Hydrogen bonds and van der Waals forces as tools for the construction of a herringbone pattern in the crystal structure of hexane-1,6-diaminium hexane-1,6-diyl bis­(hydrogen phospho­nate)

The solid-state structure of the title salt, [H₃N(CH₂)₆NH₃][(HO)O₂P(CH₂)₆PO₂(OH)], possesses a herringbone motif as a consequence of the inter­play of strong hydrogen bonds and non-covalent inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.098
• Data-to-parameter ratio = 24.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.33 Report
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      4.535 Check
PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density.          0 Note

Alert level G
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note

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

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

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Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2015); software used to prepare material for publication: publCIF (Westrip, 2010).

Hexane-1,6-diaminium hexane-1,6-diyl bis(hydrogen phosphonate)

Crystal data

C6H18N2^2+·C6H14O6P2^2^−	Dx = 1.318 Mg m^−3
Mr = 362.33	Melting point: 501 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.88242 (16) Å	Cell parameters from 8526 reflections
b = 20.2162 (5) Å	θ = 3.0–33.9°
c = 7.7574 (2) Å	µ = 0.27 mm^−1
β = 98.090 (3)°	T = 292 K
V = 913.33 (4) Å^3	Block, colorless
Z = 2	0.40 × 0.20 × 0.12 mm
F(000) = 392

Data collection

Oxford Diffraction Xcalibur with Eos detector diffractometer	2779 independent reflections
Radiation source: (Mo) X-ray Source	2339 reflections with I > 2σ(I)
Detector resolution: 16.2711 pixels mm^-1	Rint = 0.022
ω scans	θmax = 30.5°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2006)	h = −8→8
Tmin = 0.898, Tmax = 1.000	k = −28→28
14194 measured reflections	l = −11→10

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.018P)^2 + 1.P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2779 reflections	Δρmax = 0.64 e Å^−3
116 parameters	Δρmin = −0.28 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	−0.0383 (3)	0.18730 (8)	0.0899 (2)	0.0330 (3)
H11	0.005 (4)	0.2266 (12)	0.135 (3)	0.043 (6)*
H12	0.024 (4)	0.1833 (11)	−0.006 (3)	0.047 (7)*
H13	−0.190 (4)	0.1883 (11)	0.054 (3)	0.043 (6)*
C1	0.0201 (4)	0.13413 (10)	0.2199 (3)	0.0446 (5)
H1A	−0.0407	0.1459	0.3257	0.053*
H1B	0.1858	0.1315	0.2478	0.053*
C2	−0.0708 (4)	0.06670 (10)	0.1609 (3)	0.0501 (5)
H2A	−0.0529	0.0373	0.2607	0.060*
H2B	−0.2338	0.0706	0.1201	0.060*
C3	0.0423 (4)	0.03569 (11)	0.0201 (4)	0.0532 (6)
H3A	0.2072	0.0352	0.0552	0.064*
H3B	0.0107	0.0622	−0.0848	0.064*
P1	0.40040 (8)	0.30335 (2)	0.30797 (6)	0.02754 (11)
O1	0.5147 (2)	0.23351 (7)	0.28712 (19)	0.0388 (3)
H1	0.490 (4)	0.2187 (12)	0.190 (3)	0.051 (7)*
O2	0.4820 (2)	0.32500 (6)	0.49279 (16)	0.0357 (3)
O3	0.1446 (2)	0.29998 (6)	0.26262 (18)	0.0359 (3)
C4	0.5251 (3)	0.35522 (9)	0.1593 (2)	0.0367 (4)
H4A	0.6898	0.3568	0.1952	0.044*
H4B	0.4988	0.3351	0.0447	0.044*
C5	0.4345 (4)	0.42525 (9)	0.1453 (3)	0.0411 (4)
H5A	0.4665	0.4467	0.2580	0.049*
H5B	0.2693	0.4243	0.1120	0.049*
C6	0.5441 (4)	0.46516 (10)	0.0111 (3)	0.0457 (5)
H6A	0.7089	0.4664	0.0462	0.055*
H6B	0.5155	0.4427	−0.1004	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0291 (7)	0.0326 (8)	0.0383 (9)	−0.0038 (6)	0.0077 (6)	−0.0065 (6)
C1	0.0472 (11)	0.0334 (10)	0.0519 (12)	−0.0008 (8)	0.0029 (9)	−0.0008 (9)
C2	0.0533 (12)	0.0333 (10)	0.0656 (15)	−0.0034 (9)	0.0151 (11)	0.0004 (10)
C3	0.0521 (13)	0.0383 (11)	0.0710 (16)	−0.0045 (10)	0.0152 (12)	−0.0072 (11)
P1	0.0292 (2)	0.0280 (2)	0.0258 (2)	−0.00367 (16)	0.00522 (15)	0.00149 (16)
O1	0.0460 (8)	0.0380 (7)	0.0322 (7)	0.0093 (6)	0.0050 (6)	0.0007 (6)
O2	0.0410 (7)	0.0384 (7)	0.0277 (6)	−0.0069 (5)	0.0052 (5)	−0.0010 (5)
O3	0.0297 (6)	0.0351 (7)	0.0425 (7)	−0.0028 (5)	0.0042 (5)	−0.0021 (6)
C4	0.0428 (10)	0.0372 (9)	0.0321 (9)	−0.0055 (8)	0.0119 (8)	0.0024 (7)
C5	0.0538 (12)	0.0339 (9)	0.0381 (10)	−0.0053 (8)	0.0151 (9)	0.0054 (8)
C6	0.0619 (13)	0.0365 (10)	0.0412 (11)	−0.0099 (9)	0.0165 (10)	0.0066 (8)

Geometric parameters (Å, º)

N1—C1	1.481 (3)	P1—O2	1.5112 (13)
N1—H11	0.89 (2)	P1—O1	1.5817 (14)
N1—H12	0.87 (3)	P1—C4	1.7907 (18)
N1—H13	0.90 (2)	O1—H1	0.81 (3)
C1—C2	1.511 (3)	C4—C5	1.511 (3)
C1—H1A	0.9700	C4—H4A	0.9700
C1—H1B	0.9700	C4—H4B	0.9700
C2—C3	1.494 (3)	C5—C6	1.529 (3)
C2—H2A	0.9700	C5—H5A	0.9700
C2—H2B	0.9700	C5—H5B	0.9700
C3—C3^i	1.544 (4)	C6—C6^ii	1.503 (4)
C3—H3A	0.9700	C6—H6A	0.9700
C3—H3B	0.9700	C6—H6B	0.9700
P1—O3	1.4977 (13)
C1—N1—H11	110.7 (14)	O3—P1—O1	111.27 (8)
C1—N1—H12	115.2 (15)	O2—P1—O1	105.83 (8)
H11—N1—H12	107 (2)	O3—P1—C4	111.37 (9)
C1—N1—H13	110.5 (14)	O2—P1—C4	109.71 (8)
H11—N1—H13	108.3 (19)	O1—P1—C4	103.79 (8)
H12—N1—H13	105 (2)	P1—O1—H1	113.8 (18)
N1—C1—C2	114.23 (18)	C5—C4—P1	115.00 (13)
N1—C1—H1A	108.7	C5—C4—H4A	108.5
C2—C1—H1A	108.7	P1—C4—H4A	108.5
N1—C1—H1B	108.7	C5—C4—H4B	108.5
C2—C1—H1B	108.7	P1—C4—H4B	108.5
H1A—C1—H1B	107.6	H4A—C4—H4B	107.5
C3—C2—C1	115.14 (19)	C4—C5—C6	111.41 (17)
C3—C2—H2A	108.5	C4—C5—H5A	109.3
C1—C2—H2A	108.5	C6—C5—H5A	109.3
C3—C2—H2B	108.5	C4—C5—H5B	109.3
C1—C2—H2B	108.5	C6—C5—H5B	109.3
H2A—C2—H2B	107.5	H5A—C5—H5B	108.0
C2—C3—C3^i	112.1 (2)	C6^ii—C6—C5	113.6 (2)
C2—C3—H3A	109.2	C6^ii—C6—H6A	108.8
C3^i—C3—H3A	109.2	C5—C6—H6A	108.8
C2—C3—H3B	109.2	C6^ii—C6—H6B	108.8
C3^i—C3—H3B	109.2	C5—C6—H6B	108.8
H3A—C3—H3B	107.9	H6A—C6—H6B	107.7
O3—P1—O2	114.23 (8)
N1—C1—C2—C3	69.9 (3)	O1—P1—C4—C5	176.71 (15)
C1—C2—C3—C3^i	174.2 (3)	P1—C4—C5—C6	−177.99 (15)
O3—P1—C4—C5	56.90 (17)	C4—C5—C6—C6^ii	178.7 (2)
O2—P1—C4—C5	−70.57 (17)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O3	0.89 (2)	1.90 (2)	2.782 (2)	168 (2)
N1—H12···O3^iii	0.87 (3)	2.05 (3)	2.905 (2)	165 (2)
N1—H13···O2^iv	0.90 (2)	1.94 (2)	2.828 (2)	170 (2)
O1—H1···O2^iii	0.81 (3)	1.76 (3)	2.5546 (19)	168 (3)

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