A second monoclinic polymorph of ethyl-enediammonium bis-(hydrogen squarate) monohydrate.

The title compound, C(2)H(10)N(2) (2+)·2HC(4)O(4) (-)·H(2)O, a new polymorph of ethyl-enediammonium bis-(hydrogen squarate) monohydrate, was synthesized by slow evaporation of an acid solution. The asymetric unit contains two hydrogen squarate anions, two half-mol-ecules of protonated ethyl-enediamine arranged around a twofold axis and one water mol-ecule. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds between the hydrogen squarate anions, protonated N atoms from the amine group and water mol-ecules lead to a three-dimensional framework. In particular, the cohesion between the squarate groups is ensured by very short intermolecular hydrogen bonds bonds. The title compound crystallized together with the previously reported polymorph [Mathew et al. (2002 ▶). J. Mol. Struct.641, 263-279].

Related literature

For the previously reported polymorph, see: Mathew et al. (2002 ▶).

Experimental

Crystal data

C2H10N2 2+·2C4HO4 −·H2O

M = 306.23

Monoclinic,

a = 14.1907 (3) Å

b = 9.0224 (2) Å

c = 10.9412 (2) Å

β = 111.789 (1)°

V = 1300.77 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.45 × 0.44 × 0.37 mm

Data collection

Nonius KappaCCD diffractometer

16099 measured reflections

2957 independent reflections

2101 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.116

S = 1.06

2957 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.24 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009019/dn2662sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009019/dn2662Isup2.hkl

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

C2H10N22+·2C4HO4−·H2O	F(000) = 640
Mr = 306.23	Dx = 1.564 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 15363 reflections
a = 14.1907 (3) Å	θ = 2.6–27.5°
b = 9.0224 (2) Å	µ = 0.14 mm−1
c = 10.9412 (2) Å	T = 293 K
β = 111.789 (1)°	Block, colourless
V = 1300.77 (5) Å3	0.45 × 0.44 × 0.37 mm
Z = 4

Nonius KappaCCD diffractometer	2101 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
horizonally mounted graphite crystal	θmax = 27.5°, θmin = 3.7°
CCD scans	h = −13→14
16099 measured reflections	k = −11→11
2957 independent reflections	l = −18→18

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0506P)2 + 0.4175P] where P = (Fo2 + 2Fc2)/3
2957 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.24 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 > 2σ(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	0.13638 (12)	0.21953 (17)	0.23974 (14)	0.0274 (3)
C2	0.12945 (12)	0.22646 (17)	0.37292 (15)	0.0294 (3)
C3	0.13154 (12)	0.06345 (17)	0.37612 (14)	0.0280 (3)
C4	0.13514 (12)	0.05880 (16)	0.24889 (14)	0.0270 (3)
C5	0.37318 (12)	0.22227 (17)	0.53401 (14)	0.0282 (3)
C6	0.37820 (12)	0.05841 (17)	0.53440 (14)	0.0266 (3)
C7	0.37483 (12)	0.05424 (16)	0.66247 (14)	0.0264 (3)
C8	0.36698 (12)	0.21411 (17)	0.66793 (14)	0.0285 (3)
C9	0.45935 (12)	0.62029 (18)	0.68196 (15)	0.0310 (4)
H9A	0.4620	0.7123	0.6375	0.037*
H9B	0.4708	0.5391	0.6310	0.037*
C10	0.00261 (13)	0.36235 (19)	0.68282 (16)	0.0359 (4)
H10A	−0.0221	0.2683	0.6400	0.043*
H10B	−0.0408	0.4401	0.6300	0.043*
N1	0.35844 (10)	0.60417 (15)	0.69124 (14)	0.0330 (3)
H1A	0.3537	0.6630	0.7544	0.040*
H1B	0.3127	0.6300	0.6143	0.040*
H1C	0.3495	0.5112	0.7090	0.040*
N2	0.10844 (11)	0.38656 (14)	0.69090 (13)	0.0343 (3)
H2A	0.1155	0.3480	0.6209	0.041*
H2B	0.1534	0.3450	0.7642	0.041*
H2C	0.1219	0.4842	0.6931	0.041*
O1	0.14176 (10)	0.31161 (12)	0.15936 (12)	0.0406 (3)
O2	0.12416 (11)	0.32661 (14)	0.44601 (12)	0.0469 (4)
O3	0.13116 (11)	−0.03557 (13)	0.45842 (11)	0.0422 (3)
O4	0.13646 (10)	−0.05236 (12)	0.17443 (11)	0.0402 (3)
H4	0.1339	−0.0164	0.0819	0.060*
O5	0.37214 (10)	0.32156 (13)	0.45711 (11)	0.0411 (3)
O6	0.38111 (10)	−0.03993 (12)	0.45340 (10)	0.0365 (3)
O7	0.37617 (10)	−0.05505 (12)	0.73992 (11)	0.0366 (3)
H7	0.3768	−0.0150	0.8313	0.055*
O8	0.35656 (11)	0.30475 (13)	0.74692 (11)	0.0430 (3)
O1W	0.24474 (9)	−0.28124 (14)	0.43628 (12)	0.0436 (3)
H1W	0.2960	−0.2370	0.4170	0.065*
H2W	0.2063	−0.2050	0.4510	0.065*

	U11	U22	U33	U12	U13	U23
C1	0.0324 (9)	0.0254 (7)	0.0260 (7)	0.0044 (6)	0.0127 (6)	0.0034 (6)
C2	0.0340 (9)	0.0287 (8)	0.0284 (7)	0.0042 (7)	0.0152 (7)	0.0008 (7)
C3	0.0331 (9)	0.0274 (8)	0.0245 (7)	−0.0015 (6)	0.0119 (6)	0.0003 (6)
C4	0.0328 (9)	0.0261 (8)	0.0227 (8)	−0.0002 (6)	0.0110 (6)	−0.0001 (6)
C5	0.0339 (9)	0.0283 (8)	0.0242 (7)	−0.0034 (6)	0.0130 (6)	−0.0006 (6)
C6	0.0310 (8)	0.0284 (8)	0.0228 (7)	−0.0033 (6)	0.0128 (6)	−0.0015 (6)
C7	0.0338 (8)	0.0255 (7)	0.0220 (7)	−0.0013 (6)	0.0128 (6)	−0.0011 (6)
C8	0.0377 (9)	0.0257 (7)	0.0250 (7)	−0.0033 (7)	0.0149 (7)	−0.0019 (6)
C9	0.0310 (9)	0.0318 (8)	0.0315 (8)	−0.0005 (7)	0.0132 (7)	0.0010 (7)
C10	0.0392 (9)	0.0397 (9)	0.0304 (8)	0.0039 (8)	0.0147 (7)	−0.0019 (7)
N1	0.0330 (8)	0.0299 (7)	0.0359 (7)	0.0010 (6)	0.0123 (6)	−0.0002 (6)
N2	0.0462 (9)	0.0273 (7)	0.0354 (7)	−0.0004 (6)	0.0221 (7)	−0.0003 (6)
O1	0.0643 (9)	0.0280 (6)	0.0374 (6)	0.0064 (6)	0.0281 (6)	0.0086 (5)
O2	0.0751 (10)	0.0337 (7)	0.0416 (7)	0.0100 (6)	0.0328 (7)	−0.0038 (6)
O3	0.0740 (9)	0.0308 (6)	0.0279 (6)	−0.0068 (6)	0.0260 (6)	0.0024 (5)
O4	0.0723 (9)	0.0261 (6)	0.0277 (6)	−0.0030 (6)	0.0249 (6)	−0.0033 (5)
O5	0.0632 (9)	0.0314 (6)	0.0341 (6)	−0.0034 (6)	0.0241 (6)	0.0061 (5)
O6	0.0591 (8)	0.0299 (6)	0.0272 (6)	−0.0046 (5)	0.0239 (6)	−0.0059 (5)
O7	0.0646 (8)	0.0243 (6)	0.0283 (6)	0.0017 (5)	0.0260 (6)	0.0031 (5)
O8	0.0776 (10)	0.0254 (6)	0.0366 (6)	−0.0007 (6)	0.0334 (7)	−0.0046 (5)
O1W	0.0384 (7)	0.0416 (7)	0.0464 (7)	−0.0044 (6)	0.0106 (6)	0.0083 (6)

C1—O1	1.2326 (18)	C9—C9i	1.508 (3)
C1—C4	1.454 (2)	C9—H9A	0.9700
C1—C2	1.498 (2)	C9—H9B	0.9700
C2—O2	1.2273 (19)	C10—N2	1.487 (2)
C2—C3	1.471 (2)	C10—C10ii	1.499 (3)
C3—O3	1.2699 (18)	C10—H10A	0.9700
C3—C4	1.412 (2)	C10—H10B	0.9700
C4—O4	1.2966 (18)	N1—H1A	0.8933
C5—O5	1.2253 (18)	N1—H1B	0.8824
C5—C6	1.480 (2)	N1—H1C	0.8806
C5—C8	1.502 (2)	N2—H2A	0.8805
C6—O6	1.2655 (18)	N2—H2B	0.9002
C6—C7	1.420 (2)	N2—H2C	0.9002
C7—O7	1.2958 (18)	O4—H4	1.0509
C7—C8	1.450 (2)	O7—H7	1.0597
C8—O8	1.2380 (18)	O1W—H1W	0.9203
C9—N1	1.480 (2)	O1W—H2W	0.9287
O1—C1—C4	136.62 (14)	C9i—C9—H9A	109.7
O1—C1—C2	135.22 (15)	N1—C9—H9B	109.7
C4—C1—C2	88.16 (12)	C9i—C9—H9B	109.7
O2—C2—C3	136.56 (15)	H9A—C9—H9B	108.2
O2—C2—C1	134.96 (15)	N2—C10—C10ii	110.98 (17)
C3—C2—C1	88.47 (12)	N2—C10—H10A	109.4
O3—C3—C4	133.57 (14)	C10ii—C10—H10A	109.4
O3—C3—C2	135.63 (14)	N2—C10—H10B	109.4
C4—C3—C2	90.81 (12)	C10ii—C10—H10B	109.4
O4—C4—C3	131.03 (14)	H10A—C10—H10B	108.0
O4—C4—C1	136.44 (14)	C9—N1—H1A	110.3
C3—C4—C1	92.52 (12)	C9—N1—H1B	107.2
O5—C5—C6	136.10 (14)	H1A—N1—H1B	110.0
O5—C5—C8	135.69 (15)	C9—N1—H1C	109.3
C6—C5—C8	88.19 (11)	H1A—N1—H1C	109.7
O6—C6—C7	133.96 (14)	H1B—N1—H1C	110.3
O6—C6—C5	135.43 (14)	C10—N2—H2A	109.2
C7—C6—C5	90.58 (12)	C10—N2—H2B	111.0
O7—C7—C6	131.89 (14)	H2A—N2—H2B	109.8
O7—C7—C8	135.48 (14)	C10—N2—H2C	110.2
C6—C7—C8	92.61 (12)	H2A—N2—H2C	108.5
O8—C8—C7	135.81 (14)	H2B—N2—H2C	108.1
O8—C8—C5	135.57 (14)	C4—O4—H4	111.3
C7—C8—C5	88.59 (12)	C7—O7—H7	110.5
N1—C9—C9i	109.73 (16)	H1W—O1W—H2W	106.5
N1—C9—H9A	109.7

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5iii	0.89	2.14	2.9205 (17)	146.
N1—H1B···O1Wiv	0.88	1.99	2.8482 (18)	163.
N1—H1C···O8	0.88	1.90	2.7717 (18)	169.
N2—H2A···O2	0.88	1.97	2.8222 (17)	162.
N2—H2B···O1Wv	0.90	1.94	2.8279 (18)	171.
N2—H2C···O1iii	0.90	1.92	2.8071 (17)	168.
O4—H4···O3vi	1.05	1.42	2.4675 (15)	179.
O7—H7···O6v	1.06	1.41	2.4645 (14)	178.
O1W—H1W···O6	0.92	2.10	2.8724 (17)	140.
O1W—H1W···O8vi	0.92	2.40	3.0489 (18)	128.
O1W—H2W···O3	0.93	1.88	2.8035 (19)	171.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O5i	0.89	2.14	2.9205 (17)	146
N1—H1B⋯O1Wii	0.88	1.99	2.8482 (18)	163
N1—H1C⋯O8	0.88	1.90	2.7717 (18)	169
N2—H2A⋯O2	0.88	1.97	2.8222 (17)	162
N2—H2B⋯O1Wiii	0.90	1.94	2.8279 (18)	171
N2—H2C⋯O1i	0.90	1.92	2.8071 (17)	168
O4—H4⋯O3iv	1.05	1.42	2.4675 (15)	179
O7—H7⋯O6iii	1.06	1.41	2.4645 (14)	178
O1W—H1W⋯O6	0.92	2.10	2.8724 (17)	140
O1W—H1W⋯O8iv	0.92	2.40	3.0489 (18)	128
O1W—H2W⋯O3	0.93	1.88	2.8035 (19)	171

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