1-(2-Bromo-ethyl)-1,4-diazo-niabicyclo-[2.2.2]octane bromide dihydrogen phosphate-phospho-ric acid (1/1).

In the crystal structure of the title compound, C(8)H(17)BrN(2) (2+)·Br(-)·H(2)PO(4) (-)·H(3)PO(4), the cations, anions and phospho-ric acid mol-ecules are linked by O-H⋯O, N-H⋯O and O-H⋯Br hydrogen bonds into layers parallel to (101).

Related literature

For the dielectric properties of N-protonated compounds, see: Szafranski & Katrusiak (2008 ▶); Katrusiak & Szafranski (1999 ▶); Chen et al. (2008 ▶); Fu et al. (2009 ▶); Zhao et al. (2008 ▶).

Experimental

Crystal data

C8H17BrN2 2+·Br−·H2PO4 −·H3PO4

M = 496.02

Monoclinic,

a = 12.963 (3) Å

b = 7.5959 (15) Å

c = 17.721 (4) Å

β = 92.00 (3)°

V = 1743.9 (7) Å3

Z = 4

Mo Kα radiation

μ = 4.87 mm−1

T = 293 K

0.3 × 0.25 × 0.2 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.240, T max = 0.379

17431 measured reflections

3991 independent reflections

3097 reflections with I > 2σ(I)

R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.147

S = 1.10

3991 reflections

199 parameters

H-atom parameters constrained

Δρmax = 1.03 e Å−3

Δρmin = −1.30 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017071/rz2443sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017071/rz2443Isup2.hkl

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

C8H17BrN22+·Br−·H2PO4−·H3PO4	F(000) = 992
Mr = 496.02	Dx = 1.889 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7671 reflections
a = 12.963 (3) Å	θ = 3.4–27.5°
b = 7.5959 (15) Å	µ = 4.87 mm−1
c = 17.721 (4) Å	T = 293 K
β = 92.00 (3)°	Prism, colourless
V = 1743.9 (7) Å3	0.3 × 0.25 × 0.2 mm
Z = 4

Rigaku Mercury2 diffractometer	3097 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.072
graphite	θmax = 27.5°, θmin = 3.1°
CCD_Profile_fitting scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.240, Tmax = 0.379	l = −23→22
17431 measured reflections	1814 standard reflections
3991 independent 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0703P)2 + 1.8668P] where P = (Fo2 + 2Fc2)/3
3991 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 1.03 e Å−3
0 restraints	Δρmin = −1.29 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.8045 (5)	0.7487 (8)	0.5147 (3)	0.0471 (14)
H1A	0.8221	0.6458	0.5450	0.057*
H1B	0.8240	0.8527	0.5436	0.057*
C2	0.8627 (4)	0.7443 (7)	0.4414 (3)	0.0352 (11)
H2A	0.9045	0.8496	0.4374	0.042*
H2B	0.9083	0.6431	0.4413	0.042*
C3	0.6645 (5)	0.9084 (8)	0.4485 (3)	0.0458 (14)
H3A	0.6851	1.0154	0.4748	0.055*
H3B	0.5905	0.9126	0.4387	0.055*
C4	0.7193 (4)	0.8955 (6)	0.3750 (2)	0.0283 (10)
H4A	0.7610	0.9999	0.3681	0.034*
H4B	0.6690	0.8887	0.3333	0.034*
C5	0.6608 (5)	0.5869 (8)	0.4562 (3)	0.0491 (15)
H5A	0.5875	0.5894	0.4434	0.059*
H5B	0.6748	0.4858	0.4885	0.059*
C6	0.7217 (4)	0.5720 (6)	0.3848 (3)	0.0323 (11)
H6A	0.7654	0.4684	0.3877	0.039*
H6B	0.6745	0.5591	0.3415	0.039*
C7	0.8408 (4)	0.7146 (7)	0.3008 (3)	0.0378 (12)
H7A	0.8807	0.6065	0.3019	0.045*
H7B	0.7888	0.7047	0.2603	0.045*
C8	0.9111 (5)	0.8654 (8)	0.2840 (3)	0.0492 (14)
H8A	0.9638	0.8778	0.3238	0.059*
H8B	0.8722	0.9743	0.2803	0.059*
N1	0.6916 (4)	0.7512 (5)	0.4966 (2)	0.0344 (10)
H1C	0.6570	0.7580	0.5404	0.041*
N2	0.7874 (3)	0.7339 (5)	0.3752 (2)	0.0262 (8)
O1	0.4055 (3)	0.7844 (4)	0.65616 (19)	0.0342 (8)
H1D	0.3713	0.7503	0.6914	0.051*
O2	0.5835 (3)	0.8397 (4)	0.6163 (2)	0.0407 (9)
O3	0.5392 (3)	0.5469 (4)	0.6708 (2)	0.0401 (9)
O4	0.5490 (3)	0.8038 (5)	0.7549 (2)	0.0438 (9)
H4C	0.5100	0.8835	0.7667	0.066*
O5	0.2784 (3)	0.9370 (5)	0.8525 (3)	0.0589 (11)
H5C	0.3371	0.9707	0.8448	0.088*
O6	0.2824 (3)	0.6928 (6)	0.7558 (2)	0.0578 (12)
O7	0.3544 (4)	0.6584 (6)	0.8901 (2)	0.0622 (12)
H7C	0.3639	0.5548	0.8794	0.093*
O8	0.1613 (4)	0.6852 (7)	0.8600 (2)	0.0734 (15)
H8D	0.1511	0.7297	0.9099	0.110*
Br1	0.11078 (4)	0.73719 (7)	0.02823 (3)	0.03808 (18)
Br2	0.97424 (5)	0.81384 (9)	0.18848 (3)	0.0491 (2)
P1	0.52097 (10)	0.74245 (15)	0.67295 (7)	0.0260 (3)
P2	0.26999 (11)	0.73716 (17)	0.83560 (8)	0.0336 (3)

	U11	U22	U33	U12	U13	U23
C1	0.053 (4)	0.061 (4)	0.027 (3)	−0.003 (3)	−0.015 (2)	0.004 (2)
C2	0.027 (3)	0.037 (3)	0.041 (3)	−0.001 (2)	−0.010 (2)	−0.003 (2)
C3	0.054 (3)	0.045 (3)	0.039 (3)	0.018 (3)	0.011 (3)	0.008 (2)
C4	0.034 (3)	0.025 (2)	0.026 (2)	0.0043 (19)	−0.0025 (19)	0.0012 (18)
C5	0.064 (4)	0.044 (3)	0.040 (3)	−0.024 (3)	0.007 (3)	−0.005 (3)
C6	0.038 (3)	0.023 (2)	0.035 (3)	−0.004 (2)	−0.008 (2)	−0.0012 (19)
C7	0.040 (3)	0.038 (3)	0.035 (3)	0.004 (2)	0.004 (2)	−0.008 (2)
C8	0.048 (3)	0.060 (4)	0.040 (3)	−0.005 (3)	0.017 (3)	−0.013 (3)
N1	0.045 (3)	0.032 (2)	0.026 (2)	−0.0003 (18)	0.0029 (19)	0.0015 (16)
N2	0.027 (2)	0.0226 (18)	0.029 (2)	0.0039 (15)	−0.0020 (16)	−0.0014 (15)
O1	0.0329 (19)	0.0411 (19)	0.0284 (17)	0.0070 (15)	−0.0029 (15)	0.0076 (15)
O2	0.052 (2)	0.0301 (18)	0.042 (2)	−0.0086 (16)	0.0173 (17)	0.0011 (15)
O3	0.047 (2)	0.0254 (17)	0.048 (2)	0.0046 (15)	0.0133 (17)	0.0055 (15)
O4	0.041 (2)	0.058 (2)	0.0319 (19)	0.0148 (18)	−0.0095 (16)	−0.0110 (17)
O5	0.053 (2)	0.040 (2)	0.085 (3)	−0.0016 (19)	0.014 (2)	−0.010 (2)
O6	0.054 (3)	0.088 (3)	0.033 (2)	−0.016 (2)	0.0131 (19)	−0.014 (2)
O7	0.084 (3)	0.047 (2)	0.055 (3)	0.016 (2)	−0.007 (2)	−0.005 (2)
O8	0.063 (3)	0.113 (4)	0.045 (2)	−0.044 (3)	0.020 (2)	−0.022 (3)
Br1	0.0384 (3)	0.0382 (3)	0.0377 (3)	0.0004 (2)	0.0016 (2)	−0.0041 (2)
Br2	0.0453 (4)	0.0619 (4)	0.0406 (3)	−0.0004 (3)	0.0118 (3)	−0.0015 (3)
P1	0.0294 (6)	0.0237 (6)	0.0251 (6)	0.0022 (5)	0.0035 (5)	0.0006 (4)
P2	0.0386 (7)	0.0318 (7)	0.0308 (7)	−0.0040 (5)	0.0064 (6)	−0.0031 (5)

C1—N1	1.488 (7)	C7—C8	1.500 (8)
C1—C2	1.526 (8)	C7—N2	1.517 (6)
C1—H1A	0.9700	C7—H7A	0.9700
C1—H1B	0.9700	C7—H7B	0.9700
C2—N2	1.501 (6)	C8—Br2	1.945 (5)
C2—H2A	0.9700	C8—H8A	0.9700
C2—H2B	0.9700	C8—H8B	0.9700
C3—N1	1.501 (6)	N1—H1C	0.9100
C3—C4	1.510 (7)	O1—P1	1.549 (4)
C3—H3A	0.9700	O1—H1D	0.8200
C3—H3B	0.9700	O2—P1	1.507 (3)
C4—N2	1.511 (6)	O3—P1	1.505 (3)
C4—H4A	0.9700	O4—P1	1.556 (4)
C4—H4B	0.9700	O4—H4C	0.8200
C5—N1	1.486 (6)	O5—P2	1.550 (4)
C5—C6	1.519 (7)	O5—H5C	0.8200
C5—H5A	0.9700	O6—P2	1.468 (4)
C5—H5B	0.9700	O7—P2	1.554 (4)
C6—N2	1.509 (6)	O7—H7C	0.8200
C6—H6A	0.9700	O8—P2	1.539 (4)
C6—H6B	0.9700	O8—H8D	0.9600
N1—C1—C2	109.1 (4)	C8—C7—H7B	108.9
N1—C1—H1A	109.9	N2—C7—H7B	108.9
C2—C1—H1A	109.9	H7A—C7—H7B	107.7
N1—C1—H1B	109.9	C7—C8—Br2	107.2 (4)
C2—C1—H1B	109.9	C7—C8—H8A	110.3
H1A—C1—H1B	108.3	Br2—C8—H8A	110.3
N2—C2—C1	109.9 (4)	C7—C8—H8B	110.3
N2—C2—H2A	109.7	Br2—C8—H8B	110.3
C1—C2—H2A	109.7	H8A—C8—H8B	108.5
N2—C2—H2B	109.7	C5—N1—C1	109.8 (4)
C1—C2—H2B	109.7	C5—N1—C3	110.0 (4)
H2A—C2—H2B	108.2	C1—N1—C3	110.0 (4)
N1—C3—C4	109.3 (4)	C5—N1—H1C	109.0
N1—C3—H3A	109.8	C1—N1—H1C	109.0
C4—C3—H3A	109.8	C3—N1—H1C	109.0
N1—C3—H3B	109.8	C2—N2—C6	108.0 (4)
C4—C3—H3B	109.8	C2—N2—C4	108.8 (3)
H3A—C3—H3B	108.3	C6—N2—C4	109.3 (4)
C3—C4—N2	110.1 (4)	C2—N2—C7	112.3 (4)
C3—C4—H4A	109.6	C6—N2—C7	107.2 (4)
N2—C4—H4A	109.6	C4—N2—C7	111.1 (4)
C3—C4—H4B	109.6	P1—O1—H1D	109.5
N2—C4—H4B	109.6	P1—O4—H4C	109.5
H4A—C4—H4B	108.2	P2—O5—H5C	109.5
N1—C5—C6	109.0 (4)	P2—O7—H7C	109.5
N1—C5—H5A	109.9	P2—O8—H8D	109.0
C6—C5—H5A	109.9	O3—P1—O2	112.23 (19)
N1—C5—H5B	109.9	O3—P1—O1	110.5 (2)
C6—C5—H5B	109.9	O2—P1—O1	108.1 (2)
H5A—C5—H5B	108.3	O3—P1—O4	106.7 (2)
N2—C6—C5	110.2 (4)	O2—P1—O4	111.2 (2)
N2—C6—H6A	109.6	O1—P1—O4	108.1 (2)
C5—C6—H6A	109.6	O6—P2—O8	110.1 (3)
N2—C6—H6B	109.6	O6—P2—O5	113.7 (3)
C5—C6—H6B	109.6	O8—P2—O5	104.8 (3)
H6A—C6—H6B	108.1	O6—P2—O7	114.4 (3)
C8—C7—N2	113.5 (4)	O8—P2—O7	111.0 (3)
C8—C7—H7A	108.9	O5—P2—O7	102.3 (2)
N2—C7—H7A	108.9
N1—C1—C2—N2	−3.1 (6)	C1—C2—N2—C4	61.1 (5)
N1—C3—C4—N2	−2.8 (6)	C1—C2—N2—C7	−175.5 (4)
N1—C5—C6—N2	−4.0 (6)	C5—C6—N2—C2	62.0 (5)
N2—C7—C8—Br2	178.6 (3)	C5—C6—N2—C4	−56.2 (5)
C6—C5—N1—C1	−58.3 (6)	C5—C6—N2—C7	−176.8 (4)
C6—C5—N1—C3	62.8 (6)	C3—C4—N2—C2	−57.6 (5)
C2—C1—N1—C5	62.7 (5)	C3—C4—N2—C6	60.1 (5)
C2—C1—N1—C3	−58.4 (5)	C3—C4—N2—C7	178.2 (4)
C4—C3—N1—C5	−59.0 (6)	C8—C7—N2—C2	−60.4 (6)
C4—C3—N1—C1	62.0 (6)	C8—C7—N2—C6	−178.9 (4)
C1—C2—N2—C6	−57.5 (5)	C8—C7—N2—C4	61.8 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2	0.91	1.79	2.667 (6)	162
O1—H1D···O6	0.82	1.71	2.519 (5)	170
O4—H4C···O3i	0.82	1.80	2.560 (5)	155
O5—H5C···O3i	0.82	1.73	2.555 (5)	179
O7—H7C···O2ii	0.82	1.77	2.555 (5)	159
O8—H8D···Br1iii	0.96	2.18	3.100 (4)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2	0.91	1.79	2.667 (6)	162
O1—H1D⋯O6	0.82	1.71	2.519 (5)	170
O4—H4C⋯O3i	0.82	1.80	2.560 (5)	155
O5—H5C⋯O3i	0.82	1.73	2.555 (5)	179
O7—H7C⋯O2ii	0.82	1.77	2.555 (5)	159
O8—H8D⋯Br1iii	0.96	2.18	3.100 (4)	160

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