1,4-Di-aza-bicyclo-[2.2.2]octane-1,4-diium bis-(3-chloro-benzoate).

In the title salt C6H14N2 (2+)·2C7H4ClO2 (-), two 3-chloro-benzoate (3CBA) anions are bridged by one diprotonated 1,4-di-aza-bicyclo-[2.2.2]octane-1,4-diium (H2DABCO(2+)) dication through N-H⋯O hydrogen bonds. In this way, a trimeric unit is generated, in which the mean planes of the two 3CBA anions are twisted with respect to each other by a dihedral angle of 59.87 (9)°. The trimeric units are linked into a three-dimensional network via weak C-H⋯O inter-actions.

Related literature

For related studies on co-crystals of DABCO and carb­oxy­lic acids, see: Arman et al. (2011 ▶); Skovsgaard & Bond (2009 ▶); Meehan et al. (1997 ▶); Rosli et al. (2006 ▶); Burchell et al. (2001 ▶).

Experimental

Crystal data

C6H14N2 2+·2C7H4ClO2 −

M = 425.29

Triclinic,

a = 7.332 (4) Å

b = 10.512 (6) Å

c = 13.517 (7) Å

α = 79.74 (3)°

β = 76.68 (2)°

γ = 85.47 (2)°

V = 996.8 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.36 mm−1

T = 123 K

0.08 × 0.07 × 0.06 mm

Data collection

Rigaku Saturn70 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T min = 0.874, T max = 1.000

6989 measured reflections

3671 independent reflections

2777 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.097

S = 0.91

3671 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.33 e Å−3

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814000610/jj2180sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000610/jj2180Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814000610/jj2180Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H14N22+·2C7H4ClO2−	Z = 2
Mr = 425.29	F(000) = 444
Triclinic, P1	Dx = 1.417 Mg m−3
a = 7.332 (4) Å	Mo Kα radiation, λ = 0.71075 Å
b = 10.512 (6) Å	Cell parameters from 3510 reflections
c = 13.517 (7) Å	θ = 3.1–27.5°
α = 79.74 (3)°	µ = 0.36 mm−1
β = 76.68 (2)°	T = 123 K
γ = 85.47 (2)°	Block, colourless
V = 996.8 (9) Å3	0.08 × 0.07 × 0.06 mm

Rigaku Saturn70 diffractometer	3671 independent reflections
Radiation source: Rotating Anode	2777 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm-1	Rint = 0.034
ω scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −8→8
Tmin = 0.874, Tmax = 1.000	k = −12→12
6989 measured reflections	l = −16→16

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0526P)2] where P = (Fo2 + 2Fc2)/3
S = 0.91	(Δ/σ)max = 0.001
3671 reflections	Δρmax = 0.40 e Å−3
253 parameters	Δρmin = −0.33 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
Cl1	0.85741 (7)	0.29946 (5)	0.56505 (4)	0.02963 (16)
Cl2	−0.96963 (7)	−0.46471 (5)	0.18722 (4)	0.03041 (16)
O1	0.33887 (19)	0.09113 (13)	0.42587 (10)	0.0247 (3)
O2	0.26536 (19)	0.24510 (13)	0.30319 (11)	0.0277 (3)
O3	−0.40110 (18)	−0.19373 (13)	0.18759 (10)	0.0209 (3)
O4	−0.22174 (19)	−0.15730 (15)	0.02822 (10)	0.0320 (4)
N1	−0.1723 (2)	−0.05291 (14)	0.22871 (11)	0.0163 (4)
H1N	−0.2524	−0.1042	0.2147	0.020*
N2	0.0517 (2)	0.08989 (15)	0.26718 (11)	0.0170 (4)
H2N	0.1317	0.1413	0.2812	0.020*
C1	0.4754 (2)	0.29730 (18)	0.39639 (13)	0.0152 (4)
C2	0.4815 (3)	0.42300 (18)	0.34315 (14)	0.0183 (4)
H2	0.3996	0.4506	0.2977	0.022*
C3	0.6052 (3)	0.50894 (19)	0.35524 (14)	0.0204 (4)
H3	0.6092	0.5944	0.3175	0.024*
C4	0.7235 (3)	0.46978 (19)	0.42271 (14)	0.0193 (4)
H4	0.8105	0.5273	0.4309	0.023*
C5	0.7124 (2)	0.34535 (19)	0.47776 (14)	0.0178 (4)
C6	0.5904 (2)	0.25831 (18)	0.46641 (14)	0.0168 (4)
H6	0.5848	0.1735	0.5054	0.020*
C7	0.3501 (2)	0.20080 (18)	0.37673 (14)	0.0166 (4)
C8	−0.4958 (3)	−0.27845 (17)	0.05760 (14)	0.0165 (4)
C9	−0.6506 (2)	−0.33291 (17)	0.12918 (14)	0.0163 (4)
H9	−0.6695	−0.3249	0.1998	0.020*
C10	−0.7755 (3)	−0.39815 (18)	0.09679 (15)	0.0183 (4)
C11	−0.7508 (3)	−0.41311 (19)	−0.00502 (15)	0.0212 (4)
H11	−0.8381	−0.4587	−0.0262	0.025*
C12	−0.5961 (3)	−0.36021 (18)	−0.07544 (15)	0.0213 (4)
H12	−0.5769	−0.3698	−0.1457	0.026*
C13	−0.4691 (3)	−0.29346 (18)	−0.04470 (14)	0.0193 (4)
H13	−0.3633	−0.2579	−0.0938	0.023*
C14	−0.3593 (3)	−0.20410 (18)	0.09103 (14)	0.0191 (4)
C15	−0.1980 (3)	0.08017 (18)	0.17522 (15)	0.0211 (4)
H15A	−0.3308	0.1102	0.1950	0.025*
H15B	−0.1653	0.0822	0.0997	0.025*
C16	−0.0712 (3)	0.16953 (18)	0.20515 (15)	0.0210 (4)
H16A	0.0062	0.2189	0.1423	0.025*
H16B	−0.1488	0.2319	0.2457	0.025*
C17	0.0218 (2)	−0.10165 (19)	0.19240 (15)	0.0200 (4)
H17A	0.0442	−0.1082	0.1184	0.024*
H17B	0.0414	−0.1890	0.2312	0.024*
C18	0.1599 (3)	−0.00838 (18)	0.20868 (14)	0.0188 (4)
H18A	0.2499	−0.0569	0.2474	0.023*
H18B	0.2315	0.0344	0.1412	0.023*
C19	−0.2115 (3)	−0.05460 (19)	0.34127 (14)	0.0190 (4)
H19A	−0.2063	−0.1448	0.3777	0.023*
H19B	−0.3385	−0.0165	0.3649	0.023*
C20	−0.0641 (3)	0.02409 (18)	0.36553 (14)	0.0187 (4)
H20A	−0.1270	0.0892	0.4081	0.022*
H20B	0.0169	−0.0340	0.4048	0.022*

	U11	U22	U33	U12	U13	U23
Cl1	0.0312 (3)	0.0291 (3)	0.0341 (3)	−0.0036 (2)	−0.0212 (2)	−0.0007 (2)
Cl2	0.0256 (3)	0.0346 (3)	0.0307 (3)	−0.0156 (2)	−0.0003 (2)	−0.0061 (2)
O1	0.0320 (8)	0.0181 (8)	0.0259 (8)	−0.0076 (6)	−0.0121 (6)	0.0020 (6)
O2	0.0377 (9)	0.0250 (8)	0.0254 (8)	−0.0111 (6)	−0.0205 (7)	0.0046 (6)
O3	0.0248 (8)	0.0236 (8)	0.0153 (7)	−0.0077 (6)	−0.0037 (6)	−0.0042 (6)
O4	0.0295 (9)	0.0475 (10)	0.0191 (8)	−0.0213 (7)	−0.0021 (6)	−0.0013 (7)
N1	0.0186 (9)	0.0145 (8)	0.0179 (8)	−0.0035 (6)	−0.0077 (7)	−0.0025 (7)
N2	0.0176 (9)	0.0171 (9)	0.0181 (8)	−0.0045 (7)	−0.0074 (7)	−0.0014 (7)
C1	0.0157 (10)	0.0172 (10)	0.0124 (9)	−0.0011 (7)	−0.0011 (7)	−0.0040 (8)
C2	0.0199 (11)	0.0226 (11)	0.0123 (9)	−0.0002 (8)	−0.0043 (8)	−0.0017 (8)
C3	0.0258 (11)	0.0171 (10)	0.0165 (10)	−0.0039 (8)	−0.0021 (8)	0.0000 (8)
C4	0.0186 (10)	0.0217 (11)	0.0181 (10)	−0.0062 (8)	−0.0018 (8)	−0.0047 (8)
C5	0.0159 (10)	0.0228 (11)	0.0160 (10)	−0.0003 (8)	−0.0058 (8)	−0.0040 (8)
C6	0.0172 (10)	0.0169 (10)	0.0153 (9)	−0.0014 (8)	−0.0020 (7)	−0.0018 (8)
C7	0.0156 (10)	0.0203 (11)	0.0139 (10)	−0.0024 (8)	−0.0022 (7)	−0.0037 (8)
C8	0.0186 (10)	0.0126 (10)	0.0183 (10)	0.0009 (7)	−0.0055 (8)	−0.0014 (8)
C9	0.0177 (10)	0.0162 (10)	0.0153 (10)	0.0009 (8)	−0.0030 (8)	−0.0046 (8)
C10	0.0169 (10)	0.0165 (10)	0.0213 (10)	−0.0013 (8)	−0.0037 (8)	−0.0028 (8)
C11	0.0228 (11)	0.0194 (11)	0.0262 (11)	0.0000 (8)	−0.0119 (9)	−0.0080 (9)
C12	0.0272 (12)	0.0227 (11)	0.0158 (10)	0.0016 (8)	−0.0085 (8)	−0.0042 (8)
C13	0.0221 (11)	0.0194 (10)	0.0151 (10)	−0.0003 (8)	−0.0042 (8)	0.0008 (8)
C14	0.0199 (11)	0.0170 (10)	0.0206 (11)	−0.0031 (8)	−0.0064 (8)	0.0003 (8)
C15	0.0228 (11)	0.0183 (10)	0.0232 (11)	−0.0010 (8)	−0.0108 (8)	0.0016 (9)
C16	0.0253 (11)	0.0171 (10)	0.0218 (11)	−0.0016 (8)	−0.0103 (8)	0.0009 (8)
C17	0.0153 (11)	0.0236 (11)	0.0217 (10)	0.0019 (8)	−0.0037 (8)	−0.0068 (9)
C18	0.0165 (10)	0.0212 (11)	0.0184 (10)	−0.0007 (8)	−0.0029 (8)	−0.0034 (8)
C19	0.0203 (11)	0.0216 (11)	0.0145 (10)	−0.0040 (8)	−0.0022 (8)	−0.0017 (8)
C20	0.0225 (11)	0.0203 (10)	0.0135 (10)	−0.0023 (8)	−0.0040 (8)	−0.0020 (8)

Cl1—C5	1.747 (2)	C8—C9	1.397 (3)
Cl2—C10	1.749 (2)	C8—C14	1.508 (3)
O1—C7	1.222 (2)	C9—C10	1.375 (2)
O2—C7	1.290 (2)	C9—H9	0.9500
O3—C14	1.292 (2)	C10—C11	1.382 (3)
O4—C14	1.231 (2)	C11—C12	1.384 (3)
N1—C15	1.475 (2)	C11—H11	0.9500
N1—C19	1.479 (2)	C12—C13	1.385 (2)
N1—C17	1.478 (2)	C12—H12	0.9500
N1—H1N	0.9000	C13—H13	0.9500
N2—C18	1.481 (2)	C15—C16	1.536 (3)
N2—C16	1.481 (2)	C15—H15A	0.9900
N2—C20	1.487 (2)	C15—H15B	0.9900
N2—H2N	0.9000	C16—H16A	0.9900
C1—C2	1.386 (3)	C16—H16B	0.9900
C1—C6	1.396 (3)	C17—C18	1.540 (2)
C1—C7	1.516 (2)	C17—H17A	0.9900
C2—C3	1.384 (3)	C17—H17B	0.9900
C2—H2	0.9500	C18—H18A	0.9900
C3—C4	1.388 (3)	C18—H18B	0.9900
C3—H3	0.9500	C19—C20	1.537 (2)
C4—C5	1.383 (3)	C19—H19A	0.9900
C4—H4	0.9500	C19—H19B	0.9900
C5—C6	1.379 (3)	C20—H20A	0.9900
C6—H6	0.9500	C20—H20B	0.9900
C8—C13	1.387 (3)
C15—N1—C19	109.80 (15)	C13—C12—C11	120.80 (18)
C15—N1—C17	109.77 (15)	C13—C12—H12	119.6
C19—N1—C17	109.86 (14)	C11—C12—H12	119.6
C15—N1—H1N	109.2	C12—C13—C8	120.19 (18)
C19—N1—H1N	109.2	C12—C13—H13	119.9
C17—N1—H1N	109.1	C8—C13—H13	119.9
C18—N2—C16	109.80 (14)	O4—C14—O3	124.69 (17)
C18—N2—C20	109.46 (15)	O4—C14—C8	120.50 (17)
C16—N2—C20	109.79 (15)	O3—C14—C8	114.81 (16)
C18—N2—H2N	109.3	N1—C15—C16	109.14 (15)
C16—N2—H2N	109.3	N1—C15—H15A	109.9
C20—N2—H2N	109.2	C16—C15—H15A	109.9
C2—C1—C6	119.49 (17)	N1—C15—H15B	109.9
C2—C1—C7	120.69 (17)	C16—C15—H15B	109.9
C6—C1—C7	119.79 (17)	H15A—C15—H15B	108.3
C3—C2—C1	121.01 (18)	N2—C16—C15	108.98 (15)
C3—C2—H2	119.5	N2—C16—H16A	109.9
C1—C2—H2	119.5	C15—C16—H16A	109.9
C2—C3—C4	119.77 (18)	N2—C16—H16B	109.9
C2—C3—H3	120.1	C15—C16—H16B	109.9
C4—C3—H3	120.1	H16A—C16—H16B	108.3
C5—C4—C3	118.74 (18)	N1—C17—C18	109.31 (15)
C5—C4—H4	120.6	N1—C17—H17A	109.8
C3—C4—H4	120.6	C18—C17—H17A	109.8
C6—C5—C4	122.26 (18)	N1—C17—H17B	109.8
C6—C5—Cl1	119.69 (15)	C18—C17—H17B	109.8
C4—C5—Cl1	118.05 (14)	H17A—C17—H17B	108.3
C5—C6—C1	118.67 (18)	N2—C18—C17	108.61 (14)
C5—C6—H6	120.7	N2—C18—H18A	110.0
C1—C6—H6	120.7	C17—C18—H18A	110.0
O1—C7—O2	125.20 (17)	N2—C18—H18B	110.0
O1—C7—C1	121.13 (17)	C17—C18—H18B	110.0
O2—C7—C1	113.64 (17)	H18A—C18—H18B	108.3
C13—C8—C9	119.23 (17)	N1—C19—C20	108.85 (14)
C13—C8—C14	120.32 (17)	N1—C19—H19A	109.9
C9—C8—C14	120.45 (16)	C20—C19—H19A	109.9
C10—C9—C8	119.57 (17)	N1—C19—H19B	109.9
C10—C9—H9	120.2	C20—C19—H19B	109.9
C8—C9—H9	120.2	H19A—C19—H19B	108.3
C9—C10—C11	121.69 (18)	N2—C20—C19	109.05 (14)
C9—C10—Cl2	119.01 (15)	N2—C20—H20A	109.9
C11—C10—Cl2	119.29 (14)	C19—C20—H20A	109.9
C10—C11—C12	118.52 (17)	N2—C20—H20B	109.9
C10—C11—H11	120.7	C19—C20—H20B	109.9
C12—C11—H11	120.7	H20A—C20—H20B	108.3
C6—C1—C2—C3	2.6 (3)	C9—C8—C13—C12	0.9 (3)
C7—C1—C2—C3	−175.35 (16)	C14—C8—C13—C12	−179.08 (17)
C1—C2—C3—C4	−0.9 (3)	C13—C8—C14—O4	−0.8 (3)
C2—C3—C4—C5	−1.0 (3)	C9—C8—C14—O4	179.18 (18)
C3—C4—C5—C6	1.3 (3)	C13—C8—C14—O3	178.35 (17)
C3—C4—C5—Cl1	−178.13 (14)	C9—C8—C14—O3	−1.6 (3)
C4—C5—C6—C1	0.4 (3)	C19—N1—C15—C16	56.50 (19)
Cl1—C5—C6—C1	179.80 (13)	C17—N1—C15—C16	−64.36 (19)
C2—C1—C6—C5	−2.3 (3)	C18—N2—C16—C15	56.32 (19)
C7—C1—C6—C5	175.65 (15)	C20—N2—C16—C15	−64.07 (18)
C2—C1—C7—O1	−177.41 (18)	N1—C15—C16—N2	7.0 (2)
C6—C1—C7—O1	4.6 (3)	C15—N1—C17—C18	56.14 (19)
C2—C1—C7—O2	4.5 (2)	C19—N1—C17—C18	−64.69 (19)
C6—C1—C7—O2	−173.43 (16)	C16—N2—C18—C17	−64.37 (19)
C13—C8—C9—C10	−1.3 (3)	C20—N2—C18—C17	56.22 (19)
C14—C8—C9—C10	178.71 (17)	N1—C17—C18—N2	7.0 (2)
C8—C9—C10—C11	0.9 (3)	C15—N1—C19—C20	−65.01 (18)
C8—C9—C10—Cl2	−179.50 (14)	C17—N1—C19—C20	55.80 (19)
C9—C10—C11—C12	−0.2 (3)	C18—N2—C20—C19	−65.10 (19)
Cl2—C10—C11—C12	−179.78 (15)	C16—N2—C20—C19	55.49 (19)
C10—C11—C12—C13	−0.2 (3)	N1—C19—C20—N2	7.6 (2)
C11—C12—C13—C8	−0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3	0.90	1.64	2.536 (2)	178
N2—H2N···O2	0.90	1.63	2.528 (3)	175
C3—H3···O3i	0.95	2.59	3.523 (3)	169
C18—H18B···O4ii	0.99	2.43	3.311 (3)	147
C19—H19B···O1iii	0.99	2.56	3.552 (3)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3	0.90	1.64	2.536 (2)	178
N2—H2N⋯O2	0.90	1.63	2.528 (3)	175
C3—H3⋯O3i	0.95	2.59	3.523 (3)	169
C18—H18B⋯O4ii	0.99	2.43	3.311 (3)	147
C19—H19B⋯O1iii	0.99	2.56	3.552 (3)	178

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