2,2'-[4,10-Bis(carb-oxy-meth-yl)-4,10-diaza-1,7-diazo-niacyclo-dodecane-1,7-di-yl]diacetate dihydrate.

In the title compound, C(16)H(28)N(4)O(8)·2H(2)O, the 12-membered macrocycle has twofold crystallographic symmetry and the asymmetric unit comprises one half-mol-ecule. The four carbox-yl/carboxyl-ate groups reside on the same side of the macrocycle. The mol-ecule is a double zwitterion with two of the carb-oxy-lic acid H atoms transferred to the two N atoms on the opposite sides of the macrocycle, resulting in both N atoms having positive charges and leaving the two resulting carboxyl-ate groups with negative charges. The two remaining carb-oxy-lic acid groups and the carboxyl-ate groups form O-H⋯O hydrogen bonds with the crystal water mol-ecules. The H atoms bound to the N atoms within the macrocyle are engaged in two equivalent hydrogen bonds with the adjacent N atoms.

Related literature

Kumagai et al. (2002 ▶) describe different coordinations for carboxyl­ate groups. For background information about the title compound and its metal complexes, see: Viola-Villegas & Doyle (2009 ▶). For macrocycle configurations, see: Bosnich et al. (1965 ▶); Dale (1973 ▶, 1976 ▶, 1980 ▶); Meyer et al. (1998 ▶).

Experimental

Crystal data

C16H28N4O8·2H2O

M = 440.46

Orthorhombic,

a = 17.183 (2) Å

b = 6.5826 (9) Å

c = 17.983 (2) Å

V = 2034.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.43 × 0.27 × 0.27 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2003 ▶) T min = 0.810, T max = 1.000

19408 measured reflections

2520 independent reflections

2236 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.112

S = 1.08

2520 reflections

144 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON Spek (2009) ▶.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004843/kp2290sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004843/kp2290Isup2.hkl

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

Enhanced figure: interactive version of Fig. 3

C16H28N4O8·2H2O	Dx = 1.438 Mg m−3
Mr = 440.46	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 13988 reflections
a = 17.183 (2) Å	θ = 1.0–28.3°
b = 6.5826 (9) Å	µ = 0.12 mm−1
c = 17.983 (2) Å	T = 100 K
V = 2034.0 (5) Å3	Block, colourless
Z = 4	0.43 × 0.27 × 0.27 mm
F(000) = 944

Bruker SMART APEX CCD diffractometer	2520 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
graphite	Rint = 0.037
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker 2003)	h = −22→22
Tmin = 0.810, Tmax = 1.000	k = −8→8
19408 measured reflections	l = −23→23

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0616P)2 + 0.8651P] where P = (Fo2 + 2Fc2)/3
2520 reflections	(Δ/σ)max = 0.003
144 parameters	Δρmax = 0.70 e Å−3
2 restraints	Δρmin = −0.19 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
C1	0.52319 (7)	0.29809 (18)	0.59684 (7)	0.0172 (2)
H1A	0.5484	0.1817	0.5716	0.021*
H1B	0.5118	0.4028	0.5588	0.021*
C2	0.44727 (7)	0.22770 (18)	0.63205 (7)	0.0169 (2)
H2A	0.4101	0.1899	0.5923	0.020*
H2B	0.4573	0.1052	0.6625	0.020*
C3	0.35164 (7)	0.29561 (18)	0.72810 (7)	0.0161 (2)
H3A	0.3257	0.1827	0.7015	0.019*
H3B	0.3118	0.3994	0.7398	0.019*
C4	0.61331 (7)	0.21651 (18)	0.70032 (7)	0.0165 (2)
H4A	0.6542	0.1467	0.6711	0.020*
H4B	0.5724	0.1157	0.7123	0.020*
C5	0.64046 (7)	0.50850 (18)	0.61660 (7)	0.0175 (2)
H5A	0.6619	0.4297	0.5744	0.021*
H5B	0.6833	0.5319	0.6524	0.021*
C6	0.61183 (7)	0.71385 (19)	0.58773 (7)	0.0190 (3)
C7	0.37872 (7)	0.54695 (18)	0.63298 (7)	0.0167 (2)
H7A	0.3332	0.4922	0.6058	0.020*
H7B	0.4178	0.5900	0.5957	0.020*
C8	0.35349 (7)	0.73022 (18)	0.67787 (7)	0.0187 (3)
N1	0.57832 (6)	0.38475 (15)	0.65388 (5)	0.0147 (2)
H1	0.5502	0.4699	0.6852	0.018*
N2	0.41201 (5)	0.38638 (15)	0.67930 (6)	0.0156 (2)
O1	0.66535 (6)	0.81050 (15)	0.55408 (6)	0.0293 (2)
O2	0.54404 (5)	0.76758 (14)	0.59796 (6)	0.0248 (2)
O3	0.31304 (5)	0.86834 (13)	0.64068 (5)	0.0201 (2)
H3	0.3110	0.8356	0.5956	0.030*
O4	0.36798 (7)	0.75428 (15)	0.74325 (5)	0.0286 (2)
O5	0.29964 (6)	0.82984 (15)	0.50131 (5)	0.0218 (2)
H5C	0.2571 (9)	0.800 (3)	0.4810 (9)	0.033*
H5D	0.3139 (11)	0.942 (2)	0.4806 (10)	0.033*

	U11	U22	U33	U12	U13	U23
C1	0.0153 (5)	0.0185 (5)	0.0176 (5)	−0.0004 (4)	−0.0003 (4)	−0.0007 (4)
C2	0.0144 (5)	0.0160 (5)	0.0204 (6)	−0.0006 (4)	−0.0001 (4)	−0.0015 (4)
C3	0.0124 (5)	0.0153 (5)	0.0205 (6)	−0.0014 (4)	−0.0004 (4)	−0.0014 (4)
C4	0.0159 (5)	0.0127 (5)	0.0209 (6)	0.0024 (4)	−0.0001 (4)	0.0018 (4)
C5	0.0141 (5)	0.0164 (5)	0.0219 (6)	−0.0006 (4)	0.0033 (4)	0.0026 (4)
C6	0.0210 (6)	0.0160 (5)	0.0201 (6)	−0.0001 (4)	−0.0001 (4)	0.0014 (4)
C7	0.0148 (5)	0.0157 (5)	0.0195 (5)	0.0005 (4)	−0.0017 (4)	0.0005 (4)
C8	0.0183 (6)	0.0143 (5)	0.0236 (6)	−0.0037 (4)	0.0004 (4)	0.0004 (4)
N1	0.0132 (4)	0.0137 (5)	0.0173 (5)	0.0007 (3)	0.0010 (3)	0.0008 (4)
N2	0.0127 (4)	0.0142 (5)	0.0198 (5)	0.0004 (3)	0.0003 (4)	0.0010 (4)
O1	0.0287 (5)	0.0212 (5)	0.0381 (6)	0.0002 (4)	0.0111 (4)	0.0102 (4)
O2	0.0187 (5)	0.0196 (4)	0.0361 (5)	0.0025 (4)	−0.0007 (4)	0.0035 (4)
O3	0.0218 (4)	0.0158 (4)	0.0227 (4)	0.0021 (3)	0.0013 (3)	−0.0007 (3)
O4	0.0445 (6)	0.0186 (5)	0.0227 (5)	−0.0021 (4)	−0.0053 (4)	−0.0026 (4)
O5	0.0234 (5)	0.0173 (4)	0.0246 (5)	0.0009 (4)	−0.0023 (4)	0.0023 (3)

C1—N1	1.5082 (15)	C5—C6	1.5294 (17)
C1—C2	1.5223 (16)	C5—H5A	0.9900
C1—H1A	0.9900	C5—H5B	0.9900
C1—H1B	0.9900	C6—O2	1.2312 (16)
C2—N2	1.4765 (15)	C6—O1	1.2715 (16)
C2—H2A	0.9900	C7—N2	1.4622 (15)
C2—H2B	0.9900	C7—C8	1.5149 (17)
C3—N2	1.4844 (15)	C7—H7A	0.9900
C3—C4i	1.5136 (16)	C7—H7B	0.9900
C3—H3A	0.9900	C8—O4	1.2122 (16)
C3—H3B	0.9900	C8—O3	1.3255 (15)
C4—N1	1.5117 (15)	N1—H1	0.9300
C4—C3i	1.5136 (17)	O3—H3	0.8400
C4—H4A	0.9900	O5—H5C	0.840 (15)
C4—H4B	0.9900	O5—H5D	0.865 (15)
C5—N1	1.5011 (15)
N1—C1—C2	111.75 (10)	N1—C5—H5B	108.8
N1—C1—H1A	109.3	C6—C5—H5B	108.8
C2—C1—H1A	109.3	H5A—C5—H5B	107.7
N1—C1—H1B	109.3	O2—C6—O1	127.71 (12)
C2—C1—H1B	109.3	O2—C6—C5	120.50 (11)
H1A—C1—H1B	107.9	O1—C6—C5	111.78 (11)
N2—C2—C1	112.06 (10)	N2—C7—C8	112.59 (10)
N2—C2—H2A	109.2	N2—C7—H7A	109.1
C1—C2—H2A	109.2	C8—C7—H7A	109.1
N2—C2—H2B	109.2	N2—C7—H7B	109.1
C1—C2—H2B	109.2	C8—C7—H7B	109.1
H2A—C2—H2B	107.9	H7A—C7—H7B	107.8
N2—C3—C4i	111.30 (9)	O4—C8—O3	120.49 (12)
N2—C3—H3A	109.4	O4—C8—C7	124.21 (12)
C4i—C3—H3A	109.4	O3—C8—C7	115.30 (11)
N2—C3—H3B	109.4	C5—N1—C1	110.39 (9)
C4i—C3—H3B	109.4	C5—N1—C4	111.18 (9)
H3A—C3—H3B	108.0	C1—N1—C4	110.39 (9)
N1—C4—C3i	112.09 (9)	C5—N1—H1	108.3
N1—C4—H4A	109.2	C1—N1—H1	108.3
C3i—C4—H4A	109.2	C4—N1—H1	108.3
N1—C4—H4B	109.2	C7—N2—C2	110.13 (9)
C3i—C4—H4B	109.2	C7—N2—C3	110.75 (9)
H4A—C4—H4B	107.9	C2—N2—C3	110.02 (9)
N1—C5—C6	113.73 (10)	C8—O3—H3	109.5
N1—C5—H5A	108.8	H5C—O5—H5D	105.1 (18)
C6—C5—H5A	108.8
N1—C1—C2—N2	51.11 (13)	C3i—C4—N1—C5	74.84 (12)
N1—C5—C6—O2	2.30 (17)	C3i—C4—N1—C1	−162.30 (9)
N1—C5—C6—O1	−177.48 (11)	C8—C7—N2—C2	−170.60 (9)
N2—C7—C8—O4	8.99 (17)	C8—C7—N2—C3	67.48 (12)
N2—C7—C8—O3	−170.88 (10)	C1—C2—N2—C7	73.24 (12)
C6—C5—N1—C1	73.84 (12)	C1—C2—N2—C3	−164.40 (10)
C6—C5—N1—C4	−163.30 (10)	C4i—C3—N2—C7	−150.74 (10)
C2—C1—N1—C5	−162.75 (9)	C4i—C3—N2—C2	87.27 (11)
C2—C1—N1—C4	73.93 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5	0.84	1.71	2.5295 (14)	166
N1—H1···N2	0.93	2.44	2.8940 (14)	110
O5—H5D···O1ii	0.86 (1)	1.78 (2)	2.6380 (14)	173.(2)
O5—H5C···O1iii	0.84 (1)	1.85 (2)	2.6776 (14)	170.(2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5	0.84	1.71	2.5295 (14)	166
N1—H1⋯N2	0.93	2.44	2.8940 (14)	110
O5—H5D⋯O1i	0.86 (1)	1.78 (2)	2.6380 (14)	173 (2)
O5—H5C⋯O1ii	0.84 (1)	1.85 (2)	2.6776 (14)	170 (2)

Symmetry codes: (i) ; (ii) .