Tetra-guanidinium bis-[citrato(3-)]cuprate(II) dihydrate.

The asymmetric unit of the title compound, (CH(6)N(3))(4)[Cu(C(6)H(5)O(7))(2)]·2H(2)O, contains one-half of a centrosymmetric Cu(II) complex anion, two guanidinium cations and a water mol-ecule. The Cu(II) ion, lying on a crystallographic inversion center, is hexa-coordinated with two citrate anions in a distorted octahedral geometry. An intra-molecular O-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal structure, mol-ecules are linked into a three-dimensional framework by inter-molecular N-H⋯O and O-H⋯O hydrogen bonds.

Related literature

For general background to citric acid and guanidine, see: Raczyńska et al. (2003 ▶); Yamada et al. (2009 ▶); Sigman et al. (1993 ▶). For a related structure with a guanidinium cation, see: Al-Dajani et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

(CH6N3)4[Cu(C6H5O7)2]·2H2O

M = 718.12

Triclinic,

a = 9.0426 (1) Å

b = 9.7763 (2) Å

c = 10.3366 (2) Å

α = 96.503 (1)°

β = 105.441 (1)°

γ = 112.306 (1)°

V = 791.01 (2) Å3

Z = 1

Mo Kα radiation

μ = 0.78 mm−1

T = 296 K

0.60 × 0.39 × 0.32 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.653, T max = 0.787

37237 measured reflections

7051 independent reflections

6306 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.094

S = 1.05

7051 reflections

206 parameters

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046170/ci2960sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046170/ci2960Isup2.hkl

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

(CH6N3)4[Cu(C6H5O7)2]·2H2O	Z = 1
Mr = 718.12	F(000) = 375
Triclinic, P1	Dx = 1.508 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0426 (1) Å	Cell parameters from 9680 reflections
b = 9.7763 (2) Å	θ = 2.3–34.9°
c = 10.3366 (2) Å	µ = 0.78 mm−1
α = 96.503 (1)°	T = 296 K
β = 105.441 (1)°	Block, blue
γ = 112.306 (1)°	0.60 × 0.39 × 0.32 mm
V = 791.01 (2) Å3

Bruker SMART APEXII CCD area-detector diffractometer	7051 independent reflections
Radiation source: fine-focus sealed tube	6306 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 35.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
Tmin = 0.653, Tmax = 0.787	k = −15→15
37237 measured reflections	l = −16→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.108P] where P = (Fo2 + 2Fc2)/3
7051 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.49 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
Cu1	0.5000	1.0000	0.5000	0.02544 (5)
O1	0.66219 (12)	0.89568 (10)	0.55711 (9)	0.04046 (18)
O2	0.55673 (11)	1.02356 (8)	0.33541 (8)	0.03511 (15)
O3	0.32813 (9)	0.77094 (8)	0.36675 (7)	0.02790 (12)
H1O3	0.2276	0.7661	0.3035	0.042*
O4	0.76260 (15)	0.72314 (13)	0.55564 (10)	0.0536 (3)
O5	0.57936 (15)	0.90234 (12)	0.15326 (10)	0.0506 (2)
O7	0.09687 (12)	0.65390 (12)	−0.05629 (9)	0.04401 (19)
O6	0.10222 (13)	0.74648 (13)	0.15156 (9)	0.0480 (2)
C1	0.66253 (14)	0.77440 (12)	0.49850 (10)	0.03244 (18)
C2	0.53925 (14)	0.68374 (11)	0.35373 (10)	0.03180 (18)
H2A	0.4699	0.5826	0.3601	0.038*
H2B	0.6052	0.6721	0.2966	0.038*
C3	0.42059 (12)	0.74833 (10)	0.27880 (9)	0.02586 (14)
C4	0.52711 (13)	0.90199 (11)	0.25150 (10)	0.02936 (16)
C5	0.29501 (13)	0.63732 (12)	0.14090 (10)	0.03315 (18)
H5A	0.3568	0.6313	0.0784	0.040*
H5B	0.2432	0.5367	0.1567	0.040*
C6	0.15557 (13)	0.68329 (13)	0.07232 (11)	0.03335 (18)
N1	0.33925 (19)	0.13097 (19)	0.12541 (16)	0.0627 (4)
H1N1	0.3944	0.1103	0.0759	0.075*
H2N1	0.3625	0.1237	0.2099	0.075*
N2	0.13528 (17)	0.20918 (16)	0.14703 (11)	0.0503 (3)
H1N2	0.0587	0.2390	0.1118	0.060*
H2N2	0.1577	0.2022	0.2316	0.060*
N3	0.18333 (18)	0.18500 (18)	−0.05808 (13)	0.0548 (3)
H1N3	0.1067	0.2149	−0.0929	0.066*
H2N3	0.2372	0.1622	−0.1078	0.066*
C7	0.21821 (16)	0.17412 (15)	0.07130 (13)	0.0409 (2)
N4	0.86185 (16)	0.53693 (13)	0.28012 (13)	0.0475 (2)
H1N4	0.8743	0.6260	0.3163	0.057*
H2N4	0.8867	0.5223	0.2066	0.057*
N5	0.78586 (17)	0.28597 (12)	0.28065 (14)	0.0506 (3)
H1N5	0.7486	0.2106	0.3171	0.061*
H2N5	0.8111	0.2727	0.2071	0.061*
N6	0.76591 (17)	0.44356 (13)	0.45058 (12)	0.0469 (2)
H1N6	0.7286	0.3687	0.4875	0.056*
H2N6	0.7782	0.5324	0.4872	0.056*
C8	0.80435 (14)	0.42221 (12)	0.33777 (12)	0.03575 (19)
O1W	0.9973 (2)	0.13741 (17)	0.59833 (19)	0.0955 (6)
H1W1	0.9976	0.1225	0.5223	0.143*
H2W1	0.8945	0.0656	0.5902	0.143*

	U11	U22	U33	U12	U13	U23
Cu1	0.03201 (8)	0.02210 (7)	0.02568 (7)	0.01325 (6)	0.01258 (6)	0.00553 (5)
O1	0.0452 (4)	0.0371 (4)	0.0360 (4)	0.0230 (3)	0.0056 (3)	−0.0025 (3)
O2	0.0494 (4)	0.0258 (3)	0.0361 (3)	0.0148 (3)	0.0244 (3)	0.0102 (3)
O3	0.0326 (3)	0.0312 (3)	0.0270 (3)	0.0169 (3)	0.0150 (2)	0.0095 (2)
O4	0.0671 (6)	0.0638 (6)	0.0356 (4)	0.0484 (5)	0.0001 (4)	0.0013 (4)
O5	0.0680 (6)	0.0506 (5)	0.0475 (5)	0.0245 (5)	0.0415 (5)	0.0142 (4)
O7	0.0438 (4)	0.0615 (5)	0.0297 (3)	0.0260 (4)	0.0114 (3)	0.0117 (3)
O6	0.0495 (5)	0.0745 (6)	0.0368 (4)	0.0434 (5)	0.0156 (4)	0.0118 (4)
C1	0.0374 (5)	0.0347 (4)	0.0283 (4)	0.0200 (4)	0.0097 (3)	0.0055 (3)
C2	0.0381 (5)	0.0299 (4)	0.0298 (4)	0.0209 (4)	0.0075 (3)	0.0030 (3)
C3	0.0307 (4)	0.0259 (3)	0.0257 (3)	0.0156 (3)	0.0118 (3)	0.0055 (3)
C4	0.0349 (4)	0.0310 (4)	0.0297 (4)	0.0173 (3)	0.0166 (3)	0.0097 (3)
C5	0.0345 (4)	0.0344 (4)	0.0302 (4)	0.0184 (4)	0.0081 (3)	0.0007 (3)
C6	0.0317 (4)	0.0402 (5)	0.0306 (4)	0.0168 (4)	0.0118 (3)	0.0095 (4)
N1	0.0661 (8)	0.0851 (10)	0.0603 (7)	0.0545 (8)	0.0185 (6)	0.0314 (7)
N2	0.0583 (7)	0.0732 (8)	0.0362 (5)	0.0412 (6)	0.0187 (5)	0.0210 (5)
N3	0.0626 (7)	0.0884 (9)	0.0431 (5)	0.0535 (7)	0.0265 (5)	0.0286 (6)
C7	0.0425 (6)	0.0463 (6)	0.0403 (5)	0.0248 (5)	0.0127 (4)	0.0160 (4)
N4	0.0615 (7)	0.0363 (5)	0.0504 (6)	0.0167 (5)	0.0300 (5)	0.0196 (4)
N5	0.0674 (7)	0.0337 (4)	0.0606 (7)	0.0170 (5)	0.0423 (6)	0.0136 (4)
N6	0.0701 (7)	0.0422 (5)	0.0486 (6)	0.0307 (5)	0.0365 (5)	0.0214 (4)
C8	0.0382 (5)	0.0329 (4)	0.0413 (5)	0.0146 (4)	0.0197 (4)	0.0144 (4)
O1W	0.0812 (9)	0.0655 (8)	0.1106 (12)	−0.0041 (7)	0.0578 (9)	−0.0212 (8)

Cu1—O2i	1.9169 (7)	C5—H5B	0.97
Cu1—O2	1.9169 (7)	N1—C7	1.3292 (16)
Cu1—O1	2.0857 (8)	N1—H1N1	0.86
Cu1—O1i	2.0857 (8)	N1—H2N1	0.86
Cu1—O3i	2.2015 (7)	N2—C7	1.3189 (17)
Cu1—O3	2.2016 (7)	N2—H1N2	0.86
O1—C1	1.2704 (12)	N2—H2N2	0.86
O2—C4	1.2798 (12)	N3—C7	1.3162 (16)
O3—C3	1.4401 (11)	N3—H1N3	0.86
O3—H1O3	0.95	N3—H2N3	0.86
O4—C1	1.2432 (13)	N4—C8	1.3255 (14)
O5—C4	1.2286 (12)	N4—H1N4	0.86
O7—C6	1.2464 (13)	N4—H2N4	0.86
O6—C6	1.2678 (13)	N5—C8	1.3232 (15)
C1—C2	1.5261 (14)	N5—H1N5	0.86
C2—C3	1.5273 (13)	N5—H2N5	0.86
C2—H2A	0.97	N6—C8	1.3191 (15)
C2—H2B	0.97	N6—H1N6	0.86
C3—C5	1.5334 (13)	N6—H2N6	0.86
C3—C4	1.5513 (13)	O1W—H1W1	0.78
C5—C6	1.5234 (14)	O1W—H2W1	0.90
C5—H5A	0.97
O2i—Cu1—O2	179.999 (1)	O5—C4—C3	119.72 (9)
O2i—Cu1—O1	89.36 (4)	O2—C4—C3	116.95 (8)
O2—Cu1—O1	90.64 (4)	C6—C5—C3	113.23 (8)
O2i—Cu1—O1i	90.64 (4)	C6—C5—H5A	108.9
O2—Cu1—O1i	89.36 (4)	C3—C5—H5A	108.9
O1—Cu1—O1i	180.00 (3)	C6—C5—H5B	108.9
O2i—Cu1—O3i	80.58 (3)	C3—C5—H5B	108.9
O2—Cu1—O3i	99.42 (3)	H5A—C5—H5B	107.7
O1—Cu1—O3i	97.62 (3)	O7—C6—O6	123.57 (10)
O1i—Cu1—O3i	82.38 (3)	O7—C6—C5	119.46 (10)
O2i—Cu1—O3	99.42 (3)	O6—C6—C5	116.94 (9)
O2—Cu1—O3	80.58 (3)	C7—N1—H1N1	120.0
O1—Cu1—O3	82.38 (3)	C7—N1—H2N1	120.0
O1i—Cu1—O3	97.62 (3)	H1N1—N1—H2N1	120.0
O3i—Cu1—O3	180.0	C7—N2—H1N2	120.0
C1—O1—Cu1	131.70 (7)	C7—N2—H2N2	120.0
C4—O2—Cu1	116.90 (6)	H1N2—N2—H2N2	120.0
C3—O3—Cu1	102.63 (5)	C7—N3—H1N3	120.0
C3—O3—H1O3	103.2	C7—N3—H2N3	120.0
Cu1—O3—H1O3	113.8	H1N3—N3—H2N3	120.0
O4—C1—O1	122.02 (10)	N3—C7—N2	119.75 (11)
O4—C1—C2	116.47 (9)	N3—C7—N1	119.69 (13)
O1—C1—C2	121.51 (9)	N2—C7—N1	120.54 (12)
C1—C2—C3	117.43 (7)	C8—N4—H1N4	120.0
C1—C2—H2A	107.9	C8—N4—H2N4	120.0
C3—C2—H2A	107.9	H1N4—N4—H2N4	120.0
C1—C2—H2B	107.9	C8—N5—H1N5	120.0
C3—C2—H2B	107.9	C8—N5—H2N5	120.0
H2A—C2—H2B	107.2	H1N5—N5—H2N5	120.0
O3—C3—C2	107.59 (7)	C8—N6—H1N6	120.0
O3—C3—C5	109.31 (8)	C8—N6—H2N6	120.0
C2—C3—C5	110.83 (7)	H1N6—N6—H2N6	120.0
O3—C3—C4	110.36 (7)	N6—C8—N5	120.42 (10)
C2—C3—C4	109.34 (8)	N6—C8—N4	120.42 (11)
C5—C3—C4	109.39 (8)	N5—C8—N4	119.15 (11)
O5—C4—O2	123.33 (10)	H1W1—O1W—H2W1	101.6
O2i—Cu1—O1—C1	118.93 (11)	Cu1—O3—C3—C4	−32.73 (8)
O2—Cu1—O1—C1	−61.07 (11)	C1—C2—C3—O3	−55.52 (11)
O3i—Cu1—O1—C1	−160.66 (11)	C1—C2—C3—C5	−174.99 (9)
O3—Cu1—O1—C1	19.33 (11)	C1—C2—C3—C4	64.35 (11)
O1—Cu1—O2—C4	58.64 (8)	Cu1—O2—C4—O5	−169.11 (10)
O1i—Cu1—O2—C4	−121.36 (8)	Cu1—O2—C4—C3	10.43 (12)
O3i—Cu1—O2—C4	156.47 (8)	O3—C3—C4—O5	−161.50 (10)
O3—Cu1—O2—C4	−23.53 (8)	C2—C3—C4—O5	80.34 (12)
O2i—Cu1—O3—C3	−149.08 (5)	C5—C3—C4—O5	−41.19 (13)
O2—Cu1—O3—C3	30.92 (5)	O3—C3—C4—O2	18.95 (12)
O1—Cu1—O3—C3	−61.01 (5)	C2—C3—C4—O2	−99.21 (10)
O1i—Cu1—O3—C3	118.99 (5)	C5—C3—C4—O2	139.26 (9)
Cu1—O1—C1—O4	−173.35 (10)	O3—C3—C5—C6	52.33 (11)
Cu1—O1—C1—C2	6.55 (17)	C2—C3—C5—C6	170.76 (9)
O4—C1—C2—C3	−177.27 (11)	C4—C3—C5—C6	−68.62 (10)
O1—C1—C2—C3	2.83 (16)	C3—C5—C6—O7	147.04 (11)
Cu1—O3—C3—C2	86.49 (7)	C3—C5—C6—O6	−34.97 (14)
Cu1—O3—C3—C5	−153.08 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O6	0.95	1.61	2.5034 (13)	154
N1—H1N1···O5ii	0.86	2.44	3.169 (2)	143
N1—H2N1···O2iii	0.86	2.47	3.0810 (19)	129
N1—H2N1···O1iv	0.86	2.50	3.3243 (18)	161
N2—H1N2···O7v	0.86	2.06	2.906 (2)	169
N2—H2N2···O4iv	0.86	2.07	2.8811 (14)	157
N3—H1N3···O6v	0.86	2.02	2.860 (2)	167
N3—H2N3···O5ii	0.86	2.12	2.937 (2)	157
N4—H1N4···O1Wvi	0.86	2.10	2.916 (2)	157
N4—H2N4···O6vii	0.86	2.56	3.0760 (18)	119
N4—H2N4···O7ii	0.86	2.26	2.9973 (17)	144
N5—H1N5···O2iii	0.86	2.06	2.8484 (15)	152
N5—H2N5···O7ii	0.86	2.03	2.8273 (17)	153
N6—H1N6···O3iv	0.86	2.18	3.0140 (14)	164
N6—H2N6···O4	0.86	1.99	2.8387 (18)	170
O1W—H1W1···O4vi	0.78	2.52	3.032 (2)	124
O1W—H2W1···O1iii	0.90	2.03	2.932 (2)	175

Table 1

Selected bond lengths (Å)

Cu1—O2	1.9169 (7)
Cu1—O1	2.0857 (8)
Cu1—O3	2.2016 (7)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O6	0.95	1.61	2.5034 (13)	154
N1—H1N1⋯O5i	0.86	2.44	3.169 (2)	143
N1—H2N1⋯O2ii	0.86	2.47	3.0810 (19)	129
N1—H2N1⋯O1iii	0.86	2.50	3.3243 (18)	161
N2—H1N2⋯O7iv	0.86	2.06	2.906 (2)	169
N2—H2N2⋯O4iii	0.86	2.07	2.8811 (14)	157
N3—H1N3⋯O6iv	0.86	2.02	2.860 (2)	167
N3—H2N3⋯O5i	0.86	2.12	2.937 (2)	157
N4—H1N4⋯O1W v	0.86	2.10	2.916 (2)	157
N4—H2N4⋯O6vi	0.86	2.56	3.0760 (18)	119
N4—H2N4⋯O7i	0.86	2.26	2.9973 (17)	144
N5—H1N5⋯O2ii	0.86	2.06	2.8484 (15)	152
N5—H2N5⋯O7i	0.86	2.03	2.8273 (17)	153
N6—H1N6⋯O3iii	0.86	2.18	3.0140 (14)	164
N6—H2N6⋯O4	0.86	1.99	2.8387 (18)	170
O1W—H1W1⋯O4v	0.78	2.52	3.032 (2)	124
O1W—H2W1⋯O1ii	0.90	2.03	2.932 (2)	175

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