2,2′-Bipyridin-1′-ium 1-oxide bromide monohydrate

Heintz, K.; Görls, H.; Imhof, W.

doi:10.1107/S2056989018002347

2,2′-Bipyridin-1′-ium 1-oxide bromide monohydrate

Structural disorder is observed due to the fact that protonation, as well as oxidation, of the N atoms of 2,2′-bipyridine occurs either at either of the N atoms. The disorder extends to the remainder of the cation, with a refined occupancy rate of 0.717 (4) for the major moiety.

Keywords: crystal structure; bipyridine oxide; hydrobromide; hydrate.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989018002347/zl2721sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018002347/zl2721Isup2.hkl Contains datablock I

CCDC reference: 1822822

checkCIF report

Key indicators

Single-crystal X-ray study
T = 133 K
Mean () = 0.000 Å
Disorder in main residue
R factor = 0.023
wR factor = 0.052
Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         11 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         26 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records         12 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )       100% Note
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  2  )       100% Note
PLAT304_ALERT_4_G Non-Integer Number of Atoms in ...... Resd  1         15.77 Check
PLAT304_ALERT_4_G Non-Integer Number of Atoms in ...... Resd  2          6.23 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O1W      ..C1B              2.98 Ang.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         32 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          2 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         12 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  15 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2006).

2,2'-Bipyridin-1'-ium 1-oxide bromide monohydrate top

Crystal data top

C₁₀H₉N₂O⁺·Br⁻·H₂O	F(000) = 544
M_r = 271.12	D_x = 1.669 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.7882 (1) Å	Cell parameters from 12419 reflections
b = 9.2095 (2) Å	θ = 2.0–27.5°
c = 20.2485 (4) Å	µ = 3.79 mm⁻¹
β = 91.701 (1)°	T = 133 K
V = 1078.90 (4) Å³	Prism, colourless
Z = 4	0.05 × 0.04 × 0.03 mm

Data collection top

Nonius KappaCCD diffractometer	2465 independent reflections
Radiation source: fine-focus sealed tube	2226 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi– + ω–scan	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −7→7
T_min = 0.557, T_max = 0.746	k = −9→11
12419 measured reflections	l = −26→26

Refinement top

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)] = 0.023	Hydrogen site location: mixed
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0113P)² + 0.9881P] where P = (F_o² + 2F_c²)/3
2465 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.46 e Å⁻³
32 restraints	Δρ_min = −0.51 e Å⁻³

Special details top

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 > 2sigma(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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	−0.09302 (3)	0.63110 (2)	0.65415 (2)	0.02577 (7)
O1	0.0960 (3)	−0.0036 (2)	0.43461 (9)	0.0270 (5)	0.717 (4)
N1	0.2649 (12)	0.0073 (8)	0.3908 (2)	0.0199 (9)	0.717 (4)
N2	0.3050 (9)	0.1763 (6)	0.5057 (2)	0.0206 (7)	0.717 (4)
H1N2	0.188837	0.116543	0.497651	0.025*	0.717 (4)
C1	0.2378 (9)	−0.0729 (6)	0.33445 (16)	0.0236 (8)	0.717 (4)
H1	0.103588	−0.130999	0.327701	0.028*	0.717 (4)
C2	0.4039 (8)	−0.0697 (6)	0.2875 (2)	0.0252 (9)	0.717 (4)
H2	0.385065	−0.126508	0.248510	0.030*	0.717 (4)
C3	0.5987 (11)	0.0160 (10)	0.2967 (4)	0.0254 (8)	0.717 (4)
H3	0.716054	0.016114	0.264870	0.031*	0.717 (4)
C4	0.620 (2)	0.1013 (15)	0.3526 (4)	0.0211 (11)	0.717 (4)
H4	0.748457	0.165180	0.358187	0.025*	0.717 (4)
C5	0.4539 (15)	0.0933 (9)	0.4009 (4)	0.0162 (9)	0.717 (4)
C6	0.4718 (14)	0.1856 (12)	0.4606 (3)	0.0174 (9)	0.717 (4)
C7	0.6635 (19)	0.2733 (8)	0.4752 (5)	0.0217 (11)	0.717 (4)
H7	0.791700	0.274957	0.447024	0.026*	0.717 (4)
C8	0.6624 (8)	0.3582 (9)	0.5321 (3)	0.0254 (9)	0.717 (4)
H8	0.783428	0.426128	0.540232	0.031*	0.717 (4)
C9	0.4864 (8)	0.3452 (6)	0.5776 (3)	0.0276 (11)	0.717 (4)
H9	0.491253	0.398271	0.617799	0.033*	0.717 (4)
C10	0.3066 (7)	0.2532 (5)	0.5621 (2)	0.0254 (9)	0.717 (4)
H10	0.182364	0.243774	0.591417	0.030*	0.717 (4)
O1B	0.1468 (8)	0.1100 (5)	0.5162 (2)	0.0283 (14)	0.283 (4)
N1B	0.330 (3)	0.1968 (18)	0.5193 (7)	0.0206 (7)	0.283 (4)
N2B	0.263 (3)	0.018 (2)	0.4059 (7)	0.0199 (9)	0.283 (4)
H2N2	0.165293	0.014377	0.438408	0.024*	0.283 (4)
C1B	0.361 (2)	0.2832 (16)	0.5724 (6)	0.0254 (9)	0.283 (4)
H1B	0.251328	0.281476	0.606250	0.030*	0.283 (4)
C2B	0.546 (3)	0.3722 (19)	0.5783 (8)	0.0276 (11)	0.283 (4)
H2B	0.556963	0.436182	0.615077	0.033*	0.283 (4)
C3B	0.716 (3)	0.373 (3)	0.5334 (10)	0.0254 (9)	0.283 (4)
H3B	0.858710	0.421752	0.541526	0.031*	0.283 (4)
C4B	0.668 (5)	0.299 (3)	0.4753 (13)	0.0217 (11)	0.283 (4)
H4B	0.756541	0.319587	0.437556	0.026*	0.283 (4)
C5B	0.493 (4)	0.196 (3)	0.4710 (10)	0.0174 (9)	0.283 (4)
C6B	0.450 (4)	0.112 (3)	0.4118 (11)	0.0162 (9)	0.283 (4)
C7B	0.607 (6)	0.094 (4)	0.3618 (13)	0.0211 (11)	0.283 (4)
H7B	0.754015	0.139492	0.366763	0.025*	0.283 (4)
C8B	0.558 (3)	0.015 (3)	0.3049 (11)	0.0254 (8)	0.283 (4)
H8B	0.657616	0.018628	0.268447	0.031*	0.283 (4)
C9B	0.361 (3)	−0.0716 (19)	0.3024 (7)	0.0252 (9)	0.283 (4)
H9B	0.324956	−0.132271	0.265541	0.030*	0.283 (4)
C10B	0.224 (3)	−0.0649 (19)	0.3544 (5)	0.0236 (8)	0.283 (4)
H10B	0.089399	−0.124292	0.353836	0.028*	0.283 (4)
O1W	0.1320 (3)	0.31147 (18)	0.70149 (8)	0.0383 (4)
H1W1	0.067 (6)	0.400 (4)	0.6970 (16)	0.075 (10)*
H2W1	0.117 (5)	0.288 (3)	0.7415 (16)	0.064 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02760 (10)	0.02744 (12)	0.02241 (10)	0.00035 (7)	0.00334 (7)	0.00392 (7)
O1	0.0252 (10)	0.0336 (11)	0.0225 (10)	−0.0067 (8)	0.0068 (7)	−0.0001 (8)
N1	0.0208 (8)	0.0207 (15)	0.019 (3)	0.0010 (8)	0.0034 (18)	0.002 (2)
N2	0.0220 (15)	0.024 (2)	0.016 (2)	−0.0026 (11)	0.0018 (14)	−0.0009 (14)
C1	0.0280 (13)	0.0231 (12)	0.019 (2)	−0.0009 (10)	−0.006 (2)	−0.004 (2)
C2	0.030 (2)	0.0272 (11)	0.018 (2)	0.0045 (15)	0.0008 (13)	−0.0047 (17)
C3	0.022 (3)	0.0337 (11)	0.021 (2)	0.0066 (19)	0.0064 (15)	−0.0024 (15)
C4	0.0189 (17)	0.0273 (17)	0.017 (3)	0.0011 (11)	0.0040 (17)	0.003 (2)
C5	0.0186 (8)	0.015 (3)	0.015 (3)	0.0039 (14)	0.0018 (16)	−0.0031 (14)
C6	0.0199 (18)	0.0198 (19)	0.012 (3)	0.0021 (12)	−0.0014 (18)	0.0032 (18)
C7	0.0259 (10)	0.017 (3)	0.0225 (9)	0.000 (2)	0.0028 (7)	0.0005 (19)
C8	0.025 (3)	0.025 (2)	0.0259 (10)	−0.004 (2)	−0.005 (2)	−0.0014 (11)
C9	0.037 (3)	0.028 (3)	0.0183 (10)	0.000 (2)	0.0029 (19)	−0.0003 (15)
C10	0.030 (2)	0.029 (2)	0.0179 (18)	−0.0004 (15)	0.0043 (14)	−0.0005 (14)
O1B	0.025 (2)	0.034 (3)	0.026 (3)	−0.011 (2)	0.0061 (19)	−0.004 (2)
N1B	0.0220 (15)	0.024 (2)	0.016 (2)	−0.0026 (11)	0.0018 (14)	−0.0009 (14)
N2B	0.0208 (8)	0.0207 (15)	0.019 (3)	0.0010 (8)	0.0034 (18)	0.002 (2)
C1B	0.030 (2)	0.029 (2)	0.0179 (18)	−0.0004 (15)	0.0043 (14)	−0.0005 (14)
C2B	0.037 (3)	0.028 (3)	0.0183 (10)	0.000 (2)	0.0029 (19)	−0.0003 (15)
C3B	0.025 (3)	0.025 (2)	0.0259 (10)	−0.004 (2)	−0.005 (2)	−0.0014 (11)
C4B	0.0259 (10)	0.017 (3)	0.0225 (9)	0.000 (2)	0.0028 (7)	0.0005 (19)
C5B	0.0199 (18)	0.0198 (19)	0.012 (3)	0.0021 (12)	−0.0014 (18)	0.0032 (18)
C6B	0.0186 (8)	0.015 (3)	0.015 (3)	0.0039 (14)	0.0018 (16)	−0.0031 (14)
C7B	0.0189 (17)	0.0273 (17)	0.017 (3)	0.0011 (11)	0.0040 (17)	0.003 (2)
C8B	0.022 (3)	0.0337 (11)	0.021 (2)	0.0066 (19)	0.0064 (15)	−0.0024 (15)
C9B	0.030 (2)	0.0272 (11)	0.018 (2)	0.0045 (15)	0.0008 (13)	−0.0047 (17)
C10B	0.0280 (13)	0.0231 (12)	0.019 (2)	−0.0009 (10)	−0.006 (2)	−0.004 (2)
O1W	0.0614 (10)	0.0280 (8)	0.0259 (8)	0.0023 (8)	0.0041 (7)	−0.0044 (7)

Geometric parameters (Å, º) top

O1—N1	1.343 (6)	N1B—C1B	1.345 (12)
N1—C5	1.361 (7)	N1B—C5B	1.378 (19)
N1—C1	1.364 (4)	N2B—C10B	1.307 (12)
N2—C10	1.344 (4)	N2B—C6B	1.386 (19)
N2—C6	1.351 (7)	N2B—H2N2	0.8800
N2—H1N2	0.8800	C1B—C2B	1.347 (11)
C1—C2	1.373 (4)	C1B—H1B	0.9500
C1—H1	0.9500	C2B—C3B	1.362 (17)
C2—C3	1.384 (7)	C2B—H2B	0.9500
C2—H2	0.9500	C3B—C4B	1.38 (2)
C3—C4	1.381 (8)	C3B—H3B	0.9500
C3—H3	0.9500	C4B—C5B	1.392 (19)
C4—C5	1.396 (7)	C4B—H4B	0.9500
C4—H4	0.9500	C5B—C6B	1.444 (12)
C5—C6	1.478 (4)	C6B—C7B	1.390 (19)
C6—C7	1.397 (8)	C7B—C8B	1.39 (2)
C7—C8	1.393 (8)	C7B—H7B	0.9500
C7—H7	0.9500	C8B—C9B	1.390 (17)
C8—C9	1.398 (6)	C8B—H8B	0.9500
C8—H8	0.9500	C9B—C10B	1.339 (11)
C9—C10	1.371 (4)	C9B—H9B	0.9500
C9—H9	0.9500	C10B—H10B	0.9500
C10—H10	0.9500	O1W—H1W1	0.90 (3)
O1B—N1B	1.330 (12)	O1W—H2W1	0.84 (3)

O1—N1—C5	122.8 (4)	O1B—N1B—C5B	121.8 (11)
O1—N1—C1	116.4 (5)	C1B—N1B—C5B	119.5 (12)
C5—N1—C1	120.8 (5)	C10B—N2B—C6B	123.3 (15)
C10—N2—C6	123.6 (4)	C10B—N2B—H2N2	118.4
C10—N2—H1N2	118.2	C6B—N2B—H2N2	118.4
C6—N2—H1N2	118.2	N1B—C1B—C2B	121.2 (14)
N1—C1—C2	120.2 (5)	N1B—C1B—H1B	119.4
N1—C1—H1	119.9	C2B—C1B—H1B	119.4
C2—C1—H1	119.9	C1B—C2B—C3B	122.1 (15)
C1—C2—C3	120.2 (4)	C1B—C2B—H2B	119.0
C1—C2—H2	119.9	C3B—C2B—H2B	119.0
C3—C2—H2	119.9	C2B—C3B—C4B	115.9 (15)
C4—C3—C2	119.3 (5)	C2B—C3B—H3B	122.1
C4—C3—H3	120.4	C4B—C3B—H3B	122.1
C2—C3—H3	120.4	C3B—C4B—C5B	121 (2)
C3—C4—C5	119.8 (7)	C3B—C4B—H4B	119.4
C3—C4—H4	120.1	C5B—C4B—H4B	119.4
C5—C4—H4	120.1	N1B—C5B—C4B	117.6 (17)
N1—C5—C4	119.6 (5)	N1B—C5B—C6B	119.0 (17)
N1—C5—C6	119.6 (6)	C4B—C5B—C6B	121.9 (19)
C4—C5—C6	120.6 (7)	N2B—C6B—C7B	113.1 (16)
N2—C6—C7	118.2 (6)	N2B—C6B—C5B	121.5 (18)
N2—C6—C5	118.8 (6)	C7B—C6B—C5B	124 (2)
C7—C6—C5	122.8 (7)	C8B—C7B—C6B	123 (2)
C8—C7—C6	118.5 (8)	C8B—C7B—H7B	118.5
C8—C7—H7	120.7	C6B—C7B—H7B	118.5
C6—C7—H7	120.7	C7B—C8B—C9B	118.6 (16)
C7—C8—C9	121.2 (5)	C7B—C8B—H8B	120.7
C7—C8—H8	119.4	C9B—C8B—H8B	120.7
C9—C8—H8	119.4	C10B—C9B—C8B	116.8 (14)
C10—C9—C8	117.8 (5)	C10B—C9B—H9B	121.6
C10—C9—H9	121.1	C8B—C9B—H9B	121.6
C8—C9—H9	121.1	N2B—C10B—C9B	124.2 (16)
N2—C10—C9	120.4 (4)	N2B—C10B—H10B	117.9
N2—C10—H10	119.8	C9B—C10B—H10B	117.9
C9—C10—H10	119.8	H1W1—O1W—H2W1	106 (3)
O1B—N1B—C1B	118.7 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1	0.88	1.76	2.485 (4)	138
N2—H1N2···O1ⁱ	0.88	2.41	3.089 (5)	134
C1—H1···O1Wⁱ	0.95	2.22	3.138 (6)	163
C4—H4···Br1ⁱⁱ	0.95	2.75	3.687 (10)	167
C7—H7···Br1ⁱⁱ	0.95	2.86	3.769 (10)	160
C10—H10···O1W	0.95	2.34	3.074 (5)	134
N2B—H2N2···O1B	0.88	1.81	2.500 (15)	134
N2B—H2N2···O1Bⁱ	0.88	2.35	3.117 (18)	146
C1B—H1B···O1W	0.95	2.09	2.979 (14)	156
C2B—H2B···Br1ⁱⁱⁱ	0.95	2.80	3.497 (15)	131
C4B—H4B···Br1ⁱⁱ	0.95	2.77	3.70 (3)	168
C7B—H7B···Br1ⁱⁱ	0.95	2.92	3.80 (3)	155
C10B—H10B···O1Wⁱ	0.95	2.40	3.246 (17)	147
O1W—H1W1···Br1	0.90 (3)	2.47 (3)	3.3475 (18)	165 (3)
O1W—H2W1···Br1^iv	0.84 (3)	2.57 (3)	3.3754 (17)	160 (3)

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

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