catena-Poly[[[triaqua­calcium(II)]-di-μ-glycine-κ⁴O:O′] diiodide]

In the crystal structure of the title compound, {[Ca(C₂H₅NO₂)₂(H₂O)₃]I₂}_n, there are two formula units per asymmetric unit; both calcium cations are sevenfold coordinated within irregular polyhedra. The polyhedra can be divided into two halves as square pyramidal and triangular prismatic due to the presence of one and two coordinated water molecules above and below the square plane. In all the glycine zwitterions, the amino groups form three two-centred hydrogen bonds, leading to a class I hydrogen-bonding pattern. The backbone conformations of the amino acids are cis and trans.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.020
• wR factor = 0.057
• Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       5.33 Ratio

Author Response: This is due to the presence of water molecules in the coordination sphere.

Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H3W    ..  H10W    ..       1.99 Ang.
PLAT420_ALERT_2_B D-H Without Acceptor       O5W    -   H10W   ...          ?

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       1.05
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.20
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ca1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ca2
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2E    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4C    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2E    ..  I4      ..       3.19 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A    ..  I1      ..       3.11 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4C    ..  I2      ..       3.24 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          9
            O2  -C1  -O1  -CA2   169.00  2.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         10
            C2  -C1  -O1  -CA2   -14.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            O7  -CA2 -O1  -C1   -157.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            O6  -CA2 -O1  -C1    147.00  3.00   1.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            O4  -CA2 -O1  -C1     30.00  3.00   1.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         14
            O4W -CA2 -O1  -C1    116.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         15
            O5W -CA2 -O1  -C1    -75.00  3.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         16
            O6W -CA2 -O1  -C1    -37.00  3.00   1.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           24.97
           From the CIF: _reflns_number_total               2784
           From the CIF: _diffrn_reflns_limit_ max hkl   11.   15.   27.
           From the CIF: _diffrn_reflns_limit_ min hkl    0.    0.   -1.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   15.   11.   27.
           Calculated minimum hkl  -15.  -11.  -27.
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           24.97
           From the CIF: _reflns_number_total               2784
           Count of symmetry unique reflns         2649
           Completeness (_total/calc)            105.10%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       135
           Fraction of Friedel pairs measured     0.051
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         19

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  22 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

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

---

S1. Comment

Glycine, the simplest amino acid, readily forms coordination complexes with many inorganic acids. Calcium has unique biological functions such as contraction of the muscle, mitochondrial functions, activation of enzymes, passage through cell membrances and other biological processes (Kretsinger & Nelson, 1976).

A systematic study on glycine-calcium coordination complexes were carried out from our laboratory (Natarajan, 1976) and the structures of bis(glycine) calcium(II) dichloride tetrahydrate (Natarajan & Mohana Rao, 1980), tris(glycine) calcium(II) dibromide (Mohana Rao & Natarajan, 1980), tris(glycine) calcium(II) diiodide monohydrate (Natarajan & Mohana Rao, 1981) and tris(glycine) calcium (II) dichloride (Ravikumar et al., 1986) were already reported. Here, the crystal structure of another complex of glycine is presented.

The asymmetric unit of the title compound, (I), contains two calcium(II) cations, four glycine zwitterions, six water molecules and four iodine anions (Fig. 1). The zwitterionic nature of glycine is evident from the C—O and C—N bond distances. The back bone conformation angles are observed to be cis and trans forms in all the glycine zwitterions. Each calcium(II) is linked to four glycine oxygen atoms and three water oxygen atoms, leading to a sevenfold coordination. The calcium(II) ion surrounded by four glycine O atoms, within a square planar geometry. Water O atoms are oriented above and below this square-plane. One halve of the polyhedra is a square pyrimidal in which the square plane is capped by one water molecule and the other halve is a square prism with two water molecules above the square plane. The Ca(II) cations are connected by the glycine molecules into chains which elongate in the direction of the a axis (Fig. 2)..

Eventhough the metal coordination dominates, the crystal structure is further stabilized by three dimensional hydrogen bonding (Table 2). The iodine anions are acting as acceptors for N—H···I and O—H···I hydrogen bonds The amino groups of the glycine molecules are involved in three two-centered hydrogen bonds leading to class I hydrogen bonding pattern.

Related literature

For related literature on glycine-metal complexes, see: Natarajan, (1976); Natarajan & Mohana Rao (1980); Mohana Rao & Natarajan (1980); Natarajan & Mohana Rao (1981) & Ravikumar et al., (1986) and on values of bond lengths and angles, see: Allen (2002). For the information about the importance of calcium in biological systems, see Kretsinger & Nelson, (1976)

S2. Experimental

The title compound, (I), was crystallized from an aqueous solution containing glycine and calcium(II) diiodide, in the stochiometric ratio of 2:1, at room temperature, by the technique of slow evaporation.

S3. Refinement

Not all of the N—H H atoms were located in difference map but the zwitterionic nature of the glycine molecule is evident from the C—O and C—N bond distances. Thus, all the H atoms except water H atoms were positioned with idealized geometry and refined using a riding model, with C—H = 0.97 Å and N—H = 0.89 Å and U_iso(H) = 1.2–1.5 U_eq (parent atom). The H atoms of the water molecules were located in the difference fourier map and refined with varying coordinates isotropically. The absolute structure was determined and 135 Friedel pairs have been measured.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC (Bruker, 2000); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL/PC (Bruker, 2000).

Figures

	Fig. 1. The molecular structure of (I) with the atom numbering scheme and 50% probability displacement ellipsoids. H bonds are shown as dashed lines.
	Fig. 2. Crystal structure of I, viewed down the b-axis. Hydrogen bonding is not shown for clarity.

catena-Poly[[[triaquacalcium(II)]-di-µ-glycine-κ⁴O:O'] diiodide]

Crystal data

[Ca(C2H5NO2)2(H2O)3]I2	F(000) = 1888
Mr = 498.07	Dx = 2.259 Mg m^−3 Dm = 2.24 (2) Mg m^−3 Dm measured by flotation in a mixture of carbon tetrachloride and bromoform
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 13.065 (8) Å	θ = 10.4–12.9°
b = 9.861 (4) Å	µ = 4.66 mm^−1
c = 22.731 (9) Å	T = 293 K
V = 2929 (2) Å^3	Block, colourless
Z = 8	0.24 × 0.19 × 0.15 mm

Data collection

Nonius MACH-3 sealed-tube diffractometer	2406 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω–2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.337, Tmax = 0.474	l = −1→27
2784 measured reflections	3 standard reflections every 60 min
2784 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0312P)^2 + 1.5679P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.057	(Δ/σ)max = 0.001
S = 1.11	Δρmax = 0.93 e Å^−3
2784 reflections	Δρmin = −0.42 e Å^−3
342 parameters	Extinction correction: SHELXTL/PC (Bruker, 2000), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
19 restraints	Extinction coefficient: 0.00170 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 135 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (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
Ca1	0.35756 (8)	0.41229 (10)	−0.39714 (7)	0.0216 (2)
Ca2	0.41323 (8)	0.90112 (10)	−0.40719 (6)	0.0202 (2)
C1	0.3206 (4)	0.6346 (6)	−0.4993 (3)	0.0217 (12)
C2	0.2920 (5)	0.6822 (5)	−0.5600 (3)	0.0288 (16)
H2A	0.3125	0.6145	−0.5886	0.035*
H2B	0.2183	0.6927	−0.5624	0.035*
C3	0.3316 (4)	0.1391 (6)	−0.4988 (3)	0.0227 (13)
C4	0.3037 (5)	0.1800 (5)	−0.5612 (3)	0.0288 (16)
H4A	0.3312	0.1144	−0.5887	0.035*
H4B	0.2298	0.1813	−0.5655	0.035*
C5	0.4259 (4)	0.1518 (6)	−0.3058 (3)	0.0202 (12)
C6	0.4047 (5)	0.1935 (5)	−0.2419 (3)	0.0255 (13)
H6A	0.3316	0.2048	−0.2359	0.031*
H6B	0.4288	0.1235	−0.2153	0.031*
C7	0.4335 (4)	0.6509 (6)	−0.3023 (3)	0.0221 (13)
C8	0.4128 (5)	0.6959 (5)	−0.2390 (3)	0.0251 (13)
H8A	0.3397	0.7017	−0.2323	0.030*
H8B	0.4412	0.6303	−0.2117	0.030*
N1	0.3420 (4)	0.8134 (4)	−0.5744 (3)	0.0296 (12)
H1A	0.3252	0.8749	−0.5474	0.044*
H1B	0.3212	0.8414	−0.6096	0.044*
H1C	0.4096	0.8025	−0.5747	0.044*
N2	0.3458 (4)	0.3167 (4)	−0.5744 (3)	0.0292 (12)
H2C	0.3247	0.3753	−0.5472	0.044*
H2D	0.3241	0.3435	−0.6097	0.044*
H2E	0.4139	0.3131	−0.5742	0.044*
N3	0.4583 (4)	0.3227 (4)	−0.2296 (3)	0.0288 (12)
H3A	0.5256	0.3097	−0.2318	0.043*
H3B	0.4420	0.3513	−0.1937	0.043*
H3C	0.4396	0.3846	−0.2560	0.043*
N4	0.4604 (5)	0.8292 (4)	−0.2294 (3)	0.0293 (12)
H4C	0.5281	0.8213	−0.2319	0.044*
H4D	0.4435	0.8598	−0.1939	0.044*
H4E	0.4383	0.8870	−0.2567	0.044*
O1	0.3517 (4)	0.7195 (4)	−0.4632 (2)	0.0355 (10)
O2	0.3073 (3)	0.5119 (4)	−0.4883 (2)	0.0301 (10)
O3	0.3535 (4)	0.2306 (4)	−0.4641 (2)	0.0361 (10)
O4	0.3284 (3)	0.0146 (4)	−0.4867 (2)	0.0290 (10)
O5	0.4493 (3)	0.2426 (4)	−0.34088 (18)	0.0283 (9)
O6	0.4156 (3)	0.0272 (4)	−0.31733 (19)	0.0291 (10)
O7	0.4621 (4)	0.7375 (4)	−0.33814 (19)	0.0357 (10)
O8	0.4172 (3)	0.5275 (4)	−0.3127 (2)	0.0321 (10)
I1	0.32577 (3)	0.93569 (4)	−0.721030 (18)	0.03548 (13)
I2	0.32429 (3)	0.44141 (4)	−0.721120 (18)	0.03469 (12)
I3	0.43649 (3)	0.42713 (4)	−0.079737 (17)	0.03247 (12)
I4	0.43004 (3)	0.93532 (4)	−0.079283 (19)	0.03562 (12)
O1W	0.5271 (4)	0.4429 (6)	−0.4352 (2)	0.0472 (13)
O2W	0.2138 (4)	0.2778 (6)	−0.3631 (3)	0.0565 (15)
O3W	0.2119 (3)	0.5782 (5)	−0.3679 (2)	0.0352 (10)
O4W	0.2409 (3)	0.8749 (5)	−0.3696 (2)	0.0381 (10)
O5W	0.5691 (4)	0.8135 (5)	−0.4583 (3)	0.0502 (14)
O6W	0.5463 (3)	1.0843 (4)	−0.4229 (2)	0.0307 (10)
H1W	0.531 (8)	0.492 (11)	−0.469 (3)	0.15 (5)*
H2W	0.579 (4)	0.437 (7)	−0.412 (3)	0.06 (2)*
H3W	0.175 (5)	0.263 (9)	−0.395 (3)	0.07 (3)*
H4W	0.184 (6)	0.324 (8)	−0.334 (3)	0.09 (4)*
H5W	0.198 (6)	0.548 (7)	−0.329 (2)	0.06 (2)*
H6W	0.219 (6)	0.669 (4)	−0.365 (3)	0.05 (2)*
H7W	0.182 (5)	0.894 (10)	−0.392 (4)	0.12 (4)*
H8W	0.220 (5)	0.911 (7)	−0.335 (2)	0.05 (2)*
H9W	0.563 (10)	0.808 (10)	−0.498 (2)	0.16 (6)*
H10W	0.565 (5)	0.721 (4)	−0.455 (4)	0.05 (2)*
H11W	0.546 (5)	1.100 (7)	−0.460 (2)	0.05 (2)*
H12W	0.518 (5)	1.162 (5)	−0.405 (3)	0.05 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0268 (5)	0.0221 (5)	0.0158 (5)	−0.0007 (4)	−0.0028 (5)	−0.0002 (5)
Ca2	0.0252 (5)	0.0184 (5)	0.0172 (5)	−0.0015 (4)	−0.0024 (5)	0.0002 (5)
C1	0.025 (3)	0.019 (3)	0.022 (3)	0.002 (2)	−0.002 (2)	−0.001 (3)
C2	0.033 (3)	0.025 (3)	0.029 (4)	−0.005 (2)	−0.008 (3)	0.001 (2)
C3	0.026 (3)	0.023 (3)	0.019 (3)	0.006 (2)	0.000 (2)	0.000 (3)
C4	0.031 (3)	0.028 (3)	0.028 (4)	−0.005 (2)	−0.005 (3)	−0.001 (2)
C5	0.020 (3)	0.018 (3)	0.023 (3)	0.005 (2)	−0.008 (2)	0.000 (2)
C6	0.036 (3)	0.022 (3)	0.019 (3)	0.002 (2)	0.004 (3)	−0.004 (2)
C7	0.025 (3)	0.017 (3)	0.024 (4)	0.007 (2)	−0.010 (3)	0.000 (3)
C8	0.029 (3)	0.022 (3)	0.024 (4)	0.002 (2)	0.000 (3)	−0.006 (2)
N1	0.043 (3)	0.020 (2)	0.026 (3)	−0.0022 (18)	−0.004 (3)	0.004 (2)
N2	0.046 (3)	0.023 (3)	0.019 (3)	−0.0089 (19)	−0.002 (3)	0.002 (2)
N3	0.048 (3)	0.024 (3)	0.014 (3)	−0.006 (2)	−0.003 (3)	−0.001 (2)
N4	0.049 (3)	0.021 (2)	0.017 (3)	−0.003 (2)	−0.003 (3)	−0.001 (2)
O1	0.057 (3)	0.028 (2)	0.022 (2)	−0.004 (2)	−0.009 (2)	−0.004 (2)
O2	0.045 (2)	0.018 (2)	0.028 (2)	−0.0014 (18)	−0.0062 (19)	0.0009 (19)
O3	0.061 (3)	0.026 (2)	0.021 (2)	0.006 (2)	−0.006 (2)	−0.006 (2)
O4	0.038 (2)	0.021 (2)	0.028 (3)	0.0011 (16)	−0.0073 (19)	0.0024 (19)
O5	0.048 (2)	0.021 (2)	0.016 (2)	0.0006 (18)	−0.0002 (19)	−0.0008 (17)
O6	0.043 (2)	0.022 (2)	0.023 (2)	−0.0017 (18)	−0.0002 (19)	−0.0042 (18)
O7	0.064 (3)	0.022 (2)	0.021 (2)	−0.001 (2)	−0.002 (2)	0.0025 (18)
O8	0.043 (2)	0.024 (2)	0.029 (3)	−0.0011 (18)	−0.006 (2)	−0.005 (2)
I1	0.0308 (2)	0.0491 (3)	0.0266 (2)	−0.00419 (16)	−0.00330 (18)	0.0049 (2)
I2	0.0313 (2)	0.0459 (2)	0.0269 (2)	−0.00344 (15)	−0.00259 (17)	0.0064 (2)
I3	0.0314 (2)	0.0413 (2)	0.0248 (2)	0.00207 (15)	−0.00133 (19)	−0.0039 (2)
I4	0.0296 (2)	0.0507 (3)	0.0265 (2)	0.00068 (16)	−0.0012 (2)	−0.0064 (2)
O1W	0.032 (3)	0.085 (4)	0.024 (2)	−0.002 (2)	−0.005 (2)	0.012 (3)
O2W	0.046 (3)	0.058 (3)	0.065 (4)	−0.018 (3)	0.015 (3)	−0.009 (3)
O3W	0.037 (2)	0.038 (2)	0.030 (3)	0.0003 (19)	0.002 (2)	0.006 (2)
O4W	0.031 (2)	0.055 (3)	0.028 (3)	0.000 (2)	0.001 (2)	−0.007 (2)
O5W	0.049 (3)	0.049 (3)	0.053 (4)	0.008 (2)	0.004 (3)	−0.016 (3)
O6W	0.033 (2)	0.033 (2)	0.026 (3)	0.0022 (17)	0.0013 (18)	−0.003 (2)

Geometric parameters (Å, º)

Ca1—O3	2.352 (4)	C7—O7	1.239 (8)
Ca1—O8	2.362 (5)	C7—O8	1.258 (7)
Ca1—O2	2.386 (5)	C7—C8	1.529 (9)
Ca1—O1W	2.397 (5)	C8—N4	1.469 (7)
Ca1—O5	2.423 (4)	C8—H8A	0.9700
Ca1—O2W	2.427 (5)	C8—H8B	0.9700
Ca1—O3W	2.596 (5)	N1—H1A	0.8900
Ca2—O7	2.339 (4)	N1—H1B	0.8900
Ca2—O1	2.340 (4)	N1—H1C	0.8900
Ca2—O6^i	2.391 (4)	N2—H2C	0.8900
Ca2—O4^i	2.398 (4)	N2—H2D	0.8900
Ca2—O4W	2.423 (5)	N2—H2E	0.8900
Ca2—O5W	2.499 (6)	N3—H3A	0.8900
Ca2—O6W	2.533 (5)	N3—H3B	0.8900
C1—O1	1.240 (7)	N3—H3C	0.8900
C1—O2	1.248 (7)	N4—H4C	0.8900
C1—C2	1.505 (9)	N4—H4D	0.8900
C2—N1	1.485 (7)	N4—H4E	0.8900
C2—H2A	0.9700	O4—Ca2^ii	2.398 (4)
C2—H2B	0.9700	O6—Ca2^ii	2.391 (4)
C3—O3	1.231 (7)	O1W—H1W	0.90 (5)
C3—O4	1.259 (7)	O1W—H2W	0.86 (4)
C3—C4	1.519 (9)	O2W—H3W	0.90 (4)
C4—N2	1.486 (7)	O2W—H4W	0.89 (4)
C4—H4A	0.9700	O3W—H5W	0.94 (4)
C4—H4B	0.9700	O3W—H6W	0.90 (4)
C5—O5	1.237 (7)	O4W—H7W	0.94 (5)
C5—O6	1.264 (7)	O4W—H8W	0.90 (4)
C5—C6	1.535 (8)	O5W—H9W	0.92 (5)
C6—N3	1.481 (7)	O5W—H10W	0.92 (4)
C6—H6A	0.9700	O6W—H11W	0.86 (4)
C6—H6B	0.9700	O6W—H12W	0.94 (4)
O3—Ca1—O8	154.10 (16)	N3—C6—H6A	109.9
O3—Ca1—O2	75.24 (15)	C5—C6—H6A	109.9
O8—Ca1—O2	126.78 (14)	N3—C6—H6B	109.9
O3—Ca1—O1W	83.28 (18)	C5—C6—H6B	109.9
O8—Ca1—O1W	85.87 (17)	H6A—C6—H6B	108.3
O2—Ca1—O1W	83.63 (17)	O7—C7—O8	126.5 (6)
O3—Ca1—O5	80.00 (15)	O7—C7—C8	118.1 (5)
O8—Ca1—O5	74.94 (14)	O8—C7—C8	115.4 (5)
O2—Ca1—O5	151.50 (15)	N4—C8—C7	109.0 (5)
O1W—Ca1—O5	79.64 (17)	N4—C8—H8A	109.9
O3—Ca1—O2W	76.9 (2)	C7—C8—H8A	109.9
O8—Ca1—O2W	105.0 (2)	N4—C8—H8B	109.9
O2—Ca1—O2W	106.8 (2)	C7—C8—H8B	109.9
O1W—Ca1—O2W	154.1 (2)	H8A—C8—H8B	108.3
O5—Ca1—O2W	80.62 (19)	C2—N1—H1A	109.5
O3—Ca1—O3W	129.02 (16)	C2—N1—H1B	109.5
O8—Ca1—O3W	74.37 (16)	H1A—N1—H1B	109.5
O2—Ca1—O3W	76.21 (15)	C2—N1—H1C	109.5
O1W—Ca1—O3W	133.69 (17)	H1A—N1—H1C	109.5
O5—Ca1—O3W	131.48 (15)	H1B—N1—H1C	109.5
O2W—Ca1—O3W	72.24 (18)	C4—N2—H2C	109.5
O7—Ca2—O1	86.05 (16)	C4—N2—H2D	109.5
O7—Ca2—O6^i	77.39 (15)	H2C—N2—H2D	109.5
O1—Ca2—O6^i	150.14 (16)	C4—N2—H2E	109.5
O7—Ca2—O4^i	162.50 (15)	H2C—N2—H2E	109.5
O1—Ca2—O4^i	77.75 (15)	H2D—N2—H2E	109.5
O6^i—Ca2—O4^i	114.06 (15)	C6—N3—H3A	109.5
O7—Ca2—O4W	86.73 (17)	C6—N3—H3B	109.5
O1—Ca2—O4W	77.96 (16)	H3A—N3—H3B	109.5
O6^i—Ca2—O4W	76.46 (16)	C6—N3—H3C	109.5
O4^i—Ca2—O4W	83.48 (16)	H3A—N3—H3C	109.5
O7—Ca2—O5W	81.4 (2)	H3B—N3—H3C	109.5
O1—Ca2—O5W	76.25 (17)	C8—N4—H4C	109.5
O6^i—Ca2—O5W	124.48 (18)	C8—N4—H4D	109.5
O4^i—Ca2—O5W	100.82 (19)	H4C—N4—H4D	109.5
O4W—Ca2—O5W	152.23 (17)	C8—N4—H4E	109.5
O7—Ca2—O6W	113.54 (15)	H4C—N4—H4E	109.5
O1—Ca2—O6W	134.82 (16)	H4D—N4—H4E	109.5
O6^i—Ca2—O6W	74.98 (15)	C1—O1—Ca2	171.5 (4)
O4^i—Ca2—O6W	83.00 (14)	C1—O2—Ca1	122.3 (4)
O4W—Ca2—O6W	139.82 (16)	C3—O3—Ca1	167.8 (4)
O5W—Ca2—O6W	67.76 (16)	C3—O4—Ca2^ii	127.1 (4)
O1—C1—O2	124.6 (6)	C5—O5—Ca1	135.8 (4)
O1—C1—C2	118.5 (5)	C5—O6—Ca2^ii	133.1 (4)
O2—C1—C2	116.8 (5)	C7—O7—Ca2	146.6 (4)
N1—C2—C1	111.4 (5)	C7—O8—Ca1	132.4 (4)
N1—C2—H2A	109.4	Ca1—O1W—H1W	115 (7)
C1—C2—H2A	109.4	Ca1—O1W—H2W	121 (5)
N1—C2—H2B	109.4	H1W—O1W—H2W	120 (7)
C1—C2—H2B	109.4	Ca1—O2W—H3W	106 (5)
H2A—C2—H2B	108.0	Ca1—O2W—H4W	107 (6)
O3—C3—O4	125.6 (6)	H3W—O2W—H4W	116 (7)
O3—C3—C4	117.3 (5)	Ca1—O3W—H5W	100 (4)
O4—C3—C4	117.0 (5)	Ca1—O3W—H6W	125 (5)
N2—C4—C3	109.9 (5)	H5W—O3W—H6W	105 (6)
N2—C4—H4A	109.7	Ca2—O4W—H7W	123 (6)
C3—C4—H4A	109.7	Ca2—O4W—H8W	123 (5)
N2—C4—H4B	109.7	H7W—O4W—H8W	99 (6)
C3—C4—H4B	109.7	Ca2—O5W—H9W	114 (8)
H4A—C4—H4B	108.2	Ca2—O5W—H10W	106 (5)
O5—C5—O6	126.6 (6)	H9W—O5W—H10W	90 (6)
O5—C5—C6	117.4 (5)	Ca2—O6W—H11W	105 (5)
O6—C5—C6	115.9 (5)	Ca2—O6W—H12W	105 (4)
N3—C6—C5	108.9 (5)	H11W—O6W—H12W	106 (6)
O1—C1—C2—N1	21.7 (8)	O2W—Ca1—O3—C3	42 (2)
O2—C1—C2—N1	−160.9 (5)	O3W—Ca1—O3—C3	−12 (2)
O3—C3—C4—N2	21.5 (8)	O3—C3—O4—Ca2^ii	−22.0 (8)
O4—C3—C4—N2	−159.8 (5)	C4—C3—O4—Ca2^ii	159.4 (4)
O5—C5—C6—N3	−24.0 (7)	O6—C5—O5—Ca1	98.4 (7)
O6—C5—C6—N3	157.3 (5)	C6—C5—O5—Ca1	−80.2 (7)
O7—C7—C8—N4	−16.5 (7)	O3—Ca1—O5—C5	−88.7 (6)
O8—C7—C8—N4	164.9 (5)	O8—Ca1—O5—C5	97.9 (6)
O2—C1—O1—Ca2	169 (2)	O2—Ca1—O5—C5	−118.6 (6)
C2—C1—O1—Ca2	−14 (3)	O1W—Ca1—O5—C5	−173.6 (6)
O7—Ca2—O1—C1	−157 (3)	O2W—Ca1—O5—C5	−10.5 (6)
O6^i—Ca2—O1—C1	147 (3)	O3W—Ca1—O5—C5	45.5 (6)
O4^i—Ca2—O1—C1	30 (3)	O5—C5—O6—Ca2^ii	−8.6 (9)
O4W—Ca2—O1—C1	116 (3)	C6—C5—O6—Ca2^ii	170.0 (4)
O5W—Ca2—O1—C1	−75 (3)	O8—C7—O7—Ca2	89.7 (9)
O6W—Ca2—O1—C1	−37 (3)	C8—C7—O7—Ca2	−88.7 (8)
O1—C1—O2—Ca1	−6.9 (8)	O1—Ca2—O7—C7	−66.8 (8)
C2—C1—O2—Ca1	175.9 (4)	O6^i—Ca2—O7—C7	88.1 (8)
O3—Ca1—O2—C1	−156.4 (4)	O4^i—Ca2—O7—C7	−44.7 (11)
O8—Ca1—O2—C1	8.3 (5)	O4W—Ca2—O7—C7	11.3 (8)
O1W—Ca1—O2—C1	−71.7 (4)	O5W—Ca2—O7—C7	−143.5 (8)
O5—Ca1—O2—C1	−125.9 (4)	O6W—Ca2—O7—C7	155.4 (7)
O2W—Ca1—O2—C1	132.5 (4)	O7—C7—O8—Ca1	−31.9 (9)
O3W—Ca1—O2—C1	66.3 (4)	C8—C7—O8—Ca1	146.5 (4)
O4—C3—O3—Ca1	−101 (2)	O3—Ca1—O8—C7	142.7 (5)
C4—C3—O3—Ca1	77 (2)	O2—Ca1—O8—C7	−1.6 (6)
O8—Ca1—O3—C3	139 (2)	O1W—Ca1—O8—C7	77.3 (5)
O2—Ca1—O3—C3	−70 (2)	O5—Ca1—O8—C7	157.7 (5)
O1W—Ca1—O3—C3	−155 (2)	O2W—Ca1—O8—C7	−126.6 (5)
O5—Ca1—O3—C3	124 (2)	O3W—Ca1—O8—C7	−60.3 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4^i	0.89	1.95	2.817 (7)	165
N1—H1B···I1	0.89	2.70	3.551 (7)	161
N1—H1C···I3^iii	0.89	3.03	3.743 (5)	139
N2—H2C···O2	0.89	1.91	2.790 (7)	169
N2—H2D···I2	0.89	2.71	3.566 (6)	161
N2—H2E···I4^iii	0.89	3.19	3.842 (6)	132
N3—H3A···I1^iv	0.89	3.11	3.806 (6)	136
N3—H3B···I3	0.89	2.70	3.570 (6)	167
N3—H3C···O8	0.89	1.93	2.817 (7)	173
N4—H4C···I2^iv	0.89	3.24	3.882 (5)	131
N4—H4D···I4	0.89	2.72	3.592 (6)	168
N4—H4E···O6^i	0.89	1.97	2.854 (7)	170
O1W—H1W···I3^iii	0.90 (5)	2.68 (6)	3.559 (5)	164 (11)
O1W—H2W···O3W^v	0.86 (4)	2.01 (4)	2.866 (7)	173 (7)
O2W—H3W···O5W^vi	0.90 (4)	2.13 (5)	3.011 (10)	166 (8)
O2W—H4W···I2^vii	0.89 (4)	2.81 (6)	3.641 (7)	154 (7)
O3W—H5W···I2^vii	0.94 (4)	2.69 (4)	3.629 (5)	174 (6)
O3W—H6W···O4W	0.90 (4)	2.06 (4)	2.951 (7)	172 (7)
O4W—H7W···O6W^viii	0.94 (5)	1.92 (5)	2.845 (6)	167 (9)
O4W—H8W···I1^vii	0.90 (4)	2.67 (5)	3.538 (5)	161 (6)
O5W—H9W···I3^iii	0.92 (5)	2.96 (9)	3.641 (6)	132 (8)
O6W—H11W···I4^ix	0.86 (4)	2.75 (5)	3.573 (5)	161 (6)
O6W—H12W···O5^i	0.94 (4)	1.89 (5)	2.742 (6)	150 (6)

Symmetry codes: (i) x, y+1, z; (iii) −x+1, −y+1, z−1/2; (iv) −x+1, −y+1, z+1/2; (v) x+1/2, −y+1, z; (vi) x−1/2, −y+1, z; (vii) −x+1/2, y, z+1/2; (viii) x−1/2, −y+2, z; (ix) −x+1, −y+2, z−1/2.