catena-Poly[1,4-dihy­droxy-1,4-di­azoniabicyclo­[2.2.2]octane [aqua­tri-[mu]-chlorido-trichloridodicuprate(II)]]

The title compound, {(C₆H₁₄N₂O₂)[Cu₂Cl₆(H₂O)]}_n, consists of 1,4-dihy­droxy-1,4-diazo­niabicyclo­[2.2.2]octane dications and one-dimensional inorganic anionic {[Cu₂Cl₆(H₂O)]^2-}_n chains in which both five-coordinate [CuCl₃(H₂O)]^- and five-coordinate [CuCl₃]^- units exist. These two distinct type of unit are linked together by one chloride ion and are bridged across centres of inversion to further units of their own type through two chloride ions, giving rise to novel polymeric zigzag chains parallel to the c axis. The chains are connected by O-H...Cl hydrogen bonds to produce R₂⁴(16) ring motifs, resulting in two-dimensional layers parallel to the ac plane. These layers are linked into a three-dimensional framework with the organic cations via O-H...Cl hydrogen bonds. Hydrogen bonding between the chains, and between the chains and the organic cations, provides stability to the crystal structure.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

catena-Poly[1,4-dihydroxy-1,4-diazoniabicyclo[2.2.2]octane [aquatri-µ-chlorido-trichloridodicuprate(II)]]

Crystal data

(C6H14N2O2)[Cu2Cl6(H2O)]	F(000) = 1000
Mr = 504.01	Dx = 2.120 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 12903 reflections
a = 10.039 (2) Å	θ = 3.1–27.5°
b = 14.652 (3) Å	µ = 3.71 mm^−1
c = 13.976 (4) Å	T = 298 K
β = 129.823 (18)°	Block, dark green
V = 1578.9 (6) Å^3	0.36 × 0.32 × 0.28 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer	3604 independent reflections
Radiation source: fine-focus sealed tube	2891 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −12→13
Tmin = 0.274, Tmax = 0.354	k = −19→19
16253 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0294P)^2 + 2.0242P] where P = (Fo^2 + 2Fc^2)/3
3604 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.76 e Å^−3
3 restraints	Δρmin = −0.68 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3313 (4)	0.7386 (3)	0.5078 (3)	0.0259 (8)
H1A	0.2269	0.7741	0.4490	0.031*
H1B	0.2976	0.6775	0.5116	0.031*
C2	0.6024 (5)	0.7286 (3)	0.7262 (3)	0.0268 (8)
H2A	0.5743	0.6662	0.7307	0.032*
H2B	0.6683	0.7557	0.8083	0.032*
C3	0.7082 (5)	0.7297 (3)	0.6836 (3)	0.0282 (8)
H3A	0.8184	0.7597	0.7457	0.034*
H3B	0.7312	0.6677	0.6736	0.034*
C4	0.5820 (6)	0.8764 (2)	0.5788 (4)	0.0341 (9)
H4A	0.5167	0.9083	0.4998	0.041*
H4B	0.6927	0.9069	0.6375	0.041*
C5	0.4389 (5)	0.7346 (3)	0.4661 (4)	0.0355 (10)
H5A	0.4564	0.6716	0.4553	0.043*
H5B	0.3784	0.7657	0.3869	0.043*
C6	0.4826 (5)	0.8779 (2)	0.6270 (4)	0.0319 (9)
H6A	0.5529	0.9058	0.7089	0.038*
H6B	0.3773	0.9135	0.5714	0.038*
Cl1	0.86002 (14)	0.57297 (8)	0.94439 (9)	0.0463 (3)
Cl2	0.63653 (11)	0.48653 (6)	0.66805 (8)	0.0271 (2)
Cl3	0.93690 (11)	0.32752 (7)	0.78532 (8)	0.0332 (2)
Cl4	1.08359 (12)	0.56307 (7)	0.80697 (8)	0.0330 (2)
Cl5	1.31828 (12)	0.58524 (7)	0.72216 (9)	0.0323 (2)
Cl6	0.95048 (13)	0.61583 (7)	0.43827 (9)	0.0364 (2)
Cu1	0.89983 (5)	0.45770 (3)	0.85328 (4)	0.02336 (12)
Cu2	1.03329 (5)	0.56507 (3)	0.62369 (4)	0.02491 (12)
N1	0.6104 (4)	0.7795 (2)	0.5625 (3)	0.0232 (6)
N2	0.4384 (4)	0.78211 (19)	0.6339 (3)	0.0201 (6)
O1	0.6947 (4)	0.7754 (2)	0.5119 (3)	0.0402 (7)
H1	0.7979	0.7872	0.5664	0.060*
O2	0.3400 (4)	0.7895 (2)	0.6735 (3)	0.0352 (7)
H2	0.3093	0.7386	0.6766	0.053*
O1W	0.7858 (3)	0.5425 (2)	0.5365 (3)	0.0451 (8)
H1WA	0.7750	0.5079	0.5800	0.068*
H1WB	0.7146	0.5251	0.4610	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0156 (17)	0.035 (2)	0.0196 (18)	−0.0086 (15)	0.0079 (15)	−0.0062 (15)
C2	0.0230 (19)	0.032 (2)	0.0223 (18)	0.0031 (16)	0.0131 (16)	0.0082 (15)
C3	0.0230 (19)	0.034 (2)	0.0244 (19)	0.0038 (16)	0.0135 (17)	0.0076 (16)
C4	0.041 (2)	0.0200 (19)	0.042 (2)	−0.0084 (17)	0.027 (2)	0.0022 (17)
C5	0.027 (2)	0.056 (3)	0.025 (2)	−0.0230 (19)	0.0174 (18)	−0.0207 (18)
C6	0.043 (2)	0.0152 (18)	0.038 (2)	−0.0029 (16)	0.026 (2)	−0.0010 (16)
Cl1	0.0473 (6)	0.0517 (7)	0.0177 (4)	0.0312 (5)	0.0105 (4)	−0.0005 (4)
Cl2	0.0190 (4)	0.0320 (5)	0.0193 (4)	−0.0003 (4)	0.0071 (4)	−0.0007 (3)
Cl3	0.0209 (4)	0.0384 (5)	0.0301 (5)	0.0009 (4)	0.0118 (4)	−0.0149 (4)
Cl4	0.0310 (5)	0.0451 (6)	0.0239 (4)	−0.0117 (4)	0.0180 (4)	−0.0058 (4)
Cl5	0.0218 (4)	0.0386 (6)	0.0340 (5)	−0.0029 (4)	0.0167 (4)	0.0037 (4)
Cl6	0.0389 (6)	0.0375 (5)	0.0272 (5)	0.0028 (4)	0.0186 (4)	0.0115 (4)
Cu1	0.0201 (2)	0.0279 (2)	0.0152 (2)	0.00544 (18)	0.00810 (18)	−0.00236 (17)
Cu2	0.0189 (2)	0.0344 (3)	0.0201 (2)	0.00006 (19)	0.01184 (19)	0.00267 (18)
N1	0.0216 (15)	0.0295 (17)	0.0192 (15)	−0.0077 (13)	0.0134 (13)	−0.0030 (12)
N2	0.0225 (15)	0.0210 (15)	0.0213 (14)	−0.0002 (12)	0.0161 (13)	−0.0003 (12)
O1	0.0313 (15)	0.068 (2)	0.0318 (15)	−0.0181 (14)	0.0253 (14)	−0.0145 (14)
O2	0.0394 (16)	0.0397 (16)	0.0462 (17)	−0.0010 (13)	0.0365 (15)	−0.0029 (13)
O1W	0.0225 (15)	0.082 (2)	0.0259 (15)	−0.0053 (15)	0.0132 (13)	−0.0001 (15)

Geometric parameters (Å, º)

C1—N2	1.497 (4)	C6—H6A	0.9700
C1—C5	1.522 (5)	C6—H6B	0.9700
C1—H1A	0.9700	Cl1—Cu1^i	2.2975 (13)
C1—H1B	0.9700	Cl1—Cu1	2.2990 (11)
C2—N2	1.506 (4)	Cl2—Cu1	2.2589 (12)
C2—C3	1.514 (5)	Cl3—Cu1	2.2653 (11)
C2—H2A	0.9700	Cl4—Cu1	2.7812 (15)
C2—H2B	0.9700	Cl4—Cu2	2.2717 (12)
C3—N1	1.493 (4)	Cl5—Cu2	2.2636 (12)
C3—H3A	0.9700	Cl6—Cu2	2.2804 (12)
C3—H3B	0.9700	Cl6—Cu2^ii	2.8253 (13)
C4—N1	1.494 (5)	Cu1—Cl1^i	2.2975 (13)
C4—C6	1.520 (6)	Cu2—O1W	1.972 (3)
C4—H4A	0.9700	N1—O1	1.410 (4)
C4—H4B	0.9700	N2—O2	1.411 (4)
C5—N1	1.497 (4)	O1—H1	0.8200
C5—H5A	0.9700	O2—H2	0.8200
C5—H5B	0.9700	O1W—H1WA	0.8500
C6—N2	1.493 (4)	O1W—H1WB	0.8500
N2—C1—C5	108.4 (3)	N2—C6—H6B	109.9
N2—C1—H1A	110.0	C4—C6—H6B	109.9
C5—C1—H1A	110.0	H6A—C6—H6B	108.3
N2—C1—H1B	110.0	Cu1^i—Cl1—Cu1	96.92 (4)
C5—C1—H1B	110.0	Cl2—Cu1—Cl3	93.60 (4)
H1A—C1—H1B	108.4	Cl2—Cu1—Cl1^i	169.27 (5)
N2—C2—C3	108.3 (3)	Cl3—Cu1—Cl1^i	91.53 (4)
N2—C2—H2A	110.0	Cl2—Cu1—Cl1	90.37 (4)
C3—C2—H2A	110.0	Cl3—Cu1—Cl1	169.84 (5)
N2—C2—H2B	110.0	Cl1^i—Cu1—Cl1	83.08 (4)
C3—C2—H2B	110.0	O1W—Cu2—Cl5	177.75 (10)
H2A—C2—H2B	108.4	O1W—Cu2—Cl4	88.68 (9)
N1—C3—C2	109.5 (3)	Cl5—Cu2—Cl4	91.98 (4)
N1—C3—H3A	109.8	O1W—Cu2—Cl6	87.38 (9)
C2—C3—H3A	109.8	Cl5—Cu2—Cl6	92.71 (5)
N1—C3—H3B	109.8	Cl4—Cu2—Cl6	160.32 (4)
C2—C3—H3B	109.8	O1—N1—C3	112.2 (3)
H3A—C3—H3B	108.2	O1—N1—C4	110.5 (3)
N1—C4—C6	108.9 (3)	C3—N1—C4	110.0 (3)
N1—C4—H4A	109.9	O1—N1—C5	104.1 (3)
C6—C4—H4A	109.9	C3—N1—C5	110.4 (3)
N1—C4—H4B	109.9	C4—N1—C5	109.4 (3)
C6—C4—H4B	109.9	O2—N2—C6	105.4 (3)
H4A—C4—H4B	108.3	O2—N2—C1	109.8 (3)
N1—C5—C1	109.1 (3)	C6—N2—C1	110.0 (3)
N1—C5—H5A	109.9	O2—N2—C2	111.1 (3)
C1—C5—H5A	109.9	C6—N2—C2	109.7 (3)
N1—C5—H5B	109.9	C1—N2—C2	110.7 (3)
C1—C5—H5B	109.9	N1—O1—H1	109.5
H5A—C5—H5B	108.3	N2—O2—H2	109.5
N2—C6—C4	108.8 (3)	Cu2—O1W—H1WA	110.2
N2—C6—H6A	109.9	Cu2—O1W—H1WB	122.9
C4—C6—H6A	109.9	H1WA—O1W—H1WB	108.5
N2—C2—C3—N1	−2.6 (4)	C1—C5—N1—O1	−177.5 (3)
N2—C1—C5—N1	−2.7 (4)	C1—C5—N1—C3	62.0 (4)
N1—C4—C6—N2	−3.4 (4)	C1—C5—N1—C4	−59.3 (4)
Cu1^i—Cl1—Cu1—Cl2	171.47 (5)	C4—C6—N2—O2	−177.3 (3)
Cu1^i—Cl1—Cu1—Cl3	58.4 (2)	C4—C6—N2—C1	−59.1 (4)
Cu1^i—Cl1—Cu1—Cl1^i	0.0	C4—C6—N2—C2	63.0 (4)
C2—C3—N1—O1	−174.3 (3)	C5—C1—N2—O2	178.1 (3)
C2—C3—N1—C4	62.2 (4)	C5—C1—N2—C6	62.6 (4)
C2—C3—N1—C5	−58.7 (4)	C5—C1—N2—C2	−58.9 (4)
C6—C4—N1—O1	177.0 (3)	C3—C2—N2—O2	−175.5 (3)
C6—C4—N1—C3	−58.5 (4)	C3—C2—N2—C6	−59.4 (4)
C6—C4—N1—C5	62.9 (4)	C3—C2—N2—C1	62.3 (4)

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl5^iii	0.82	2.32	3.108 (3)	161
O1—H1···Cl3^iv	0.82	2.16	2.978 (3)	175
O1W—H1WB···Cl5^ii	0.85	2.86	3.581 (3)	143
O1W—H1WB···Cl2^v	0.85	2.75	3.287 (3)	123
O1W—H1WA···Cl2	0.85	2.40	3.135 (3)	146

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+2, y+1/2, −z+3/2; (v) −x+1, −y+1, −z+1.