)	0.0000 (12)	0.0063 (12)	0.0004 (11)
C13	0.0228 (15)	0.0186 (15)	0.0171 (14)	−0.0040 (12)	0.0095 (12)	−0.0033 (11)
C14	0.0253 (16)	0.0242 (17)	0.0130 (13)	−0.0068 (13)	0.0056 (12)	−0.0053 (12)

Cu1—N2	2.011 (3)	C5—C6	1.386 (5)
Cu1—N3	2.016 (3)	C5—H5	0.9500
Cu1—N1	2.064 (3)	C6—H6	0.9500
Cu1—Cl2	2.2532 (8)	C7—C8	1.506 (4)
Cu1—Cl1	2.5612 (10)	C7—H7A	0.9900
N1—C1	1.473 (4)	C7—H7B	0.9900
N1—C7	1.480 (4)	C8—C9	1.387 (5)
N1—C13	1.501 (4)	C9—C10	1.389 (5)
N2—C6	1.345 (4)	C9—H9	0.9500
N2—C2	1.348 (4)	C10—C11	1.379 (5)
N3—C12	1.344 (4)	C10—H10	0.9500
N3—C8	1.348 (4)	C11—C12	1.379 (5)
C1—C2	1.504 (5)	C11—H11	0.9500
C1—H1A	0.9900	C12—H12	0.9500
C1—H1B	0.9900	C13—C14	1.527 (4)
C2—C3	1.388 (5)	C13—H13A	0.9900
C3—C4	1.387 (5)	C13—H13B	0.9900
C3—H3	0.9500	C14—C14i	1.526 (7)
C4—C5	1.378 (5)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
N2—Cu1—N3	160.10 (11)	C4—C5—H5	120.5
N2—Cu1—N1	81.33 (11)	C6—C5—H5	120.5
N3—Cu1—N1	80.87 (11)	N2—C6—C5	121.9 (3)
N2—Cu1—Cl2	97.73 (8)	N2—C6—H6	119.1
N3—Cu1—Cl2	95.75 (8)	C5—C6—H6	119.1
N1—Cu1—Cl2	159.16 (8)	N1—C7—C8	107.1 (3)
N2—Cu1—Cl1	92.63 (8)	N1—C7—H7A	110.3
N3—Cu1—Cl1	98.35 (8)	C8—C7—H7A	110.3
N1—Cu1—Cl1	97.23 (8)	N1—C7—H7B	110.3
Cl2—Cu1—Cl1	103.61 (3)	C8—C7—H7B	110.3
C1—N1—C7	114.3 (3)	H7A—C7—H7B	108.5
C1—N1—C13	111.4 (2)	N3—C8—C9	122.1 (3)
C7—N1—C13	111.9 (3)	N3—C8—C7	114.2 (3)
C1—N1—Cu1	105.3 (2)	C9—C8—C7	123.7 (3)
C7—N1—Cu1	103.27 (19)	C8—C9—C10	118.3 (3)
C13—N1—Cu1	110.15 (18)	C8—C9—H9	120.9
C6—N2—C2	119.1 (3)	C10—C9—H9	120.9
C6—N2—Cu1	127.7 (2)	C11—C10—C9	119.8 (3)
C2—N2—Cu1	113.2 (2)	C11—C10—H10	120.1
C12—N3—C8	118.7 (3)	C9—C10—H10	120.1
C12—N3—Cu1	128.0 (2)	C12—C11—C10	118.7 (3)
C8—N3—Cu1	113.0 (2)	C12—C11—H11	120.7
N1—C1—C2	108.3 (3)	C10—C11—H11	120.7
N1—C1—H1A	110.0	N3—C12—C11	122.4 (3)
C2—C1—H1A	110.0	N3—C12—H12	118.8
N1—C1—H1B	110.0	C11—C12—H12	118.8
C2—C1—H1B	110.0	N1—C13—C14	114.9 (3)
H1A—C1—H1B	108.4	N1—C13—H13A	108.5
N2—C2—C3	121.7 (3)	C14—C13—H13A	108.5
N2—C2—C1	115.5 (3)	N1—C13—H13B	108.5
C3—C2—C1	122.7 (3)	C14—C13—H13B	108.5
C4—C3—C2	118.8 (3)	H13A—C13—H13B	107.5
C4—C3—H3	120.6	C14i—C14—C13	110.2 (3)
C2—C3—H3	120.6	C14i—C14—H14A	109.6
C5—C4—C3	119.4 (3)	C13—C14—H14A	109.6
C5—C4—H4	120.3	C14i—C14—H14B	109.6
C3—C4—H4	120.3	C13—C14—H14B	109.6
C4—C5—C6	119.1 (3)	H14A—C14—H14B	108.1
N2—Cu1—N1—C1	32.6 (2)	Cu1—N2—C2—C3	175.9 (3)
N3—Cu1—N1—C1	−156.3 (2)	C6—N2—C2—C1	177.7 (3)
Cl2—Cu1—N1—C1	121.5 (2)	Cu1—N2—C2—C1	−4.3 (4)
Cl1—Cu1—N1—C1	−59.0 (2)	N1—C1—C2—N2	32.3 (4)
N2—Cu1—N1—C7	152.7 (2)	N1—C1—C2—C3	−147.9 (3)
N3—Cu1—N1—C7	−36.2 (2)	N2—C2—C3—C4	1.6 (5)
Cl2—Cu1—N1—C7	−118.3 (2)	C1—C2—C3—C4	−178.1 (3)
Cl1—Cu1—N1—C7	61.1 (2)	C2—C3—C4—C5	−0.1 (6)
N2—Cu1—N1—C13	−87.6 (2)	C3—C4—C5—C6	−0.9 (5)
N3—Cu1—N1—C13	83.5 (2)	C2—N2—C6—C5	1.0 (5)
Cl2—Cu1—N1—C13	1.3 (4)	Cu1—N2—C6—C5	−176.7 (3)
Cl1—Cu1—N1—C13	−179.20 (18)	C4—C5—C6—N2	0.5 (5)
N3—Cu1—N2—C6	134.7 (3)	C1—N1—C7—C8	162.1 (3)
N1—Cu1—N2—C6	161.4 (3)	C13—N1—C7—C8	−70.1 (3)
Cl2—Cu1—N2—C6	2.5 (3)	Cu1—N1—C7—C8	48.3 (3)
Cl1—Cu1—N2—C6	−101.6 (3)	C12—N3—C8—C9	1.8 (5)
N3—Cu1—N2—C2	−43.1 (5)	Cu1—N3—C8—C9	−172.4 (3)
N1—Cu1—N2—C2	−16.4 (2)	C12—N3—C8—C7	−179.0 (3)
Cl2—Cu1—N2—C2	−175.3 (2)	Cu1—N3—C8—C7	6.9 (3)
Cl1—Cu1—N2—C2	80.5 (2)	N1—C7—C8—N3	−38.3 (4)
N2—Cu1—N3—C12	−129.5 (3)	N1—C7—C8—C9	140.9 (3)
N1—Cu1—N3—C12	−156.2 (3)	N3—C8—C9—C10	−2.2 (5)
Cl2—Cu1—N3—C12	3.0 (3)	C7—C8—C9—C10	178.6 (3)
Cl1—Cu1—N3—C12	107.7 (3)	C8—C9—C10—C11	0.9 (5)
N2—Cu1—N3—C8	44.0 (4)	C9—C10—C11—C12	0.8 (5)
N1—Cu1—N3—C8	17.2 (2)	C8—N3—C12—C11	0.0 (5)
Cl2—Cu1—N3—C8	176.5 (2)	Cu1—N3—C12—C11	173.2 (2)
Cl1—Cu1—N3—C8	−78.8 (2)	C10—C11—C12—N3	−1.3 (5)
C7—N1—C1—C2	−154.9 (3)	C1—N1—C13—C14	73.2 (3)
C13—N1—C1—C2	77.0 (3)	C7—N1—C13—C14	−56.1 (3)
Cu1—N1—C1—C2	−42.4 (3)	Cu1—N1—C13—C14	−170.4 (2)
C6—N2—C2—C3	−2.1 (5)	N1—C13—C14—C14i	−168.8 (3)

Table 1

Selected bond lengths (Å)

Cu1—N2	2.011 (3)
Cu1—N3	2.016 (3)
Cu1—N1	2.064 (3)
Cu1—Cl2	2.2532 (8)
Cu1—Cl1	2.5612 (10)