4,11-Diaza-1,8-diazo-niacyclo-tetra-decane bis-(pyridine-2-carboxyl-ate) dihydrate.

The asymmetric unit of the title compound, C(10)H(26)N(4) (2+)·2C(6)H(4)NO(2) (-)·2H(2)O, consists of half of a doubly protonated 1,4,8,11-tetra-azacyclo-tetra-decane (cyclam) dication, a pyridine-2-carboxyl-ate anion and a solvent water mol-ecule. The complete dication is generated by a crystallographic centre and adopts an endodentate conformation which may be influenced by intra-molecular N-H⋯N hydrogen bonding. The carboxyl-ate group of the anion appears to be delocalized on the basis of the C-O bond lengths [1.257 (2) and 1.250 (2) Å]. In the crystal structure, the components are linked by inter-molecular N-H⋯O, N-H⋯N and O-H⋯O hydrogen bonds.

Related literature

For the crystal structures of [H2(cyclam)]X [X = (ClO4)2 or Cl2], see: Nave & Truter (1974 ▶); Kim et al. (2009 ▶). For the crystal structures of [H4(cyclam)]X·nH2O [X = Cl4, Br4, (ClO4)4, (SCN)4, (SO4)2 or (p-CH3C6H4SO3)4], see: Robinson et al. (1989 ▶); Subramanian & Zaworotko (1995 ▶). For the structure of pyridine-2-carboxylic acid, see: Hamazaki et al. (1998 ▶). For the crystal structures of pyridine-2-carboxyl­ate compounds, see: Kim & Ha (2009a ▶,b ▶).

Experimental

Crystal data

C10H26N4 2+·2C6H4NO2 −·2H2O

M = 482.58

Monoclinic,

a = 10.2746 (8) Å

b = 12.0551 (9) Å

c = 10.3244 (8) Å

β = 93.104 (2)°

V = 1276.92 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 200 K

0.22 × 0.17 × 0.11 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS: Sheldrick, 1996 ▶) T min = 0.868, T max = 1.000

9364 measured reflections

3152 independent reflections

1540 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.123

S = 1.02

3152 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037258/nk2004sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037258/nk2004Isup2.hkl

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

C10H26N42+·2C6H4NO2−·2(H2O)	F(000) = 520
Mr = 482.58	Dx = 1.255 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1456 reflections
a = 10.2746 (8) Å	θ = 2.6–24.3°
b = 12.0551 (9) Å	µ = 0.09 mm−1
c = 10.3244 (8) Å	T = 200 K
β = 93.104 (2)°	Block, colourless
V = 1276.92 (17) Å3	0.22 × 0.17 × 0.11 mm
Z = 2

Bruker SMART 1000 CCD diffractometer	3152 independent reflections
Radiation source: fine-focus sealed tube	1540 reflections with I > 2σ(I)
graphite	Rint = 0.070
ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS: Sheldrick, 1996)	h = −11→13
Tmin = 0.868, Tmax = 1.000	k = −16→15
9364 measured reflections	l = −13→13

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0315P)2] where P = (Fo2 + 2Fc2)/3
3152 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.25 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
O1	0.84295 (15)	0.05500 (12)	0.30790 (13)	0.0377 (4)
O2	0.71238 (16)	0.00216 (13)	0.46269 (15)	0.0433 (5)
N1	0.67291 (18)	0.21986 (15)	0.23751 (17)	0.0333 (5)
C1	0.5839 (2)	0.29517 (19)	0.1972 (2)	0.0383 (6)
H1	0.6109	0.3538	0.1434	0.046*
C2	0.4558 (2)	0.2926 (2)	0.2290 (2)	0.0434 (6)
H2	0.3960	0.3481	0.1984	0.052*
C3	0.4166 (2)	0.2074 (2)	0.3066 (2)	0.0449 (7)
H3	0.3282	0.2017	0.3283	0.054*
C4	0.5066 (2)	0.1306 (2)	0.3524 (2)	0.0384 (6)
H4	0.4818	0.0725	0.4082	0.046*
C5	0.6339 (2)	0.13915 (18)	0.31597 (19)	0.0278 (5)
C6	0.7385 (2)	0.05841 (18)	0.3658 (2)	0.0312 (5)
N2	0.14631 (18)	0.09306 (16)	0.05713 (17)	0.0374 (5)
H21	0.1475	0.0811	0.1452	0.045*
N3	0.12754 (18)	−0.12813 (15)	−0.05896 (17)	0.0360 (5)
H31	0.1456	−0.1194	−0.1447	0.043*
H32	0.0565	−0.0845	−0.0438	0.043*
C7	0.0412 (3)	0.2719 (2)	0.0986 (3)	0.0510 (7)
H7A	0.0561	0.3529	0.0946	0.061*
H7B	0.0435	0.2503	0.1912	0.061*
C8	0.1501 (2)	0.2132 (2)	0.0340 (2)	0.0446 (7)
H8A	0.1424	0.2276	−0.0605	0.054*
H8B	0.2349	0.2430	0.0681	0.054*
C9	0.2570 (2)	0.0350 (2)	0.0057 (2)	0.0459 (7)
H9A	0.3388	0.0598	0.0519	0.055*
H9B	0.2625	0.0525	−0.0875	0.055*
C10	0.2406 (2)	−0.0876 (2)	0.0229 (2)	0.0485 (7)
H10A	0.3206	−0.1264	−0.0015	0.058*
H10B	0.2270	−0.1042	0.1151	0.058*
C11	0.0922 (3)	−0.24601 (19)	−0.0372 (3)	0.0487 (7)
H11A	0.0928	−0.2609	0.0571	0.058*
H11B	0.1577	−0.2949	−0.0748	0.058*
O3	0.11622 (16)	0.04470 (16)	0.33220 (14)	0.0609 (6)
H3A	0.0351	0.0418	0.3385	0.091*
H3B	0.1593	0.0314	0.4019	0.091*

	U11	U22	U33	U12	U13	U23
O1	0.0313 (10)	0.0450 (11)	0.0374 (9)	0.0095 (8)	0.0064 (8)	0.0074 (8)
O2	0.0425 (11)	0.0484 (11)	0.0389 (9)	−0.0014 (8)	0.0010 (8)	0.0163 (8)
N1	0.0335 (12)	0.0338 (11)	0.0327 (10)	0.0028 (9)	0.0026 (9)	0.0033 (9)
C1	0.0439 (16)	0.0346 (14)	0.0361 (13)	0.0048 (12)	−0.0003 (12)	0.0055 (11)
C2	0.0398 (16)	0.0423 (16)	0.0476 (15)	0.0118 (13)	−0.0042 (13)	−0.0027 (13)
C3	0.0305 (15)	0.0573 (18)	0.0473 (15)	0.0062 (13)	0.0050 (12)	0.0018 (14)
C4	0.0377 (15)	0.0464 (15)	0.0314 (13)	−0.0027 (13)	0.0038 (11)	0.0052 (12)
C5	0.0289 (13)	0.0303 (13)	0.0239 (11)	−0.0024 (11)	−0.0012 (10)	−0.0007 (10)
C6	0.0365 (15)	0.0284 (13)	0.0281 (12)	−0.0041 (11)	−0.0045 (11)	−0.0015 (11)
N2	0.0427 (13)	0.0406 (12)	0.0296 (10)	0.0016 (10)	0.0071 (9)	−0.0003 (9)
N3	0.0392 (12)	0.0361 (12)	0.0333 (10)	0.0082 (10)	0.0086 (9)	0.0035 (9)
C7	0.074 (2)	0.0301 (14)	0.0499 (16)	−0.0049 (14)	0.0144 (16)	0.0006 (12)
C8	0.0459 (17)	0.0431 (16)	0.0448 (15)	−0.0104 (13)	0.0036 (13)	0.0033 (13)
C9	0.0392 (16)	0.0610 (18)	0.0377 (14)	−0.0040 (14)	0.0035 (12)	−0.0116 (13)
C10	0.0424 (16)	0.0643 (19)	0.0383 (14)	0.0160 (14)	−0.0020 (13)	−0.0044 (13)
C11	0.0565 (18)	0.0364 (16)	0.0554 (17)	0.0108 (13)	0.0231 (15)	0.0159 (13)
O3	0.0392 (11)	0.1048 (16)	0.0385 (10)	−0.0009 (11)	0.0012 (9)	0.0222 (10)

O1—C6	1.257 (2)	N3—H31	0.9200
O2—C6	1.250 (2)	N3—H32	0.9200
N1—C1	1.339 (3)	C7—C8	1.509 (3)
N1—C5	1.341 (2)	C7—C11i	1.511 (4)
C1—C2	1.374 (3)	C7—H7A	0.9900
C1—H1	0.9500	C7—H7B	0.9900
C2—C3	1.377 (3)	C8—H8A	0.9900
C2—H2	0.9500	C8—H8B	0.9900
C3—C4	1.374 (3)	C9—C10	1.499 (3)
C3—H3	0.9500	C9—H9A	0.9900
C4—C5	1.385 (3)	C9—H9B	0.9900
C4—H4	0.9500	C10—H10A	0.9900
C5—C6	1.519 (3)	C10—H10B	0.9900
N2—C9	1.459 (3)	C11—C7i	1.511 (4)
N2—C8	1.468 (3)	C11—H11A	0.9900
N2—H21	0.9200	C11—H11B	0.9900
N3—C10	1.482 (3)	O3—H3A	0.8400
N3—C11	1.487 (3)	O3—H3B	0.8400
C1—N1—C5	117.3 (2)	C11i—C7—H7A	108.9
N1—C1—C2	123.9 (2)	C8—C7—H7B	108.9
N1—C1—H1	118.1	C11i—C7—H7B	108.9
C2—C1—H1	118.1	H7A—C7—H7B	107.7
C1—C2—C3	118.0 (2)	N2—C8—C7	111.34 (19)
C1—C2—H2	121.0	N2—C8—H8A	109.4
C3—C2—H2	121.0	C7—C8—H8A	109.4
C4—C3—C2	119.4 (2)	N2—C8—H8B	109.4
C4—C3—H3	120.3	C7—C8—H8B	109.4
C2—C3—H3	120.3	H8A—C8—H8B	108.0
C3—C4—C5	119.0 (2)	N2—C9—C10	109.6 (2)
C3—C4—H4	120.5	N2—C9—H9A	109.8
C5—C4—H4	120.5	C10—C9—H9A	109.8
N1—C5—C4	122.4 (2)	N2—C9—H9B	109.8
N1—C5—C6	116.15 (19)	C10—C9—H9B	109.8
C4—C5—C6	121.4 (2)	H9A—C9—H9B	108.2
O2—C6—O1	126.1 (2)	N3—C10—C9	110.3 (2)
O2—C6—C5	116.1 (2)	N3—C10—H10A	109.6
O1—C6—C5	117.80 (19)	C9—C10—H10A	109.6
C9—N2—C8	112.69 (19)	N3—C10—H10B	109.6
C9—N2—H21	108.4	C9—C10—H10B	109.6
C8—N2—H21	108.5	H10A—C10—H10B	108.1
C10—N3—C11	114.79 (19)	N3—C11—C7i	110.9 (2)
C10—N3—H31	108.6	N3—C11—H11A	109.5
C11—N3—H31	108.6	C7i—C11—H11A	109.5
C10—N3—H32	108.6	N3—C11—H11B	109.5
C11—N3—H32	108.6	C7i—C11—H11B	109.5
H31—N3—H32	107.5	H11A—C11—H11B	108.0
C8—C7—C11i	113.3 (2)	H3A—O3—H3B	113.9
C8—C7—H7A	108.9
C5—N1—C1—C2	−1.6 (3)	C4—C5—C6—O2	−16.4 (3)
N1—C1—C2—C3	−0.2 (4)	N1—C5—C6—O1	−17.0 (3)
C1—C2—C3—C4	2.0 (4)	C4—C5—C6—O1	164.4 (2)
C2—C3—C4—C5	−1.9 (3)	C9—N2—C8—C7	−174.9 (2)
C1—N1—C5—C4	1.7 (3)	C11i—C7—C8—N2	−68.7 (3)
C1—N1—C5—C6	−176.94 (19)	C8—N2—C9—C10	−175.26 (19)
C3—C4—C5—N1	0.0 (3)	C11—N3—C10—C9	−172.71 (19)
C3—C4—C5—C6	178.6 (2)	N2—C9—C10—N3	66.5 (2)
N1—C5—C6—O2	162.19 (18)	C10—N3—C11—C7i	165.97 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3	0.92	2.02	2.932 (2)	170
N3—H32···N2	0.92	2.53	2.926 (3)	106
N3—H32···N2i	0.92	2.08	2.846 (3)	139
N3—H31···O1ii	0.92	1.86	2.749 (2)	161
N3—H31···N1ii	0.92	2.46	3.039 (2)	121
O3—H3A···O1iii	0.84	1.99	2.808 (2)	165
O3—H3B···O2iv	0.84	1.91	2.739 (2)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3	0.92	2.02	2.932 (2)	170
N3—H32⋯N2	0.92	2.53	2.926 (3)	106
N3—H32⋯N2i	0.92	2.08	2.846 (3)	139
N3—H31⋯O1ii	0.92	1.86	2.749 (2)	161
N3—H31⋯N1ii	0.92	2.46	3.039 (2)	121
O3—H3A⋯O1iii	0.84	1.99	2.808 (2)	165
O3—H3B⋯O2iv	0.84	1.91	2.739 (2)	168

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