Diaqua-bis(1,3-propane-diamine)nickel(II) squarate tetrahydrate.

The asymmetric unit of the title compound, [Ni(C(3)H(10)N(2))(2)(H(2)O)(2)](C(4)O(4))·4H(2)O, contains one-half of the diaqua-bis(1,3-propane-diamine)nickel(II) cation, one-half of the centrosymmetric squarate anion and two uncoordinated water mol-ecules. In the cation, the Ni(II) atom is located on a crystallographic inversion centre and has a slightly distorted octa-hedral coordination geometry. The six-membered chelate ring adopts a chair conformation. O-H⋯O hydrogen bonds link the cation and anion through the water mol-ecule, while N-H⋯O hydrogen bonds link the cation and anion and cation and water mol-ecules. In the crystal structure, inter-molecular O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network structure.

Related literature

For general background, see: Bertolasi et al. (2001 ▶); Gollogly & Hawkins (1972 ▶); Lam & Mak (2000 ▶); Liebeskind et al. (1993 ▶); Mathew et al. (2002 ▶); Reetz et al. (1994 ▶); Seitz & Imming (1992 ▶); Zaman et al. (2001 ▶). For related structures, see: Ghosh et al. (1997 ▶); Mukherjee et al. (1990 ▶); Pariya et al. (1995 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(C3H10N2)2(n class="Chemical">H2O)2](C4O4)·4H2O

M = 427.09

Monoclinic,

a = 8.0429 (4) Å

b = 9.1752 (5) Å

c = 14.6510 (8) Å

β = 117.570 (4)°

V = 958.40 (9) Å3

Z = 2

Mo Kα radiation

μ = 1.06 mm−1

T = 296 K

0.75 × 0.45 × 0.05 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.638, T max = 0.949

7288 measured reflections

2204 independent reflections

2003 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.054

S = 1.06

2204 reflections

139 parameters

H atoms treated by a mixture of inden class="Chemical">pendent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.17 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S160053680902087X/hk2703sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902087X/hk2703Isup2.hkl

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

[Ni(C3H10N2)2(H2O)2](C4O4)·4H2O	F(000) = 456.0
Mr = 427.09	Dx = 1.480 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2204 reflections
a = 8.0429 (4) Å	θ = 2.2–28.0°
b = 9.1752 (5) Å	µ = 1.06 mm−1
c = 14.6510 (8) Å	T = 296 K
β = 117.570 (4)°	Plate, violet
V = 958.40 (9) Å3	0.75 × 0.45 × 0.05 mm
Z = 2

Stoe IPDS II diffractometer	2204 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2003 reflections with I > 2σ(I)
plane graphite	Rint = 0.020
Detector resolution: 6.67 pixels mm-1	θmax = 27.5°, θmin = 2.7°
w–scan rotation method	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
Tmin = 0.638, Tmax = 0.949	l = −19→17
7288 measured 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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0282P)2 + 0.2118P] where P = (Fo2 + 2Fc2)/3
2204 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

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.

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.02232 (7)
O1	0.64732 (15)	0.39000 (12)	0.43015 (8)	0.0383 (2)
H1E	0.713 (3)	0.432 (2)	0.4113 (14)	0.051 (5)*
H1F	0.692 (3)	0.315 (3)	0.4515 (15)	0.063 (6)*
O2	0.73874 (13)	1.09844 (11)	0.49933 (8)	0.0414 (2)
O3	0.86500 (14)	0.77497 (10)	0.46843 (9)	0.0434 (2)
O4	0.34274 (18)	0.07964 (14)	0.36302 (9)	0.0489 (3)
H4A	0.455 (3)	0.082 (2)	0.3910 (16)	0.067 (6)*
H4B	0.317 (3)	0.029 (3)	0.401 (2)	0.075 (7)*
O5	0.85562 (18)	0.53525 (13)	0.35580 (11)	0.0462 (3)
H5A	0.871 (3)	0.611 (3)	0.3859 (17)	0.066 (6)*
H5B	0.803 (3)	0.550 (3)	0.2975 (19)	0.072 (8)*
N1	0.24635 (14)	0.41813 (12)	0.38210 (8)	0.0317 (2)
H1A	0.2548	0.3203	0.3845	0.038*
H1B	0.1547	0.4421	0.3983	0.038*
N2	0.47942 (14)	0.69084 (11)	0.41632 (8)	0.0294 (2)
H2A	0.4236	0.7588	0.4372	0.035*
H2B	0.5970	0.7221	0.4355	0.035*
C1	0.1833 (2)	0.46195 (17)	0.27461 (10)	0.0423 (3)
H1C	0.0568	0.4263	0.2326	0.051*
H1D	0.2640	0.4173	0.2497	0.051*
C2	0.1860 (2)	0.62587 (16)	0.26262 (11)	0.0438 (3)
H2C	0.1144	0.6502	0.1902	0.053*
H2D	0.1242	0.6710	0.2987	0.053*
C3	0.3806 (2)	0.68931 (16)	0.30294 (10)	0.0406 (3)
H3A	0.4520	0.6320	0.2776	0.049*
H3B	0.3718	0.7880	0.2774	0.049*
C4	0.88219 (16)	1.04411 (13)	0.49952 (9)	0.0269 (2)
C5	0.93844 (16)	0.89777 (13)	0.48539 (9)	0.0271 (2)

	U11	U22	U33	U12	U13	U23
Ni1	0.02176 (11)	0.02133 (11)	0.02386 (11)	0.00055 (7)	0.01055 (8)	0.00121 (7)
O1	0.0460 (6)	0.0308 (5)	0.0522 (6)	0.0070 (4)	0.0346 (5)	0.0041 (4)
O2	0.0319 (5)	0.0362 (5)	0.0643 (7)	0.0049 (4)	0.0291 (5)	0.0006 (5)
O3	0.0453 (5)	0.0286 (5)	0.0636 (7)	−0.0116 (4)	0.0314 (5)	−0.0089 (4)
O4	0.0416 (6)	0.0539 (7)	0.0491 (6)	−0.0045 (5)	0.0191 (5)	0.0039 (5)
O5	0.0530 (7)	0.0407 (6)	0.0538 (7)	−0.0009 (5)	0.0321 (6)	−0.0024 (5)
N1	0.0279 (5)	0.0315 (5)	0.0311 (5)	−0.0026 (4)	0.0097 (4)	−0.0008 (4)
N2	0.0309 (5)	0.0258 (5)	0.0317 (5)	0.0005 (4)	0.0147 (4)	0.0031 (4)
C1	0.0455 (8)	0.0434 (7)	0.0282 (6)	−0.0033 (6)	0.0089 (6)	−0.0053 (5)
C2	0.0453 (8)	0.0452 (8)	0.0278 (6)	0.0055 (6)	0.0058 (6)	0.0062 (6)
C3	0.0517 (8)	0.0407 (7)	0.0322 (6)	0.0026 (6)	0.0219 (6)	0.0086 (5)
C4	0.0251 (5)	0.0269 (5)	0.0296 (6)	0.0008 (4)	0.0134 (4)	0.0015 (4)
C5	0.0269 (5)	0.0263 (5)	0.0290 (6)	−0.0021 (4)	0.0138 (4)	−0.0006 (4)

Ni1—O1i	2.1429 (9)	C1—N1	1.4695 (17)
Ni1—N1i	2.1090 (10)	C1—C2	1.516 (2)
Ni1—N2i	2.0997 (10)	C1—H1C	0.9700
O1—Ni1	2.1429 (9)	C1—H1D	0.9700
O1—H1E	0.80 (2)	C2—C3	1.511 (2)
O1—H1F	0.77 (2)	C2—H2C	0.9700
O4—H4A	0.80 (2)	C2—H2D	0.9700
O4—H4B	0.82 (3)	C3—N2	1.4728 (16)
O5—H5A	0.80 (2)	C3—H3A	0.9700
O5—H5B	0.77 (2)	C3—H3B	0.9700
N1—Ni1	2.1090 (10)	C4—O2	1.2557 (15)
N1—H1A	0.9000	C4—C5ii	1.4557 (16)
N1—H1B	0.9000	C4—C5	1.4619 (17)
N2—Ni1	2.0997 (10)	C5—O3	1.2427 (15)
N2—H2A	0.9000	C5—C4ii	1.4557 (16)
N2—H2B	0.9000
O1—Ni1—O1i	180.00 (5)	C3—N2—Ni1	120.41 (8)
N1i—Ni1—N1	180.0	C3—N2—H2A	107.2
N1i—Ni1—O1	91.14 (4)	C3—N2—H2B	107.2
N1—Ni1—O1	88.86 (4)	H2A—N2—H2B	106.9
N1i—Ni1—O1i	88.86 (4)	N1—C1—C2	112.30 (11)
N1—Ni1—O1i	91.14 (4)	N1—C1—H1C	109.1
N2i—Ni1—O1	88.54 (4)	C2—C1—H1C	109.1
N2—Ni1—O1	91.46 (4)	N1—C1—H1D	109.1
N2i—Ni1—O1i	91.46 (4)	C2—C1—H1D	109.1
N2—Ni1—O1i	88.54 (4)	H1C—C1—H1D	107.9
N2i—Ni1—N2	180.0	C3—C2—C1	113.88 (12)
N2i—Ni1—N1i	91.94 (4)	C3—C2—H2C	108.8
N2—Ni1—N1i	88.06 (4)	C1—C2—H2C	108.8
N2i—Ni1—N1	88.06 (4)	C3—C2—H2D	108.8
N2—Ni1—N1	91.94 (4)	C1—C2—H2D	108.8
Ni1—O1—H1E	122.4 (14)	H2C—C2—H2D	107.7
Ni1—O1—H1F	118.8 (15)	N2—C3—C2	111.42 (11)
H1E—O1—H1F	108.4 (19)	N2—C3—H3A	109.3
H4A—O4—H4B	104 (2)	C2—C3—H3A	109.3
H5A—O5—H5B	109 (2)	N2—C3—H3B	109.3
Ni1—N1—H1A	107.3	C2—C3—H3B	109.3
Ni1—N1—H1B	107.3	H3A—C3—H3B	108.0
C1—N1—Ni1	120.23 (9)	O2—C4—C5ii	134.42 (12)
C1—N1—H1A	107.3	O2—C4—C5	135.11 (12)
C1—N1—H1B	107.3	C5ii—C4—C5	90.46 (9)
H1A—N1—H1B	106.9	O3—C5—C4ii	135.11 (12)
Ni1—N2—H2A	107.2	O3—C5—C4	135.35 (12)
Ni1—N2—H2B	107.2	C4ii—C5—C4	89.54 (9)
C1—N1—Ni1—O1	−63.90 (10)	N1—C1—C2—C3	72.93 (17)
C1—N1—Ni1—O1i	116.10 (10)	C1—C2—C3—N2	−73.63 (16)
C1—N1—Ni1—N2i	−152.47 (10)	C2—C3—N2—Ni1	52.35 (14)
C1—N1—Ni1—N2	27.53 (10)	O2—C4—C5—O3	−0.2 (3)
C3—N2—Ni1—O1	60.31 (10)	C5ii—C4—C5—O3	179.50 (19)
C3—N2—Ni1—O1i	−119.69 (10)	O2—C4—C5—C4ii	−179.72 (18)
C2—C1—N1—Ni1	−50.38 (16)	C5ii—C4—C5—C4ii	0.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O5iii	0.90	2.35	3.1715 (16)	152
N2—H2A···O2iv	0.90	2.33	3.2174 (14)	170
O1—H1F···O2v	0.77 (2)	2.08 (2)	2.8345 (15)	165 (2)
O4—H4A···O2v	0.80 (2)	2.10 (2)	2.8765 (16)	165 (2)
O4—H4B···O2i	0.82 (3)	2.07 (3)	2.8965 (16)	178 (2)
O5—H5B···O4vi	0.77 (2)	2.10 (3)	2.8730 (19)	177 (2)
N1—H1A···O4	0.90	2.38	3.2442 (17)	160
N2—H2B···O3	0.90	2.04	2.9333 (14)	174
O1—H1E···O5	0.80 (2)	1.93 (2)	2.7311 (16)	175.8 (19)
O5—H5A···O3	0.80 (2)	1.94 (2)	2.7296 (16)	166 (2)

O1—Ni1	2.1429 (9)
N1—Ni1	2.1090 (10)
N2—Ni1	2.0997 (10)

N1—Ni1—O1	88.86 (4)
N2—Ni1—O1	91.46 (4)
N2—Ni1—N1	91.94 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O5i	0.90	2.35	3.1715 (16)	152
N2—H2A⋯O2ii	0.90	2.33	3.2174 (14)	170
O1—H1F⋯O2iii	0.77 (2)	2.08 (2)	2.8345 (15)	165 (2)
O4—H4A⋯O2iii	0.80 (2)	2.10 (2)	2.8765 (16)	165 (2)
O4—H4B⋯O2iv	0.82 (3)	2.07 (3)	2.8965 (16)	178 (2)
O5—H5B⋯O4v	0.77 (2)	2.10 (3)	2.8730 (19)	177 (2)
N1—H1A⋯O4	0.90	2.38	3.2442 (17)	160
N2—H2B⋯O3	0.90	2.04	2.9333 (14)	174
O1—H1E⋯O5	0.80 (2)	1.93 (2)	2.7311 (16)	175.8 (19)
O5—H5A⋯O3	0.80 (2)	1.94 (2)	2.7296 (16)	166 (2)

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