The whole range of hydrogen bonds in one crystal structure: neutron diffraction and charge-density studies of N,N-dimethylbiguanidinium bis(hydrogensquarate)

N,N-Dimethylbiguanidinium bis(hydrogensquarate) features an impressive range of hydrogen bonds within the same crystal structure: neighbouring anions aggregate to a dianionic pair through two strong O—H...O interactions; one of these can be classified among the shortest hydrogen bonds ever studied. Cations and anions in this organic salt further interact via conventional N—H...O and nonclassical C—H...O contacts to an extended structure. As all these interactions occur in the same sample, the title compound is particularly suitable to monitor even subtle trends in hydrogen bonds. Neutron and high-resolution X-ray diffraction experiments have enabled us to determine the electron density precisely and to address its properties with an emphasis on the nature of the X—H...O interactions. Sensitive criteria such as the Laplacian of the electron density and energy densities in the bond-critical points reveal the incipient covalent character of the shortest O—H...O bond. These findings are in agreement with the precise geometry from neutron diffraction: the shortest hydrogen bond is also significantly more symmetric than the longer interactions.

Computing details

Data collection: Bruker SMART for iam, multipole; PRON2010 for neutron. Cell refinement: Bruker SMART for iam, multipole. Data reduction: Bruker SAINT for iam, multipole. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a) for iam, multipole; SHELXS97 (Sheldrick, 1990) for neutron. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b) for iam; Volkov et al., (2006) for multipole; SHELXL97 (Sheldrick, 1997) for neutron. Molecular graphics: PLATON (Spek, 2003) for iam; Volkov et al., (2006) for multipole. Software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b) for iam; Volkov et al., (2006) for multipole.

Figures

(iam)

Crystal data

C4H13N5·2(C4HO4)	Z = 2
Mr = 357.29	F(000) = 372
Triclinic, P1	Dx = 1.596 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0689 (2) Å	Cell parameters from 8412 reflections
b = 8.5538 (2) Å	θ = 2.4–50.7°
c = 13.0736 (3) Å	µ = 0.14 mm^−1
α = 90.4259 (9)°	T = 100 K
β = 105.1185 (9)°	Block, colorless
γ = 102.4251 (10)°	0.38 × 0.21 × 0.13 mm
V = 743.58 (3) Å^3

Data collection

CCD area detector diffractometer	9502 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 52.2°, θmin = 2.4°
ω scans	h = −15→15
38327 measured reflections	k = −18→18
15808 independent reflections	l = −28→28

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.025P)^2] where P = (Fo^2 + 2Fc^2)/3
15808 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	1.02728 (7)	0.82013 (6)	0.61291 (3)	0.01380 (8)
H1	0.9664 (17)	0.7536 (14)	0.5513 (9)	0.052 (3)*
O2	0.75953 (7)	0.48456 (5)	0.67218 (3)	0.01204 (8)
O3	0.90716 (7)	0.62233 (5)	0.91952 (3)	0.01256 (8)
O4	1.18711 (7)	0.93588 (6)	0.85855 (3)	0.01435 (8)
C1	0.99404 (8)	0.75549 (7)	0.69774 (4)	0.00932 (9)
C2	0.87282 (8)	0.60914 (7)	0.72196 (4)	0.00887 (8)
C3	0.94112 (8)	0.66909 (7)	0.83570 (4)	0.00911 (9)
C4	1.06825 (8)	0.81400 (7)	0.80734 (4)	0.00950 (9)
O5	0.60656 (7)	0.35580 (6)	0.48209 (3)	0.01331 (8)
H5	0.6708 (17)	0.4186 (14)	0.5423 (9)	0.051 (3)*
O6	0.91444 (7)	0.67924 (6)	0.43705 (4)	0.01821 (10)
O7	0.76472 (7)	0.57743 (6)	0.18786 (3)	0.01252 (8)
O8	0.46746 (7)	0.25345 (6)	0.23237 (3)	0.01397 (8)
C5	0.65640 (8)	0.42058 (7)	0.40000 (4)	0.00989 (9)
C6	0.79065 (9)	0.56210 (7)	0.38264 (4)	0.01082 (9)
C7	0.72452 (8)	0.51730 (7)	0.26748 (4)	0.00974 (9)
C8	0.58712 (8)	0.36880 (7)	0.28791 (4)	0.01003 (9)
N1	0.63044 (7)	0.12212 (6)	0.72119 (4)	0.00965 (8)
N2	0.52866 (8)	0.16658 (6)	0.87015 (4)	0.01028 (8)
H2	0.4262 (13)	0.0901 (11)	0.8482 (7)	0.018 (2)*
N3	0.39972 (8)	0.18275 (7)	1.01241 (4)	0.01187 (9)
H3A	0.4056 (13)	0.2263 (12)	1.0734 (7)	0.025 (2)*
H3B	0.3178 (13)	0.0959 (11)	0.9852 (7)	0.023 (2)*
N4	0.87102 (8)	0.24052 (7)	0.87271 (4)	0.01209 (9)
H4A	0.9082 (14)	0.2667 (12)	0.9410 (8)	0.029 (3)*
H4B	0.9620 (13)	0.2700 (10)	0.8380 (7)	0.014 (2)*
N5	0.65777 (8)	0.38725 (6)	0.99499 (4)	0.01082 (8)
H5A	0.6627 (14)	0.4359 (12)	1.0556 (8)	0.027 (3)*
H5B	0.7293 (14)	0.4329 (12)	0.9578 (7)	0.026 (3)*
C9	0.78222 (10)	0.09007 (9)	0.67128 (5)	0.01460 (11)
H9A	0.8304 (13)	0.1804 (12)	0.6341 (7)	0.024 (2)*
H9B	0.7220 (14)	−0.0065 (11)	0.6255 (7)	0.026 (2)*
H9C	0.8943 (14)	0.0679 (11)	0.7230 (7)	0.023 (2)*
C10	0.42488 (10)	0.08860 (9)	0.65249 (5)	0.01488 (11)
H10A	0.3661 (14)	−0.0235 (12)	0.6383 (7)	0.030 (3)*
H10B	0.4293 (14)	0.1421 (11)	0.5864 (7)	0.025 (2)*
H10C	0.3366 (13)	0.1299 (11)	0.6835 (7)	0.019 (2)*
C11	0.68078 (8)	0.17996 (7)	0.82051 (4)	0.00891 (8)
C12	0.53214 (8)	0.24935 (7)	0.96159 (4)	0.00903 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0183 (2)	0.01233 (19)	0.00824 (17)	−0.00355 (16)	0.00494 (15)	−0.00034 (14)
O2	0.01403 (18)	0.00950 (17)	0.00948 (17)	−0.00224 (15)	0.00182 (14)	−0.00152 (13)
O3	0.01373 (18)	0.01367 (19)	0.00851 (17)	−0.00120 (15)	0.00337 (14)	0.00108 (14)
O4	0.01462 (19)	0.01294 (19)	0.01184 (18)	−0.00490 (16)	0.00388 (14)	−0.00372 (14)
C1	0.0098 (2)	0.0088 (2)	0.0086 (2)	−0.00002 (17)	0.00285 (16)	−0.00054 (16)
C2	0.0088 (2)	0.0090 (2)	0.0082 (2)	0.00081 (17)	0.00199 (15)	0.00018 (16)
C3	0.0083 (2)	0.0092 (2)	0.0088 (2)	0.00031 (17)	0.00184 (15)	−0.00058 (16)
C4	0.0095 (2)	0.0096 (2)	0.0085 (2)	−0.00020 (18)	0.00285 (16)	−0.00071 (16)
O5	0.0164 (2)	0.01345 (19)	0.00788 (17)	−0.00186 (16)	0.00377 (14)	0.00036 (14)
O6	0.0211 (2)	0.0183 (2)	0.00984 (18)	−0.00826 (18)	0.00526 (16)	−0.00417 (15)
O7	0.01484 (19)	0.01390 (19)	0.00844 (17)	0.00120 (16)	0.00416 (14)	0.00077 (14)
O8	0.01384 (19)	0.0144 (2)	0.01071 (18)	−0.00174 (16)	0.00232 (14)	−0.00279 (14)
C5	0.0098 (2)	0.0112 (2)	0.0083 (2)	0.00126 (18)	0.00262 (16)	−0.00018 (16)
C6	0.0112 (2)	0.0124 (2)	0.0081 (2)	0.00053 (19)	0.00310 (16)	−0.00033 (17)
C7	0.0098 (2)	0.0112 (2)	0.0079 (2)	0.00201 (18)	0.00213 (16)	−0.00052 (16)
C8	0.0096 (2)	0.0118 (2)	0.0085 (2)	0.00213 (18)	0.00241 (16)	−0.00004 (17)
N1	0.01006 (19)	0.01043 (19)	0.00796 (18)	0.00028 (16)	0.00323 (14)	−0.00100 (14)
N2	0.00995 (19)	0.0106 (2)	0.00914 (18)	−0.00241 (16)	0.00445 (14)	−0.00294 (15)
N3	0.0120 (2)	0.0124 (2)	0.0099 (2)	−0.00268 (17)	0.00514 (15)	−0.00251 (16)
N4	0.00968 (19)	0.0159 (2)	0.00938 (19)	−0.00037 (17)	0.00296 (15)	−0.00190 (16)
N5	0.0114 (2)	0.0102 (2)	0.00981 (19)	−0.00160 (16)	0.00430 (15)	−0.00213 (15)
C9	0.0162 (3)	0.0170 (3)	0.0130 (2)	0.0041 (2)	0.0078 (2)	−0.0007 (2)
C10	0.0124 (2)	0.0189 (3)	0.0101 (2)	−0.0010 (2)	0.00124 (18)	−0.0008 (2)
C11	0.0099 (2)	0.0079 (2)	0.0089 (2)	0.00091 (17)	0.00346 (16)	0.00040 (15)
C12	0.0092 (2)	0.0096 (2)	0.0079 (2)	0.00137 (17)	0.00221 (15)	−0.00060 (16)

Geometric parameters (Å, º)

O1—C1	1.2962 (7)	N1—C9	1.4633 (8)
O1—H1	0.930 (12)	N2—C12	1.3768 (7)
O2—C2	1.2453 (7)	N2—C11	1.3794 (7)
O3—C3	1.2332 (7)	N2—H2	0.848 (9)
O4—C4	1.2492 (7)	N3—C12	1.3201 (7)
C1—C4	1.4364 (8)	N3—H3A	0.865 (9)
C1—C2	1.4448 (8)	N3—H3B	0.847 (9)
C2—C3	1.4883 (7)	N4—C11	1.3261 (7)
C3—C4	1.4774 (8)	N4—H4A	0.875 (10)
O5—C5	1.3058 (7)	N4—H4B	0.876 (8)
O5—H5	0.904 (12)	N5—C12	1.3077 (7)
O6—C6	1.2502 (7)	N5—H5A	0.881 (10)
O7—C7	1.2362 (7)	N5—H5B	0.832 (10)
O8—C8	1.2354 (7)	C9—H9A	0.963 (10)
C5—C6	1.4282 (8)	C9—H9B	0.964 (9)
C5—C8	1.4512 (8)	C9—H9C	0.953 (9)
C6—C7	1.4762 (8)	C10—H10A	0.955 (10)
C7—C8	1.4958 (8)	C10—H10B	0.985 (9)
N1—C11	1.3156 (7)	C10—H10C	0.951 (9)
N1—C10	1.4617 (8)
C1—O1—H1	113.5 (7)	C12—N2—H2	114.0 (6)
O1—C1—C4	130.73 (5)	C11—N2—H2	117.7 (6)
O1—C1—C2	136.50 (5)	C12—N3—H3A	118.7 (6)
C4—C1—C2	92.75 (4)	C12—N3—H3B	117.9 (6)
O2—C2—C1	137.15 (5)	H3A—N3—H3B	123.3 (9)
O2—C2—C3	134.32 (5)	C11—N4—H4A	122.3 (6)
C1—C2—C3	88.53 (4)	C11—N4—H4B	120.3 (5)
O3—C3—C4	134.09 (5)	H4A—N4—H4B	116.7 (8)
O3—C3—C2	136.53 (5)	C12—N5—H5A	120.4 (6)
C4—C3—C2	89.38 (4)	C12—N5—H5B	120.6 (7)
O4—C4—C1	136.17 (5)	H5A—N5—H5B	118.9 (9)
O4—C4—C3	134.54 (5)	N1—C9—H9A	111.2 (6)
C1—C4—C3	89.28 (4)	N1—C9—H9B	107.1 (6)
C5—O5—H5	111.2 (7)	H9A—C9—H9B	112.9 (8)
O5—C5—C6	135.97 (5)	N1—C9—H9C	110.9 (5)
O5—C5—C8	131.14 (5)	H9A—C9—H9C	108.2 (8)
C6—C5—C8	92.88 (5)	H9B—C9—H9C	106.4 (8)
O6—C6—C5	137.70 (5)	N1—C10—H10A	113.0 (6)
O6—C6—C7	132.52 (5)	N1—C10—H10B	107.2 (5)
C5—C6—C7	89.78 (4)	H10A—C10—H10B	111.3 (8)
O7—C7—C6	135.42 (5)	N1—C10—H10C	112.1 (5)
O7—C7—C8	135.39 (5)	H10A—C10—H10C	105.0 (8)
C6—C7—C8	89.19 (4)	H10B—C10—H10C	108.2 (8)
O8—C8—C5	136.55 (6)	N1—C11—N4	121.51 (5)
O8—C8—C7	135.31 (5)	N1—C11—N2	117.19 (5)
C5—C8—C7	88.14 (4)	N4—C11—N2	121.20 (5)
C11—N1—C10	123.70 (5)	N5—C12—N3	122.13 (5)
C11—N1—C9	121.02 (5)	N5—C12—N2	121.66 (5)
C10—N1—C9	115.27 (5)	N3—C12—N2	116.21 (5)
C12—N2—C11	127.70 (5)

(multipole)

Crystal data

?	Z = 2
Mr = ?	F(000) = 372
?, ?	Dx = 1.596 Mg m^−3
a = 7.0689 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5538 (2) Å	Cell parameters from 8412 reflections
c = 13.0736 (3) Å	θ = 2.4–50.7°
α = 90.4260 (9)°	µ = 0.14 mm^−1
β = 105.1180 (9)°	T = 100 K
γ = 102.425 (1)°	Block, colorless
V = 743.58 (3) Å^3	0.38 × 0.21 × 0.13 mm

Data collection

CCD area detector diffractometer	9502 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Graphite monochromator	θmax = 52.2°, θmin = 2.4°
ω scans	h = −15→15
38327 measured reflections	k = −18→18
15808 independent reflections	l = −28→28

Refinement

Refinement on F^2	950 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.034	w1 = 1/[s^2(Fo)]
wR(F^2) = 0.047	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.13 e Å^−3
15808 reflections	Δρmin = −0.12 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O(1)	1.02713 (9)	0.82004 (6)	0.61293 (4)	0.013
O(2)	0.75979 (8)	0.48450 (6)	0.67228 (4)	0.011
O(3)	0.90715 (8)	0.62250 (6)	0.91944 (4)	0.012
O(4)	1.18689 (8)	0.93559 (6)	0.85841 (4)	0.014
O(5)	0.60656 (8)	0.35590 (6)	0.48207 (4)	0.013
O(6)	0.91444 (10)	0.67914 (8)	0.43696 (4)	0.018
O(7)	0.76498 (8)	0.57744 (7)	0.18799 (4)	0.012
O(8)	0.46732 (8)	0.25368 (7)	0.23242 (4)	0.013
N(1)	0.63034 (7)	0.12207 (6)	0.72110 (4)	0.009
N(2)	0.52868 (7)	0.16648 (6)	0.87014 (4)	0.01
N(3)	0.39946 (7)	0.18258 (6)	1.01252 (4)	0.011
N(4)	0.87139 (7)	0.24075 (6)	0.87279 (4)	0.011
N(5)	0.65814 (7)	0.38762 (6)	0.99499 (4)	0.01
C(1)	0.99400 (6)	0.75564 (5)	0.69753 (3)	0.009
C(2)	0.87259 (6)	0.60900 (5)	0.72191 (3)	0.009
C(3)	0.94121 (6)	0.66909 (5)	0.83581 (3)	0.009
C(4)	1.06835 (6)	0.81401 (5)	0.80726 (3)	0.009
C(5)	0.65613 (6)	0.42036 (5)	0.40015 (3)	0.01
C(6)	0.79090 (7)	0.56219 (6)	0.38274 (3)	0.01
C(7)	0.72436 (6)	0.51738 (5)	0.26745 (3)	0.009
C(8)	0.58700 (6)	0.36876 (5)	0.28786 (3)	0.01
C(9)	0.78181 (7)	0.08988 (6)	0.67125 (4)	0.014
C(10)	0.42517 (7)	0.08865 (6)	0.65247 (3)	0.015
C(11)	0.68065 (6)	0.18009 (5)	0.82055 (3)	0.008
C(12)	0.53207 (6)	0.24928 (5)	0.96156 (3)	0.009
H(1)	0.962833	0.74725	0.542267	0.022
H(5)	0.681041	0.420274	0.552466	0.022
H(2)	0.406665	0.070604	0.844638	0.021
H(3A)	0.409038	0.227701	1.086102	0.021
H(3B)	0.303889	0.076392	0.981355	0.023
H(4A)	0.919565	0.268785	0.952287	0.023
H(4B)	0.974804	0.279987	0.832511	0.023
H(5A)	0.667386	0.443632	1.066111	0.021
H(5B)	0.746759	0.44951	0.951662	0.021
H(9A)	0.833769	0.188174	0.628072	0.044
H(9B)	0.714163	−0.017483	0.618206	0.043
H(9C)	0.908312	0.067698	0.73182	0.034
H(10A)	0.368041	−0.038869	0.637265	0.04
H(10B)	0.426276	0.144067	0.57895	0.038
H(10C)	0.326707	0.139119	0.688136	0.034
DUM0	0	0	0	0	0

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O(1)	0.0175 (2)	0.01192 (17)	0.00764 (16)	−0.00344 (16)	0.00442 (14)	−0.00051 (14)
O(2)	0.01345 (17)	0.00900 (15)	0.00856 (16)	−0.00220 (15)	0.00179 (13)	−0.00158 (12)
O(3)	0.01292 (17)	0.01275 (18)	0.00773 (16)	−0.00217 (15)	0.00314 (13)	0.00080 (13)
O(4)	0.01433 (18)	0.01230 (17)	0.01080 (18)	−0.00519 (16)	0.00411 (14)	−0.00367 (14)
O(5)	0.01505 (18)	0.01302 (18)	0.00731 (16)	−0.00179 (16)	0.00331 (14)	0.00040 (14)
O(6)	0.0207 (2)	0.0180 (2)	0.00875 (18)	−0.0083 (2)	0.00523 (16)	−0.00438 (16)
O(7)	0.01405 (18)	0.01324 (18)	0.00739 (16)	0.00044 (16)	0.00372 (13)	0.00033 (13)
O(8)	0.01353 (18)	0.01360 (18)	0.00970 (17)	−0.00204 (16)	0.00227 (13)	−0.00254 (14)
N(1)	0.00968 (15)	0.01035 (15)	0.00744 (15)	0.00041 (13)	0.00318 (12)	−0.00130 (12)
N(2)	0.00935 (15)	0.01025 (16)	0.00912 (16)	−0.00205 (14)	0.00440 (12)	−0.00300 (12)
N(3)	0.01138 (16)	0.01185 (17)	0.00950 (16)	−0.00246 (14)	0.00531 (13)	−0.00231 (13)
N(4)	0.00860 (15)	0.01567 (18)	0.00872 (16)	−0.00003 (15)	0.00235 (12)	−0.00209 (14)
N(5)	0.01074 (16)	0.00925 (15)	0.00971 (16)	−0.00180 (14)	0.00424 (12)	−0.00234 (12)
C(1)	0.01035 (15)	0.00858 (15)	0.00716 (15)	−0.00052 (13)	0.00277 (11)	−0.00046 (12)
C(2)	0.00903 (14)	0.00787 (14)	0.00743 (14)	−0.00047 (12)	0.00177 (11)	−0.00039 (11)
C(3)	0.00875 (14)	0.00922 (15)	0.00713 (15)	−0.00045 (12)	0.00205 (11)	−0.00015 (11)
C(4)	0.00949 (15)	0.00878 (15)	0.00797 (15)	−0.00152 (13)	0.00245 (11)	−0.00124 (12)
C(5)	0.00999 (15)	0.01082 (16)	0.00719 (15)	0.00040 (13)	0.00253 (11)	0.00003 (12)
C(6)	0.01115 (16)	0.01157 (16)	0.00713 (15)	−0.00090 (14)	0.00259 (12)	−0.00118 (12)
C(7)	0.01027 (15)	0.01099 (16)	0.00663 (15)	0.00128 (13)	0.00249 (11)	0.00014 (12)
C(8)	0.00936 (15)	0.01090 (16)	0.00765 (15)	0.00067 (13)	0.00183 (11)	−0.00085 (12)
C(9)	0.01559 (17)	0.01629 (19)	0.01268 (16)	0.00399 (15)	0.00730 (14)	−0.00043 (14)
C(10)	0.01233 (16)	0.0184 (2)	0.00973 (16)	−0.00108 (15)	0.00145 (12)	−0.00091 (13)
C(11)	0.00868 (14)	0.00858 (14)	0.00778 (14)	0.00044 (12)	0.00289 (11)	−0.00059 (11)
C(12)	0.00871 (14)	0.00878 (14)	0.00789 (14)	−0.00007 (12)	0.00307 (11)	−0.00134 (11)
H(1)	0.024874	0.022793	0.01538	0.000769	0.003481	0.004255
H(5)	0.023403	0.020312	0.016839	−0.002539	0.003184	0.000907
H(2)	0.022952	0.016328	0.018963	−0.004243	0.004935	−0.004547
H(3A)	0.026083	0.025656	0.005277	−0.004724	0.00287	−0.00294
H(3B)	0.023082	0.020473	0.019246	−0.007597	0.006256	−0.000597
H(4A)	0.02127	0.026484	0.016451	−0.000697	0.000416	0.002639
H(4B)	0.016925	0.032498	0.017194	−0.001909	0.007459	0.001808
H(5A)	0.022019	0.019624	0.015525	−0.001242	0.000448	−0.003383
H(5B)	0.019857	0.018256	0.020845	−0.005355	0.00648	−0.000694
H(9A)	0.051541	0.044359	0.050765	0.014241	0.03705	0.02668
H(9B)	0.032271	0.044818	0.04706	0.000685	0.009473	−0.026902
H(9C)	0.03067	0.050923	0.022949	0.016762	0.005632	0.001197
H(10A)	0.033853	0.027846	0.040911	−0.009079	−0.005591	−0.004303
H(10B)	0.027467	0.061747	0.017657	0.005287	−0.000146	0.011619
H(10C)	0.023137	0.060588	0.019199	0.01284	0.002449	−0.009426

Geometric parameters (Å, º)

O(1)—C(1)	1.2925 (6)	N(4)—H(4A)	1.0150 (5)
O(1)—H(1)	1.0480 (5)	N(4)—H(4B)	1.0110 (5)
O(2)—C(2)	1.2431 (6)	N(5)—C(12)	1.3118 (6)
O(3)—C(3)	1.2307 (6)	N(5)—H(5A)	1.0230 (5)
O(4)—C(4)	1.2464 (6)	N(5)—H(5B)	1.0200 (5)
O(5)—C(5)	1.3019 (6)	C(1)—C(2)	1.4480 (6)
O(5)—H(5)	1.0210 (5)	C(1)—C(4)	1.4376 (6)
O(6)—C(6)	1.2476 (6)	C(2)—C(3)	1.4905 (5)
O(7)—C(7)	1.2351 (6)	C(3)—C(4)	1.4785 (6)
O(8)—C(8)	1.2334 (6)	C(5)—C(6)	1.4322 (6)
N(1)—C(9)	1.4613 (6)	C(5)—C(8)	1.4534 (6)
N(1)—C(10)	1.4592 (6)	C(6)—C(7)	1.4779 (6)
N(1)—C(11)	1.3177 (6)	C(7)—C(8)	1.4964 (6)
N(2)—C(11)	1.3779 (6)	C(9)—H(9A)	1.0690 (5)
N(2)—C(12)	1.3768 (6)	C(9)—H(9B)	1.0870 (5)
N(2)—H(2)	1.0340 (5)	C(9)—H(9C)	1.0810 (5)
N(3)—C(12)	1.3227 (6)	C(10)—H(10A)	1.0760 (5)
N(3)—H(3A)	1.0140 (5)	C(10)—H(10B)	1.0760 (5)
N(3)—H(3B)	1.0170 (5)	C(10)—H(10C)	1.0880 (5)
N(4)—C(11)	1.3293 (6)
C(1)—O(1)—H(1)	115.43 (5)	O(5)—C(5)—C(8)	131.31 (5)
C(5)—O(5)—H(5)	113.87 (5)	C(6)—C(5)—C(8)	92.77 (4)
C(9)—N(1)—C(10)	115.23 (4)	O(6)—C(6)—C(5)	137.74 (5)
C(9)—N(1)—C(11)	121.08 (5)	O(6)—C(6)—C(7)	132.51 (5)
C(10)—N(1)—C(11)	123.68 (4)	C(5)—C(6)—C(7)	89.75 (3)
C(11)—N(2)—C(12)	127.67 (4)	O(7)—C(7)—C(6)	135.31 (5)
C(11)—N(2)—H(2)	117.18 (4)	O(7)—C(7)—C(8)	135.45 (5)
C(12)—N(2)—H(2)	114.24 (4)	C(6)—C(7)—C(8)	89.24 (3)
C(12)—N(3)—H(3A)	119.92 (5)	O(8)—C(8)—C(5)	136.43 (5)
C(12)—N(3)—H(3B)	118.14 (5)	O(8)—C(8)—C(7)	135.34 (5)
H(3A)—N(3)—H(3B)	121.22 (5)	C(5)—C(8)—C(7)	88.23 (3)
C(11)—N(4)—H(4A)	124.00 (5)	N(1)—C(9)—H(9A)	111.82 (4)
C(11)—N(4)—H(4B)	120.22 (5)	N(1)—C(9)—H(9B)	107.69 (4)
H(4A)—N(4)—H(4B)	114.97 (5)	N(1)—C(9)—H(9C)	109.29 (4)
C(12)—N(5)—H(5A)	120.93 (5)	H(9A)—C(9)—H(9B)	110.17 (4)
C(12)—N(5)—H(5B)	123.56 (5)	H(9A)—C(9)—H(9C)	108.93 (4)
H(5A)—N(5)—H(5B)	115.43 (5)	H(9B)—C(9)—H(9C)	108.89 (4)
O(1)—C(1)—C(2)	136.53 (4)	N(1)—C(10)—H(10A)	109.86 (4)
O(1)—C(1)—C(4)	130.79 (5)	N(1)—C(10)—H(10B)	108.70 (4)
C(2)—C(1)—C(4)	92.66 (3)	N(1)—C(10)—H(10C)	111.31 (4)
O(2)—C(2)—C(1)	137.12 (4)	H(10A)—C(10)—H(10B)	109.89 (4)
O(2)—C(2)—C(3)	134.34 (5)	H(10A)—C(10)—H(10C)	109.51 (4)
C(1)—C(2)—C(3)	88.54 (3)	H(10B)—C(10)—H(10C)	107.53 (5)
O(3)—C(3)—C(2)	136.48 (5)	N(1)—C(11)—N(2)	117.19 (4)
O(3)—C(3)—C(4)	134.18 (4)	N(1)—C(11)—N(4)	121.42 (4)
C(2)—C(3)—C(4)	89.33 (3)	N(2)—C(11)—N(4)	121.27 (4)
O(4)—C(4)—C(1)	136.17 (5)	N(2)—C(12)—N(3)	116.24 (4)
O(4)—C(4)—C(3)	134.42 (5)	N(2)—C(12)—N(5)	121.61 (4)
C(1)—C(4)—C(3)	89.40 (3)	N(3)—C(12)—N(5)	122.15 (4)
O(5)—C(5)—C(6)	135.92 (4)

(neutron)

Crystal data

C4H13N5·C8H2O8	V = 743.58 (3) Å^3
Mr = 357.28	Z = 2
Triclinic, P1	F(000) = 23
Hall symbol: -P 1	Dx = 1.596 Mg m^−3
a = 7.0689 (2) Å	Neutron radiation, λ = 0.86800 Å
b = 8.5538 (2) Å	µ = 0.15 mm^−1
c = 13.0736 (3) Å	T = 100 K
α = 90.4260 (9)°	Plate, colorless
β = 105.1180 (9)°	3.5 × 3.5 × 3 mm
γ = 102.425 (1)°

Data collection

Closed Eulerian cradle HEiDi diffractometer	4116 reflections with I > 2σ(I)
Radiation source: FRM II	Rint = 0.073
Graphite monochromator	θmax = 45.4°, θmin = 3.5°
rocking scan	h = −11→10
7815 measured reflections	k = −13→13
5560 independent reflections	l = −18→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.061	All H-atom parameters refined
wR(F^2) = 0.156	w = 1/[σ^2(Fo^2) + (0.0563P)^2 + 0.0635P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
5560 reflections	Δρmax = 0.10 e Å^−3
362 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 1.67 (15)

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	1.0273 (3)	0.8197 (2)	0.61322 (17)	0.0205 (3)
H1	0.9630 (6)	0.7471 (4)	0.5425 (3)	0.0298 (6)
O2	0.7594 (3)	0.48481 (18)	0.67219 (16)	0.0179 (3)
O3	0.9069 (3)	0.62245 (19)	0.91923 (16)	0.0186 (3)
O4	1.1864 (3)	0.9356 (2)	0.85841 (16)	0.0196 (3)
C1	0.9940 (2)	0.75569 (15)	0.69745 (13)	0.0153 (2)
C2	0.87228 (19)	0.60890 (15)	0.72189 (12)	0.0145 (2)
C3	0.9411 (2)	0.66886 (15)	0.83606 (13)	0.0153 (2)
C4	1.0685 (2)	0.81410 (15)	0.80731 (13)	0.0156 (2)
O5	0.6064 (3)	0.3562 (2)	0.48223 (16)	0.0194 (3)
H5	0.6819 (5)	0.4211 (4)	0.5524 (3)	0.0297 (7)
O6	0.9143 (3)	0.6790 (2)	0.43688 (18)	0.0242 (4)
O7	0.7644 (3)	0.5772 (2)	0.18796 (16)	0.0188 (3)
O8	0.4680 (3)	0.2535 (2)	0.23228 (17)	0.0199 (3)
C5	0.6560 (2)	0.42020 (16)	0.40033 (13)	0.0163 (3)
C6	0.7908 (2)	0.56227 (16)	0.38259 (13)	0.0168 (3)
C7	0.7247 (2)	0.51746 (16)	0.26726 (13)	0.0159 (2)
C8	0.5869 (2)	0.36876 (16)	0.28797 (13)	0.0162 (2)
N1	0.63032 (15)	0.12227 (11)	0.72094 (9)	0.01618 (19)
N2	0.52882 (15)	0.16629 (12)	0.87032 (10)	0.01702 (19)
H2	0.4059 (5)	0.0713 (4)	0.8443 (3)	0.0290 (6)
N3	0.39937 (16)	0.18272 (12)	1.01253 (10)	0.01786 (19)
H3A	0.4083 (6)	0.2284 (4)	1.0859 (3)	0.0303 (7)
H3B	0.3032 (6)	0.0767 (4)	0.9817 (3)	0.0322 (7)
N4	0.87128 (15)	0.24078 (13)	0.87288 (10)	0.0185 (2)
H4A	0.9178 (6)	0.2694 (5)	0.9523 (3)	0.0321 (7)
H4B	0.9744 (5)	0.2791 (5)	0.8324 (4)	0.0323 (7)
N5	0.65845 (15)	0.38779 (11)	0.99528 (10)	0.01688 (19)
H5A	0.6660 (6)	0.4443 (4)	1.0659 (3)	0.0297 (6)
H5B	0.7462 (6)	0.4493 (4)	0.9515 (3)	0.0302 (7)
C9	0.7821 (2)	0.09005 (19)	0.67127 (15)	0.0204 (3)
H9A	0.8338 (9)	0.1900 (7)	0.6292 (6)	0.0537 (14)
H9B	0.7154 (8)	−0.0186 (7)	0.6194 (5)	0.0527 (14)
H9C	0.9094 (7)	0.0663 (6)	0.7307 (5)	0.0434 (10)
C10	0.4254 (2)	0.08860 (19)	0.65261 (15)	0.0208 (3)
H10A	0.3663 (8)	−0.0387 (5)	0.6376 (5)	0.0501 (13)
H10B	0.4263 (7)	0.1434 (7)	0.5789 (4)	0.0477 (12)
H10C	0.3253 (6)	0.1382 (7)	0.6875 (4)	0.0445 (11)
C11	0.6816 (2)	0.18013 (15)	0.82042 (13)	0.0151 (2)
C12	0.5324 (2)	0.24947 (15)	0.96148 (13)	0.0149 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0235 (7)	0.0176 (6)	0.0165 (9)	−0.0026 (5)	0.0045 (6)	0.0014 (5)
H1	0.0323 (14)	0.0285 (13)	0.0255 (19)	−0.0005 (11)	0.0082 (12)	0.0009 (11)
O2	0.0192 (6)	0.0144 (5)	0.0155 (9)	−0.0027 (4)	0.0022 (5)	−0.0010 (5)
O3	0.0181 (6)	0.0173 (6)	0.0171 (9)	−0.0016 (5)	0.0039 (5)	0.0012 (5)
O4	0.0191 (6)	0.0169 (6)	0.0183 (9)	−0.0047 (5)	0.0043 (5)	−0.0036 (5)
C1	0.0142 (5)	0.0144 (5)	0.0153 (7)	0.0005 (4)	0.0025 (4)	0.0006 (4)
C2	0.0134 (4)	0.0134 (4)	0.0143 (7)	0.0004 (3)	0.0017 (4)	0.0005 (4)
C3	0.0138 (4)	0.0140 (5)	0.0167 (7)	0.0006 (4)	0.0036 (4)	0.0010 (4)
C4	0.0136 (5)	0.0142 (5)	0.0160 (7)	−0.0012 (4)	0.0025 (4)	0.0001 (4)
O5	0.0196 (6)	0.0188 (6)	0.0167 (9)	−0.0004 (5)	0.0034 (5)	0.0016 (5)
H5	0.0304 (14)	0.0301 (13)	0.0231 (18)	−0.0022 (11)	0.0049 (11)	−0.0004 (11)
O6	0.0247 (7)	0.0235 (7)	0.0176 (10)	−0.0074 (6)	0.0047 (6)	−0.0042 (6)
O7	0.0191 (6)	0.0183 (6)	0.0169 (9)	0.0002 (5)	0.0045 (5)	0.0018 (5)
O8	0.0190 (6)	0.0195 (6)	0.0170 (9)	−0.0016 (5)	0.0025 (5)	−0.0028 (5)
C5	0.0152 (5)	0.0161 (5)	0.0156 (7)	0.0013 (4)	0.0023 (4)	0.0010 (4)
C6	0.0162 (5)	0.0158 (5)	0.0152 (7)	−0.0003 (4)	0.0023 (4)	−0.0011 (4)
C7	0.0143 (5)	0.0168 (5)	0.0149 (7)	0.0018 (4)	0.0022 (4)	0.0013 (4)
C8	0.0150 (5)	0.0163 (5)	0.0145 (7)	0.0013 (4)	0.0007 (4)	0.0005 (4)
N1	0.0161 (4)	0.0154 (3)	0.0151 (5)	0.0008 (3)	0.0031 (3)	−0.0008 (3)
N2	0.0157 (4)	0.0155 (3)	0.0177 (5)	−0.0010 (3)	0.0046 (3)	−0.0021 (3)
H2	0.0251 (12)	0.0285 (13)	0.0289 (19)	−0.0025 (10)	0.0068 (11)	−0.0060 (11)
N3	0.0174 (4)	0.0176 (4)	0.0170 (6)	−0.0010 (3)	0.0059 (3)	−0.0006 (3)
H3A	0.0319 (14)	0.0332 (14)	0.0228 (19)	−0.0020 (11)	0.0096 (12)	−0.0015 (11)
H3B	0.0313 (14)	0.0285 (14)	0.031 (2)	−0.0092 (11)	0.0111 (13)	−0.0013 (12)
N4	0.0150 (4)	0.0205 (4)	0.0177 (6)	0.0010 (3)	0.0032 (3)	−0.0009 (3)
H4A	0.0299 (14)	0.0368 (16)	0.026 (2)	0.0048 (12)	0.0037 (12)	0.0014 (12)
H4B	0.0213 (12)	0.0409 (17)	0.033 (2)	0.0006 (11)	0.0089 (12)	−0.0007 (13)
N5	0.0152 (3)	0.0146 (3)	0.0183 (6)	−0.0009 (3)	0.0037 (3)	−0.0018 (3)
H5A	0.0318 (14)	0.0285 (13)	0.0254 (19)	0.0003 (11)	0.0075 (12)	−0.0039 (11)
H5B	0.0297 (14)	0.0292 (13)	0.030 (2)	−0.0016 (11)	0.0113 (12)	0.0003 (11)
C9	0.0213 (6)	0.0219 (6)	0.0192 (9)	0.0052 (5)	0.0071 (5)	0.0005 (5)
H9A	0.062 (3)	0.051 (2)	0.068 (4)	0.019 (2)	0.044 (3)	0.028 (3)
H9B	0.045 (2)	0.055 (3)	0.053 (3)	0.005 (2)	0.012 (2)	−0.030 (2)
H9C	0.0350 (18)	0.056 (2)	0.042 (3)	0.0225 (18)	0.0048 (16)	0.0018 (19)
C10	0.0180 (5)	0.0237 (6)	0.0174 (8)	−0.0007 (4)	0.0037 (5)	0.0002 (5)
H10A	0.041 (2)	0.0348 (18)	0.057 (3)	−0.0065 (16)	−0.005 (2)	−0.0066 (18)
H10B	0.0346 (18)	0.073 (3)	0.025 (3)	0.0020 (19)	−0.0016 (15)	0.012 (2)
H10C	0.0275 (16)	0.070 (3)	0.036 (3)	0.0156 (17)	0.0045 (15)	−0.006 (2)
C11	0.0144 (5)	0.0140 (4)	0.0153 (7)	0.0008 (4)	0.0034 (4)	−0.0006 (4)
C12	0.0140 (5)	0.0128 (4)	0.0165 (7)	0.0012 (4)	0.0031 (4)	−0.0008 (4)

Geometric parameters (Å, º)

O1—C1	1.287 (3)	N1—C11	1.317 (2)
O1—H1	1.048 (4)	N1—C10	1.4564 (19)
O2—C2	1.2412 (19)	N1—C9	1.462 (2)
O3—C3	1.225 (3)	N2—C12	1.375 (2)
O4—C4	1.244 (2)	N2—C11	1.385 (2)
C1—C4	1.439 (2)	N2—H2	1.034 (3)
C1—C2	1.4503 (19)	N3—C12	1.3258 (19)
C1—C3	2.057 (2)	N3—H3A	1.015 (4)
C2—C3	1.493 (2)	N3—H3B	1.016 (3)
C2—C4	2.0898 (19)	N4—C11	1.3243 (16)
C3—C4	1.4827 (19)	N4—H4A	1.015 (4)
O5—C5	1.300 (3)	N4—H4B	1.010 (4)
O5—H5	1.021 (4)	N5—C12	1.3124 (16)
O6—C6	1.247 (2)	N5—H5A	1.022 (4)
O7—C7	1.230 (2)	N5—H5B	1.019 (4)
O8—C8	1.234 (2)	C9—H9A	1.069 (5)
C5—C6	1.435 (2)	C9—H9B	1.087 (5)
C5—C8	1.454 (2)	C9—H9C	1.082 (5)
C5—C7	2.060 (2)	C10—H10A	1.076 (5)
C6—C7	1.478 (2)	C10—H10B	1.076 (6)
C6—C8	2.088 (2)	C10—H10C	1.088 (5)
C7—C8	1.500 (2)
C1—O1—H1	115.5 (2)	O7—C7—C5	179.11 (15)
O1—C1—C4	130.78 (13)	C6—C7—C5	44.17 (8)
O1—C1—C2	136.55 (15)	C8—C7—C5	44.88 (9)
C4—C1—C2	92.65 (13)	O8—C8—C5	136.58 (17)
O1—C1—C3	176.07 (14)	O8—C8—C7	135.00 (18)
C4—C1—C3	46.13 (8)	C5—C8—C7	88.42 (11)
C2—C1—C3	46.55 (9)	O8—C8—C6	179.32 (15)
O2—C2—C1	137.02 (17)	C5—C8—C6	43.37 (8)
O2—C2—C3	134.36 (16)	C7—C8—C6	45.06 (9)
C1—C2—C3	88.62 (11)	C11—N1—C10	123.92 (13)
O2—C2—C4	178.37 (14)	C11—N1—C9	120.69 (12)
C1—C2—C4	43.47 (9)	C10—N1—C9	115.38 (13)
C3—C2—C4	45.19 (8)	C12—N2—C11	127.54 (11)
O3—C3—C4	134.30 (15)	C12—N2—H2	114.4 (3)
O3—C3—C2	136.47 (13)	C11—N2—H2	117.3 (3)
C4—C3—C2	89.21 (12)	C12—N3—H3A	120.0 (2)
O3—C3—C1	177.46 (14)	C12—N3—H3B	118.5 (3)
C4—C3—C1	44.41 (8)	H3A—N3—H3B	120.9 (3)
C2—C3—C1	44.83 (8)	C11—N4—H4A	123.7 (3)
O4—C4—C1	136.24 (16)	C11—N4—H4B	119.7 (3)
O4—C4—C3	134.28 (17)	H4A—N4—H4B	115.7 (3)
C1—C4—C3	89.46 (11)	C12—N5—H5A	121.0 (2)
O4—C4—C2	179.54 (15)	C12—N5—H5B	123.0 (2)
C1—C4—C2	43.89 (8)	H5A—N5—H5B	115.9 (3)
C3—C4—C2	45.60 (8)	N1—C9—H9A	110.9 (3)
C5—O5—H5	113.5 (3)	N1—C9—H9B	107.7 (3)
C6—O6—H1	136.6 (2)	H9A—C9—H9B	112.0 (6)
O5—C5—C6	135.95 (15)	N1—C9—H9C	110.5 (4)
O5—C5—C8	131.48 (14)	H9A—C9—H9C	108.7 (5)
C6—C5—C8	92.57 (13)	H9B—C9—H9C	107.0 (5)
O5—C5—C7	177.97 (13)	N1—C10—H10A	110.5 (3)
C6—C5—C7	45.86 (9)	N1—C10—H10B	108.7 (3)
C8—C5—C7	46.71 (8)	H10A—C10—H10B	109.8 (5)
O6—C6—C5	137.51 (19)	N1—C10—H10C	112.1 (3)
O6—C6—C7	132.53 (17)	H10A—C10—H10C	108.2 (5)
C5—C6—C7	89.96 (11)	H10B—C10—H10C	107.5 (5)
O6—C6—C8	178.40 (17)	N1—C11—N4	121.99 (14)
C5—C6—C8	44.07 (9)	N1—C11—N2	116.93 (12)
C7—C6—C8	45.90 (8)	N4—C11—N2	120.98 (14)
O7—C7—C6	135.51 (14)	N5—C12—N3	121.93 (14)
O7—C7—C8	135.44 (15)	N5—C12—N2	121.96 (13)
C6—C7—C8	89.05 (12)	N3—C12—N2	116.10 (11)